CN101451324A - Pulp and black liquor prepared by grass type raw material, preparation method and use thereof - Google Patents

Pulp and black liquor prepared by grass type raw material, preparation method and use thereof Download PDF

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CN101451324A
CN101451324A CN 200710300209 CN200710300209A CN101451324A CN 101451324 A CN101451324 A CN 101451324A CN 200710300209 CN200710300209 CN 200710300209 CN 200710300209 A CN200710300209 A CN 200710300209A CN 101451324 A CN101451324 A CN 101451324A
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pulp
hardness
raw material
black liquor
slurry
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CN101451324B (en
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李洪法
宋建军
宋明信
陈松涛
杨吉慧
毕衍金
王万磊
赵淑晶
郭良进
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Shandong Fuyin Paper and Environmental Protection Technology Co Ltd
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Shandong Tralin Paper Co Ltd
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Priority to PCT/CN2008/001377 priority patent/WO2009015555A1/en
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Abstract

The invention relates to unbleached pulp prepared by the ammonium sulfite cooking of a rice straw raw material and a preparation method thereof. The whiteness of the unbleached pulp is 35 to 48 percent ISO, the fracture length is between 5.0 and 7.5km, the tearability is between 200 and 275mN, and the folding times are between 30 and 100. The method comprises the steps of ammonium sulfite cooking and oxygen delignification, wherein the ammonium sulfite cooking is to cook the raw material into the pulp the harness of which has a potassium permanganate value of between 16 and 28 and is equivalent to a Kappa number of between 24 and 50. The unbleached pulp has higher strength, particularly has the fracture length and the folding times which exceed the level of hardwood pulp, can be used for manufacturing corrugated paper, lunch boxes, and packing paper which have quite high strength, or is applied to manufacturing other paper products more widely only by adding little wood pulp, greatly reduces the cost for products, and also ensures the strength of the products. The method can ensure that lignin is effectively removed and also try to reduce the degradation of fiber, thereby obtaining the unbleached pulp with good strength.

Description

A kind of slurry of grass feedstock production and black liquor, its preparation method and application thereof
Technical field
The present invention relates to a kind of slurry and black liquor, particularly a kind of slurry of grass feedstock production and black liquor, its preparation method and application thereof.
Background technology
At present, world's paper pulp raw material major part is a timber, and particularly developed countries such as the U.S., Canada, various countries, Northern Europe and Russia almost all use pulping wood.Along with the increase year by year of timber demand amount, timber price also rises steadily.The country that many timber resources are few needs a large amount of timber of introducing, even and the more rich country of timber resources as Canada, also estimates will occur soon the log situation that supply falls short of demand.Therefore, the raw material problem has become the significant problem of various countries' development pulp industry, and the source of pulping raw material is also in continuous expansion.
In the pulping and paper-making industry, utilizing the grass raw material to carry out slurrying is comparatively common a kind of pulping process in China.The grass kind plant pulping raw material mainly comprises straw, wheat straw, bagasse, Chinese alpine rush, reed, bamboo, straw, cotton stalk, sorghum stalk etc., " the non-wood-fiber soda pulping process application manual commonly used " that its pulping process commonly used can be write with reference to " non-wood-fiber soda pulping process application manual commonly used " and alkaline straw-pulp Professional Committee of China Paper Industry Technical Association.
The method of producing paper pulp with string has: chemical method, Mechanical Method, chemical mechanical pulping.Chemical pulping is by chemical action, make raw material disassociation pulping by some composition of removing in the plant fiber material, be a kind of most widely used pulping process, in the chemical method boiling, divide lime method, soda processes, anthraquinone-soda processes, sulfate process, sulfite cooking again.
As sulphite process of the prior art, its technical process is at first to get the raw materials ready, the raw material that will carry out pretreated production paper pulp pack into rotary spherical digester, upright pot and connect in the equipment such as (digester, vertical digester, continuous steamers) of steaming, add chemicalss such as ammonium sulfite again, feed Steam Heating toward rotary spherical digester, upright pot or in even steaming, slightly starched after insulation a period of time.
At present, most enterprises in pulp and paper industry be faced with all that paper making raw material is in short supply, energy shortage, environmental pollution, paper pulp straw pulp problem of low quality particularly.Along with China's accession to the WTO, the situation that paper industry faces is severe more, and the competition between the enterprise also is growing more intense.How to reduce production costs, reduce and pollute, improving the quality of products to satisfy with paper is the downstream industry of raw material, as industries such as printing, journalism, packing, cigarette, is the problem that the papermaker need consider.Based on above-mentioned factor, make how people's further research of having to reduces the cost of papermaking.
The making grass pulp technology is a system engineering, to study the overall process of slurrying according to the inhomogeneity of the biological structure of grass fiber raw material and the particularity of chemical composition, fibers in grass class slurrying has following characteristics: 1. heavily get the raw materials ready, silica removal, remove heteroproteose cell, improve pulp quality and drainability, reduce the discharging of black liquor; 2. the characteristic of grass fiber delignification.Owing in the grass fiber the easy molten lignin of more alkali is arranged, its slurrying difficulty is reduced, but it requires higher delignification rate that fiber is dissociated again simultaneously, so its pulping process should be very different with timber.3. owing to silicone content height in the raw material, the carbohydrate content height causes its black liquor viscosity height, and recovery difficult is big.4. contain a large amount of heteroproteose cells in the fibers in grass class, papermaking is formed a series of harm.5. the bleachability of straw pulp is good than timber, easily adopts short flow process to bleach.
The article of " the straw ammonium sulfite is optimized cooking schedule " has been delivered and be entitled as to 2003 the 4th phases of Heilungkiang papermaking, and this article discloses the optimal conditions of straw ammonium sulfite boiling, but the prepared pulp quality of the method for this boiling is not high.
In addition, the range of application of the paper product that the brown stock that whiteness is lower is made is more and more wider, and as corrugated paper, cutlery box, wrapping paper etc., but the brown stock intensity that is made by straw raw material also is not very high, need to add other and improve intensity, thereby improved cost by the slurry that timber makes.
Summary of the invention
Therefore, one of purpose of the present invention is to provide a kind of brown stock of straw raw material ammonium sulfite boiling preparation, and this slurry intensity is good, has higher fracture length, tearability and folding number.
In order to realize purpose of the present invention, a kind of brown stock of straw raw material ammonium sulfite boiling preparation is provided, a kind of brown stock of straw raw material ammonium sulfite boiling preparation, the whiteness of described brown stock is 35-48%ISO, fracture length is 5.0-7.5km, tearability is 200-275mN, and folding number is 30-100 times, and beating degree is 33-38 ° of SR; The fracture length of preferred described brown stock is 5.5-7.5km, and tearability is 220-275mN, and folding number is 40-80 times, and beating degree is 32-36 ° of SR; More preferably the fracture length of described brown stock is 6.0-7.5km, and tearability is 240-275mN, and folding number is 50-70 times.
Another object of the present invention is to provide a kind of preparation method of above-mentioned brown stock, comprise ammonium sulfite boiling, oxygen delignification, through obtaining high-hardness pulp after the ammonium sulfite boiling, the hardness of described high-hardness pulp is equivalent to card uncle valency 24-50 for permanganate number 16-28 in the method for the present invention; Described high-hardness pulp preferred hardness is equivalent to card uncle valency 29-48 for permanganate number 18-27; Described high-hardness pulp most preferably hardness is equivalent to card uncle valency 34-42 for permanganate number 20-25.
Traditional technology is often boiled the hardness of slurry very low, causes declining to a great extent of pulp strength, and the present invention obtains the higher slurry of hardness by boiling, carries out follow-up treatment step again, has guaranteed the intensity of the brown stock that obtains.
Need to prove that brown stock of the present invention refers to raw material through the slurry before bleaching after boiling, the oxygen delignification.
The preferred ammonium sulfite of the present invention comprises the steps:
1) add steaming preparation in straw raw material, wherein the ammonium sulfite consumption is to over dry material quantity 9-13%, and liquor ratio is 1:2-4;
2) feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20-40 minutes when temperature is 120-140 ℃, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minutes.
Digestion process is the committed step of slurrying, because institutional framework, microstructure, chemical composition and the lignin molecular structure etc. of timber and grass as raw material are all variant, therefore, the delignification reaction course also has very big difference in digestion process.For grass as raw material alkaline cooking delignification reaction course, comprise intensification and be incubated two sections.The common feature of grass as raw material is that delignification is more or less freely, and compares with wood raw material, and the temperature of a large amount of strippings of lignin is more in advance.In the method for the present invention, boiling chemical liquid consumption is few, and the time of boiling and insulation is short, in a large amount of lignins of removing in the grass raw material, has reduced the degraded and the damage of cellulose and hemicellulose as much as possible.
In the process of the boiling of prior art, because the use of thermophilic digestion and chemical steaming soup, certain chemical change all can take place in the lignin in the raw material, cellulose and hemicellulose and other composition, be subjected in various degree degraded and damage, and exist the time of boiling and insulation long, the problem that stewing temperature is high.And in the method for the invention, the consumption of cooking liquor is few, and the time of boiling and insulation shortens greatly.At this special pulping raw material of straw, in the method for the present invention, the chemical steaming soup has been carried out strict control, its concentration is reduced, reduce degraded and damage to the required composition of slurrying such as cellulose, hemicellulose.Simultaneously, in the process of thermophilic digestion, adopt the method reduce temperature retention time as far as possible in the method for the present invention, the time that makes grass kind plant be in high temperature shortens, thereby has reduced the degraded of cellulose and hemicellulose in the raw material.Therefore, protect the required composition of slurrying in the raw material in the method for the present invention to greatest extent, shortened temperature retention time greatly simultaneously, significantly reduced energy consumption.
The preferred oxygen delignification of the present invention comprises:
1) regulates the concentration of starching;
2) this stock pump is delivered to the oxygen delignification reaction tower, and add NaOH and oxygen; And
3) this slurry carries out delignification reaction in this oxygen delignification reaction tower, and obtaining hardness is permanganate number 10-14, is equivalent to the slurry of card uncle valency 13-19.8;
Wherein, the starch degree that more preferably carries out in the step 3) obtaining behind the delignification is permanganate number 11-13, is equivalent to card uncle valency 14.5-17.7.
The hardness that the present invention starches after to oxygen delignification is controlled, and is in order to guarantee that lignin is sloughed as much as possible on the one hand, has guaranteed the intensity of the slurry that obtains in addition on the one hand again.Equally, the method for oxygen delignification can adopt any method of prior art, and the hardness that only needs control to handle the back slurry gets final product in the framework of the present definition.
The concentration that the present invention preferably regulates slurry be meant will slurry concentration adjustment be 8-18%, that is to say in carry out oxygen delignification under the dense condition.In the major advantage of dense oxygen delignification be: invest less; Since in the success of dense mixing and pumping technology, the processing of slurry is dense more much easier than high; Slurry concentration is lower, and the corrosion of equipment is few, also the danger of not burning in oxygen.
The preferred described oxygen delignification of the present invention is the single hop oxygen delignification, uses an oxygen delignification reaction tower.In the oxygen delignification process, described slurry is 95-100 ℃ in the temperature of this reaction tower import department, and pressure is 0.9-1.2MPa, and the temperature in exit is 100-105 ℃, and pressure is 0.2-0.6MPa.Alkali charge is that the addition of oxygen is 20-40kg slurry per ton in the 2-4% of NaOH to the oven dry stock amount in the preferred described oxygen delignification; The reaction time of described slurry in this reaction tower is 60-90 minutes.Adopting the single hop oxygen delignification mainly is the intensity that guarantees paper pulp for further, relative multistage oxygen delignification, and single hop is less to cellulosic degradation.Generally speaking temperature is lower for the technological parameter of the preferred single hop oxygen delignification of the present invention, comparatively speaking the time longer, mainly be for the gentle more delignification reaction that carries out, avoid cellulosic degraded as far as possible.
The delignification rate is 86-98% in the preferred described oxygen delignification process of the present invention.
Underflow pipe during the present invention also preferably was transported to this high-hardness pulp before described oxygen delignification, and in this slurry pipe, slurry is carried out the air that modifier treatment gets rid of in the slurry and make it fluidization, again with in dense pump slurry is delivered to the oxygen delignification tower.The further preferred conveying worm that adopts is heated to 70-80 ℃ and be transported to underflow pipe in this with slurry.
Add the magnesium salts of oven dry stock weight 0.2-1% in the oxygen delignification process of the present invention as protective agent.
The present invention also comprises the process that raw material is flooded before boiling, can adopt the dipping spiral organ.The mode that said impregnation process adopts is: maceration extract is flooded raw material, make liquor ratio reach 1:2-4, in insulation and mixing more than 10 minutes in the spiral macerator more than 85 ℃, wherein insulation mixes 10-40 minutes for well between 85-95 ℃ under normal pressure.Maceration extract is fully contacted with raw material, make the dipping of raw material evenly complete.Described maceration extract can be certain density aqueous slkali, for being 4% aqueous slkali in NaOH to the over dry material quantity, also can be the mixed liquor of above-mentioned alkali lye and black liquor as alkalinity, and the concentration of used black liquor is 11-14 ° of Be ' (20 ℃).
Raw material has been carried out the dipping preliminary treatment, utilized black liquor as waste material, make black liquor obtain cycling and reutilization, reduced the pressure that environment is handled black liquor, because to the preliminary treatment of raw material dipping, make that heteroproteose cell, hemicellulose, the lignin deviate from are that main black liquid separation is discharged when heat treated, for next step digestion process is prepared.
The present invention also can be before flooding raw material, can adopt prior art that raw material is carried out preliminary treatment, promptly adopt conventional dried, wet feed preparation, to remove impurity such as defoliation, fringe, grain, marrow, can alleviate the pressure of subsequent technique like this, and improve the quality of straw pulp.Dried, wet feed preparation can adopt existing conventional equipment, as chaffcutter, screening machine, dust removal machine, wet scrubbing Straw-crumbling machine, inclined screw Water Extraction Machinery etc.Fibers in grass class raw material through the removal moisture after getting the raw materials ready also can be fine fodder, and the moisture of deduction dogstail is the over dry grass, and the length of general blade is at 15-30mm, and the technology of getting the raw materials ready of raw material is technology as well known to those skilled in the art.
Can be after boiling in the method for the present invention, the high-hardness pulp after the boiling is carried out shove before the oxygen delignification.Can be 8-15% high-hardness pulp with gained concentration after the boiling enters from the inlet of press master, carries out shove, and after the extruding black liquor, concentration is that 20-30% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 22-28 ° of SR, and the beating degree after the shove is 23-29 ° of SR.The Baume degrees of the black liquor that shove is extruded is 7-11 ° of Be ' at 20 ℃.High-hardness pulp for raw material being carried out ammonium sulfite boiling gained carries out after the shove, and the black liquor of being extruded Baume degrees in the time of 20 ℃ is 7-9 ° of Be ', and the concentration of the ammonium sulfite of the remnants in the black liquor is 8-10g/L.The slurry that comes out from the outlet of press master dilutes with the black liquor that pulp washing the subsequent technique displaces, and described black liquor is 3-6 ° of Be ' at 20 ℃ of Baume degrees, the concentration to 2.5-3% of slurry is delivered to jump to screen.
Press master described in the present invention is the acroll press washer that is used for extracting black liquor in the prior art.When using press master to carry out shove, because the process at shove can produce very big extruding force, temperature rises rapidly, impel fiber separation, divide silk, brooming, conquassation, primary wall is destroyed, the enough energy of fiber absorbs make fibrous inside produce very big stress, and the reactivity worth of high-hardness pulp is greatly improved.Simultaneously, fiber produces fibrillating, and impurity is dissolved in the black digestion liquid between epidermis organic matter and fiber, discharges by liquid outlet groove, and fiber fineness is greatly improved.Some ash contents in the black liquor and impurity are also along with black liquor is discharged from, for sufficient preparation has been carried out in next step pulp washing and bleaching.Press master of the present invention is that the acroll press washer that the extraction black liquor is used in the prior art is single-screw press master or Double screw pulp extruder; Preferred described press master is the Reducing screw press master.Utilize the reducing press master, make slurry in the space that slowly diminishes, make the about dehydration of compressed slurry layer consistent.The press master that the present invention is selected, after high-hardness pulp is carried out shove, the beating degree of described high-hardness pulp changes little, that is to say, described high-hardness pulp is through after the press master shove, can the fibre length that fiber is intrinsic keep relatively goodly, reduce the damage of fiber to greatest extent.
The press master that adopts among the present invention also can be Var-nip press, can realize the effect that the present invention will reach equally, and water consumption significantly reduces.
Can after boiling, discongest slurry before the oxygen delignification in the method for the present invention, can adopt the existing equipment of discongesting, can in carding process of the present invention, use as mill fluffer in deflaker, kneading machine, dry pan, the beating equipment and defibrator, because they can play the effect of discongesting fiber and reducing cut staple as far as possible.In the process of discongesting, fiber naturally separately is easy to wherein lignin is come out, and can reach the effect of getting well in the processing procedure so afterwards.This is discongested and can carry out immediately after boiling, also can carry out before oxygen delignification, can also carry out behind shove.In fact, between any processing step between boiling and the oxygen delignification, can carry out this and discongest, can both reach the effect that needs.
In addition, brown stock of the present invention can be used for preparing newsprint, supercalendered paper, wrapping paper, paper diaper, crepe toilet paper, tissue, face tissue, napkin paper, tissue, paper for kitchen, writing paper, offset paper, offset printing paper, single face writing paper, M.G.offset paper and corrugated paper.
Also can be used for preparing moulded paper pulp product, described goods comprise: bowl, basin, cup, bucket, dish, dish, pallet and cutlery box; Carriage, electric welding protective cover, Indoor decorative plate, molding flowerpot, molding seedling-raising cup, molding slippers and adsorptive pads toilet seat cushion; Molding medical tray container, molding medical nursing product and disposable medical vessel.
Brown stock intensity of the present invention is higher, especially fracture length and folding number have surpassed the level of hardwood pulp, can be used to make the very high corrugated paper of intensity, cutlery box, wrapping paper etc., perhaps only need add wood pulp seldom and be applied to make other paper products widely, significantly reduce the cost of product, guaranteed the intensity of product simultaneously again.Method of the present invention is by the hardness of the slurry that obtains of control boiling, carry out oxygen delignification then, both made that lignin is wherein effectively removed, reduced degradation of fiber again as far as possible, delignification rate 86-98% in its oxygen delignification process, thus can access the good brown stock of intensity.
Two of purpose of the present invention is to provide a kind of brown stock of straw raw material alkaline cooking preparation, and this slurry intensity is good, has higher fracture length, tearability and folding number.
In order to realize purpose of the present invention, the technical solution used in the present invention is:
A kind of brown stock of straw raw material alkaline cooking preparation, the whiteness of described brown stock is 40-55%ISO, and fracture length is 5.0-7.6km, and tearability is 230-280mN, and folding number is 25-90 time, beating degree is 32-38 ° of SR; Preferred described unbleached pulp is 45-55%ISO, and fracture length is 6.0-7.6km, and tearability is 250-280mN, and folding number is 35-90 time, and beating degree is 32-36 ° of SR.
Another object of the present invention is to provide a kind of preparation method of above-mentioned brown stock, comprise alkaline cooking, oxygen delignification, described alkaline cooking is that material cooking is become hardness is permanganate number 16-28, the high-hardness pulp that is equivalent to card uncle valency 24-50, preferred hardness is permanganate number 18-27, is equivalent to the high-hardness pulp of card uncle valency 29-48; More preferably hardness is equivalent to the high-hardness pulp of card uncle valency 34-42 for permanganate number 20-25.Traditional technology is often boiled the hardness of slurry very low, causes declining to a great extent of pulp strength, and the present invention obtains the higher slurry of hardness by boiling, carries out follow-up treatment step again, has guaranteed the intensity of the brown stock that obtains.
Need to prove that brown stock of the present invention refers to the slurry that obtains after raw material process alkaline cooking, the oxygen delignification.
Alkaline cooking of the present invention comprises anthraquinone-soda cooking, comprises the steps:
1) in straw raw material, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 9-15%, liquor ratio is 1:2-4, the anthraquinone addition is 0.5-0.8% of an over dry material quantity; Preferred described alkali charge is in the 9-13% of NaOH to the over dry material quantity; More preferably described alkali charge is in the 9-11% of NaOH to the over dry material quantity;
2) feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20-40 minutes when temperature is 100-130 ℃, continues heat temperature raising to 160-165 ℃, is incubated 60-90 minute.
Alkaline cooking of the present invention is a kraft cooking, comprises the steps:
1) in straw raw material, add steaming preparation, wherein alkali charge in NaOH to 8-11% of over dry material quantity, liquor ratio is 1: 2-4, sulphidity is 5-8%;
2) go into steam and heat, heat temperature raising carries out little steam bleeding to temperature is 110-140 ℃ time insulation 20-40 minute, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minutes.
Described alkaline cooking is the boiling of alkaline sodium sulfite method, comprises the steps:
1) add steaming preparation in straw raw material, wherein, sodium hydroxide concentration counts 11-15% with the over dry raw material weight, and sodium sulfite is 2-6%, and anthraquinone is 0.02-0.08%, and cooking liquor is than being 1:3-4;
2) feed steam and heat, heat temperature raising is incubated 20-40 minutes when temperature is 100-120 ℃, carry out little steam bleeding, continues heat temperature raising to 160-165 ℃, is incubated 60-90 minute.
Digestion process is the committed step of slurrying, because institutional framework, microstructure, chemical composition and the lignin molecular structure etc. of timber and grass as raw material are all variant, therefore, the delignification reaction course also has very big difference in digestion process.For straw raw material alkaline cooking delignification reaction course, comprise intensification and be incubated two sections.The characteristics of straw raw material are that delignification is more or less freely, and compare with wood raw material, and the temperature of a large amount of strippings of lignin is more in advance.When the straw raw material sulphate cook, just find the secondary wall lignin, meet intercellular layer and cell angle block element all removes at the very start simultaneously in boiling.Straw raw material generally contains more hemicellulose and less lignin, and hemicellulose mainly is present in the cell membrane, and this just helps the process of boiling delignification.In the method for the present invention, boiling chemical liquid consumption is few, and the time of boiling and insulation is short, in a large amount of lignins of removing in the straw raw material, has reduced the degraded and the damage of cellulose and hemicellulose as much as possible.In the process of the boiling of prior art, when preparation paper pulp, exist the time of boiling and insulation long, stewing temperature height, the problem that temperature retention time is grown.And in the method for the invention, the consumption of cooking liquor is few, and the time of boiling and insulation shortens greatly.
The process of boiling generally comprises three processes: (1) cooking liquor is to the process of raw material internal penetration; (2) alkali lye and raw material play the process that answer chemistry side; (3) process of reactant stripping from raw material.This three process both stage by stage, youngster is intersected simultaneously and is carried out again, according to the needs of different paper pulp, suitably removes lignin and impurity in the raw material, and the adhesion between the fiber is descended, and impels the frotation pulping.Therefore, the purpose of boiling is to utilize the effect of cooking liquor, suitably removes the lignin in the raw material, keeps cellulose as far as possible and the part hemicellulose is beneficial to copy paper.In digestion process, because the use of thermophilic digestion and chemical steaming soup, certain chemical change all can take place in the lignin in the raw material, cellulose and hemicellulose and other composition, is subjected in various degree degraded and damage.
Because the use of thermophilic digestion and chemical steaming soup, certain chemical change all can take place in the lignin in the raw material, cellulose and hemicellulose and other composition, is subjected in various degree degraded and damage.At this special pulping raw material of grass kind plant fiber, in the method for the present invention, the chemical steaming soup has been carried out strict control, its concentration is reduced, reduce degraded and damage to the required composition of slurrying such as cellulose, hemicellulose.Simultaneously, in the process of thermophilic digestion, adopt the method reduce temperature retention time as far as possible in the method for the present invention, the time that makes straw raw material be in high temperature shortens, thereby has reduced the degraded of cellulose and hemicellulose in the raw material.Therefore, protect the required composition of slurrying in the raw material in the method for the present invention to greatest extent, shortened temperature retention time greatly simultaneously, significantly reduced energy consumption.
Oxygen delignification of the present invention comprises:
1) concentration of the high-hardness pulp of gained after the adjusting boiling;
2) this stock pump is delivered to the oxygen delignification reaction tower, and add NaOH and oxygen; And
3) this slurry carries out the oxygen delignification reaction in the oxygen delignification reaction tower, and obtaining hardness is permanganate number 10-14, is equivalent to the slurry of card uncle valency 13-19.8.
Wherein, preferred steps 3) in carry out obtaining behind the oxygen delignification the starch degree be permanganate number 11-13.
The hardness that the present invention starches after to oxygen delignification is controlled, and is in order to guarantee that lignin is sloughed as much as possible on the one hand, has guaranteed the intensity of the slurry that obtains in addition on the one hand again.Equally, the method for oxygen delignification can adopt any method of prior art, and the hardness that only needs control to handle the back slurry gets final product in the framework of the present definition.
The concentration that the present invention regulates the high-hardness pulp of gained after the boiling is meant that the concentration adjustment with described high-hardness pulp is 8-18%, that is to say in carry out oxygen delignification under the dense condition.In the major advantage of dense oxygen delignification be: invest less; Since in the success of dense mixing and pumping technology, the processing of slurry is dense more much easier than high; Slurry concentration is lower, and the corrosion of equipment is few, also the danger of not burning in oxygen.
Oxygen delignification of the present invention is the single hop oxygen delignification, uses an oxygen delignification reaction tower.In the oxygen delignification process, described high-hardness pulp is 95-100 ℃ in the temperature of this reaction tower import department, and pressure is 0.9-1.2MPa, and the temperature in exit is 100-105 ℃, and pressure is 0.2-0.6MPa.Alkali charge is that the addition of oxygen is 20-40kg slurry per ton in the 2-4% of NaOH to the oven dry stock amount in the described oxygen delignification; The reaction time of described slurry in this reaction tower is 60-90 minutes.Adopting the single hop oxygen delignification mainly is the intensity that guarantees paper pulp for further, relative multistage oxygen delignification, and single hop is less to cellulosic degradation.Generally speaking temperature is lower for the technological parameter of the preferred single hop oxygen delignification of the present invention, comparatively speaking the time longer, mainly be for the gentle more delignification reaction that carries out, avoid cellulosic degraded as far as possible.
The delignification rate is 86-98% in the oxygen delignification process of the present invention.
The present invention was transported to this high-hardness pulp underflow pipe in before described oxygen delignification, and in this slurry pipe high-hardness pulp was carried out the air that modifier treatment gets rid of in the slurry and make it fluidization, then with in dense pump conveying.Further preferred adopt conveying worm with high-hardness pulp be heated to 70-80 ℃ and be transported in the underflow pipe.
Add the magnesium salts of oven dry stock weight 0.2-1% in the oxygen delignification process of the present invention as protective agent.
The present invention also can be before carrying out boiling to straw, adopt prior art that straw is carried out preliminary treatment, promptly adopt conventional dried, wet feed preparation, to remove impurity such as defoliation, fringe, grain, marrow, can alleviate the pressure of subsequent technique like this, and improve the quality of rice straw pulp.Dried, wet feed preparation can adopt existing conventional equipment, as chaffcutter, screening machine, dust removal machine, wet scrubbing Straw-crumbling machine, inclined screw Water Extraction Machinery etc.Fibers in grass class raw material through the removal moisture after getting the raw materials ready also can be fine fodder, and the moisture of deduction dogstail is the over dry grass, and the length of general blade is at 15-30mm, and the technology of getting the raw materials ready of raw material is technology as well known to those skilled in the art.
The present invention carries out shove to the high-hardness pulp after the boiling after boiling, before the oxygen delignification.Can be 8-15% high-hardness pulp with gained concentration after the boiling enters from the inlet of press master, carries out shove, and after the extruding black liquor, concentration is that 20-30% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 22-28 ° of SR, and the beating degree after the shove is 23-29 ° of SR.For straw raw material being carried out the prepared high-hardness pulp of anthraquinone-soda cooking, carry out after the shove, the black liquor of being extruded Baume degrees in the time of 20 ℃ is 9-11 ° of Be ', the content of residual alkali is 8-10g/L in the black liquor.The slurry that comes out from the outlet of press master dilutes with the black liquor that pulp washing the subsequent technique displaces, and described black liquor is 3-6 ° of Be ' at 20 ℃ of Baume degrees, perhaps can directly dilute with clear water, makes underflow deliver to jump to 2.5-3% and screens.
Press master described in the present invention is the acroll press washer that is used for extracting black liquor in the prior art.When using press master to carry out shove, because the process at shove can produce very big extruding force, temperature rises rapidly, impel fiber separation, divide silk, brooming, conquassation, primary wall is destroyed, the enough energy of fiber absorbs make fibrous inside produce very big stress, and the reactivity worth of high-hardness pulp is greatly improved.Simultaneously, fiber produces fibrillating, and impurity is dissolved in the black digestion liquid between epidermis organic matter and fiber, discharges by liquid outlet groove, and fiber fineness is greatly improved.Some ash contents in the black liquor and impurity are also along with black liquor is discharged from, for next step step has been carried out sufficient preparation.The acroll press washer that the extraction black liquor is used in the prior art of the present invention is single-screw press master or Double screw pulp extruder; Preferred described press master is the Reducing screw press master.Utilize the reducing press master, make slurry in the space that slowly diminishes, make the about dehydration of compressed slurry layer consistent.The acroll press washer that the present invention is selected, after high-hardness pulp is carried out shove, described high-hardness pulp beating degree changes little, that is to say, described high-hardness pulp is through after the press master shove, can the fibre length that fiber is intrinsic keep relatively goodly, reduce the damage of fiber to greatest extent.
The press master that adopts among the present invention also can be Var-nip press, can realize the effect that the present invention will reach equally, and can significantly reduce water consumption.
The present invention can discongest slurry before the oxygen delignification after boiling, can adopt the existing equipment of discongesting, can in carding process of the present invention, use as mill fluffer in deflaker, kneading machine, dry pan, the beating equipment and defibrator, because they can play the effect of discongesting fiber and reducing cut staple as far as possible.In the process of discongesting, separately, lignin wherein is easy to come out fiber naturally, for oxygen delignification is afterwards got ready.Described discongesting can be carried out after boiling immediately, also can carry out before oxygen delignification, can also carry out behind shove.In fact, between any processing step between boiling and the oxygen delignification, can carry out this and discongest, can both reach the effect that needs.
In addition, brown stock of the present invention can be used for preparing newsprint, supercalendered paper, wrapping paper, paper diaper, crepe toilet paper, tissue, face tissue, napkin paper, tissue, paper for kitchen, writing paper, offset paper, offset printing paper, single face writing paper, M.G.offset paper and corrugated paper.
Also can be used for preparing moulded paper pulp product, described goods comprise: bowl, basin, cup, bucket, dish, dish, pallet and cutlery box; Carriage, electric welding protective cover, Indoor decorative plate, molding flowerpot, molding seedling-raising cup, molding slippers and adsorptive pads toilet seat cushion; Molding medical tray container, molding medical nursing product and disposable medical vessel.
Brown stock intensity of the present invention is higher, especially fracture length and folding number have surpassed the level of hardwood pulp, can be used to make the very high corrugated paper of intensity, cutlery box, wrapping paper etc., perhaps only need add wood pulp seldom and be applied to make other paper products widely, significantly reduce the cost of product, guaranteed the intensity of product simultaneously again.Method of the present invention is by the hardness of the slurry that obtains of control boiling, carry out oxygen delignification then, both made that lignin is wherein effectively removed, reduced degradation of fiber again as far as possible, delignification rate 86-98% in its oxygen delignification process, thus can access the good brown stock of intensity.
Three of purpose of the present invention is brown stock of a kind of wheat straw raw material Ammonium Sulfite Method boiling preparation and preparation method thereof.
To achieve these goals, the technical solution used in the present invention is:
A kind of brown stock of wheat straw raw material Ammonium Sulfite Method boiling preparation, described brown stock is feedstock production with the wheat straw, the fracture length of described brown stock is 5.0-7.8km, folding strength is 25-80 time, tearability is 180-255mN, and whiteness is 37-45%ISO, and beating degree is 33-38 ° of SR; The fracture length of preferred described brown stock is 6.0-7.8km, and folding number is 32-80 time, and tearability is 230-255mN, and beating degree is 33-36 ° of SR.
The preparation method of brown stock of the present invention, described method comprises the step of Ammonium Sulfite Method boiling, oxygen delignification, obtaining hardness after the boiling is permanganate number 16-28, is equivalent to the high-hardness pulp of card uncle valency 24-50.
Ammonium Sulfite Method boiling of the present invention is: the consumption of ammonium sulfite is the 9-13% to over dry wheat straw amount, and liquor ratio is 1:2-4.
In the Ammonium Sulfite Method boiling of the present invention, feed steam and heat, heat temperature raising is incubated 20-40 minute when temperature is 110-140 ℃, carry out little steam bleeding, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minute, preferably is incubated 75-90 minute.
Oxygen delignification of the present invention is:
(1) be permanganate number 16-28 with obtaining hardness after the boiling, the high-hardness pulp that is equivalent to card uncle valency 24-50 is pumped to the oxygen delignification reaction tower, and adds NaOH and oxygen; And
(2) this high-hardness pulp carries out delignification reaction in this oxygen delignification reaction tower, and obtaining hardness is permanganate number 10-14, is equivalent to the slurry of card uncle valency 12.5-19.5;
Wherein, high-hardness pulp hardness in the preferred steps (1) is permanganate number 20-24, be equivalent to card uncle valency 31.2-39.3, the described hardness through oxygen delignification reaction back gained slurry in the step (2) is permanganate number 11-13, is equivalent to card uncle valency 14.3-19.4.
Oxygen delignification of the present invention is the single hop oxygen delignification, uses an oxygen delignification reaction tower; Described high-hardness pulp is 95-100 ℃ in the temperature of this reaction tower import department, and pressure is 0.9-1.2MPa; The temperature in exit is 100-105 ℃, and pressure is 0.2-0.6MPa; The consumption of alkali is that the addition of oxygen is 20-40kg slurry per ton in the 2-4% of NaOH to oven dry stock weight in the described oxygen delignification; The reaction time of described high-hardness pulp in this reaction tower is 75-90 minutes.
In the method for the present invention after the Ammonium Sulfite Method boiling, before the oxygen delignification, also comprise shove, described shove is equivalent to carry out shove under the extruding force effect of card uncle's valency 24-50 high-hardness pulp in press master for being permanganate number 16-28 with the hardness that obtains after the Ammonium Sulfite Method boiling; The hardness of preferred described high-hardness pulp is equivalent to card uncle valency 29-48 for permanganate number 18-27; Described high-hardness pulp more preferably hardness is equivalent to card uncle valency 34-42 for permanganate number 20-25.
Also can be after the Ammonium Sulfite Method boiling in the method for the present invention, before the oxygen delignification, also comprise and discongesting, described discongest into: according to the method for prior art, hardness to gained after the boiling is permanganate number 16-28, the high-hardness pulp that is equivalent to card uncle valency 24-50 is discongested, and makes fibre structure become loose.
Press master of the present invention is single-screw press master or Var-nip press.
In the method for the present invention when discongesting used fluffer be deflaker or mill fluffer.
Brown stock of the present invention is meant after the boiling of wheat straw raw material Ammonium Sulfite Method, oxygen delignification and resulting slurry before the bleaching.
Specifically, a kind of brown stock of wheat straw raw material Ammonium Sulfite Method boiling preparation, described brown stock is feedstock production with the wheat straw, the fracture length of described brown stock is 5.0-7.8km, and folding strength is 25-80 time, and tearability is 180-255mN, whiteness is 37-45%ISO, and beating degree is 33-38 ° of SR; The fracture length of preferred described brown stock is 6.0-7.8km, and folding number is 32-80 time, and tearability is 230-255mN, and beating degree is 33-36 ° of SR.
Brown stock of the present invention is that raw material prepares through the Ammonium Sulfite Method boiling with the wheat straw, and its fracture length reaches more than the 5000m, and folding strength reaches more than 25 times, is a kind of high-quality careless class brown stock, can be used as the slurry that corrugated paper, cutlery box and wrapping paper are produced in preparation.
In the method for the invention, at first can adopt prior art that wheat straw is got the raw materials ready, promptly adopt conventional dried, wet feed preparation,, can alleviate the pressure of subsequent technique like this, and improve the quality of Straw Pulp to remove impurity such as defoliation, fringe, grain, marrow.Dried, wet feed preparation can adopt existing conventional equipment, as chaffcutter, screening machine, dust removal machine, wet scrubbing Straw-crumbling machine, inclined screw Water Extraction Machinery etc.Wheat straw raw material through the removal moisture after getting the raw materials ready also can be fine fodder, and the moisture of deduction wheat straw is the over dry grass, and the length of general blade is at 15-30mm, and the technology of getting the raw materials ready of raw material is technology as well known to those skilled in the art.
In the melting process in the present invention, also can utilize hammer mill to carry out dry raw material preparation, may further comprise the steps:
(1) wheat straw raw material is utilized hammer mill cut off rubbing and handle, obtain cutting off the raw material after the rubbing;
Wheat straw raw material is delivered in the hammer mill by belt conveyor or other conveyer in this step, and described hammer mill comprises to be carried feeding section, fragmentation and rubbing section and break up the discharge section.Wheat straw at first enters the conveying feeding section of hammer mill, this section mainly works to carry feeding, enter fragmentation and rubbing section again, the wheat straw effect of power and percussion power that is squeezed in this section, to be that the grass raw material of 300-800mm is hammered into shape disconnected for length when entering hammer mill, so this hammer mill has at first played the effect of chaffcutter.In broken and rubbing section, being squeezed effect of wheat straw raw material, cross section is for the wheat straw raw material of circle is crushed, make leaf,, wheat, etc. impurity separate with stalk, separation rate is 70-90%.Discharge section from hammer crushing crusher machine and the rubbing section wheat straw raw material of coming through breaing up, the wheat straw that presses together is broken up, therefore this raw material when boiling and the contact-making surface of cooking liquor big, infiltrate into the inside of wheat straw raw material easily, thus the process of accelerating delignification.Last grass raw material is discharged from the outlet of hammer mill.The 20-50mm of the wheat straw raw material of being discharged.
Hammer mill among the present invention is the beater grinder that ore dressing or bark are pulverized usefulness in the prior art.The rotating speed of described hammer mill is 500-800rpm, the speed that wheat straw enters hammer mill is 0.5-1.0m/s, and rotating speed is crossed low or charging is too fast, can cause some raw materials not crumpled fully, the uniformly penetrating of cooking liquor after the influence, and then the quality of influence slurry.
The wheat straw raw material skin has one deck wax, and there is one deck its bar inside, and in the general method of getting the raw materials ready, when skin was flooded by cooking liquor, wax can be removed soon, but because the internal layer of its bar has air, so cooking liquor is difficult to enter.After the present invention utilizes hammer mill to cut off wheat straw raw material and crumples, help the abundant dipping of raw material, obtain the measured slurry of matter after the boiling easily.
(2) raw material that will cut off after the fragmentation carries out dust removal process;
Carry out dust removal process through the raw material after the cut-out fragmentation, this is owing to contain impurity such as dust, sandstone, blade of grass, grass in the blade after cutting off, through dust removal process, above-mentioned impurity major part is removed, therefore in the digestion process after getting the raw materials ready, chemicals consumption in the time of can reducing boiling, the time of boiling also can shorten accordingly.
Carrying out dust removal machine that dust removal process adopted among the present invention can comprise roll-type dust removal machine, double cone dust removal machine and cyclone dust removal machine for the used dust removal machine of getting the raw materials ready of wheat straw raw material in the prior art, and preferred described dust removal machine is the cyclone dust removal machine.Air quantity is 30000-38000m when carrying out dust removal process in cyclone dust collectors 3/ h, blast 200-230mmHgO.Under such condition, can remove dust contained in the raw material in a large number, alleviate the burden of follow-up boiling.
(3) will carry out Screening Treatment through the raw material of dust removal process.
Wheat straw raw material often has foreign material such as thick blade and broken end through after the dust removal process, and in digestion process, these foreign material have is difficult for being permeated by cooking liquor, thus generation steaming separate thing; Though react with cooking liquor at the broken end that has, but black liquor viscosity is increased, influence the circulation of cooking liquor, cause half steaming, cause operating difficulties, influence the amount of black liquor extraction and the wash degree of slurry, so this step of Screening Treatment is a crucial step in the wheat straw raw material dry raw material preparation.
Drum sieve of the present invention is the drum sieve that is used for grass raw material dry raw material preparation in the prior art.The rotating speed of described drum sieve is 18-23r/min, the inclination angle is 6-12 °, drum sieve of the present invention is a double-layer cylinder screen, the length of side of the square sieve aperture of the nexine sieve plate of drum sieve is 30-50mm, the diameter 4-8mm of outer sieve plate sieve aperture, in the process of Screening Treatment, big blade and other tiny impurity such as silt, dust etc. are screened to come out, and has guaranteed the clean of slurry.
Adopt dry raw material preparation method of the present invention, the edulcoration rate of wheat straw raw material reaches more than 90%, and general method to carry out the edulcoration rate of dry raw material preparation be 80%, so not only can reduce the dust in the slurry, make that prepared slurry is clean, the yield height, yield improves 1-3% than general method, reduces 0.5-2% with method production cost of the present invention.
Can before boiling, carry out impregnation process in the method for the present invention to raw material, maceration extract is flooded wheat straw raw material, make liquor ratio reach 1:2-4, in insulation and mixing more than 10 minutes in the spiral macerator more than 85 ℃, wherein insulation mixes 10-40 minute for well between 85-95 ℃ under normal pressure.Maceration extract is fully contacted with wheat straw raw material, make the dipping of wheat straw raw material evenly complete.Described maceration extract can be certain density aqueous slkali, in the aqueous slkali of NaOH to over dry material quantity 4%, also can be the mixed liquor of above-mentioned aqueous slkali and black liquor as alkali charge, and the concentration of used black liquor is 11-14 ° of Be ' (20 ℃).Raw material has been carried out impregnation process, utilized black liquor on the one hand as waste material, make black liquor obtain cycling and reutilization, reduced the pressure that environment is handled black liquor, on the other hand to the preliminary treatment of raw material dipping, make that heteroproteose cell, hemicellulose, the lignin deviate from are that main black liquid separation is discharged when heat treated, for next step digestion process is prepared.The described process that raw material is carried out impregnation process belongs to preprocessing process, its main purpose be for after in the digestion process infiltration of cooking liquor get ready, so this step can be omitted.
Boiling step in the inventive method is the pass of slurrying, because institutional framework, microstructure, chemical composition and the lignin molecular structure etc. of timber and wheat straw raw material are all variant, therefore, the delignification reaction course also has very big difference in digestion process.For wheat straw raw material Ammonium Sulfite Method boiling delignification reaction course, comprise intensification and be incubated two sections.The characteristics of wheat straw raw material are that delignification is more or less freely, and compare with wood raw material, and the temperature of a large amount of strippings of lignin is more in advance.
Ammonium Sulfite Method of the present invention comprises the steps:
(1) add ammonium sulfite solution in wheat straw raw material, the ammonium sulfite consumption is to over dry material quantity 9-13%, and wherein liquor ratio is 1:2-4;
(2) feed steam and heat, heat temperature raising is incubated 20-40 minute when temperature is 110-140 ℃, carry out little steam bleeding, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minute.
Wheat straw ammonium sulfite slurrying is exactly the effect that utilizes ammonium sulfite solution, suitably removes the lignin in the wheat straw raw material, keeps cellulose and hemicellulose as far as possible and is beneficial to copy paper.In fact in digestion process because action of high temperature, certain chemical change all can take place in the lignin in the raw material, cellulose, hemicellulose and other composition, be subjected in various degree degraded and damage, therefore must study the Changing Pattern of raw material in digestion process, formulate suitable conditions of cooking.In the pulping with ammonium sulfite method method of the present invention, by consumption and concentration to cooking liquor, the length of boiling and temperature retention time, the height of boiling temperature carries out systematic research, under the conditions of cooking that reduces the infringement of cellulose and hemicellulose as much as possible, carry out boiling, both reduce production cost thereby reach, energy savings can improve the purpose of the yield of slurrying again.
Through obtaining high-hardness pulp after the Ammonium Sulfite Method boiling, the hardness of described high-hardness pulp is equivalent to card uncle valency 24-50 for permanganate number 16-28 in the method for the present invention; Described high-hardness pulp preferred hardness is equivalent to card uncle valency 29-48 for permanganate number 18-27; Described high-hardness pulp most preferably hardness is equivalent to card uncle valency 34-42 for permanganate number 20-25.
The high-hardness pulp of the wheat straw ammonium sulfite boiling preparation among the present invention is as the raw material of preparation wheat straw brown stock.In the preparation method of the Ammonium Sulfite Method boiling of prior art, exist the time of boiling and insulation long, the stewing temperature height, the cooking liquor consumption is big, the problem that temperature retention time is long.Adopt boiling method of the present invention, by consumption and concentration to cooking liquor, the length of boiling and temperature retention time, the height of boiling temperature carries out systematic research, under the condition that reduces the infringement of cellulose and hemicellulose as much as possible, carry out boiling, both reduce production cost thereby reach, energy savings can improve the purpose of the yield of slurrying again.The yield of the resulting high-hardness pulp of described boiling method is 58-68%.
In the method for the invention, after boiling finishes, spurt to spraying pot after the pressure dilution that the high-hardness pulp maintenance of gained is certain, described pressure is 0.75MPa.Dilution can be clear water, also can be the used black liquor of aforementioned impregnation process.The concentration of the high-hardness pulp in the spraying pot is 8-15% at this moment, hardness is equivalent to card uncle valency 26-50 for permanganate number 16-28, beating degree is 22-28 ° of SR, be connected by delivery pump between spraying pot and the acroll press washer, delivery pump is transported to the high-hardness pulp in the spraying pot inlet of acroll press washer, high-hardness pulp enters from the inlet of acroll press washer, through after the shove, above-mentioned high-hardness pulp is sent from the outlet of press master, the concentration of the slurry of sending is brought up to 20-38% by 8-15%, become the high-hardness pulp of high concentration, temperature is 70-80 ℃.In shove, most of black liquor is extruded the back and stores in the black liquor groove.Selected press master is to extract the acroll press washer that black liquor is used in the prior art, is preferably single-screw press master or the Double screw pulp extruder and the Var-nip press of reducing.
Described acroll press washer can be one, also can for two be that described shove can be for carrying out shove through one acroll press washer, also can for through after the first road acroll press washer shove again through the second road acroll press washer shove.
When using press master to carry out shove, because the process at shove can produce very big extruding force, temperature rises rapidly, impel fiber separation, divide silk, brooming, conquassation, primary wall is to destroying, the enough energy of fiber absorbs make fibrous inside produce very big stress, and the reactivity worth of high-hardness pulp is greatly improved.Simultaneously, fiber produces fibrillating, and impurity is dissolved in the black digestion liquid between epidermis organic matter and fiber, discharges by liquid outlet groove, and fiber fineness is greatly improved.Some ash contents in the black liquor and impurity are also along with black liquor is discharged from, for next step operation has been carried out sufficient preparation.Most preferred press master is the single-screw press master of reducing among the present invention, utilizes the reducing press master, makes slurry in the space that slowly diminishes, and makes the about dehydration of compressed slurry layer consistent.The more important thing is the single-screw reducing press master that the present invention is selected, after high-hardness pulp was carried out shove, the beating degree of high-hardness pulp changed little, and beating degree is 22-28 ° of SR before the shove, and beating degree is 23-29 ° of SR after the shove.That is to say that described high-hardness pulp can the fibre length that fibers in grass class is intrinsic keep relatively goodly through after the press master shove, has reduced the damage of fiber to greatest extent.
When carrying out shove, also can adopt Var-nip press, the use of Var-nip press, also can be the same with the single-screw press master, reduce the damage of wheat straw fiber, and because the extraction rate of black liquor height of Var-nip press, therefore make that water consumption significantly reduces in the subsequent washing process, the pulp washing water consumption is less than the water consumption of pulp washing behind single-screw press master shove greatly, reaches more than 30% through the concentration of high-hardness pulp after the shove, and high energy reaches 38%.
In the method for the present invention, when carrying out the washing of high-hardness pulp, resulting high concentration high-hardness pulp after resulting high-hardness pulp after the boiling or the shove dilutes in general elder generation, being diluted to concentration with rarer black liquor such as the used black liquor of pre-preg is 2.5-3.5%, screening technique through prior art screens as jumping the sieve screening method again, and loss is 0.2-0.5% in the screening.Next wash, can adopt vacuum pulp washing machine of the prior art or pressure washer to wash.The purpose that adopts vacuum pulp washing machine is the easier inside and outside pressure difference of fibrocyte that is formed in the washing process, so more helps the wash degree that reaches high in washing process.In order to reach higher wash degree, the number of times of washing can suitably increase.
In the method for the present invention, after carrying out pulp washing, the concentration of slurry can be delivered to fluffer through conveying worm with this slurry and discongest processing between 9-11%, and the button degree of separating of handling the back slurry is 26-28 ° of SR, weight in wet base 1.5-1.7g, temperature 65-70 ℃.Described fluffer is the existing equipment of discongesting, as deflaker, and the mill fluffer.By discongesting, fiber can be rubbed with the hands and open, the lignin between fiber and the fiber is exposed out, helps the carrying out of the oxygen delignification step of back.
With the high-hardness pulp that obtains after the boiling or after discongesting after the slurry of gained or the pulp washing slurry of gained carry out oxygen delignification, described oxygen delignification is: alkali charge is in the 2-4% of NaOH to the oven dry stock amount, the addition of oxygen is 20-40kg slurry per ton, carries out oxygen delignification 75-90 minutes under these conditions.The hardness k value (permanganate number) of starching this moment is reduced to 11-13 and is equivalent to card uncle valency 12.5-17, and beating degree is 30-36 ° of SR.The preferred described oxygen delignification of the present invention is the single hop oxygen delignification, uses an oxygen delignification reaction tower, and high-hardness pulp is 95-100 ℃ in the temperature of this reaction tower import department, and pressure is 0.9-1.2MPa; The temperature in exit is 100-105 ℃, and pressure is 0.2-0.6MPa.Adopting the single hop oxygen delignification mainly is the intensity that guarantees paper pulp for further, relative multistage oxygen delignification, and the single hop oxygen delignification is less to cellulosic degradation.Generally speaking temperature is lower for the technological parameter of the preferred single hop oxygen delignification of the present invention, comparatively speaking the time longer, mainly be for the gentle more delignification reaction that carries out, avoid cellulosic degraded as far as possible.The concentration of the preferred high-hardness pulp of the present invention before carrying out oxygen delignification is 8-18%.In carry out oxygen delignification under the dense condition.In the major advantage of dense oxygen delignification be: invest less; Since in the success of dense mixing and pumping technology, the processing of slurry is dense more much easier than high; Slurry concentration is lower, and the corrosion of equipment is few, also the danger of not burning in oxygen.
Brown stock described in the present invention is resulting slurry after process boiling, the oxygen delignification; Described brown stock is feedstock production with the wheat straw, and the fracture length of described brown stock is 5.0-7.8km, and folding strength is 25-80 time, and tearability is 180-255mN, and whiteness is 37-45%ISO, and beating degree is 33-38 ° of SR; The fracture length of preferred described brown stock is 6.0-7.8km, and folding number is 32-80 time, and tearability is 230-255mN, and beating degree is 33-36 ° of SR.
In addition, brown stock of the present invention can be used for preparing newsprint, supercalendered paper, wrapping paper, paper diaper, crepe toilet paper, tissue, face tissue, napkin paper, tissue, paper for kitchen, writing paper, offset paper, offset printing paper, single face writing paper, M.G.offset paper and corrugated paper.
Also can be used for preparing moulded paper pulp product, described goods comprise: bowl, basin, cup, bucket, dish, dish, pallet and cutlery box; Carriage, electric welding protective cover, Indoor decorative plate, molding flowerpot, molding seedling-raising cup, molding slippers and adsorptive pads toilet seat cushion; Molding medical tray container, molding medical nursing product and disposable medical vessel.
With the brown stock of wheat straw raw material Ammonium Sulfite Method boiling preparation, its fracture length is 5.0-7.8km, and folding strength is 25-80 time, and tearability is 180-255mN, and whiteness is 37-45%ISO, and beating degree is 33-38 ° of SR; The fracture length of preferred described brown stock is 6.0-7.8km, and folding number is 32-80 time, and tearability is 230-255mN, and beating degree is 33-36 ° of SR.Described brown stock can be used as the slurry of corrugation, paper meal and wrapping paper.Owing in the process of preparation, do not handle, so can not be subjected to the pollution of bleaching agent in the slurry that obtains through bleaching.And wheat straw raw material used among the present invention is very abundant, and price is low.Among the preparation method of the present invention,, shorten the time of boiling, prepare high-hardness pulp by reducing the consumption of cooking liquor.The minimizing of chemical liquid consumption and the shortening of digestion time all can reduce enterprise's production cost greatly, and yield is greatly improved, thereby have improved production efficiency greatly.Simultaneously, the high-hardness pulp of wheat straw ammonium sulfite boiling preparation of the present invention can be used as the raw material of preparation brown stock, because the concentration of used soup reduces during boiling, and the time of boiling and insulation also shortens greatly, thereby on to greatest extent, having reduced the loss of needed cellulose and hemicellulose in the paper pulp, the yield of paper pulp is greatly improved.
Four of purpose of the present invention is to provide a kind of low brightness pulp of straw raw material alkaline cooking preparation, and this slurry intensity is good, has higher fracture length, tearability and folding number.
In order to realize purpose of the present invention, the technical solution used in the present invention is:
A kind of low brightness pulp of straw raw material alkaline cooking preparation, the whiteness of described low brightness pulp is 45-60%ISO, and fracture length is 4.8-7.0km, and tearability is 240-285mN, and folding number is 30-110 time; The whiteness of preferred described low brightness pulp is 50-60%ISO, and fracture length is 4.5-7.0km, and tearability is 250-285mN, and folding number is 50-110 time.
Another object of the present invention is to provide a kind of preparation method of above-mentioned low brightness pulp, comprise alkaline cooking, oxygen delignification, chlorination, alkali treatment, described boiling is that the straw raw material alkaline cooking is become hardness is permanganate number 16-28, the high-hardness pulp that is equivalent to card uncle valency 24-50, preferred hardness are equivalent to the high-hardness pulp of card uncle valency 29-48 for permanganate number 18-27; More hardness is equivalent to the high-hardness pulp of card uncle valency 34-42 for permanganate number 20-25.
Traditional technology is often boiled the hardness of slurry very low, causes declining to a great extent of pulp strength, and the present invention obtains the higher slurry of hardness by whole boiling, and carries out follow-up treatment step again, has guaranteed the intensity of the low brightness pulp that obtains.
Alkaline cooking of the present invention comprises anthraquinone-soda cooking, comprises the steps:
1) in straw raw material, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 9-15%, liquor ratio is 1:2-4, the anthraquinone addition is 0.5-0.8% of an over dry material quantity; Preferred described alkali charge is in the 9-13% of NaOH to the over dry material quantity; More preferably described alkali charge is in the 9-11% of NaOH to the over dry material quantity;
2) feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20-40 minutes when temperature is 100-130 ℃, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minute.
Alkaline process of the present invention also comprises kraft cooking, comprises the steps:
1) in straw raw material, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 8-11%, liquor ratio is 1:2-4, sulphidity is 5-8%;
2) feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20-40 minute when temperature is 110-140 ℃, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minutes.
Alkaline cooking of the present invention comprises the boiling of alkaline sodium sulfite method, comprises the steps:
1) add steaming preparation in straw raw material, wherein, sodium hydroxide concentration counts 11-15% with the over dry raw material weight, and sodium sulfite is 2-6%, and anthraquinone is 0.02-0.08%, and cooking liquor is than being 1:3-4;
2) feed steam and heat, heat temperature raising is incubated 20-40 minutes when temperature is 100-120 ℃, carry out little steam bleeding, continues heat temperature raising to 160-165 ℃, is incubated 60-90 minute.
Digestion process is the committed step of slurrying, because institutional framework, microstructure, chemical composition and the lignin molecular structure etc. of timber and grass as raw material are all variant, therefore, the delignification reaction course also has very big difference in digestion process.For straw raw material alkaline cooking delignification reaction course, comprise intensification and be incubated two sections.The straw raw material delignification is more or less freely, and compares with wood raw material, and the temperature of a large amount of strippings of lignin is more in advance.In the process of the boiling of prior art, this several method exists the time of boiling and insulation long when preparing paper pulp, stewing temperature height, the problem that temperature retention time is long.And in the method for the invention, the consumption of cooking liquor is few, and the time of boiling and insulation shortens greatly.
The process of boiling generally comprises three processes: (1) cooking liquor is to the process of raw material internal penetration; (2) process of alkali lye and raw material chemically reactive; (3) process of reactant stripping from raw material.This three process both stage by stage, was almost intersected simultaneously again and was carried out, and according to the needs of different paper pulp, suitably removed lignin and impurity in the raw material, and the adhesion between the fiber is descended, and impelled the frotation pulping.Therefore, the purpose of boiling is to utilize the effect of cooking liquor, suitably removes the lignin in the straw raw material, keeps cellulose as far as possible and the part hemicellulose is beneficial to copy paper.In digestion process, because the use of thermophilic digestion and chemical steaming soup, certain chemical change all can take place in the lignin in the raw material, cellulose and hemicellulose and other composition, is subjected in various degree degraded and damage.Therefore; in the method for the present invention; the chemical steaming soup has been carried out strict control; its concentration is reduced; minimizing is to the degraded and the damage of the required composition of slurrying such as cellulose, hemicellulose; protect the required composition of slurrying in the raw material to greatest extent, shortened temperature retention time greatly simultaneously, significantly reduced energy consumption.
Oxygen delignification among the present invention may further comprise the steps:
1) concentration of high-hardness pulp after the adjusting boiling;
2) this stock pump is delivered to the oxygen delignification reaction tower, and add NaOH and oxygen; And
3) this slurry carries out the oxygen delignification reaction in this oxygen delignification reaction tower, and obtaining hardness is permanganate number 10-14, is equivalent to the slurry of card uncle valency 13-19.8.
Wherein, preferred steps 3) the starch degree that carries out obtaining after the oxygen delignification reaction is permanganate number 11-13.
The hardness that the present invention starches after to oxygen delignification is controlled, and is in order to guarantee that lignin is sloughed as much as possible on the one hand, has guaranteed the intensity of the slurry that obtains in addition on the one hand again.Equally, the method for oxygen delignification can adopt any method of prior art, and the hardness that only needs control to handle the back slurry gets final product in the framework of the present definition.
The concentration that the present invention regulates high-hardness pulp is meant that the concentration adjustment with described slurry is 8-18%, that is to say in carry out oxygen delignification under the dense condition.In the major advantage of dense oxygen delignification be: invest less; Since in the success of dense mixing and pumping technology, the processing of slurry is dense more much easier than high; Slurry concentration is lower, and the corrosion of equipment is few, also the danger of not burning in oxygen.
Oxygen delignification of the present invention is the single hop oxygen delignification, carries out at oxygen delignification reaction turret clock.In the oxygen delignification process, described slurry is 95-100 ℃ in the temperature of this reaction tower import department, and pressure is 0.9-1.2MPa, and the temperature in exit is 100-105 ℃, and pressure is 0.2-0.6MPa.Alkali charge is the 2-4% in NaOH oven dry stock amount in the described oxygen delignification, and the addition of oxygen is slurry 20-40kg per ton; The reaction of above-mentioned slurry in this reaction tower 75-90 minutes.Adopting the single hop oxygen delignification mainly is the intensity that guarantees paper pulp for further, relative multistage oxygen delignification, and single hop is less to cellulosic degradation.Generally speaking temperature is lower for the technological parameter of the preferred single hop oxygen delignification of the present invention, comparatively speaking the time longer, mainly be for the gentle more delignification reaction that carries out, avoid cellulosic degraded as far as possible.The delignification rate is 86-98% in the preferred described oxygen delignification process of the present invention.
The present invention was transported to a slurry pipe with this high-hardness pulp by middle underflow pump before described oxygen delignification, and the air that in this slurry pipe above-mentioned slurry is carried out in the modifier treatment eliminating slurry makes it fluidization.Can adopt conveying worm that high-hardness pulp is heated to 70-80 ℃ and be transported to this slurry pipe among the present invention.Add the magnesium salts of oven dry stock weight 0.2-1% in the oxygen delignification process of the present invention as protective agent.
Chlorination of the present invention is 2.5-3% of an oven dry stock at chlorine dosage, and the concentration of slurry is 3-3.5%, and temperature is to carry out 45-60 minutes under 50-55 ℃ the condition.
In the alkali treatment of the present invention at alkali charge in the 2-4% of NaOH to the oven dry stock amount, the concentration of slurry is 10-12%, temperature is to carry out 100-150 minutes under 50-55 ℃ the condition.
The present invention also comprises the process that straw raw material is flooded before boiling, can adopt the dipping spiral organ.The mode that said impregnation process adopts is preferably: maceration extract is flooded raw material, make liquor ratio reach 1:2-4, in insulation and mixing more than 10 minutes in the spiral macerator more than 85 ℃, wherein insulation mixes 10-40 minutes for well between 85-95 ℃ under normal pressure.Maceration extract is fully contacted with raw material, make the dipping of raw material evenly complete.Described maceration extract can be certain density aqueous slkali, in the aqueous slkali of NaOH to over dry material quantity 4%, also can be the mixed liquor of above-mentioned aqueous slkali and black liquor as alkalinity, and the concentration of used black liquor is 11-14 ° of Be ' (20 ℃).
Raw material has been carried out impregnation process, utilized black liquor as waste material, make black liquor obtain cycling and reutilization, reduced the pressure that environment is handled black liquor, because to the preliminary treatment of raw material dipping, make that heteroproteose cell, hemicellulose, the lignin deviate from are that main black liquid separation is discharged when heat treated, for next step digestion process is prepared.
The present invention also can be before flooding raw material, can adopt prior art that raw material is carried out preliminary treatment, promptly adopt conventional do, wet feed preparation, with remove defoliation, fringe, grain, etc. impurity, can alleviate the pressure of subsequent technique like this, and improve the quality of straw pulp.Dried, wet feed preparation can adopt existing conventional equipment, as chaffcutter, screening machine, dust removal machine, wet scrubbing Straw-crumbling machine, inclined screw Water Extraction Machinery etc.Fibers in grass class raw material through the removal moisture after getting the raw materials ready also can be fine fodder, and the moisture of deduction dogstail is the over dry grass, and the length of general blade is at 15-30mm, and the technology of getting the raw materials ready of raw material is technology as well known to those skilled in the art.
Can be after boiling in the method for the present invention, the high-hardness pulp after the boiling is carried out shove before the oxygen delignification.Can be 8-15% high-hardness pulp with gained concentration after the boiling enters from the inlet of press master, carries out shove, and after the extruding black liquor, concentration is that 20-30% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 22-28 ° of SR, and the beating degree after the shove is 23-29 ° of SR.The Baume degrees of the black liquor that shove is extruded is 7-11 ° of Be ' at 20 ℃.Straw raw material is carried out the prepared high-hardness pulp of anthraquinone-soda cooking, carry out after the shove, the black liquor of being extruded Baume degrees in the time of 20 ℃ is 9-11 ° of Be ', and the content of residual alkali is 8-10g/L in the black liquor.The slurry that comes out from the outlet of press master dilutes with the black liquor that pulp washing the subsequent technique displaces, and described black liquor is 3-6 ° of Be ' at 20 ℃ of Baume degrees, perhaps can directly dilute with clear water, makes underflow to 2.5-3% deliver to jumping and screens.
Press master described in the present invention is the acroll press washer that is used for extracting black liquor in the prior art.When using press master to carry out shove, because the process at shove can produce very big extruding force, temperature rises rapidly, impel fiber separation, divide silk, brooming, conquassation, primary wall is destroyed, the enough energy of fiber absorbs make fibrous inside produce very big stress, and the reactivity worth of high-hardness pulp is greatly improved.Simultaneously, fiber produces fibrillating, and impurity is dissolved in the black digestion liquid between epidermis organic matter and fiber, discharges by liquid outlet groove, and fiber fineness is greatly improved.Some ash contents in the black liquor and impurity are also along with black liquor is discharged from, for subsequent step has been carried out sufficient preparation.Press master of the present invention is that the acroll press washer that the extraction black liquor is used in the prior art is single-screw press master and Double screw pulp extruder; Preferred described press master is the acroll press washer of reducing.
Press master among the present invention is the Reducing screw press master, utilizes the reducing press master, makes slurry in the space that slowly diminishes, and makes the about dehydration of compressed slurry layer consistent.The acroll press washer that the present invention is selected, after high-hardness pulp is carried out shove, the beating degree of described high-hardness pulp changes little, that is to say, described high-hardness pulp is through after the press master shove, can the fibre length that fiber is intrinsic keep relatively goodly, reduce the damage of fiber to greatest extent.The press master that adopts among the present invention also can be Var-nip press, can realize the effect that the present invention will reach equally, and water consumption significantly reduces.
Can after boiling, discongest slurry before the oxygen delignification in the method for the present invention, can adopt the existing equipment of discongesting, can in carding process of the present invention, use as mill fluffer in deflaker, kneading machine, dry pan, the beating equipment and defibrator, because they can play the effect of discongesting fiber and reducing cut staple as far as possible.In the process of discongesting, fiber naturally separately is easy to wherein lignin is come out, and can reach the effect of getting well in the processing procedure so afterwards.This is discongested and can carry out immediately after boiling, also can carry out before oxygen delignification, can also carry out behind shove.In fact, between any processing step between boiling and the oxygen delignification, can carry out this and discongest, can both reach the effect that needs.
In addition, low brightness pulp of the present invention can be used for preparing newsprint, supercalendered paper, wrapping paper, paper diaper, crepe toilet paper, tissue, face tissue, napkin paper, tissue, paper for kitchen, writing paper, offset paper, offset printing paper, single face writing paper, M.G.offset paper and corrugated paper.
Also can be used for preparing moulded paper pulp product, described goods comprise: bowl, basin, cup, bucket, dish, dish, pallet and cutlery box; Carriage, electric welding protective cover, Indoor decorative plate, molding flowerpot, molding seedling-raising cup, molding slippers and adsorptive pads toilet seat cushion; Molding medical tray container, molding medical nursing product and disposable medical vessel.
Low brightness pulp intensity of the present invention is higher, especially fracture length and folding number have surpassed the level of hardwood pulp, can be directly used in the paper of framing news, books, napkin paper etc., perhaps only need add wood pulp seldom and be applied to make other paper products widely, significantly reduce the cost of product, guarantee the intensity of product simultaneously again.Method of the present invention is by the hardness of the slurry that obtains of control boiling, carry out oxygen delignification then, both made that lignin is wherein effectively removed, reduced degradation of fiber again as far as possible, delignification rate 86-98% in its oxygen delignification process, thus can access the good low brightness pulp of intensity.
Low brightness pulp that provides a kind of wheat straw raw material alkaline cooking preparation and preparation method thereof is provided five of purpose of the present invention.
In order to achieve the above object, the technical solution used in the present invention is:
A kind of low brightness pulp of wheat straw raw material alkaline cooking preparation, described low brightness pulp is feedstock production with the wheat straw, and its fracture length is 5.5-7.2km, and folding strength is 20-60 time, and tearability is 180-240mN, and whiteness is 55-60%ISO, and beating degree is 33-38 ° of SR; The fracture length of preferred described low brightness pulp is 6.0-7.2km, and folding number is 35-60 time, and tearability is 210-240mN, and beating degree is 33-36 ° of SR.
A kind of method for preparing above-mentioned low brightness pulp comprises the step of alkaline cooking, oxygen delignification, chlorination, alkali treatment, is permanganate number 18-25 with wheat straw raw material alkaline cooking to hardness, is equivalent to the high-hardness pulp of card uncle valency 27-43.
Alkaline cooking described in the present invention comprises anthraquinone-soda cooking and kraft cooking.
Anthraquinone-soda cooking of the present invention is:
(1) alkali charge is for measuring 9-15% in NaOH to the over dry wheat straw, and liquor ratio is 1:2-4, and the anthraquinone addition is the 0.5-0.8% of over dry material quantity;
(2) feed steam and heat, heat temperature raising is incubated 20-40 minute when temperature is 110-130 ℃, carry out little steam bleeding, continues heat temperature raising to 160-170 ℃, is incubated 60-90 minute; The preferred heat temperature raising that continues is to 160-165 ℃.
Kraft cooking of the present invention is
(1) to over dry wheat straw amount 8-11%, liquor ratio is 1:2-4 to alkali charge in NaOH, and sulphidity is 5-8%;
(2) feed steam and heat, heat temperature raising is incubated 20-40 minute when temperature is 110-140 ℃, carry out little steam bleeding, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minute.
Alkaline sodium sulfite method method of the present invention boiling is
(1) add steaming preparation in wheat straw raw material, wherein, sodium hydroxide concentration counts 11-15% with the over dry raw material weight, and sodium sulfite is 2-6%, and anthraquinone is 0.02-0.08%, and cooking liquor is than being 1:3-4;
(2) feed steam and heat, heat temperature raising is incubated 20-40 minutes when temperature is 100-120 ℃, carry out little steam bleeding, continues heat temperature raising to 160-165 ℃, is incubated 60-90 minute.
Oxygen delignification of the present invention is:
(1) be permanganate number 18-25 with obtaining hardness after the boiling, the high-hardness pulp that is equivalent to card uncle valency 27-43 is pumped to the oxygen delignification reaction tower, and adds NaOH and oxygen; And
(2) this high-hardness pulp carries out delignification reaction in this oxygen delignification reaction tower, and obtaining hardness is permanganate number 10-14, is equivalent to the slurry of card uncle valency 12.5-19.3;
Wherein, the hardness of the high-hardness pulp in the preferred steps (1) is permanganate number 20-24, is equivalent to card uncle valency 31-39.2; Starch degree in the step (2) is permanganate number 11-13, is equivalent to card uncle valency 14-17.8.
Oxygen delignification of the present invention is the single hop oxygen delignification, uses an oxygen delignification reaction tower; Described high-hardness pulp is 95-100 ℃ in the temperature of this reaction tower import department, and pressure is 0.9-1.2MPa, and the temperature in exit is 100-105 ℃, and pressure is 0.2-0.6MPa; Alkali charge is that the addition of oxygen is 20-40kg slurry per ton in the 2-4% of NaOH to the oven dry stock amount in the described oxygen delignification; The reaction time of described high-hardness pulp in this reaction tower is 75-90 minute.
In the method for the present invention, after alkaline cooking, before the oxygen delignification, also comprise shove, described shove is for being permanganate number 18-25 with the hardness that obtains behind the wheat straw alkaline cooking, and the high-hardness pulp that is equivalent to card uncle valency 27-43 carries out shove under the extruding force effect of single-screw press master or Var-nip press.
Chlorination of the present invention is: chlorine dosage is the 2.5-3% of oven dry stock, and the concentration of slurry is 3-3.5%, and the temperature of bleaching is 50-55 ℃, and the time of bleaching is 45-60 minute.
Alkali treatment of the present invention is: alkali charge in NaOH to oven dry stock amount 2-4%, the concentration of slurry is 10-12%, bleaching temperature is 50-55 ℃, the time is 100-150 minute.
In the method for the present invention, after alkaline cooking, before the oxygen delignification, also comprise shove, described shove is for being permanganate number 16-28 with the hardness that obtains behind the wheat straw raw material alkaline cooking, and the high-hardness pulp that is equivalent to card uncle valency 24-50 carries out shove under the extruding force effect of single-screw press master or Var-nip press.
In the method for the present invention, after alkaline cooking, before the oxygen delignification, also comprise and discongesting, described discongest into: according to the method for prior art, hardness to gained after the boiling is permanganate number 16-28, and the high-hardness pulp that is equivalent to card uncle valency and is 24-50 is discongested, and makes fibre structure become loose.
In the method for the present invention when discongesting used fluffer be deflaker or mill fluffer.
Specifically, described low brightness pulp is feedstock production with the wheat straw, and its fracture length is 5.5-7.2km, and folding strength is 20-60 time, and tearability is 180-240mN, and whiteness is 55-60%ISO, and beating degree is 33-38 ° of SR; The fracture length of preferred described low brightness pulp is 6.2-7.2km, and folding number is 35-65 time, and tearability is 225-245mN, and beating degree is 33-36 ° of SR.
Low brightness pulp of the present invention, with the wheat straw is feedstock production, and its fracture length reaches more than 5500 meters, and folding strength reaches more than 20 times, be a kind of high-quality wheat straw low brightness pulp, can be used as high-quality paper for daily use of preparation and student slurry with paper and newsprint.
In the method for the invention, at first can adopt prior art that wheat straw is got the raw materials ready, promptly adopt conventional dried, wet feed preparation,, can alleviate the pressure of subsequent technique like this, and improve the quality of Straw Pulp to remove impurity such as defoliation, fringe, grain, marrow.Dried, wet feed preparation can adopt existing conventional equipment, as chaffcutter, screening machine, dust removal machine, wet scrubbing Straw-crumbling machine, inclined screw Water Extraction Machinery etc.Wheat straw raw material through the removal moisture after getting the raw materials ready also can be fine fodder, and the moisture of deduction wheat straw is the over dry grass, and the length of general blade is at 15-30mm, and the technology of getting the raw materials ready of raw material is technology as well known to those skilled in the art.
In the melting process in the present invention, also can utilize hammer mill to carry out dry raw material preparation, may further comprise the steps:
(1) wheat straw raw material is utilized hammer mill cut off rubbing and handle, obtain cutting off the raw material after the rubbing;
Wheat straw raw material is delivered in the hammer mill by belt conveyor or other conveyer in this step, and described hammer mill comprises to be carried feeding section, fragmentation and rubbing section and break up the discharge section.Wheat straw raw material at first enters the conveying feeding section of hammer mill, this section mainly plays a part to carry and feeding, enter fragmentation and rubbing section again, the wheat straw raw material effect of power and percussion power that is squeezed in this section, length is that the wheat straw raw material of 300-800mm is hammered into shape disconnected when entering hammer mill, therefore this hammer mill has at first played the effect of chaffcutter, the wheat straw raw material effect of power that is squeezed simultaneously, cross section is crushed for circular wheat straw raw material, impurity such as leaf, fringe, wheat, marrow are separated with stalk, and separation rate is 70-90%.Discharge section from the wheat straw raw material that hammer mill rubbing section is come through breaing up, the wheat straw raw material that presses together is broken up, therefore the contact-making surface of raw material and cooking liquor is big when boiling, and soup permeates easily, thus the process of accelerating delignification.Last wheat straw raw material is discharged from the outlet of hammer mill.The 20-50mm of the wheat straw raw material of being discharged.
Hammer mill among the present invention is the beater grinder that ore dressing or bark are pulverized usefulness in the prior art.The rotating speed of described hammer mill is 500-800rpm, the speed that wheat straw raw material enters hammer mill is 0.5-1.0m/s, rotating speed is crossed words low or that charging is too fast, can cause some wheat straw raw materials not crumpled fully, the infiltration of cooking liquor after the influence, and then influence pulp quality.
The wheat straw raw material skin has one deck wax, and there is one deck marrow its bar inside, and in the general method of getting the raw materials ready, when skin was flooded by cooking liquor, wax can be removed soon, but because the internal layer of its bar has air, so cooking liquor is difficult to enter.After utilizing hammer mill to cut off the wheat straw raw material and crumpling, help the abundant dipping of raw material, obtain the measured slurry of matter after the boiling easily.
(2) raw material that will cut off after the fragmentation carries out dust removal process;
Carry out dust removal process through the raw material after the cut-out fragmentation, this is owing to contain impurity such as dust, sandstone, blade of grass, careless fringe in the blade after cutting off, through dust removal process, above-mentioned impurity major part is removed, therefore in the digestion process after getting the raw materials ready, chemicals consumption in the time of can reducing boiling, the time of boiling also can shorten accordingly.
Carrying out dust removal machine that dust removal process adopted among the present invention can comprise roll-type dust removal machine, double cone dust removal machine and cyclone dust removal machine for the used dust removal machine of getting the raw materials ready of wheat straw raw material in the prior art, and preferred described dust removal machine is the cyclone dust removal machine.Air quantity is 30000-38000m when carrying out dust removal process in cyclone dust collectors 3/ h, blast 210mmHgO.Under such condition, can remove dust contained in the wheat straw raw material in a large number, alleviate the burden of follow-up boiling.
(3) will carry out Screening Treatment through the raw material of dust removal process.
Wheat straw raw material often has foreign material such as thick blade and broken end through after the dust removal process, and in digestion process, these foreign material have is difficult for being permeated by cooking liquor, thus generation steaming separate thing; Though react with cooking liquor at the broken end that has, but black liquor viscosity is increased, influence the circulation of cooking liquor, cause half steaming, cause operating difficulties, influence the amount of black liquor extraction and the wash degree of slurry, so this step of Screening Treatment is a crucial step in the wheat straw raw material dry raw material preparation.
Drum sieve of the present invention is the drum sieve that is used for the wheat straw raw material dry raw material preparation in the prior art.The rotating speed of described drum sieve is 18-23r/min, the inclination angle is 6-12 °, drum sieve of the present invention is a double-layer cylinder screen, the length of side of the nexine sieve plate square sieve aperture of drum sieve is 30-50mm, the diameter 4-8mm of outer sieve plate sieve aperture, in the process of this Screening Treatment, big blade and other tiny impurity such as silt, dust etc. are screened to come out, and paper pulp is clean after having guaranteed.
Adopt the inventive method to get the raw materials ready, the edulcoration rate of wheat straw raw material reaches more than 90%, and general method to carry out the edulcoration rate of dry raw material preparation be 80%, so not only can reduce the dust in the slurry, make that prepared slurry is clean, the yield height, yield improves 1-3% than general method, and production cost reduces 0.5-2%.
Can before boiling, carry out impregnation process in the method for the present invention to raw material, maceration extract is flooded wheat straw raw material, make liquor ratio reach 1:2-4, in insulation and mixing more than 10 minutes in the spiral macerator more than 85 ℃, wherein insulation mixes 10-40 minute for well between 85-95 ℃ under normal pressure.Maceration extract is fully contacted with wheat straw raw material, make the dipping of wheat straw raw material evenly complete.Described maceration extract can be certain density aqueous slkali, for being 4% in NaOH to the over dry material quantity, also can be the mixed liquor of above-mentioned aqueous slkali and black liquor as alkali charge, and the concentration of used black liquor is 11-14 ° of Be ' (20 ℃).Raw material has been carried out impregnation process, utilized black liquor, made black liquor obtain cycling and reutilization, reduced the pressure that environment is handled black liquor as waste material.Owing to, make that heteroproteose cell, hemicellulose, the lignin deviate from are that main black liquid separation is discharged when heat treated, for next step digestion process is prepared to the preliminary treatment of raw material dipping.The described process that raw material is carried out impregnation process belongs to preprocessing process, its main purpose be for after in the digestion process infiltration of cooking liquor get ready, so this step can be omitted.
Boiling step in the inventive method is the key of slurrying, because institutional framework, microstructure, chemical composition and the lignin molecular structure etc. of wheat straw raw material and timber are all variant, therefore, the delignification reaction course also has very big difference in digestion process.For wheat straw raw material alkaline cooking delignification reaction course, comprise intensification and be incubated two sections.The characteristics of wheat straw raw material are that delignification is more or less freely, and compare with wood raw material, and the temperature of a large amount of strippings of lignin is more in advance.
Anthraquinone-soda cooking of the present invention is:
(1) alkali charge is for measuring 9-15% in NaOH to the over dry wheat straw, and liquor ratio is 1:2-4, and the anthraquinone addition is the 0.5-0.8% of over dry material quantity; The 9-13% of preferred described alkali charge for the over dry wheat straw being measured in NaOH; The 9-11% of more preferably described alkali charge for the over dry wheat straw being measured in NaOH;
(2) feed steam and heat, heat temperature raising is incubated 20-40 minute when temperature is 110-130 ℃, carry out little steam bleeding, continues heat temperature raising to 160-170 ℃, is incubated 60-90 minute.
Kraft cooking of the present invention is
(1) to over dry wheat straw amount 8-11%, liquor ratio is 1:2-4 to alkali charge in NaOH, and sulphidity is 5-8%;
(2) feed steam and heat, heat temperature raising is incubated 20-40 minute when temperature is 110-140 ℃, carry out little steam bleeding, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minute.
Alkaline sodium sulfite method method of the present invention boiling is
(1) add steaming preparation in wheat straw raw material, wherein, sodium hydroxide concentration counts 11-15% with the over dry raw material weight, and sodium sulfite is 2-6%, and anthraquinone is 0.02-0.08%, and cooking liquor is than being 1:3-4;
(2) feed steam and heat, heat temperature raising is incubated 20-40 minutes when temperature is 100-120 ℃, carry out little steam bleeding, continues heat temperature raising to 160-165 ℃, is incubated 60-90 minute.
Soda pulping process is exactly to utilize the effect of alkali lye, suitably removes the lignin in the raw material, keeps cellulose and hemicellulose as far as possible and is beneficial to copy paper.In fact in digestion process because the effect of high temperature highly basic, certain chemical change all can take place in the lignin in the raw material, cellulose, hemicellulose and other composition, be subjected in various degree degraded and damage, therefore must study the Changing Pattern of raw material in digestion process, formulate suitable conditions of cooking.In the alkaline pulping method of the present invention, by consumption and concentration to cooking liquor, the length of boiling and temperature retention time, the height of boiling temperature carries out systematic research, under the condition that reduces the infringement of cellulose and hemicellulose as much as possible, carry out boiling, both reduce production cost thereby reach, energy savings can improve the purpose of the yield of slurrying again.
Through obtaining high-hardness pulp after the alkaline cooking, the hardness of described high-hardness pulp is equivalent to card uncle valency 24-50 for permanganate number 16-28 in the method for the present invention; The hardness of preferred described high-hardness pulp is equivalent to card uncle valency 29-48 for permanganate number 18-27; Described high-hardness pulp most preferably hardness is equivalent to card uncle valency 34-42 for permanganate number 20-25.
The high-hardness pulp of the alkaline cooking preparation among the present invention is as the raw material of preparation low brightness pulp.In the preparation method of the alkaline cooking of prior art, exist the time of boiling and insulation long, the stewing temperature height, the cooking liquor consumption is big, the problem that temperature retention time is long.And in the method for the invention, the consumption of cooking liquor is few, and the time of boiling and insulation shortens greatly.The present invention is by consumption and concentration to cooking liquor, the length of boiling and temperature retention time, the height of boiling temperature carries out systematic research, under the condition that reduces the infringement of cellulose and hemicellulose as much as possible, carry out boiling, both reduce production cost thereby reach, energy savings can improve the purpose of the yield of slurrying again.The described yield that goes out the resulting high-hardness pulp of boiling method is 58-68%.
In the method for the invention, after boiling finishes, spurt to spraying pot after the pressure dilution that the high-hardness pulp maintenance of gained is certain, described pressure is 0.75MPa.Dilution can be the used black liquor of aforementioned impregnation process.The concentration of the high-hardness pulp in the spraying pot is 8-15% at this moment, hardness is equivalent to card uncle valency 26-50 for permanganate number 16-28, beating degree is 22-28 ° of SR, be connected by delivery pump between spraying pot and the acroll press washer, delivery pump is transported to the high-hardness pulp in the spraying pot inlet of acroll press washer, high-hardness pulp enters from the inlet of acroll press washer, through after the shove, above-mentioned high-hardness pulp is sent from the outlet of press master, the concentration of the slurry of sending is brought up to 20-38% by 8-15%, become the high-hardness pulp of high concentration, temperature is 70-80 ℃.In shove, most of black liquor is extruded the back and stores in the black liquor groove.Selected press master is to extract the acroll press washer that black liquor is used in the prior art, is preferably single-screw press master, Double screw pulp extruder or the Var-nip press of reducing.
Described acroll press washer can be one, also can for two be that described shove can be for carrying out shove through one acroll press washer, also can for through after the first road acroll press washer shove again through the second road acroll press washer shove.
When using press master to carry out shove, because the process at shove can produce very big extruding force, temperature rises rapidly, impel fiber separation, divide silk, brooming, conquassation, primary wall is destroyed, the enough energy of fiber absorbs make fibrous inside produce very big stress, and the reactivity worth of high-hardness pulp is greatly improved.Simultaneously, fiber produces fibrillating, and impurity is dissolved in the black digestion liquid between epidermis organic matter and fiber, discharges by liquid outlet groove, and fiber fineness is greatly improved.Some ash contents in the black liquor and impurity are also along with black liquor is discharged from, for sufficient preparation has been carried out in next step pulp washing and bleaching.Most preferred press master is the press master of spiral reducing among the present invention, utilizes the reducing press master, makes slurry in the space that slowly diminishes, and makes the about dehydration of compressed slurry layer consistent.The single-screw reducing press master that the present invention is selected, after high-hardness pulp was carried out shove, the beating degree of described high-hardness pulp changed little, and beating degree is 22-28 ° of SR before the shove, and beating degree is 23-29 ° of SR after the shove.That is to say that described high-hardness pulp can the fibre length that wheat straw fiber is intrinsic keep relatively goodly through after the press master shove, has reduced the damage of fiber to greatest extent.
When carrying out shove, also can adopt Var-nip press, the use of Var-nip press, also can be the same with the single-screw press master, reduce the damage of fiber to greatest extent, and because the extraction rate of black liquor height of described Var-nip press, therefore make that water consumption significantly reduces in the subsequent washing process, water consumption is less than the single-screw press master greatly, reaches more than 30% through the concentration of high-hardness pulp after the shove, and high energy reaches 38%.
In the method for the present invention, when carrying out the washing of high-hardness pulp, resulting high concentration high-hardness pulp after resulting high-hardness pulp after the boiling or the shove dilutes in general elder generation, being diluted to concentration with rarer black liquor is 2.5-3.5%, screening technique through prior art screens as jumping the sieve screening method again, and loss is 0.2-0.5% in the screening.Next wash, can adopt vacuum pulp washing machine of the prior art or pressure washer to wash.The purpose that adopts vacuum pulp washing machine is the easier inside and outside pressure difference of fibrocyte that is formed in the washing process, so more helps the wash degree that reaches high in washing process.In order to reach higher wash degree, the number of times of washing can also can be twice or three times for once.
In the method for the present invention, after carrying out pulp washing, the concentration of slurry can be delivered to fluffer through conveying worm with this slurry and discongest processing between 9-11%, and the button degree of separating of handling the back slurry is 26-28 ° of SR, weight in wet base 1.5-1.7g, temperature 65-70 ℃.Described fluffer is the existing equipment of discongesting, as deflaker, and the mill fluffer.By discongesting, fiber can be rubbed with the hands and open, the lignin between fiber and the fiber is exposed out, helps the carrying out of the oxygen delignification step of back.
With the high-hardness pulp that obtains after the boiling or after discongesting after the slurry of gained or the pulp washing slurry of gained carry out oxygen delignification, described oxygen delignification is: alkali charge is in the 2-4% of NaOH to the oven dry stock amount, and the addition of oxygen is to bleach 75-90 minutes under the condition of 20-40kg slurry per ton.The hardness k value (permanganate number) of starching this moment is reduced to 11-13 and is equivalent to card uncle valency 12.5-17, and beating degree is 30--36 ° of SR.The preferred described oxygen delignification of the present invention is the single hop oxygen delignification, uses an oxygen delignification reaction tower, and high-hardness pulp is 95-100 ℃ in the temperature of this reaction tower import department, and pressure is 0.9-1.2MPa; The temperature in exit is 100-105 ℃, and pressure is 0.2-0.6MPa.Adopting the single hop oxygen delignification mainly is the intensity that guarantees paper pulp for further, relative multistage oxygen delignification, and the single hop oxygen delignification is less to cellulosic degradation.Generally speaking temperature is lower for the technological parameter of the preferred single hop oxygen delignification of the present invention, comparatively speaking the time longer, mainly be for the gentle more delignification reaction that carries out, avoid cellulosic degraded as far as possible.The concentration of the preferred chemical pulp of the present invention before carrying out oxygen delignification is 8-18%.In carry out oxygen delignification under the dense condition.In the major advantage of dense oxygen delignification be: invest less; Since in the success of dense mixing and pumping technology, the processing of slurry is dense more much easier than high; Slurry concentration is lower, and the corrosion of equipment is few, also the danger of not burning in oxygen.
To carry out chlorination earlier through the slurry of oxygen delignification among the present invention: chlorine dosage is the 2.5-3% of oven dry stock, and the concentration of slurry is 3-3.5%, and the temperature of bleaching is 50-55 ℃, and the time of bleaching is 45-60 minute; Carrying out alkali treatment again is: alkali charge in NaOH to oven dry stock amount 2-4%, the concentration of slurry is 10-12%, bleaching temperature is 50-55 ℃, the time is 100-150 minute.
Low brightness pulp described in the present invention is resulting slurry after process boiling, oxygen delignification, chlorination and the alkali treatment, the fracture length of described low brightness pulp is 5.5-7.2km, and folding strength is 20-60 time, and tearability is 180-240mN, whiteness is 55-60%ISO, and beating degree is 33-38 ° of SR.
In addition, low brightness pulp of the present invention can be used for preparing newsprint, supercalendered paper, wrapping paper, paper diaper, crepe toilet paper, tissue, face tissue, napkin paper, tissue, paper for kitchen, writing paper, offset paper, offset printing paper, single face writing paper, M.G.offset paper and corrugated paper.
Also can be used for preparing moulded paper pulp product, described goods comprise: bowl, basin, cup, bucket, dish, dish, pallet and cutlery box; Carriage, electric welding protective cover, Indoor decorative plate, molding flowerpot, molding seedling-raising cup, molding slippers and adsorptive pads toilet seat cushion; Molding medical tray container, molding medical nursing product and disposable medical vessel.
With the low brightness pulp of wheat straw raw material alkaline cooking preparation, the fracture length of its described low brightness pulp is 5.5-7.2km, and folding strength is 20-60 time, and tearability is 180-240mN, and whiteness is 55-60%ISO, and beating degree is 33-38 ° of SR.Described low brightness pulp can be used as the slurry of high-quality student with paper and paper for daily use etc.Because in the process of preparation; do not handle through traditional hypochlorite bleaching; so effect that the slurry that obtains can not make cellulose in the slurry and hemicellulose be degraded because of the adding of hypochlorite; the intensity of slurry has obtained protection simultaneously; and used wheat straw raw material is very abundant and price is low among the present invention.Among the preparation method of the present invention,, shorten the time of boiling, prepare high-hardness pulp by reducing the consumption of cooking liquor.The minimizing of chemical liquid consumption and the shortening of digestion time all can reduce enterprise's production cost greatly, and yield is greatly improved, thereby have improved production efficiency greatly.Simultaneously, the high-hardness pulp of wheat straw alkaline cooking preparation of the present invention can be used as the raw material of preparation low brightness pulp, because the concentration of used soup reduces during boiling, and the time of boiling and insulation also shortens greatly, thereby on to greatest extent, having reduced the loss of needed cellulose and hemicellulose in the paper pulp, the yield of paper pulp is greatly improved.
It is the method for feedstock production high-hardness pulp that six of purpose of the present invention is to provide with the grass kind plant.The time weak point of Steam Heating insulation has been saved the energy in the described method.
In order to achieve the above object, the technical solution used in the present invention is:
A kind of is the method for feedstock production high-hardness pulp with the grass kind plant, described method comprise get the raw materials ready, the boiling step, described boiling method is a kind of in ammonium sulfite, anthraquinone-soda processes, sulfate process or the Arbiso process boiling, when adopting the ammonium sulfite boiling, the consumption of ammonium sulfite is the 15-25% of over dry material quantity; When adopting anthraquinone-soda cooking, alkali charge is in the 15-25% of NaOH to the over dry material quantity; When adopting kraft cooking, alkali charge is in the 13-25% of NaOH to the over dry material quantity; During the Arbiso process boiling, total acid is greater than 5%, and combined acid is 2.0-4.0%; Obtain the high-hardness pulp that hardness is permanganate number 16-28 after the boiling, preferred hardness is a permanganate number 18-27 high-hardness pulp; Most preferably hardness is the high-hardness pulp of permanganate number 20-25.
Grass kind plant raw material of the present invention is a kind of in wheat straw, straw, bagasse, cotton stalk, the reed or more than one mixing.
High-hardness pulp of the present invention can be used for preparing bleach chemical pulp.
Ammonium sulfite boiling of the present invention comprises the steps:
(1) add the ammonium sulfite cooking liquor in the grass kind plant raw material, wherein liquor ratio is 1:2-4;
(2) feed steam and heat, heat temperature raising is incubated 15-25 minute when temperature is 100-120 ℃, carry out little steam bleeding, continues heat temperature raising to 165-173 ℃, is incubated 35-55 minute.
Anthraquinone-soda cooking of the present invention comprises the steps:
(1) add anthraquinone-soda cooking soup in the grass kind plant raw material, wherein the anthraquinone addition is the 0.5-0.8% of over dry material quantity; Liquor ratio is 1:2-4;
(2) feed steam and heat, heat temperature raising is incubated 15-25 minute when temperature is 100-120 ℃, carry out little steam bleeding, continues heat temperature raising to 165-173 ℃, is incubated 35-55 minute.
Kraft cooking of the present invention comprises the steps:
(1) add the kraft cooking soup in the grass kind plant raw material, liquor ratio is 1:2-4, and sulphidity is 5-15%;
(2) feed steam and heat, heat temperature raising is incubated 15-25 minute when temperature is 110-140 ℃, carry out little steam bleeding, continues heat temperature raising to 165-173 ℃, is incubated 35-55 minute.
Arbiso process boiling of the present invention comprises the steps:
(1) add the Arbiso process cooking liquor in the grass kind plant raw material, liquor ratio is 1:2-4;
(2) feed steam in the boiling vessel and heat, little steam bleeding is carried out in heat temperature raising insulation 15-25 minute when temperature is 100-120 ℃, continues heat temperature raising to 165-173 ℃, is incubated 35-55 minute.
After getting the raw materials ready, also comprise the process of the grass kind plant raw material being carried out pre-preg before the boiling in the method for the present invention.
When carrying out heat temperature raising described grass kind plant raw material is placed in the boiling vessel among the present invention, described boiling vessel comprises rotary spherical digester, vertical digester and continuous steamer.
Of the present invention get the raw materials ready into:
(1) grass prepared using hammer mill is cut off rubbing and handle, obtain cutting off the raw material after the rubbing;
(2) raw material that will cut off after the fragmentation carries out dust removal process;
(3) will carry out Screening Treatment through the raw material of dust removal process.
Specifically, of the present invention a kind of be the high-hardness pulp that is used for preparing bleach chemical pulp of feedstock production with the grass kind plant, described high-hardness pulp hardness is equivalent to card uncle valency 24-50 for permanganate number 16-28; Described high-hardness pulp preferred hardness is equivalent to card uncle valency 29-48 for permanganate number 18-27; Described high-hardness pulp most preferably hardness is equivalent to card uncle valency 34-42 for permanganate number 20-25.
Grass kind plant raw material of the present invention is a kind of in wheat straw, straw, bagasse, cotton stalk, the reed or more than one combination.
Boiling method described in the present invention is a kind of in ammonium sulfite boiling, anthraquinone-soda processes, the sulfate process.
Ammonium sulfite boiling of the present invention comprises the steps:
(1) the grass kind plant raw material is got the raw materials ready after, deliver in the boiling vessel, the consumption of ammonium sulfite is the 15-25% of over dry material quantity, liquor ratio is 1:2-4;
(2) feed steam in the boiling vessel and heat, heat temperature raising to temperature is 100-120 ℃, and pressure is to be incubated 15-25 minute constantly about 0.4MPa, carry out little steam bleeding pressure and reduce to 0.02MPa, continue heat temperature raising to 165-173 ℃, pressure is about 0.75MPa, is incubated 35-55 minute.
Anthraquinone-soda cooking of the present invention comprises the steps:
(1) the grass kind plant raw material is got the raw materials ready after, deliver in the boiling vessel, alkali charge is in the 15-25% of NaOH to the over dry material quantity, the anthraquinone addition is the 0.5-0.8% of over dry material quantity, liquor ratio is 1:2-4;
(2) feed steam in the boiling vessel and heat, heat temperature raising to temperature is 100-120 ℃, pressure insulation 15-25 minute during for 0.4MPa, carry out little steam bleeding pressure and reduce to 0.02MPa, continue heat temperature raising to 165-173 ℃, pressure is 0.75MPa, is incubated 35-55 minute.
Kraft cooking of the present invention comprises the steps:
(1) the grass kind plant raw material is got the raw materials ready after, deliver in the boiling vessel, alkali charge is in the 13-25% of NaOH to the over dry material quantity, liquor ratio is 1:2-4, sulphidity is 5-15%;
(2) feed steam in the boiling vessel and heat, heat temperature raising to temperature is 110-140 ℃, pressure insulation 15-25 minute during for 0.5MPa, carry out little steam bleeding pressure and reduce to 0.02MPa, continue heat temperature raising to 165-173 ℃, pressure is 0.75MPa, is incubated 35-55 minute.
Also comprise the process of flooding before in above-mentioned step (1), after the grass kind plant raw material is got the raw materials ready, delivering to boiling vessel through the dipping spiral organ.
Chemical pulping is exactly the effect that utilizes chemical agent, suitably removes the lignin in the raw material, keeps cellulose and hemicellulose as far as possible and is beneficial to copy paper.In fact in digestion process because the effect of high temperature highly basic, certain chemical change all can take place in the lignin in the raw material, cellulose, hemicellulose and other composition, be subjected in various degree degraded and damage, therefore must study the Changing Pattern of raw material in digestion process, formulate suitable conditions of cooking.In the pulping process of the present invention, the time by control boiling and insulation, reduce the time that raw material is in high temperature as far as possible, thereby reduce cellulose and hemicellulose infringement, reach and both reduce production cost, energy savings can improve the purpose of the yield of slurrying again.The yield of the resulting high-hardness pulp of described boiling method is 58-68%.
Bleach chemical pulp described in the present invention is meant that whiteness is 68-82%ISO, and the delignification rate is the chemical pulp of 84-98%.
Before boiling, raw material is adopted conventional dried, wet feed preparation, to remove impurity such as defoliation, fringe, grain, marrow, can alleviate the pressure of subsequent technique like this, and improve the quality of straw pulp.Dried, wet feed preparation can adopt existing conventional equipment, as chaffcutter, screening machine, dust removal machine, wet scrubbing Straw-crumbling machine, inclined screw Water Extraction Machinery etc.Fibers in grass class raw material through the removal moisture after getting the raw materials ready also can be fine fodder, and the moisture of deduction dogstail is the over dry grass, and the length of general blade is at 15-30mm, and the technology of getting the raw materials ready of raw material is technology as well known to those skilled in the art.
In the melting process in the present invention, also can utilize hammer mill to carry out dry raw material preparation.
After getting the raw materials ready, can be earlier with maceration extract dipping fibers in grass class raw material, make liquor ratio reach 1:2-4, in insulation and mixing more than 10 minutes in the spiral macerator more than 85 ℃, wherein insulation mixes 10-40 minute for well between 85-95 ℃ under normal pressure.Maceration extract is fully contacted with raw material, make the dipping of raw material evenly complete.Described maceration extract can be certain density aqueous slkali, in 4% the solution of NaOH to the over dry material quantity, also can be the mixed liquor of above-mentioned alkali lye and black liquor as alkali charge, and the concentration of used black liquor is 11-14 ° of Be ' (20 ℃).
Raw material has been carried out the dipping preliminary treatment, utilized black liquor as waste material, make black liquor obtain cycling and reutilization, reduced the pressure that environment is handled black liquor, because to the preliminary treatment of raw material dipping, make that heteroproteose cell, hemicellulose, the lignin deviate from are that main black liquid separation is discharged when heat treated, for next step digestion process is prepared.
High-hardness pulp among the present invention is as the raw material of preparation bleach chemical pulp, and the boiling method of high-hardness pulp can be ammonium sulfite, sulfate process, anthraquinone-soda processes.In the process of the boiling of prior art, this several method exists the time of boiling and insulation long when preparing paper pulp, stewing temperature height, the problem that temperature retention time is long.And in the method for the invention, the consumption of cooking liquor is few, and the time of boiling and insulation shortens greatly.
Because the use of thermophilic digestion and chemical steaming soup, certain chemical change all can take place in the lignin in the raw material, cellulose and hemicellulose and other composition, is subjected in various degree degraded and damage.At this special pulping raw material of grass kind plant fiber, in the method for the present invention, time to boiling and insulation has been carried out strict control, has shortened the time of boiling and insulation, thereby has reduced the degraded of cellulose and hemicellulose in the grass kind plant raw material.Therefore, protect the required composition of slurrying in the grass kind plant raw material in the method for the present invention to greatest extent, shortened temperature retention time greatly simultaneously, significantly reduced energy consumption, improved the yield of slurry.
High-hardness pulp of the present invention is a raw material with the grass kind plant, is prepared by the method except that organic solvent pulping, by shortening the time of boiling, prepares high-hardness pulp in the process of preparation.The shortening of digestion time all can cut down the consumption of energy greatly, and the yield of slurry improves a lot than the yield that in the prior art material cooking is become the soft slurry, and the slurrying time shortens greatly, thereby has improved production efficiency greatly.Simultaneously, high-hardness pulp of the present invention can be used as the raw material of preparation bleach chemical pulp, because the time of boiling and insulation shortens greatly, thereby reduced time that paper pulp is in the condition of high temperature, therefore reduced the loss of needed cellulose and hemicellulose in the paper pulp, the yield of paper pulp is improved.With high-hardness pulp of the present invention is raw material, the preparation bleach chemical pulp, and the whiteness of described bleach chemical pulp is 68-82%ISO, the delignification rate is 84-98%.With described high-hardness pulp is the prepared bleach chemical pulp of raw material, fracture length is 5000-8100m, folding number is 20-60 time, whiteness is 68-82%ISO, the quality of prepared with the grass kind plant the is bleach chemical pulp of feedstock production is comparable to existing leaf wood paper pulp, even has also surpassed existing leaf wood pulp quality.
It is the preparation method of the bleach chemical pulp of raw material with the grass kind plant that seven of purpose of the present invention is to provide a kind of.Described method cooperates the bleach chemical pulp delignification rate height of producing, intensity height by oxygen delignification with general method for bleaching.
To achieve these goals, the technical solution used in the present invention is:
A kind of is the method for feedstock production bleach chemical pulp with the grass kind plant, and described method may further comprise the steps:
(1) the grass raw material after will getting the raw materials ready carries out boiling and obtains the slurry that hardness is permanganate number 12-15;
(2) slurry after the boiling is carried out shove, processing is discongested in washing then;
(3) will carry out oxygen delignification and bleaching processing through discongesting the slurry of handling gained, obtain described bleach chemical pulp.
Grass kind plant of the present invention is one or more the combination in straw, wheat straw, cotton stalk, bagasse or the reed.
Of the present invention get the raw materials ready into:
(1) the grass raw material is cut off rubbing under the effect of frictional force, impulsive force and grinding pressure and handle, the raw material length that obtains cutting off after the rubbing is 20-80mm;
(2) raw material that will cut off after crumpling carries out dust removal process;
(3) will carry out Screening Treatment through the raw material of dust removal process.
Grass raw material of the present invention cuts off the process of rubbing processing to carry out in hammer mill; Described hammer mill is preferably the hammer mill that ore dressing in the prior art or bark are pulverized usefulness.
Boiling of the present invention is a kind of in ammonium sulfite boiling, anthraquinone-soda cooking or the kraft cooking;
Described ammonium sulfite boiling is:
(1) add steaming preparation in the grass kind plant raw material, wherein the consumption of ammonium sulfite is to over dry material quantity 14-20%, and liquor ratio is 1:2-4;
(2) feed steam and heat, heat temperature raising is incubated 60-120 minute when temperature is 120-140 ℃, carry out little steam bleeding, continues heat temperature raising to 160-170 ℃, is incubated 90-150 minute;
Described anthraquinone-soda cooking is:
(1) in the grass kind plant raw material, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 13-16%, liquor ratio is 1:2-4, the anthraquinone addition is the 0.5-0.8% of over dry material quantity;
(2) feed steam and heat, heat temperature raising is incubated 60-120 minute when temperature is 120-140 ℃, carry out little steam bleeding, continues heat temperature raising to 160-170 ℃, is incubated 90-150 minute;
Described kraft cooking is:
(1) in the grass kind plant raw material, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 12-15%, liquor ratio is 1:2-4, sulphidity is 5-8%;
(2) feed steam and heat, heat temperature raising is incubated 60-120 minute when temperature is 120-140 ℃, carry out little steam bleeding, continues heat temperature raising to 160-170 ℃, is incubated 90-150 minute.
Shove of the present invention enters for described high-hardness pulp being regulated concentration inlet from press master to the 8-15%, carries out shove under the effect of extruding force, and after the extruding black liquor, concentration is that the slurry of 20-35% is discharged from the outlet of press master; Described press master is to extract reducing single-screw press master or the Var-nip press that black liquor is used in the prior art.
Pulp washing of the present invention is to utilize the clear water of normal temperature or concentration to wash in three sections vacuum pulp washing machines for cleaning solution for the black liquor of 3-6.2 ° of Be ' and pH8-8.3.
Of the present invention discongesting to utilizing fluffer to discongest in the slurry behind the pulp washing makes fibre structure become loose; Described fluffer is a kind of in mill fluffer in deflaker, kneading machine, dry pan, the beating equipment or the defibrator.
Oxygen delignification of the present invention is: carry out in the oxygen delignification reaction tower; Described slurry through discongesting processing is 95-100 ℃ in the temperature of this reaction tower import department, and pressure is 0.9-1.2MPa, and the temperature in exit is 100-105 ℃, and pressure is 0.2-0.6MPa; Alkali charge in NaOH to 2-4% of oven dry stock amount, the addition of oxygen is slurry 20-40kg per ton; The reaction time of described slurry in this reaction tower is 60-90 minutes.
Bleaching of the present invention is handled and is comprised chlorination, alkali treatment; Described chlorination is: at chlorine dosage is the 2.5-3% of oven dry stock, and the concentration of slurry is 3-3.5%, and temperature is to handle 45-60 minute under 50-55 ℃ the condition; Described alkali treatment is: alkali charge in NaOH to oven dry stock amount 2-4%, the concentration of slurry is 10-12%, temperature is to handle 100-150 minute under 50-55 ℃ the condition.
Bleach chemical pulp described in the present invention is meant that whiteness is 68-82%ISO, and the delignification rate is the chemical pulp of 84-98%.
In the method for the invention, at first can adopt prior art that raw material is got the raw materials ready, promptly adopt conventional dried, wet feed preparation,, can alleviate the pressure of subsequent technique like this, and improve the quality of straw pulp to remove impurity such as defoliation, fringe, grain, marrow.Dried, wet feed preparation can adopt existing conventional equipment, as chaffcutter, screening machine, dust removal machine, wet scrubbing Straw-crumbling machine, inclined screw Water Extraction Machinery etc.Fibers in grass class raw material through the removal moisture after getting the raw materials ready also can be fine fodder, and the moisture of deduction dogstail is the over dry grass, and the length of general blade is at 20-80mm, and the technology of getting the raw materials ready of raw material is technology as well known to those skilled in the art.
In the melting process in the present invention, also can utilize hammer mill to carry out dry raw material preparation.
Can before boiling, carry out impregnation process in the method for the present invention to raw material, maceration extract is flooded wheat straw raw material, make liquor ratio reach 1:2-4, in insulation and mixing more than 10 minutes in the spiral macerator more than 85 ℃, wherein insulation mixes 10-40 minute for well between 85-95 ℃ under normal pressure.Maceration extract is fully contacted with wheat straw raw material, make the dipping of wheat straw raw material evenly complete.Described maceration extract can be certain density aqueous slkali, for being 4% in NaOH to the over dry material quantity, also can be the mixed liquor of above-mentioned aqueous slkali and black liquor as alkali charge, and the concentration of used black liquor is 11-14 ° of Be ' (20 ℃).Raw material has been carried out impregnation process, utilized black liquor as waste material, make black liquor obtain cycling and reutilization, reduced the pressure that environment is handled black liquor, because to the preliminary treatment of raw material dipping, make that heteroproteose cell, hemicellulose, the lignin deviate from are that main black liquid separation is discharged when heat treated, for next step digestion process is prepared.The described process that raw material is carried out impregnation process belongs to preprocessing process, its main purpose be for after in the digestion process infiltration of cooking liquor get ready, so this step can be omitted.
Ensuing digestion process is the pass step of slurrying, because institutional framework, microstructure, chemical composition and the lignin molecular structure etc. of timber and grass as raw material are all variant, therefore, the delignification reaction course also has very big difference in digestion process.For grass as raw material alkaline cooking delignification reaction course, comprise intensification and be incubated two sections.The common feature of grass as raw material is that delignification is more or less freely, and compares with wood raw material, and the temperature of a large amount of strippings of lignin is more in advance.When the grass as raw material sulphate cook, just find the secondary wall lignin, meet intercellular layer and cell angle block element all removes at the very start simultaneously in boiling.Grass as raw material generally contains more hemicellulose and less lignin, and hemicellulose mainly is present in the cell membrane, and this just helps the process of boiling delignification.Can adopt ammonium sulfite boiling, Arbiso process, anthraquinone-soda processes, sulfate process etc. to carry out boiling in the method for the present invention.
After boiling finishes, spurt to spraying pot after the pressure dilution that the high-hardness pulp maintenance of gained is certain, described pressure is 0.75MPa.Dilution can be clear water, also can be the used black liquor of aforementioned impregnation process.The concentration of the high-hardness pulp in the spraying pot is 8-15% at this moment, hardness is permanganate number 12-15, be connected by delivery pump between spraying pot and the acroll press washer, delivery pump is transported to the inlet of acroll press washer with the slurry in the spraying pot, and high-hardness pulp enters from the inlet of acroll press washer, through after the shove, above-mentioned high-hardness pulp is sent from the outlet of press master, the concentration of the slurry of sending is brought up to 20-38% by 8-15%, has become the high-hardness pulp of high concentration, and temperature is 70-80 ℃.In shove, most of black liquor is extruded the back and stores in the black liquor groove.Selected press master is to extract the acroll press washer that black liquor is used in the prior art, is preferably reducing single-screw press master or Var-nip press.
Described acroll press washer can be one, also can be two, and promptly described shove can be for carrying out shove through one acroll press washer, also can for through after the first road acroll press washer shove again through the second road acroll press washer shove.
When using press master to carry out shove, because the process at shove can produce very big extruding force, temperature rises rapidly, impel fiber separation, divide silk, brooming, conquassation, primary wall is to destroying, the enough energy of fiber absorbs make fibrous inside produce very big stress, and the reactivity worth of high-hardness pulp is greatly improved.Simultaneously, fiber produces fibrillating, and impurity is dissolved in the black digestion liquid between epidermis organic matter and fiber, discharges by liquid outlet groove, and fiber fineness is greatly improved.Some ash contents in the black liquor and impurity are also along with black liquor is discharged from, for sufficient preparation has been carried out in next step pulp washing and bleaching.
Selecting reducing single-screw press master or Var-nip press among the present invention, is little to the fibre damage in the slurry because handle slurry with these two kinds of press masters, has and utilizes the intensity that keeps slurry.
The slurry that will come out from shove through jumping the sieve screening, washs earlier then, can adopt vacuum pulp washing machine or pressure washer to wash.Go out the concentration of starching behind the wash engine between 9-11%, this slurry is delivered to fluffer through conveying worm handle, the slurry weight in wet base after the processing is 1.5-1.7g, temperature 65-70 ℃.Described fluffer is the existing equipment of discongesting, as deflaker, and the mill fluffer.By discongesting, fiber can be rubbed with the hands and open, the lignin between fiber and the fiber is exposed out, helps the carrying out of the bleaching process of back.
Oxygen delignification of the present invention is: carry out in the oxygen delignification reaction tower; Described slurry through discongesting processing is 95-100 ℃ in the temperature of this reaction tower import department, and pressure is 0.9-1.2MPa, and the temperature in exit is 100-105 ℃, and pressure is 0.2-0.6MPa; Alkali charge in NaOH to 2-4% of oven dry stock amount, the addition of oxygen is slurry 20-40kg per ton; The reaction time of described slurry in this reaction tower is 60-90 minutes.
Bleaching of the present invention is handled and is comprised chlorination, alkali treatment; Described chlorination is: at chlorine dosage is the 2.5-3% of oven dry stock, and the concentration of slurry is 3-3.5%, and temperature is to handle 45-60 minute under 50-55 ℃ the condition; Described alkali treatment is: alkali charge in NaOH to oven dry stock amount 2-4%, the concentration of slurry is 10-12%, temperature is to handle 100-150 minute under 50-55 ℃ the condition.
With the grass kind plant is the bleach chemical pulp of feedstock production, and fracture length is 4500-6500m, and folding number is 20-50, and whiteness is 68-82%ISO, and the delignification rate is 84-98%.Described bleach chemical pulp can be used as the slurry that the high-quality cultural paper is produced in preparation.And raw material used among the present invention is a grass kind plant, comprises straw, wheat straw, cotton stalk, bagasse, reed etc., and these raw materials are very abundant, and price is low.Bleach chemical pulp described in the present invention can be copied into general cultural paper, because the function admirable of itself, therefore when the higher-quality paper of preparation, compared with prior art, can use with wood pulp collocation still less,, alleviate the contradiction between high-quality paper demand and the timber resources shortage greatly therefore in today that the forest reserves lack day by day, simultaneously also reduced the production cost of enterprise, for enterprise brings good economic benefit.Among the preparation method of the present invention,, do not need to carry out hypochlorite bleaching and can make slurry reach required whiteness, a series of environmental problems that hypochlorite bleaching brings by combining of boiling and shove, pulp washing, oxygen delignification and chlorination and alkali treatment.
It is the preparation method of the bleach chemical pulp of raw material with the grass kind plant that eight of purpose of the present invention is to provide a kind of.
To achieve these goals, the technical solution used in the present invention is:
A kind of is the method for feedstock production bleach chemical pulp with the grass kind plant, and described method may further comprise the steps:
(1) the grass kind plant raw material is carried out boiling and obtain the high-hardness pulp that hardness is permanganate number 16-28;
(2) described high-hardness pulp is carried out shove, processing is discongested in washing then;
(3) will carry out two sections oxygen delignification and bleaching processing through the slurry of discongesting processing, obtain described bleach chemical pulp.
Grass kind plant raw material of the present invention is one or more the combination in straw, wheat straw, cotton stalk, bagasse or the reed.
Two sections oxygen delignification of the present invention are:
(1) will send into the oxygen delignification reaction tower through the slurry of discongesting processing, is 85-95 ℃ in inlet temperature earlier, and pressure is 0.8-1.0MPa, and outlet temperature is 98-100 ℃, and pressure is to carry out one section oxygen delignification 40-60 minute under the condition of 0.5-0.7MPa;
(2) will be 98-100 ℃ in inlet temperature through the slurry after one section oxygen delignification, pressure be 0.5-0.7MPa, and outlet temperature is 103-108 ℃, and pressure is to carry out two sections oxygen delignification 20-40 minutes under the condition of 0.2-0.4MPa.
When carrying out oxygen delignification, add aqueous slkali in the slurry after discongesting among the present invention, wherein alkali charge is that the addition of oxygen is slurry 20-40kg per ton in the 2-4% of NaOH to the oven dry stock amount.
Boiling of the present invention is a kind of in ammonium sulfite boiling, anthraquinone-soda cooking or the kraft cooking;
Described ammonium sulfite boiling is:
(1) add steaming preparation in the grass kind plant raw material, wherein the consumption of ammonium sulfite is to over dry material quantity 9-13%, and liquor ratio is 1:2-4;
(2) feed steam and heat, heat temperature raising is incubated 20-40 minute when temperature is 100-120 ℃, carry out little steam bleeding, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minute.
Described anthraquinone-soda cooking is:
(1) in the grass kind plant raw material, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 9-12%, liquor ratio is 1:2-4, the anthraquinone addition is the 0.5-0.8% of over dry material quantity;
(2) feed steam and heat, heat temperature raising is incubated 20-40 minute when temperature is 100-120 ℃, carry out little steam bleeding, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minute.
Described kraft cooking is:
(1) in the grass kind plant raw material, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 8-11%, liquor ratio is 1:2-4, sulphidity is 5-8%;
(2) feed steam and heat, heat temperature raising is incubated 20-40 minute when temperature is 110-140 ℃, carry out little steam bleeding, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minute.
Shove described in the present invention is: described high-hardness pulp is regulated concentration inlet from press master to the 8-15% enter, carry out shove under the effect of extruding force, after the extruding black liquor, concentration is that the slurry of 20-35% is discharged from the outlet of press master.
Press master of the present invention is to extract reducing single-screw press master or the Var-nip press that black liquor is used in the prior art.
Pulp washing of the present invention is to utilize the clear water of normal temperature or concentration to wash in three sections vacuum pulp washing machines for cleaning solution for the black liquor of 3-6.2 ° of Be ' and pH8-8.3.
Of the present invention discongesting to utilizing fluffer to discongest in the slurry behind the pulp washing makes fibre structure become loose.
Fluffer of the present invention is a kind of in mill fluffer in deflaker, kneading machine, dry pan, the beating equipment or the defibrator.
Bleaching of the present invention is handled and is comprised chlorination, alkali treatment, post-bleach.
Chlorination of the present invention is: at chlorine dosage is the 2.5-3% of oven dry stock, and the concentration of slurry is 3-3.5%, and temperature is to handle 45-60 minute under 50-55 ℃ the condition; Described alkali treatment is: alkali charge in NaOH to oven dry stock amount 2-4%, the concentration of slurry is 10-12%, temperature is to handle 100-150 minute under 50-55 ℃ the condition; Described post-bleach is: the addition at clorox is the 2-4% of oven dry stock amount, and temperature is to handle 100-150 minute under 30-35 ℃ the condition.Bleach chemical pulp described in the present invention is meant that whiteness is 68-82%ISO, and the delignification rate is the chemical pulp of 84-98%.
With the grass kind plant is feedstock production, and its fracture length reaches more than 5200 meters, and folding strength reaches more than 30 times, and beating degree is 25-36 ° of SR, is a kind of high-quality chemical pulp, can be used as the slurry that the high-quality cultural paper is produced in preparation.And raw material used among the present invention is a grass kind plant, comprises straw, wheat straw, cotton stalk, bagasse, reed etc., and these raw materials are very abundant, and price is low.Bleach chemical pulp described in the present invention can be copied into general cultural paper, because the function admirable of itself, therefore when the higher-quality paper of preparation, compared with prior art, can use with wood pulp collocation still less,, alleviate the contradiction between high-quality paper demand and the timber resources shortage greatly therefore in today that the forest reserves lack day by day, simultaneously also reduced the production cost of enterprise, for enterprise brings good economic benefit.
In the method for the invention, at first can adopt prior art that raw material is got the raw materials ready, promptly adopt conventional do, wet feed preparation, with remove defoliation, fringe, grain, etc. impurity, can alleviate the pressure of subsequent technique like this, and improve the quality of straw pulp.Dried, wet feed preparation can adopt existing conventional equipment, as chaffcutter, screening machine, dust removal machine, wet scrubbing Straw-crumbling machine, inclined screw Water Extraction Machinery etc.Fibers in grass class raw material through the removal moisture after getting the raw materials ready also can be fine fodder, and the moisture of deduction dogstail is the over dry grass, and the length of general blade is at 15-30mm, and the technology of getting the raw materials ready of raw material is technology as well known to those skilled in the art.
Then raw material is carried out impregnation process, maceration extract is flooded the fibers in grass class raw material, make liquor ratio reach 1:2-4, in insulation and mixing more than 10 minutes in the spiral macerator more than 85 ℃, wherein insulation mixes 10-40 minute for well between 85-95 ℃ under normal pressure.Maceration extract is fully contacted with raw material, make the dipping of raw material evenly complete.Described maceration extract can be certain density aqueous slkali, as being 4% sodium hydroxide solution, also can be the mixed liquor of alkali and black liquor to the over dry material quantity, and the concentration of used black liquor is 11-14 ° of Be ' (20 ℃).Raw material has been carried out impregnation process, utilized black liquor as waste material, make black liquor obtain cycling and reutilization, reduced the pressure that environment is handled black liquor, because to the preliminary treatment of raw material dipping, make that heteroproteose cell, hemicellulose, the lignin deviate from are that main black liquid separation is discharged when heat treated, for next step digestion process is prepared.
Ensuing digestion process is the committed step of slurrying, because institutional framework, microstructure, chemical composition and the lignin molecular structure etc. of timber and grass as raw material are all variant, therefore, the delignification reaction course also has very big difference in digestion process.For grass as raw material alkaline cooking delignification reaction course, comprise intensification and be incubated two sections.The common feature of grass as raw material is that delignification is more or less freely, and compares with wood raw material, and the temperature of a large amount of strippings of lignin is more in advance.When the grass as raw material sulphate cook, just find the secondary wall lignin, meet born of the same parents subtract the layer and cell angle block element all remove simultaneously at the very start in boiling.Grass as raw material generally contains more hemicellulose and less lignin, and hemicellulose mainly is present in cell and stands like a wall, and this just helps the process of boiling delignification.In the method for the present invention, boiling chemical liquid consumption is few, and the time of boiling and insulation is short, in a large amount of lignins of removing in the grass raw material, has reduced the degraded and the damage of cellulose and hemicellulose as much as possible.Can adopt ammonium sulfite boiling, Arbiso process, anthraquinone-soda processes, sulfate process etc. to carry out boiling in the method for the present invention.
Through the high-hardness pulp of gained after the boiling, hardness is equivalent to card uncle valency 24-50 for permanganate number 16-28 in the method for the present invention; Described high-hardness pulp preferred hardness is equivalent to card uncle valency 29-48 for permanganate number 18-27; Described high-hardness pulp most preferably hardness is equivalent to card uncle valency 34-42 for permanganate number 20-25.
High-hardness pulp among the present invention is as the raw material of preparation bleach chemical pulp, and the boiling method of high-hardness pulp can be ammonium sulfite, sulfate process, anthraquinone-soda processes.In the process of the boiling of prior art, this several method exists the time of boiling and insulation long when preparing paper pulp, stewing temperature height, the problem that temperature retention time is long.And in the method for the invention, the consumption of cooking liquor is few, and the time of boiling and insulation shortens greatly.In the boiling method of the present invention, by consumption and concentration to cooking liquor, the length of boiling and temperature retention time, the height of boiling temperature carries out systematic research, under the condition that reduces the infringement of cellulose and hemicellulose as much as possible, carry out boiling, both reduce production cost thereby reach, energy savings can improve the purpose of the yield of slurrying again.The yield of the resulting high-hardness pulp of described boiling method is 58-68%.
After boiling finishes, spurt to spraying pot after the pressure dilution that the high-hardness pulp maintenance of gained is certain, described pressure is 0.75MPa.Dilution can be clear water, also can be the used black liquor of aforementioned impregnation process.The concentration of the high-hardness pulp in the spraying pot is 8-15% at this moment, hardness is equivalent to card uncle valency 26-50 for permanganate number 16-28, beating degree is 22-28 ° of SR, be connected by delivery pump between spraying pot and the acroll press washer, delivery pump is transported to the high-hardness pulp in the spraying pot inlet of acroll press washer, high-hardness pulp enters from the inlet of acroll press washer, through after the shove, above-mentioned high-hardness pulp is sent from the outlet of press master, the concentration of the slurry of sending is brought up to 20-30% by 8-15%, become the high-hardness pulp of high concentration, temperature is 70-80 ℃.In shove, most of black liquor is extruded the back and stores in the black liquor groove.Selected press master is to extract the press master that black liquor is used in the prior art, is preferably the single-screw press master or the Var-nip press of reducing.
When using press master to carry out shove, because the process at shove can produce very big extruding force, temperature rises rapidly, impel fiber separation, divide silk, brooming, conquassation, primary wall is destroyed, the enough energy of fiber absorbs make fibrous inside produce very big stress, and the reactivity worth of high-hardness pulp is greatly improved.Simultaneously, fiber produces fibrillating, and impurity is dissolved in the black digestion liquid between epidermis organic matter and fiber, discharges by liquid outlet groove, and fiber fineness is greatly improved.Some ash contents in the black liquor and impurity are also along with black liquor is discharged from, for sufficient preparation has been carried out in next step pulp washing and bleaching.The press master that the present invention is selected, after high-hardness pulp was carried out shove, the beating degree of described high-hardness pulp changed little, and beating degree is 22-28 ° of SR before the shove, and beating degree is 23-29 ° of SR after the shove.That is to say that described high-hardness pulp can the fibre length that fibers in grass class is intrinsic keep relatively goodly through after the press master shove, reduces the damage of fiber preferably.
The slurry that will come out from shove through jumping the sieve screening, washs earlier then, can adopt vacuum pulp washing machine or pressure washer to wash.Go out the concentration of starching behind the wash engine between 9-11%, this slurry is delivered to fluffer through conveying worm handle, the button degree of separating of handling the back slurry is at 26-28 ° of SR, weight in wet base 1.5-1.7g, temperature 65-70 ℃.Described fluffer is the existing equipment of discongesting, as deflaker, and the mill fluffer.By discongesting, fiber can be rubbed with the hands and open, the lignin between fiber and the fiber is exposed out, helps the carrying out of the bleaching process of back.
To carry out two sections oxygen delignifications through discongesting the gained slurry, described two sections oxygen delignification are:
(1) will send into the oxygen delignification reaction tower through the slurry of discongesting processing, is 85-95 ℃ in inlet temperature earlier, and pressure is 0.8-1.0MPa, and outlet temperature is 98-100 ℃, and pressure is to carry out one section oxygen delignification 40-60 minute under the condition of 0.5-0.7MPa;
(2) will be 98-100 ℃ in inlet temperature through the slurry after one section oxygen delignification, pressure be 0.5-0.7MPa, and outlet temperature is 103-108 ℃, and pressure is to carry out two sections oxygen delignification 20-40 minutes under the condition of 0.2-0.4MPa.The hardness k value (permanganate number) of starching this moment is reduced to 11-13 and is equivalent to card uncle valency 12.5-17, and beating degree is 30--36 ° of SR.
Adopt two sections above-mentioned oxygen delignify treating methods, slurry after discongesting is mixed with alkali and oxygen under lower temperature earlier fully, the lignin that exposes in the fiber outside is removed, and then under higher temperature, carry out oxygen delignification, do like this and can under gentle more condition, remove lignin, reduce cellulosic degraded, increase the intensity of slurry.
After carrying out two sections oxygen delignifications, can adopt the method for bleaching of prior art to bleach, as C-E-H tri-stage bleaching, wherein chlorination: chlorine dosage is the 2.5-3% of oven dry stock, and the concentration of slurry is 3-3.5%, the temperature of bleaching is 50-55 ℃, and the time of bleaching is 45-60 minute; The condition of alkali treatment is: alkali charge in NaOH to oven dry stock amount 2-4%, the concentration of slurry is 10-12%, bleaching temperature is 50-55 ℃, the time is 100-150 minute; Hypochlorite bleaching: the addition of clorox is the 2-4% of oven dry stock amount, and the temperature of bleaching is 30-35 ℃, and the time of bleaching is 100-150 minute.Also can directly bleach by above-mentioned C-E-H mode discongesting the gained slurry, bleaching obtains bleach chemical pulp after finishing.
With the grass kind plant is the bleach chemical pulp of feedstock production, and beating degree is 25-36 ° of SR, and fracture length is 5200-8000m, and folding number is 30-70, and whiteness is 68-82%ISO, and the delignification rate is 84-98%.Described bleach chemical pulp can be used as the slurry that the high-quality cultural paper is produced in preparation.And raw material used among the present invention is a grass kind plant, comprises straw, wheat straw, cotton stalk, bagasse, reed etc., and these raw materials are very abundant, and price is low.Bleach chemical pulp described in the present invention can be copied into general cultural paper, because the function admirable of itself, therefore when the higher-quality paper of preparation, compared with prior art, can use with wood pulp collocation still less,, alleviate the contradiction between high-quality paper demand and the timber resources shortage greatly therefore in today that the forest reserves lack day by day, simultaneously also reduced the production cost of enterprise, for enterprise brings good economic benefit.Among the preparation method of the present invention,, shorten the time of boiling, prepare the high-hardness pulp of high rigidity by reducing the consumption of cooking liquor.The minimizing of chemical liquid consumption and the shortening of digestion time all can reduce enterprise's production cost greatly, and yield is greatly improved, thereby have improved production efficiency greatly.Simultaneously, high-hardness pulp of the present invention can be used as the raw material of preparation bleach chemical pulp, because the concentration of used soup reduces during boiling, and the time of boiling and insulation also shortens greatly, thereby on to greatest extent, having reduced the loss of needed cellulose and hemicellulose in the paper pulp, the yield of paper pulp is improved.
A kind of grass type stalk method of comprehensive utilization of providing is provided nine of purpose of the present invention,
To achieve these goals, the technical scheme of employing comprises:
(1) boiling obtains high-hardness pulp
Grass type stalk is carried out slurrying by boiling method, obtain concentration and be 8-15% slurry, hardness is permanganate number 16-28; Preferred hardness is a permanganate number 18-27; Most preferably hardness is permanganate number 20-25;
(2) the high-hardness pulp post processing obtains rare black liquor
High-hardness pulp is carried out post processing, and to obtain solid content be 4-15%, and Baume degrees is rare black liquor of 2-9; Washing process and methods such as described post processing comprises by dilution, concentrates, press filtration or displacement will be stored between fiber and the fiber, and waste liquid and fiber separation in cell membrane, the lumen are opened;
(3) add auxiliary material in the black liquor
In rare black liquor or with rare black liquor vaporizing, concentrate to remove and add auxiliary material in the concentrated black liquid that portion of water obtains and form solid-state fertilizer or liquid fertile.
Wherein, described grass comprises a kind of in wheat straw, cotton, straw, giantreed or the reed or more than one mixing; Described boiling method comprises Ammonium Sulfite Method and alkaline process, and described alkaline process is anthraquinone-soda processes, sulfate process or alkaline sodium sulfite method.
Described Ammonium Sulfite Method comprises the steps:
(1) add steaming preparation in grass type stalk, wherein the consumption of ammonium sulfite is an over dry material quantity 9-13%, and liquor ratio is 1:2-4;
(2) feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20-40 minutes when temperature is 100-120 ℃, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minutes;
Described anthraquinone--soda processes comprises the steps:
(1) in grass type stalk, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 9-12%, liquor ratio is 1:2-4, the anthraquinone addition is 0.5-0.8% of an over dry material quantity;
(2) feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20-40 minutes when temperature is 100-120 ℃, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minutes;
Described sulfate process comprises the steps:
(1) in grass type stalk, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 8-11%, liquor ratio is 1:2-4, sulphidity is 5-15%;
(2) feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20-40 minutes when temperature is 110-140 ℃, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minutes;
Described alkaline sodium sulfite method comprises:
(1) add steaming preparation in wheat straw raw material, wherein, sodium hydroxide concentration counts 11-15% with the over dry raw material weight, and sodium sulfite is 2-6%, and anthraquinone is 0.02-0.08%, and cooking liquor is than being 1:3-4;
(2) feed steam and heat, heat temperature raising is incubated 20-40 minutes when temperature is 100-120 ℃, carry out little steam bleeding, continues heat temperature raising to 160-165 ℃, is incubated 60-90 minute.
Described Ammonium Sulfite Method, anthraquinone--step (1) of soda processes, sulfate process and alkaline sodium sulfite method can also comprise the process that grass type stalk is flooded before, comprise maceration extract is flooded grass type stalk, make liquor ratio reach 1:2-4, under normal pressure in more than 85 ℃ in the spiral macerator insulation and mix more than 10 minutes, preferably insulation mixed 10-40 minutes between 85-95 ℃, maceration extract is fully contacted with raw material, make the dipping of raw material evenly complete.
Add rare black liquor in the auxiliary material in described step (three) black liquor and be rare black liquor that a kind of pulping process post processing obtains or two or more pulping process respectively rare black liquor of obtaining of post processing mix the rare black liquor of mixing that the back forms; The rare black liquor of Ammonium Sulfite Method that obtains behind the preferred pulping with ammonium sulfite method or mix rare black liquor with obtaining Ammonium Sulfite Method and alkaline process that rare black liquor of Ammonium Sulfite Method and the rare black liquor of alkaline process mix formation then after Ammonium Sulfite Method and the soda pulping process respectively.
Described Ammonium Sulfite Method and alkaline process mix that the mixed proportion of the rare black liquor of Ammonium Sulfite Method and the rare black liquor of alkaline process is 1:100-100:1 in rare black liquor, preferred 1:10-10:1, more preferably 1:4-4:1, the rare black liquid wave hairdressing 2-9 of described Ammonium Sulfite Method, solid content is 4-15%, and pH is 7-10; The rare black liquid wave hairdressing 2-9 of described alkaline process, solid content are 4-15%, and pH is 9-13.
The solid content of described concentrated black liquid is 15.1-65%, and Baume degrees is 9-40; Preferred solid content is 30-65%, and Baume degrees is 18-40, and more preferably solid content is 40-47%, and Baume degrees is 25-29, and the pH of described concentrated black liquid is preferably 5-11; More preferably pH is 6-8.
Described auxiliary material is organic auxiliary material; In rare black liquor or with rare black liquor vaporizing, concentrate to remove and add organic auxiliary material in the concentrated black liquid that portion of water obtains and form slip, dry then, promptly obtain a kind of Yellow humic acid fertilizer, described organic auxiliary material is lignin and humic acid; The percentage by weight of each component is:
Rare black liquor or concentrated black liquid 30-80%
Lignin 1-45%
Humic acid 1-25%;
The percentage by weight of preferred each component is:
Rare black liquor or concentrated black liquid 50-60%
Lignin 15-35%
Humic acid 10-15%.
Also add mud and/or ardealite in described rare black liquor or the concentrated black liquid; Its percentage by weight is a mud: 0-45%; Ardealite: 0-30%; Preferred weight percent is a mud: 10-20%; Ardealite: 5-15%; The biochemical sludge that described mud produces for the papermaking wastewater processing procedure, the content of organic matter is more than or equal to 50%.
Also add inorganic auxiliary material in described rare black liquor or the concentrated black liquid, described inorganic auxiliary material is the inorganic salts that contain N, P or K, the perhaps mixture more than 2 kinds wherein, preferred KCl, inorganic auxiliary material addition is to make the total amount of N, P2O5 and K2O account for the mass percent 4-30% of described prescription dry weight, preferred 5%.
Described drying is spray drying or slurry-spraying pelletizing, and the slurry-spraying pelletizing head temperature is 550～600 ℃ when preferred slurry-spraying pelletizing, described slurry-spraying pelletizing, 47-55 ℃ of tail temperature, returning charge amount 〉=50%;
The fulvic acid weight percent content is 5-40% in the described Yellow humic acid fertilizer, and the content of organic matter is 20-85%, and described Yellow humic acid fertilizer also can comprise N, P and K total content 4-30%.
Described auxiliary material is the solubility macroelement fertilizer; Add the solubility macroelement fertilizer in rare black liquor or in the concentrated black liquid and obtain Yellow humic acid water flush fertilizer; Described solubility macroelement fertilizer is one or more of solubility nitrogenous fertilizer, soluble phosphoric manure and solubility potash fertilizer; Preferred solubility nitrogenous fertilizer and the solubility potash fertilizer of adding;
The percentage by weight of each component is:
Rare black liquor or concentrated black liquid 20-98%
Solubility macroelement fertilizer 2-80%;
The percentage by weight of preferred each component is:
Rare black liquor or concentrated black liquid 50-90%
Solubility macroelement fertilizer 10-50%.
The combination of one or more that described solubility nitrogenous fertilizer is urea, carbonic hydroammonium, ammonium sulfate, ammonium chloride, ammonium dihydrogen phosphate (ADP) or diammonium hydrogen phosphate, preferred urea, solubility nitrogenous fertilizer is 2-60% at the weight percent content of Yellow humic acid water flush fertilizer, is preferably 2-30%;
Described soluble phosphoric manure is one or more combination of ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, potassium dihydrogen phosphate or dipotassium hydrogen phosphate, the preferably phosphoric acid ammonium dihydrogen, soluble phosphoric manure is 2-60% at the weight percent content of Yellow humic acid water flush fertilizer, is preferably 2-30%;
Described soluble potassium salt is one or more combination of potassium sulfate, potassium chloride, potassium dihydrogen phosphate or dipotassium hydrogen phosphate, preferred potassium chloride, and soluble potassium salt is 2-50% at the weight percent content of Yellow humic acid water flush fertilizer, is preferably 2-30%.
Also add trace-element fertilizers such as solubility iron content, copper, boron, zinc or magnesium in described rare black liquor or in the concentrated black liquid.
The fulvic acid weight percent content is 5-40% in the described Yellow humic acid water flush fertilizer, can also comprise that weight percent content is 3-25% nitrogen and/or percentage by weight and counts 3-25% phosphorus and/or percentage by weight are counted 3-25% with K2O potassium with P2O5.
Described auxiliary material is a soluble trace elements fertilizer; Add soluble trace elements fertilizer in rare black liquor or in the concentrated black liquid and promptly get Yellow humic acid foliage fertilizer, the envelope-bulk to weight ratio of the two is 1000ml:0.2-45g.
Described soluble trace elements fertilizer is ferrous salt and zinc salt, and its addition is to add 0.1-15g and 0.1-20g respectively in every 1000ml alkaline process and the Ammonium Sulfite Method mixed straw black liquor, can be used as the field crop foliage fertilizer;
Or described soluble trace elements fertilizer is boron fertilizer and zinc salt, and its addition is to add 0.1-15g and 0.1-20g respectively in every 1000ml alkaline process and the Ammonium Sulfite Method mixed straw black liquor, can be used as the vegetable leaf leaven;
Or described soluble trace elements fertilizer is boron salt, zinc salt and ferrous salt, and its addition is to add 0.1-15g, 0.1-20g and 0.1-15g respectively in every 1000ml alkaline process and the Ammonium Sulfite Method mixed straw black liquor, can be used as the fruit tree leaves leaven;
Described ferrous salt is a ferrous sulfate; Described zinc salt is zinc sulfate and/or zinc chloride, preferably sulfuric acid zinc; Described boron fertilizer is boric acid and/or borax, preferred borax.
The pH of described Yellow humic acid foliage fertilizer is 6-10, and the fulvic acid weight content is 5-40%.
General idea of the present invention is as follows, since grass type stalk mainly consist of cellulose and lignin, therefore, from then on the present invention sets about, at first slurrying, remove the cellulose in the stalk, in pulping process, lignin dissolution is called the main component that contains thing in the black liquor admittedly behind shove in cooking liquor, because lignin is through fully refinement after the boiling, degraded is easy, and crop is easy to absorb, and becomes good organic fertilizer, simultaneously, in the pulping process at high temperature, condition of high voltage down can form a considerable number of fulvic acid, so the black liquor behind the shove can be made into the high-quality Yellow humic acid fertilizer, and in the stalk cellulose by slurrying step formation paper pulp, as byproduct, can be used for multiple use.By above-mentioned steps, reach the purpose of comprehensive utilization grass type stalk, and paper pulp and Yellow humic acid fertilizer are expensive, can obtain good economic benefit.
Below be detailed step of the present invention:
(1) boiling obtains high-hardness pulp
Grass type stalk is carried out slurrying by boiling method, obtain concentration and be 8-15% slurry; The hardness of slurry is permanganate number 16-28; Preferred hardness is a permanganate number 18-27; Most preferably hardness is permanganate number 20-25.
Grass type stalk can be any annual herb straw, consider that suitability for industrialized production needs a large amount of raw materials, include but not limited to the grass type stalk of common implant masses such as wheat straw, straw, cotton, giantreed or reed, can be one or more combination wherein; Boiling method comprises Ammonium Sulfite Method and alkaline process, and alkaline process comprises anthraquinone-soda processes, sulfate process or alkaline sodium sulfite method, and the whole bag of tricks detailed process is as follows:
Ammonium Sulfite Method comprises the steps:
(1) add steaming preparation in grass type stalk, wherein the consumption of ammonium sulfite is an over dry material quantity 9-13%, and liquor ratio is 1:2-4;
(2) feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20-40 minutes when temperature is 100-120 ℃, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minutes;
Anthraquinone-soda processes comprises the steps:
(1) in grass type stalk, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 9-12%, liquor ratio is 1:2-4, the anthraquinone addition is 0.5-0.8% of an over dry material quantity;
(2) feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20-40 minutes when temperature is 100-120 ℃, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minutes;
Sulfate process comprises the steps:
(1) in grass type stalk, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 8-11%, liquor ratio is 1:2-4, sulphidity is 5-15%;
(2) feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20-40 minutes when temperature is 110-140 ℃, continues heat temperature raising to 165-173 ℃, is incubated 60-90 minutes;
Described alkaline sodium sulfite method comprises:
(1) add steaming preparation in wheat straw raw material, wherein, sodium hydroxide concentration counts 11-15% with the over dry raw material weight, and sodium sulfite is 2-6%, and anthraquinone is 0.02-0.08%, and cooking liquor is than being 1:3-4;
(2) feed steam and heat, heat temperature raising is incubated 20-40 minutes when temperature is 100-120 ℃, carry out little steam bleeding, continues heat temperature raising to 160-165 ℃, is incubated 60-90 minute.
The step of above-mentioned four kinds of methods can also comprise the process that grass type stalk is flooded in (1), comprise maceration extract is flooded grass type stalk, make liquor ratio reach 1:2-4, under normal pressure in more than 85 ℃ in the spiral macerator insulation and mix more than 10 minutes, preferably insulation mixed 10-40 minutes between 85-95 ℃, maceration extract is fully contacted with raw material, make the dipping of raw material evenly complete.Described maceration extract can be certain density aqueous slkali, as being 4% sodium hydroxide solution, also can be the mixed liquor of alkali and black liquor to the over dry material quantity, and the Baume degrees of used black liquor is 11-14.Raw material has been carried out the dipping preliminary treatment, utilized black liquor as waste material, make black liquor obtain cycling and reutilization, reduced the pressure that environment is handled black liquor, because to the preliminary treatment of raw material dipping, make that heteroproteose cell, hemicellulose, the lignin deviate from are that main black liquid separation is discharged when heat treated, for next step digestion process is prepared.
Before raw material is flooded, can adopt prior art that raw material is carried out preliminary treatment, promptly adopt conventional do, wet feed preparation, with remove defoliation,, grain, etc. impurity, can alleviate the pressure of subsequent technique like this, and improve the quality of straw pulp.Dried, wet feed preparation can adopt existing conventional equipment, as chaffcutter, screening machine, dust removal machine, wet scrubbing Straw-crumbling machine, inclined screw Water Extraction Machinery etc.Fibers in grass class raw material through the removal moisture after getting the raw materials ready also can be fine fodder, and the moisture of deduction dogstail is the over dry grass, and the length of general blade is at 15-30mm, and the technology of getting the raw materials ready of raw material is technology as well known to those skilled in the art.
Because the use of thermophilic digestion and chemical steaming soup, certain chemical change all can take place in the lignin in the raw material, cellulose and hemicellulose and other composition, is subjected in various degree degraded and damage.At this special pulping raw material of grass kind plant fiber, in the method for the present invention, the chemical steaming soup has been carried out strict control, its concentration is reduced, reduce degraded and damage to the required composition of slurrying such as cellulose, hemicellulose.Simultaneously, in the process of thermophilic digestion, adopt the method reduce temperature retention time as far as possible in the method for the present invention, the time that makes grass kind plant be in high temperature shortens, thereby has reduced the degraded of cellulose and hemicellulose in the grass kind plant raw material.Therefore, protect the required composition of slurrying in the grass kind plant raw material in the method for the present invention to greatest extent, shortened temperature retention time greatly simultaneously, significantly reduced energy consumption.
In addition, the inventor also finds, adopt said method slurrying, not only can reduce cellulosic damage, and fulvic acid content is higher in the boiling raffinate, primary fulvic acid, be by plant residue under the condition that air and moisture content exist, experienced very long natural process, through partly decomposing and forming. and the fulvic acid in the boiling raffinate, by investigation and analysis, be because at high temperature, add the process of depressing cooking plant fiber, be equivalent to quicken original natural process, except main generation supplies the paper pulp fiber of paper grade (stock), also generated a considerable number of fulvic acid.The black liquor that boiling slurry shove is gone out the formation of boiling raffinate is analyzed, adopt Ammonium Sulfite Method black liquor in the said method to contain admittedly that fulvic acid content is 10-20% in the thing, the alkaline process black liquor contains admittedly that fulvic acid content is 5-10% in the thing, fulvic acid content is 6-12% in the thing and contain admittedly according to the black liquor that common pulping with ammonium sulfite method method obtains, and the alkaline process black liquor contains admittedly that fulvic acid content is 1-6% in the thing; Trace it to its cause, though may be that common pulping process cooking liquor concentration is higher, temperature retention time is longer, help the plant residue degraded and generate fulvic acid, but too high cooking liquor concentration and long temperature retention time are further degraded fulvic acid, generate littler molecule, so the yield of fulvic acid reduces on the contrary.
(2) the high-hardness pulp post processing obtains rare black liquor
High-hardness pulp is carried out post processing, and to obtain solid content be 4-15%, and Baume degrees is rare black liquor of 2-9.
Washing process and methods such as post processing comprises by dilution, concentrates, press filtration or displacement will be stored between fiber and the fiber, and waste liquid and fiber separation in cell membrane, the lumen are opened, and isolated waste liquid is rare black liquor; Generally speaking, post processing generally includes shove and pulp washing, and wherein the black liquor of pulp washing generation wants solid content lower than the black liquor that shove produces comparatively speaking, can repeat to be used for pulp washing, constantly increase of the solid content of black liquor in the process that repeats.
Post processing shove process is used press master, is used for extracting the acroll press washer of black liquor in the preferred prior art of press master.When using press master to carry out shove, because the process at shove can produce very big extruding force, temperature rises rapidly, impel fiber separation, divide silk, brooming, conquassation, primary wall is destroyed, the enough energy of fiber absorbs make fibrous inside produce very big stress, and the reactivity worth of slurry is greatly improved.Simultaneously, fiber produces fibrillating, and impurity is dissolved in the black digestion liquid between epidermis organic matter and fiber, discharges by liquid outlet groove, and fiber fineness is greatly improved.Some ash contents in the black liquor and impurity are also along with black liquor is discharged from.Press master of the present invention is that the acroll press washer that the extraction black liquor is used in the prior art is single-screw press master and Double screw pulp extruder; Preferred described press master is the acroll press washer of reducing or varying pitch.
Preferred press master is the acroll press washer of reducing varying pitch among the present invention, utilizes reducing varying pitch press master, makes slurry in the space that slowly diminishes, and makes the about dehydration of compressed slurry layer consistent.The acroll press washer that the present invention is selected, after slurry was carried out shove, the beating degree of slurry changed little, that is to say, slurry can the fibre length that fibers in grass class is intrinsic keep relatively goodly through after the press master shove, has reduced the damage of fiber to greatest extent.
The hardness of the slurry that press master is extruded is high-hardness pulp also than higher, and permanganate number is 16-28; Preferred hardness is a permanganate number 18-27; Most preferably hardness is permanganate number 20-25, because hardness is higher, has therefore reduced pollution, has reduced production cost.The more important thing is, because the use of press master, the beating degree of described high-hardness pulp before and after shove changes little, therefore this just illustrates that high-hardness pulp damage to fibers in grass class in the shove process is very little, and the use of press master can not reduce the performance of prepared chemical pulp in the process that with the grass kind plant is the feedstock production chemical pulp.And in the process of shove, because lignin and other impurity such as ash content equal size are higher in the high-hardness pulp, and the pass through lignin of fiber between fiber adheres to, the process of boiling is because condition is relatively gentleer, the time of boiling and insulation is all shorter, used chemicals is few, thereby the hardness height that gained is starched after the boiling, content of lignin in the described high-hardness pulp is higher, the fibre bundle that in the process of shove some is sticked together unclamps, for sufficient preparation has been carried out in the washing and the bleaching of step later on.
Shove generally can extract the black liquor that is free between the fiber, for be present in the lumen and cell membrane in the part black liquor, can only just can extract with the way of diffusion.Must carry out pulp washing to the slurry that press master comes out; Pulp washing can adopt vacuum pulp washing machine, horizontal belt wash engine, pressure wash engine, high-speed pulp washer or slanted screen wash engine; Drum-type vacuum pulp washing machine or level band vacuum pulp washing machine in the preferred vacuum pulp washing machine.
High-hardness pulp behind the pulp washing is in the present invention as byproduct, of many uses, can be used as the raw material of layered product, be used to make mess tin, industrial buffering package, medical appliance, toy for children etc., natural degradation, good seismic resistance, high temperature are difficult for producing distortion down, do not produce static, the tool intussusception can be saved multiple advantages such as storage and transportation space, recovery utilization rate 100% but have.Can also bleach the high-quality bleached pulp of back preparation, and then make high-grade culture paper.
(3) add auxiliary material in the black liquor
The black liquor that above-mentioned steps obtains is the main raw material of product of the present invention.
Rare black liquor is rare black liquor that the post processing of one of above-mentioned pulping process obtains; Or the rare black liquor of mixing that forms after pulping process rare black liquor mixing that post processing obtains respectively more than 2 kinds; Wherein, the rare black liquid wave hairdressing 2-9 of the Ammonium Sulfite Method that obtains behind the pulping with ammonium sulfite method, solid content are 4-15%, and pH is 7-10; The rare black liquid wave hairdressing 2-9 of the alkaline process that soda pulping process obtains, solid content are 4-15%, and pH is 9-13.
Preferred rare black liquor of Ammonium Sulfite Method or the rare black liquor of Ammonium Sulfite Method and the rare black liquor of alkaline process mix the Ammonium Sulfite Method and the alkaline process that form and mix rare black liquor.This be since the nutrition composition content of the rare black liquor of Ammonium Sulfite Method generally than the alkaline process height, so preferred rare black liquor of Ammonium Sulfite Method in the actual production, but because there is NH in the Ammonium Sulfite Method black liquor when evaporation and concentration 3Volatilization, can cause the rapid decline of black liquor pH, equipment is caused serious corrosion, therefore obtain Ammonium Sulfite Method after more preferably the rare black liquor of Ammonium Sulfite Method and the rare black liquor of alkaline process being mixed and alkaline process mixes rare black liquor, can make and contain more nutrient in the fertilizer that makes, fertilizer efficiency is higher, can reduce the corrosion to equipment again, can also handle two kinds of black liquor simultaneously.
Ammonium Sulfite Method and alkaline process mix that the mixed proportion of the rare black liquor of Ammonium Sulfite Method and the rare black liquor of alkaline process is 1:100-100:1 in rare black liquor, preferred 1:10-10:1, more preferably 1:4-4:1.
Consider the suitability for industrialized production spray drying or the slurry-spraying pelletizing that help the subsequent technique drying steps, therefore preferably reduce the moisture in the black liquor, above-mentioned rare black liquor vaporizing is concentrated, obtain adding organic auxiliary material behind the concentrated black liquid.The solid content of concentrated black liquid is 15.1-65%, and Baume degrees is 9-40; Preferred solid content is 30-65%, and Baume degrees is 18-40, and more preferably solid content is 40-47%, and Baume degrees is 25-29, because NH in the evaporation and concentration 3Volatilization, the pH of black liquor can descend to some extent, is generally 5-11, preferred pH is 6-8, in order to avoid the fertilizer that makes causes the rapid variation of native pH, to doing the deposits yields harmful effect.
With rare black liquor vaporizing simmer down to concentrated black liquid, preferably use multiple-effect evaporation technology, this is that steam per ton can be taken away the moisture in 3-5 tons of black liquor because multiple-effect evaporation technology is thermal source with steam, the efficient height, and utilize energy savings.But along with the increase of multi-effect evaporator effect number, the unit steam consumption reduces gradually, therefore takes all factors into consideration, and preferably uses five to imitate evaporation technologies.
In rare black liquor or with rare black liquor vaporizing, concentrate to remove and add auxiliary material in the concentrated black liquid that portion of water obtains and form and can form various solid-state fertilizer or liquid fertile, described respectively below:
(1) Yellow humic acid fertilizer is solid-state fertilizer
Add organic auxiliary material in rare black liquor or in the concentrated black liquid and form slip, organic auxiliary material is lignin and humic acid.Wherein the effect of lignin is to adjust the viscosity of concentrated black liquor and adjust pH, is beneficial to the carrying out of subsequent production.The effect of humic acid is to change the outward appearance and the color of fertilizer, can also increase the fertilizer efficiency of fertilizer simultaneously.
The percentage by weight of each component is:
Rare black liquor or concentrated black liquid 30-80%
Lignin 1-45%
Humic acid 1-25%;
The percentage by weight of preferred each component is:
Rare black liquor or concentrated black liquid 50-60%
Lignin 15-35%
Humic acid 10-15%.
Above-mentioned Yellow humic acid fertilizer mixes when forming slip and can also comprise that percentage by weight is 0-45% mud; Preferred weight percent is 10-20%, and described mud is the biochemical sludge that the papermaking wastewater processing procedure produces, and the content of organic matter is more than or equal to 50%, wherein total nitrogen content 2-3%, content of tatal phosphorus 0.2-0.6% usually, full potassium content 2-4%.Mud can increase consolidating of black liquor and contain substrate concentration, adjusts pH.In addition, because biochemical sludge very easily causes secondary pollution, the conventional treatment expense is high, adds biochemical sludge in prescription, both can save the expense of handling biochemical sludge, also turns waste into wealth, and has reduced production cost.
In addition, in order to increase the fertilizer efficiency of fertilizer, also can in black liquor, add inorganic auxiliary material, inorganic auxiliary material is the inorganic salts that contain N, P or K, the perhaps mixture more than 2 kinds wherein, purpose is to adjust the content of N in the fertilizer, P, K, makes N, P, K content summation 4-30% in the fertilizer, for cost consideration, preferred 5%.Wherein P content is with P 2O 5Meter, K is with K 2The O meter, meet and be better than the standard of the relevant fertilizer of the Ministry of Agriculture, because baking temperature is generally than higher in the actual production, N salt volatilizees easily, cause the loss of nutrient, and it is less to lack the P situation in the present soil, and generally lacks K in the soil, therefore the preferred inorganic salts that add are KCl, and also visual actual conditions add the inorganic salts and the trace elements such as iron, copper, boron, zinc or magnesium of other kind certainly.
In addition, mix when forming slip and can also comprise that percentage by weight is 0-30% ardealite, preferred weight percent is 5-15%.The solid slag that ardealite produces when being meant in phosphoric acid production with sulfuric acid treating phosphorite, its main component is a calcium sulfate, contains multiple other impurity in addition.Simultaneously, in the production process, the HPO4 in the solution 2-Root replaces part SO4 in the crystal lattice of gypsum 2-, ardealite impurity divides two big classes, insoluble impurities: as quartz, undecomposed apatite, insoluble P 2O 5, eutectic P 2O 5, fluoride and fluorine, aluminium, magnesium phosphate and sulfate; Soluble impurity: as water-soluble P 2O 5, fluoride that solubility is lower and sulfate.Storing up in a large number of ardealite not only occupied land resource, also can cause the pollution of atmosphere, water system and soil owing to wind erosion, weathering.In fertilizer formula of the present invention, increase ardealite, both can utilize the solubility P that wherein contains 2O 5, the content of increase a great number of elements can also be handled industrial residue, prevents the pollution to environment.Simultaneously, the main component in the ardealite is a calcium sulfate, and saline-alkali soil is had good chemical modifying effect.
With the slip drying, promptly obtain a kind of Yellow humic acid fertilizer.
The fulvic acid weight percent content is 5-40% in the Yellow humic acid fertilizer, and the content of organic matter is 20-85%, if add inorganic auxiliary material, N, P and K total content are generally 4-30%.Drying can adopt slurry-spraying pelletizing to make granular organic fertilizer, also can spray drying make the powdery fertilizer or adopt other method drying.Too fast in view of the general fertilizers dissolving, nutrient runs off easily, and fertilizer efficiency is short, and therefore preferred employing slurry-spraying pelletizing causes granulated fertilizer, below its technology is done detailed description:
At first in the black liquor that concentrates, add lignin and humic acid formation slip; also can select to add mud and/or inorganic auxiliary material, then, slip enters the slurry-spraying pelletizing machine and carries out slurry-spraying pelletizing; 550～600 ℃ of the head temperatures of slurry-spraying pelletizing machine; 47-55 ℃ of tail temperature, for carrying out continuously of guaranteeing to produce, the returning charge amount wants 〉=50%; crude product is through behind the rotary screen; bulky grain after granule and the fragmentation returns the slurry-spraying pelletizing machine, and granularity forms product at the particle of 3-5mm, and packing, warehouse entry get final product.
The product that obtains promptly is a Yellow humic acid fertilizer, granularity 3-5mm (being mass fraction 〉=80% of 3-5mm in the actual product), and hardness 6-30N, the content of organic matter 20-85%, the fulvic acid weight percent content is 5-40%.
If drying means is selected spray-dired words, the product that obtains is a powdery, does not do granularity requirements, so except granularity and hardness, other index and last same.
Above-mentioned Yellow humic acid fertilizer is except meeting Ministry of Agriculture's fertilizer standard, and it contains abundant fulvic acid content 〉=5%, the part that the source of fulvic acid is contained in the humic acid that adds, mainly comes from concentrated black liquor.Fulvic acid contains the various active group and to the physiological activator of plant, is the less macromolecular organic compound of molecular weight, and acidic-group is many, and permeability is strong, can be dissolved in acid, alkali and water, easily by plant absorbing.It is used in agricultural production widely as non-harmful organic substance, shows as the drought resisting, the cold tolerance that improve crops on practical application effect, strengthen the resistance against diseases of crop, stimulate the growth of crop, thereby improve the output of crop, improve the quality of crop.
In addition, organic matter is mainly the refinement lignin in the above-mentioned Yellow humic acid fertilizer, degraded easily, crop is easy to absorb, and with present stages such as animal wastes, municipal refuse main fertilizer source compare, the Na ion concentration is low, generally is not more than 3%, be applicable to lack organic and fertility such as N, P, K are low, ventilation is got well sand and basic soil on use, can not cause the salinization of soil; And heavy metals such as the arsenic that unavoidably contains among both, cadmium, lead, chromium, mercury have prevented secondary pollution without male offspring.
Therefore, this Yellow humic acid fertilizer fulvic acid content height, fertilizer efficiency is lasting, the utilization rate height, wide accommodation is difficult for running off, and does not have any pollution, environmental protection, efficient, the particle homogeneous, glossiness is strong; Behind this incorporation of fertilizerin the soil, energy balance crop is improved the soil to the absorption of nitrogen, phosphorus, potassium, improves crop quality, improves crop anti-adversity, promotes the crop precocity, improves the output of crop; It is the high-efficiency organic fertilizer that is applicable to field crop, industrial crops.
(2) Yellow humic acid water flush fertilizer is for liquid fertile
In rare black liquor or with rare black liquor vaporizing, concentrate to remove and add the solubility macroelement fertilizer in the concentrated black liquid that portion of water obtains and obtain Yellow humic acid water flush fertilizer;
The percentage by weight of each component is:
Rare black liquor or concentrated black liquid 20-98%
Solubility macroelement fertilizer 2-80%;
The percentage by weight of preferred each component is:
Rare black liquor or concentrated black liquid 50-90%
Solubility macroelement fertilizer 10-50%.
Why need add the solubility macroelement fertilizer in rare black liquor or concentrated black liquid, be because nutrient wherein is very unbalanced, therefore, needs to add the purpose that reaches balance fertilizing.The solubility macroelement fertilizer is one or more of solubility nitrogenous fertilizer, soluble phosphoric manure and solubility potash fertilizer, this be because:
In rare black liquor or the concentrated black liquid, C/N is bigger, if directly be manured into soil, microbial decomposition is very slow, and to consume available state nitrogen in the soil, therefore can add solubility nitrogenous fertilizer to adjust the C/N ratio, added solubility nitrogenous fertilizer is 2-60% at the weight percent content of Yellow humic acid water flush fertilizer, is preferably 2-30%.Solubility nitrogenous fertilizer is one or more of urea or solubility ammonium salt, the solubility ammonium salt is one or more combination of ammonium sulfate, carbonic hydroammonium, ammonium chloride, ammonium dihydrogen phosphate (ADP) or diammonium hydrogen phosphate, but because the content of N is the highest in the urea, and sulphate-containing ion and chlorion etc. may not cause the ion that soil disease reacts, therefore preferred urea.
Phosphate fertilizer, can increase crop yield, improve product quality, can also improve crop drought resistance, cold-resistant and anti-resistance such as saline and alkaline, therefore, in black liquor, can add soluble phosphoric manure, soluble phosphoric manure is one or more combination of ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, potassium dihydrogen phosphate or dipotassium hydrogen phosphate, the preferably phosphoric acid ammonium dihydrogen, added soluble phosphoric manure is 2-60% at the weight percent content of Yellow humic acid water flush fertilizer, is preferably 2-30%.
In addition because therefore present general potassium deficiency in the soil, also can add solubility potash fertilizer in black liquor, to add solubility potash fertilizer be 2-50% at the weight percent content of Yellow humic acid water flush fertilizer, be preferably 2-30%.Solubility potash fertilizer is one or more combination of potassium sulfate, potassium chloride, potassium dihydrogen phosphate or dipotassium hydrogen phosphate, preferred potassium chloride or potassium sulfate.Potassium can promote photosynthesis, improve absorption and the utilization of plant to nitrogen significantly, and is converted into protein very soon.Potassium can also promote the plant water for economy, helps the resistance of crop.
In fact, owing to generally have no lack of phosphorus in the soil at present, therefore, preferably in black liquor, add solubility nitrogenous fertilizer and solubility potash fertilizer.Respectively add the component except above-mentioned, can also add the inorganic salts and the trace-element fertilizers such as soluble iron, copper, boron, zinc or magnesium of other kind according to actual conditions.
Make Yellow humic acid water flush fertilizer according to above-mentioned prescription and method, the fulvic acid percentage by weight is 5-40%, can comprise that also weight percent content is 3-25% nitrogen, and/or percentage by weight is with P 2O 5Count 3-25% phosphorus and/or percentage by weight with K 2O counts the potassium of 3-25%, and fertilizer efficiency is remarkable.
Fulvic acid contains the various active group and to the physiological activator of plant, is the less macromolecular organic compound of molecular weight, and acidic-group is many, and permeability is strong, can be dissolved in acid, alkali and water, easily by plant absorbing.It is used in agricultural production widely as non-harmful organic substance, shows as the drought resisting, the cold tolerance that improve crops on practical application effect, strengthen the resistance against diseases of crop, stimulate the growth of crop, thereby improve the output of crop, improve the quality of crop.
Yellow humic acid water flush fertilizer of the present invention owing to add the elemental constituent of extra composition balanced feritilizers such as nitrogen, phosphorus or potassium, is implemented the technology of balance fertilizing among fertilizer formula, uses the back nutrient and is absorbed easily, be difficult for by soil fixing, knotts clay not, nonhazardous is residual; Use conveniently, save labor; Nutritional labeling is many and comprehensive, and fertilizer efficiency is fast, helps crop yield.In plant growth vigorous season, avoided common fertilizer topdress fertilizer nutrient discharge transform slow, fertilizer efficiency is slow, the shortcoming that influences crop yield and quality.
(3) Yellow humic acid foliage fertilizer
Concentrate to remove in rare black liquor or with rare black liquor vaporizing and add soluble trace elements fertilizer in the concentrated black liquid that portion of water obtains and promptly get Yellow humic acid foliage fertilizer, the envelope-bulk to weight ratio of the two is 1000ml:0.2-45g.
Owing to contain abundant fertilizer in the black liquor, therefore very suitable be that liquid fertilizer is made on the basis.Because foliage fertilizer directly absorbs instant effect, plant recovery of nutrient height, can improve crop nutrition content supply situation rapidly, therefore, the present invention is made into foliage fertilizer.In addition, concentration and purity based on macronutrient in the present commodity fertilizer continue to increase, the fertilizer efficiency of trace element is also more and more obvious, as enrich trace-element fertilizer and can obviously increase production, increase income and improve product quality, therefore in rare black liquor or concentrated black liquid, add trace element and can strengthen fertilizer efficiency significantly, improve the yield and quality of crop.
Trace element is meant the very low nutrient of content in soil and the plant, studies and use more 6 kinds of iron, copper, zinc, manganese, molybdenum, the boron etc. that have at present.Though trace element is few at the crop in-vivo content, has very strong selectivity, be crop growth indispensable and trans-substitution mutually.Therefore, when crop lacked any trace element, growing just was suppressed, and caused the underproduction and quality to descend, serious even total crop failure.Otherwise, if these elements are too much, again intoxicating phenomenon can appear, influence crop yield and quality, also can cause some endemic generation of people, animal.
Boron can promote the normal development of reproductive organs, and an important symptom of boron deficiency is that seed can not normal development, even can not form, thereby influences the harvest of crop.Synthetic and the transportation of sugar has facilitation to boron in the object to doing, and chloroplast is degenerated during boron deficiency, influences photosynthesis.Boron can improve the nitrogenase activity of legume rhizobium, increases amount of nitrogen fixation.During boron deficiency, root nodule is undeveloped, influences amount of nitrogen fixation.Boron can also strengthen crop anti-adversity.
Zinc can promote crop to carry out photosynthesis, and stagnating appears in crop growth when lacking zinc.
It is indispensable that iron is that chlorophyll forms, and is difficult to shift in the plant body, so blade " chlorosis " is the performance of plant iron deficiency, and this chlorosis at first appears on the young leaflet tablet.In addition, iron is all influential to photosynthesis of plants, respiration.
Based on above-mentioned effect of trace elements, Yellow humic acid foliage fertilizer of the present invention is different according to trace element that is added and amount, can be divided into following three series:
(I) field crop foliage fertilizer
Wherein added soluble trace elements fertilizer is ferrous salt and zinc salt, and its addition is to add 0.1-15g and 0.1-20g in every 1000ml alkaline process and the Ammonium Sulfite Method mixed straw black liquor; Be applicable to field crops such as corn, wheat, paddy rice, soybean;
(II) vegetable leaf leaven,
Wherein added soluble trace elements fertilizer is boron fertilizer and zinc salt, and its addition is to add 0.1-15g and 0.1-20g in every 1000ml alkaline process and the Ammonium Sulfite Method mixed straw black liquor, is applicable to vegetables such as spinach, celery, cucumber, garlic, capsicum;
(III) fruit tree leaves leaven
Wherein added soluble trace elements fertilizer is boron salt, zinc and ferrous salt, and its addition is to add 0.1-15g, 0.1-20g and 0.1-15g in every 1000ml alkaline process and the Ammonium Sulfite Method mixed straw black liquor, is applicable to fruit trees such as apple, peach, apricot.
Wherein, above-mentioned ferrous salt is a ferrous sulfate; Above-mentioned zinc salt is zinc sulfate and/or zinc chloride, preferably sulfuric acid zinc; Above-mentioned boron fertilizer is boric acid and/or borax, preferred borax.
Fulvic acid content is very high in the present invention series Yellow humic acid foliage fertilizer, can arrive 5-40%, and fulvic acid contains the various active group and to the physiological activator of plant, be the less macromolecular organic compound of molecular weight, acidic-group is many, and permeability is strong, can be dissolved in acid, alkali and water, easily by plant absorbing.It is used in agricultural production widely as non-harmful organic substance, shows as the drought resisting, the cold tolerance that improve crops on practical application effect, strengthen the resistance against diseases of crop, stimulate the growth of crop, thereby improve the output of crop, improve the quality of crop.
The Yellow humic acid foliage fertilizer that the present invention makes adds extra micro-component, and the technology of balance fertilizing is implemented among fertilizer formula; And use the back and directly absorb instant effect, plant recovery of nutrient height, can improve crop nutrition content supply situation rapidly; Use conveniently, save labor; Nutritional labeling is many and comprehensive, and fertilizer efficiency is fast, helps crop yield.In plant growth vigorous season, avoided common fertilizer topdress fertilizer nutrient discharge transform slow, fertilizer efficiency is slow, the shortcoming that influences crop yield and quality.
Grass type stalk method of comprehensive utilization provided by the invention has made full use of lignin and the cellulose in the grass type stalk, and prepared paper pulp and Yellow humic acid fertilizer are expensive, can obtain good economic benefit.
The present invention also provides a kind of grass type stalk to extract the method for fulvic acid, comprising:
(1) boiling obtains high-hardness pulp
Grass type stalk is carried out slurrying by the boiling method except that organic solvent pulping, obtain concentration and be 8-15% slurry, hardness is permanganate number 16-28; Preferred hardness is a permanganate number 18-27; Most preferably hardness is permanganate number 20-25;
(2) the high-hardness pulp post processing obtains rare black liquor
High-hardness pulp is carried out post processing, and to obtain solid content be 4-15%, and Baume degrees is rare black liquor of 2-9; Washing process and methods such as described post processing comprises by dilution, concentrates, press filtration or displacement will be stored between fiber and the fiber, and waste liquid and fiber separation in cell membrane, the lumen are opened;
(3) prepare fulvic acid solution by black liquor
Concentrate to remove in rare black liquor or with rare black liquor vaporizing and add acid in the concentrated black liquid that portion of water obtains and regulate and make it to separate out lignin, add flocculant then, remove by filter lignin, filtrate is fulvic acid solution;
(4) extract fulvic acid in the fulvic acid solution
From fulvic acid solution, extract fulvic acid.
Grass type stalk extracts step () boiling in the method for fulvic acid and obtains high-hardness pulp and the post processing of (two) high-hardness pulp and obtain the detailed process of rare black liquor and step with one of grass type stalk method of comprehensive utilization; The detailed process of following steps is:
(3) prepare fulvic acid solution by black liquor
Concentrate to remove in rare black liquor or with rare black liquor vaporizing and add acid in the concentrated black liquid that portion of water obtains and regulate and make it to separate out lignin, add flocculant then, remove by filter lignin, filtrate is fulvic acid solution;
Rare black liquor is rare black liquor that the post processing of one of above-mentioned pulping process obtains; Or the rare black liquor of mixing that forms after pulping process rare black liquor mixing that post processing obtains respectively more than 2 kinds; Wherein, the rare black liquid wave hairdressing 2-9 of the Ammonium Sulfite Method that obtains behind the pulping with ammonium sulfite method, solid content are 4-15%, and pH is 7-10; The rare black liquid wave hairdressing 2-9 of the alkaline process that soda pulping process obtains, solid content are 4-15%, and pH is 9-13.
Preferred rare black liquor of Ammonium Sulfite Method or the rare black liquor of Ammonium Sulfite Method and the rare black liquor of alkaline process mix the Ammonium Sulfite Method and the alkaline process that form and mix rare black liquor.This be since the nutrition composition content of the rare black liquor of Ammonium Sulfite Method generally than the alkaline process height, so preferred rare black liquor of Ammonium Sulfite Method in the actual production, but because there is NH in the Ammonium Sulfite Method black liquor when evaporation and concentration 3Volatilization, can cause the rapid decline of black liquor pH, equipment is caused serious corrosion, therefore obtain Ammonium Sulfite Method after more preferably the rare black liquor of Ammonium Sulfite Method and the rare black liquor of alkaline process being mixed and alkaline process mixes rare black liquor, can make and contain more nutrient in the fertilizer that makes, fertilizer efficiency is higher, can reduce the corrosion to equipment again, can also handle two kinds of black liquor simultaneously.
Ammonium Sulfite Method and alkaline process mix that the mixed proportion of the rare black liquor of Ammonium Sulfite Method and the rare black liquor of alkaline process is 1:100-100:1 in rare black liquor.But when the alkaline straw-pulp black liquid proportion is big, often pH is bigger for the Yellow humic acid foliage fertilizer that forms, may cause adverse effect to blade, therefore preferably adding sour pH to Yellow humic acid foliage fertilizer regulates, its pH is adjusted to 6-10, the acid that adds can be organic acid or inorganic acid, but considers H 2SO 4Not only unnecessary invalid but also certain harm, preferred H arranged with sulfate ion among the HCl and chlorion 3PO 4And HNO 3
Owing to need to add extra acid, certainly will increase cost, and the Ammonium Sulfite Method black liquor is generally than the nutrient content height of alkaline process black liquor, therefore often increase the shared volume ratio of straw pulp black liquor by ammonium sulfite method in producing, the percent by volume that preferred straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid mix is 1:10-10:1, can significantly reduce the amount of the acid of adding, even can need not add extra acid fully and can make that the pH of Yellow humic acid foliage fertilizer is 6-10.
But in actual production, there is NH in straw pulp black liquor by ammonium sulfite method when evaporation and concentration 3Volatilization, can cause the rapid decline of black liquor pH, thereby can cause serious corrosion equipment, what influence was produced carries out continuously.Therefore, through a large amount of tests, the percent by volume of further preferably working as the mixing of straw pulp black liquor by ammonium sulfite method and alkaline straw-pulp black liquid is 1:4-4:1, in this scope, the corrosion that equipment causes is extenuated greatly, and mixed black liquor vaporizing is concentrated to solid content when being 40-47%, it is 6-8 that alkaline process that forms and Ammonium Sulfite Method are mixed the pH that concentrates straw pulp black liquor, the Yellow humic acid foliage fertilizer that adds soluble trace elements and obtain is applicable to various soil, and can not cause the significant variation of soil pH.
The solid content of Ammonium Sulfite Method and alkaline process mixed straw black liquor can be and mixes the unconcentrated straw pulp black liquor in back, solid content is 4-15%, Baume degrees is the straw pulp black liquor that concentrated after 2-9 or the mixing, solid content is 15.1-65%, Baume degrees is 9-40, but consider in order to reduce the moisture of fertilizer, increase active ingredient, reduce cost of transportation, the straw pulp black liquor that concentrated after preferred the mixing, but consider the mobile relatively poor of the too high black liquor of solid content simultaneously, the influence of factors such as the energy that need expend is excessive, the solid content of the straw pulp black liquor that concentrated after preferred the mixing is 30-50%, Baume degrees is 17-31, preferred solid content is 40-47%, and Baume degrees is 25-29.
With rare black liquor vaporizing simmer down to concentrated black liquid, preferably use multiple-effect evaporation technology, this is that steam per ton can be taken away the moisture in 3-5 tons of black liquor because multiple-effect evaporation technology is thermal source with steam, the efficient height, and utilize energy savings.But along with the increase of multi-effect evaporator effect number, the unit steam consumption reduces gradually, therefore takes all factors into consideration, and preferably uses five to imitate evaporation technologies.
Concentrate to remove in rare black liquor or with rare black liquor vaporizing and add acid in the concentrated black liquid that portion of water obtains and regulate and make it to separate out lignin, add flocculant then, remove by filter lignin, filtrate is fulvic acid solution;
In rare black liquor or with rare black liquor vaporizing, concentrate to remove in the concentrated black liquid that portion of water obtains and add acid, regulating pH is below 5, make it to separate out lignin, consider the cost and the precipitation efficiency of acid, preferred pH is 2-4, used acid can be organic acid and inorganic acid, and organic acid includes but not limited to formic acid, acetate, propionic acid, benzoic acid etc.; Inorganic acid includes but not limited to hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc.
Behind the lignin by acid separation,, therefore add the flocculant of black liquor weight 2-50ppm, make it precipitation, preferred 5-15ppm, most preferably 5ppm owing to there is the part lignin to be suspended in the black liquor; Flocculant includes but not limited to bodied ferric sulfate, aluminium chloride, ammonium polyacrylate etc., behind the adding flocculant, black liquor is filtered, and removes delignification, and the filtrate that obtains promptly is fulvic acid solution.
With the fulvic acid solution concentration, can obtain the fulvic acid solution of variable concentrations, also can be dried, can obtain the crude product fulvic acid.Also can be as the described method supercritical CO of Chinese patent CN01141835.4 2Extract high-purity xanthohumic acid, or purified, to such an extent as to can obtain the higher fulvic acid medical xanthonumic acid of purity with other method of prior art.
The specific embodiment
What embodiment 1-8 related to is that the straw Ammonium Sulfite Method prepares brown stock:
Embodiment 1
To flood through the straw of the back 30mm that gets the raw materials ready, adopt the dipping spiral organ, maceration extract is that alkalinity is in 4% the aqueous slkali of NaOH to the over dry material quantity, liquor ratio 1:4,85 ℃ of insulations mixed after 40 minutes under normal pressure, and the raw material behind the dipping is delivered in the rotary spherical digester.Add steaming preparation in rotary spherical digester, the consumption of ammonium sulfite is an over dry material quantity 11%, and liquor ratio is 1:3; Feed steam in the rotary spherical digester and heat, insulation is 40 minutes during heat temperature raising to 125 ℃, carries out little steam bleeding, continues heat temperature raising to 170 ℃, is incubated 75 minutes.
Obtaining hardness after the boiling is permanganate number 18, is equivalent to the high-hardness pulp of card uncle valency 27.Then the slurry after the boiling is carried out shove.Can be 15% high-hardness pulp with gained concentration after the boiling enters from the inlet of two rod press masters, carries out shove, and after the extruding black liquor, concentration is that 30% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 28 ° of SR, and the beating degree after the shove is 29 ° of SR.The Baume degrees of the black liquor that shove is extruded is 7 ° of Be ' at 20 ℃, and the concentration of the ammonium sulfite of the remnants in the black liquor is 8g/L.
The slurry that comes out from the outlet of press master dilutes with 60 ℃ warm water, and the concentration that makes slurry is 2.5% to deliver to jump and screen, and carries out pulp washing according to the method for routine then, regulates the concentration to 10% of starching behind the pulp washing.Next adopt deflaker to discongest in resulting slurry.Heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 4% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa stops and made this slurry can carry out sufficient delignification reaction in 75 minutes, and tower top temperature is 100 ℃; pressure remains 0.5MPa, and the delignification rate is 86% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness of slurry was reduced to permanganate number 10, was equivalent to card uncle valency 13.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, can obtain a kind of brown stock of straw raw material ammonium sulfite boiling preparation, the whiteness of brown stock is 35%ISO, fracture length is 5.5km, tearability is 259mN, and folding number is 75 times, and beating degree is 36 ° of SR.
Embodiment 2
To be that the straw of 15-20mm carries out boiling through length behind the conventional dry raw material preparation: add steaming preparation in rotary spherical digester, wherein the consumption of ammonium sulfite be an over dry material quantity 9%, and liquor ratio is 1:4; Feed steam again and heat in rotary spherical digester, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 130 ℃, continues heat temperature raising to 165 ℃, is incubated 90 minutes.Obtaining hardness after the boiling is permanganate number 24, is equivalent to the high-hardness pulp of card uncle valency 39.Then the high-hardness pulp after the boiling is carried out shove, being 10% high-hardness pulp with gained concentration after the boiling enters from the inlet of reducing single-screw press master, carries out shove, and after the extruding black liquor, concentration is that 25% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 24 ° of SR, and the beating degree after the shove is 25 ° of SR.The Baume degrees of the black liquor that shove is extruded is 8 ° of Be ' at 20 ℃, and the concentration of the ammonium sulfite of the remnants in the black liquor is 9g/L.
The slurry that comes out from the outlet of press master dilutes with the black liquor that pulp washing the subsequent technique displaces, and described black liquor is 6 ° of Be ' at 20 ℃ of Baume degrees, make slurry dense deliver to jump to 3% screen, carry out then regulating the concentration to 12% of starching behind the pulp washing.
Slurry carries out deflaker before oxygen delignification discongests, and after discongesting this slurry is heated to 70 ℃ and be transported to the oxygen delignification reaction tower by the positive displacement middle underflow pump.This slurry before entering reaction tower in pipeline with the oxygen of the 40kg slurry per ton that adds and alkalinity for mixing in 2% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, 100 ℃ of inlet temperatures, pressure 1.2Mpa, stopping in 90 minutes makes this slurry can carry out sufficient delignification reaction, tower top temperature is 105 ℃, pressure remains 0.2MPa, and the delignification rate is 90% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 14, was equivalent to card uncle valency 19, and beating degree is 28 ° of SR.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, can obtain a kind of brown stock of straw raw material ammonium sulfite boiling preparation, the whiteness of described brown stock is 45%ISO, fracture length is 5.0km, tearability is 249mN, and folding number is 50 times, and beating degree is 35 ° of SR.
Embodiment 3
To be that the straw of 20-25mm is put into rotary spherical digester and carried out boiling through the length after conventional the getting the raw materials ready, in rotary spherical digester, add steaming preparation, the consumption of ammonium sulfite is to 10% of over dry material quantity, liquor ratio is 1:2, feed steam and heat, heat temperature raising is incubated 30 minutes when temperature is 120 ℃, carried out little steam bleeding 25 minutes, continue heat temperature raising to 173 ℃, be incubated 60 minutes.Obtaining hardness after the boiling is permanganate number 25, the high-hardness pulp that is equivalent to card uncle valency 43, then described high-hardness pulp is carried out shove, being about to gained concentration after the boiling and being 8% high-hardness pulp enters from the inlet of reducing Double screw pulp extruder, carry out shove, after the extruding black liquor, concentration is that 20% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 22 ° of SR, and the beating degree after the shove is 23 ° of SR.The Baume degrees of the black liquor that shove is extruded is 9 ° of Be ' at 20 ℃, and the concentration of the ammonium sulfite of the remnants in the black liquor is 10g/L.
The slurry that comes out from the outlet of press master dilutes with the black liquor that pulp washing the subsequent technique displaces, described black liquor is 4 ° of Be ' at 20 ℃ of Baume degrees, make slurry dense deliver to jump to 2.8% screen, method is routinely carried out pulp washing then, regulates the concentration to 18% of starching afterwards.
Before oxygen delignification, adopt dry pan to discongest, heat this slurry to 80 ℃ then and be transported to the slurry tower slurry.The air that this slurry is got rid of in the slurry through modifier treatment earlier in the slurry tower makes it fluidization, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower, advance the oxygen that adds 20kg slurry per ton before the tower and alkalinity in 3.5% the aqueous slkali of NaOH, and in pipeline, feed steam and should starch heat temperature raising the oven dry stock amount.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate, and addition is 1% of an oven dry stock weight, 90 ℃ of inlet temperatures; pressure 1.2Mpa; stopped 85 minutes, tower top temperature is 105 ℃, and pressure remains 0.4MPa; the delignification rate is 98% in the oxygen delignification process; this slurry is spurted stock tank and dilution, and this moment, the hardness K (permanganate number) of slurry was reduced to 14, was equivalent to card uncle valency 19.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, can obtain a kind of brown stock of straw raw material ammonium sulfite boiling preparation, whiteness is 38%ISO, fracture length is 6.5km, tearability is 265mN, and folding number is 65 times, and beating degree is 36 ° of SR.
Embodiment 4
To put into the spiral macerator through the straw of 20mm behind the conventional dry raw material preparation, add alkali charge again for 4% aqueous slkali of over dry material quantity being carried out impregnation process in NaOH, liquor ratio 1:3,85 ℃ of insulations mixed 30 minutes under normal pressure.Afterwards, will send in the boiling vessel through the raw material of impregnation process, and add steaming preparation, wherein the addition of ammonium sulfite is 11% of an over dry material quantity, and liquor ratio is 1:3; Feed steam again and heat, heat temperature raising carries out little steam bleeding to temperature is 130 ℃ time insulation 40 minutes, continues heat temperature raising to 170 ℃, is incubated 80 minutes.
Obtaining hardness after the boiling is permanganate number 20, is equivalent to the high-hardness pulp of card uncle valency 31, then the slurry after the boiling is carried out shove.Being 12% high-hardness pulp with gained concentration after the boiling enters from the inlet of the single-screw press master of reducing, carries out shove, and after the extruding black liquor, concentration is that 26% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 25 ° of SR, and the beating degree after the shove is 26 ° of SR.The Baume degrees of the black liquor that shove is extruded is 9 ° of Be ' at 20 ℃.Residual ammonium sulfite is 12g/L in the black liquor.The slurry that comes out from the outlet of press master dilutes with the black liquor that pulp washing the subsequent technique displaces, described black liquor is 5 ° of Be ' at 20 ℃ of Baume degrees, the concentration to 3% of slurry is delivered to jump and screened, carry out pulp washing according to the method for routine then, and regulate the concentration to 15% of starching.
Heat this slurry to 80 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower, advance the oxygen that adds 20kg slurry per ton before the tower and alkalinity in 4% the aqueous slkali of NaOH, and in pipeline, feed steam and should starch heat temperature raising the oven dry stock amount.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, and protective agent is a magnesium sulfate, and addition is 0.5% of an oven dry stock weight; 100 ℃ of inlet temperatures; pressure 0.9Mpa stopped 90 minutes, and tower top temperature is 104 ℃; pressure remains 0.4MPa; the delignification rate is 92% in the oxygen delignification process, and this slurry is spurted stock tank and dilution, and this moment, the hardness (permanganate number) of slurry was reduced to 10; be equivalent to card uncle valency 12.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, can obtain a kind of brown stock of straw raw material ammonium sulfite boiling preparation, whiteness is 40%ISO, fracture length is 7.5km, tearability is 275mN, and folding number is 100 times, and beating degree is 33 ° of SR.
Embodiment 5
To be that the straw of 15-20mm is put into the dipping spiral organ through length behind the conventional dry raw material preparation, add alkali charge in 3% the dipping solution of NaOH to the over dry material quantity, liquor ratio 1:4,95 ℃ of insulations mixed 40 minutes under normal pressure, after the black liquor discharge, in steamer, add steaming preparation, wherein the consumption of ammonium sulfite is with 12% of over dry material quantity, liquor ratio is 1:4, feed steam and heat, heat temperature raising is incubated 30 minutes when temperature is 125 ℃, carry out little steam bleeding, continue heat temperature raising to 168 ℃, be incubated 75 minutes.
Obtaining hardness after the boiling is permanganate number 22, is equivalent to the high-hardness pulp of card uncle valency 34.Being 13% high-hardness pulp with gained concentration after the boiling enters from the inlet of Var-nip press, carries out shove, and after the extruding black liquor, concentration is that 28% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 24 ° of SR, and the beating degree after the shove is 25 ° of SR, and the Baume degrees of the black liquor that shove is extruded is 11 ° of Be ' at 20 ℃, and residual ammonium sulfite is 13g/L in the black liquor.To regulate concentration to 2.5% through the slurry of shove, and deliver to jump and screen, and use three sections vacuum pulp washing machines to carry out pulp washing then, regulate the concentration to 14% of slurry behind the pulp washing.
Before oxygen delignification, slurry is discongested, adopt the mill fluffer in the beating equipment, heat this slurry to 70 ℃ and be transported to the oxygen delignification reaction tower through the positive displacement middle underflow pump.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for mixing in 3% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock amount; 98 ℃ of inlet temperatures; pressure 1.0Mpa stops in 80 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 102 ℃; pressure remains 0.4MPa, and the delignification rate is 88% in the oxygen delignification process.After finishing dealing with this slurry being spurted stock tank also dilutes, this moment, the hardness (permanganate number) of slurry was reduced to 13, be equivalent to card uncle valency 18, with pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, can obtain a kind of brown stock of straw raw material ammonium sulfite boiling preparation, whiteness is 45%ISO, fracture length is 6.8km, tearability is 200mN, and folding number is 80 times, and beating degree is 32 ° of SR.
Embodiment 6
To be that the straw of 25-30mm is put into the dipping spiral organ through length behind the conventional dry raw material preparation, add alkali charge in NaOH to 3.5% the aqueous slkali of over dry material quantity and the mixed liquor of black liquor, the concentration of used black liquor is 14 ° of Be ' (20 ℃), liquor ratio 1:2,85 ℃ of insulations mixed 40 minutes under normal pressure.After impregnation process is intact raw material is delivered in the vertical digester, the consumption of ammonium sulfite is to over dry material quantity 13%, and liquor ratio is 1:2.5; Feed steam in the digester and heat, heat temperature raising insulation 40 minutes when temperature is 140 ℃ was carried out little steam bleeding after 30 minutes, continued heat temperature raising to 173 ℃, was incubated 90 minutes.
Obtaining hardness after the boiling is permanganate number 16, the high-hardness pulp that is equivalent to card uncle valency 24 is 14% high-hardness pulp again with the concentration of boiling gained to be entered from the inlet of two rod press masters, carries out shove, after the extruding black liquor, concentration is that 28% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 26 ° of SR, and the beating degree after the shove is 27 ° of SR.The Baume degrees of the black liquor that shove is extruded is 10 ° of Be ' at 20 ℃, and the ammonium sulfite that participates in the black liquor is 9g/L.The slurry that comes out from the outlet of press master dilutes with 60 ℃ warm water, and the concentration that makes slurry is to deliver to jump in 3% o'clock to screen, and washs with conventional method then.Regulating slurry afterwards dense is 25%, heats this slurry to 80 ℃ and is transported to slurry by conveying worm and manage chute and be transported to the oxygen delignification reaction tower by single rotor formula high density stock pump.Add the oxygen of 20kg slurry per ton and alkalinity in the reaction tower for mixing in 4% the aqueous slkali of NaOH to the oven dry stock amount; and feeding steam should be starched heat temperature raising in pipeline; this slurry enters this oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate, and addition is 0.8% of an oven dry stock weight, 95 ℃ of inlet temperatures; pressure 1.0Mpa; stopped 80 minutes, tower top temperature is 105 ℃, and pressure remains 0.4MPa.The delignification rate is 91% in the oxygen delignification process, this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 11, was equivalent to card uncle valency 14, with pump the stock pump of dilution was gone into two sections vacuum pulp washing machine washings afterwards, can obtain a kind of brown stock of straw raw material ammonium sulfite boiling preparation, whiteness is 48%ISO, and fracture length is 7.5km, and tearability is 230mN, folding number is 70 times, and beating degree is 36 ° of SR.
Embodiment 7
To be that the straw of 20-40mm floods through length behind the conventional dry raw material preparation, put into the dipping spiral organ, add alkali charge in NaOH to 4% the aqueous slkali of over dry material quantity and the mixed liquor of black liquor, the concentration of used black liquor is 14 ° of Be ' (20 ℃), liquor ratio 1:2,85 ℃ of insulations mixed 25 minutes under normal pressure.After impregnation process is intact raw material is delivered in the vertical digester, the consumption of ammonium sulfite is to over dry material quantity 11%, and liquor ratio is 1:2.8; Feed steam in the digester and heat, heat temperature raising insulation 40 minutes when temperature is 134 ℃ was carried out little steam bleeding after 25 minutes, continued heat temperature raising to 170 ℃, was incubated 60 minutes.
Obtaining hardness after the boiling is permanganate number 23, the high-hardness pulp that is equivalent to card uncle valency 34 is 12% high-hardness pulp with gained concentration after the boiling to be entered from the inlet of reducing single-screw press master, carries out shove, after the extruding black liquor, concentration is that 24% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 24 ° of SR, and the beating degree after the shove is 25 ° of SR.Directly dilute with rare black liquor then, the concentration that makes slurry is 2.5% to deliver to jump and screen, and carries out pulp washing then, and regulating the concentration of starching is 20%.
Before oxygen delignification, slurry is discongested, adopts defibrator, heat this slurry to 70 ℃ and through the gear type high density stock pump be transported to the oxygen delignification reaction tower and in pipeline feeding steam should starch heat temperature raising.Add the oxygen of 30kg slurry per ton and alkalinity in the reaction tower in 4% the aqueous slkali of NaOH to the oven dry stock amount; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 100 ℃ of inlet temperatures; pressure 1.1Mpa stops in 90 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 105 ℃; pressure remains 0.5MPa, and the delignification rate is 94% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 13, was equivalent to card uncle valency 17.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, can obtain a kind of brown stock of straw raw material ammonium sulfite boiling preparation, whiteness is 40%ISO, fracture length is 7.0km, tearability is 250mN, and folding number is 30 times, and beating degree is 36 ° of SR.
Embodiment 8
To be that the straw of 30-35mm is put into rotary spherical digester and carried out boiling through length behind the conventional dry raw material preparation, and add steaming preparation, wherein the consumption of ammonium sulfite be to over dry material quantity 9%, and liquor ratio is 1:2; Feed steam again and heat, insulation is 20 minutes during heat temperature raising to 120 ℃, carries out little steam bleeding 20 minutes, continues heat temperature raising to 165 ℃, is incubated 60 minutes.
Obtaining hardness after the boiling is permanganate number 28, is equivalent to the high-hardness pulp of card uncle valency 50, then the slurry after the boiling is carried out shove.Being 11% high-hardness pulp with gained concentration after the boiling enters from the inlet of the single-screw press master of reducing, carries out shove, and after the extruding black liquor, concentration is that 22% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 27 ° of SR, and the beating degree after the shove is 28 ° of SR.The slurry that comes out from the outlet of press master dilutes with the black liquor that pulp washing the subsequent technique displaces, make slurry dense deliver to jump to 3% screen, pulp washing then, regulating slurry dense is 23%, then heats this slurry to 80 ℃ and is transported to the oxygen delignification reaction tower through the positive displacement high density stock pump.Add the oxygen of 30kg slurry per ton in the reaction tower and in 3.5% the aqueous slkali of NaOH, and in pipeline, feed steam and should starch heat temperature raising the oven dry stock amount.Protective agent is a magnesium sulfate, and addition is 0.8% of an oven dry stock weight, 100 ℃ of inlet temperatures; pressure 0.9Mpa stops in 75 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 108 ℃; pressure remains 0.6MPa, and the delignification rate is 86% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 14, was equivalent to card uncle valency 19.5.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, can obtain a kind of brown stock of straw raw material ammonium sulfite boiling preparation, whiteness is 35%ISO, fracture length is 4.3km, tearability is 220mN, and folding number is 90 times, and beating degree is 38 ° of SR.
What embodiment 9-21 related to is the brown stock of straw raw material alkaline cooking preparation.
Embodiment 9
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 30mm, in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 12% of over dry material quantity, liquor ratio is 1:2, the anthraquinone addition is 0.8% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 125 ℃, continues heat temperature raising to 165 ℃, is incubated 90 minutes.Obtaining hardness after the boiling is permanganate number 18, is equivalent to the high-hardness pulp of card uncle valency 27.Then the slurry after the boiling is carried out shove.Can be 15% high-hardness pulp with gained concentration after the boiling enters from the inlet of Var-nip press, carries out shove, and after the extruding black liquor, concentration is that 30% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 28 ° of SR, and the beating degree after the shove is 29 ° of SR.The Baume degrees of the black liquor that shove is extruded is 7 ° of Be ' at 20 ℃, and the concentration of the residual alkali in the black liquor is 8g/L.
The slurry that comes out from the outlet of press master dilutes with 60 ℃ warm water, make slurry dense deliver to jump to 2.5% screen, utilize three sections vacuum pulp washing machines to carry out pulp washing then, regulate the concentration to 10% of starching behind the pulp washing.The gained slurry adopts deflaker to discongest before oxygen delignification.Heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 4% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa stops and made this slurry can carry out sufficient delignification reaction in 75 minutes, and tower top temperature is 100 ℃; pressure remains 0.5MPa, and the delignification rate is 86% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness of slurry was reduced to permanganate number 10, was equivalent to card uncle valency 13.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Can obtain a kind of brown stock of straw raw material alkaline cooking preparation, whiteness is 52%ISO, and fracture length is 5.0km, and tearability is 260mN, and folding number is 90 times, and beating degree is 36 ° of SR.
Embodiment 10
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 15-20mm, in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 9% of over dry material quantity, liquor ratio is 1:4, the anthraquinone addition is 0.5% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 120 ℃, continues heat temperature raising to 165 ℃, is incubated 70 minutes.Obtaining hardness after the boiling is permanganate number 24, is equivalent to the slurry of card uncle valency 39.Then the slurry after the boiling is carried out shove.Can be 10% high-hardness pulp with gained concentration after the boiling enters from the inlet of single-screw press master, carries out shove, and after the extruding black liquor, concentration is that 25% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 24 ° of SR, and the beating degree after the shove is 25 ° of SR.The Baume degrees of the black liquor that shove is extruded is 8 ° of Be ' at 20 ℃, and the content of the residual alkali in the black liquor is 9g/L.The slurry that comes out from the outlet of press master dilutes with the black liquor that pulp washing the subsequent technique displaces, and described black liquor is 6 ° of Be ' at 20 ℃ of Baume degrees, make slurry dense deliver to jump to 3% screen, adopt conventional method to carry out pulp washing then, regulate again starch dense to 12%.
The gained slurry can adopt kneading machine to discongest before oxygen delignification, heats this slurry to 70 ℃ and is transported to the oxygen delignification reaction tower by the positive displacement middle underflow pump.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 2% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, 100 ℃ of inlet temperatures, pressure 1.2Mpa, stopping in 90 minutes makes this slurry can carry out sufficient delignification reaction, tower top temperature is 105 ℃, pressure remains 0.2MPa, and the delignification rate is 90% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 14, was equivalent to card uncle valency 19.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Can obtain a kind of brown stock of straw raw material alkaline cooking preparation, whiteness is 46%ISO, and fracture length is 5.5km, and tearability is 270mN, and folding number is 65 times, and beating degree is 32 ° of SR.
Embodiment 11
To put into upright steamer through the straw that length behind the conventional dry raw material preparation is about 20-25mm, in steamer, add steaming preparation and carry out boiling, alkali charge in NaOH to 10% of over dry material quantity, liquor ratio is 1:3, the anthraquinone addition is 0.7% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 100 ℃, continues heat temperature raising to 165 ℃, is incubated 60 minutes.Obtaining hardness after the boiling is permanganate number 26, is equivalent to the slurry of card uncle valency 43.Then the slurry after the boiling is carried out shove.Can be 8% high-hardness pulp with gained concentration after the boiling enters from the inlet of Double screw pulp extruder, carries out shove, and after the extruding black liquor, concentration is that 20% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 22 ° of SR, and the beating degree after the shove is 23 ° of SR.The Baume degrees of the black liquor that shove is extruded is 9 ° of Be ' at 20 ℃, and the residual alkali number in the black liquor is 10g/L.The slurry that comes out from the outlet of press master dilutes with the black liquor that pulp washing the subsequent technique displaces, described black liquor is 4 ° of Be ' at 20 ℃ of Baume degrees, make slurry dense deliver to jump to 2.8% screen, carry out pulp washing according to the method for routine then, regulate the concentration to 18% of starching behind the pulp washing.
Before oxygen delignification, adopt dry pan to discongest, heat this slurry to 80 ℃ then and be transported to the slurry tower slurry.The air that this slurry is got rid of in the slurry through modifier treatment earlier in the slurry tower makes it fluidization, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower, advance the oxygen that adds 20kg slurry per ton before the tower and alkalinity in 4% the aqueous slkali of NaOH, and in pipeline, feed steam and should starch heat temperature raising oven dry stock weight.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate, and addition is 1% of an oven dry stock weight, 95 ℃ of inlet temperatures; pressure 1.2Mpa; stopped 75 minutes, tower top temperature is 105 ℃, and pressure remains 0.4MPa; the delignification rate is 88% in the oxygen delignification process; this slurry is spurted stock tank and dilution, and this moment, the hardness K (permanganate number) of slurry was reduced to 14, with pump the stock pump of dilution was gone into two sections vacuum pulp washing machine washings afterwards.Can obtain a kind of brown stock of straw raw material alkaline cooking preparation, the whiteness of brown stock is 45%ISO, and fracture length is 6.2km, and tearability is 250mN, and folding number is 75 times, and beating degree is 33 ° of SR.。
Embodiment 12
To put into upright steamer through the straw that length behind the conventional dry raw material preparation is about 20-25mm, in steamer, add steaming preparation and carry out boiling, alkali charge in NaOH to 13% of over dry material quantity, liquor ratio is 1:3, the anthraquinone addition is 0.7% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 110 ℃, continues heat temperature raising to 168 ℃, is incubated 60 minutes.Obtaining hardness after the boiling is permanganate number 20, is equivalent to the high-hardness pulp of card uncle valency 31, then the slurry after the boiling is carried out shove.Being 12% high-hardness pulp with gained concentration after the boiling enters from the inlet of reducing single-screw press master, carries out shove, and after the extruding black liquor, concentration is that 26% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 25 ° of SR, and the beating degree after the shove is 26 ° of SR.The Baume degrees of the black liquor that shove is extruded is 9 ° of Be ' at 20 ℃.The content of residual alkali is 10g/L in the black liquor.The slurry that comes out from the outlet of press master dilutes with the black liquor that pulp washing the subsequent technique displaces, described black liquor is 5 ° of Be ' at 20 ℃ of Baume degrees, the slurry of gained is diluted, the concentration to 3% of slurry is delivered to jump and screened, adopt conventional method to carry out pulp washing then, regulate the concentration to 15% of slurry behind the pulp washing.
Heat this slurry to 80 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower, advance the oxygen that adds 20kg slurry per ton before the tower and alkalinity in NaOH to the oven dry stock amount 3.5% aqueous slkali, and in pipeline, feed steam and should starch heat temperature raising.This slurry enters the first oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 90 ℃ of inlet temperatures; pressure 0.9Mpa; stopped 90 minutes; tower top temperature is 104 ℃; pressure remains 0.4MPa; the delignification rate is 92% in the oxygen delignification process, and this slurry is spurted stock tank and dilution, and this moment, the hardness (permanganate number) of slurry was reduced to 13; be equivalent to card uncle valency 17, with pump the stock pump of dilution gone into two sections vacuum pulp washing machine washings afterwards.Can obtain a kind of brown stock of straw raw material alkaline cooking preparation, whiteness is 55%ISO, and fracture length is 7.0km, and tearability is 230mN, and folding number is 85 times, and beating degree is 37 ° of SR.
Embodiment 13
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 20-25mm, in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 15% of over dry material quantity, liquor ratio is 1:3, the anthraquinone addition is 0.7% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 130 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes.Obtaining hardness after the boiling is permanganate number 16, is equivalent to the high-hardness pulp of card uncle valency 24, then the slurry after the boiling is carried out shove.Being 13% high-hardness pulp with gained concentration after the boiling enters from the inlet of Var-nip press, carries out shove, and after the extruding black liquor, concentration is that 32% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 24 ° of SR, and the beating degree after the shove is 25 ° of SR.It is to deliver to jump after 2.5% to screen that slurry is diluted to concentration with 70 ℃ warm water, adopts conventional method to carry out pulp washing then, the concentration to 14% that adjusting is starched behind the pulp washing.
To transfer slurry after dense to be heated to 70 ℃ and be transported to the oxygen delignification reaction tower through the positive displacement middle underflow pump.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for mixing in 3% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 98 ℃ of inlet temperatures; pressure 1.0Mpa stops in 80 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 102 ℃; pressure remains 0.4MPa, and the delignification rate is 88% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 10, was equivalent to card uncle valency 13.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Can obtain a kind of brown stock of straw raw material alkaline cooking preparation, whiteness is 55%ISO, and fracture length is 6.5km, and tearability is 230mN, and folding number is 45 times, and beating degree is 35 ° of SR.
Embodiment 14
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 25-30mm, in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 9% of over dry material quantity, liquor ratio is 1:2, the anthraquinone addition is 0.5% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 100 ℃, continues heat temperature raising to 165 ℃, is incubated 60 minutes.Obtaining hardness after the boiling is permanganate number 28, is equivalent to the high-hardness pulp of card uncle valency 50, then the slurry after the boiling is carried out shove.Being 14% high-hardness pulp with gained concentration after the boiling enters from the inlet of Var-nip press, carries out shove, and after the extruding black liquor, concentration is that 30% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 26 ° of SR, and the beating degree after the shove is 27 ° of SR.The Baume degrees of the black liquor that shove is extruded is 10 ° of Be ' at 20 ℃, and the content of residual alkali is 8g/L in the black liquor.The slurry that comes out from the outlet of press master dilutes with 65 ℃ warm water, make slurry dense deliver to jump to 3% screen, wash with three sections vacuum pulp washing machines then, regulating slurry then dense is 18%, heats this slurry to 80 ℃ and is transported to slurry by conveying worm and manage chute and be transported to the oxygen delignification reaction tower by single rotor formula high density stock pump.The oxygen and the alkalinity that add 25kg slurry per ton in the reaction tower are to mix in the aqueous slkali of NaOH to oven dry stock amount 3.5%; and feeding steam should be starched heat temperature raising in pipeline; this slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate, and addition is 0.6% of an oven dry stock weight, 98 ℃ of inlet temperatures; pressure 1.0Mpa; stopped 85 minutes, tower top temperature is 105 ℃, and pressure remains 0.4MPa.The delignification rate is 91% in the oxygen delignification process, and this slurry is spurted stock tank and dilution, and this moment, the hardness (permanganate number) of slurry was reduced to 14, is equivalent to card uncle valency 19.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Can obtain a kind of brown stock of straw raw material alkaline cooking preparation, whiteness is 40%ISO, and fracture length is 7.6km, and tearability is 260mN, and folding number is 55 times, and beating degree is 32 ° of SR.
Embodiment 15
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 15-20mm, and in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 10% of over dry material quantity, liquor ratio is 1:2, sulphidity is 5%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 110 ℃, continues heat temperature raising to 168 ℃, is incubated 80 minutes.Obtaining hardness after the boiling is permanganate number 23, is equivalent to the high-hardness pulp of card uncle valency 38, then the slurry after the boiling is carried out shove.Being 12% high-hardness pulp with gained concentration after the boiling enters from the inlet of reducing single-screw press master, carries out shove, and after the extruding black liquor, concentration is that 24% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 24 ° of SR, and the beating degree after the shove is 25 ° of SR.Directly dilute then with clear water, make slurry dense deliver to jump to 2.5% screen, wash then.
Adopt defibrator that slurry is discongested before oxygen delignification, regulating slurry concentration then is 20%, heat this slurry to 70 ℃ and through the gear type high density stock pump be transported to the oxygen delignification reaction tower and in pipeline feeding steam should starch heat temperature raising.The oxygen and the alkali charge that add 25kg slurry per ton in the reaction tower are to 3.5% of oven dry stock amount in NaOH; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 100 ℃ of inlet temperatures; pressure 1.1Mpa stops in 75 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 105 ℃; pressure remains 0.5MPa, and the delignification rate is 94% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 14, was equivalent to card uncle valency 20.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Can obtain a kind of brown stock of straw raw material alkaline cooking preparation, whiteness is 47%ISO, and fracture length is 5.8km, and tearability is 275mN, and folding number is 35 times, and beating degree is 36 ° of SR.
Embodiment 16
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 15-20mm, and in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 10% of over dry material quantity, liquor ratio is 1:2, sulphidity is 5%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 120 ℃, continues heat temperature raising to 165 ℃, is incubated 70 minutes.Obtaining hardness after the boiling is permanganate number 25, is equivalent to the high-hardness pulp of card uncle valency 43, then the slurry after the boiling is carried out shove.Being 11% high-hardness pulp with gained concentration after the boiling enters from the inlet of reducing single-screw press master, carries out shove, and after the extruding black liquor, concentration is that 22% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 27 ° of SR, and the beating degree after the shove is 28 ° of SR.
The slurry that comes out from the outlet of press master dilutes with the black liquor that pulp washing the subsequent technique displaces, make slurry dense deliver to jump to 3% screen, pulp washing then, regulating slurry dense is 15%, heats this slurry to 80 ℃ then and is transported to the oxygen delignification reaction tower through the positive displacement high density stock pump.Add the oxygen of 30kg slurry per ton and alkalinity in the reaction tower in 4% the aqueous slkali of NaOH, and in pipeline, feed steam and should starch heat temperature raising the oven dry stock amount.Protective agent is a magnesium sulfate, and addition is 0.8% of an oven dry stock weight, 100 ℃ of inlet temperatures; pressure 0.9Mpa stops in 60 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 108 ℃; pressure remains 0.6MPa, and the delignification rate is 86% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 14, was equivalent to card uncle valency 21.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Can obtain a kind of brown stock of straw raw material alkaline cooking preparation, whiteness is 49%ISO, and fracture length is 6.5km, and tearability is 266mN, and folding number is 80 times, and beating degree is 38 ° of SR.
Embodiment 17
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 15-20mm, and in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 11% of over dry material quantity, liquor ratio is 1:2, sulphidity is 8%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 140 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes.Obtain the slurry that hardness is permanganate number 19 after the boiling, make underflow to 3% deliver to jumping and screen, then pulp washing.
Regulating slurry dense is 12%, heats this slurry to 70 ℃ and is transported to middle underflow pipe by conveying worm then.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry mixed with the oxygen of the 40kg slurry per ton that adds and the NaOH of oven dry stock weight 4% in pipeline before entering reaction tower, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, 100 ℃ of inlet temperatures, pressure 1.2Mpa, stopping in 90 minutes makes this slurry can carry out sufficient delignification reaction, tower top temperature is 105 ℃, pressure remains 0.5MPa, and the delignification rate is 90% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 11, was equivalent to card uncle valency 14.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Chlorine dosage is 5% of an oven dry stock during chlorination, and the concentration of slurry is 3.5%, and the temperature of bleaching is 52 ℃, and the time of bleaching is 50 minutes; The amount that adds NaOH during alkali treatment is an oven dry stock amount 2%, the concentration of slurry is 10%, bleaching temperature is 55 ℃, time is 150 minutes, can obtain a kind of brown stock of straw raw material alkaline cooking preparation, and whiteness is 48%ISO, fracture length is 7.6km, tearability is 230mN, and folding number is 25 times, and beating degree is 36 ° of SR.
Embodiment 18
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 20mm, and in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 10% of over dry material quantity, liquor ratio is 1:2, sulphidity is 8%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 110 ℃, continues heat temperature raising to 173 ℃, is incubated 60 minutes.Obtaining hardness after the boiling is permanganate number 22, is equivalent to the high-hardness pulp of card uncle valency 35, adopts deflaker that high-hardness pulp is discongested then, utilizes three sections vacuum pulp washing machines to carry out pulp washing afterwards, regulates the concentration to 12% of slurry behind the pulp washing again.
Heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkali charge for to mix in the aqueous slkali of NaOH to oven dry stock amount 4%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa stops in 90 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 104 ℃; pressure remains 0.5MPa, and the delignification rate is 86% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 14, was equivalent to card uncle valency 19.5.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Can obtain a kind of brown stock of straw raw material alkaline cooking preparation, whiteness is 52%ISO, and fracture length is 6.7km, and tearability is 260mN, and folding number is 56 times, and beating degree is 32 ° of SR.
Embodiment 19
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 20mm, and add steaming preparation and carry out boiling in rotary spherical digester, in the over dry material quantity, sodium hydroxide concentration 15%, sodium sulfite consumption are 2%, and the anthraquinone consumption is 0.04%, and liquor ratio is 1:3; Feed steam and heat, heat temperature raising carried out little steam bleeding 5 minutes when temperature is 120 ℃, continued heat temperature raising to 55 ℃, was incubated 40 minutes.Obtaining hardness after the boiling is permanganate number 22, is equivalent to the high-hardness pulp of card uncle valency 35, adopts deflaker that high-hardness pulp is discongested then, utilizes three sections vacuum pulp washing machines to carry out pulp washing afterwards, regulates the concentration to 12% of slurry behind the pulp washing again.
Heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkali charge for to mix in the aqueous slkali of NaOH to oven dry stock amount 4%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa stops in 90 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 104 ℃; pressure remains 0.5MPa, and the delignification rate is 86% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 14, was equivalent to card uncle valency 19.5.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Can obtain a kind of brown stock of straw raw material preparation, whiteness is 53%ISO, and fracture length is 6.8km, and tearability is 280mN, and folding number is 90 times, and beating degree is 33 ° of SR.
Embodiment 20
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 20-25mm, and in rotary spherical digester, add steaming preparation and carry out boiling, in the over dry material quantity, sodium hydroxide concentration 11%, the sodium sulfite consumption is 6%, and the anthraquinone consumption is 0.02%, and liquor ratio is 1:4; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 130 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes.Obtaining hardness after the boiling is permanganate number 16, is equivalent to the high-hardness pulp of card uncle valency 24, then the slurry after the boiling is carried out shove.Being 13% high-hardness pulp with gained concentration after the boiling enters from the inlet of Var-nip press, carries out shove, and after the extruding black liquor, concentration is that 32% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 24 ° of SR, and the beating degree after the shove is 25 ° of SR.It is to deliver to jump after 2.5% to screen that slurry is diluted to concentration with 70 ℃ warm water, adopts conventional method to carry out pulp washing then, the concentration to 14% that adjusting is starched behind the pulp washing.
To transfer slurry after dense to be heated to 70 ℃ and be transported to the oxygen delignification reaction tower through the positive displacement middle underflow pump.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for mixing in 3% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 98 ℃ of inlet temperatures; pressure 1.0Mpa stops in 80 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 102 ℃; pressure remains 0.4MPa, and the delignification rate is 88% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 10, was equivalent to card uncle valency 13.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Can obtain a kind of brown stock of straw raw material alkaline cooking preparation, whiteness is 55%ISO, and fracture length is 6.5km, and tearability is 240mN, and folding number is 45 times, and beating degree is 34 ° of SR.
Embodiment 21
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 25-30mm, and in rotary spherical digester, add steaming preparation and carry out boiling, in the over dry material quantity, sodium hydroxide concentration 13%, the sodium sulfite consumption is 4%, and the anthraquinone consumption is 0.08%, and liquor ratio is 1:4; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 100 ℃, continues heat temperature raising to 165 ℃, is incubated 60 minutes.Obtaining hardness after the boiling is permanganate number 18, is equivalent to the high-hardness pulp of card uncle valency 27, then the slurry after the boiling is carried out shove.Being 14% high-hardness pulp with gained concentration after the boiling enters from the inlet of Var-nip press, carries out shove, and after the extruding black liquor, concentration is that 30% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 26 ° of SR, and the beating degree after the shove is 27 ° of SR.The Baume degrees of the black liquor that shove is extruded is 10 ° of Be ' at 20 ℃, and the content of residual alkali is 8g/L in the black liquor.The slurry that comes out from the outlet of press master dilutes with 65 ℃ warm water, make slurry dense deliver to jump to 3% screen, wash with three sections vacuum pulp washing machines then, regulating slurry then dense is 18%, heats this slurry to 80 ℃ and is transported to slurry by conveying worm and manage chute and be transported to the oxygen delignification reaction tower by single rotor formula high density stock pump.The oxygen and the alkalinity that add 25kg slurry per ton in the reaction tower are to mix in the aqueous slkali of NaOH to oven dry stock amount 3.5%; and feeding steam should be starched heat temperature raising in pipeline; this slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate, and addition is 0.6% of an oven dry stock weight, 98 ℃ of inlet temperatures; pressure 1.0Mpa; stopped 85 minutes, tower top temperature is 105 ℃, and pressure remains 0.4MPa.The delignification rate is 91% in the oxygen delignification process, and this slurry is spurted stock tank and dilution, and this moment, the hardness (permanganate number) of slurry was reduced to 14, is equivalent to card uncle valency 19.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Can obtain a kind of brown stock of straw raw material alkaline cooking preparation, whiteness is 48%ISO, and fracture length is 7.0km, and tearability is 260mN, and folding number is 55 times, and beating degree is 34 ° of SR.
What embodiment 22-28 related to is brown stock of a kind of wheat straw raw material Ammonium Sulfite Method boiling preparation and preparation method thereof
Embodiment 22
Wheat straw raw material is adopted in the digester of packing into after the conventional dry raw material preparation, in digester, add cooking liquor, the ammonium sulfite addition is 10% of an over dry material quantity, liquor ratio 1:4, heat temperature raising to 110 ℃ for the first time, insulation is 20 minutes under this temperature, littler steam bleeding 20 minutes, post bake heat up 60 minutes to temperature be 168 ℃, be incubated 75 minutes.The hardness of resulting high-hardness pulp is 22 to be equivalent to card uncle valency 35.5 after the boiling, and being diluted to concentration with rarer black liquor is 2.5-3.5%, and the screening technique through prior art screens as jumping the sieve screening method again, and loss is 0.2-0.5% in the screening.Adopt again that three sections vacuum pulp washing machines wash in the prior art.Obtaining concentration after the washing is 10% high-hardness pulp, heats this slurry to 70 ℃ and is transported to middle underflow pipe by conveying worm then.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 4% the aqueous slkali of NaOH to the oven dry stock amount, and in pipeline, feed steam and should starch heat temperature raising.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock amount; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 100 ℃, and pressure remains 0.6MPa.After finishing dealing with this slurry is spurted stock tank and dilution, obtain described brown stock.The fracture length of described brown stock is 6.5km, and folding strength is 70 times, and tearability is 255mN, and whiteness is 40%ISO, and beating degree is 32 ° of SR.
Embodiment 23
Wheat straw raw material is passed through in the digester of packing into after the dry method routine is got the raw materials ready, in digester, add cooking liquor, the ammonium sulfite addition is 9% of an over dry material quantity, liquor ratio 1:2, heat temperature raising to 110 ℃ for the first time, insulation is 40 minutes under this temperature, littler steam bleeding 25 minutes, post bake heat up 40 minutes to temperature be 165 ℃, be incubated 75 minutes.It is 21 to be equivalent to the high-hardness pulp of card uncle valency 34 that boiling obtains hardness, then high-hardness pulp is sent into the Var-nip press that the extraction black liquor is used in the prior art and carried out shove, obtain concentration after the shove and be 32% high-hardness pulp, after 70 ℃ warm water are diluted to 2.5%, deliver to three sections vacuum pulp washing machines and wash, then the slurry of gained is heated this slurry to 70 ℃ by conveying worm and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 3%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1.2% of an oven dry stock weight; 98 ℃ of inlet temperatures; pressure 1.05Mpa; stop and made this slurry can carry out sufficient delignification reaction in 85 minutes, tower top temperature is 102 ℃, and pressure remains 0.4MPa.After finishing dealing with this slurry is spurted stock tank and dilution, obtain described brown stock.The fracture length of described brown stock is 5.3km, and folding strength is 80 times, and tearability is 220mN, and whiteness is 45%ISO, and beating degree is 38 ° of SR.
Embodiment 24
Wheat straw is packed in the digester, in digester, add cooking liquor, the ammonium sulfite addition is 11% of an over dry material quantity, liquor ratio 1:3, heat temperature raising to 115 ℃ for the first time, insulation is 25 minutes under this temperature, littler steam bleeding 20-30 minute, post bake heat up 30 minutes to temperature be 170 ℃, be incubated 85 minutes.Obtain hardness after the boiling and be 20 and be equivalent to the high-hardness pulp of card uncle valency 31, regulate the concentration to 18% of high-hardness pulp, after be transported in the deflaker and discongest, wash through conventional washing methods again, heat this slurry to 70 ℃ and be transported to middle underflow pipe by conveying worm afterwards.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 35kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 3.5%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1.5% of an oven dry stock weight; 100 ℃ of inlet temperatures; pressure 1.2Mpa; stop and made this slurry can carry out sufficient delignification reaction in 80 minutes, tower top temperature is 105 ℃, and pressure remains 0.6MPa.After finishing dealing with this slurry is spurted stock tank and dilution, obtain described brown stock.The fracture length of described brown stock is 7.2km, and folding strength is 65 times, and tearability is 210mN, and whiteness is 42%ISO, and beating degree is 35 ° of SR.
Embodiment 25
Wheat straw is packed in the digester, in digester, add cooking liquor, the ammonium sulfite addition is 12% of an over dry material quantity, liquor ratio 1:2.5, heat temperature raising to 120 ℃ for the first time, insulation is 20 minutes under this temperature, littler steam bleeding 20-30 minute, post bake heat up 50 minutes to temperature be 173 ℃, be incubated 60 minutes.Obtain hardness after the boiling and be 24 high-hardness pulps that are equivalent to card uncle valency 40, then high-hardness pulp is sent into the reducing single-screw press master that the extraction black liquor is used in the prior art and carried out shove, obtain concentration after the shove and be 20% high-hardness pulp, wash with conventional washing methods such as pressure washer again, after be transported in the mill fluffer and discongest, heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 4% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 100 degree, and pressure remains 0.6MPa.After finishing dealing with this slurry is spurted stock tank and dilution, obtain described brown stock.The fracture length of described brown stock is 7.8km, and folding strength is 60 times, and tearability is 230mN, and whiteness is 41%ISO, and beating degree is 34 ° of SR.
Embodiment 26
Wheat straw is packed in the digester, in digester, add cooking liquor, the ammonium sulfite addition is 13% of an over dry material quantity, liquor ratio 1:3.5, heat temperature raising to 110 ℃ for the first time, insulation is 40 minutes under this temperature, littler steam bleeding 20-30 minute, post bake heat up 45 minutes to temperature be 166 ℃, be incubated 90 minutes.Obtain hardness after the boiling and be 16 high-hardness pulps that are equivalent to card uncle valency 24, be transported in the deflaker and discongest, again high-hardness pulp is sent into the Var-nip press that the extraction black liquor is used in the prior art and carried out shove, obtain concentration after the shove and be 32% high-hardness pulp, regulate concentration to 15% with 60 ℃ of clear water again, heat this slurry to 70 ℃ and be transported to middle underflow pipe by conveying worm then.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 2%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 90 minutes, tower top temperature is 100 ℃, and pressure remains 0.6MPa.After finishing dealing with this slurry is spurted stock tank and dilution, obtain described brown stock.The fracture length of described brown stock is 5.4km, and folding strength is 56 times, and tearability is 240mN, and whiteness is 45%ISO, and beating degree is 33 ° of SR.
Embodiment 27
After getting the raw materials ready, the hammer mill that utilizes ore dressing to use wheat straw packs in the digester, in digester, add cooking liquor, the ammonium sulfite addition is 9.5% of an over dry material quantity, liquor ratio 1:4, heat temperature raising to 110 ℃ for the first time, insulation is 20 minutes under this temperature, littler steam bleeding 20-30 minute, post bake heat up 40 minutes to temperature be 168 ℃, be incubated 90 minutes.The hardness that obtains after the boiling is 25 to be equivalent to the high-hardness pulp of card uncle valency 42, deliver to the Var-nip press that conventional extraction black liquor uses again and carry out shove, the slurry that comes out from press master is diluted to the concentration to 2.5% of slurry with clear water, deliver to jump to sieve and carry out thick pulp screen choosing, jumping the sieve loss is 0.2%, remove impurity by the high concentration scummer again, loss 0.1%, the slurry that will obtain after will removing the gred again enters the horizontal belt wash engine and washs, slurry concentration during washing is 3.0%, the slurry concentration of coming out from wash engine is 9%, remain on 70 ℃ in the washing process, be transported in the deflaker again and discongest, heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for to mix in 2.5% aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 100 degree, and pressure remains 0.6MPa.After finishing dealing with this slurry is spurted stock tank and dilution, obtain described brown stock.The fracture length of described brown stock is 5.0km, and folding strength is 25 times, and tearability is 180mN, and whiteness is 34%ISO, and beating degree is 36 ° of SR.
Embodiment 28
The hammer mill that utilizes ore dressing to use wheat straw carries out dry raw material preparation and packs in the digester, in digester, add cooking liquor, the ammonium sulfite addition is 9% of an over dry material quantity, liquor ratio 1:4, heat temperature raising to 110 ℃ for the first time, insulation is 20 minutes under this temperature, littler steam bleeding 30 minutes, post bake heat up 30 minutes to temperature be 165 ℃, be incubated 65 minutes.Obtain hardness after the boiling and be 28 and be equivalent to card uncle valency 50 high-hardness pulps, deliver to the reducing single-screw press master that conventional extraction black liquor uses again and carry out shove, the slurry that comes out from press master is diluted to the concentration to 3.0% of slurry with rare black liquor, deliver to jump to sieve and carry out thick pulp screen choosing, jumping the sieve loss is 0.2%, remove impurity by the high concentration scummer again, loss 0.1%, the slurry that will obtain after will removing the gred again enters the horizontal belt wash engine and washs, slurry concentration during washing is 3.0%, the slurry concentration of coming out from wash engine is 9%, keep 68-70 ℃ in the washing process, be transported in the deflaker again and discongest,, heat this slurry to 70 ℃ and be transported to middle underflow pipe by conveying worm then through conventional method washing.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 3.5%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 102 ℃ of inlet temperatures; pressure 1.12Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 104 degree, and pressure remains 0.5MPa.After finishing dealing with this slurry is spurted stock tank and dilution, obtain described brown stock.The fracture length of described brown stock is 5.2km, and folding strength is 35 times, and tearability is 255mN, and whiteness is 37%ISO, and beating degree is 37 ° of SR.
What embodiment 29-42 related to is the low brightness pulp of straw alkaline process preparation
Embodiment 29
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 30mm, in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 12% of over dry material quantity, liquor ratio is 1:2, the anthraquinone addition is 0.8% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 125 ℃, continues heat temperature raising to 165 ℃, is incubated 90 minutes.Obtaining hardness after the boiling is permanganate number 18, is equivalent to the high-hardness pulp of card uncle valency 27.Then the slurry after the boiling is carried out shove.Can be 15% high-hardness pulp with gained concentration after the boiling enters from the inlet of Var-nip press, carries out shove, and after the extruding black liquor, concentration is that 30% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 28 ° of SR, and the beating degree after the shove is 29 ° of SR.The Baume degrees of the black liquor that shove is extruded is 7 ° of Be ' at 20 ℃, and the concentration of the residual alkali in the black liquor is 8g/L.
The slurry that comes out from the outlet of press master dilutes with 60 ℃ warm water, make slurry dense deliver to jump to 2.5% screen, utilize three sections vacuum pulp washing machines to carry out pulp washing then, regulate the concentration to 10% of starching behind the pulp washing.The gained slurry adopts deflaker to discongest before oxygen delignification.Heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 4% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa stops and made this slurry can carry out sufficient delignification reaction in 75 minutes, and tower top temperature is 100 ℃; pressure remains 0.5MPa, and the delignification rate is 86% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness of slurry was reduced to permanganate number 11, was equivalent to card uncle valency 14.6.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Carry out chlorination and alkali treatment again, wherein chlorine dosage is 3% of an oven dry stock during chlorination, and the concentration of slurry is 3.2%, and the temperature of bleaching is 55 ℃, and the time of bleaching is 45 minutes; Alkali charge is to oven dry stock amount 2.5% in NaOH during alkali treatment, the concentration of slurry is 12%, bleaching temperature is 50 ℃, and the time is 120 minutes, can obtain a kind of low brightness pulp of straw raw material alkaline cooking preparation, it is characterized in that, the whiteness of described low brightness pulp is 54%ISO, and fracture length is 4.8km, and tearability is 260mN, folding number is 90 times, and beating degree is 36 ° of SR.
Embodiment 30
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 15-20mm, in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 9% of over dry material quantity, liquor ratio is 1:4, the anthraquinone addition is 0.5% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 120 ℃, continues heat temperature raising to 165 ℃, is incubated 70 minutes.Obtaining hardness after the boiling is permanganate number 24, is equivalent to the slurry of card uncle valency 39.Then the slurry after the boiling is carried out shove.Can be 10% high-hardness pulp with gained concentration after the boiling enters from the inlet of single-screw press master, carries out shove, and after the extruding black liquor, concentration is that 25% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 24 ° of SR, and the beating degree after the shove is 25 ° of SR.The Baume degrees of the black liquor that shove is extruded is 8 ° of Be ' at 20 ℃, and the content of the residual alkali in the black liquor is 9g/L.The slurry that comes out from the outlet of press master dilutes with the black liquor that pulp washing the subsequent technique displaces, and described black liquor is 6 ° of Be ' at 20 ℃ of Baume degrees, make slurry dense deliver to jump to 3% screen, adopt conventional method to carry out pulp washing then, regulate again starch dense to 12%.
The gained slurry can adopt kneading machine to discongest before oxygen delignification, heats this slurry to 70 ℃ and is transported to the oxygen delignification reaction tower by the positive displacement middle underflow pump.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 2% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, 100 ℃ of inlet temperatures, pressure 1.2Mpa, stopping in 90 minutes makes this slurry can carry out sufficient delignification reaction, tower top temperature is 105 ℃, pressure remains 0.2MPa, and the delignification rate is 90% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 14, was equivalent to card uncle valency 19.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Carry out chlorination and alkali treatment again, chlorine dosage is 4% of an oven dry stock during chlorination, and the concentration of slurry is 3%, and the temperature of bleaching is 55 ℃, and the time of bleaching is 50 minutes; Alkali charge is to oven dry stock amount 2% in NaOH during alkali treatment, the concentration of slurry is 12%, bleaching temperature is 52 ℃, and the time is 100 minutes, can obtain a kind of low brightness pulp of straw raw material alkaline cooking preparation, it is characterized in that, the whiteness of described low brightness pulp is 50%ISO, and fracture length is 5.2km, and tearability is 265mN, folding number is 80 times, and beating degree is 34 ° of SR.
Embodiment 31
To put into upright steamer through the straw that length behind the conventional dry raw material preparation is about 20-25mm, in steamer, add steaming preparation and carry out boiling, alkali charge in NaOH to 10% of over dry material quantity, liquor ratio is 1:3, the anthraquinone addition is 0.7% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 100 ℃, continues heat temperature raising to 165 ℃, is incubated 60 minutes.Obtaining hardness after the boiling is permanganate number 26, is equivalent to the slurry of card uncle valency 43.Then the slurry after the boiling is carried out shove.Can be 8% high-hardness pulp with gained concentration after the boiling enters from the inlet of Double screw pulp extruder, carries out shove, and after the extruding black liquor, concentration is that 20% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 22 ° of SR, and the beating degree after the shove is 23 ° of SR.The Baume degrees of the black liquor that shove is extruded is 9 ° of Be ' at 20 ℃, and the residual alkali number in the black liquor is 8g/L.The slurry that comes out from the outlet of press master dilutes with the black liquor that pulp washing the subsequent technique displaces, described black liquor is 4 ° of Be ' at 20 ℃ of Baume degrees, make slurry dense deliver to jump to 2.8% screen, carry out pulp washing according to the method for routine then, regulate the concentration to 18% of starching behind the pulp washing.
Before oxygen delignification, adopt dry pan to discongest, heat this slurry to 80 ℃ then and be transported to the slurry tower slurry.The air that this slurry is got rid of in the slurry through modifier treatment earlier in the slurry tower makes it fluidization, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower, advance the oxygen that adds 20kg slurry per ton before the tower and alkalinity in 4% the aqueous slkali of NaOH, and in pipeline, feed steam and should starch heat temperature raising oven dry stock weight.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate, and addition is 1% of an oven dry stock weight, 95 ℃ of inlet temperatures; pressure 1.2Mpa; stopped 75 minutes, tower top temperature is 105 ℃, and pressure remains 0.4MPa; the delignification rate is 88% in the oxygen delignification process; this slurry is spurted stock tank and dilution, and this moment, the hardness K (permanganate number) of slurry was reduced to 14, with pump the stock pump of dilution was gone into two sections vacuum pulp washing machine washings afterwards.Carry out chlorination and alkali treatment again.Chlorine dosage is 5% of an oven dry stock during chlorination, and the concentration of slurry is 3%, and the temperature of bleaching is 52 ℃, and the time of bleaching is 60 minutes; The amount that adds NaOH during alkali treatment is an oven dry stock amount 2%, the concentration of slurry is 12%, bleaching temperature is 55 ℃, time is 100 minutes, can obtain a kind of low brightness pulp of straw raw material alkaline cooking preparation, and whiteness is 49%ISO, fracture length is 5.5km, tearability is 285mN, and folding number is 100 times, and beating degree is 34 ° of SR.
Embodiment 32
To put into upright steamer through the straw that length behind the conventional dry raw material preparation is about 20-25mm, in steamer, add steaming preparation and carry out boiling, alkali charge in NaOH to 13% of over dry material quantity, liquor ratio is 1:3, the anthraquinone addition is 0.7% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 110 ℃, continues heat temperature raising to 168 ℃, is incubated 60 minutes.Obtaining hardness after the boiling is permanganate number 20, is equivalent to the high-hardness pulp of card uncle valency 31, then the slurry after the boiling is carried out shove.Being 12% high-hardness pulp with gained concentration after the boiling enters from the inlet of reducing single-screw press master, carries out shove, and after the extruding black liquor, concentration is that 26% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 25 ° of SR, and the beating degree after the shove is 26 ° of SR.The Baume degrees of the black liquor that shove is extruded is 9 ° of Be ' at 20 ℃, and the content of residual alkali is 10g/L in the black liquor.The slurry that comes out from the outlet of press master dilutes with the black liquor that pulp washing the subsequent technique displaces, described black liquor is 5 ° of Be ' at 20 ℃ of Baume degrees, the slurry of gained is diluted, the concentration to 3% of slurry is delivered to jump and screened, adopt conventional method to carry out pulp washing then, regulate the concentration to 15% of slurry behind the pulp washing.
Heat this slurry to 80 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower, advance the oxygen that adds 20kg slurry per ton before the tower and alkalinity in NaOH to the oven dry stock amount 3.5% aqueous slkali, and in pipeline, feed steam and should starch heat temperature raising.This slurry enters the first oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 90 ℃ of inlet temperatures; pressure 0.9Mpa; stopped 90 minutes; tower top temperature is 104 ℃; pressure remains 0.4MPa; the delignification rate is 92% in the oxygen delignification process, and this slurry is spurted stock tank and dilution, and this moment, the hardness (permanganate number) of slurry was reduced to 11; be equivalent to card uncle valency 13, with pump the stock pump of dilution gone into two sections vacuum pulp washing machine washings afterwards.Carry out chlorination and alkali treatment again, chlorine dosage is 5% of an oven dry stock during chlorination, and the concentration of slurry is 3.2%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 60 minutes; Alkali charge is an oven dry stock amount 2.5 during alkali treatment, the concentration of slurry is 10%, bleaching temperature is 55 ℃, time is 120 minutes, can obtain a kind of low brightness pulp of straw raw material alkaline cooking preparation, and whiteness is 57%ISO, fracture length is 6.5km, tearability is 255mN, and folding number is 110 times, and beating degree is 37 ° of SR.
Embodiment 33
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 20-25mm, in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 15% of over dry material quantity, liquor ratio is 1:3, the anthraquinone addition is 0.7% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 130 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes.Obtaining hardness after the boiling is permanganate number 16, is equivalent to the high-hardness pulp of card uncle valency 24, then the slurry after the boiling is carried out shove.Being 13% high-hardness pulp with gained concentration after the boiling enters from the inlet of Var-nip press, carries out shove, and after the extruding black liquor, concentration is that 32% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 24 ° of SR, and the beating degree after the shove is 25 ° of SR.It is to deliver to jump after 2.5% to screen that slurry is diluted to concentration with 70 ℃ warm water, adopts conventional method to carry out pulp washing then, the concentration to 14% that adjusting is starched behind the pulp washing.
To transfer slurry after dense to be heated to 70 ℃ and be transported to the oxygen delignification reaction tower through the positive displacement middle underflow pump.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for mixing in 3% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 98 ℃ of inlet temperatures; pressure 1.0Mpa stops in 80 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 102 ℃; pressure remains 0.4MPa, and the delignification rate is 88% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 10, was equivalent to card uncle valency 13, with pump the stock pump of dilution was gone into two sections vacuum pulp washing machine washings afterwards.Carry out chlorination and alkali treatment again, chlorine dosage is 4% of an oven dry stock during chlorination, and the concentration of slurry is 3.5%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 50 minutes; Alkali charge is to oven dry stock amount 3% in NaOH during alkali treatment, the concentration of slurry is 10%, bleaching temperature is 52 ℃, time is 150 minutes, can obtain a kind of low brightness pulp of straw raw material alkaline cooking preparation, and whiteness is 60%ISO, fracture length is 5.8km, tearability is 260mN, and folding number is 76 times, and beating degree is 35 ° of SR.
Embodiment 34
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 25-30mm, in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 9% of over dry material quantity, liquor ratio is 1:2, the anthraquinone addition is 0.5% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 100 ℃, continues heat temperature raising to 165 ℃, is incubated 60 minutes.Obtaining hardness after the boiling is permanganate number 28, is equivalent to the high-hardness pulp of card uncle valency 50, then the slurry after the boiling is carried out shove.Being 14% high-hardness pulp with gained concentration after the boiling enters from the inlet of Var-nip press, carries out shove, and after the extruding black liquor, concentration is that 30% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 23 ° of SR, and the beating degree after the shove is 24 ° of SR.The Baume degrees of the black liquor that shove is extruded is 8 ° of Be ' at 20 ℃, and the content of residual alkali is 8g/L in the black liquor.The slurry that comes out from the outlet of press master dilutes with 65 ℃ warm water, make slurry dense deliver to jump to 3% screen, wash with three sections vacuum pulp washing machines then, regulating slurry then dense is 18%, heats this slurry to 80 ℃ and is transported to slurry by conveying worm and manage chute and be transported to the oxygen delignification reaction tower by single rotor formula high density stock pump.The oxygen and the alkalinity that add 25kg slurry per ton in the reaction tower are to mix in the aqueous slkali of NaOH to oven dry stock amount 3.5%; and feeding steam should be starched heat temperature raising in pipeline; this slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate, and addition is 0.6% of an oven dry stock weight, 98 ℃ of inlet temperatures; pressure 1.0Mpa; stopped 85 minutes, tower top temperature is 105 ℃, and pressure remains 0.4MPa.The delignification rate is 95% in the oxygen delignification process, and this slurry is spurted stock tank and dilution, and this moment, the hardness (permanganate number) of slurry was reduced to 14, is equivalent to card uncle valency 19.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Carry out chlorination and alkali treatment again, chlorine dosage is 3% of an oven dry stock during chlorination, and the concentration of slurry is 3.5%, and the temperature of bleaching is 52 ℃, and the time of bleaching is 45 minutes; The amount that adds NaOH during alkali treatment is an oven dry stock amount 3%, the concentration of slurry is 11%, bleaching temperature is 50 ℃, time is 150 minutes, can obtain a kind of low brightness pulp of straw raw material alkaline cooking preparation, and whiteness is 45%ISO, fracture length is 6.8km, tearability is 250mN, and folding number is 90 times, and beating degree is 37 ° of SR.
Embodiment 35
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 15-20mm, and in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 10% of over dry material quantity, liquor ratio is 1:2, sulphidity is 5%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 110 ℃, continues heat temperature raising to 168 ℃, is incubated 80 minutes.Obtaining hardness after the boiling is permanganate number 23, is equivalent to the high-hardness pulp of card uncle valency 38, then the slurry after the boiling is carried out shove.Being 12% high-hardness pulp with gained concentration after the boiling enters from the inlet of reducing single-screw press master, carries out shove, and after the extruding black liquor, concentration is that 24% slurry is discharged from the outlet of press master.The beating degree of this high-hardness pulp before carrying out shove is 24 ° of SR, and the beating degree after the shove is 25 ° of SR.Directly dilute then with clear water, make slurry dense deliver to jump to 2.5% screen, wash then.
Adopt defibrator that slurry is discongested before oxygen delignification, regulating slurry concentration then is 20%, heat this slurry to 70 ℃ and through the gear type high density stock pump be transported to the oxygen delignification reaction tower and in pipeline feeding steam should starch heat temperature raising.The oxygen and the alkali charge that add 25kg slurry per ton in the reaction tower are to 3.5% of oven dry stock amount in NaOH; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 100 ℃ of inlet temperatures; pressure 1.1Mpa stops in 75 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 105 ℃; pressure remains 0.5MPa, and the delignification rate is 94% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 13, was equivalent to card uncle valency 17.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, carry out chlorination and alkali treatment again, chlorine dosage is 3% of an oven dry stock during chlorination, and the concentration of slurry is 3%, and the temperature of bleaching is 52 ℃, and the time of bleaching is 50 minutes; Alkali charge is to oven dry stock amount 3% in NaOH during alkali treatment, the concentration of slurry is 12%, bleaching temperature is 50 ℃, time is 100 minutes, can obtain a kind of low brightness pulp of straw raw material alkaline cooking preparation, and whiteness is 50%ISO, fracture length is 7.0km, tearability is 265mN, and folding number is 70 times, and beating degree is 32 ° of SR.
Embodiment 36
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 20mm, and in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 10% of over dry material quantity, liquor ratio is 1:2, sulphidity is 8%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 110 ℃, continues heat temperature raising to 173 ℃, is incubated 60 minutes.Obtaining hardness after the boiling is permanganate number 22, is equivalent to the high-hardness pulp of card uncle valency 35, adopts deflaker that high-hardness pulp is discongested then, utilizes three sections vacuum pulp washing machines to carry out pulp washing afterwards, regulates the concentration to 12% of slurry behind the pulp washing again.
Heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkali charge for to mix in the aqueous slkali of NaOH to oven dry stock amount 4%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa stops in 90 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 104 ℃; pressure remains 0.5MPa, and the delignification rate is 86% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 13, was equivalent to card uncle valency 17.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Chlorine dosage is 4% of an oven dry stock during chlorination, and the concentration of slurry is 3.2%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 45 minutes; Alkali charge is to oven dry stock amount 3% in NaOH during alkali treatment, the concentration of slurry is 12%, bleaching temperature is 52 ℃, time is 120 minutes, can obtain a kind of low brightness pulp of straw raw material alkaline cooking preparation, and whiteness is 57%ISO, fracture length is 6.5km, tearability is 240mN, and folding number is 30 times, and beating degree is 32 ° of SR.
Embodiment 37
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 20mm, and in rotary spherical digester, add steaming preparation and carry out boiling, alkali charge in NaOH to 10% of over dry material quantity, liquor ratio is 1:2, sulphidity is 8%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 110 ℃, continues heat temperature raising to 173 ℃, is incubated 60 minutes.Obtaining hardness after the boiling is permanganate number 22, is equivalent to the high-hardness pulp of card uncle valency 35, adopts deflaker that high-hardness pulp is discongested then, utilizes three sections vacuum pulp washing machines to carry out pulp washing afterwards, regulates the concentration to 12% of slurry behind the pulp washing again.
Heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkali charge for to mix in the aqueous slkali of NaOH to oven dry stock amount 4%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa stops in 90 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 104 ℃; pressure remains 0.5MPa, and the delignification rate is 86% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 14, was equivalent to card uncle valency 19.5.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Can obtain a kind of brown stock of straw raw material alkaline cooking preparation, whiteness is 52%ISO, and fracture length is 6.7km, and tearability is 280mN, and folding number is 56 times, and beating degree is 32 ° of SR.
Embodiment 38
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 20mm, and add steaming preparation and carry out boiling in rotary spherical digester, in the over dry material quantity, sodium hydroxide concentration 14%, sodium sulfite consumption are 5%, and the anthraquinone consumption is 0.04%, and liquor ratio is 1:4; Feed steam and heat, heat temperature raising carried out little steam bleeding 5 minutes when temperature is 120 ℃, continued heat temperature raising to 165 ℃, was incubated 60 minutes.Obtaining hardness after the boiling is permanganate number 22, is equivalent to the high-hardness pulp of card uncle valency 35, adopts deflaker that high-hardness pulp is discongested then, utilizes three sections vacuum pulp washing machines to carry out pulp washing afterwards, regulates the concentration to 12% of slurry behind the pulp washing again.
Heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkali charge for to mix in the aqueous slkali of NaOH to oven dry stock amount 4%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa stops in 90 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 104 ℃; pressure remains 0.5MPa, and the delignification rate is 86% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 14, was equivalent to card uncle valency 19.5.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Can obtain a kind of brown stock of straw raw material preparation, whiteness is 53%ISO, and fracture length is 6.8km, and tearability is 285mN, and folding number is 58 times, and beating degree is 31 ° of SR.
Embodiment 39
Wheat straw is packed in the digester, in digester, add cooking liquor, in the over dry material quantity, sodium hydroxide concentration 11%, the sodium sulfite consumption is 6%, the anthraquinone consumption is 0.08%, and liquor ratio is 1:4, for the first time heat temperature raising to 110 ℃, insulation is 30 minutes under this temperature, again little steam bleeding 30 minutes, post bake heat up 25 minutes to temperature be 163 ℃, be incubated 75 minutes.Obtain hardness after the boiling and be 21 and be equivalent to the high-hardness pulp of card uncle valency 33, wash through conventional method again, regulate the concentration to 18% of high-hardness pulp again, after be transported in the deflaker and discongest, the beating degree of the Straw Pulp before discongesting is 20 ° of SR, can see by naked eyes, after breaking into two with one's hands through the Straw Pulp of discongesting operation, there is not bar-shaped fiber, the beating degree of the Straw Pulp after discongesting is 22 ° of SR, wash through conventional washing methods again, heat this slurry to 70 ℃ and be transported to middle underflow pipe by conveying worm afterwards.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 35kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 3.5%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1.5% of an oven dry stock weight; 100 ℃ of inlet temperatures; pressure 1.2Mpa; stop 75 clocks and make this slurry can carry out sufficient delignification reaction, tower top temperature is 105 ℃, and pressure remains 0.6MPa.After finishing dealing with this slurry is spurted stock tank and dilution, obtain described brown stock.The fracture length of described brown stock is 6.0km, and folding strength is 55 times, and tearability is 220mN, and whiteness is 40%ISO, and beating degree is 37 ° of SR.
Embodiment 40
Wheat straw is packed in the digester, in digester, add cooking liquor, in the over dry material quantity, sodium hydroxide concentration 13%, the sodium sulfite consumption is 4%, the anthraquinone consumption is 0.02%, and liquor ratio is 1:3, for the first time heat temperature raising to 120 ℃, insulation is 20 minutes under this temperature, again little steam bleeding 30 minutes, post bake heat up 55 minutes to temperature be 160 ℃, be incubated 90 minutes.Obtain hardness after the boiling and be 19 high-hardness pulps that are equivalent to card uncle valency 29, then high-hardness pulp is sent into the reducing single-screw press master that the extraction black liquor is used in the prior art and carried out shove, obtain concentration after the shove and be 20% high-hardness pulp, wash with conventional washing methods such as pressure washer again, after be transported in the mill fluffer and discongest, the beating degree of the Straw Pulp before discongesting is 22 ° of SR, the beating degree of the Straw Pulp after discongesting is 24 ° of SR, heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 4% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 100 ℃, and pressure remains 0.4MPa.After finishing dealing with this slurry is spurted stock tank and dilution, obtain described brown stock.The fracture length of described brown stock is 5.4km, and folding strength is 72 times, and tearability is 250mN, and whiteness is 48%ISO, and beating degree is 36 ° of SR.
Embodiment 41
To put into rotary spherical digester through the straw that length behind the conventional dry raw material preparation is about 15mm, and add steaming preparation and carry out boiling in rotary spherical digester, in the over dry material quantity, sodium hydroxide concentration 11%, sodium sulfite consumption are 6%, and the anthraquinone consumption is 0.02%, and liquor ratio is 1:3; Feed steam and heat, heat temperature raising insulation 20 minutes when temperature is 120 ℃ was carried out little steam bleeding 10 minutes, continued heat temperature raising to 160 ℃, was incubated 90 minutes.Obtaining hardness after the boiling is permanganate number 22, is equivalent to the high-hardness pulp of card uncle valency 35, adopts deflaker that high-hardness pulp is discongested then, utilizes three sections vacuum pulp washing machines to carry out pulp washing afterwards, regulates the concentration to 12% of slurry behind the pulp washing again.
Heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkali charge for to mix in the aqueous slkali of NaOH to oven dry stock amount 4%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa stops in 90 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 104 ℃; pressure remains 0.5MPa, and the delignification rate is 86% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 14, was equivalent to card uncle valency 19.5.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Carry out chlorination and alkali treatment again, chlorine dosage is 5% of an oven dry stock during chlorination, and the concentration of slurry is 3.2%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 60 minutes; Alkali charge is an oven dry stock amount 2.5% during alkali treatment, and the concentration of slurry is 10%, and bleaching temperature is 55 ℃, and the time is 120 minutes, can obtain described low brightness pulp, whiteness is 54%ISO, and fracture length is 6.9km, tearability is 250mN, and folding number is 59 times, and beating degree is 33 ° of SR.
Embodiment 42
To pack in the digester through the straw behind the conventional dry raw material preparation, and add cooking liquor in digester, in the over dry material quantity, sodium hydroxide concentration 15%, sodium sulfite consumption are 2%, and the anthraquinone consumption is 0.08%, and liquor ratio is 1:4; , heat temperature raising to 100 ℃ for the first time, insulation is 40 minutes under this temperature, littler steam bleeding 25 minutes, post bake heat up 45 minutes to temperature be 165 ℃, be incubated 60 minutes.Obtain hardness after the boiling and be 25 high-hardness pulps that are equivalent to card uncle valency 43, be transported in the deflaker and discongest, then high-hardness pulp is sent into the Var-nip press that the extraction black liquor is used in the prior art and carried out shove, obtain concentration after the shove and be 32% high-hardness pulp, regulate concentration to 2.5% with rare black liquor again, wash through conventional washing methods after slagging-off, the slurry that goes out pulp washing is dense to be adjusted to 15%. again, heats this slurry to 70 ℃ and is transported to middle underflow pipe by conveying worm then.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock weight 3%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 60 minutes, tower top temperature is 100 ℃, and pressure remains 0.4MPa.After finishing dealing with this slurry is spurted stock tank and dilution, carry out chlorination and alkali treatment again, chlorine dosage is 4% of an oven dry stock during chlorination, and the concentration of slurry is 3.2%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 45 minutes; Alkali charge is to oven dry stock amount 3% in NaOH during alkali treatment, the concentration of slurry is 12%, bleaching temperature is 52 ℃, time is 120 minutes, can obtain described low brightness pulp, and its fracture length is 4.8km, folding strength is 65 times, tearability is 255mN, and whiteness is 48%ISO, and beating degree is 35 ° of SR.
What enforcement 43-53 related to is that the wheat straw alkaline process prepares low brightness pulp
Embodiment 43
Wheat straw raw material is adopted in the digester of packing into after the conventional dry raw material preparation, in digester, add cooking liquor, alkali charge is to 10% of over dry material quantity in NaOH, liquor ratio 1:4, the anthraquinone addition is 0.5% of an over dry raw material, for the first time heat temperature raising to 110 ℃, insulation is 20 minutes under this temperature, again little steam bleeding 25 minutes, post bake heat up 45 minutes to temperature be 165 ℃, be incubated 90 minutes.The hardness 22 of resultant high-hardness pulp is equivalent to card uncle valency 31 after the boiling, and being diluted to concentration with rarer black liquor is 3.5%, and the screening technique through prior art screens as jumping the sieve screening method again, and loss is 0.2-0.5% in the screening.Adopt three sections vacuum pulp washing machines of the prior art to wash again.Obtaining concentration after the washing is 10% high-hardness pulp, heats this slurry to 70 ℃ and is transported to middle underflow pipe by conveying worm then.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 4% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock amount; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 100 degree, and pressure remains 0.6MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, carry out two sections bleachings again, chlorine dosage is 2.5% of an oven dry stock, the concentration of slurry is 3%, and the temperature of bleaching is 52 ℃, and the time of bleaching is 50 minutes, alkali treatment is: the addition of NaOH is 2% of an oven dry stock amount, the concentration of slurry is 10%, and bleaching temperature is 52 ℃, and the time is 120 minutes.The fracture length of described low brightness pulp is 7.0km, and folding strength is 55 times, and tearability is 235mN, and whiteness is 60%ISO, and beating degree is 33 ° of SR.
Embodiment 44
Wheat straw raw material is passed through in the digester of packing into after the dry method routine is got the raw materials ready, in digester, add cooking liquor, alkali charge is to 9% of over dry material quantity in NaOH, liquor ratio 1:2, the anthraquinone addition is 0.8% of an over dry material quantity, for the first time heat temperature raising to 120 ℃, insulation is 40 minutes under this temperature, again little steam bleeding 20 minutes, post bake heat up 45 minutes to temperature be 165 ℃, be incubated 90 minutes.It is 24 to be equivalent to the high-hardness pulp of card uncle valency 41 that boiling obtains hardness, then high-hardness pulp is sent into the Var-nip press that the extraction black liquor is used in the prior art and carried out shove, obtain concentration after the shove and be 32% high-hardness pulp, be diluted to the washing of delivering to three sections vacuum pulp washing machines after 2.5% through black liquor, slurry concentration is 13%, then the slurry of gained heated this slurry to 70 ℃ and is transported to middle underflow pipe by conveying worm.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity in 3% the aqueous slkali of NaOH to the oven dry stock amount, and in pipeline, feed steam and should starch heat temperature raising.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1.2% of an oven dry stock weight; 98 ℃ of inlet temperatures; pressure 1.05Mpa; stop and made this slurry can carry out sufficient delignification reaction in 85 minutes, tower top temperature is 102 ℃, and pressure remains 0.4MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, carry out two sections bleachings again, chlorine dosage is 3% of an oven dry stock, the concentration of slurry is 3.2%, and the temperature of bleaching is 55 ℃, and the time of bleaching is 60 minutes, alkali treatment is: alkali charge is to oven dry stock amount 4% in NaOH, the concentration of slurry is 12%, and bleaching temperature is 50 ℃, and the time is 110 minutes.The fracture length of described low brightness pulp is 5.5km, and folding strength is 40 times, and tearability is 190mN, and whiteness is 55%ISO, and beating degree is 38 ° of SR.
Embodiment 45
Utilize the method for getting the raw materials ready of the present invention to carry out packing into behind the dry raw material preparation in the digester wheat straw, in digester, add cooking liquor, alkali charge is to 11% of over dry material quantity in NaOH, liquor ratio 1:3, the anthraquinone addition is 0.7% of an over dry material quantity, for the first time heat temperature raising to 130 ℃, insulation is 25 minutes under this temperature, again little steam bleeding 20 minutes, post bake heat up 50 minutes to temperature be 170 ℃, be incubated 80 minutes.Obtain hardness after the boiling and be 20 and be equivalent to the high-hardness pulp of card uncle valency 31, regulate the concentration to 18% of high-hardness pulp, after be transported in the deflaker and discongest, the beating degree of the Straw Pulp before discongesting is 20 ° of SR, can see by naked eyes, after breaking into two with one's hands through the Straw Pulp of discongesting operation, there is not bar-shaped fiber, the beating degree of the Straw Pulp after discongesting is 22 ° of SR, washs through conventional washing methods again, heats this slurry to 70 ℃ and is transported to middle underflow pipe by conveying worm afterwards.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 35kg slurry per ton that adds and alkali charge for to mix in the aqueous slkali of NaOH to oven dry stock weight 3.5%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1.5% of an oven dry stock weight; 100 ℃ of inlet temperatures; pressure 1.2Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 105 ℃, and pressure remains 0.6MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, carry out two sections bleachings again, chlorine dosage is 3% of an oven dry stock, the concentration of slurry is 3.5%, and the temperature of bleaching is 52 ℃, and the time of bleaching is 55 minutes, alkali treatment is: alkali charge is to oven dry stock amount 3.5% in NaOH, the concentration of slurry is 11.5%, and bleaching temperature is 53 ℃, and the time is 140 minutes.The fracture length of described low brightness pulp is 6.5km, and folding strength is 60 times, and tearability is 200mN, and whiteness is 58%ISO, and beating degree is 35 ° of SR.
Embodiment 46
Wheat straw is packed in the digester, in digester, add cooking liquor, alkali charge is to 11% of over dry material quantity in NaOH, liquor ratio 1:2.5, sulphidity are 5%, for the first time heat temperature raising to 140 ℃, insulation is 20 minutes under this temperature, again little steam bleeding 25 minutes, post bake heat up 60 minutes to temperature be 173 ℃, be incubated 60 minutes.Obtain hardness after the boiling and be 23 high-hardness pulps that are equivalent to card uncle valency 37, then high-hardness pulp is sent into the reducing single-screw press master that the extraction black liquor is used in the prior art and carried out shove, obtain concentration after the shove and be 20% high-hardness pulp, wash with conventional washing methods such as pressure washer again, after be transported in the mill fluffer and discongest, heat this slurry to 70 ℃ by conveying worm again and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 4% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 100 degree, and pressure remains 0.6MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, carry out two sections bleachings again, chlorine dosage is 2.5% of an oven dry stock amount, the concentration of slurry is 3.2%, and the temperature of bleaching is 55 ℃, and the time of bleaching is 45 minutes, alkali treatment is: alkali charge is to oven dry stock amount 3% in NaOH, the concentration of slurry is 10%, and bleaching temperature is 55 ℃, and the time is 120 minutes.The fracture length of described low brightness pulp is 6.0km, and folding strength is 30 times, and tearability is 180mN, and whiteness is 57%ISO, and beating degree is 35 ° of SR.
Embodiment 47
Will be in the wheat straw that the method for getting the raw materials ready of the present invention is carried out dry raw material preparation be packed digester into, in digester, add cooking liquor, alkali charge is to 8% of over dry material quantity in NaOH, sulphidity is 8%, liquor ratio 1:3.5, for the first time heat temperature raising to 110 ℃, insulation is 40 minutes under this temperature, again little steam bleeding 30 minutes, post bake heat up 45 minutes to temperature be 165 ℃, be incubated 90 minutes.Obtaining hardness after the boiling is 25, the high-hardness pulp that is equivalent to card uncle valency 43, be transported in the deflaker and discongest, again high-hardness pulp is sent into the Var-nip press that the extraction black liquor is used in the prior art and carried out shove, obtain concentration after the shove and be 32% high-hardness pulp, be that 60 ℃ clear water is regulated concentration to 15% with temperature again, heat this slurry to 70 ℃ and be transported to middle underflow pipe by conveying worm then.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 3.5% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 100 degree, and pressure remains 0.6MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, carry out two sections bleachings again, chlorine dosage is 3% of an oven dry stock during chlorination, the concentration of slurry is 3%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 50 minutes, alkali treatment is: alkali charge is to oven dry stock amount 2% in NaOH, the concentration of slurry is 12%, and bleaching temperature is 55 ℃, and the time is 120 minutes.The fracture length of described low brightness pulp is 5.8km, and folding strength is 20 times, and tearability is 220mN, and whiteness is 56%ISO, and beating degree is 37 ° of SR.
Embodiment 48
Wheat straw is packed in the digester, in digester, add cooking liquor, alkali charge is to 15% of over dry material quantity in NaOH, liquor ratio 1:4, the anthraquinone addition is 0.5% of an over dry raw material, for the first time heat temperature raising to 110 ℃, insulation is 20 minutes under this temperature, again little steam bleeding 30 minutes, post bake heat up 50 minutes to temperature be 160 ℃, be incubated 90 minutes.The hardness that obtains after the boiling is 16 to be equivalent to the high-hardness pulp of card uncle valency 24, deliver to the single-screw press master that conventional extraction black liquor uses again and carry out shove, the slurry that comes out from press master is diluted to the concentration to 2.8% of slurry with rarer black liquor, deliver to jump to sieve and carry out thick pulp screen choosing, jumping the sieve loss is 0.2%, remove impurity by the high concentration scummer again, loss 0.1%, the slurry that will obtain after will removing the gred again enters the horizontal belt wash engine and washs, slurry concentration during washing is 3.0%, the slurry concentration of coming out from wash engine is 9%, keeps 68-70 ℃ in the washing process, is transported in the deflaker and discongests, the beating degree of the Straw Pulp before discongesting is 26 ° of SR, can see after breaking into two with one's hands through the Straw Pulp of discongesting operation, not having bar-shaped fiber by naked eyes, the beating degree of the Straw Pulp after discongesting is 28 ° of SR, heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 2.5% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 100 ℃, and pressure remains 0.6MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, bleaching chlorine dosage again is 2.5% of oven dry stock, the concentration of slurry is 3.5%, the temperature of bleaching is 55 ℃, the time of bleaching is 60 minutes, and alkali treatment is: the amount that adds NaOH is an oven dry stock amount 3.5%, and the concentration of slurry is 10%, bleaching temperature is 54 ℃, and the time is 130 minutes.The fracture length of described low brightness pulp is 6.2km, and folding strength is 25 times, and tearability is 230mN, and whiteness is 58%ISO, and beating degree is 34.5 ° of SR.
Embodiment 49
Wheat straw behind the art methods dry raw material preparation is packed in the digester, in digester, add cooking liquor, alkali charge is to 12% of over dry material quantity in NaOH, liquor ratio 1:2, the anthraquinone addition is 0.6% of an over dry material quantity, for the first time heat temperature raising to 110 ℃, insulation is 20 minutes under this temperature, again little steam bleeding 30 minutes, post bake heat up 50 minutes to temperature be 168 ℃, be incubated 90 minutes.Obtaining hardness after the boiling is 18, the high-hardness pulp that is equivalent to card uncle valency 27, deliver to the reducing single-screw press master that conventional extraction black liquor uses again and carry out shove, the slurry that comes out from press master is diluted to the concentration to 3.0% of slurry with rarer black liquor, deliver to jump to sieve and carry out thick pulp screen choosing, jumping the sieve loss is 0.2%, remove impurity by the high concentration scummer again, loss 0.1%, the slurry that will obtain after will removing the gred again enters the horizontal belt wash engine and washs, slurry concentration during washing is 3.0%, and the slurry concentration of coming out from wash engine is 9%, keeps 70 ℃ in the washing process, be transported in the deflaker again and discongest, through washing, transferring the concentration that obtains starching after dense is 10%, heats this slurry to 70 ℃ and is transported to middle underflow pipe by conveying worm then.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 2% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 102 ℃ of inlet temperatures; pressure 1.12Mpa; stop and made this slurry can carry out sufficient delignification reaction in 80 minutes, tower top temperature is 104 ℃, and pressure remains 0.5MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, carry out two sections bleachings again, chlorine dosage is 2.5% of an oven dry stock, the concentration of slurry is 3%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 45 minutes, alkali treatment is: alkali charge is to oven dry stock amount 2% in NaOH, the concentration of slurry is 10%, and bleaching temperature is 50 ℃, and the time is 150 minutes.The fracture length of described low brightness pulp is 7.2km, and folding strength is 38 times, and tearability is 240mN, and whiteness is 60%ISO, and beating degree is 33 ° of SR.
Embodiment 50
Wheat straw raw material is passed through in the digester of packing into after the dry method routine is got the raw materials ready, in digester, add cooking liquor, alkali charge is to 9% of over dry material quantity in NaOH, liquor ratio 1:2, the anthraquinone addition is 0.6% of an over dry material quantity, for the first time heat temperature raising to 115 ℃, insulation is 40 minutes under this temperature, again little steam bleeding 20 minutes, post bake heat up 45 minutes to temperature be 165 ℃, be incubated 60 minutes.It is 28 to be equivalent to the high-hardness pulp of card uncle valency 50 that boiling obtains hardness, then high-hardness pulp is sent into the Var-nip press that the extraction black liquor is used in the prior art and carried out shove, obtain concentration after the shove and be 32% high-hardness pulp, be diluted to the washing of delivering to three sections vacuum pulp washing machines after 2.5% through 50 ℃ of warm water, slurry concentration is 13%, then the slurry of gained heated this slurry to 70 ℃ and is transported to middle underflow pipe by conveying worm.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity in 3% the aqueous slkali of NaOH to the oven dry stock amount, and in pipeline, feed steam and should starch heat temperature raising.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1.2% of an oven dry stock weight; 98 ℃ of inlet temperatures; pressure 1.05MPa; stop and made this slurry can carry out sufficient delignification reaction in 85 minutes, tower top temperature is 102 ℃, and pressure remains 0.4MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, carry out two sections bleachings again, chlorine dosage is 3% of an oven dry stock, the concentration of slurry is 3.2%, and the temperature of bleaching is 55 ℃, and the time of bleaching is 60 minutes, alkali treatment is: alkali charge is to oven dry stock amount 4% in NaOH, the concentration of slurry is 12%, and bleaching temperature is 50 ℃, and the time is 110 minutes.The fracture length of described low brightness pulp is 6.8km, and folding strength is 50 times, and tearability is 220mN, and whiteness is 55%ISO, and beating degree is 38 ° of SR.
Embodiment 51
To put into rotary spherical digester through the wheat straw that length behind the conventional dry raw material preparation is about 15mm, and add steaming preparation and carry out boiling in rotary spherical digester, in the over dry material quantity, sodium hydroxide concentration 14%, sodium sulfite consumption are 6%, and the anthraquinone consumption is 0.03%, and liquor ratio is 1:3; Feed steam and heat, heat temperature raising carried out little steam bleeding 10 minutes when temperature is 120 ℃, continued heat temperature raising to 155 ℃, was incubated 60 minutes.Obtaining hardness after the boiling is permanganate number 22, is equivalent to the high-hardness pulp of card uncle valency 35, adopts deflaker that high-hardness pulp is discongested then, utilizes three sections vacuum pulp washing machines to carry out pulp washing afterwards, regulates the concentration to 12% of slurry behind the pulp washing again.
Heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkali charge for to mix in the aqueous slkali of NaOH to oven dry stock amount 4%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa stops in 90 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 104 ℃; pressure remains 0.5MPa, and the delignification rate is 86% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 14, was equivalent to card uncle valency 19.5.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Carry out two sections bleachings again, chlorine dosage is 3% of an oven dry stock during chlorination, the concentration of slurry is 3%, the temperature of bleaching is 50 ℃, the bleaching time be 50 minutes, alkali treatment is: alkali charge in NaOH to oven dry stock amount 2%, the concentration of slurry is 12%, bleaching temperature is 55 ℃, and the time is 120 minutes.Can obtain a kind of low brightness pulp of wheat straw raw material preparation, whiteness is 55%ISO, and fracture length is 6.9km, and tearability is 200mN, and folding number is 59 times, and beating degree is 33 ° of SR.
Embodiment 52
To put into rotary spherical digester through the wheat straw that length behind the conventional dry raw material preparation is about 15mm, and add steaming preparation and carry out boiling in rotary spherical digester, in the over dry material quantity, sodium hydroxide concentration 11%, sodium sulfite consumption are 6%, and the anthraquinone consumption is 0.02%, and liquor ratio is 1:3; Feed steam and heat, heat temperature raising insulation 20 minutes when temperature is 120 ℃ was carried out little steam bleeding 10 minutes, continued heat temperature raising to 160 ℃, was incubated 90 minutes.Obtaining hardness after the boiling is permanganate number 22, is equivalent to the high-hardness pulp of card uncle valency 35, adopts deflaker that high-hardness pulp is discongested then, utilizes three sections vacuum pulp washing machines to carry out pulp washing afterwards, regulates the concentration to 12% of slurry behind the pulp washing again.
Heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkali charge for to mix in the aqueous slkali of NaOH to oven dry stock amount 4%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.5% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa stops in 90 minutes and makes this slurry can carry out sufficient delignification reaction, and tower top temperature is 104 ℃; pressure remains 0.5MPa, and the delignification rate is 86% in the oxygen delignification process.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness (permanganate number) of slurry was reduced to 14, was equivalent to card uncle valency 19.5.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards.Carry out chlorination and alkali treatment again, chlorine dosage is 5% of an oven dry stock during chlorination, and the concentration of slurry is 3.2%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 60 minutes; Alkali charge is an oven dry stock amount 2.5% during alkali treatment, and the concentration of slurry is 10%, and bleaching temperature is 55 ℃, and the time is 120 minutes, can obtain described low brightness pulp, whiteness is 55%ISO, and fracture length is 6.9km, tearability is 230mN, and folding number is 60 times, and beating degree is 33 ° of SR.
Embodiment 53
To pack in the digester through the wheat straw behind the conventional dry raw material preparation, and add cooking liquor in digester, in the over dry material quantity, sodium hydroxide concentration 15%, sodium sulfite consumption are 2%, and the anthraquinone consumption is 0.08%, and liquor ratio is 1:4; , heat temperature raising to 100 ℃ for the first time, insulation is 40 minutes under this temperature, littler steam bleeding 25 minutes, post bake heat up 45 minutes to temperature be 165 ℃, be incubated 60 minutes.Obtain hardness after the boiling and be 25 high-hardness pulps that are equivalent to card uncle valency 43, be transported in the deflaker and discongest, then high-hardness pulp is sent into the Var-nip press that the extraction black liquor is used in the prior art and carried out shove, obtain concentration after the shove and be 32% high-hardness pulp, regulate concentration to 2.5% with rare black liquor again, wash through conventional washing methods after slagging-off, the slurry that goes out pulp washing is dense to be adjusted to 15%. again, heats this slurry to 70 ℃ and is transported to middle underflow pipe by conveying worm then.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock weight 3%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 60 minutes, tower top temperature is 100 ℃, and pressure remains 0.4MPa.After finishing dealing with this slurry is spurted stock tank and dilution, carry out chlorination and alkali treatment again, chlorine dosage is 4% of an oven dry stock during chlorination, and the concentration of slurry is 3.2%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 45 minutes; Alkali charge is to oven dry stock amount 3% in NaOH during alkali treatment, the concentration of slurry is 12%, bleaching temperature is 52 ℃, time is 120 minutes, can obtain described low brightness pulp, and its fracture length is 5.8km, folding strength is 65 times, tearability is 240mN, and whiteness is 57%ISO, and beating degree is 35 ° of SR.
That embodiment 54-70 relates to is the preparation method of high-hardness pulp.
Embodiment 54
Through the process of the straw behind dry raw material preparation dipping screw machine, in the dipping screw machine, add the dipping soup, wherein alkali charge is in NaOH and to 16% of over dry straw amount, send into rotary spherical digester then, the anthraquinone addition is 0.6% of an over dry material quantity, liquor ratio 1:3, straw fill back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 100 ℃, and insulation is 25 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 165 ℃, be incubated 55 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 20 is equivalent to card uncle valency 32, and the pH value is 11 during boiling end, and the residual alkali concn in the black liquor is 15g/l.The yield of prepared high-hardness pulp is 60%.
Embodiment 55
To send into rotary spherical digester through the wheat straw that hammer mill carries out behind the dry raw material preparation, add cooking liquor in rotary spherical digester, wherein to 18% of over dry material quantity, the anthraquinone addition is 0.7% of an over dry material quantity to alkali charge in NaOH, liquor ratio 1:4, wheat straw is filled back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 110 ℃, and insulation is 20 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 168 ℃, be incubated 40 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 18 is equivalent to card uncle valency 30, and the pH value is 12 during boiling end, and the residual alkali concn in the black liquor is 16g/l.The yield of prepared high-hardness pulp is 62%.
Embodiment 56
Through the process of the straw behind dry raw material preparation dipping screw machine, in the dipping screw machine, add the dipping soup, wherein alkali charge is 20% in NaOH to over dry straw amount, hybrid infusion, send into rotary spherical digester then, the anthraquinone addition is 0.8% of an over dry material quantity, and liquor ratio 1:2.5, straw fill back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 120 ℃, and insulation is 25 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 173 ℃, be incubated 35 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 16 is equivalent to card uncle valency 23, and the pH value is 12.5 during boiling end, and the residual alkali concn in the black liquor is 18g/l.The yield of described high-hardness pulp is 64%.
Embodiment 57
To send into rotary spherical digester through the cotton stalk that hammer mill carries out behind the dry raw material preparation, in rotary spherical digester, add cooking liquor, alkali charge in NaOH to over dry material quantity 25%, the anthraquinone addition is 0.8% of an over dry material quantity, liquor ratio 1:3, cotton stalk fill back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 100 ℃, and insulation is 20 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 165 ℃, be incubated 55 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 25 is equivalent to card uncle valency 40, and the pH value is 13 during boiling end, and the residual alkali concn in the black liquor is 13.5g/l.The yield of described high-hardness pulp is 58%.
Embodiment 58
Wheat straw after the process hammer mill is got the raw materials ready is through the dipping screw machine, in the dipping screw machine 4% dipping soup hybrid infusion in NaOH to over dry wheat straw amount with alkali charge, send into rotary spherical digester then, adding adds ammonium sulfite solution to over dry material quantity 15% in the rotary spherical digester to the over dry material quantity, liquor ratio 1:4, wheat straw is filled back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 110 ℃, and insulation is 25 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 168 ℃, be incubated 55 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 18 is equivalent to card uncle valency 30, and the pH value is 12 during boiling end, and the residual ammonium concentration in the black liquor is 8.5g/l.The yield of described high-hardness pulp is 63%.
Embodiment 59
Through the cotton stalk process dipping screw machine behind the dry raw material preparation, in the dipping screw machine 4% dipping soup hybrid infusion in NaOH to the cotton stalk amount of over dry with alkali charge, send into rotary spherical digester then, in rotary spherical digester, add cooking liquor, wherein the consumption of ammonium sulfite is to over dry material quantity 18%, liquor ratio 1:2.5, cotton stalk fill back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 120 ℃, and insulation is 20 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 173 ℃, be incubated 45 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 16 is equivalent to card uncle valency 24, and the pH value is 12 during boiling end, and the residual ammonium concentration in the black liquor is 12g/l.The yield of described high-hardness pulp is 66%.
Embodiment 60
Send into upright steamer through the wheat straw behind the dry raw material preparation, add steaming preparation, wherein the ammonium sulfite consumption is to over dry material quantity 20%, liquor ratio 1:3, and wheat straw is filled back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 100 ℃, and insulation is 18 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 165 ℃, be incubated 45 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 25 is equivalent to card uncle valency 44, and the pH value is 12.5 during boiling end, and the residual ammonium concentration in the black liquor is 15g/l.The yield of described high-hardness pulp is 65%.
Embodiment 61
Be 1:1 proportioning process dipping screw machine through cotton stalk behind the dry raw material preparation and wheat straw by mass ratio, in the dipping screw machine with alkali charge for being 4% dipping soup hybrid infusion to the over dry material quantity in NaOH, send into rotary spherical digester then, in rotary spherical digester, add steaming preparation, wherein the ammonium sulfite consumption is to over dry material quantity 25%, liquor ratio 1:3, raw material fill back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 100 ℃, and insulation is 25 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 165 ℃, be incubated 35 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 23 is equivalent to card uncle valency 38, and the pH value is 12.5 during boiling end, and the residual ammonium concentration in the black liquor is 9.6g/l.The yield of described high-hardness pulp is 67%.
Embodiment 62
Through the process of the straw behind dry raw material preparation dipping screw machine, in the dipping screw machine with alkali charge for being 13% dipping soup hybrid infusion to over dry straw amount in NaOH, send into rotary spherical digester then, sulphidity is 5%, liquor ratio 1:3, straw fill back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 100 ℃, and insulation is 30 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 165 ℃, be incubated 45 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 28 is equivalent to card uncle valency 50, and the pH value is 11 during boiling end, and the residual alkali concn in the black liquor is 12g/l.The yield of described high-hardness pulp is 61%.
Embodiment 63
Through the process of the wheat straw behind dry raw material preparation dipping screw machine, be 17% maceration extract hybrid infusion in NaOH to over dry wheat straw amount with alkali charge in the dipping screw machine, send into rotary spherical digester then, sulphidity is 8%, liquor ratio 1:4, wheat straw is filled back rotary spherical digester idle running 15 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 110 ℃, and insulation is 20 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 168 ℃, be incubated 55 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 19 is equivalent to card uncle valency 30.5, and the pH value is 12 during boiling end, and the residual alkali concn in the black liquor is 12g/l.
Embodiment 64
Through the process of the reed behind dry raw material preparation dipping screw machine, in the dipping screw machine with the sodium hydroxide solution and the black liquor mixed liquor hybrid infusion that to over dry reed amount are 4%, send into rotary spherical digester then, add steaming preparation, wherein alkali charge is to over dry material quantity 21% in NaOH, sulphidity is 10%, liquor ratio 1:2.5, and reed is filled back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 140 ℃, and insulation is 40 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 173 ℃, be incubated 90 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 17 is equivalent to card uncle valency 26, and the pH value is 12 during boiling end, and the residual alkali concn in the black liquor is 14g/l.
Embodiment 65
Bagasse behind the dry raw material preparation is sent into rotary spherical digester, adds cooking liquor, wherein alkali charge in NaOH to over dry material quantity 25%, sulphidity is 15%, liquor ratio 1:3, bagasse fill back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 120 ℃, and insulation is 20 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 165 ℃, be incubated 40 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 26 is equivalent to card uncle valency 44, and the pH value is 12.5 during boiling end, and the residual alkali concn in the black liquor is 13.5g/l.
Embodiment 66
Through wheat straw behind the dry raw material preparation and straw process dipping screw machine, wherein the mass ratio of wheat straw and straw is 2:1, in the dipping screw machine with alkali charge for being 4% dipping soup hybrid infusion to over dry wheat straw and straw amount in NaOH, send into rotary spherical digester then, adding in NaOH to over dry material quantity 23% cooking liquor, sulphidity is 15%, and liquor ratio 1:3, wheat straw straw fill back rotary spherical digester idle running 23 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 115 ℃, and insulation is 20 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 165 ℃, be incubated 43 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 26 is equivalent to card uncle valency 45, and the pH value is 12.5 during boiling end, and the residual alkali concn in the black liquor is 13.5g/l.
Embodiment 67
Through the wheat straw behind the dry and wet stock preparation, wheat straw and cotton stalk process feeding serew, the mass ratio of three kinds of raw materials is 1:1:1, enter continuously cooking Guan Zhongyu alkali charge for steaming mixed to the cooking liquor of over dry material quantity 25% in NaOH, the anthraquinone addition is 0.8% of an over dry material quantity, liquor ratio 1:3, logical steam is heated to 110 ℃, be incubated 20 minutes, heated up 30 minutes, after the little steam bleeding, be warming up to 165 ℃, be incubated 40 minutes; Before spurting, in the intervalve of continuous steamer, add black liquor dilute control starch concentration 8-12%, keep 0.75MPa to spurt continuously simultaneously, this moment, the hardness of slurry was that permanganate number 24 is equivalent to card uncle valency 42, the pH value is 11.5 during boiling end, and the residual alkali concn in the black liquor is 11.5g/l.
Embodiment 68
Send into rotary spherical digester through the reed behind the dry raw material preparation, toward rotary spherical digester in, add cooking liquor, wherein alkali charge in NaOH to 22% of over dry material quantity, sulphidity is 15%, liquor ratio 1:3, reed is filled the back rotary spherical digester and dallied 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 115 ℃, and insulation is 15 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 165 ℃, be incubated 55 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 26 is equivalent to card uncle valency 46, and the pH value is 12.5 during boiling end, and the residual alkali concn in the black liquor is 13.5g/l.
Embodiment 69
Through reed behind the dry raw material preparation and wheat straw is that 1:3 mixes through the dipping screw machine with the mass ratio, the mass ratio of reed and wheat straw is 1:1, the dipping screw machine in alkali charge be 4% maceration extract hybrid infusion in NaOH to over dry reed and wheat straw mixed material amount, send into rotary spherical digester then, adding alkali charge is in the cooking liquor of NaOH to over dry material quantity 17%, sulphidity is 8%, liquor ratio 1:3, and reed and wheat straw mix fills back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 115 ℃, and insulation is 20 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 165 ℃, be incubated 60 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 26 is equivalent to card uncle valency 45, and the pH value is 12.5 during boiling end, and the residual alkali concn in the black liquor is 13.5g/l.
Embodiment 70
Through reed, wheat straw and straw behind the dry raw material preparation is 1:1:1 with the mass ratio, send into rotary spherical digester and carry out the Arbiso process boiling, wherein the mass ratio of reed, wheat straw and straw is 1:1:1, add total acid 6%, the cooking liquor of combined acid 3.0%, reed, wheat straw and straw mix fills back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 115 ℃, and insulation is 15 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 165 ℃, be incubated 55 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 26 is equivalent to card uncle valency 45.
That embodiment 71-91 relates to is the preparation method of bleach chemical pulp
Embodiment 71
Wheat straw raw material is removed leaf, the fringe in the forage, the part of going rotten, length is the 300-500mm wheat straw raw material, and to be 0.8m/s with the rate of feeding by belt conveyor enter from the inlet of hammer mill, the rotating speed of described hammer mill is 500rpm, through after cutting off the rubbing processing, length was that the wheat straw raw material of 20-40mm is discharged from the outlet of hammer mill when raw material entered hammer mill.Described hammer mill is the hammer mill of ore dressing or bark in the prior art.The wheat straw raw material of discharging from hammer mill enters in the cyclone dust removal machine, is 30000m at air quantity 3/ h, blast carry out dust removal process under the condition of 200mm water column.The wheat straw raw material that comes out from dust removal machine enters in the drum sieve and screens, drum sieve rotating speed 19r/min during screening, and the inclination angle is 8 °.Described drum sieve is the double-layer cylinder screen that plays the screening effect in the prior art in the getting the raw materials ready in making grass pulp.At last, the wheat straw raw material that comes out from the discharging opening of drum sieve enters and carries out boiling in the boiling vessel.The method edulcoration rate of getting the raw materials ready of the present invention reaches 90%.
With the boiling of the process of the wheat straw after getting the raw materials ready ammonium sulfite, pre-preg is carried out in the spiral macerator, alkali charge is to oven dry stock amount 4% in NaOH during pre-preg, liquor ratio is 1:4, temperature is 80 ℃, time is 40 minutes, then the resulting raw material of pre-preg is sent in the boiling vessel, adds steaming preparation, wherein the ammonium sulfite consumption is 14% of an over dry material quantity, liquor ratio 1:4, heat temperature raising to 140 ℃ for the first time, insulation is 90 minutes under this temperature, again little steam bleeding 20-30 minute, post bake heat up 40 minutes to temperature be 168 ℃, be incubated 120 minutes, it is 15 slurry that boiling obtains hardness afterwards.The slurry adjusting concentration to 10% that obtains after the boiling is sent into reducing single-screw press master carry out shove, obtain 25% slurry, utilize three sections vacuum pulp washing machines to wash then, slurry after the washing is discongested in deflaker, heat this slurry to 70 ℃ by conveying worm again and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 4%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock amount; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 100 ℃, and pressure remains 0.6MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, carry out two sections bleachings again, chlorine dosage is 2.5% of an oven dry stock, the concentration of slurry is 3%, and the temperature of bleaching is 52 ℃, and the time of bleaching is 60 minutes, alkali treatment is: alkali charge is to 2% of oven dry stock amount in NaOH, the concentration of slurry is 10%, and bleaching temperature is 52 ℃, and the time is 120 minutes.Can obtain whiteness is 82%ISO, 6500 meters of fracture lengths, the high-quality dogstail slurry that folding strength is 45 times.
Embodiment 72
Straw raw material is removed leaf, the fringe in the forage, the part of going rotten, length is the 500-800mm straw raw material, and to be 0.6m/s with the rate of feeding by belt conveyor enter from the inlet of hammer mill, the rotating speed of described hammer mill is 600rpm, after process when raw material enters hammer mill was cut off the rubbing processing, length was that the straw raw material of 30-50mm is discharged from the outlet of hammer mill.Described hammer mill is the hammer mill that ore dressing or bark are used in the prior art.The straw raw material of discharging from hammer mill enters in the cyclone dust removal machine, is 35000m at air quantity 3/ h, blast carry out dust removal process under the condition of 220mm water column.The straw raw material that comes out from dust removal machine enters in the drum sieve and screens, drum sieve rotating speed 20r/min during screening, and the inclination angle is 10 °.Described drum sieve is the double-layer cylinder screen that plays the screening effect in the prior art in the getting the raw materials ready in making grass pulp.The square sieve aperture 30x30mm of the nexine sieve plate of drum sieve, the diameter 4-6mm of outer sieve plate sieve aperture.At last, the straw raw material that comes out from the discharging opening of drum sieve enters and carries out boiling in the boiling vessel.Adopt this method to carry out the dry raw material preparation edulcoration rate and reach 92%.
With the straw process caustic soda-anthraquinone boiling of getting the raw materials ready, being specially the caustic soda addition is 13% of over dry material quantity, the anthraquinone addition is 0.7% of an over dry material quantity, liquor ratio 1:4, heat temperature raising to 140 ℃ for the first time, insulation is 90 minutes under this temperature, littler steam bleeding 20-30 minute, for the second time heat temperature raising 30 minutes to temperature is 170 ℃, is incubated 90 minutes.Obtain hardness after the boiling and be 13 slurry, regulating and obtaining concentration after the concentration is 12% slurry, after sending into Var-nip press and carrying out shove, black liquor is extruded, obtain concentration and be 25% slurry, then the slurry of gained is regulated concentration to 12% with clear water, heat this slurry to 70 ℃ and be transported to middle underflow pipe by conveying worm again.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for mixing in 3% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1.2% of an oven dry stock weight; 98 ℃ of inlet temperatures; pressure 1.05Mpa; stop and made this slurry can carry out sufficient delignification reaction in 85 minutes, tower top temperature is 102 ℃, and pressure remains 0.4MPa.After finishing dealing with this slurry being spurted stock tank also dilutes.The gained slurry is carried out two sections bleachings, chlorine dosage is 2.8% of an oven dry stock, the concentration of slurry is 3.2%, the temperature of bleaching is 55 ℃, the bleaching time be 45 minutes, alkali treatment is: alkali charge in NaOH to oven dry stock amount 4%, the concentration of slurry is 12%, bleaching temperature is 50 ℃, and the time is 120 minutes.Can obtain whiteness is 74%ISO, 5500 meters of fracture lengths, the high-quality dogstail slurry that folding strength is 35 times.
Embodiment 73
After wheat straw and reed mixed according to 1:1 through the ammonium sulfite boiling, in rotary spherical digester, carry out, add steaming preparation, wherein the consumption of ammonium sulfite is to over dry material quantity 16%, liquor ratio 1:3, for the first time heat temperature raising to 140 ℃, insulation is 120 minutes under this temperature, again little steam bleeding 20-30 minute, for the second time heat temperature raising 30 minutes to temperature was 168 ℃, is incubated 150 minutes.Obtain hardness after the boiling and be 12 slurry, will starch and carry out shove through reducing single-screw press master after regulating concentration to 12%, obtain concentration after the shove and be 20% slurry, wash with three sections vacuum pulp washing machines again.Slurry after the washing is sent in the kneading machine and is discongested, and carries out oxygen delignification again.This slurry before entering the oxygen delignification reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 3%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 0.2% of an oven dry stock weight; this slurry before entering reaction tower in pipeline with the oxygen of the 35kg slurry per ton that adds and alkalinity for mixing in 3.5% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1.5% of an oven dry stock weight; 100 ℃ of inlet temperatures; pressure 1.2Mpa; stop and made this slurry can carry out sufficient delignification reaction in 60 minutes, tower top temperature is 105 ℃, and pressure remains 0.6MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, carry out two sections bleachings again, chlorine dosage is 3% of an oven dry stock, the concentration of slurry is 3.5%, and the temperature of bleaching is 52 ℃, and the time of bleaching is 55 minutes, alkali treatment is: alkali charge is an oven dry stock amount 3.5%, the concentration of slurry is 11.5%, and bleaching temperature is 53 ℃, and the time is 140 minutes.Can obtain whiteness is 80%ISO, 7000 meters of fracture lengths, the high-quality dogstail slurry that folding strength is 50 times.
Embodiment 74
Be the cotton stalk raw material of 400-700mm being 0.5m/s with the rate of feeding by belt conveyor with length enters from the inlet of hammer mill, the rotating speed of described hammer mill is 700rpm, after process when raw material enters hammer mill was cut off and crumpled and handles, length was that the cotton stalk raw material of 25-35mm is discharged from the outlet of hammer mill.Described hammer mill is the hammer mill that bark is pulverized usefulness in the prior art.The cotton stalk raw material of discharging from hammer mill enters in the cyclone dust removal machine, is 32000m at air quantity 3/ h, blast carry out dust removal process under the condition of 210mm water column.The cotton stalk raw material that comes out from dust removal machine enters in the drum sieve and screens, drum sieve rotating speed 23r/min during screening, and the inclination angle is 12 °.Described drum sieve is the double-layer cylinder screen that plays the screening effect in the prior art in the getting the raw materials ready in making grass pulp.The nexine sieve plate sieve diameter of drum sieve is 30mm, and the diameter 4-6mm of outer sieve plate sieve aperture is last, and the cotton stalk raw material that comes out from the discharging opening of drum sieve enters and carries out boiling in the boiling vessel.Adopt the method to carry out the dry raw material preparation edulcoration rate and reach 91.5%.
Through the cotton stalk process dipping screw machine behind the dry raw material preparation, in the dipping screw machine with alkalinity in NaOH being 4% sodium hydroxide solution mixed liquor hybrid infusion to the cotton stalk amount of over dry, send into rotary spherical digester then, adding adds steaming preparation to the over dry material quantity in rotary spherical digester, wherein the consumption of ammonium sulfite is to over dry material quantity 20%, liquor ratio 1:2.5, cotton stalk fill back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 130 ℃, and insulation is 100 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 165 ℃, be incubated 110 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was permanganate number 13.The intact gained slurry afterwards of boiling is regulated concentration to 15%, send into Var-nip press again and carry out shove, obtain concentration and be 32% slurry, in three sections vacuum pulp washing machines, carry out pulp washing with warm water dilution back, adopt dry pan to discongest after the pulp washing, heat this slurry to 76 ℃ then and be transported to the oxygen delignification reaction tower through the positive displacement middle underflow pump.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 4% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.Protective agent is a magnesium sulfate, and addition is 1% of an oven dry stock weight, 95 ℃ of inlet temperatures, and pressure 0.9Mpa stops and made this slurry can carry out sufficient delignification reaction in 75 minutes, and tower top temperature is 100 degree, and pressure remains 0.6MPa.After finishing dealing with this slurry is spurted stock tank and dilution, carry out two sections bleachings again, chlorine dosage is 3% of an oven dry stock, the concentration of slurry is 3.5%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 60 minutes, alkali treatment is: alkali charge is to oven dry stock amount 4% in NaOH, the concentration of slurry is 12%, and bleaching temperature is 50 ℃, and the time is after bleaching in 150 minutes finishes, the whiteness of paper pulp is 72%ISO, fracture length is 8000m, and folding strength is 70 times, is a kind of high-quality slurry.
Embodiment 75
Straw is carried out anthraquinone-soda cooking: add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 14%, wherein liquor ratio is 1:2, the anthraquinone addition is 0.6% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 100 minutes when temperature is 120 ℃, continues heat temperature raising to 160 ℃, is incubated 90 minutes, obtains the slurry that hardness is permanganate number 15.Earlier carry out shove with Var-nip press, through shove black liquor is extruded, impurity in the black liquor is also discharged together in company with black liquor simultaneously, slurry with gained washs with three sections suction washers afterwards, utilize defibrator to discongest again, heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 4% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 100 degree, and pressure remains 0.6MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, carry out two sections bleachings again, chlorine dosage is 3% of an oven dry stock, the concentration of slurry is 3%, and the temperature of bleaching is 55 ℃, and the time of bleaching is 50 minutes, alkali treatment is: alkali charge is to oven dry stock amount 4% in NaOH, the concentration of slurry is 12%, and bleaching temperature is 55 ℃, and the time is 120 minutes.The whiteness of resulting bleach chemical pulp is 75%ISO, and fracture length is 5200m, and folding strength 30 times is a kind of high-quality slurry.
Embodiment 76
Be 600-800mm reed raw material being 0.9m/s with the rate of feeding by belt conveyor with length enters from the inlet of hammer mill, the rotating speed of described hammer mill is 800rpm, after process when raw material enters hammer mill was cut off the rubbing processing, length was that the reed raw material of 35-50mm is discharged from the outlet of hammer mill.Described hammer mill is the hammer mill that ore dressing is used in the prior art.The reed raw material of discharging from hammer mill enters in the cyclone dust removal machine, is 38000m at air quantity 3/ h, blast carry out dust removal process under the condition of 230mm water column.The reed raw material that comes out from dust removal machine enters in the drum sieve and screens, drum sieve rotating speed 21r/min during screening, and the inclination angle is 11 °.Described drum sieve is the double-layer cylinder screen that plays the screening effect in the prior art in the getting the raw materials ready in making grass pulp.The nexine sieve plate sieve aperture 30 x 30mm of drum sieve, the diameter 4-6mm of outer sieve plate sieve aperture.At last, the reed raw material that comes out from the discharging opening of drum sieve enters and carries out boiling in the boiling vessel.
Reed after getting the raw materials ready is carried out anthraquinone-soda cooking: alkali charge in NaOH to over dry material quantity 15%, liquor ratio is 1:2, the anthraquinone addition is 0.6% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 90 minutes when temperature is 135 ℃, continues heat temperature raising to 163 ℃, is incubated 140 minutes.With the intact hardness of gained afterwards of boiling is the slurry of permanganate number 14, earlier carry out shove with reducing single-screw press master, through shove black liquor is extruded, impurity in the black liquor is also discharged together in company with black liquor simultaneously, slurry with gained washs with three sections vacuum pulp washing machines afterwards, after the washing high-hardness pulp is diluted, being diluted to concentration is 12%.Utilize the mill fluffer to discongest then, this slurry is delivered to the air of getting rid of in the slurry through modifier treatment at middle underflow Guan Zhongxian and is made it fluidization after discongesting, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for mixing in 4% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 100 ℃, and pressure remains 0.6MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, carry out two sections bleachings again, chlorine dosage is 3% of an oven dry stock, the concentration of slurry is 3.5%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 60 minutes, alkali treatment is: alkali charge is to oven dry stock amount 3.5% in NaOH, the concentration of slurry is 10%, and bleaching temperature is 54 ℃, and the time is 130 minutes.The whiteness that bleaching finishes the resulting bleach chemical pulp in back is 72%ISO, and fracture length is 5500m, and folding strength is 60 times, is a kind of high-quality slurry.
Embodiment 77
Straw and bagasse are mixed after the persulfuric acid bisulfite cooking according to 1:1, be specially sodium hydroxide solution and the black liquor mixed liquor hybrid infusion used over dry material quantity 4%, send into rotary spherical digester then, add the soda bath to over dry material quantity 12%, sulphidity is 10%, liquor ratio 1:2.5, heat temperature raising to 140 ℃ for the first time, insulation is 40 minutes under this temperature, littler steam bleeding 20-30 minute, for the second time heat temperature raising 30 minutes to temperature is 173 ℃, is incubated 90 minutes.Obtain hardness after the boiling and be 28 slurries that are equivalent to card uncle valency 50, through carrying out pulp washing with three sections vacuum pulp washing machines again behind the Var-nip press shove, the slurry concentration of coming out from wash engine is 12%, keep 68-70 ℃ in the washing process, be transported in the deflaker again and discongest, heat this slurry to 70 ℃ by conveying worm then and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkali charge in 4% the aqueous slkali of NaOH to the oven dry stock amount, and in pipeline, feed steam and should starch heat temperature raising.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 102 ℃ of inlet temperatures; pressure 1.12Mpa; stop and made this slurry can carry out sufficient delignification reaction in 90 minutes, tower top temperature is 104 ℃, and pressure remains 0.5MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, carry out two sections bleachings again, chlorine dosage is 2.5% of an oven dry stock, the concentration of slurry is 3%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 58 minutes, alkali treatment is: alkali charge is to oven dry stock amount 3% in NaOH, the concentration of slurry is 10%, and bleaching temperature is 50 ℃, and the time is 150 minutes.Can obtain whiteness is 78%ISO, fracture length 6500m, the high-quality dogstail slurry that folding strength is 50 times.
Embodiment 78
Wheat straw, cotton stalk and bagasse are mixed after the persulfuric acid bisulfite cooking according to 1:1:1, be specially in rotary spherical digester and add steaming preparation, alkali charge is to over dry material quantity 12% in NaOH, sulphidity is 8%, liquor ratio 1:3, for the first time heat temperature raising to 120 ℃, insulation is 120 minutes under this temperature, again little steam bleeding 20-30 minute, for the second time heat temperature raising 30 minutes to temperature was 168 ℃, is incubated 90 minutes.Obtain hardness after the boiling and be 13 slurry, through washing with three sections vacuum pulp washing machines again behind the reducing single-screw press master shove, regulate concentration to 15% with clear water again, enter in the deflaker then and discongest, heat this slurry to 70 ℃ and be transported to middle underflow pipe by conveying worm again.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for mixing in 4% the aqueous slkali of NaOH to the oven dry stock amount, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock weight; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 100 degree, and pressure remains 0.6MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, carry out two sections bleachings again, chlorine dosage is 3% of an oven dry stock, the concentration of slurry is 3%, and the temperature of bleaching is 55 ℃, and the time of bleaching is 50 minutes, alkali treatment is: alkali charge is to oven dry stock amount 4% in NaOH, the concentration of slurry is 12%, and bleaching temperature is 55 ℃, and the time is 120 minutes.Can obtain whiteness is 78%ISO, 6300 meters of fracture lengths, the high-quality dogstail slurry that folding strength is 45 times.
Embodiment 79
Straw, bagasse and reed are mixed after the persulfuric acid bisulfite cooking adds steaming preparation in rotary spherical digester according to 1:1:1, and wherein alkali charge is to 15% of over dry material quantity in NaOH, sulphidity is 5%, liquor ratio 1:3, afterwards, logical steam carries out the heat temperature raising first time, be warming up to 140 ℃, insulation is 120 minutes under this temperature, littler steam bleeding 30 minutes, and heating for the second time begins logical steam, heat up 30 minutes to temperature be 170 ℃, be incubated 150 minutes.Obtain hardness after the boiling and be 12 slurry, carry out shove through Var-nip press again, send into three sections vacuum pulp washing machines then and wash, utilize defibrator to discongest Russia then, heat this slurry to 80 ℃ again and be transported to the oxygen delignification reaction tower through the positive displacement high density stock pump.Add in the reaction tower oxygen of 35kg slurry per ton and alkalinity in NaOH to oven dry stock amount 3% aqueous slkali, and in pipeline, feed steam and should starch heat temperature raising.Protective agent is a magnesium sulfate, addition is 0.8% of an oven dry stock weight, this slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, protective agent is a magnesium sulfate, addition is 0.2% of an oven dry stock weight, is 95 ℃ in inlet temperature earlier, and pressure is 1.0MPa, outlet temperature is 100 ℃, and pressure is to carry out one section oxygen delignification 60 minutes under the condition of 0.7MPa; To be 100 ℃ in inlet temperature through the slurry after one section oxygen delignification again, pressure be 0.7MPa, and outlet temperature is 108 ℃, and pressure is to carry out two sections oxygen delignification 40 minutes under the condition of 0.4MPa.After finishing dealing with this slurry is spurted stock tank and dilution, the hardness K (permanganate number) that starches this moment is reduced to 10 and is equivalent to card uncle valency 13, and beating degree is 38 ° of SR.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, traditional CEH tri-stage bleaching is adopted in the back, and be specially: C section chlorine dosage is 4% of an oven dry stock, and the concentration of slurry is 3.2%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 45 minutes; E section alkali charge in NaOH to oven dry stock amount 3%, the concentration of slurry is 12%, bleaching temperature is 52 ℃, the time is 120 minutes, can obtain whiteness is 81%ISO, 6800 meters of fracture lengths, high-quality dogstail that folding strength is 48 times slurry.
Embodiment 80
Giantreed through the ammonium sulfite boiling, is carried out in upright steamer, add steaming preparation, the consumption of ammonium sulfite is to over dry material quantity 18%, and liquor ratio 1:4 fills back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out the heat temperature raising first time, is warming up to 130 ℃, and insulation is 100 minutes under this temperature, and littler steam bleeding 20-30 minute, heating for the second time began logical steam, heat up 30 minutes to temperature be 168 ℃, be incubated 90 minutes.Obtain hardness after the boiling and be 13.5 slurry, carry out shove with reducing single-screw press master again, enter then in three sections vacuum pulp washing machines and wash, obtaining concentration after the washing is 10% slurry, utilize dry pan to discongest then, heat this slurry to 70 ℃ by conveying worm again and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 4%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards; protective agent is a magnesium sulfate; addition is 1% of an oven dry stock amount; 95 ℃ of inlet temperatures; pressure 0.9Mpa; stop and made this slurry can carry out sufficient delignification reaction in 75 minutes, tower top temperature is 100 ℃, and pressure remains 0.6MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, carry out two sections bleachings again, chlorine dosage is 2.5% of an oven dry stock, the concentration of slurry is 3%, and the temperature of bleaching is 52 ℃, and the time of bleaching is 60 minutes, alkali treatment is: alkali charge is to 2% of oven dry stock amount in NaOH, the concentration of slurry is 10%, and bleaching temperature is 52 ℃, and the time is 120 minutes.Can obtain whiteness is 77%ISO, 5500 meters of fracture lengths, the high-quality dogstail slurry that folding strength is 40 times.
What embodiment 79-89 related to is in order to realize goal of the invention eight preparation bleach chemical pulps.
Embodiment 81
With the boiling of wheat straw process ammonium sulfite, be specially pre-preg and adopt 4% sodium hydroxide solution, the ammonium sulfite addition is 10% of an over dry material quantity, liquor ratio 1:4, heat temperature raising to 110 ℃ for the first time, insulation is 20 minutes under this temperature, littler steam bleeding 20-30 minute, post bake heat up 30 minutes to temperature be 168 ℃, be incubated 90 minutes.Obtain hardness and be 20 high-hardness pulps that are equivalent to card uncle valency 31.With concentration is that 10% high-hardness pulp reducing single-screw press master carries out shove, obtain 25% slurry, utilize three sections vacuum pulp washing machines to wash then, the slurry after the washing is discongested by deflaker, heat this slurry to 70 ℃ by conveying worm again and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal middle underflow pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 20kg slurry per ton that adds and alkalinity for oven dry stock weight 4% aqueous slkali is mixed in NaOH, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, protective agent is a magnesium sulfate, addition is 1% of an oven dry stock weight, it is 85 ℃ in inlet temperature earlier, pressure is 0.9MPa, outlet temperature is 98 ℃, and pressure is to carry out one section oxygen delignification 50 minutes under the condition of 0.6MPa; To be 98 ℃ in inlet temperature through the slurry after one section oxygen delignification again, pressure be 0.6MPa, and outlet temperature is 108 ℃, and pressure is to carry out two sections oxygen delignification 30 minutes under the condition of 0.4MPa.After finishing dealing with this slurry being spurted stock tank also dilutes, with pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, traditional CEH tri-stage bleaching is adopted in the back, be specially: C section chlorine dosage is 3% of an oven dry stock, the concentration of slurry is 3.2%, the temperature of bleaching is 55 ℃, and the time of bleaching is 45 minutes; The amount that the E section adds NaOH is an oven dry stock amount 2.5%, and the concentration of slurry is 12%, and bleaching temperature is 50 ℃, and the time is 120 minutes; The addition of H section clorox is 3% of an oven dry stock amount, and the temperature of bleaching is 30 ℃, and the time of bleaching is 120 minutes, and can obtain whiteness is 82%ISO, 6500 meters of fracture lengths, the high-quality dogstail slurry that folding strength is 45 times.
Embodiment 82
With the caustic soda-anthraquinone boiling of straw process, being specially the caustic soda addition is 10% of over dry material quantity, the anthraquinone addition is 0.7% of an over dry material quantity, liquor ratio 1:4, heat temperature raising to 110 ℃ for the first time, insulation is 20 minutes under this temperature, littler steam bleeding 20-30 minute, for the second time heat temperature raising 30 minutes to temperature is 168 ℃, is incubated 90 minutes.Obtain hardness after the boiling and be 22 high-hardness pulps that are equivalent to card uncle valency 36, regulating and obtaining concentration after the concentration is 12% slurry, after sending into Var-nip press and carrying out shove, black liquor is extruded, obtain concentration and be 25% slurry, regulate with warm water and to send into three sections vacuum pulp washing machines after the concentration and carry out pulp washing, adopt kneading machine to discongest then, heat this slurry to 60 ℃ again and be transported to the oxygen delignification reaction tower by the positive displacement middle underflow pump.This slurry before entering reaction tower in pipeline with the oxygen of the 40kg slurry per ton that adds and alkalinity for oven dry stock weight 2% is mixed in NaOH, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, protective agent is a magnesium sulfate, addition is 2% of an oven dry stock weight, it is 95 ℃ in inlet temperature earlier, pressure is 1.0MPa, outlet temperature is 100 ℃, and pressure is to carry out one section oxygen delignification 40 minutes under the condition of 0.7MPa; To be 100 ℃ in inlet temperature through the slurry after one section oxygen delignification again, pressure be 0.7MPa, and outlet temperature is 108 ℃, and pressure is to carry out two sections oxygen delignification 20 minutes under the condition of 0.4MPa.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, traditional CEH tri-stage bleaching is adopted in the back, and be specially: C section chlorine dosage is 4% of an oven dry stock, and the concentration of slurry is 3%, and the temperature of bleaching is 55 ℃, and the time of bleaching is 50 minutes; The amount that the E section adds NaOH is an oven dry stock amount 2%, and the concentration of slurry is 12%, and bleaching temperature is 52 ℃, and the time is 100 minutes; The addition of H section clorox is 3% of an oven dry stock amount, and the temperature of bleaching is 32 ℃, and the time of bleaching is 100 minutes, and can obtain whiteness is 74%ISO, 5500 meters of fracture lengths, the high-quality dogstail slurry that folding strength is 35 times.
Embodiment 83
After wheat straw and reed mixed according to 1:1 through the ammonium sulfite boiling, be specially the sodium hydroxide solution hybrid infusion of using over dry raw material 4%, send into rotary spherical digester then, adding is to the ammonium sulfite of over dry material quantity 11.5%, liquor ratio 1:3, heat temperature raising to 100 ℃ for the first time, insulation is 20 minutes under this temperature, again little steam bleeding 20-30 minute, for the second time heat temperature raising 30 minutes to temperature was 165 ℃, is incubated 60 minutes.Obtain hardness after the boiling and be 18 slurries that are equivalent to card uncle valency 27, carry out shove through reducing single-screw press master after will starching adjusting concentration to 12%, obtain concentration after the shove and be 20% slurry, wash with three sections vacuum pulp washing machines again, heat this slurry to 76 ℃ then and be transported to the oxygen delignification reaction tower through the positive displacement middle underflow pump.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 3%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, protective agent is a magnesium sulfate, addition is 0.2% of an oven dry stock weight, it is 95 ℃ in inlet temperature earlier, pressure is 1.0MPa, outlet temperature is 100 ℃, and pressure is to carry out one section oxygen delignification 55 minutes under the condition of 0.65MPa; To be 100 ℃ in inlet temperature through the slurry after one section oxygen delignification again, pressure be 0.65MPa, and outlet temperature is 108 ℃, and pressure is to carry out two sections oxygen delignification 25 minutes under the condition of 0.4MPa.After finishing dealing with this slurry is spurted stock tank and dilution, this moment, the hardness K (permanganate number) of slurry was reduced to 13, and beating degree is 32 ° of SR.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, traditional CEH tri-stage bleaching is adopted in the back, and be specially: C section chlorine dosage is 4% of an oven dry stock, and the concentration of slurry is 3.5%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 50 minutes; The amount that the E section adds NaOH is an oven dry stock amount 3%, and the concentration of slurry is 10%, and bleaching temperature is 52 ℃, and the time is 150 minutes; The addition of H section clorox is 2% of an oven dry stock amount, and the temperature of bleaching is 32 ℃, and the time of bleaching is 150 minutes, and can obtain whiteness is 80%ISO, 7000 meters of fracture lengths, the high-quality dogstail slurry that folding strength is 50 times.
Embodiment 84
Through the cotton stalk process dipping screw machine behind the dry raw material preparation, in the dipping screw machine with alkalinity in NaOH being 4% sodium hydroxide solution mixed liquor hybrid infusion to the cotton stalk amount of over dry, send into rotary spherical digester then, adding adds steaming preparation to the over dry material quantity in rotary spherical digester, wherein the consumption of ammonium sulfite is to over dry material quantity 12%, liquor ratio 1:2.5, cotton stalk fill back rotary spherical digester idle running 20 minutes; Afterwards, logical steam carries out heat temperature raising one time, is warming up to 120 ℃, and insulation is 40 minutes under this temperature, and littler steam bleeding 20-30 minute, post bake began logical steam, heat up 30 minutes to temperature be 173 ℃, be incubated 90 minutes; Before spurting, in rotary spherical digester, add black liquor and dilute, pressure keeps 0.75MPa to spurt simultaneously, and this moment, the hardness of slurry was that permanganate number 16 is equivalent to card uncle valency 24, and the pH value is 12 during boiling end, and the residual ammonium concentration in the black liquor is 9g/l.The yield of described high-hardness pulp is 66%.With the intact hardness of gained afterwards of boiling is the high-hardness pulp adjusting concentration to 15% that permanganate number 23 is equivalent to card uncle valency 37, send into Var-nip press again and carry out shove, obtain concentration and be 38% slurry, in three sections vacuum pulp washing machines, carry out pulp washing with warm water dilution back, discongest with dry pan then, heat this slurry to 76 ℃ again and be transported to the oxygen delignification reaction tower through the positive displacement middle underflow pump.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 3%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, protective agent is a magnesium sulfate, addition is 0.2% of an oven dry stock weight, it is 90 ℃ in inlet temperature earlier, pressure is 0.85MPa, outlet temperature is 99 ℃, and pressure is to carry out one section oxygen delignification 45 minutes under the condition of 0.55MPa; To be 99 ℃ in inlet temperature through the slurry after one section oxygen delignification again, pressure be 0.5MPa, and outlet temperature is 105 ℃, and pressure is to carry out two sections oxygen delignification 25 minutes under the condition of 0.25MPa.Bleach in more traditional mode again, chlorination-alkali treatment-hypochlorite bleaching, the condition of bleaching is: chlorine dosage is 3% of an oven dry stock, and the concentration of slurry is 3%5, and the temperature of bleaching is 55 ℃, and the time of bleaching is 60 minutes; The condition of alkali treatment be alkali charge be in NaOH to oven dry stock amount 3%, the concentration of slurry is 12%, bleaching temperature is 52 ℃, the time is 150 minutes; Hypochlorite bleaching: the addition of clorox is 2% of an oven dry stock amount, and the temperature of bleaching is 35 ℃, and the time of bleaching is 100 minutes.After bleaching finished, the whiteness of described bleach chemical pulp was 72%ISO, and fracture length is 8000m, and folding strength is 70 times, is a kind of high-quality slurry.
Embodiment 85
Straw is carried out anthraquinone-soda cooking: add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 9%, wherein liquor ratio is 1:2, the anthraquinone addition is 0.6% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 120 ℃, continues heat temperature raising to 165 ℃, be incubated 60 minutes, obtains hardness and is 28 and be equivalent to the high-hardness pulp of card primary valency 50.Earlier carry out shove with the single-screw press master, through shove black liquor is extruded, impurity in the black liquor is also discharged together in company with black liquor simultaneously, slurry with gained washs with three sections suction washers afterwards, high-hardness pulp is diluted to concentration is 8-12% after the washing, heats this slurry to 76 ℃ then and is transported to the oxygen delignification reaction tower through the positive displacement middle underflow pump.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 3%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, protective agent is a magnesium sulfate, addition is 0.2% of an oven dry stock weight, it is 88 ℃ in inlet temperature earlier, pressure is 0.95MPa, outlet temperature is 99 ℃, and pressure is to carry out one section oxygen delignification 60 minutes under the condition of 0.65MPa; To be 99 ℃ in inlet temperature through the slurry after one section oxygen delignification again, pressure be 0.65MPa, and outlet temperature is 106 ℃, and pressure is to carry out two sections oxygen delignification 20 minutes under the condition of 0.4MPa.Bleach in more traditional mode again, chlorination-alkali treatment-hypochlorite bleaching, the condition of bleaching is: chlorine dosage is 2.5% of an oven dry stock, and the concentration of slurry is 3%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 55 minutes; The condition of alkali treatment is: alkali charge in NaOH to oven dry stock amount 4%, the concentration of slurry is 11%, bleaching temperature is 54 ℃, the time is 120 minutes; Hypochlorite bleaching: the addition of clorox is 4% of an oven dry stock amount, and the temperature of bleaching is 35 ℃, and the time of bleaching is 150 minutes.After bleaching finished, the whiteness of described bleach chemical pulp was 75%ISO, and fracture length is 5200m, and folding strength 30 times is a kind of high-quality slurry.
Embodiment 86
Reed is carried out anthraquinone-soda cooking: alkali charge in NaOH to over dry material quantity 9%, liquor ratio is 1:2, the anthraquinone addition is 0.6% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 115 ℃, continues heat temperature raising to 165 ℃, is incubated 60 minutes.The hardness of the intact gained afterwards of boiling is carried out shove with the single-screw press master earlier for the high-hardness pulp that permanganate number 18-20 is equivalent to card uncle valency 29-33, through shove black liquor is extruded, impurity in the black liquor is also discharged together in company with black liquor simultaneously, slurry with gained washs with three sections vacuum pulp washing machines afterwards, after the washing high-hardness pulp is diluted, being diluted to concentration is 5-12%, and then discongest with the mill fluffer, heat this slurry to 76 ℃ then and be transported to the oxygen delignification reaction tower through the positive displacement middle underflow pump.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 3%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, protective agent is a magnesium sulfate, addition is 0.2% of an oven dry stock weight, it is 92 ℃ in inlet temperature earlier, pressure is 0.85MPa, outlet temperature is 98 ℃, and pressure is to carry out one section oxygen delignification 48 minutes under the condition of 0.55MPa; To be 98 ℃ in inlet temperature through the slurry after one section oxygen delignification again, pressure be 0.55MPa, and outlet temperature is 104 ℃, and pressure is to carry out two sections oxygen delignification 38 minutes under the condition of 0.25MPa.Bleach in more traditional mode again, chlorination-alkali treatment-hypochlorite bleaching, the condition of bleaching is: chlorine dosage is 2.5% of an oven dry stock, and the concentration of slurry is 3%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 60 minutes; The condition of alkali treatment is: alkali charge in NaOH to oven dry stock amount 3%, the concentration of slurry is 10%, bleaching temperature is 55 ℃, the time is 140 minutes; Hypochlorite bleaching: the addition of clorox is 2% of an oven dry stock amount, and the temperature of bleaching is 35 ℃, and the time of bleaching is 110 minutes.After bleaching finished, the whiteness of paper pulp was 72%ISO, and fracture length is 5500m, and folding strength is 60 times, is a kind of high-quality slurry.
Embodiment 87
Straw is carried out the Arbiso process boiling, in straw, add total acid 5%, the cooking liquor of combined acid 2%; Feed steam in the boiling vessel and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 110 ℃, continues heat temperature raising to 170 ℃, is incubated 60 minutes, and obtaining hardness is that permanganate number is 24.Described high-hardness pulp carries out shove with the single-screw press master earlier, through shove black liquor is extruded, impurity in the black liquor is also discharged together in company with black liquor simultaneously, slurry with gained washs with suction washer afterwards, after the washing high-hardness pulp is diluted, being diluted to concentration is 8-12%, this slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 3%, and feeding steam should be starched heat temperature raising in pipeline.After this slurry in blender, enter the oxygen delignification reaction tower after fully mixed, protective agent is a magnesium sulfate, addition is 0.2% of an oven dry stock weight, it is 90 ℃ in inlet temperature earlier, pressure is 1.0MPa, outlet temperature is 99 ℃, and pressure is to carry out one section oxygen delignification 60 minutes under the condition of 0.7MPa; To be 99 ℃ in inlet temperature through the slurry after one section oxygen delignification again, pressure be 0.7MPa, and outlet temperature is 106 ℃, and pressure is to carry out two sections oxygen delignification 35 minutes under the condition of 0.4MPa.Bleach in more traditional mode again, chlorination-alkali treatment-hypochlorite bleaching, the condition of bleaching is: chlorine dosage is 3% of an oven dry stock, and the concentration of slurry is 3.5%, and the temperature of bleaching is 53 ℃, and the time of bleaching is 60 minutes; The condition of alkali treatment is: alkali charge in NaOH to oven dry stock amount 4%, the concentration of slurry is 10%, bleaching temperature is 50 ℃, the time is 130 minutes; Hypochlorite bleaching: the addition of clorox is 2% of an oven dry stock amount, and the temperature of bleaching is 33 ℃, and the time of bleaching is 150 minutes.After bleaching finished, the whiteness of paper pulp was 78%ISO, and fracture length is 6400m, and folding strength is 40 times, is a kind of high-quality paper pulp.
Embodiment 88
Straw and bagasse are mixed after the persulfuric acid bisulfite cooking according to 1:1, be specially sodium hydroxide solution and the black liquor mixed liquor hybrid infusion used over dry material quantity 4%, send into rotary spherical digester then, add the soda bath to over dry material quantity 12%, sulphidity is 10%, liquor ratio 1:2.5, heat temperature raising to 140 ℃ for the first time, insulation is 40 minutes under this temperature, littler steam bleeding 20-30 minute, for the second time heat temperature raising 30 minutes to temperature is 173 ℃, is incubated 90 minutes.Obtain hardness after the boiling and be 28 slurries that are equivalent to card uncle valency 50,, discongest with defibrator then, heat this slurry to 80 ℃ and be transported to middle underflow pipe by conveying worm again through carrying out pulp washing with three sections vacuum pulp washing machines again behind the Var-nip press shove.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, after centrifugal high density stock pump is transported to the oxygen delignification reaction tower.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 3%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, protective agent is a magnesium sulfate, addition is 0.2% of an oven dry stock weight, it is 95 ℃ in inlet temperature earlier, pressure is 0.9MPa, outlet temperature is 100 ℃, and pressure is to carry out one section oxygen delignification 58 minutes under the condition of 0.5MPa; To be 100 ℃ in inlet temperature through the slurry after one section oxygen delignification again, pressure be 0.57MPa, and outlet temperature is 104 ℃, and pressure is to carry out two sections oxygen delignification 20-40 minutes under the condition of 0.3MPa.This slurry is spurted stock tank and dilution, and this moment, the hardness K (permanganate number) of slurry was reduced to 12, and beating degree is 34 ° of SR.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, traditional CEH tri-stage bleaching is adopted in the back, and be specially: C section chlorine dosage is 3% of an oven dry stock, and the concentration of slurry is 3.5%, and the temperature of bleaching is 52 ℃, and the time of bleaching is 45 minutes; The amount that the E section adds NaOH is an oven dry stock amount 3%, and the concentration of slurry is 11%, and bleaching temperature is 50 ℃, and the time is 150 minutes; The addition of H section clorox is 2.5% of an oven dry stock amount, and the temperature of bleaching is 30 ℃, and the time of bleaching is 150 minutes, and can obtain whiteness is 78%ISO, fracture length 6500m, the high-quality dogstail slurry that folding strength is 50 times.
Embodiment 89
After wheat straw, cotton stalk and bagasse mixed according to 1:1:1 through ammonium sulfite-anthraquinone boiling, be specially the ammonium sulfite solution that adds in the rotary spherical digester over dry material quantity 13%, the anthraquinone addition is 0.8% of an over dry material quantity, liquor ratio 1:3, heat temperature raising to 100 ℃ for the first time, insulation is 20 minutes under this temperature, littler steam bleeding 20-30 minute, for the second time heat temperature raising 30 minutes to temperature is 165 ℃, is incubated 60 minutes.Obtain hardness after the boiling and be 26 slurries that are equivalent to card uncle valency 45, through washing with three sections vacuum pulp washing machines again behind the reducing single-screw press master shove, utilize deflaker to discongest then, again by heating this slurry to 70 ℃ and being transported to through single rotor formula high density stock pump that oxygen floats reaction tower and feed steam in pipeline should starch heat temperature raising.This slurry before entering reaction tower in pipeline with the oxygen of the 30kg slurry per ton that adds and alkalinity for to mix in the aqueous slkali of NaOH to oven dry stock amount 3%, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, protective agent is a magnesium sulfate, addition is 0.5% of an oven dry stock weight, it is 85 ℃ in inlet temperature earlier, pressure is 0.8MPa, outlet temperature is 98 ℃, and pressure is to carry out one section oxygen delignification 40-60 minute under the condition of 0.5MPa; To be 98 ℃ in inlet temperature through the slurry after one section oxygen delignification again, pressure be 0.5MPa, and outlet temperature is 103 ℃, and pressure is to carry out two sections oxygen delignification 40 minutes under the condition of 0.2MPa.After finishing dealing with this slurry is spurted stock tank and dilution, the hardness K (permanganate number) that starches this moment is reduced to 10 and is equivalent to card uncle valency 13, and beating degree is 36 ° of SR.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, traditional CEH tri-stage bleaching is adopted in the back, and be specially: C section chlorine dosage is 3% of an oven dry stock, and the concentration of slurry is 3%, and the temperature of bleaching is 52 ℃, and the time of bleaching is 50 minutes; The amount that the E section adds NaOH is an oven dry stock amount 3%, and the concentration of slurry is 12%, and bleaching temperature is 50 ℃, and the time is 100 minutes; The addition of H section clorox is 2.5% of an oven dry stock amount, and the temperature of bleaching is 32 ℃, and the time of bleaching is 150 minutes, and can obtain whiteness is 78%ISO, 6300 meters of fracture lengths, the high-quality dogstail slurry that folding strength is 45 times.
Embodiment 90
With straw, bagasse and reed mix after the persulfuric acid bisulfite cooking according to 1:1:1, be specially in the dipping screw machine with alkali charge in aqueous slkali and the black liquor mixed liquor hybrid infusion of NaOH to over dry material quantity 4%, send into rotary spherical digester then, in rotary spherical digester, add steaming preparation, wherein alkali charge is to 9% of over dry material quantity in NaOH, sulphidity is 15%, liquor ratio 1:3, afterwards, logical steam carries out the heat temperature raising first time, be warming up to 120 ℃, insulation is 20 minutes under this temperature, and littler steam bleeding 20-30 minute, heating for the second time began logical steam, heat up 30 minutes to temperature be 165 ℃, be incubated 60 minutes.Obtain hardness after the boiling and be 22 slurries that are equivalent to card uncle valency 35, carry out shove through Var-nip press again, send into three sections vacuum pulp washing machines then and wash, utilize kneading machine to discongest then, again by heating this slurry to 80 ℃ and being transported to the oxygen delignification reaction tower through the positive displacement high density stock pump.Add in the reaction tower oxygen of 35kg slurry per ton and alkalinity in NaOH to oven dry stock amount 3% aqueous slkali, and in pipeline, feed steam and should starch heat temperature raising.Protective agent is a magnesium sulfate, addition is 0.8% of an oven dry stock weight, this slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, protective agent is a magnesium sulfate, addition is 0.2% of an oven dry stock weight, is 95 ℃ in inlet temperature earlier, and pressure is 1.0MPa, outlet temperature is 100 ℃, and pressure is to carry out one section oxygen delignification 60 minutes under the condition of 0.7MPa; To be 100 ℃ in inlet temperature through the slurry after one section oxygen delignification again, pressure be 0.7MPa, and outlet temperature is 108 ℃, and pressure is to carry out two sections oxygen delignification 40 minutes under the condition of 0.4MPa.After finishing dealing with this slurry is spurted stock tank and dilution, the hardness K (permanganate number) that starches this moment is reduced to 10 and is equivalent to card uncle valency 13, and beating degree is 38 ° of SR.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, traditional CEH tri-stage bleaching is adopted in the back, and be specially: C section chlorine dosage is 4% of an oven dry stock, and the concentration of slurry is 3.2%, and the temperature of bleaching is 50 ℃, and the time of bleaching is 45 minutes; E section alkali charge in NaOH to oven dry stock amount 3%, the concentration of slurry is 12%, bleaching temperature is 52 ℃, the time is 120 minutes; The addition of H section clorox is 2% of an oven dry stock amount, and the temperature of bleaching is 30 ℃, and the time of bleaching is 150 minutes, and can obtain whiteness is 81%ISO, 6800 meters of fracture lengths, the high-quality dogstail slurry that folding strength is 48 times.
Embodiment 91
Bagasse through the ammonium sulfite boiling, is specially the ammonium sulfite solution that adds in the rotary spherical digester over dry material quantity 11%, and liquor ratio 1:4 fills the back rotary spherical digester and dallied 20 minutes; Afterwards, logical steam carries out the heat temperature raising first time, is warming up to 110 ℃, and insulation is 20 minutes under this temperature, and littler steam bleeding 20-30 minute, heating for the second time began logical steam, heat up 30 minutes to temperature be 168 ℃, be incubated 90 minutes.Obtain hardness after the boiling and be 20 slurries that are equivalent to card uncle valency 31, carry out shove with reducing single-screw press master again, enter then in three sections vacuum pulp washing machines and wash, utilize defibrator to heat this slurry to 60 ℃ again by conveying worm and be transported in the underflow pipe.This slurry makes it fluidization at the air that middle underflow Guan Zhongxian gets rid of in the slurry through modifier treatment, floats reaction tower after centrifugal middle underflow pump is transported to oxygen.This slurry mixed with the oxygen of the 40kg slurry per ton that adds and the NaOH of oven dry stock weight 4% in pipeline before entering reaction tower, and feeding steam should be starched heat temperature raising in pipeline.This slurry enters the oxygen delignification reaction tower after fully mixed in blender afterwards, protective agent is a magnesium sulfate, addition is 0.2% of an oven dry stock weight, it is 95 ℃ in inlet temperature earlier, pressure is 1.0MPa, outlet temperature is 99 ℃, and pressure is to carry out one section oxygen delignification 40 minutes under the condition of 0.7MPa; To be 100 ℃ in inlet temperature through the slurry after one section oxygen delignification again, pressure be 0.7MPa, and outlet temperature is 108 ℃, and pressure is to carry out two sections oxygen delignification 40 minutes under the condition of 0.4MPa.With pump the stock pump of dilution is gone into two sections vacuum pulp washing machine washings afterwards, traditional CEH tri-stage bleaching is adopted in the back, and be specially: C section chlorine dosage is 5% of an oven dry stock, and the concentration of slurry is 3.5%, and the temperature of bleaching is 52 ℃, and the time of bleaching is 50 minutes; E section alkali charge in NaOH to oven dry stock amount 2%, the concentration of slurry is 10%, bleaching temperature is 55 ℃, the time is 150 minutes; The addition of H section clorox is 2.5% of an oven dry stock amount, and the temperature of bleaching is 32 ℃, and the time of bleaching is 100 minutes, and can obtain whiteness is 77%ISO, 5500 meters of fracture lengths, the high-quality dogstail slurry that folding strength is 40 times.
Embodiment 92-105 is the preparation embodiment of Yellow humic acid fertilizer
Embodiment 92
(1) Ammonium Sulfite Method boiling
In rice straw, add steaming preparation, wherein the consumption of ammonium sulfite is an over dry material quantity 9%, liquor ratio is 1:2, feed steam and heat, heat temperature raising is incubated 20 minutes when temperature is 100 ℃, carry out little steam bleeding, continue heat temperature raising to 165 ℃, be incubated 60 minutes, obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 16.
(2) the high-hardness pulp post processing obtains rare black liquor
Slurry enters from the inlet of press master, and extruding black liquor after the extruding black liquor, carries out pulp washing, the black liquor that merging is extruded and the black liquor of pulp washing, and obtaining solid content is 15%, and Baume degrees is rare black liquor of 9, and pH is 10.
(3) add auxiliary material and drying in the black liquor
Add lignin and humic acid in rare black liquor, directly evaporation drying promptly gets Yellow humic acid fertilizer.
Wherein, each component weight percent content is respectively
Rare black liquor 30%
Lignin 45%
Humic acid 25%;
The fulvic acid weight percent content is 20% in the Yellow humic acid fertilizer of gained, and the content of organic matter is 85%
Embodiment 93
(1) wheat straw waste is used Ammonium Sulfite Method and anthraquinone-soda cooking respectively
Maceration extract dipping wheat straw waste makes liquor ratio reach 1:2, and in 85 ℃ of insulations and mixing 10 minutes in the spiral macerator, maceration extract is 4% sodium hydroxide solution for the over dry material quantity under normal pressure.
Add steaming preparation in a part of wheat straw waste, wherein the consumption of ammonium sulfite is an over dry material quantity 13%, and liquor ratio is 1:4; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 120 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes; Obtain concentration and be 15% slurry, the hardness of slurry is permanganate number 28.
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 9%, liquor ratio is 1:2, the anthraquinone addition is 0.5% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 100 ℃, continues heat temperature raising to 165 ℃, is incubated 60 minutes; Obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 16.
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 4%, and Baume degrees is rare black liquor of 2, and wherein the rare black liquor pH of Ammonium Sulfite Method is 7, and the rare black liquor pH of anthraquinone-soda processes is 9.
(3) add auxiliary material and drying in the black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare black liquor of anthraquinone-soda processes mixed according to volume ratio 1:100, obtain the rare black liquor of mixed straw, to mix the direct evaporation and concentration of rare straw pulp black liquor to solid content is 30%, Baume degrees is 18, obtains mixing concentrated black liquid, its pH=11, become slip with mixing concentrated black liquid, lignin and humic acid mixed according to mass percent 30%, 45%, 25%, convection drying obtains Yellow humic acid fertilizer then, the content of organic matter 70%, N+P 2O 5+ K 2O total content 4%, fulvic acid 5%.
Embodiment 94
(1) wheat straw waste is used Ammonium Sulfite Method and anthraquinone-soda cooking respectively
Maceration extract dipping wheat straw waste makes liquor ratio reach 1:4, and in 95 ℃ of insulations and mixing 40 minutes in the spiral macerator, maceration extract is the mixed liquor of the black liquor of 4% sodium hydroxide solution and Baume degrees 11 for the over dry material quantity under normal pressure.
Add steaming preparation in a part of wheat straw waste, wherein the consumption of ammonium sulfite is an over dry material quantity 10%, and liquor ratio is 1:3; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 110 ℃, continues heat temperature raising to 170 ℃, is incubated 80 minutes; Obtain concentration and be 9% slurry, the hardness of slurry is permanganate number 18
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 12%, liquor ratio is 1:4, the anthraquinone addition is 0.8% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 120 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes; Obtain concentration and be 15% slurry, the hardness of slurry is permanganate number 28.
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 8%, and Baume degrees is rare black liquor of 5, and wherein the rare black liquor pH of Ammonium Sulfite Method is 8, and the rare black liquor pH of anthraquinone-soda processes is 13.
(3) add auxiliary material and drying in the black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare straw pulp black liquor of anthraquinone-soda processes mixed according to volume ratio 100:1, obtaining the rare black liquor of mixed straw, is 65% with the direct evaporation and concentration of mixed straw black liquor to solid content, and Baume degrees is 40, obtain mixing concentrated black liquid, pH=5 becomes slip with mixing concentrated black liquid, lignin and the humic acid mixed according to mass percent 80%, 5%, 15%, adds KCl, spray drying then, obtain solid-state Yellow humic acid fertilizer, the content of organic matter 67%, N+P 2O 5+ K 2O total content 4%, fulvic acid 40%.
Embodiment 95
(1) kraft cooking
Maceration extract dipping wheat straw waste makes liquor ratio reach 1:3, and in 90 ℃ of insulations and mixing 30 minutes in the spiral macerator, maceration extract is the mixed liquor of the black liquor of 4% sodium hydroxide solution and Baume degrees 14 for the over dry material quantity under normal pressure.
In reed straw, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 8%, liquor ratio is 1:2, sulphidity is 5%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 110 ℃, continues heat temperature raising to 165 ℃, is incubated 60 minutes; Obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 20.
(2) the high-hardness pulp post processing obtains rare black liquor
Slurry enters from the inlet of press master, after the extruding black liquor, carries out pulp washing, the black liquor that merging is extruded and the black liquor of pulp washing, and obtaining solid content is 8%, and Baume degrees is rare black liquor of 5, and pH is 9.
(3) add auxiliary material and drying in the black liquor
At first evaporation and concentration is to solid content 15.1% for rare black liquor, and Baume degrees 9 obtains concentrated black liquid, adds lignin and humic acid then, and directly evaporation drying promptly gets Yellow humic acid fertilizer.
Wherein, each component weight percent content is respectively
Concentrated black liquid 80%
Lignin 5%
Humic acid 1%;
Mud 14%
The fulvic acid weight percent content is 5% in the Yellow humic acid fertilizer of gained, and the content of organic matter is 20%.
Embodiment 96
(1) the giantreed stalk is used Ammonium Sulfite Method and kraft cooking respectively
Add steaming preparation in a part of giantreed stalk, wherein the consumption of ammonium sulfite is an over dry material quantity 10%, and liquor ratio is 1:3.5; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 35 minutes when temperature is 115 ℃, continues heat temperature raising to 172 ℃, is incubated 70 minutes; Obtain concentration and be 14% slurry, the hardness of slurry is permanganate number 27;
In another part giantreed stalk, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 11%, liquor ratio is 1:4, sulphidity is 15%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 140 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes; Obtain concentration and be 15% slurry, the hardness of slurry is permanganate number 25;
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, wash, the black liquor that merging is extruded and the black liquor of washing, obtaining solid content is 10%, and Baume degrees is rare black liquor of 6, and wherein the rare black liquor pH of Ammonium Sulfite Method is 9, and the rare black liquor pH of sulfate process is 10.
(3) add auxiliary material and drying in the black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare black liquor of sulfate process mixed according to volume ratio 1:4, obtain the rare black liquor of mixed straw, adopt five to imitate evaporation the mixed straw black liquor, its solid content of mixing concentrated black liquid that obtains is 40%, Baume degrees is 20, pH=6 will mix concentrated black liquid, lignin, humic acid, mud is according to mass percent 40%, 14%, 1%, 45% mixed becomes slip, adds KCl and ammonium chloride, slurry-spraying pelletizing then, head temperature is 550 ℃ during slurry-spraying pelletizing, and 47 ℃ of tail temperature obtain solid-state Yellow humic acid fertilizer, granularity 3-5mm, hardness 23.4N, the content of organic matter 20%, N+P 2O 5+ K 2O total content 30%, fulvic acid 9%.
Embodiment 97
(1) wheat straw waste is used Ammonium Sulfite Method and anthraquinone-soda cooking respectively
The Ammonium Sulfite Method boiling is with embodiment 94
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 11%, liquor ratio is 1:3, the anthraquinone addition is 0.7% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 110 ℃, continues heat temperature raising to 169 ℃, is incubated 75 minutes; Obtain concentration and be 14% slurry, the hardness of slurry is permanganate number 27
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 12%, and Baume degrees is rare black liquor of 7, and wherein the rare black liquor pH of Ammonium Sulfite Method is 8, and the rare black liquor pH of anthraquinone-soda processes is 12
(3) add auxiliary material and drying in the black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare black liquor of anthraquinone-soda processes mixed according to volume ratio 4:1, obtain the rare black liquor of mixed straw, adopt five to imitate evaporation the rare black liquor of mixed straw, its solid content of mixing concentrated black liquid that obtains is 47%, and Baume degrees is 29, pH=6, to mix concentrated black liquid, lignin, humic acid, mud is according to mass percent 60%, 25%, 10%, 5% mixed becomes slip, slurry-spraying pelletizing then, head temperature is 600 ℃ during slurry-spraying pelletizing, 55 ℃ of tail temperature, obtain solid-state Yellow humic acid fertilizer, granularity 3-5mm, hardness 9.2N obtains solid-state Yellow humic acid fertilizer, granularity 3-5mm, hardness 23.4N, the content of organic matter 60%, N+P 2O 5+ K 2O total content 4%, fulvic acid 30%.
Embodiment 98
(1) wheat straw waste is used Ammonium Sulfite Method and kraft cooking respectively
The Ammonium Sulfite Method boiling is with embodiment 96
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 10%, liquor ratio is 1:3, sulphidity is 10%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 130 ℃, continues heat temperature raising to 170 ℃, is incubated 80 minutes; Obtain concentration and be 13% slurry, the hardness of slurry is permanganate number 22.
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 8%, and Baume degrees is rare black liquor of 5, and wherein the rare black liquor pH of Ammonium Sulfite Method is 9, and the rare black liquor pH of sulfate process is 12.
(3) add auxiliary material and drying in the black liquor
The rare black liquor of Ammonium Sulfite Method and the rare black liquor of sulfate process according to the mixed of volume ratio 3:1, are obtained the rare black liquor of mixed straw; Adopt five to imitate evaporation the rare black liquor of mixed straw, its solid content of mixing concentrated black liquid that obtains is 45%, and Baume degrees is 28, pH=7 becomes slip with mixing concentrated black liquid, lignin, humic acid, mud according to the mixed of mass percent 50%, 35%, 10%, 5%, adds KCl, slurry-spraying pelletizing then, head temperature is 560 ℃ during slurry-spraying pelletizing, and 52 ℃ of tail temperature obtain solid-state Yellow humic acid fertilizer, granularity 3-5mm, hardness 19.4N, the content of organic matter 65%, N+P 2O 5+ K 2O total content 5%, fulvic acid 24%.
Embodiment 99
Step (one) (two) is with embodiment 97
(3) add auxiliary material and drying in the black liquor
Other condition is with embodiment 97, rare black liquor of Ammonium Sulfite Method and the rare black liquor volume ratio of anthraquinone-caustic soda 10:1, the solid-state Yellow humic acid fertilizer that obtains, granularity 3-5mm, hardness 19.4N, the content of organic matter 60%, N+P 2O 5+ K 2O total content 4%, fulvic acid 35%.
Embodiment 100
Step (one) (two) is with embodiment 98
(3) add auxiliary material and drying in the black liquor
Other condition is with embodiment 96, rare black liquor of Ammonium Sulfite Method and the rare black liquor volume ratio of sulfate process 1:10, the solid-state Yellow humic acid fertilizer that obtains, granularity 3-5mm, hardness 14.5N, the content of organic matter 60%, N+P2O5+K2O total content 16%, fulvic acid 22%.
Embodiment 101,
Other condition is with embodiment 98
Wherein, each component weight percent content is respectively
Mix concentrated black liquid 55%
Lignin 1%
Humic acid 14%
Ardealite 30%;
The fulvic acid weight percent content is 16% in the Yellow humic acid fertilizer of gained, and the content of organic matter is 40%, N, P 2O 5And K 2O total content 6%.
Embodiment 102
Other condition is with embodiment 97
Wherein, each component weight percent content is respectively
Mix concentrated black liquid 60%
Lignin 1%
Humic acid 14%
Mud 20%
Ardealite 5%;
The fulvic acid weight percent content is 25% in the Yellow humic acid fertilizer of gained, and the content of organic matter is 80%, N, P 2O 5And K 2O total content 5%.
Embodiment 103
Other condition is with embodiment 98
Wherein, each component weight percent content is respectively
Mix concentrated black liquid 65%
Lignin 15%
Humic acid 5%
Ardealite 15%;
The fulvic acid weight percent content is 29% in the Yellow humic acid fertilizer of gained, and the content of organic matter is 75%, N, P 2O 5And K 2O total content 5%.
Embodiment 104
(1) alkaline Ya Nafa boiling
Add steaming preparation in the giantreed stalk, wherein sodium hydroxide concentration counts 11% with the over dry raw material weight, and sodium sulfite is 2%, and anthraquinone is 0.02%, and cooking liquor is than being 1:3; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 100 ℃, continues heat temperature raising to 160 ℃, is incubated 60 minutes; Obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 20; All the other conditions are with embodiment 95, and the fulvic acid weight percent content is 6% in the Yellow humic acid fertilizer of gained, and the content of organic matter is 22%.
Embodiment 105
(1) alkaline Ya Nafa boiling
Add steaming preparation in the giantreed stalk, wherein sodium hydroxide concentration counts 15% with the over dry raw material weight, and sodium sulfite is 6%, and anthraquinone is 0.08%, and cooking liquor is than being 1:4; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 120 ℃, continues heat temperature raising to 165 ℃, is incubated 90 minutes; Obtain concentration and be 10% slurry, the hardness of slurry is permanganate number 20;
All the other conditions are with embodiment 95, and the fulvic acid weight percent content is 7% in the Yellow humic acid fertilizer of gained, and the content of organic matter is 24%.
Experimental example 1
2006 in peanut, each 100 mu experiment contrast of corn, use the fertile X-1 of fulvic acid of the embodiment of the invention 92 preparations, consumption 50kg/ mu, contrast farm manure 2000kg/ mu amount of application, the result increases by 90 kilograms for the peanut per mu yield of using fulvic acid fertilizer of the present invention than the per mu yield of use farm manure, volume increase 10.2%: corn increases production 19.5% than using the farm manure per mu yield to increase by 132 kilograms.
This shows that the fulvic acid fertilizer of formulation is more concentrated than the nutriment in a fertilizer of farm manure according to the present invention, be far smaller than at amount of application under the situation of farm manure that tangible effect of increasing production is still arranged, help saving the field labour cost.
Experimental example 2
Continuous 4 seasons of this experimental example are carried out long-acting experiment to wheat,
Wheat breed: raise wheat No. 7,2 groups are established in experiment, and one group of fulvic acid fertilizer of using the embodiment of the invention 93 preparations, control group are commercially available bright spring day of composite fertilizer, and consumption is 50kg/ mu.
Experimental result such as table 1:
The long-acting experiment of table 1 wheat
Figure A200710300209D00771
As seen the fertilizer efficiency time of the present invention is long, reserve strength is sufficient, production-increasing function is obvious.
Experimental example 3
The effect of fulvic acid fertilizer on wheat that the embodiment of the invention 94 was prepared in 2006 studied.
Wheat breed: raise wheat No. 7, soil is sandy loam, middle fertility.3 groups are established in test, use respectively in wheat during jointing stage:
(1) the fulvic acid fertilizer of the embodiment of the invention 3 preparations, consumption 50kg/ mu;
(2) commercially available Dongfanghong composite fertilizer 50kg/ mu;
(3) blank
Result of the test is as shown in table 3:
Table 2 wheat economic characters and output
Figure A200710300209D00772
Figure A200710300209D00781
As seen from Table 2,
(1) wheat best result tiller number, effective tillering number and the percentage of earbearing tiller of executing fertilizer of the present invention improved 3.5%, 22.2% and 6.75% than sealing fertilizer respectively, improved 8.7%, 57.2% and 13.5% than the contrast of not applying fertilizer.
(2) wheat yield of executing fertilizer of the present invention, composite fertilizer does not more apply fertilizer all increases to some extent.Through variance analysis and multiple comparison shows that: spray fertilizer of the present invention, composite fertilizer's contrast volume increase all reaches the utmost point level of signifiance, growth rate is respectively 28.67%, 17.65%.
Experimental example 4
Experiment soil is red earth, the content of organic matter is 0.62%, pH value 4.98, it is divided into 5 groups, the product that in soil, adds embodiment 3-6 respectively, consumption 50kg/ mu, remaining one group as blank CK, surveys soil specific surface area, the soil quantity of electric charge, soil cation exchange capacity (CEC) and soil pH of each group then respectively.
Experimental result is as shown in table 3:
Table 3 Yellow humic acid fertilizer of the present invention is to the influence of soil property
Figure A200710300209D00782
Soil specific surface area is one of key property of soil colloid.The surface type of soil colloid can be divided into inner surface and outer surface.Different component, dissimilar surfaces are not individualisms in soil, but the staggered weave in that mixes, interacts.Soil specific surface area increases, and illustrates that the reactivity of soil increases.
Soil with electric charge mainly concentrate on the colloid part of soil.Soil surface charged kind, quantity and charge density influence the interaction of soil and soil liquid intermediate ion, thereby influence the character of soil.
The soil cation exchange capacity (CEC) also is very important chemical property of soil, and it has directly reflected guarantor's fertilizer, nutrient supplying capability energy and the buffering ability of soil.Because soil is to be caused by the coulomb electrostatic force between soil surface negative electrical charge and CATION to cationic absorption, soil with the quantity of electric charge big more, the CATION of absorption is many more, the cation exchange capacity (CEC) of soil is big more, thereby the activity of soil is also just big more.
PH is 4.89 for the examination soil sample, belongs to strongly acidic soil, is unfavorable for plant growing.Applied the soil-repairing agent of the present invention's preparation in soil after, the acidity of soil weakens, and the pH of soil improves.
As seen the Yellow humic acid fertilizer of formulation has good improved effect to acid ground according to the present invention.
Experimental example 5
Experiment applies the product of embodiment 103, consumption 60kg/ mu, the various ion concentrations such as the table 4 of upper soll layer before and after the experiment with the soil saline-alkali wasteland of attaching most importance to
The ion concentration of table 4 upper soll layer (g/kg of unit)
Figure A200710300209D00783
Figure A200710300209D00791
As seen, the soil-repairing agent of the present invention's preparation has tangible desalting effect on the salt-soda soil, salt rejection rate reaches 73.50%, still obviously minimizing of sodium ion absorption ratio in the soil simultaneously, handle back soil sodium ion absorption than having reduced 60.72%, sodium ion adsorbs than being one of index that shows the alkalization of soils degree.Add pH in soil and significantly reduce, so the Yellow humic acid fertilizer of formulation also has tangible improving effect to the salt-soda soil according to the present invention.
Embodiment 106-116 is the preparation embodiment of Yellow humic acid water flush fertilizer
Embodiment 106
(1) Ammonium Sulfite Method boiling
In rice straw, add steaming preparation, wherein the consumption of ammonium sulfite is an over dry material quantity 9%, liquor ratio is 1:2, feed steam and heat, heat temperature raising is incubated 20 minutes when temperature is 100 ℃, carry out little steam bleeding, continue heat temperature raising to 165 ℃, be incubated 60 minutes, obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 16.
(2) the high-hardness pulp post processing obtains rare black liquor
Slurry enters from the inlet of press master, and extruding black liquor after the extruding black liquor, carries out pulp washing, the black liquor that merging is extruded and the black liquor of pulp washing, and obtaining solid content is 15%, and Baume degrees is rare black liquor of 9, and pH is 10.
(3) add the solubility macroelement fertilizer in the black liquor
Add ammonium dihydrogen phosphate (ADP) in rare black liquor, promptly get Yellow humic acid water flush fertilizer.
Wherein, each component weight percent content is respectively:
Rare black liquor 98%
Ammonium dihydrogen phosphate (ADP) 2%,
The weight percent content of nitrogen is 3% in the described Yellow humic acid water flush fertilizer, and the percentage by weight of phosphorus is with P 2O 5Count 3%, fulvic acid percentage by weight 5%.
Embodiment 107
(1) wheat straw waste is used Ammonium Sulfite Method and anthraquinone-soda cooking respectively
Maceration extract dipping wheat straw waste makes liquor ratio reach 1:2, and in 85 ℃ of insulations and mixing 10 minutes in the spiral macerator, maceration extract is 4% sodium hydroxide solution for the over dry material quantity under normal pressure.
Add steaming preparation in a part of wheat straw waste, wherein the consumption of ammonium sulfite is an over dry material quantity 13%, and liquor ratio is 1:4; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 120 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes; Obtain concentration and be 15% slurry, the hardness of slurry is permanganate number 28
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 9%, liquor ratio is 1:2, the anthraquinone addition is 0.5% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 100 ℃, continues heat temperature raising to 165 ℃, is incubated 60 minutes; Obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 16.
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 4%, and Baume degrees is rare black liquor of 2, and wherein the rare black liquor pH of Ammonium Sulfite Method is 7, and the rare black liquor pH of anthraquinone-soda processes is 9.
(3) add the solubility macroelement fertilizer in the black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare black liquor of anthraquinone-soda processes mixed according to volume ratio 1:100, obtain the rare black liquor of mixed straw, to mix the direct evaporation and concentration of rare straw pulp black liquor to solid content is 30%, Baume degrees is 18, obtain mixing concentrated black liquid, its pH=11 will mix and add ammonium dihydrogen phosphate (ADP) in the concentrated black liquid, promptly get Yellow humic acid water flush fertilizer.
Wherein, each component weight percent content is respectively:
Mix concentrated black liquid 98%
Ammonium dihydrogen phosphate (ADP) 2%,
Adjustment pH with Yellow humic acid water flush fertilizer is 10 then
The weight percent content of nitrogen is 3% in the described Yellow humic acid water flush fertilizer, and the percentage by weight of phosphorus is with P 2O 5Count 3%, fulvic acid percentage by weight 15%.
Embodiment 108
(1) wheat straw waste is used Ammonium Sulfite Method and anthraquinone-soda cooking respectively
Maceration extract dipping wheat straw waste makes liquor ratio reach 1:4, and in 95 ℃ of insulations and mixing 40 minutes in the spiral macerator, maceration extract is the mixed liquor of the black liquor of 4% sodium hydroxide solution and Baume degrees 11 for the over dry material quantity under normal pressure.
Add steaming preparation in a part of wheat straw waste, wherein the consumption of ammonium sulfite is an over dry material quantity 10%, and liquor ratio is 1:3; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 110 ℃, continues heat temperature raising to 170 ℃, is incubated 80 minutes; Obtain concentration and be 9% slurry, the hardness of slurry is permanganate number 18
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 12%, liquor ratio is 1:4, the anthraquinone addition is 0.8% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 120 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes; Obtain concentration and be 15% slurry, the hardness of slurry is permanganate number 28.
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 8%, and Baume degrees is rare black liquor of 5, and wherein the rare black liquor pH of Ammonium Sulfite Method is 8, and the rare black liquor pH of anthraquinone-soda processes is 13.
(3) add the solubility macroelement fertilizer in the black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare straw pulp black liquor of anthraquinone-soda processes mixed according to volume ratio 100:1, obtain the rare black liquor of mixed straw, with the direct evaporation and concentration of mixed straw black liquor to solid content is 65%, Baume degrees is 40, obtain mixing concentrated black liquid, pH=5 will mix and add diammonium hydrogen phosphate and potassium sulfate in the concentrated black liquid, promptly get Yellow humic acid water flush fertilizer.
Wherein, each component weight percent content is respectively:
Mix concentrated black liquid 20%
Diammonium hydrogen phosphate 60%
Potassium sulfate 20%;
Adjustment pH with Yellow humic acid water flush fertilizer is 6 then
The weight percent content of nitrogen is 25% in the described Yellow humic acid water flush fertilizer, and the percentage by weight of phosphorus is with P 2O 5Count 25%, the percentage by weight of potassium is with K 2O counts 3%, fulvic acid percentage by weight 7%.
Embodiment 109
(1) kraft cooking
Maceration extract dipping wheat straw waste makes liquor ratio reach 1:3, and in 90 ℃ of insulations and mixing 30 minutes in the spiral macerator, maceration extract is the mixed liquor of the black liquor of 4% sodium hydroxide solution and Baume degrees 14 for the over dry material quantity under normal pressure.
In reed straw, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 8%, liquor ratio is 1:2, sulphidity is 5%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 110 ℃, continues heat temperature raising to 165 ℃, is incubated 60 minutes; Obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 20.
(2) the high-hardness pulp post processing obtains rare black liquor
Slurry enters from the inlet of press master, after the extruding black liquor, washs, and bleaching then with the bleached pulp washing, merges black liquor of extruding and the black liquor that washs for 2 times, and obtaining solid content is 8%, and Baume degrees is rare black liquor of 5, and pH is 9.
(3) add the solubility macroelement fertilizer in the black liquor
At first evaporation and concentration is to solid content 15.1% for rare black liquor, and Baume degrees 9 obtains concentrated black liquid, adds urea, ammonium sulfate, ammonium dihydrogen phosphate (ADP) and potassium chloride then, regulates pH to 8, promptly gets Yellow humic acid water flush fertilizer.
Wherein, each component weight percent content is respectively:
Concentrated black liquid 30%
Urea 30%
Ammonium sulfate 8%
Ammonium dihydrogen phosphate (ADP) 30%
Potassium chloride 2%
The weight percent content of nitrogen is 20% in the described Yellow humic acid water flush fertilizer, and the percentage by weight of phosphorus is with P 2O 5Count 10%, the percentage by weight of potassium is with K 2O counts 3%, fulvic acid percentage by weight 5%.
Embodiment 110
(1) the giantreed stalk is used Ammonium Sulfite Method and kraft cooking respectively
Add steaming preparation in a part of giantreed stalk, wherein the consumption of ammonium sulfite is an over dry material quantity 10%, and liquor ratio is 1:3.5; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 35 minutes when temperature is 115 ℃, continues heat temperature raising to 172 ℃, is incubated 70 minutes; Obtain concentration and be 14% slurry, the hardness of slurry is permanganate number 27;
In another part giantreed stalk, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 11%, liquor ratio is 1:4, sulphidity is 15%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 140 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes; Obtain concentration and be 15% slurry, the hardness of slurry is permanganate number 25;
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, wash, the black liquor that merging is extruded and the black liquor of washing, obtaining solid content is 10%, and Baume degrees is rare black liquor of 6, and wherein the rare black liquor pH of Ammonium Sulfite Method is 9, and the rare black liquor pH of sulfate process is 10.
(3) add the solubility macroelement fertilizer in the black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare black liquor of sulfate process mixed according to volume ratio 1:4, obtain the rare black liquor of mixed straw, adopt five to imitate evaporation the mixed straw black liquor, its solid content of mixing concentrated black liquid that obtains is 40%, Baume degrees is 20, pH=6, in mixing concentrated black liquid, add ammonium dihydrogen phosphate (ADP), carbonic hydroammonium,, potassium chloride and potassium sulfate, promptly get Yellow humic acid water flush fertilizer, need not additionally adjust pH.
Wherein, each component weight percent content is respectively:
Mix concentrated black liquid 60%
Ammonium dihydrogen phosphate (ADP) 20%
Carbonic hydroammonium, 10%,
Potassium chloride 2%;
Potassium sulfate 8%;
The weight percent content of nitrogen is 14% in the described Yellow humic acid water flush fertilizer, and the percentage by weight of phosphorus is with P 2O 5Count 8%, the percentage by weight of potassium is with K 2O counts 6%, fulvic acid percentage by weight 15%.
Embodiment 111
(1) wheat straw waste is used Ammonium Sulfite Method and anthraquinone-soda cooking respectively
The Ammonium Sulfite Method boiling is with embodiment 108.
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 11%, liquor ratio is 1:3, the anthraquinone addition is 0.7% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 110 ℃, continues heat temperature raising to 169 ℃, is incubated 75 minutes; Obtain concentration and be 14% slurry, the hardness of slurry is permanganate number 27.
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 12%, and Baume degrees is rare black liquor of 7, and wherein the rare black liquor pH of Ammonium Sulfite Method is 8, and the rare black liquor pH of anthraquinone-soda processes is 12
(3) add the solubility macroelement fertilizer in the black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare black liquor of anthraquinone-soda processes mixed according to volume ratio 4:1, obtain the rare black liquor of mixed straw, adopt five to imitate evaporation the rare black liquor of mixed straw, its solid content of mixing concentrated black liquid that obtains is 47%, Baume degrees is 29, and pH=6 will mix and add urea, ammonium dihydrogen phosphate (ADP) and potassium chloride in the concentrated black liquid, promptly get Yellow humic acid water flush fertilizer, need not adjust pH.
Wherein, each component weight percent content is respectively:
Mix concentrated black liquid 80%
Urea 7%,
Ammonium dihydrogen phosphate (ADP) 8%
Potassium chloride 5%;
The weight percent content of nitrogen is 10% in the described Yellow humic acid water flush fertilizer, and the percentage by weight of phosphorus is with P 2O 5Count 4%, the percentage by weight of potassium is with K 2O counts 6%, fulvic acid percentage by weight 40%.
Embodiment 112
(1) wheat straw waste is used Ammonium Sulfite Method and kraft cooking respectively
The Ammonium Sulfite Method boiling is with embodiment 110
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 10%, liquor ratio is 1:3, sulphidity is 10%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 130 ℃, continues heat temperature raising to 170 ℃, is incubated 80 minutes; Obtain concentration and be 13% slurry, the hardness of slurry is permanganate number 22
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 8%, and Baume degrees is rare black liquor of 5, and wherein the rare black liquor pH of Ammonium Sulfite Method is 9, and the rare black liquor pH of sulfate process is 12.
(3) add the solubility macroelement fertilizer in the black liquor
The rare black liquor of Ammonium Sulfite Method and the rare black liquor of sulfate process according to the mixed of volume ratio 3:1, are obtained the rare black liquor of mixed straw; Adopt five to imitate evaporation the rare black liquor of mixed straw, its solid content of mixing concentrated black liquid that obtains is 45%, and Baume degrees is 28, and pH=7 will mix and add urea and potassium chloride in the concentrated black liquid, promptly get Yellow humic acid water flush fertilizer, need not adjust pH.
Wherein, each component weight percent content is respectively:
Mix concentrated black liquid 70%
Urea 10%,
Potassium chloride 20%;
The weight percent content of nitrogen is 8% in the described Yellow humic acid water flush fertilizer, and the percentage by weight of potassium is with K 2O counts 7%, fulvic acid percentage by weight 32%.
Embodiment 113
Step (one) (two) is with embodiment 111.
(3) add the solubility macroelement fertilizer in the black liquor
Other condition is with embodiment 111, and rare black liquor of Ammonium Sulfite Method and the rare black liquor volume ratio of anthraquinone-caustic soda 10:1 mix careless concentrated black liquid solid content 50%, and Baume degrees is 31, wherein adds potassium dihydrogen phosphate, promptly gets Yellow humic acid water flush fertilizer, does not need additionally to adjust pH.
Wherein, each component weight percent content is respectively:
Mix concentrated black liquid 50%
Potassium dihydrogen phosphate 50%;
The percentage by weight of potassium is with K in the described Yellow humic acid water flush fertilizer 2O counts 25%, and the percentage by weight of phosphorus is with P 2O 5Count 25%, fulvic acid percentage by weight 30%.
Embodiment 114
Step (one) (two) is with embodiment 112
(3) add the solubility macroelement fertilizer in the black liquor
Other condition is with embodiment 112, and rare black liquor of Ammonium Sulfite Method and the rare black liquor volume ratio of sulfate process 1:10 mix concentrated black liquid solid content 30%, and Baume degrees is 17, wherein adds urea, ammonium sulfate, ammonium dihydrogen phosphate (ADP) and potassium chloride, promptly gets Yellow humic acid water flush fertilizer.
Wherein, each component weight percent content is respectively:
Mix concentrated black liquid 30%
Urea 30%
Ammonium sulfate 8%
Ammonium dihydrogen phosphate (ADP) 30%
Potassium chloride 2%
Adjustment pH with Yellow humic acid water flush fertilizer is 8 then
The weight percent content of nitrogen is 20% in the described Yellow humic acid water flush fertilizer, and the percentage by weight of phosphorus is with P 2O 5Count 10%, the percentage by weight of potassium is with K 2O counts 3%, fulvic acid percentage by weight 8%.
Embodiment 115
(1) alkaline Ya Nafa boiling
Add steaming preparation in the giantreed stalk, wherein sodium hydroxide concentration counts 11% with the over dry raw material weight, and sodium sulfite is 2%, and anthraquinone is 0.02%, and cooking liquor is than being 1:3; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 100 ℃, continues heat temperature raising to 160 ℃, is incubated 60 minutes; Obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 20;
All the other conditions are with embodiment 109, and the weight percent content of nitrogen is 19% in the Yellow humic acid water flush fertilizer of gained, and the percentage by weight of phosphorus is with P 2O 5Count 11%, the percentage by weight of potassium is with K 2O counts 4%, fulvic acid percentage by weight 6%.
Embodiment 116
(1) alkaline Ya Nafa boiling
Add steaming preparation in the giantreed stalk, wherein sodium hydroxide concentration counts 15% with the over dry raw material weight, and sodium sulfite is 6%, and anthraquinone is 0.08%, and cooking liquor is than being 1:4; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 120 ℃, continues heat temperature raising to 165 ℃, is incubated 90 minutes; Obtain concentration and be 10% slurry, the hardness of slurry is permanganate number 20;
All the other conditions are with embodiment 109, and the weight percent content of nitrogen is 18% in the Yellow humic acid water flush fertilizer of gained, and the percentage by weight of phosphorus is with P 2O 5Count 10%, the percentage by weight of potassium is with K 2O counts 4%, fulvic acid percentage by weight 5.4%.
Experimental example 6
This experimental example is the manure trial of Yellow humic acid water flush fertilizer of the present invention on green vegetables.
Test is carried out in the farmland, and experimental cultivar is the tetraploid SUZHOUQING, and the farmland is divided into a plurality of sub-districts, and each sub-district is 20m 2, blank group is for being left intact, and control group was used " heart is in fact " organic fertilization fertilizer I number (total nutrient 〉=4%, organic 〉=20%, the real fertilizer of Jiangsu heart Co., Ltd) 600kg/hm in back 10 days for plantation 2Dash and to execute, other is for using embodiment of the invention group, the same control group of consumption, and be the 70th day picking time.
The result is as shown in table 5:
The green vegetables proterties and the output of table 5 different disposal
Figure A200710300209D00831
Experimental example 7
This experimental example is the manure trial of Yellow humic acid water flush fertilizer of the present invention on cucumber.
Test is carried out in agricultural booth, and experimental cultivar is excellent No. 3 of capital, and the farmland is divided into a plurality of sub-districts, each sub-district is 20m2, and blank group is for being left intact, and other is for using embodiment of the invention group, consumption is 600kg/hm2, when time of application is cucumber plant height 90-100cm.
Result of the test such as table 6
The cucumber proterties and the output of table 6 different disposal
Figure A200710300209D00832
Figure A200710300209D00841
Therefore Yellow humic acid water flush fertilizer of the present invention is used the back nutrient and is absorbed easily, be difficult for by soil fixing, and the soil that do not harden, nonhazardous is residual; Use conveniently, save labor; Nutritional labeling is many and comprehensive, and fertilizer efficiency is fast, helps crop yield.In plant growth vigorous season, avoided common fertilizer topdress fertilizer nutrient discharge transform slow, fertilizer efficiency is slow, the shortcoming that influences crop yield and quality.Embodiment 117-130 is the preparation embodiment of Yellow humic acid foliage fertilizer
Embodiment 117
(1) Ammonium Sulfite Method boiling
In rice straw, add steaming preparation, wherein the consumption of ammonium sulfite is an over dry material quantity 9%, liquor ratio is 1:2, feed steam and heat, heat temperature raising is incubated 20 minutes when temperature is 100 ℃, carry out little steam bleeding, continue heat temperature raising to 165 ℃, be incubated 60 minutes, obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 16.
(2) the high-hardness pulp post processing obtains rare black liquor
Slurry enters from the inlet of press master, and extruding black liquor after the extruding black liquor, carries out pulp washing, the black liquor that merging is extruded and the black liquor of pulp washing, and obtaining solid content is 15%, and Baume degrees is rare black liquor of 9, and pH is 10.
(3) add soluble trace elements fertilizer in the black liquor
In rare black liquor, add 0.1g ferrous sulfate and 20g zinc sulfate, use H by every 1000ml 3PO 4With pH regulator is 10; Promptly get Yellow humic acid foliage fertilizer, the fulvic acid weight percent content is 5%, is applicable to field crop.
Embodiment 118
(1) wheat straw waste is used Ammonium Sulfite Method and anthraquinone-soda cooking respectively
Maceration extract dipping wheat straw waste makes liquor ratio reach 1:2, and in 85 ℃ of insulations and mixing 10 minutes in the spiral macerator, maceration extract is 4% sodium hydroxide solution for the over dry material quantity under normal pressure.
Add steaming preparation in a part of wheat straw waste, wherein the consumption of ammonium sulfite is an over dry material quantity 13%, and liquor ratio is 1:4; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 120 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes; Obtain concentration and be 15% slurry, the hardness of slurry is permanganate number 28.
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 9%, liquor ratio is 1:2, the anthraquinone addition is 0.5% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 100 ℃, continues heat temperature raising to 165 ℃, is incubated 60 minutes; Obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 16.
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 4%, and Baume degrees is rare black liquor of 2, and wherein the rare black liquor pH of Ammonium Sulfite Method is 7, and the rare black liquor pH of anthraquinone-soda processes is 9.
(3) add soluble trace elements fertilizer in the black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare black liquor of anthraquinone-soda processes mixed according to volume ratio 1:100, obtain the rare black liquor of mixed straw, to mix the direct evaporation and concentration of rare straw pulp black liquor to solid content is 30%, Baume degrees is 18, obtain mixing concentrated black liquid, its pH=11 adds 0.1g borax, 15g ferrous sulfate and 20g zinc sulfate by every 1000ml in mixing dense straw pulp black liquor, use H 3PO 4With pH regulator is 8; Promptly get Yellow humic acid foliage fertilizer, fulvic acid percentage by weight 8% is applicable to fruit tree.
Embodiment 119
(1) wheat straw waste is used Ammonium Sulfite Method and anthraquinone-soda cooking respectively
Maceration extract dipping wheat straw waste makes liquor ratio reach 1:4, and in 95 ℃ of insulations and mixing 40 minutes in the spiral macerator, maceration extract is the mixed liquor of the black liquor of 4% sodium hydroxide solution and Baume degrees 11 for the over dry material quantity under normal pressure.
Add steaming preparation in a part of wheat straw waste, wherein the consumption of ammonium sulfite is an over dry material quantity 10%, and liquor ratio is 1:3; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 110 ℃, continues heat temperature raising to 170 ℃, is incubated 80 minutes; Obtain concentration and be 9% slurry, the hardness of slurry is permanganate number 18
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 12%, liquor ratio is 1:4, the anthraquinone addition is 0.8% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 120 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes; Obtain concentration and be 15% slurry, the hardness of slurry is permanganate number 28.
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 8%, and Baume degrees is rare black liquor of 5, and wherein the rare black liquor pH of Ammonium Sulfite Method is 8, and the rare black liquor pH of anthraquinone-soda processes is 13.
(3) add soluble trace elements fertilizer in the black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare straw pulp black liquor of anthraquinone-soda processes mixed according to volume ratio 100:1, obtain the rare black liquor of mixed straw, with the direct evaporation and concentration of mixed straw black liquor to solid content is 65%, Baume degrees is 40, obtain mixing concentrated black liquid, pH=5 adds 15g boric acid and 0.1g zinc sulfate by every 1000ml in mixing concentrated black liquid, use HNO 3Adjusting pH is 6, promptly gets Yellow humic acid foliage fertilizer, and fulvic acid percentage by weight 40% is applicable to vegetables.
Embodiment 120
(1) kraft cooking
Maceration extract dipping wheat straw waste makes liquor ratio reach 1:3, and in 90 ℃ of insulations and mixing 30 minutes in the spiral macerator, maceration extract is the mixed liquor of the black liquor of 4% sodium hydroxide solution and Baume degrees 14 for the over dry material quantity under normal pressure.
In reed straw, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 8%, liquor ratio is 1:2, sulphidity is 5%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 110 ℃, continues heat temperature raising to 165 ℃, is incubated 60 minutes; Obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 20.
(2) the high-hardness pulp post processing obtains rare black liquor
Slurry enters from the inlet of press master, after the extruding black liquor, carries out pulp washing, the black liquor that merging is extruded and the black liquor of pulp washing, and obtaining solid content is 8%, and Baume degrees is rare black liquor of 5, and pH is 9.
(3) add soluble trace elements fertilizer in the black liquor
At first evaporation and concentration is to solid content 15.1% for rare black liquor, and Baume degrees 9 obtains concentrated black liquid, adds 0.1g ferrous sulfate and 20g zinc sulfate by every 1000ml in concentrated black liquid, uses H 3PO 4With pH regulator is 10; Promptly get Yellow humic acid foliage fertilizer, the fulvic acid weight percent content is 5%, is applicable to field crop.
Embodiment 121
(1) the giantreed stalk is used Ammonium Sulfite Method and kraft cooking respectively
Add steaming preparation in a part of giantreed stalk, wherein the consumption of ammonium sulfite is an over dry material quantity 10%, and liquor ratio is 1:3.5; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 35 minutes when temperature is 115 ℃, continues heat temperature raising to 172 ℃, is incubated 70 minutes; Obtain concentration and be 14% slurry, the hardness of slurry is permanganate number 27;
In another part giantreed stalk, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 11%, liquor ratio is 1:4, sulphidity is 15%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 140 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes; Obtain concentration and be 15% slurry, the hardness of slurry is permanganate number 25;
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, wash, the black liquor that merging is extruded and the black liquor of washing, obtaining solid content is 10%, and Baume degrees is rare black liquor of 6, and wherein the rare black liquor pH of Ammonium Sulfite Method is 9, and the rare black liquor pH of sulfate process is 10.
(3) add soluble trace elements fertilizer in the black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare black liquor of sulfate process mixed according to volume ratio 1:4, obtain the rare black liquor of mixed straw, adopt five to imitate evaporation the mixed straw black liquor, its solid content of mixing concentrated black liquid that obtains is 40%, and Baume degrees is 20, pH=6, in mixing concentrated black liquid, add 0.1g boric acid and 20g zinc chloride, do not need additionally to adjust pH, promptly get Yellow humic acid foliage fertilizer by every 1000ml, fulvic acid percentage by weight 15% is applicable to vegetables.
Embodiment 122
(1) wheat straw waste is used Ammonium Sulfite Method and anthraquinone-soda cooking respectively
The Ammonium Sulfite Method boiling is with embodiment 119
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 11%, liquor ratio is 1:3, the anthraquinone addition is 0.7% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 110 ℃, continues heat temperature raising to 169 ℃, is incubated 75 minutes; Obtain concentration and be 14% slurry, the hardness of slurry is permanganate number 27
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 12%, and Baume degrees is rare black liquor of 7, and wherein the rare black liquor pH of Ammonium Sulfite Method is 8, and the rare black liquor pH of anthraquinone-soda processes is 12
(3) add soluble trace elements fertilizer in the black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare black liquor of anthraquinone-soda processes mixed according to volume ratio 4:1, obtain the rare black liquor of mixed straw, adopt five to imitate evaporation the rare black liquor of mixed straw, its solid content of mixing concentrated black liquid that obtains is 47%, Baume degrees is 29, pH=6 adds 15g borax, 0.1g ferrous sulfate and 0.1g zinc sulfate by every 1000ml in mixing concentrated black liquid, do not need additionally to adjust pH; Promptly get Yellow humic acid foliage fertilizer, fulvic acid percentage by weight 30% is applicable to fruit tree.
Embodiment 123
(1) wheat straw waste is used Ammonium Sulfite Method and kraft cooking respectively
The Ammonium Sulfite Method boiling is with embodiment 121
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 10%, liquor ratio is 1:3, sulphidity is 10%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 130 ℃, continues heat temperature raising to 170 ℃, is incubated 80 minutes; Obtain concentration and be 13% slurry, the hardness of slurry is permanganate number 22.
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 8%, and Baume degrees is rare black liquor of 5, and wherein the rare black liquor pH of Ammonium Sulfite Method is 9, and the rare black liquor pH of sulfate process is 12.
(3) add soluble trace elements fertilizer in the black liquor
The rare black liquor of Ammonium Sulfite Method and the rare black liquor of sulfate process according to the mixed of volume ratio 3:1, are obtained the rare black liquor of mixed straw; Adopt five to imitate evaporation the rare black liquor of mixed straw, its solid content of mixing concentrated black liquid that obtains is 45%, and Baume degrees is 28, and pH=7 adds 15g ferrous sulfate and 0.1g zinc chloride by every 1000ml in mixing concentrated black liquid, do not need additionally to adjust pH; Promptly get Yellow humic acid foliage fertilizer, fulvic acid percentage by weight 35% is applicable to field crop.
Embodiment 124
Step (one) (two) is with embodiment 122
(3) add soluble trace elements fertilizer in the black liquor
Other condition is with embodiment 122, and rare black liquor of Ammonium Sulfite Method and the rare black liquor volume ratio of anthraquinone-caustic soda 10:1 add 0.1g boric acid and 15g zinc sulfate by every 1000ml in mixing concentrated black liquid, do not need additionally to adjust pH, promptly get Yellow humic acid foliage fertilizer, fulvic acid percentage by weight 37% is applicable to vegetables.
Embodiment 125
Step (one) (two) is with embodiment 123
(3) add soluble trace elements fertilizer in the black liquor
Other condition is with embodiment 121, and rare black liquor of Ammonium Sulfite Method and the rare black liquor volume ratio of sulfate process 1:10 add 15g borax, 0.1g ferrous sulfate and 0.1g zinc sulfate by every 1000ml in alkaline process and the concentrated straw pulp black liquor of Ammonium Sulfite Method mixing, do not need additionally to adjust pH; Promptly get Yellow humic acid foliage fertilizer, fulvic acid percentage by weight 30% is applicable to fruit tree.
Embodiment 126,
Other condition is with embodiment 123
In mixing concentrated black liquid, add 5g borax, 10g ferrous sulfate and 6g zinc sulfate, do not need additionally to adjust pH by every 1000ml; Promptly get Yellow humic acid foliage fertilizer, fulvic acid percentage by weight 25% is applicable to fruit tree.
Embodiment 127
Other condition is with embodiment 122
In mixing concentrated black liquid, add 9g ferrous sulfate and 3g zinc sulfate, use H by every 1000ml 3PO 4With pH regulator is 10; Promptly get Yellow humic acid foliage fertilizer, fulvic acid percentage by weight 28% is applicable to field crop.
Embodiment 128
Other condition is with embodiment 123
In mixing concentrated black liquid, add 10g boric acid and 13g zinc sulfate, use HNO by every 1000ml 3Adjusting pH is 6, promptly gets Yellow humic acid foliage fertilizer, and fulvic acid percentage by weight 26% is applicable to vegetables.
Embodiment 129
(1) alkaline Ya Nafa boiling
Add steaming preparation in the giantreed stalk, wherein sodium hydroxide concentration counts 11% with the over dry raw material weight, and sodium sulfite is 2%, and anthraquinone is 0.02%, and cooking liquor is than being 1:3; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 100 ℃, continues heat temperature raising to 160 ℃, is incubated 60 minutes; Obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 20;
All the other conditions add 12g borax, 11g ferrous sulfate and 7g zinc sulfate by every 1000ml with embodiment 4 in concentrated black liquid, use H 3PO 4With pH regulator is 8; Promptly get Yellow humic acid foliage fertilizer, fulvic acid percentage by weight 8% is applicable to fruit tree.
Embodiment 130
(1) alkaline Ya Nafa boiling
Add steaming preparation in the giantreed stalk, wherein sodium hydroxide concentration counts 15% with the over dry raw material weight, and sodium sulfite is 6%, and anthraquinone is 0.08%, and cooking liquor is than being 1:4; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 120 ℃, continues heat temperature raising to 165 ℃, is incubated 90 minutes; Obtain concentration and be 10% slurry, the hardness of slurry is permanganate number 20;
All the other conditions add 6g borax, 7g ferrous sulfate and 5g zinc sulfate by every 1000ml with embodiment 120 in concentrated black liquid, use H 3PO 4With pH regulator is 8; Promptly get Yellow humic acid foliage fertilizer, fulvic acid percentage by weight 7% is applicable to fruit tree.
Experimental example 8
1, test material and method
Da Qu method of comparison, every demonstration test district area 2.0hm are adopted in test 23 processing are established in test altogether, handle 1,2 on the basis of conventional fertilizer application, 1000 times of liquid foliage spray of Yellow humic acid foliage fertilizer that obtain with embodiment 117 and 120 in earlier stage at seedling stage, flower respectively, per hectare consumption 450g; Processing 3 on the basis of conventional fertilizer application, is used the foliage spray of equivalent clear water at seedling stage, flower for contrast respectively in earlier stage.Rice varieties is that sky educates 131 for trying the water.
2, determination of yield result
Table 7
Figure A200710300209D00871
Result of the test shows, uses square metre spike number, plant height, spike length, the real grain of fringe number, mass of 1000 kernel, the output of the paddy rice of product of the present invention and compares than control group, and significant increase is all arranged.Wherein, embodiment contrasts per hectare volume increase 1135.0kg for 117 groups, volume increase 18.4%, and embodiment contrasts per hectare volume increase 1460.5, volume increase 23.6%, remarkable in economical benefits for 120 groups.
Experimental example 9
1, experimental cultivar
No. 8 apples of the U.S. are the improved seeds of U.S.'s seed selection
2, experimental design and method
This test is established 4 and different is used processing, and first three groups with 1000 times of foliage-sprays of foliage fertilizer dilution of embodiment 118,122,125, is established one group of contrast in addition and sprayed clear water respectively.Sub-district area 60m 2(long 30m, wide 2m).There are apple tree 10 strains every sub-district.Foliage dressing is carried out about 10 o'clock of the fine morning.
3, result of the test
Table 8
Figure A200710300209D00881
As seen, the apple of using the Yellow humic acid foliage fertilizer that embodiment 118,122,125 obtains contrast increase production 7.23%, 12.22%, 11.83% respectively, remarkable in economical benefits.
Experimental example 10
1, for the examination material
(1) for the organic humic acid liquid fertilizer of examination fertilizer: Hui Manfeng 4000mg/kg, mainly contains humic acid and each kind of plant required a great number of elements and trace element;
The embodiment of the invention 119 and 121 gained Yellow humic acid foliage fertilizers
(2) No. five capsicums of experimental cultivar Soviet Union green pepper, the development of academy of agricultural sciences, Jiangsu Province Vegetable Research Institute.
2, test method
Tested in 2005-2006 years and carry out in the booth.On October 20th, 2006 grew seedlings in the booth, and November 30 was heeled in nutritive cube, field planting on February 5, wide row space 65cm, little line-spacing 35cm, spacing in the rows 33cm, the high furrow of zanjon.Sub-district final singling 30 strains.Carry out the 1st foliage-spray and handle when the door green pepper blooms, Men Jiaozhi carries out the 2nd foliage-spray when 2cm handles, and the door green pepper carries out the 3rd foliage-spray when gathering handles, and is contrast with the clear water.Phase beginning of gathering is April 25, gather final be July 2, totally 68 days.
3, result of the test
The total output of table 9 different disposal
As seen, use the Yellow humic acid foliage fertilizer obvious effect of increasing production of the embodiment of the invention 119 and 121.
Embodiment 131
(1) Ammonium Sulfite Method boiling
In rice straw, add steaming preparation, wherein the consumption of ammonium sulfite is an over dry material quantity 9%, liquor ratio is 1:2, feed steam and heat, heat temperature raising is incubated 20 minutes when temperature is 100 ℃, carry out little steam bleeding, continue heat temperature raising to 165 ℃, be incubated 60 minutes, obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 16.
(2) the high-hardness pulp post processing obtains rare black liquor
Slurry enters from the inlet of press master, and extruding black liquor after the extruding black liquor, carries out pulp washing, the black liquor that merging is extruded and the black liquor of pulp washing, and obtaining solid content is 15%, and Baume degrees is rare black liquor of 9, and pH is 10.
(3) prepare fulvic acid solution by black liquor
With the pH regulator to 5 of formic acid with rare black liquor, separate out lignin, add the bodied ferric sulfate of black liquor weight 2ppm, leave standstill, then black liquor to be filtered, filtrate is fulvic acid solution.
With fulvic acid solution drying, obtain fulvic acid.
Embodiment 132
(1) wheat straw waste is used Ammonium Sulfite Method and anthraquinone-soda cooking respectively
Maceration extract dipping wheat straw waste makes liquor ratio reach 1:2, and in 85 ℃ of insulations and mixing 10 minutes in the spiral macerator, maceration extract is 4% sodium hydroxide solution for the over dry material quantity under normal pressure.
Add steaming preparation in a part of wheat straw waste, wherein the consumption of ammonium sulfite is an over dry material quantity 13%, and liquor ratio is 1:4; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 120 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes; Obtain concentration and be 15% slurry, the hardness of slurry is permanganate number 28.
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 9%, liquor ratio is 1:2, the anthraquinone addition is 0.5% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 100 ℃, continues heat temperature raising to 165 ℃, is incubated 60 minutes; Obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 16.
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 4%, and Baume degrees is rare black liquor of 2, and wherein the rare black liquor pH of Ammonium Sulfite Method is 7, and the rare black liquor pH of anthraquinone-soda processes is 9.
(3) prepare fulvic acid solution by black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare black liquor of anthraquinone-soda processes mixed according to volume ratio 1:100, obtain the rare black liquor of mixed straw, will mix the direct evaporation and concentration of rare straw pulp black liquor to solid content is 30%, and Baume degrees is 18, obtain mixing concentrated black liquid, its pH=11 with the pH regulator to 2 of acetate with concentrated black liquid, separates out lignin, the aluminium chloride that adds black liquor weight 50ppm, leave standstill, then black liquor is filtered, filtrate is fulvic acid solution.With fulvic acid solution drying, obtain fulvic acid.
Embodiment 133
(1) wheat straw waste is used Ammonium Sulfite Method and anthraquinone-soda cooking respectively
Maceration extract dipping wheat straw waste makes liquor ratio reach 1:4, and in 95 ℃ of insulations and mixing 40 minutes in the spiral macerator, maceration extract is the mixed liquor of the black liquor of 4% sodium hydroxide solution and Baume degrees 11 for the over dry material quantity under normal pressure.
Add steaming preparation in a part of wheat straw waste, wherein the consumption of ammonium sulfite is an over dry material quantity 10%, and liquor ratio is 1:3; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 110 ℃, continues heat temperature raising to 170 ℃, is incubated 80 minutes; Obtain concentration and be 9% slurry, the hardness of slurry is permanganate number 18
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 12%, liquor ratio is 1:4, the anthraquinone addition is 0.8% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 120 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes; Obtain concentration and be 15% slurry, the hardness of slurry is permanganate number 28.
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 8%, and Baume degrees is rare black liquor of 5, and wherein the rare black liquor pH of Ammonium Sulfite Method is 8, and the rare black liquor pH of anthraquinone-soda processes is 13.
(3) prepare fulvic acid solution by black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare straw pulp black liquor of anthraquinone-soda processes mixed according to volume ratio 100:1, obtaining the rare black liquor of mixed straw, is 65% with the direct evaporation and concentration of mixed straw black liquor to solid content, and Baume degrees is 40, obtain mixing concentrated black liquid, pH=5 with the pH regulator to 4 of propionic acid with concentrated black liquid, separates out lignin, the ammonium polyacrylate that adds black liquor weight 5ppm, leave standstill, then black liquor is filtered, filtrate is fulvic acid solution.
With fulvic acid solution with the described method supercritical CO of Chinese patent CN01141835.4 2Extract, promptly get high-purity xanthohumic acid.
Embodiment 134
(1) kraft cooking
Maceration extract dipping wheat straw waste makes liquor ratio reach 1:3, and in 90 ℃ of insulations and mixing 30 minutes in the spiral macerator, maceration extract is the mixed liquor of the black liquor of 4% sodium hydroxide solution and Baume degrees 14 for the over dry material quantity under normal pressure.
In reed straw, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 8%, liquor ratio is 1:2, sulphidity is 5%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 110 ℃, continues heat temperature raising to 165 ℃, is incubated 60 minutes; Obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 20.
(2) the high-hardness pulp post processing obtains rare black liquor
Slurry enters from the inlet of press master, after the extruding black liquor, carries out pulp washing, the black liquor that merging is extruded and the black liquor of pulp washing, and obtaining solid content is 8%, and Baume degrees is rare black liquor of 5, and pH is 9.
(3) prepare fulvic acid solution by black liquor
At first evaporation and concentration is to solid content 15.1% for rare black liquor, and Baume degrees 9 obtains concentrated black liquid, with the pH regulator to 3.5 of benzoic acid with concentrated black liquid, separate out lignin, add the ammonium polyacrylate of black liquor weight 15ppm, leave standstill, then black liquor is filtered, filtrate is fulvic acid solution.
With fulvic acid solution with the described method supercritical CO of Chinese patent CN01141835.4 2Extract, promptly get high-purity xanthohumic acid.
Embodiment 135
(1) the giantreed stalk is used Ammonium Sulfite Method and kraft cooking respectively
Add steaming preparation in a part of giantreed stalk, wherein the consumption of ammonium sulfite is an over dry material quantity 10%, and liquor ratio is 1:3.5; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 35 minutes when temperature is 115 ℃, continues heat temperature raising to 172 ℃, is incubated 70 minutes; Obtain concentration and be 14% slurry, the hardness of slurry is permanganate number 27;
In another part giantreed stalk, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 11%, liquor ratio is 1:4, sulphidity is 15%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 140 ℃, continues heat temperature raising to 173 ℃, is incubated 90 minutes; Obtain concentration and be 15% slurry, the hardness of slurry is permanganate number 25;
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, wash, the black liquor that merging is extruded and the black liquor of washing, obtaining solid content is 10%, and Baume degrees is rare black liquor of 6, and wherein the rare black liquor pH of Ammonium Sulfite Method is 9, and the rare black liquor pH of sulfate process is 10.
(3) prepare fulvic acid solution by black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare black liquor of sulfate process mixed according to volume ratio 1:4, obtain the rare black liquor of mixed straw, adopt five to imitate evaporation the mixed straw black liquor, its solid content of mixing concentrated black liquid that obtains is 40%, Baume degrees is 20, pH=6 with the pH regulator to 3.7 of hydrochloric acid with concentrated black liquid, separates out lignin, the aluminium chloride that adds black liquor weight 10ppm, leave standstill, then black liquor is filtered, filtrate is fulvic acid solution.
With fulvic acid solution with the described method supercritical CO of Chinese patent CN01141835.4 2Extract, promptly get high-purity xanthohumic acid.
Embodiment 136
(1) wheat straw waste is used Ammonium Sulfite Method and anthraquinone-soda cooking respectively
The Ammonium Sulfite Method boiling is with embodiment 133
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 11%, liquor ratio is 1:3, the anthraquinone addition is 0.7% of an over dry material quantity; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 110 ℃, continues heat temperature raising to 169 ℃, is incubated 75 minutes; Obtain concentration and be 14% slurry, the hardness of slurry is permanganate number 27
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 12%, and Baume degrees is rare black liquor of 7, and wherein the rare black liquor pH of Ammonium Sulfite Method is 8, and the rare black liquor pH of anthraquinone-soda processes is 12.
(3) prepare fulvic acid solution by black liquor
With the rare black liquor of Ammonium Sulfite Method and the rare black liquor of anthraquinone-soda processes mixed according to volume ratio 4:1, obtain the rare black liquor of mixed straw, adopt five to imitate evaporation the rare black liquor of mixed straw, its solid content of mixing concentrated black liquid that obtains is 47%, Baume degrees is 29, pH=6 with the pH regulator to 4.5 of sulfuric acid with concentrated black liquid, separates out lignin, the aluminium chloride that adds black liquor weight 30ppm, leave standstill, then black liquor is filtered, filtrate is fulvic acid solution.Fulvic acid solution is drying to obtain the crude product fulvic acid.
Embodiment 137
(1) wheat straw waste is used Ammonium Sulfite Method and kraft cooking respectively
The Ammonium Sulfite Method boiling is with embodiment 135
In another part wheat straw waste, add steaming preparation, wherein alkali charge in NaOH to over dry material quantity 10%, liquor ratio is 1:3, sulphidity is 10%; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 30 minutes when temperature is 130 ℃, continues heat temperature raising to 170 ℃, is incubated 80 minutes; Obtain concentration and be 13% slurry, the hardness of slurry is permanganate number 22.
(2) the high-hardness pulp post processing obtains rare black liquor
The slurry of above step gained is carried out shove respectively with press master, and obtaining solid content is 8%, and Baume degrees is rare black liquor of 5, and wherein the rare black liquor pH of Ammonium Sulfite Method is 9, and the rare black liquor pH of sulfate process is 12.
(3) prepare fulvic acid solution by black liquor
The rare black liquor of Ammonium Sulfite Method and the rare black liquor of sulfate process according to the mixed of volume ratio 3:1, are obtained the rare black liquor of mixed straw; Adopt five to imitate evaporation the rare black liquor of mixed straw, its solid content of mixing concentrated black liquid that obtains is 45%, Baume degrees is 28, pH=7 with the pH regulator to 2.5 of nitric acid with concentrated black liquid, separates out lignin, the aluminium chloride that adds black liquor weight 7ppm, leave standstill, then black liquor is filtered, filtrate is fulvic acid solution.
Fulvic acid solution is drying to obtain the crude product fulvic acid.
Embodiment 138
Step (one) (two) is with embodiment 136
(3) prepare fulvic acid solution by black liquor
Other condition is with embodiment 136, and rare black liquor of Ammonium Sulfite Method and the rare black liquor volume ratio of anthraquinone-caustic soda 10:1 are with the pH regulator to 2.8 of nitric acid with concentrated black liquid, separate out lignin, add the aluminium chloride of black liquor weight 8ppm, leave standstill, then black liquor is filtered, filtrate is fulvic acid solution.
Fulvic acid solution is drying to obtain the crude product fulvic acid.
Embodiment 139
Step (one) (two) is with embodiment 137
(3) prepare fulvic acid solution by black liquor
Other condition is with embodiment 135, and rare black liquor of Ammonium Sulfite Method and the rare black liquor volume ratio of sulfate process 1:10 are with the pH regulator to 2.1 of nitric acid with concentrated black liquid, separate out lignin, add the ammonium polyacrylate of black liquor weight 9ppm, leave standstill, then black liquor is filtered, filtrate is fulvic acid solution.
Fulvic acid solution is drying to obtain the crude product fulvic acid.
Embodiment 140,
Other condition is with embodiment 137
With the pH regulator to 1 of phosphoric acid with concentrated black liquid, separate out lignin, add the polyaluminium sulfate of black liquor weight 14ppm, leave standstill, then black liquor to be filtered, filtrate is fulvic acid solution.
Fulvic acid solution is drying to obtain the crude product fulvic acid.
Embodiment 141
Other condition is with embodiment 136
With the pH regulator to 1.5 of phosphoric acid with concentrated black liquid, separate out lignin, add the polyaluminium sulfate of black liquor weight 20ppm, leave standstill, then black liquor to be filtered, filtrate is fulvic acid solution.
With fulvic acid solution with the described method supercritical CO of Chinese patent CN01141835.4 2Extract, promptly get high-purity xanthohumic acid.
Embodiment 142
Other condition is with embodiment 137
With the pH regulator to 2.8 of phosphoric acid with concentrated black liquid, separate out lignin, add the polyaluminium sulfate of black liquor weight 18ppm, leave standstill, then black liquor to be filtered, filtrate is fulvic acid solution.
Fulvic acid solution is drying to obtain the crude product fulvic acid.
Embodiment 143
(1) alkaline Ya Nafa boiling
Add steaming preparation in the giantreed stalk, wherein sodium hydroxide concentration counts 11% with the over dry raw material weight, and sodium sulfite is 2%, and anthraquinone is 0.02%, and cooking liquor is than being 1:3; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 20 minutes when temperature is 100 ℃, continues heat temperature raising to 160 ℃, is incubated 60 minutes; Obtain concentration and be 8% slurry, the hardness of slurry is permanganate number 20;
All the other conditions with the pH regulator to 3.2 of phosphoric acid with concentrated black liquid, are separated out lignin with embodiment 134, add the polyaluminium sulfate of black liquor weight 11ppm, leave standstill, and then black liquor are filtered, and filtrate is fulvic acid solution.
Fulvic acid solution is drying to obtain the crude product fulvic acid.
Embodiment 144
(1) alkaline Ya Nafa boiling
Add steaming preparation in the giantreed stalk, wherein sodium hydroxide concentration counts 15% with the over dry raw material weight, and sodium sulfite is 6%, and anthraquinone is 0.08%, and cooking liquor is than being 1:4; Feed steam and heat, little steam bleeding is carried out in heat temperature raising insulation 40 minutes when temperature is 120 ℃, continues heat temperature raising to 165 ℃, is incubated 90 minutes; Obtain concentration and be 10% slurry, the hardness of slurry is permanganate number 20;
All the other conditions with the pH regulator to 2.7 of nitric acid with concentrated black liquid, are separated out lignin with embodiment 134, add the polyaluminium sulfate of black liquor weight 6ppm, leave standstill, and then black liquor are filtered, and filtrate is fulvic acid solution.
With fulvic acid solution with the described method supercritical CO of Chinese patent CN01141835.4 2Extract, promptly get high-purity xanthohumic acid.
Experimental example 11
Crude product fulvic acid to embodiment 137 is measured, and the result is as follows:
(1), architectural feature
1, element is formed: C 54.82% H 2.29% O 41.14% N 0.66% S 1.09%
2, functional group content: total acidic group 8.76 milliequivalent/grams (antelope base 6.12 milliequivalent/grams, phenolic hydroxyl group 2.64 milliequivalent/grams).
3, number-average molecular weight: Mn=1032
(2), target level of product quality fulvic acid solid is dark-brown, flavor acid, odorless, soluble in water, ethanol.Diluted acid, diluted alkaline and aqueous acetone.
1, fulvic acid content 〉=95%2,10% solution ph 2.5-3
3, heavy metal＜20PPM 4, arsenic salt＜2PPM
5, E4//E6 ratio is between 10-15.
As seen fulvic acid of the present invention and common biochemical fulvic acid, weathering fulvic acid difference are little.

Claims (10)

1. the brown stock of a straw raw material ammonium sulfite boiling preparation is characterized in that the whiteness of described brown stock is 35-48%ISO, fracture length is 5.0-7.5km, tearability is 200-275mN, and folding number is 30-100 times, and beating degree is 32-38 ° of SR; The fracture length of preferred described brown stock is 5.5-7.5km, and tearability is 220-275mN, and folding number is 40-80 times, and beating degree is 32-36 ° of SR; The fracture length of preferred described brown stock is 6.0-7.5km, and tearability is 240-275mN, and folding number is 50-70 times.
2. the brown stock of a straw raw material alkaline cooking preparation is characterized in that the whiteness of described brown stock is 40-55%ISO, and fracture length is 5.0-7.6km, and tearability is 230-280mN, and folding number is 25-90 time, and beating degree is 32-38 ° of SR; Preferred described unbleached pulp is 45-55%ISO, and fracture length is 6.0-7.6km, and tearability is 250-280mN, and folding number is 35-90 time, and beating degree is 32-36 ° of SR.
3. the brown stock of a wheat straw raw material Ammonium Sulfite Method boiling preparation is characterized in that described brown stock is feedstock production with the wheat straw, the fracture length of described brown stock is 5.0-7.8km, and folding strength is 25-80 time, and tearability is 180-255mN, whiteness is 37-45%IS0, and beating degree is 33-38 ° of SR; The fracture length of preferred described brown stock is 6.0-7.8km, and folding number is 32-80 time, and tearability is 230-255mN, and beating degree is 33-36 ° of SR.
4. the low brightness pulp of a straw raw material alkaline cooking preparation is characterized in that the whiteness of described low brightness pulp is 45-60%ISO, and fracture length is 4.8-7.0km, and tearability is 240-285mN, and folding number is 30-110 time, and beating degree is 32-38 ° of SR; The whiteness of preferred described low brightness pulp is 50-60%ISO, and fracture length is 4.5-7.0km, and tearability is 250-285mN, and folding number is 50-110 time.
5. the brown stock of a wheat straw raw material alkaline cooking preparation is characterized in that described brown stock is feedstock production with the wheat straw, the fracture length of described brown stock is 5.5-7.8km, and folding strength is 20-70 time, and tearability is 180-250mN, whiteness is 33-42%ISO, and beating degree is 33-38 ° of SR; The fracture length of described brown stock is 6.0-7.8km, and folding number is 30-70 time, and tearability is 210-250mN, and beating degree is 33-36 ° of SR.
6. one kind is the method for feedstock production high-hardness pulp with the grass kind plant, described method comprise get the raw materials ready, the boiling step, it is characterized in that described boiling method is a kind of in ammonium sulfite, anthraquinone-soda processes, sulfate process or the Arbiso process boiling, when adopting the ammonium sulfite boiling, the consumption of ammonium sulfite is the 15-25% of over dry material quantity; When adopting anthraquinone-soda cooking, alkali charge is in the 16-25% of NaOH to the over dry material quantity; When adopting kraft cooking, alkali charge is in the 13-25% of NaOH to the over dry material quantity; During the Arbiso process boiling, total acid is greater than 5%, and combined acid is 2.0-4.0%; Obtain the high-hardness pulp that hardness is permanganate number 16-28 after the boiling, preferred hardness is a permanganate number 18-27 high-hardness pulp; Most preferably hardness is the high-hardness pulp of permanganate number 20-25.
7, a kind of is the method for feedstock production bleach chemical pulp with the grass kind plant, it is characterized in that, described method may further comprise the steps:
(1) the grass raw material after will getting the raw materials ready carries out boiling and obtains the slurry that hardness is permanganate number 12-15;
(2) slurry after the boiling is carried out shove, processing is discongested in washing then;
(3) will carry out oxygen delignification and bleaching processing through discongesting the slurry of handling gained, obtain described bleach chemical pulp.
8. one kind is the method for feedstock production bleach chemical pulp with the grass kind plant, it is characterized in that described method may further comprise the steps:
(1) the grass kind plant raw material is carried out boiling and obtain the high-hardness pulp that hardness is permanganate number 16-28;
(2) described high-hardness pulp is carried out shove, processing is discongested in washing then;
(3) will carry out two sections oxygen delignification and bleaching processing through the slurry of discongesting processing, obtain described bleach chemical pulp.
9, a kind of grass type stalk method of comprehensive utilization is characterized in that, comprising:
(1) boiling obtains high-hardness pulp
Grass type stalk is carried out slurrying by boiling method, obtain concentration and be 8-15% slurry, hardness is permanganate number 16-28; Preferred hardness is a permanganate number 18-27; Most preferably hardness is permanganate number 20-25;
(2) the high-hardness pulp post processing obtains rare black liquor
High-hardness pulp is carried out post processing, and to obtain solid content be 4-15%, and Baume degrees is rare black liquor of 2-9; Washing process and methods such as described post processing comprises by dilution, concentrates, press filtration or displacement will be stored between fiber and the fiber, and waste liquid and fiber separation in cell membrane, the lumen are opened;
(3) add auxiliary material in the black liquor
In rare black liquor or with rare black liquor vaporizing, concentrate to remove and add auxiliary material in the concentrated black liquid that portion of water obtains and form solid-state fertilizer or liquid fertile;
Described auxiliary material is organic auxiliary material; In rare black liquor or with rare black liquor vaporizing, concentrate to remove and add organic auxiliary material in the concentrated black liquid that portion of water obtains and form slip, dry then, promptly obtain a kind of Yellow humic acid fertilizer, described organic auxiliary material is lignin and humic acid; The percentage by weight of each component is:
Rare black liquor or concentrated black liquid 30-80%
Lignin 1-45%
Humic acid 1-25%;
The percentage by weight of preferred each component is:
Rare black liquor or concentrated black liquid 50-60%
Lignin 15-35%
Humic acid 10-15%;
Or described auxiliary material is the solubility macroelement fertilizer; Add the solubility macroelement fertilizer in rare black liquor or in the concentrated black liquid and obtain Yellow humic acid water flush fertilizer; Described solubility macroelement fertilizer is one or more of solubility nitrogenous fertilizer, soluble phosphoric manure and solubility potash fertilizer; Preferred solubility nitrogenous fertilizer and the solubility potash fertilizer of adding;
The percentage by weight of each component is:
Rare black liquor or concentrated black liquid 20-98%
Solubility macroelement fertilizer 2-80%;
The percentage by weight of preferred each component is:
Rare black liquor or concentrated black liquid 50-90%
Solubility macroelement fertilizer 10-50%;
Or described auxiliary material is a soluble trace elements fertilizer; Add soluble trace elements fertilizer in rare black liquor or in the concentrated black liquid and promptly get Yellow humic acid foliage fertilizer, the envelope-bulk to weight ratio of the two is 1000ml:0.2-45g.
10, a kind of grass type stalk extracts the method for fulvic acid, it is characterized in that, comprising:
(1) boiling obtains high-hardness pulp
Grass type stalk is carried out slurrying by the boiling method except that organic solvent pulping, obtain concentration and be 8-15% slurry, hardness is permanganate number 16-28; Preferred hardness is a permanganate number 18-27; Most preferably hardness is permanganate number 20-25;
(2) the high-hardness pulp post processing obtains rare black liquor
High-hardness pulp is carried out post processing, and to obtain solid content be 4-15%, and Baume degrees is rare black liquor of 2-9; Washing process and methods such as described post processing comprises by dilution, concentrates, press filtration or displacement will be stored between fiber and the fiber, and waste liquid and fiber separation in cell membrane, the lumen are opened;
(3) prepare fulvic acid solution by black liquor
Concentrate to remove in rare black liquor or with rare black liquor vaporizing and add acid in the concentrated black liquid that portion of water obtains and regulate and make it to separate out lignin, add flocculant then, remove by filter lignin, filtrate is fulvic acid solution;
(4) extract fulvic acid in the fulvic acid solution
From fulvic acid solution, extract fulvic acid.
CN 200710300209 2007-07-27 2007-12-05 Pulp and black liquor prepared by grass type raw material, preparation method and use thereof Active CN101451324B (en)

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CN2008100938628A Division CN101451328B (en) 2007-12-05 2007-12-05 Un-bleaching pulp prepared by alkaline steam cooking wheat straw raw material, preparation method and use thereof
CN2008100938613A Division CN101451327B (en) 2007-12-05 2007-12-05 Low brightness pulp prepared by alkaline steam cooking wheat straw raw material, preparation method and use thereof
CN2008100938670A Division CN101451315B (en) 2007-12-05 2007-12-05 Method for comprehensive utilization of grass type stalk
CN 200810093866 Division CN101450955B (en) 2007-12-05 2007-12-05 Method for producing yellow humic acid from grass type stalk
CN2008100938651A Division CN101451314B (en) 2007-12-05 2007-12-05 Method for preparing high-hardness pulp by using grass type plants as raw materials
CN2008100938596A Division CN101451325B (en) 2007-12-05 2007-12-05 Low brightness pulp prepared by alkaline steam cooking wheat straw raw material, preparation method and use thereof
CN2008100938647A Division CN101451313B (en) 2007-12-05 2007-12-05 Method for preparing bleached chemical pulp by using grass type plants as raw materials
CN2008100938609A Division CN101451326B (en) 2007-12-05 2007-12-05 Un-bleaching pulp prepared by ammonium sulfite steam cooking wheat straw raw material, preparation method and use thereof
CN2008100938632A Division CN101451312B (en) 2007-12-05 2007-12-05 Method for preparing bleached chemical pulp by using grass type plants as raw materials

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CN108265084A (en) * 2017-01-04 2018-07-10 山东泉林纸业有限责任公司 A kind of method that ethyl alcohol is prepared using agricultural crop straw
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CN111747779A (en) * 2019-03-29 2020-10-09 崔强 Preparation method and application of fulvic acid
US12098507B2 (en) 2020-11-06 2024-09-24 Kimberly-Clark Worldwide, Inc. High porosity non-wood pulp
CN114774303A (en) * 2022-03-14 2022-07-22 齐鲁工业大学 Microbial agent for desiliconizing pretreated straw pulp raw material and application thereof in desiliconizing pulping of straw pulp raw material
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