CN103898786B - A kind of comprehensive utilization process of biomass material - Google Patents
A kind of comprehensive utilization process of biomass material Download PDFInfo
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Abstract
The present invention relates to a kind of method of comprehensive utilization of biomass material, specifically a kind ofly utilize biomass material to prepare paper pulp and the method for the lignin reclaimed in black liquor and wood sugar.Method of the present invention is under the catalytic action of hydrogen peroxide, by the mixed organic acid boiling biomass material of formic acid and acetic acid, in the process preparing paper pulp, reclaims the lignin in black liquor and wood sugar.The present invention, by technological parameter reasonable in design, make whole process route simple, and whole technique is not only applicable to wooden class raw material, is also applicable to grass as raw material, and the following bleaching technique of process route of the present invention is simple, and the Pulp Drainage Properties obtained is good.
Description
Technical field
The present invention relates to a kind of method of comprehensive utilization of biomass material, specifically one utilizes biomass material to prepare paper pulp, and reclaims the method for lignin and wood sugar.
Background technology
Biomass material exists with the form of plant, main component is cellulose, hemicellulose and lignin, wherein, cellulose accounts for about 40%, hemicellulose accounts for about 25%, lignin accounts for about 20%, and the biomass material total amount that the earth is generated by photosynthesis is every year more than 2,000 hundred million tons, and therefore biomass material is renewable resource abundant, the most cheap on the earth.
Cellulose is the main component of plant cell wall.The whole world, for the cellulose of papermaking of weaving, reaches 8,000,000 tons every year.Cellulose forms the main component of paper pulp, also has hemicellulose, lignin, resin, pigment, pectin and ash in various degree to grade material in addition.Wherein cellulose and hemicellulose are the basis that paper pulp needs, and other composition all belongs to the row removed.
At occurring in nature, the reserves of lignin are only second to cellulose, and all regenerate with the speed of 50,000,000,000 tons every year.Lignin is a kind of of great value industrial chemicals, highly purified sulphur-free lignin can be used as polymeric additive and soil conditioner, the pesticide slow-releasing agents etc. such as phenolic resin, polyurethane foam, epoxy resin, and lignin application can make its added value far above as the added value reclaiming heat after fuel combustion in these areas.Pulp and paper industry will isolate about 1.4 hundred million tons of celluloses every year from plant, obtain the lignin byproduct of about 5,000 ten thousand tons simultaneously, but up to now, the lignin more than 95% still directly enters rivers with " black liquor " or burns after concentrating, and is seldom utilized effectively.
Chinese patent CN101864683A discloses a kind of preprocess method of lignocellulose raw material, after the mixed liquor of lignin raw material and organic acid soln and catalyst mixes by this patent, carry out first step process, obtain liquid-solid mixture and carry out Separation of Solid and Liquid, obtaining pretreatment fluid and cellulose solids; Organic acid soln washing is adopted to obtain cellulose solids; The preliminary treatment black liquor obtained mixes Posterior circle for first step processing procedure with the washing black liquid obtained; Then the mixing black liquor recycling at least 3 times is carried out organic acid, lignin products and syrup solution to reclaim.The black liquor of collection is carried out flash distillation or evaporation, obtain organic acid and concentrated black liquor, the water adding 2-10 times of volume in black liquor obtains lignin products and syrup solution, and the organic acid reclaimed then refluxes for first step process, thus realizes the higher value application of lignocellulose raw material.But also there is following shortcoming in this patent: 1, as can be seen from the description in description, this technique adopts organic acid to carry out first step catalysis with the catalyst mix taking sulfuric acid as representative, need to add sulfuric acid in course of reaction and carry out catalysis, inevitably make sulfur-bearing in the follow-up lignin obtained; 2, this technique adopts organic acid and take sulfuric acid as the common boiling living beings of catalyst of representative, in distillation organic acid step, if organic acid distillation not exclusively, then lignin cannot be separated out completely, if after organic acid is distilled out completely, the sulfuric acid concentration then added wherein rises, and can make lignin charing wherein, affect the recovery rate of lignin; Although extraction and washing the fibre element all use identical organic acid in 3 whole techniques, and the pretreatment fluid of collection and cleaning solution are directly used in are circulated in the reactor of the first step, but also gather the lignin and pentose solution that dissolve wherein in whole mixed liquor in a large number, in view of the saturation degree restriction of organic acid extraction, the significant degree of its mixing black liquid extraction lignin can significantly reduce, therefore, although this step is circular response, the extraction efficiency effect for entirety is also little; 4, collect pretreatment fluid and cleaning solution in due to be dissolved with a large amount of hemicellulose boiling generate pentose, and pentose is along with can constantly contact with organic acid in mixed liquor repeatedly cyclic process, there is esterification and generate ester class, this patent is for the purpose of the comprehensive utilization of biomass material, therefore whether whole piece technique can be obtained pentose separately and be paid no attention to, but for for be separated and to obtain for the purpose of pentose technique, this technique is also inapplicable; 5, the black liquor be mixed to get needs circulation more than 3 times to carry out evaporation process again to isolate organic acid, and the concentrate that dilution obtains makes lignin separate out, the black liquor of disposable process and the high number of concentrate can be made, not only affect treatment effeciency but also be difficult to realize the continuity of technique; 6, as can be seen from description, in this technique, cellulosic recovery rate is only 38-55%, lignin extraction rate is 6-16%, and the recovery rate of whole technique is relatively low.
Chinese patent CN101514349A discloses a kind of method being prepared alcohol fuel by bamboo fiber.This patent is also the mix acid liquor boiling hydrolyzed hemicellulose with formic acid and acetic acid, and separates out lignin deposit directly to adding water in the filtrate of deviating from and isolate lignin with this and be used.Although this patent in a process line by cellulose, hemicellulose and lignin are separated, the design of this technique is to extract cellulose as final purpose, the loss of lignin and pentose is not considered in the design of whole piece technique, in the step of its extracting in water precipitation in separating lignin one step, can because make lignin be difficult to all deviate from containing formic acid and acetic acid in a large number in solution, even if add water in a large number also wherein can cannot ensure that lignin is separated out completely because of formic acid and acetic acid, lignin is caused to lose, obviously, this technique only emphasis considers and extracts cellulosic technique to greatest extent, directive significance is not had for high efficiency extraction lignin and wood sugar.
Summary of the invention
For this reason, technical problem to be solved by this invention is that in prior art, biomass material preparation has in the process of paper pulp, lignin and wood sugar can not obtain the problem of high efficiente callback, and then provide a kind of comprehensive utilization process that can be obtained the paper pulp of high yield the wood sugar in further high efficiente callback black liquor and lignin by rational optimum configurations.
For solving the problems of the technologies described above, the comprehensive utilization process of biomass material of the present invention, comprises the steps:
(1) after biomass material being pulverized, under the catalytic action of hydrogen peroxide, the organic acid solution formed by formic acid, acetic acid is used to carry out boiling to described raw material, control boiling temperature 90-120 DEG C, solid-liquid mass ratio is 1:5-1:15, reaction time 30-90min, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid; In described organic acid solution, total acid is dense is 70-85%, and the mass ratio of described acetic acid and formic acid is 15:1-1:1, and surplus is water, and hydrogen peroxide accounts for the 1-8% of biomass material;
(2) described first time solid of obtaining of Separation of Solid and Liquid is collected, under the catalytic action of hydrogen peroxide, the mix acid liquor adopting formic acid, acetic acid to be formed carries out pickling to described solid, control pickling temperature 20-100 DEG C, solid-liquid mass ratio is 1:4-1:10, and the reactant liquor obtained is carried out second time Separation of Solid and Liquid; Hydrogen peroxide accounts for the 1-8% of biomass material; In described mix acid liquor, total acid is dense is 60-90%, and the mass ratio of described acetic acid and formic acid is 10:1-6:1, and surplus is water;
(3) collect the solid that described second time Separation of Solid and Liquid obtains, and wash, control washing temperature is 50-90 DEG C, and starching dense is 1-3%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(4) collect described third time solid of obtaining of Separation of Solid and Liquid screening obtains screened stock cellulose, described screened stock cellulose obtains required paper pulp through bleaching.
(5) collect first time and the liquid that obtains of second time Separation of Solid and Liquid, evaporate, obtain formic acid and acetic acid steam and concentrate, the solids content of described concentrate is 70-90wt%;
(6) by the concentrate thin up of gained in step (5), stir, and carry out the 4th Separation of Solid and Liquid, the solid obtained obtains required lignin through washing;
(7), after described 4th Separation of Solid and Liquid, the liquid obtained obtains wood sugar after decolouring, filtration and condensing crystallizing process.
In the comprehensive utilization process of above-mentioned biomass material, described bleaching comprises the steps:
Alkali treatment, described alkali consumption accounts for the 1-3% of described screened stock cellulose quality, and temperature is 40-100 DEG C, and extraction times 0.5-2h starches dense 6-15%; Alkaline hydrogen peroxide bleaching, the quality of hydrogen peroxide accounts for the 1-3% of described screened stock cellulose quality, and pH value controls between 10-12, temperature 50-100 DEG C, bleaching time 1-3h, starches dense 3-5%; And acid treatment, the quality of described acid accounts for the 3-7% of described screened stock cellulose quality, and pH value controls between 2-4, temperature 30-55 DEG C, time 0.5-1h, starches dense 1.5-3%.
Preferably, in the step of described alkaline hydrogen peroxide bleaching, temperature 60-90 DEG C; In described acid-treated step, temperature 35-45 DEG C.
Preferably, described water add quality be the 2-5 of described concentrate quality doubly.
Preferably, also comprise in described step (5) and will the formic acid and acetic acid steam condensation that obtain be evaporated, and be back in the reactor of step (1), for the step of the boiling of step (1).
Preferably, also comprise liquid third time Separation of Solid and Liquid obtained in described step (3) and carry out water acid rectifying, the formic acid obtained and the mix acid liquor of acetic acid are back in the reactor of step (1), for the step of the boiling of step (1), and using the Water circulation that obtains in step (3) as washing water.
Preferably, in described step (1), solid-liquid mass ratio is 1:6-1:10, reaction time 40-70min, and in organic acid solution, the mass ratio of acetic acid and formic acid is 10:1-6:1, and the quality adding hydrogen peroxide accounts for the 3-8% of biomass material quality.
Preferably, the pickling temperature of described step (2) is 30-90 DEG C, and solid-liquid mass ratio is 1:6-1: 8, and the addition of hydrogen peroxide is the 4-7% of described biomass material quality.
Preferably, evaporating temperature 50-100, pressure 100-300kpa in described step (5)
Described biomass material is wooden class raw material or grass as raw material.
Described biomass material is one or more in the wooden classes such as reed, beanstalk stalk, wheat stalk, straw, maize straw, melon seed cases, bamboo chip, melon seeds bar or grass as raw material.
Technique scheme of the present invention has the following advantages compared to existing technology:
1, the present invention is by technological parameter reasonable in design, make whole process route simple, and whole technique is not only applicable to wooden class raw material, is also applicable to grass as raw material; The following bleaching technique of process route is simple, and the Pulp Drainage Properties obtained is good.
2, digestion process of the present invention carries out in airtight reaction vessel, because the part of formic acid, acetic acid and hydrogen peroxide is evaporated, makes to have certain pressure in container, thus shortens the digestion time of raw material, decrease cellulosic destruction.
3, after the technique first step of the present invention boiling and the pentose solution collected after acid elution directly evaporate, evaporate formic acid and acetic acid, can be used for the circulation of raw material on the one hand, also reduce the acid content in pentose solution simultaneously as far as possible, avoid esterification occurs, retain boiling to greatest extent and obtain pentose solution.
4, process selection formic acid of the present invention, the common boiling biomass material of acetic acid, formic acid is as a kind of strong organic acid, urge the lignin done in degraded raw material, alpha-cellulose in cellulose can be destroyed owing to being used alone formic acid, not only protect alpha-cellulose be not destroyed so add appropriate acetic acid, and the organic solvent dissolution lignin molecule utilizing formic acid and acetic acid to be formed, also utilize its acid boiling hemicellulose wherein, hydrogen peroxide add the environment that can form peroxide acid solution, exacerbate degraded and the dissolving of lignin, and prevent the hydrolytic cleavage of fiber high polymer.
5, adding hydrogen peroxide in cooking liquor of the present invention is catalyst, make the lignin of biomass material middle-shallow layer and hemicellulose and HO+ ionic reaction, constantly dissolved, and HO+ is little on cellulosic impact, after a period of time, the consumption of HO+ ion is complete, and the activity of H+ ion increases greatly, makes hemicellulose and be soluble in sour lignin to remove rapidly.Thus improve the recovery rate of lignin.
6, after first time boiling, formic acid, acetic acid and hydrogen peroxide carry out pickling to solid, adjust on the one hand to front and continued digestion process, are decomposed and stripping by a small amount of lignin of its internal residual on the other hand, further except delignification.
7, before adding auxiliary agent precipitation lignin, formic acid and acetic acid is evaporated, the formic acid steamed on the one hand and acetic acid can be used for the circular response of boiling step to economize in raw materials, simultaneously except after formic acid removal, acetic acid concentration, ensure with the auxiliary agent of minimum dose, lignin all to be separated out, energy efficient;
Accompanying drawing explanation
In order to make content of the present invention be more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the flow chart of technique of the present invention.
Detailed description of the invention
Below will the invention will be further described by specific embodiment.
In the application, apart from outside specified otherwise, percentage composition used all represents mass percentage, i.e. " % " expression " wt% "; In described organic acid solution or mix acid liquor except a certain amount of formic acid, acetic acid, surplus is water, the total acid dense nail acid of organic acid solution and the gross mass of acetic acid account for the percentage of described organic acid solution quality, the formic acid added in the total acid dense finger acid pickling step of mix acid liquor and the gross mass of acetic acid account for the percentage of described mix acid liquor quality
Slurry described in each step is dense=this step in solid quality/this step in Zhi Liang He ╳ 100% of solid and liquid
Hydrogen peroxide H in each embodiment
2o
2be that the form of the aqueous hydrogen peroxide solution of 27% adds with mass concentration.Such as need as calculated to add 2.7g hydrogen peroxide, then corresponding should be add 10g (2.7 ÷ 0.27=10) described aqueous hydrogen peroxide solution.
The measuring brightness method of paper pulp is with reference to FZ/T50010.7-1998, and ash determination adopts FZ/T50010.5-1998 method, and Kappa number is identical with Chinese patent literature CN1170031C with the assay method of hemicellulose.Solids content adopts halogen fast tester for water content (plum Teller-Tuo benefit, model: HB43-S) to measure at 115 DEG C.The concentration of pentose or xylose solution adopts high-efficient liquid phase color instrument (model: U-3000, producer: ThermoFisher Dai An company) to measure.
In each embodiment,
Quality × 100% of the quality/raw material of the productive rate=paper pulp of paper pulp.
Wood sugar recovery rate %=wood sugar quality/(in material quality × raw material hemicellulose level) × 100%.
Lignin extraction rate=lignin quality/the content of lignin (in the material quality × raw material) × 100%;
Furfural content % in furfural yield=furfural stock solution quality × liquid/(liquid glucose quality × liquid glucose furfural content %) × 100%.
Embodiment 1
In the present embodiment, described biomass material is reed (one-tenth is grouped into: cellulose 49.5%, hemicellulose level 22.7%, lignin 18.9%), and first will smash, washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
The present embodiment, from the comprehensive utilization process of described biomass material, comprises the steps:
(1) by after reed comminution pretreatment, under the catalytic action of hydrogen peroxide, total acid concentration is used to be that the formic acid of 85% and the organic acid solution of acetic acid carry out boiling to the reed after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:1, and before adding reed raw material, add the hydrogen peroxide (H accounting for raw material 3%
2o
2) as catalyst, controlling reaction temperature 90 DEG C, reaction 70min, solid-liquid mass ratio is 1:5, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that above-mentioned separation obtains being added total acid concentration is that the formic acid of 60% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for raw material 3% in the organic acid solution of 60%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 10:1, temperature is 60 DEG C, wash time 1h, and solid-liquid mass ratio is 1:4, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid that in step (1) and step (2), twice Separation of Solid and Liquid obtains is collected, 50 DEG C, 100kpa carries out decompression distillation, the steam and the solids content that obtain formic acid and acetic acid are 70% concentrate, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that second time Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 50 DEG C, and starching dense is 1%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) liquid that Separation of Solid and Liquid for the third time obtains is collected, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes water with water in step (5);
(6) solid that collection third time Separation of Solid and Liquid obtains also is screened and obtains screened stock cellulose, the screened stock cellulose obtained by said process, and measuring Kappa number is 9, and hemicellulose level is 12%, whiteness 40%ISO, ash content 2%, productive rate 42%; The screened stock cellulose obtained is carried out bleaching and obtains paper pulp; Its productive rate of paper pulp adopting the method for the present embodiment to obtain after measured is 38%.
(7) concentrate of gained in step (3) is added the water dilution accounting for concentrate quality 2 times, 60-70 DEG C of stirring, and carrying out the 4th Separation of Solid and Liquid, the solid obtained is washed deesterify further and is obtained required lignin, and the recovery rate of its lignin is 85.2%.
The liquid that (8) the 4th times Separation of Solid and Liquid obtains is pentose solution, and described pentose solution obtains xylose crystals, wood sugar recovery rate 65% through decolouring, filtration and condensing crystallizing.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the NaOH accounting for screened stock cellulose quality 1% to carry out alkali treatment the screened stock cellulose through screening, control temperature is 40 DEG C, and extraction times 0.5h starches dense 6%;
(2) carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is 1% of screened stock cellulose quality, and utilizes NaOH control ph between 10-12, temperature 100 DEG C, and bleaching time 1h, starches dense 3%; With
(3) acid treatment, the acid adopted in this step is hydrochloric acid, and its consumption is 3% of screened stock cellulose quality, and control ph is between 2-4, temperature 30 DEG C, time 0.5h, starches dense 1.5%.
Embodiment 2
In the present embodiment, first smashed by straw (one-tenth is grouped into: cellulose 35.8%, hemicellulose 28.6%, lignin 14.3%), being crushed to particle diameter is 0.5-20cm.
The present embodiment, from the comprehensive utilization process of described straw, comprises the steps:
(1) by after straw comminution pretreatment, total acid concentration is used to be that the formic acid of 82% and the organic acid solution of acetic acid carry out boiling to the straw after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 6:1, and before adding straw raw material, add the hydrogen peroxide (H accounting for raw material 1%
2o
2) as catalyst, controlling reaction temperature 100 DEG C, reaction 40min, solid-liquid mass ratio is 1:6, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that above-mentioned separation obtains being added total acid concentration is that the formic acid of 70% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for raw material 7% in the organic acid solution of 70%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 6:1, temperature is 20 DEG C, wash time 1h, and solid-liquid mass ratio is 1:6, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid that in step (1) and step (2), twice Separation of Solid and Liquid obtains is collected, 60 DEG C, 150kpa carries out decompression distillation, the steam and the solids content that obtain formic acid and acetic acid are 80% concentrate, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that second time Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 60 DEG C, and starching dense is 2%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) liquid that Separation of Solid and Liquid for the third time obtains is collected, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes water with water in step (4);
(6) solid that collection third time Separation of Solid and Liquid obtains also is screened and obtains screened stock cellulose, the screened stock cellulose obtained by said process, and measure Kappa number 7, hemicellulose level is 13%, whiteness 42%ISO, ash content 4%, productive rate 37%; The screened stock cellulose obtained is carried out bleaching and obtains paper pulp; Its productive rate of paper pulp adopting the method for the present embodiment to obtain after measured is 36%.
(7) concentrate of gained in step (3) is added the water dilution accounting for concentrate quality 3 times, 60-70 DEG C of stirring, and carrying out the 4th Separation of Solid and Liquid, the solid obtained is washed deesterify further and is obtained required lignin, and the recovery rate of its lignin is 84.5%.
The liquid that (8) the 4th times Separation of Solid and Liquid obtains is pentose solution, and described pentose solution obtains xylose crystals through decolouring, filtration and condensing crystallizing, and its wood sugar recovery rate is 64%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) by through screening screened stock cellulose first utilize account for screened stock cellulose quality 3% potassium hydroxide carry out alkali treatment, control temperature is 60 DEG C, and extraction times 50min starches dense 7%;
(2) carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is 1.5% of screened stock cellulose quality, and by potassium hydroxide control ph between 10-12, temperature 90 DEG C, bleaching time 80min, starches dense 4%; With
(3) acid treatment, the acid adopted in this step is sulfuric acid, and its consumption is 4% of screened stock cellulose quality, and control ph is between 2-4, and temperature 35 DEG C, time 45min, starches dense 2.2%.
Embodiment 3
In the present embodiment, described biomass material is bamboo chip (one-tenth is grouped into: cellulose 47.3%, hemicellulose 24.6%, lignin 25.8%), and first will smash, washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
The comprehensive utilization process of bamboo chip described in the present embodiment, comprises the steps:
(1) by after broken for bamboo chip preliminary treatment, total acid concentration is used to be that the formic acid of 79% and the organic acid solution of acetic acid carry out boiling to the bamboo chip after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 10:1, and before adding bamboo chip raw material, add the hydrogen peroxide (H accounting for raw material 6%
2o
2) as catalyst, controlling reaction temperature 110 DEG C, reaction 30min, solid-liquid mass ratio is 1:10, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that above-mentioned separation obtains being added total acid concentration is that the formic acid of 90% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for over dry raw material 5% in the organic acid solution of 90%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 8:1, temperature is 30 DEG C, wash time 1h, and solid-liquid mass ratio is 1:8, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid that in step (1) and step (2), twice Separation of Solid and Liquid obtains is collected, 70 DEG C, 200kpa carries out decompression distillation, the steam and the solids content that obtain formic acid and acetic acid are 90% concentrate, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that second time Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 70 DEG C, and starching dense is 3%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) liquid that Separation of Solid and Liquid for the third time obtains is collected, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes water with water in step (5);
(6) solid that collection third time Separation of Solid and Liquid obtains also is screened and obtains screened stock cellulose, the screened stock cellulose obtained by said process, and measure Kappa number 6, hemicellulose level is 15%, whiteness 41%ISO, ash content 6%, productive rate 38%; The screened stock cellulose obtained is carried out bleaching and obtains paper pulp; Adopt the paper pulp that the method for the present embodiment obtains after measured, its productive rate is 33%.
(7) concentrate of gained in step (3) is added the water dilution accounting for concentrate quality 4 times, 60-70 DEG C of stirring, and carrying out the 4th Separation of Solid and Liquid, the solid obtained is washed deesterify further and is obtained required lignin, and the recovery rate of its lignin is 86%.
The liquid that (8) the 4th times Separation of Solid and Liquid obtains is pentose solution, and described pentose solution obtains xylose crystals through decolouring, filtration and condensing crystallizing, and its wood sugar recovery rate is 63%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) by through screening screened stock cellulose first utilize account for screened stock cellulose quality 1.5% NaOH carry out alkali treatment, control temperature is 50 DEG C, and extraction times 70min starches dense 9%;
(2) carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is 2% of screened stock cellulose quality, and by potassium hydroxide control ph between 10-12, temperature 70 C, bleaching time 100min, starches dense 5%; With
(3) acid treatment, the acid adopted in this step is hydrochloric acid, and its consumption is 6% of screened stock cellulose quality, and control ph is between 2-4, and temperature 40 DEG C, time 50min, starches dense 3%.
Embodiment 4
In the present embodiment, described biomass material is wheat straw (one-tenth is grouped into: cellulose 40.5, hemicellulose 31.9%, lignin 15.4%), and first will smash, washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
The present embodiment, from the comprehensive utilization process of described wheat straw, comprises the steps:
(1) by after broken for wheat straw preliminary treatment, total acid concentration is used to be that the formic acid of 76% and the organic acid solution of acetic acid carry out boiling to the wheat straw after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 15:1, and before adding wheat straw raw material, add the hydrogen peroxide (H accounting for raw material 4%
2o
2) as catalyst, controlling reaction temperature 120 DEG C, reaction 90min, solid-liquid mass ratio is 1:12, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that above-mentioned separation obtains being added total acid concentration is that the formic acid of 80% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for raw material 8% in the organic acid solution of 80%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 9:1, temperature is 50 DEG C, wash time 1h, and solid-liquid mass ratio is 1:7, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid that in step (1) and step (2), twice Separation of Solid and Liquid obtains is collected, 100 DEG C, 250kpa carries out decompression distillation, the steam and the solids content that obtain formic acid and acetic acid are 75% concentrate, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that second time Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 80 DEG C, and starching dense is 1.8%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) liquid that Separation of Solid and Liquid for the third time obtains is collected, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes water with water in step (4);
(6) solid that collection third time Separation of Solid and Liquid obtains also is screened and obtains screened stock cellulose, the screened stock cellulose obtained by said process, and measure Kappa number 8, hemicellulose level is 15%, whiteness 43%ISO, ash content 9%, productive rate 45%; The screened stock cellulose obtained is carried out bleaching and obtains paper pulp; Adopt the paper pulp that the method for the present embodiment obtains after measured, its productive rate is 41%.
(7) concentrate of gained in step (3) is added the water dilution accounting for over dry material quality 5 times, 60-70 DEG C of stirring, and carrying out the 4th Separation of Solid and Liquid, the solid obtained is washed deesterify further and is obtained required lignin, and the recovery rate of its lignin is 84.2%.
The liquid that (8) the 4th times Separation of Solid and Liquid obtains is pentose solution, and described pentose solution obtains xylose crystals through decolouring, filtration and condensing crystallizing, and its wood sugar recovery rate is 62%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the NaOH accounting for screened stock cellulose quality 2.5% to carry out alkali treatment the screened stock cellulose through screening, control temperature is 70 DEG C, and extraction times 1.5h starches dense 11%;
(2) carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is 2.5% of screened stock cellulose quality, and by potassium hydroxide control ph between 10-12, temperature 50 C, bleaching time 120min, starches dense 3.5%; With
(3) acid treatment, the acid adopted in this step is sulfuric acid, and its consumption is 3.5% of screened stock cellulose quality, and control ph is between 2-4, and temperature 45 C, time 35min, starches dense 2.5%.
Embodiment 5
In the present embodiment, described biomass material is melon seeds bar (one-tenth is grouped into: hemicellulose 31.91%, lignin 23.94%, cellulose 44.15%), and first will smash, washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
The present embodiment, from the comprehensive utilization process of described melon seeds bar, comprises the steps:
(1) by after broken for melon seeds bar preliminary treatment, total acid concentration is used to be that the formic acid of 73% and the organic acid solution of acetic acid carry out boiling to the melon seeds bar after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 12:1, and before adding melon seeds bar raw material, add the hydrogen peroxide (H accounting for raw material 8%
2o
2) as catalyst, controlling reaction temperature 95 DEG C, reaction 60min, solid-liquid mass ratio is 1:15, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that above-mentioned separation obtains being added total acid concentration is that the formic acid of 75% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for raw material 6% in the organic acid solution of 75%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 6:1, temperature is 90 DEG C, wash time 1h, and solid-liquid mass ratio is 1:9, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid that in step (1) and step (2), twice Separation of Solid and Liquid obtains is collected, 90 DEG C, 100kpa carries out decompression distillation, the steam and the solids content that obtain formic acid and acetic acid are 85% concentrate, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that second time Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 90 DEG C, and starching dense is 2.4%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) liquid that Separation of Solid and Liquid for the third time obtains is collected, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes water with water in step (4);
(6) solid that collection third time Separation of Solid and Liquid obtains also is screened and obtains screened stock cellulose, the screened stock cellulose obtained by said process, and measure Kappa number 5, hemicellulose level is 14%, whiteness 44%ISO, ash content 7%, productive rate 52%; The screened stock cellulose obtained is carried out bleaching process and obtains paper pulp, its productive rate is 39%.
(7) concentrate of gained in step (3) is added the water dilution accounting for concentrate quality 2.5 times, 60-70 DEG C of stirring, and carrying out the 4th Separation of Solid and Liquid, the solid obtained is washed deesterify further and is obtained required lignin, and the recovery rate of its lignin is 85.6%.
The liquid that (8) the 4th times Separation of Solid and Liquid obtains is pentose solution, and described pentose solution obtains xylose crystals through decolouring, filtration and condensing crystallizing, and its wood sugar recovery rate is 64.5%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the NaOH accounting for screened stock cellulose quality 3% to carry out alkali density the screened stock cellulose through screening, control temperature is 80 DEG C, and extraction times 110min starches dense 13%;
(2) carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is 3% of screened stock cellulose quality, and by potassium hydroxide control ph between 10-12, temperature 60 C, bleaching time 140min, starches dense 4.5%; With
(3) acid treatment, the acid adopted in this step is hydrochloric acid, and its consumption is 7% of screened stock cellulose quality, and control ph is between 2-4, and temperature 50 C, time 1h, starches dense 1.8%.
Embodiment 6
In the present embodiment, described biomass material is cotton stem (one-tenth is grouped into: hemicellulose 22.1%, lignin 23.3%, cellulose 54.5%), and first will smash, washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
The comprehensive utilization process of cotton stem described in the present embodiment, comprises the steps:
(1) by after broken for cotton stem preliminary treatment, total acid concentration is used to be that the formic acid of 70% and the organic acid solution of acetic acid carry out boiling to the cotton stem after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 8:1, and before adding cotton stem raw material, add the hydrogen peroxide (H accounting for raw material 7%
2o
2) as catalyst, controlling reaction temperature 115 DEG C, reaction 50min, solid-liquid mass ratio is 1:9, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that above-mentioned separation obtains being added total acid concentration is that the formic acid of 65% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for raw material 1% in the organic acid solution of 65%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 7:1, temperature is 100 DEG C, wash time 1h, and solid-liquid mass ratio is 1:10, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid that in step (1) and step (2), twice Separation of Solid and Liquid obtains is collected, 80 DEG C, 270kpa carries out decompression distillation, the steam and the solids content that obtain formic acid and acetic acid are 80% concentrate, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that second time Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 65 DEG C, and washing slurry is dense is 2.6%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) liquid that Separation of Solid and Liquid for the third time obtains is collected, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes water with water in step (5);
(6) solid that collection third time Separation of Solid and Liquid obtains also is screened and obtains screened stock cellulose, the screened stock cellulose obtained by said process, and measuring Kappa number is 9, and hemicellulose level is 12%, whiteness 45%ISO, ash content 8%, productive rate 53%; The screened stock cellulose obtained is carried out bleaching and obtains paper pulp; Adopt the paper pulp that the method for the present embodiment obtains after measured, its productive rate is 41%.
(7) concentrate of gained in step (3) is added the water dilution accounting for over dry material quality 4.5 times, 60-70 DEG C of stirring, and carrying out the 4th Separation of Solid and Liquid, the solid obtained is washed deesterify further and is obtained required lignin, and the recovery rate of its lignin is 86%.
The liquid that (8) the 4th times Separation of Solid and Liquid obtains is pentose solution, and described pentose solution obtains xylose crystals through decolouring, filtration and condensing crystallizing, and its wood sugar recovery rate is 63.8%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the potassium hydroxide accounting for screened stock cellulose quality 2.5% to carry out alkali treatment the screened stock cellulose through screening, control temperature is 100 DEG C, and extraction times 2h starches dense 15%;
(2) carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is 1.5% of screened stock cellulose quality, and by NaOH pH value between 10-12, temperature 80 DEG C, bleaching time 3h, starches dense 5%; With
(3) acid treatment, the acid adopted in this step is sulfuric acid, and its consumption is 4.5% of screened stock cellulose quality, and control ph is between 2-4, and temperature 55 DEG C, time 40min, starches dense 2%.
Comparative example 1
Raw materials used in the present embodiment, processing step and technological parameter and embodiment 1 basically identical, its difference is, except the processing step of bleaching process, does not all add hydrogen peroxide as catalyst in each step.Adopt the screened stock cellulose that method described in the present embodiment obtains, measuring Kappa number is 30.2, and hemicellulose level is 10.5%, whiteness 25%ISO, and productive rate is 30%, is 25% by its productive rate of paper pulp obtained after fiber bleached for the screened stock obtained.The recovery rate of lignin is 65%, wood sugar recovery rate 40.2%
Comparative example 2
Raw material used in the present embodiment and processing step and technological parameter and embodiment 1 basically identical, its difference is, the digestion process of step (1) is under the catalytic action of hydrogen peroxide, and the organic acid solution of employing is made up of the formic acid of 85wt% and 15wt% water.The acid pickling step of its step (2) is under the catalytic action of hydrogen peroxide, the organic acid solution be made up of formic acid and the 40wt% water of 60wt% adopted carries out pickling, in each step, the adding proportion of hydrogen peroxide is consistent with embodiment 3, adopt the screened stock cellulose that the method for the present embodiment obtains after measured, measuring Kappa number is 26.8, and hemicellulose level is 8%, whiteness 25%ISO, productive rate is 35%, is 30.3% by its productive rate of paper pulp obtained after fiber bleached for the screened stock obtained.The recovery rate of lignin is 68%, wood sugar recovery rate 44%.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. a comprehensive utilization process for biomass material, is characterized in that, comprises the steps:
(1) after biomass material being pulverized, under the catalytic action of hydrogen peroxide, the organic acid solution formed by formic acid, acetic acid is used to carry out boiling to described raw material, control boiling temperature 90-120 DEG C, solid-liquid mass ratio is 1:5-1:15, reaction time 30-90min, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
In described organic acid solution, total acid concentration is 70-85%, and the mass ratio of described acetic acid and formic acid is 15:1-1:1, and surplus is water,
The quality of hydrogen peroxide accounts for the 1-8% of biomass material quality;
(2) described first time solid of obtaining of Separation of Solid and Liquid is collected, under the catalytic action of hydrogen peroxide, the mix acid liquor adopting formic acid, acetic acid to be formed carries out pickling to described solid, control pickling temperature 20-100 DEG C, solid-liquid mass ratio is 1:4-1:10, and the reactant liquor obtained is carried out second time Separation of Solid and Liquid;
Hydrogen peroxide quality accounts for the 1-8% of biomass material quality;
In described mix acid liquor, total acid concentration is 60-90%, and the mass ratio of described acetic acid and formic acid is 10:1-6:1, and surplus is water;
(3) collect the solid that described second time Separation of Solid and Liquid obtains, and wash, control washing temperature is 50-90 DEG C, and slurry concentration is 1-3%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(4) collect described third time solid of obtaining of Separation of Solid and Liquid screening obtains screened stock cellulose, described screened stock cellulose obtains required paper pulp through bleaching; (5) collect first time and the liquid that obtains of second time Separation of Solid and Liquid, evaporate, obtain formic acid and acetic acid steam and concentrate, the solids content of described concentrate is 70-90wt%;
(6) by the concentrate thin up of gained in step (5), stir, and carry out the 4th Separation of Solid and Liquid, the solid obtained obtains required lignin through washing;
(7), after described 4th Separation of Solid and Liquid, the liquid obtained obtains wood sugar after decolouring, filtration and condensing crystallizing process.
2. the comprehensive utilization process of biomass material according to claim 1, is characterized in that:
Described bleaching comprises the steps:
Alkali treatment, described alkali consumption accounts for the 1-3% of described screened stock cellulose quality, and temperature is 40-100 DEG C, extraction times 0.5-2h, slurry concentration 6-15%;
Alkaline hydrogen peroxide bleaching, the quality of hydrogen peroxide accounts for the 1-3% of described screened stock cellulose quality, and pH value controls between 10-12, temperature 50-100 DEG C, bleaching time 1-3h, slurry concentration 3-5%; With
Acid treatment, the quality of described acid accounts for the 3-7% of described screened stock cellulose quality, and pH value controls between 2-4, temperature 30-55 DEG C, time 0.5-1h, slurry concentration 1.5-3%.
3. the comprehensive utilization process of biomass material according to claim 2, is characterized in that:
In the step of described alkaline hydrogen peroxide bleaching, temperature 60-90 DEG C; In described acid-treated step, temperature 35-45 DEG C.
4., according to the comprehensive utilization process of the arbitrary biomass material of claim 1-3, it is characterized in that:
Described water add quality be the 2-5 of described concentrate quality doubly.
5. the comprehensive utilization process of biomass material according to claim 4, is characterized in that:
Also comprise in described step (5) and will evaporate the formic acid and acetic acid steam condensation that obtain, and be back in the reaction vessel of step (1), for the step of the boiling of step (1), described reaction vessel is reactor.
6. the comprehensive utilization process of biomass material according to claim 5, is characterized in that:
Also comprise liquid third time Separation of Solid and Liquid obtained in described step (3) and carry out water acid rectifying, the formic acid obtained and the mix acid liquor of acetic acid are back in the reaction vessel of step (1), for the step of the boiling of step (1), described reaction vessel is reactor, and using the Water circulation that obtains in step (3) as washing water.
7. the comprehensive utilization process of the biomass material according to claim 1,2,3,5 or 6, is characterized in that:
In described step (1), solid-liquid mass ratio is 1:6-1:10, reaction time 40-70min, and in organic acid solution, the mass ratio of acetic acid and formic acid is 10:1-6:1, and the quality adding hydrogen peroxide accounts for the 3-8% of biomass material quality.
8. the comprehensive utilization process of biomass material according to claim 7, is characterized in that:
The pickling temperature of described step (2) is 30-90 DEG C, and solid-liquid mass ratio is 1:6-1:8, and the addition of hydrogen peroxide is the 4-7% of described biomass material quality.
9. the comprehensive utilization process of biomass material according to claim 8, is characterized in that:
Evaporating temperature 50-100, pressure 100-300kPa in described step (5).
10. the comprehensive utilization process of biomass material according to claim 9, is characterized in that:
Described biomass material is wooden class raw material or grass as raw material.
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| US6562191B1 (en) * | 1998-05-05 | 2003-05-13 | Chempolis Oy | Process for producing pulp with a mixture of formic acid and acetic acid as cooking chemical |
| US7402224B1 (en) * | 1999-05-06 | 2008-07-22 | Compagnie Industrielle De La Matiere Vegetale | Method for producing paper pulp, lignins, sugars and acetic acid by frantionation of lignocellulosic vegetable material in formic/acetic acid medium |
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| US6562191B1 (en) * | 1998-05-05 | 2003-05-13 | Chempolis Oy | Process for producing pulp with a mixture of formic acid and acetic acid as cooking chemical |
| US7402224B1 (en) * | 1999-05-06 | 2008-07-22 | Compagnie Industrielle De La Matiere Vegetale | Method for producing paper pulp, lignins, sugars and acetic acid by frantionation of lignocellulosic vegetable material in formic/acetic acid medium |
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