CN103898786A - Comprehensive utilization method of biomass raw material - Google Patents
Comprehensive utilization method of biomass raw material Download PDFInfo
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Abstract
The invention relates to a comprehensive utilization method of a biomass raw material, and concretely relates to a method for preparing a paper pulp by utilizing the biomass raw material and recovering lignin and xylose in a black liquor. The method is characterized in that the biomass raw material is boiled through a formic acid and acetic acid mixed organic acid under the catalysis action of hydrogen peroxide, and lignin and xylose in the black liquor are recovered in the paper pulp preparation process. The whole method has a simple route by designing reasonable technological parameters, is suitable for wood raw materials, and is also suitable for grass raw materials; and a subsequent bleaching technology of the process route is simple, and the drainability of the obtained paper pulp 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 40% left and right, hemicellulose accounts for 25% left and right, lignin accounts for 20% left and right, and the biomass material total amount being generated by photosynthesis every year on the earth exceedes 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 the papermaking of weaving, reaches 8,000,000 tons every year.Cellulose is to form the main component of paper pulp, also has in addition hemicellulose, lignin, resin, pigment, pectin and the ash in various degree material that grades.Wherein cellulose and hemicellulose are the basis that paper pulp needs, and other composition all belongs to the row of removing.
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 the polymeric additives such as phenolic resin, polyurethane foam, epoxy resin and soil conditioner, pesticide slow-releasing agent etc., and lignin application can make its added value far above the added value as reclaiming heat after fuel combustion in these areas.Pulp and paper industry will be isolated about 1.4 hundred million tons of celluloses every year from plant, obtain the lignin byproduct of 5,000 ten thousand tons of left and right simultaneously, but up to now, exceed 95% lignin still with " black liquor " directly enter rivers or concentrated after burn, be seldom utilized effectively.
Chinese patent CN101864683A discloses a kind of preprocess method of lignocellulose raw material, this patent is mixed lignin raw material with the mixed liquor of organic acid soln and catalyst after, carry out first step processing, obtain liquid-solid mixture and carry out Separation of Solid and Liquid, obtain pretreatment fluid and cellulose solids; Adopt organic acid soln washing to obtain cellulose solids; The preliminary treatment black liquor obtaining is cycled to used in first step processing procedure after mixing with the washing black liquid obtaining; Then the mixing black liquor that recycles at least 3 times being carried out to organic acid, lignin products and syrup solution reclaims.The black liquor of collection is carried out to flash distillation or evaporation, obtain organic acid and concentrated black liquor, obtain lignin products and syrup solution to the water that adds 2-10 times of volume in black liquor, the organic acid reclaiming refluxes for first step processing, thereby realizes the higher value application of lignocellulose raw material.But also there is following shortcoming in this patent: 1, the description from description can be found out, this technique is to adopt organic acid and the catalyst mix take sulfuric acid as representative to carry out first step catalysis, in course of reaction, need to add sulfuric acid and carry out catalysis, inevitably make sulfur-bearing in the follow-up lignin obtaining; 2, the common boiling living beings of this process using organic acid and the catalyst take sulfuric acid as representative, in distillation organic acid step, if organic acid distillation not exclusively, lignin cannot be separated out completely, if after organic acid is distilled out completely, add sulfuric acid concentration wherein to rise, 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 the reactor that is circulated to the first step, dissolve lignin and pentose solution wherein but also gathered in a large number in whole mixed liquor, in view of the saturation degree restriction of organic acid extraction, its significant degree of mixing black liquid extraction lignin can significantly reduce, therefore, although this step is circular response, for overall extraction efficiency effect little; 4, in the pretreatment fluid of collecting and cleaning solution due to the pentose that is dissolved with a large amount of hemicellulose boilings and generates, and pentose is along with mixed liquor repeatedly can constantly contact with organic acid in cyclic process, there is esterification and generate ester class, this patent is that comprehensive utilization take biomass material is as object, therefore whether can obtain separately pentose and pay no attention to for whole piece technique, but for obtaining pentose for the technique of object to separate, this technique is also inapplicable; 5, the black liquor being mixed to get need to circulate and carry out above evaporation process for 3 times to isolate organic acid again, and the concentrate that dilution obtains is separated out lignin, can make the black liquor of disposable processing and the quantity of concentrate very big, not only affect treatment effeciency but also be difficult to realize the continuity of technique; 6, from description, can find out, in this technique, cellulosic recovery rate is only for 38-55%, lignin extraction rate are 6-16%, and the recovery rate of whole technique is relatively low.
Chinese patent CN101514349A discloses a kind of method of 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 directly separates out lignin precipitation to adding water in the filtrate of deviating from and isolate lignin with this and be used.Although this patent in a technique circuit 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 make lignin be difficult to all deviate from because containing in a large number formic acid and acetic acid in solution, can dissolve and wherein cannot guarantee that lignin separates out completely because of formic acid and acetic acid even if add water in a large number also, cause lignin loss, obviously, this technique only emphasis has considered to extract to greatest extent cellulosic technique, do not have directive significance 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 is prepared with 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 and can obtain the paper pulp of high yield the further wood sugar in high efficiente callback black liquor and the comprehensive utilization process of lignin by rational parameter setting.
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 is pulverized, under the catalytic action of hydrogen peroxide, use the organic acid solution being formed by formic acid, acetic acid to carry out boiling to described raw material, control boiling temperature 90-120 ℃, solid-liquid mass ratio is 1:5-1:15, reaction time 30-90min, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time; 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) solid that described in collection, Separation of Solid and Liquid obtains for the first time, under the catalytic action of hydrogen peroxide, the mix acid liquor that adopts formic acid, acetic acid to form carries out pickling to described solid, control pickling temperature 20-100 ℃, solid-liquid mass ratio is 1:4-1:10, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the second time; 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) solid that described in collection, Separation of Solid and Liquid obtains for the second time, and wash, control washing temperature is 50-90 ℃, starching dense is 1-3%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(4) described in collection, Separation of Solid and Liquid obtains for the third time solid screening obtain screened stock cellulose, and described screened stock cellulose obtains required paper pulp through bleaching.
(5) collect for the first time and the liquid that Separation of Solid and Liquid obtains for the second time, 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 Separation of Solid and Liquid the 4th time, the solid obtaining obtains required lignin through washing;
(7), after described the 4th Separation of Solid and Liquid, the liquid obtaining obtains wood sugar after decolouring, filtration and condensing crystallizing are processed.
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 ℃, and extracting time 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 is controlled between 10-12, temperature 50-100 ℃, 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 is controlled between 2-4, temperature 30-55 ℃, time 0.5-1h, starches dense 1.5-3%.
Preferably, in the step of described alkaline hydrogen peroxide bleaching, temperature 60-90 ℃; In described acid-treated step, temperature 35-45 ℃.
Preferably, described water add quality be described concentrate quality 2-5 doubly.
Preferably, in described step (5), also comprise formic acid and acetic acid steam condensation that evaporation is obtained, and be back in the reactor of step (1), for the step of the boiling of step (1).
Preferably, in described step (3), also comprise the liquid that Separation of Solid and Liquid obtains is for the third time carried out to water acid rectifying, the formic acid obtaining and the mix acid liquor of acetic acid are back in the reactor of step (1), be used for the step of the boiling of step (1), and the water obtaining is back to 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, adds the quality of hydrogen peroxide to account for the 3-8% of biomass material quality.
Preferably, the pickling temperature of described step (2) is 30-90 ℃, 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 in described step (5), pressure 100-300kpa
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 by technological parameter reasonable in design, makes 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 obtaining is good.
2, digestion process of the present invention carries out in airtight reaction vessel, due to the part evaporation of formic acid, acetic acid and hydrogen peroxide, makes in container, to have certain pressure, thereby has shortened the digestion time of raw material, has reduced cellulosic destruction.
3, after the technique first step of the present invention boiling and the pentose solution of collecting after acid elution directly evaporate, evaporate formic acid and acetic acid, can be used on the one hand the circulation of raw material, also reduce the acid content in pentose solution simultaneously as far as possible, avoid occurring esterification, retain to greatest extent boiling 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 of doing in degraded raw material, owing to using separately formic acid can destroy the alpha-cellulose in cellulose, not only protect alpha-cellulose not to be destroyed so add appropriate acetic acid, and the organic solvent dissolution lignin molecule that utilizes formic acid and acetic acid to form, also utilize its acid boiling hemicellulose wherein, hydrogen peroxide add the environment that can form peroxide acid solution, degraded and the dissolving of lignin are aggravated, and prevent the hydrolytic cleavage of fiber high polymer.
5, in cooking liquor of the present invention, adding hydrogen peroxide is catalyst, make lignin and hemicellulose and the HO+ ionic reaction of biomass material middle-shallow layer, 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.Thereby improve the recovery rate of lignin.
6, after boiling for the first time, formic acid, acetic acid and hydrogen peroxide carry out pickling to solid, on the one hand front and continued digestion process are adjusted, on the other hand its inner remaining a small amount of lignin is decomposed and stripping, and further except delignification.
7, adding auxiliary agent to evaporate formic acid and acetic acid before separating out lignin, the circular response that the formic acid steaming on the one hand and acetic acid can be used for boiling step is to economize in raw materials, except after formic acid removal, acetic acid concentration, guarantee with the auxiliary agent of minimum dose, lignin all to be separated out energy efficient simultaneously;
Accompanying drawing explanation
For content of the present invention is 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.
The specific embodiment
Below will by specific embodiment, the invention will be further described.
In the application, outside specified otherwise, percentage composition used all represents quality percentage composition, 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 dense nail acid of total 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 adding in the dense finger acid pickling step of total acid 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 quality/this step of solid the Zhi Liang of solid and liquid with ╳ 100%
Hydrogen peroxide H in each embodiment
2o
2the form of the aqueous hydrogen peroxide solution take mass concentration as 27% adds.For example need as calculated to add 2.7g hydrogen peroxide, corresponding should be to add the described aqueous hydrogen peroxide solution of 10g (2.7 ÷ 0.27=10).
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 the assay method of Kappa number and hemicellulose is identical with Chinese patent literature CN1170031C.Solids content adopts halogen fast tester for water content (plum Teller-Tuo benefit, model: HB43-S) to measure at 115 ℃.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/(hemicellulose level in material quality × raw material) × 100%.
Lignin extraction rate=lignin quality/(content of lignin in 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%), first will smash, and 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, using total acid concentration is that 85% formic acid and the organic acid solution of acetic acid carry out boiling to reed after treatment, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:1, and before reed raw material, adds the hydrogen peroxide (H that accounts for raw material 3% adding
2o
2) as catalyst, control 90 ℃ of reaction temperatures, reaction 70min, solid-liquid mass ratio is 1:5, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time;
(2) it is that 60% formic acid and the organic acid solution of acetic acid carry out acid elution that the solid above-mentioned separation being obtained adds total acid concentration, in the organic acid solution that wherein above-mentioned total acid concentration is 60%, has added the hydrogen peroxide (H that accounts for raw material 3%
2o
2) be 10:1 as the mass ratio of catalyst and acetic acid and formic acid, temperature is 60 ℃, wash time 1h, solid-liquid mass ratio is 1:4, and reactant liquor is carried out to Separation of Solid and Liquid for the second time;
(3) collect the liquid that in step (1) and step (2), twice Separation of Solid and Liquid obtains, 50 ℃, 100kpa carries out decompression distillation, the steam and the solids content that obtain formic acid and acetic acid are 70% concentrate, and in using formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that Separation of Solid and Liquid obtains for the second time, and wash, controlling washing temperature is 50 ℃, and starching dense is 1%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(5) collect the liquid that Separation of Solid and Liquid obtains for the third time, carry out water, sour rectifying, the mix acid liquor obtaining is back to the boiling for step (1) as cooking liquor in the reactor of step (1), and the water obtaining is back to step (5) and washes water with water;
(6) collect solid the screening that Separation of Solid and Liquid obtains for the third time and obtain screened stock cellulose, the screened stock cellulose obtaining by said process, measuring Kappa number is 9, hemicellulose level is 12%, whiteness 40%ISO, ash content 2%, productive rate 42%; The screened stock cellulose obtaining is bleached and obtained paper pulp; Adopting after measured its productive rate of paper pulp that the method for the present embodiment obtains is 38%.
(7) concentrate of gained in step (3) is added to the water dilution that accounts for 2 times of concentrate quality, 60-70 ℃ of stirring, and carry out Separation of Solid and Liquid the 4th time, and the solid obtaining is further washed deesterify 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 wood sugar crystal, wood sugar recovery rate 65% through decolouring, filtration and condensing crystallizing.
Described in the present embodiment, bleaching process comprises the following steps:
(1) will first utilize the NaOH that accounts for screened stock cellulose quality 1% to carry out alkali treatment through the screened stock cellulose of screening, controlling temperature be 40 ℃, and extracting time 0.5h, starches dense 6%;
(2) carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is 1% of screened stock cellulose quality again, and utilizes NaOH control pH value between 10-12,100 ℃ of temperature, and bleaching time 1h, starches dense 3%; With
(3) acid treatment, the acid adopting in this step is hydrochloric acid, its consumption is 3% of screened stock cellulose quality, controls pH value between 2-4,30 ℃ of temperature, time 0.5h, starch dense 1.5%.
Embodiment 2
In the present embodiment, first straw (one-tenth is grouped into: cellulose 35.8%, hemicellulose 28.6%, lignin 14.3%) is smashed, 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, using total acid concentration is that 82% formic acid and the organic acid solution of acetic acid carry out boiling to straw after treatment, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 6:1, and before straw raw material, adds the hydrogen peroxide (H that accounts for raw material 1% adding
2o
2) as catalyst, control 100 ℃ of reaction temperatures, reaction 40min, solid-liquid mass ratio is 1:6, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time;
(2) it is that 70% formic acid and the organic acid solution of acetic acid carry out acid elution that the solid above-mentioned separation being obtained adds total acid concentration, in the organic acid solution that wherein above-mentioned total acid concentration is 70%, has added the hydrogen peroxide (H that accounts for raw material 7%
2o
2) be 6:1 as the mass ratio of catalyst and acetic acid and formic acid, temperature is 20 ℃, wash time 1h, solid-liquid mass ratio is 1:6, and reactant liquor is carried out to Separation of Solid and Liquid for the second time;
(3) collect the liquid that in step (1) and step (2), twice Separation of Solid and Liquid obtains, 60 ℃, 150kpa carries out decompression distillation, the steam and the solids content that obtain formic acid and acetic acid are 80% concentrate, and in using formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that Separation of Solid and Liquid obtains for the second time, and wash, controlling washing temperature is 60 ℃, and starching dense is 2%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(5) collect the liquid that Separation of Solid and Liquid obtains for the third time, carry out water, sour rectifying, the mix acid liquor obtaining is back to the boiling for step (1) as cooking liquor in the reactor of step (1), and the water obtaining is back to step (4) and washes water with water;
(6) collect solid the screening that Separation of Solid and Liquid obtains for the third time and obtain screened stock cellulose, the screened stock cellulose obtaining by said process, measures Kappa number 7, and hemicellulose level is 13%, whiteness 42%ISO, ash content 4%, productive rate 37%; The screened stock cellulose obtaining is bleached and obtained paper pulp; Adopting after measured its productive rate of paper pulp that the method for the present embodiment obtains is 36%.
(7) concentrate of gained in step (3) is added to the water dilution that accounts for 3 times of concentrate quality, 60-70 ℃ of stirring, and carry out Separation of Solid and Liquid the 4th time, and the solid obtaining is further washed deesterify 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 wood sugar crystal 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) will first utilize 3% the potassium hydroxide that accounts for screened stock cellulose quality to carry out alkali treatment through the screened stock cellulose of screening, controlling temperature be 60 ℃, and extracting time 50min, starches dense 7%;
(2) carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is 1.5% of screened stock cellulose quality again, and by potassium hydroxide control pH value between 10-12,90 ℃ of temperature, bleaching time 80min, starches dense 4%; With
(3) acid treatment, the acid adopting in this step is sulfuric acid, its consumption is 4% of screened stock cellulose quality, controls pH value between 2-4,35 ℃ of temperature, 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%), first will smash, and washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
Described in the present embodiment, the comprehensive utilization process of bamboo chip, comprises the steps:
(1) by after broken bamboo chip preliminary treatment, using total acid concentration is that 79% formic acid and the organic acid solution of acetic acid carry out boiling to bamboo chip after treatment, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 10:1, and before bamboo chip raw material, adds the hydrogen peroxide (H that accounts for raw material 6% adding
2o
2) as catalyst, control 110 ℃ of reaction temperatures, reaction 30min, solid-liquid mass ratio is 1:10, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time;
(2) it is that 90% formic acid and the organic acid solution of acetic acid carry out acid elution that the solid above-mentioned separation being obtained adds total acid concentration, in the organic acid solution that wherein above-mentioned total acid concentration is 90%, has added the hydrogen peroxide (H that accounts for over dry raw material 5%
2o
2) be 8:1 as the mass ratio of catalyst and acetic acid and formic acid, temperature is 30 ℃, wash time 1h, solid-liquid mass ratio is 1:8, and reactant liquor is carried out to Separation of Solid and Liquid for the second time;
(3) collect the liquid that in step (1) and step (2), twice Separation of Solid and Liquid obtains, 70 ℃, 200kpa carries out decompression distillation, the steam and the solids content that obtain formic acid and acetic acid are 90% concentrate, and in using formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that Separation of Solid and Liquid obtains for the second time, and wash, controlling washing temperature is 70 ℃, and starching dense is 3%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(5) collect the liquid that Separation of Solid and Liquid obtains for the third time, carry out water, sour rectifying, the mix acid liquor obtaining is back to the boiling for step (1) as cooking liquor in the reactor of step (1), and the water obtaining is back to step (5) and washes water with water;
(6) collect solid the screening that Separation of Solid and Liquid obtains for the third time and obtain screened stock cellulose, the screened stock cellulose obtaining by said process, measures Kappa number 6, and hemicellulose level is 15%, whiteness 41%ISO, ash content 6%, productive rate 38%; The screened stock cellulose obtaining is bleached and obtained paper pulp; The paper pulp that adopts after measured the method for the present embodiment to obtain, its productive rate is 33%.
(7) concentrate of gained in step (3) is added to the water dilution that accounts for 4 times of concentrate quality, 60-70 ℃ of stirring, and carry out Separation of Solid and Liquid the 4th time, and the solid obtaining is further washed deesterify 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 wood sugar crystal 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) will first utilize 1.5% the NaOH that accounts for screened stock cellulose quality to carry out alkali treatment through the screened stock cellulose of screening, controlling temperature be 50 ℃, and extracting time 70min, starches dense 9%;
(2) carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is 2% of screened stock cellulose quality again, and by potassium hydroxide control pH value between 10-12, temperature 70 C, bleaching time 100min, starches dense 5%; With
(3) acid treatment, the acid adopting in this step is hydrochloric acid, its consumption is 6% of screened stock cellulose quality, controls pH value between 2-4,40 ℃ of temperature, 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%), first will smash, and 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 wheat straw preliminary treatment, using total acid concentration is that 76% formic acid and the organic acid solution of acetic acid carry out boiling to wheat straw after treatment, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 15:1, and before wheat straw raw material, adds the hydrogen peroxide (H that accounts for raw material 4% adding
2o
2) as catalyst, control 120 ℃ of reaction temperatures, reaction 90min, solid-liquid mass ratio is 1:12, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time;
(2) it is that 80% formic acid and the organic acid solution of acetic acid carry out acid elution that the solid above-mentioned separation being obtained adds total acid concentration, in the organic acid solution that wherein above-mentioned total acid concentration is 80%, has added the hydrogen peroxide (H that accounts for raw material 8%
2o
2) be 9:1 as the mass ratio of catalyst and acetic acid and formic acid, temperature is 50 ℃, wash time 1h, solid-liquid mass ratio is 1:7, and reactant liquor is carried out to Separation of Solid and Liquid for the second time;
(3) collect the liquid that in step (1) and step (2), twice Separation of Solid and Liquid obtains, 100 ℃, 250kpa carries out decompression distillation, the steam and the solids content that obtain formic acid and acetic acid are 75% concentrate, and in using formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that Separation of Solid and Liquid obtains for the second time, and wash, controlling washing temperature is 80 ℃, and starching dense is 1.8%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(5) collect the liquid that Separation of Solid and Liquid obtains for the third time, carry out water, sour rectifying, the mix acid liquor obtaining is back to the boiling for step (1) as cooking liquor in the reactor of step (1), and the water obtaining is back to step (4) and washes water with water;
(6) collect solid the screening that Separation of Solid and Liquid obtains for the third time and obtain screened stock cellulose, the screened stock cellulose obtaining by said process, measures Kappa number 8, and hemicellulose level is 15%, whiteness 43%ISO, ash content 9%, productive rate 45%; The screened stock cellulose obtaining is bleached and obtained paper pulp; The paper pulp that adopts after measured the method for the present embodiment to obtain, its productive rate is 41%.
(7) concentrate of gained in step (3) is added to the water dilution that accounts for 5 times of over dry material qualities, 60-70 ℃ of stirring, and carry out Separation of Solid and Liquid the 4th time, and the solid obtaining is further washed deesterify 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 wood sugar crystal 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) will first utilize the NaOH that accounts for screened stock cellulose quality 2.5% to carry out alkali treatment through the screened stock cellulose of screening, controlling temperature be 70 ℃, and extracting time 1.5h, starches dense 11%;
(2) carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is 2.5% of screened stock cellulose quality again, and by potassium hydroxide control pH value between 10-12, temperature 50 C, bleaching time 120min, starches dense 3.5%; With
(3) acid treatment, the acid adopting in this step is sulfuric acid, its consumption is 3.5% of screened stock cellulose quality, controls pH value between 2-4, 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%), first will smash, and 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 melon seeds bar preliminary treatment, using total acid concentration is that 73% formic acid and the organic acid solution of acetic acid carry out boiling to melon seeds bar after treatment, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 12:1, and before melon seeds bar raw material, adds the hydrogen peroxide (H that accounts for raw material 8% adding
2o
2) as catalyst, control 95 ℃ of reaction temperatures, reaction 60min, solid-liquid mass ratio is 1:15, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time;
(2) it is that 75% formic acid and the organic acid solution of acetic acid carry out acid elution that the solid above-mentioned separation being obtained adds total acid concentration, in the organic acid solution that wherein above-mentioned total acid concentration is 75%, has added the hydrogen peroxide (H that accounts for raw material 6%
2o
2) be 6:1 as the mass ratio of catalyst and acetic acid and formic acid, temperature is 90 ℃, wash time 1h, solid-liquid mass ratio is 1:9, and reactant liquor is carried out to Separation of Solid and Liquid for the second time;
(3) collect the liquid that in step (1) and step (2), twice Separation of Solid and Liquid obtains, 90 ℃, 100kpa carries out decompression distillation, the steam and the solids content that obtain formic acid and acetic acid are 85% concentrate, and in using formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that Separation of Solid and Liquid obtains for the second time, and wash, controlling washing temperature is 90 ℃, and starching dense is 2.4%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(5) collect the liquid that Separation of Solid and Liquid obtains for the third time, carry out water, sour rectifying, the mix acid liquor obtaining is back to the boiling for step (1) as cooking liquor in the reactor of step (1), and the water obtaining is back to step (4) and washes water with water;
(6) collect solid the screening that Separation of Solid and Liquid obtains for the third time and obtain screened stock cellulose, the screened stock cellulose obtaining by said process, measures Kappa number 5, and hemicellulose level is 14%, whiteness 44%ISO, ash content 7%, productive rate 52%; The screened stock cellulose obtaining is carried out to bleaching process and obtain paper pulp, its productive rate is 39%.
(7) concentrate of gained in step (3) is added to the water dilution that accounts for 2.5 times of concentrate quality, 60-70 ℃ of stirring, and carry out Separation of Solid and Liquid the 4th time, and the solid obtaining is further washed deesterify 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 wood sugar crystal 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) will first utilize the NaOH that accounts for screened stock cellulose quality 3% to carry out alkali extracting through the screened stock cellulose of screening, controlling temperature be 80 ℃, and extracting time 110min, starches dense 13%;
(2) carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is 3% of screened stock cellulose quality again, and by potassium hydroxide control pH value between 10-12, temperature 60 C, bleaching time 140min, starches dense 4.5%; With
(3) acid treatment, the acid adopting in this step is hydrochloric acid, its consumption is 7% of screened stock cellulose quality, controls pH value between 2-4, 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%), first will smash, and washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
Described in the present embodiment, the comprehensive utilization process of cotton stem, comprises the steps:
(1) by after broken cotton stem preliminary treatment, using total acid concentration is that 70% formic acid and the organic acid solution of acetic acid carry out boiling to cotton stem after treatment, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 8:1, and before cotton stem raw material, adds the hydrogen peroxide (H that accounts for raw material 7% adding
2o
2) as catalyst, control 115 ℃ of reaction temperatures, reaction 50min, solid-liquid mass ratio is 1:9, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time;
(2) it is that 65% formic acid and the organic acid solution of acetic acid carry out acid elution that the solid above-mentioned separation being obtained adds total acid concentration, in the organic acid solution that wherein above-mentioned total acid concentration is 65%, has added the hydrogen peroxide (H that accounts for raw material 1%
2o
2) be 7:1 as the mass ratio of catalyst and acetic acid and formic acid, temperature is 100 ℃, wash time 1h, solid-liquid mass ratio is 1:10, and reactant liquor is carried out to Separation of Solid and Liquid for the second time;
(3) collect the liquid that in step (1) and step (2), twice Separation of Solid and Liquid obtains, 80 ℃, 270kpa carries out decompression distillation, the steam and the solids content that obtain formic acid and acetic acid are 80% concentrate, and in using formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that Separation of Solid and Liquid obtains for the second time, and wash, controlling washing temperature is 65 ℃, and washing slurry is dense is 2.6%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(5) collect the liquid that Separation of Solid and Liquid obtains for the third time, carry out water, sour rectifying, the mix acid liquor obtaining is back to the boiling for step (1) as cooking liquor in the reactor of step (1), and the water obtaining is back to step (5) and washes water with water;
(6) collect solid the screening that Separation of Solid and Liquid obtains for the third time and obtain screened stock cellulose, the screened stock cellulose obtaining by said process, measuring Kappa number is 9, hemicellulose level is 12%, whiteness 45%ISO, ash content 8%, productive rate 53%; The screened stock cellulose obtaining is bleached and obtained paper pulp; The paper pulp that adopts after measured the method for the present embodiment to obtain, its productive rate is 41%.
(7) concentrate of gained in step (3) is added to the water dilution that accounts for 4.5 times of over dry material qualities, 60-70 ℃ of stirring, and carry out Separation of Solid and Liquid the 4th time, and the solid obtaining is further washed deesterify 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 wood sugar crystal 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) will first utilize the potassium hydroxide that accounts for screened stock cellulose quality 2.5% to carry out alkali treatment through the screened stock cellulose of screening, controlling temperature be 100 ℃, and extracting time 2h, starches dense 15%;
(2) carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is 1.5% of screened stock cellulose quality again, and by NaOH pH value processed between 10-12,80 ℃ of temperature, bleaching time 3h, starches dense 5%; With
(3) acid treatment, the acid adopting in this step is sulfuric acid, its consumption is 4.5% of screened stock cellulose quality, controls pH value between 2-4,55 ℃ of temperature, time 40min, starches dense 2%.
Comparative example 1
Raw materials used in the present embodiment, processing step and technological parameter and embodiment 1 are basically identical, and its difference is, except the processing step of bleaching process, does not all add hydrogen peroxide as catalyst in each step.The screened stock cellulose that described in employing the present embodiment, method obtains, measuring Kappa number is 30.2, hemicellulose level is 10.5%, whiteness 25%ISO, productive rate is 30%, is 25% by its productive rate of paper pulp obtaining after fiber bleached the screened stock obtaining.The recovery rate of lignin is 65%, wood sugar recovery rate 40.2%
Comparative example 2
In the present embodiment, raw material used and processing step and technological parameter and embodiment 1 are 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 formic acid and the 15wt% water of 85wt%.The acid pickling step of its step (2) is under the catalytic action of hydrogen peroxide, the organic acid solution that the formic acid by 60wt% adopting and 40wt% water form carries out pickling, in each step, the adding proportion of hydrogen peroxide is consistent with embodiment 3, the screened stock cellulose that adopts after measured the method for the present embodiment to obtain, 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 obtaining after fiber bleached the screened stock obtaining.The recovery rate of lignin is 68%, wood sugar recovery rate 44%.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction 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 without also giving exhaustive to all embodiments.And the apparent variation of being extended out thus or variation are still among the protection domain in the invention.
Claims (10)
1. a comprehensive utilization process for biomass material, is characterized in that, comprises the steps:
(1) after biomass material is pulverized, under the catalytic action of hydrogen peroxide, use the organic acid solution being formed by formic acid, acetic acid to carry out boiling to described raw material, control boiling temperature 90-120 ℃, solid-liquid mass ratio is 1:5-1:15, reaction time 30-90min, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time;
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,
Hydrogen peroxide accounts for the 1-8% of biomass material;
(2) solid that described in collection, Separation of Solid and Liquid obtains for the first time, under the catalytic action of hydrogen peroxide, the mix acid liquor that adopts formic acid, acetic acid to form carries out pickling to described solid, control pickling temperature 20-100 ℃, solid-liquid mass ratio is 1:4-1:10, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the second time;
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) solid that described in collection, Separation of Solid and Liquid obtains for the second time, and wash, control washing temperature is 50-90 ℃, starching dense is 1-3%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(4) described in collection, Separation of Solid and Liquid obtains for the third time solid screening obtain screened stock cellulose, and described screened stock cellulose obtains required paper pulp through bleaching.
(5) collect for the first time and the liquid that Separation of Solid and Liquid obtains for the second time, 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 Separation of Solid and Liquid the 4th time, the solid obtaining obtains required lignin through washing;
(7), after described the 4th Separation of Solid and Liquid, the liquid obtaining obtains wood sugar after decolouring, filtration and condensing crystallizing are processed.
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 ℃, and extracting time 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 is controlled between 10-12, temperature 50-100 ℃, bleaching time 1-3h, starches dense 3-5%; With
Acid treatment, the quality of described acid accounts for the 3-7% of described screened stock cellulose quality, and pH value is controlled between 2-4, temperature 30-55 ℃, time 0.5-1h, starches dense 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 ℃; In described acid-treated step, temperature 35-45 ℃.
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 described concentrate quality 2-5 doubly.
5. according to the comprehensive utilization process of the arbitrary described biomass material of claim 1-5, it is characterized in that:
In described step (5), also comprise formic acid and acetic acid steam condensation that evaporation is obtained, and be back in the reactor of step (1), for the step of the boiling of step (1).
6. according to the comprehensive utilization process of the arbitrary described biomass material of claim 1-5, it is characterized in that:
In described step (3), also comprise the liquid that Separation of Solid and Liquid obtains is for the third time carried out to water acid rectifying, the formic acid obtaining and the mix acid liquor of acetic acid are back in the reactor of step (1), be used for the step of the boiling of step (1), and the water obtaining is back to step (3) as washing water.
7. according to the comprehensive utilization process of the arbitrary described biomass material of claim 1-6, it 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, adds the quality of hydrogen peroxide to account 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 ℃, 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. according to the comprehensive utilization process of the arbitrary described biomass material of claim 1-8, it is characterized in that:
Evaporating temperature 50-100 in described step (5), pressure 100-300kpa
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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Cited By (1)
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| WO2021032195A1 (en) | 2019-08-22 | 2021-02-25 | 济南圣泉唐和唐生物科技有限公司 | Method for separating xylose and lignin from mixed sugar solution |
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| CN103898786B (en) | 2016-02-10 |
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Denomination of invention: Comprehensive utilization technology of biomass raw materials Effective date of registration: 20171221 Granted publication date: 20160210 Pledgee: Branch Bank of Zhangqiu District, Ji'nan City, China Agricultural Development Bank Pledgor: JINAN SHENGQUAN GROUP SHARE HOLDING Co.,Ltd. Registration number: 2017990001203 |
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Date of cancellation: 20221202 Granted publication date: 20160210 Pledgee: Branch Bank of Zhangqiu District, Ji'nan City, China Agricultural Development Bank Pledgor: JINAN SHENGQUAN GROUP SHARE HOLDING Co.,Ltd. Registration number: 2017990001203 |