CN101532260B - Method for pulping by cooking solid base in plant fiber - Google Patents
Method for pulping by cooking solid base in plant fiber Download PDFInfo
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- CN101532260B CN101532260B CN2009100387386A CN200910038738A CN101532260B CN 101532260 B CN101532260 B CN 101532260B CN 2009100387386 A CN2009100387386 A CN 2009100387386A CN 200910038738 A CN200910038738 A CN 200910038738A CN 101532260 B CN101532260 B CN 101532260B
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Abstract
The invention discloses a method for pulping by cooking solid base in a plant fiber, comprising three steps such as pre-processing, cooking pulping and unbleached pulp preparation; in the step of cooking pulping, the pre-processed plant fiber raw material is added with solid base, O2, H2O2 and water, the temperature is raised to 125-175 DEG C within 1-2.5h and then maintained, and mixed slurry isobtained after reaction; the solid base is the solid base which is slightly soluble in water or the solid base which is resistant to wash load; in the step of unbleached pulp preparation, the mixed slurry is filtered by a pressurized screen with aperture not more than 40 meshes or squeezed to obtain unbleached pulp and suspension of solid products of cellulose containing hemicellulose. In the cooking reaction process of the invention, the environment-friendly solid base containing Ca and Mg, O2, H2O2 and other clean chemicals are used. The solid base can be recycled by simple methods without producing pollution, thus conducing to technology industrialization of clean production of cooking pulping, cellulose energy ethanol and conversion of high-value chemicals.
Description
Technical field
The present invention relates to string and use, particularly relate to a kind of method of pulping by cooking solid base of string.
Background technology
Cellulosic material generally contains cellulose 35%～45%, hemicellulose 20%～30%, lignin 15%～25%.Pulping by cooking is to use chemical method to remove the lignin composition of plant fiber material, isolates cellulose and part hemicellulose.Pulping by cooking is the important process process of paper industry, also is a kind of important preprocess method in cellulosic ethanol and following biomass energy and the chemical industry system.
The pulping by cooking of plant fiber material generally uses sulfur-bearing to contain the chemicals such as the Na of caustic soda at present
2S, Na
2SO
4, Na
2SO
3, CaSO
3, NaOH and Na
2CO
3Deng, waste liquid that boiling produces such as black liquor pollution load are big, are difficult to biochemical treatment, cause the severe contamination to environment.Except that using sulfur-bearing to contain the pulping process of caustic soda chemicals, cellulosic ethanol and biomass energy comprise that with chemical industry the main method that pulp industry separates the wood fibre component also has physics method (mechanical crushing, pyrolytic, microwave treatment, steam blasting, high-energy radiation, liquid hot water preliminary treatment etc.), chemical method (ammonia treatment, organic solvent processing, ozone treatment etc.), physical-chemical process and bioanalysis, these methods some in conjunction with the slurrying separation process, reach the purpose of efficient separation component.
The physical treatment method comprises ball milling, compression ball milling, pulverizing, explosion, freezing pulverizing, gamma-radiation, sound wave, electron ray etc., all can make cellulose efflorescence, softening, to improve cellulosic enzymolysis conversion ratio.This method under general condition acts on not obvious.Behind the ball mill grinding cellulose, enzymatic hydrolyzation diminishes with cellulosic particle and slightly rises; For electron radiation, only greater than behind the 100Mrad, the binder course of hemicellulose and lignin is just influenced, and hydroxyl and the carbonyl maximum of being damaged, and degree of crystallinity descends.Simultaneously, this method preliminary treatment cost is higher.Use ball milling 48h, just can reach the fineness about 270 orders; Electron ray and gamma-radiation all need high energy jet generator, and equipment cost height, energy consumption are big, account for 50%～60% of saccharification total energy consumption.Also having a kind of is Demolition Pulping, be under high temperature action, hemicellulose takes place from hydrolysis and fusible, the part degraded also takes place in lignin, become easily by organic solvent or diluted alkaline extracting, the this moment of decompression explosion has suddenly then destroyed the eucaryotic cell structure of string, and the cellulose hydrolyzation conversion coefficient is improved.
The chemical Treatment method is removed Na
2S, Na
2SO
4, Na
2SO
3, CaSO
3, NaOH and Na
2CO
3Contain outside the caustic soda boiling separation Deng sulfur-bearing, also comprise methods such as inorganic acid, alkali, organic solvent, its mechanism mainly is the chemical constitution of effectively destroying between the crude fibre, is convenient to the decomposition and the release of crude fibre material, reaches the purpose that component is separated.Mineral acid treatment raw material with high concentration, separablely go out lignin, but hemicellulose comprises cellulose and is hydrolyzed into monose, other product is varied, as cellodextrin, cellobiose, glucose, glucan etc., the product yield is lower, and waste liquor contamination is serious after the acid treatment, is difficult for by the yeast digestibility and utilization in the sweat of cellulosic ethanol.Acid corrosion is strong, needs acid-resistant system, the cost height, and cause the decomposition reaction of gained glucose, and reduced the purity and the yield of product, to use diluted acid instead and handle, the gained material almost all is hydrolyzed into glucose.But this method exists problems such as reagent recovery, neutralization, washing.It mainly is that the sulfur-bearing that pulp and paper industry generally adopts contains caustic soda chemicals pulping by cooking that alkaline process is handled, and the cellulose of this method and hemicellulose loss are bigger, and yield has only 50%.Organic solvent pulping by cooking effect is better, and is easy to reclaim, and the cellulose yield is higher, but exists the restriction of problems such as corrosion and toxicity.Because its environmental pollution is serious, presses for solution, has hindered its scale in cellulosic ethanol industry and used.
Physical-chemical method is exactly that physics method and chemical method are organically combined, and as raw material is carried out NaOH pre-preg chemical treatment earlier, uses the quick-fried method of vapour to handle sample then; Perhaps raw material is after the physics method is handled, and again through the chemical method reaction, the digestibility after handling like this can reach higher level, but energy consumption height, hemicellulose loses in a large number, produces toxic compounds such as furfural, brings the obstacle that is difficult to overcome for subsequent wastewater treatment or cellulose alcoholic fermentation.
Bioanalysis is that the microbe species that utilizes nature to participate in lignin degrading has fungi, actinomyces and the bacterium lignin in the degrading plant fibrous raw material enough effectively and selectively, the defibre element, and hydrolysis obtains fermentable sugars.Study at most and show the white-rot fungi of effective degradation capability at present in the world.Whiterot fungi facture action condition gentleness, energy consumption is low, has special advantages.But the processing time is long, causes the production cycle long, apart from realizing that suitability for industrialized production also has certain distance.
Summary of the invention
The objective of the invention is to shortcoming, the pulping by cooking solid base method of a kind of brown stock yield plant fiber material high, environmental protection is provided at the prior art existence.
Purpose of the present invention is achieved through the following technical solutions:
A kind of method of pulping by cooking solid base of string comprises the steps:
(1) preliminary treatment: plant fiber material is sheared and screening, and single or monolithic raw material is long to be 1-3cm;
(2) pulping by cooking: the pretreated plant fiber material of step (1) is added solid base, O
2, H
2O
2And water; Earlier in 1～2.5h, be warming up to 125～175 ℃, be incubated 1.5～3.0h then, obtain mixed slurry after the reaction; H
2O
2Mixing back 0.5～2h before boiling with water joins in the raw material; In weight ratio, described solid base consumption be the raw material over dry heavy 10%～30%; H
2O
2Consumption be the raw material over dry heavy 2%～15%; The consumption of water is heavy 4～10 times of raw material over dry; Press O in oxygen
2Be 1～3MPa; Described solid base is solid base or the water-fast wash load type solid bases that is slightly soluble in the water class; The described solid base type that is slightly soluble in water is MgO, CaO, Mg (OH)
2Or Ca (OH)
2Described water-fast wash load type solid base type is MgO/NaY or CaO/NaY;
(3) brown stock preparation: the pressurized screen of mixed slurry through being not more than 40 order apertures filter or squeezing after obtain containing the brown stock and the suspension of the cellulose solids product of hemicellulose.
Described plant fiber material is wheat straw, bagasse, straw, cornstalk or timber.
Described suspension is the mixture that contains part hemicellulose compound sugar and monose, lignin, fiber and solid base; Solid base and fiber fines are through gravitational settling or centrifugation in the suspension, and the direct burning under 350～750 ℃ of conditions of its sediment obtains solid base again, and this solid base is as the solid base of the pulping by cooking of step (2); Described fiber fines is the fiber by 40 order aperture sieve apertures.
In weight ratio, in described solid base and the fibre blend sediment, fines content is not higher than 50% of solid base weight.
Described suspension also obtains supernatant after gravitational settling or centrifugation, supernatant contains lignin and hemicellulose compound sugar and monose, and the direct concentrate drying of described supernatant obtains containing the lignin of sugar.
Described supernatant directly is concentrated to 20% above concentration (volume), adds the Vinsol that is precipitated as that obtains behind the inorganic acid.
Described brown stock is used to the paper of manufacturing paper with pulp after making beating; During making beating, in weight ratio, the water yield of adding is slurry 5～20 times of weight, and rotating speed 3000～6000r/min directly copies the paper of manufacturing paper with pulp after paper or the bleaching after the making beating.
Solid base just be meant can chemisorbed acid solid maybe can make the solid of acid indicator variable color, it is compared with homogeneous phase solution alkali has several outstanding advantages: catalyst is separated from reactant mixture easily, and post catalyst reaction is regenerated easily; Consersion unit there is not corrosiveness; In addition, solid base catalyst also has the geometric space effect in some reaction.Solid base is of a great variety, mainly contains supported solid, loads on SiO as KOH
2Or Al
2O
3On; Anion exchange resin; Metal oxide and hydroxide BeO, MgO, CuO, CaO, BaO, Mg (OH)
2, Ca (OH)
2Deng; Metallic salt Na
2CO
3, K
2CO
3, KHCO
3, etc.; Mixed oxide S iO
2-MgO; The molecular sieve of various alkali metal or alkaline-earth metal exchange.Relative solid acid catalyst, the alkalescence of solid catalyst has special catalytic action, thereby the application in chemical industry is very wide application prospect as catalyst or carrier to solid base.The solid base that is slightly soluble in water that the present invention uses is MgO, CaO, Mg (OH)
2Or Ca (OH)
2With the water-fast load-type solid that washes away be MgO/NaY or CaO/NaY.
With respect to existing pulping technique, the present invention has following advantage and beneficial effect:
1) pulping by cooking solid base does not use sulfur-bearing to contain the caustic soda chemicals, avoids cooking reaction to produce the waste water of high-pollution load such as black liquor; And the whole cooking reaction process of the present invention is all used the O of environmental protection
2, H
2O
2With cleaning chemistry product such as solid bases, do not use sulfur-bearing or contain the chemical substance of caustic soda; Solid base can reclaim with simple method, does not therefore produce pollution, has improved raw material availability, reaches the purpose of economical and efficient environmental protection, and pulping by cooking cleaner production and cellulose energy ethanol skilled industryization are significant for promoting.
2) pulping by cooking solid base can remove the lignin in the cellulosic material, separates to obtain more complete cellulose, and keeps most hemicellulose, and higher brown stock yield is arranged;
3) solid base provides a kind of alkaline environment in the cooking reaction system, and itself does not react, and when boiling because the solid base surface adsorption combines partly fiber fines, the phenomenon of scale deposition in digestion reactors can not take place during boiling yet.Solid base can the reactant liquor after boiling easily gravitational settling or centrifugation come out, the solid base that post precipitation obtains obtains new solid base again after calcining, continue to use;
4) the plain enzymatic hydrolysis reaction of the brown stock lotus root condensating fiber that obtains of pulping by cooking solid base, total percent hydrolysis is 85%～98%, is higher than the cellulose hydrolysis rate that other processing method obtains, and has improved raw material availability; The cooking solid base reaction does not produce harmful substances such as phenols or furfural, helps cellulosic ethanol and energy ethanol and the industrial process that transforms the high added value chemicals.
The specific embodiment
The present invention is further illustrated below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope of embodiment statement.W refers to weight among the following embodiment, and V refers to volume; W/W is meant weight ratio; W/V is meant w/v; V/V is meant volume ratio.Lignin, hemicellulose and content of cellulose and yield are pressed national standard method and are surveyed the shallow lake before and after the cooking reaction.Copy paper after the making beating and pulp brightness is measured by national standard method.
Embodiment 1
Cellulosic material is the masson pine wood chip, in weight ratio, and its content of cellulose 38%, hemicellulose amount 20%, content of lignin 25%; About 4～the 5cm of the big small size of wood chip
2With the preliminary treatment of masson pine wood chip is single or the long 1-3cm of monolithic raw material.Add solid base, O in the pretreated masson pine wood chip
2, H
2O
2And water, adopting the solid base type is MgO; In weight ratio, the solid base consumption be equivalent to the raw material over dry heavy 30%; O
2Count 3MPa with the oxygen pressure; In weight ratio, H
2O
2Consumption be equivalent to the raw material over dry heavy 2%, H
2O
20.5h joins in the raw material before being blended in boiling with water, plays dipping; In weight ratio, the consumption of water is equivalent to heavy 10 times of raw material over dry.Pulping by cooking solid base is reflected under 175 ℃ the temperature conditions and carries out, and the reaction time comprises heating-up time 2.5h (from 0 ℃ to 175 ℃), temperature retention time 1.5h (temperature remains on 175 ℃); The delignification rate 91.3% of plant material (with respect to the content of lignin in the raw material) behind the cooking reaction; Hemicellulose yield 63.7%% (with respect to the hemicellulose level in the raw material); Cellulose yield 92.7% (with respect to the content of cellulose in the raw material).Obtain the brown stock yield after filtration or after the squeezing, yield 65.2%%, whiteness are 26.0%ISO.Brown stock is used to the paper of manufacturing paper with pulp after making beating; During making beating, the water yield of adding is slurry 10 times of weight (5～20 times all can), beater rotating speed 4000r/min (3000～6000r/min all can).
The sediment of the suspension gravitational settling (natural sedimentation 3h) that after squeezing, obtains, in weight ratio, fines content 18.3% (by the fiber of 40 order aperture sieve apertures), this is deposited under 750 ℃ of conditions directly that burning 5h obtains solid base again, is reused for the pulping by cooking reaction by the same reaction system after being dissolved in hot water; During recycling use three times, same raw material similarity condition boiling, three times the boiling situation is: when recycling for the first time, brown stock yield 64.7%%, whiteness are 25.9%ISO; When recycling for the second time, brown stock yield 65.8%%, whiteness are 26.8%ISO; When recycling for the third time, brown stock yield 65.9%%, whiteness are 26.7%ISO; There is not significant difference between three times.
Behind the suspension separating solids alkali precipitation through obtaining after the squeezing, obtain containing the lignin of water-soluble sugar behind the concentrate drying; In weight ratio, the weight of water-soluble sugar is 20% of lignin weight.Obtain carboxyl-content 6.5% in the molecule of lignin, reactivity is preferably arranged.
The plain enzymatic hydrolysis reaction of the brown stock lotus root condensating fiber that obtains after squeezing or the filtration is produced fermentable sugars.With above-mentioned brown stock through the dehydration, the washing after, hydrolysis in containing the cellulase reaction system of buffer solution; The cellulase reaction system comprises cellulase, cellulose and hemicellulose, buffer solution and water; Cellulase is available from Guangzhou enzyme preparation company.It is 320U/g that cellulase contains filter paper enzyme activity (FPA), and the cellobiohydrolase vigor is 600U/g, and endoglucanase vigor (CMCase) is 300U/g, and (β-Glase) is 700U/g to the beta-glucosidase enzyme activity.Enzyme hydrolysis pH value is 3.2; 45 ℃ of hydrolysis temperatures, reaction time 40h; Buffer solution is dibastic sodium phosphate-sodium hydrogen phosphate, concentration 0.5mol/L; Total percent hydrolysis is 95.8% (W/W, heavy with respect to the raw material over dry before the hydrolysis); By weight percentage, glucose content 53.9% in the soluble sugar that obtains of hydrolysis; Cellobiose content 14.6%; Wood sugar content 16.1%.
As a comparison, during with the general alkaline cooking pulping process of present industrialization, above-mentioned same raw material through 15% NaOH solution behind reaction 2.5h under 165 ℃ of conditions, washing back with above-mentioned same enzyme through same method hydrolysis, total percent hydrolysis is 73.8% (W/W, heavy with respect to the raw material over dry before the hydrolysis); Glucose content 82.5% in the soluble sugar that hydrolysis obtains; Cellobiose content 10.3%; Wood sugar content 0.4%.
Compare with the cellulose hydrolyzation result of above-mentioned NaOH processing method, by weight, the cellulosic material percent hydrolysis of this embodiment has improved 1.29 times; Separate the corresponding fermentable sugars weight that obtains by same weight raw water, the wood sugar yield of the pulping by cooking solid base lotus root synthase hydrolysis of present embodiment improves 53.2 times, illustrates that more hemicellulose is retained when solid base is handled down.
Embodiment 2
Cellulosic material is a straw, in weight ratio, and cellulose 40%, hemicellulose 25%, lignin 15%; Clean and be cut into about 2cm length with preceding.In the cooking solid base reaction system, adopting the solid base type is Mg (OH)
2The cooking reaction system is by cellulosic material, solid base, O
2, H
2O
2And water is formed; In weight ratio, the solid base consumption be equivalent to the raw material over dry heavy 15%; O
2Count 1MPa with the oxygen pressure; In weight ratio, H
2O
2Consumption be equivalent to the raw material over dry heavy 15%, H
2O
22h joins in the raw material before being blended in boiling with water, plays dipping; The consumption of water is equivalent to heavy 4 times of raw material over dry.Pulping by cooking solid base is reflected under 165 ℃ the temperature conditions and carries out, and the reaction time comprises heating-up time 1.5h (from 0 ℃ to 165 ℃), temperature retention time 2.5h (temperature remains on 165 ℃); Behind the cooking reaction to the delignification rate 92.6% (with respect to the content of lignin in the raw material) of plant material; Hemicellulose yield 58.9%% (with respect to the hemicellulose level in the raw material); Cellulose yield 95.8% (with respect to the content of cellulose in the raw material).Brown stock yield after squeezing or the filtration is 52.7%, and whiteness is 37.8%ISO.
The sediment of (centrifuge speed 4000rpm) after the suspension centrifugation that obtains after filtering, in weight ratio, fines content is with respect to 19.5% of solid base weight, this is deposited under 500 ℃ of conditions directly that burning 7h obtains solid base again, is reused for the pulping by cooking reaction by the same reaction system after being dissolved in hot water.During recycling use three times, same raw material similarity condition boiling, three times the boiling situation is: when recycling for the first time, brown stock yield 52.3%%, whiteness are 31.6%ISO; When recycling for the first time, brown stock yield 52.5%%, whiteness are 31.8%ISO; When recycling for the first time, brown stock yield 51.9%%, whiteness are 31.4%ISO; There is not significant difference between three times.
When being concentrated to 20% concentration in the suspension that obtains after filtering, add sulphur acid for adjusting pH value to 3.2, what obtain is precipitated as Vinsol, obtains carboxyl-content 6.7% in the molecule of lignin after the vacuumize, and reactivity is preferably arranged.Supernatant is through Ca (OH)
2Adjusting pH value 6.8 back concentrate dryings obtain the solid content based on wood sugar; In weight ratio, wood sugar content is 53.4% in the solid content.
The plain enzymatic hydrolysis reaction of the brown stock lotus root condensating fiber that obtains after squeezing or the filtration is produced the fermentable sugars process.Brown stock through the dehydration, the washing after, hydrolysis in containing the cellulase reaction system of buffer solution; Cellulase is available from Ningxia sky Sheng company, and wherein containing filter paper enzyme activity is 200U/g, and the cellobiohydrolase vigor is 400U/g, and the endoglucanase vigor is 700U/g, and the beta-glucosidase enzyme activity is 300U/g; Enzyme hydrolysis pH value is 7.5; 55 ℃ of hydrolysis temperatures, reaction 100h; Described buffer solution is a citric acid-sodium citrate solution, and concentration is 0.05mol/L; By weight percentage, total percent hydrolysis is 97.7% (W/W, heavy with respect to the raw material over dry before the hydrolysis); Glucose content 59.4% in the soluble sugar that hydrolysis obtains; Cellobiose content 15.3%; Wood sugar content 16.3%.
Same raw material is without pulping by cooking solid base, directly pulverizes behind 40 mesh sieves with above-mentioned enzyme hydrolysis 100h in the same way, and total percent hydrolysis is 11.2% (W/W is with respect to the weight of the raw material over dry before the hydrolysis); Glucose content 49.7% in the soluble sugar that hydrolysis obtains; Cellobiose content 23.4%; Wood sugar yield content 24.6%.
With handle the back without cooking solid base but lotus root synthase method for hydrolysis result compares, in weight ratio, adopt the cellulosic material percent hydrolysis of the inventive method of cooking solid base lotus root synthase hydrolysis to improve 7.7 times; Separate the corresponding fermentable sugars weight that obtains by same weight raw water, the glucose yield that adopts pulping by cooking solid base to separate the inventive method of brown stock lotus root synthase hydrolysis improves 10.5 times, illustrate that plant fiber material is unfavorable for the hydrolysis of cellulase without pulping by cooking solid base, the cellulosic material utilization rate significantly reduces, and is difficult at cellulosic ethanol energy ethanol and transforms in the industry of high added value chemicals use.
Embodiment 3
Cellulosic material is a wheat straw, in weight ratio, and its content of cellulose 45%, hemicellulose level 30%, content of lignin 15%; With preceding being cut into long back washing about 1cm.Used solid base is CaO/NaY (zeolite); In the reaction system, in weight ratio, the solid base consumption be equivalent to the raw material over dry heavy 15%; O
2Count 2MPa with the oxygen pressure; H
2O
2Consumption be equivalent to the raw material over dry heavy 13%, H
2O
2Being blended in before the boiling 1.5h with water joins in the raw material and floods; The consumption of water is equivalent to heavy 6 times of raw material over dry.Pulping by cooking solid base is reflected under 170 ℃ the temperature conditions and carries out, and the reaction time comprises heating-up time 1.5h (from 0 ℃ to 170 ℃), temperature retention time 2.0h (temperature remains on 170 ℃); Behind the cooking reaction to delignification rate＞91.4% (with respect to the content of lignin in the raw material) of plant material; Hydrolysis of hemicellulose rate 29.7% (with respect to the hemicellulose level in the raw material); Cellulose yield 93.6% (with respect to the content of cellulose in the raw material).After filtration or squeezing back brown stock yield be 61.1%%, whiteness is 34.3%ISO.
The sediment of the suspension gravitational settling (natural sedimentation 3h) that after squeezing, obtains, in weight ratio, fiber fines content in sediment is 22.4%, this sediment under 300 ℃ of conditions directly burning 8h obtain solid base again, be reused for the pulping by cooking reaction by the same reaction system after being dissolved in hot water; During recycling use three times, same raw material similarity condition boiling, three times the boiling situation is: when recycling for the first time, brown stock yield 61.5%%, whiteness are 34.6%ISO; When recycling for the second time, brown stock yield 61.3%%, whiteness are 34.1%ISO; When recycling for the third time, brown stock yield 65.6%%, whiteness are 34.7%ISO; There is not significant difference between three times.
The above-mentioned suspension that obtains behind the separating solids alkali precipitation after squeezing can directly be concentrated to 75% concentration, and viscosity only is 273mPas, the heat production of can burning.
The brown stock that solid base (recycling use for the third time) boiling obtains can connect after making beating and be used for paper.During making beating, the water yield of adding is in weight ratio, is 20 times of slurry weight; PFI mill beating rate is 6000 revolutions/rmin during making beating
-1The main performance figure of the slurry that obtains after the making beating is: burst index 3.1kPam
2G
-1Tear index 4.3nNm
2G
-1Fracture length 4.5km; Tensile index 28.7Nmg
-1
Compare with the kraft cooking pulping process that present paper industry generally adopts, the sulphate cook condition is: in weight ratio, and NaOH+Na
2The S consumption be the raw material over dry heavy 20%, (S accounts for NaOH+Na to sulphidity
2The ratio of S total amount) be 21%, other condition is identical with the cooking solid base condition.The brown stock yield of sulphate cook gained is 41.7%, and whiteness is 29.3%ISO, all is lower than the cooking solid base brown stock.The brown stock of sulfate pulp and employing cooking solid base gained is pulled an oar under similarity condition, and the main performance figure that obtains starching is: burst index 3.6kPam
2G
-1, tear index 4.7nNm
2G
-1, fracture length 4.6km, tensile index 29.1Nmg
-1Suitable with cooking solid base brown stock quality.
Solid base (recycling use for the third time) boiling adopts identical D-P to float the preface bleaching with the brown stock that sulphate cook obtains, and D is ClO
2Bleaching, in weight ratio, consumption is 2% of an oven dry stock, 60 ℃ of bleaching temperatures, bleaching time 30min; P is H
2O
2Bleaching, in weight ratio, consumption is 2% of an oven dry stock, 90 ℃ of bleaching temperatures, bleaching time 150min; Cooking solid base slurry bleaching back whiteness reaches 79%ISO, and sulfate pulp only is 73%ISO; The main performance figure of cooking solid base bleached pulp is: burst index 3.7kPam
2G
-1, tear index 6.7nNm
2G
-1, fracture length 5.9km, tensile index 51.4Nmg
-1And the main performance figure of sulphate cook bleached pulp is: burst index 3.9kPam
2G
-1, tear index 6.8nNm
2G
-1, fracture length 4.9km, tensile index 29.6Nmg
-1, both are suitable.
Compare sulfate (NaOH+Na with the pulping by cooking solid base black liquor
2S) black liquor that obtains of boiling is in the concentration that is concentrated to 21%, and viscosity has surpassed 532mPas, is difficult to further concentrate and burning.Simultaneously because NaOH is easy to water-soluble characteristic, can not the same easy recovery with solid base; And the Containing Sulfur product can produce poisonous and harmful substances such as thiophenol in steaming person's process, cause the pollution to environment.
Therefore, from boiling brown stock yield, whiteness, the recovery of boiling chemicals, aspects such as harmfulness that chemicals produces and steaming work waste liquid concentrate relatively, cooking solid base will obviously be better than traditional sulphate cook slurrying, and before the brown stock that two kinds of processes obtain or the main performance figure of bleached pulp be close.
Claims (7)
1. the method for the pulping by cooking solid base of a string is characterized in that comprising the steps:
(1) preliminary treatment: plant fiber material is sheared and screening, and single or monolithic raw material is long to be 1-3cm;
(2) pulping by cooking: the pretreated plant fiber material of step (1) is added solid base, O
2, H
2O
2And water; Earlier in 1～2.5h, be warming up to 125～175 ℃, be incubated 1.5～3.0h then, obtain mixed slurry after the reaction; H
2O
2Mixing back 0.5～2h before boiling with water joins in the raw material; In weight ratio, described solid base consumption be the raw material over dry heavy 10%～30%; H
2O
2Consumption be the raw material over dry heavy 2%～15%; The consumption of water is heavy 4～10 times of raw material over dry; Press O in oxygen
2Be 1～3MPa; Described solid base is solid base or the water-fast wash load type solid base that is slightly soluble in water; The described solid base that is slightly soluble in water is MgO, CaO, Mg (OH)
2Or Ca (OH)
2Described water-fast wash load type solid base is MgO/NaY or CaO/NaY;
(3) brown stock preparation: the pressurized screen of mixed slurry through being not more than 40 order apertures filter or squeezing after obtain containing the brown stock and the suspension of the cellulose solids product of hemicellulose.
2. the method for the pulping by cooking solid base of string according to claim 1, it is characterized in that: described plant fiber material is wheat straw, bagasse, straw, cornstalk, bamboo, reed or timber.
3. the method for the pulping by cooking solid base of string according to claim 1 is characterized in that: described suspension is the mixture that contains hemicellulose compound sugar partly and monose, lignin, fiber and solid base; Solid base and fiber fines are through gravitational settling or centrifugation in the suspension, and the direct burning under 350～750 ℃ of conditions of its sediment obtains solid base again, and this solid base is as the solid base of the pulping by cooking of step (2); Described fiber fines is the fiber by 40 order aperture sieve apertures.
4. the method for the pulping by cooking solid base of string according to claim 3, it is characterized in that: in weight ratio, in the described sediment, fines content is not higher than 50% of solid base weight.
5. the method for the pulping by cooking solid base of string according to claim 1, it is characterized in that: described suspension is after gravitational settling or centrifugation, also obtain supernatant, supernatant contains lignin and hemicellulose compound sugar and monose, and the direct concentrate drying of described supernatant obtains containing the lignin of sugar.
6. the method for the pulping by cooking solid base of string according to claim 1, it is characterized in that: described supernatant directly is concentrated to 20% above volumetric concentration, adds the Vinsol that is precipitated as that obtains behind the inorganic acid.
7. the method for the pulping by cooking solid base of string according to claim 1 is characterized in that: described brown stock is used to the paper of manufacturing paper with pulp after making beating; During making beating, in weight ratio, the water yield of adding is slurry 5～20 times of weight, and rotating speed 3000～6000r/min directly copies the paper of manufacturing paper with pulp after paper or the bleaching after the making beating.
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| CN102391522A (en) * | 2011-10-10 | 2012-03-28 | 华南理工大学 | Preparation method of novel water-soluble ligin |
| US9434788B2 (en) * | 2012-07-11 | 2016-09-06 | The United States Of America, As Represented By The Secretary Of Agriculture | Bio-based fiber gums (BFGs) and processes for producing BFGs |
| CN106948207A (en) * | 2017-03-29 | 2017-07-14 | 厦门大学 | A kind of alkaline salt solution oxidation system boiling delignification pulping process of string |
| CN107912758B (en) * | 2017-12-08 | 2021-02-09 | 厦门大学 | Preparation method of drying-promoting and moisture-absorption-resisting composite functional xylo-oligosaccharide composition |
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| CN109337936A (en) * | 2018-10-30 | 2019-02-15 | 孙金良 | Association fibre element Ethanol Method |
| CN109619674B (en) * | 2018-11-22 | 2021-12-03 | 湖北中烟工业有限责任公司 | Preparation method of lotus fiber for cigarettes and moisturizing filter tip containing lotus fiber |
| CN109837791A (en) * | 2019-03-27 | 2019-06-04 | 北京林业大学 | A kind of bagasse alkaline pulping method based on hydrothermal pretreatment |
| CN115431429A (en) * | 2021-06-04 | 2022-12-06 | 唐禹豪 | Plastic/thermoplastic elastomer regenerated coarse grain capable of being modified or directly used and preparation method thereof |
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