CN103045697B - Comprehensive utilization method of lignocellulose biomass - Google Patents
Comprehensive utilization method of lignocellulose biomass Download PDFInfo
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Abstract
The invention relates to a comprehensive utilization method of lignocellulose biomass. The method comprises the following steps of (a) performing acid hydrolysis on the lignocellulose biomass to obtain a pentose solution and acid hydrolysis residues after separation; (b) treating the acid hydrolysis residues with an alkali solution so as to extract alkali lignin; (c) performing enzymatic hydrolysis on the alkali hydrolysis residues obtained by alkali solution treatment in the step (b) by using cellulose so as to obtain a glucose solution and enzymatic hydrolysis residues, wherein the cellulose is obtained by culturing a strain of penicillium, the penicillium is named as penicillium recumbent PD-G3-08; and (d) returning the enzymatic hydrolysis residues obtained by alkali solution treatment to the step (b) so as to perform alkali solution treatment, or firstly the enzymatic hydrolysis residues with fresh acid hydrolysis residues and then carrying out the alkali solution treatment of the step (b), performing the step (c) and the step (d) successively, repeating such process, and further extracting the lignin and performing cellulose enzymatic hydrolysis. The above method increases conversion rate of cellulose enzymatic hydrolysis and realizes comprehensive utilization of the lignocellulose biomass resources.
Description
Technical field
The present invention relates to a kind of method fully utilizing lignocellulose biomass, specifically a kind of method fully utilizing Mierocrystalline cellulose in lignocellulose biomass, hemicellulose and xylogen.
Background technology
Along with the exhaustion increasingly of fossil fuel resource and the day by day serious of environmental pollution, the substitute that the renewable energy resources are petroleum chemicals is utilized to become further important.And alcohol fuel is the principal mode of the material of the bio liquid energy, it is also the most probable substitute of fossil oil.At present, world's alcohol production is mainly using starch based (corn, cassava etc.) and carbohydrate (sugarcane, beet etc.) as the raw material of fermentation.Adopt microbial method fermentative production of ethanol technology maturation, but high raw materials cost makes the industrial application of grain fermentative production of ethanol be restricted, exist simultaneously to strive with people grain and grain strive etc. drawback, and cause provision price Continued, therefore find new raw material imperative.Present scientist is more cheap for sight trend of purchasing cost, lignocellulose biomass widely of originating.
Lignocellulose biomass exists with the form of plant materials, main component is Mierocrystalline cellulose, hemicellulose and xylogen, wherein, Mierocrystalline cellulose accounts for about 40%, hemicellulose accounts for about 25%, xylogen accounts for about 20%, and the lignocellulose biomass total amount that the earth is generated by photosynthesis is every year more than 2,000 hundred million tons, and therefore Wooden Biomass is renewable resources abundant, the most cheap on the earth.
If can take lignocellulose biomass as raw material production ethanol, will greatly solve the energy problem of the mankind, but still there is a lot of technical barrier in this respect not yet solves.At present, be in raw material production ethanol process with lignocellulose biomass, the first problem run into fails to fully utilize well to hemicellulose, Mierocrystalline cellulose and xylogen, the Technology of existing process biomass, obtain for the purpose of ethanol mainly with degraded carbohydrate greatly, can not extract simultaneously obtain high purity, highly active xylogen, often xylogen be removed object as one; Another greatest problem is the low conversion rate of cellulase hydrolysis, and the high cost (accounting for the 40-50% of total cost of production) of enzymolysis, production cost is too high, really cannot realize industrialization.The reason of the low conversion rate of cellulase hydrolysis is: hemicellulose is combined between Mierocrystalline cellulose and xylogen as molecule tamanori on the one hand, and the reticulated structure that xylogen has, surround as support frame and add set Mierocrystalline cellulose and hemicellulose, xylogen and hemicellulose spatially can hinder contacting of cellulosic molecule and enzyme, enzyme accessibility is poor, adds the difficulty of enzymolysis.Therefore be necessary to carry out effective pre-treatment to lignocellulose biomass, destroy the spatial obstacle of xylogen and hemicellulose, pre-treatment also to be avoided simultaneously to produce the enzyme inhibitor (as furfural, acetic acid etc.) being unfavorable for enzymolysis, thus be conducive to cellulosic enzymolysis; On the other hand, cellulase is low to crystalline cellulose enzymatic reaction vigour, therefore, in order to improve the transformation efficiency of cellulase hydrolysis, needs the vigor improving cellulase.
Summary of the invention
For this reason, technical problem to be solved by this invention overcomes prior art when fully utilizing hemicellulose, xylogen and Mierocrystalline cellulose, low and the problem of the low conversion rate of cellulase hydrolysis to the utilization ratio of xylogen, thus the method proposing the comprehensive utilization of a kind of lignocellulose biomass.
For achieving the above object, the invention provides a kind of method of comprehensive utilization of lignocellulose biomass, the method comprises the following steps:
A () carries out acid hydrolysis to lignocellulose biomass, obtain pentose solution and acid hydrolysis residue after separation;
B () uses acid hydrolysis residue described in alkaline solution treatment, thus extract alkali lignin;
C () uses cellulase to carry out enzymolysis to the alkaline hydrolysis residue that alkaline solution treatment described in step (b) obtains, obtain glucose solution and enzymolysis residue, described cellulase is cultivate by a penicillium cellulase obtained, this Penicillium notatum Classification And Nomenclature is Penicillium decumbens PD-G3-08, be preserved in Wuhan University's China typical culture collection center, its deposit number is CCTCC M 2011195; Preservation date is on June 13rd, 2011;
D () step (c) completes after, the described enzymolysis residue obtained is returned the alkaline solution treatment that step (b) is carried out alkaline solution treatment or carried out step (b) after described enzymolysis residue and new acid hydrolysis residue being merged again, then step (c) and (d) is carried out successively, circulation like this, thus extract xylogen further and carry out cellulase hydrolysis.
There is no particular limitation for the kind of described acid solution, and can be the acid that lignocellulose biomass carries out acid-hydrolyzed routine use, such as acid can be one or more in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
Described acid-hydrolyzed temperature is 100-150 DEG C, time is when within 0.5-3 hour, carrying out described acid hydrolysis, the concentration of acid solution is that (as the acid of selecting is strong acid for 0.5-30 % by weight, then the concentration of acid solution is lower, be about 0.5-5 % by weight, acid as selected is weak acid, then the concentration of acid solution is higher, is about 5-30 % by weight).Described acid solution is phosphoric acid solution, and the concentration of described phosphoric acid solution is 1-20 % by weight.
Described lignocellulose biomass can be one or more of maize straw, wheat straw, rice straw, bagasse, cotton bavin, cotton seed hull, corn cob, straw, kaoliang stalk, broad-leaved wood and wood chip.
Carry out pre-treatment according to raw material condition, lignocellulose biomass raw material is cut or pulverized, then scrubbing dust collection is carried out to this stalk section.
Described alkaline solution treatment carries out at 40-100 DEG C.
In described alkaline solution treatment, liquid-solid volume ratio is 5: 1-20: 1.
In described alkaline solution treatment, the concentration of alkaline solution is 0.8-5 % by weight.
The time of described alkaline solution treatment is 1-6 hour.
Various alkali may be used to the present invention, includes but not limited to aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, ammoniacal liquor etc.But according to some preferred embodiment, alkaline solution is the aqueous solution of sodium hydroxide.
The condition of described cellulase hydrolysis is: substrate consumption is 80-150g/L, and the addition of cellulase is 10-15FPU/g Mierocrystalline cellulose, and temperature is 45-55 DEG C, pH is 4-6, mixing speed is 50-200rpm, and enzymolysis transformation time is 2-7 days.
Technique scheme of the present invention compared with prior art has the following advantages:
1, present invention employs first acid hydrolysis, alkaline hydrolysis again, the operational path of last enzymolysis, because cellulase used is cultivate by a penicillium cellulase obtained, this Penicillium notatum Classification And Nomenclature is Penicillium decumbens PD-G3-08, has been preserved in Wuhan University's China typical culture collection center, and its deposit number is CCTCC M 2011195, the cellulase adopting this Penicillium notatum to produce has higher vigor, improves the extraction yield of cellulase hydrolysis; The present invention adopts circulation technology to carry out alternately extraction process to Mierocrystalline cellulose, xylogen respectively simultaneously, improve the extraction yield of Mierocrystalline cellulose and xylogen on the one hand, the treatment condition of acidolysis, alkaline hydrolysis can be weakened on the other hand by this method, thus protection xylogen and Mierocrystalline cellulose are not destroyed further, xylogen and cellulosic utilization are maximized;
As can be seen here, aforesaid method of the present invention solves the problem of complex utilization of lignocellulose biomass in prior art, makes the utilization of resources reach maximization.
2. what the present invention was used cultivates by Penicillium notatum the cellulase obtained, be 80-150g/L at substrate consumption, the addition of cellulase is 10-15FPU/g Mierocrystalline cellulose, temperature is 45-55 DEG C, pH is 4-6, mixing speed is 50-200rpm, enzymolysis transformation time is that under the condition of 2-7 days, enzymolysis transformation efficiency is the highest.
3. the temperature of reacting in acid hydrolysis described in is 100-150 DEG C, and the time is 0.5-3 hour, can relatively thorough by hydrolysis of hemicellulose under this temperature and time, and high temperature and reaction times under acidic conditions can be stoped again long to xylogen and cellulosic destruction.
4, the acid that acid hydrolysis of the present invention is used is phosphoric acid solution, and when the concentration of phosphoric acid solution is 1-20 % by weight, avoids considerable damage xylogen and Mierocrystalline cellulose to greatest extent, and due to phosphoric acid corrosion more weak, therefore, maintenance of the equipment is simple, duration of service is long.
5. liquid-solid ratio, alkali consumption, the temperature and time of the condition employing of alkaline solution treatment of the present invention, the activity of the alkali lignin finally obtained is very high.
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 schematic diagram of present invention process flow process.
Embodiment
Below will the invention will be further described by specific embodiment.
The self-control cellulase that following examples use is cultivated by Penicillium notatum and is obtained, and concrete cultural method is:
(A) bacterial classification multiplication culture
Be Penicillium decumbens PD-G3-08 Penicillium notatum seed liquor by naming number with the inoculum size of 5% (v/v) be linked into through 121 DEG C of sterilizing 30min containing the fermentor tank of seed culture medium in activate, keep tank pressure 0.02-0.05MPa, air flow 0.5vvm, mixing speed 100-150rpm, 30 DEG C of cultivation 30-60 hour, obtain the seed liquor after activating.
Component in described seed culture medium and consumption are: acid hydrolysis residue 10-30g/L, the wheat bran 20-50g/L of Example 1, peptone 1-4g/L, ammonium sulfate 2-4g/L, all the other are water.
Component in described seed culture medium and consumption are preferably: acid hydrolysis residue 20g/L, wheat bran 40
G/L, peptone 3g/L, ammonium sulfate 3g/L, all the other are water.
(B) cellulase is prepared
What step (A) is obtained seed liquor accesses sterilizing with the inoculum size of 10% (v/v) is equipped with in the 5L fermentor tank of 3L fermention medium, add defoamer in fermenting process and control foaming, keep tank pressure 0.02-0.05MPa, air flow 0.5-0.6vvm, mixing speed 100-150rpm, 30 DEG C of cultivation 80-136 hour, obtain fermented liquid.
In described fermention medium, each amounts of components is respectively: acid hydrolysis residue 30-50g/L, wheat bran 20-50g/L, Microcrystalline Cellulose or carboxymethyl cellulose 4-8g/L, ammonium sulfate 2-5g/L, potassium primary phosphate 2-4g/L, magnesium sulfate 0.4-0.6g/L, all the other are water, and the initial pH of substratum is 5.0-6.0.
In described fermention medium, each amounts of components is preferably: acid hydrolysis residue 45g/L, wheat bran 35g/L, Microcrystalline Cellulose 5g/L, ammonium sulfate 4g/L, potassium primary phosphate 3g/L, magnesium sulfate 0.6g/L, all the other are water, and the initial pH of substratum is 5.0-6.0.
The fermented liquid 8000rpm centrifuging and taking obtained obtains supernatant liquor, and obtain the crude enzyme liquid containing cellulase, this crude enzyme liquid can be directly used in cellulosic enzymolysis.
(2) the various performances of xylogen in following examples are tested as follows
The mensuration of content of lignin: comprise sour insoluble xylogen and sour solvable xylogen.Wherein the mensuration of sour insoluble xylogen adopts Klason method, carries out according to GB GB/T2677.8-94; The solvable xylogen of acid carries out according to GB GB 10337-89.
The mensuration of moisture: carry out according to GB/T 2667.3-93.
Following examples are see Fig. 1.
The pressure that in following examples, acid hydrolysis temperature is corresponding is the pressure of saturated vapor, therefore no longer provides pressure data for each embodiment.
In following examples, apart from outside specified otherwise, percentage composition used all represents weight percentage, i.e. " % " expression " % by weight ".
Embodiment 1
(1) acid hydrolysis
By 10.6kg corn cob, (mass component forms: moisture 6.12%, Mierocrystalline cellulose 35.19%, hemicellulose 32.1%, xylogen 23.7%, other is 2.95% years old, lower same) smash, wash dedusting with water, then be hydrolyzed with 80kg phosphoric acid solution, the mass concentration of phosphoric acid solution is 10%, acid-hydrolyzed temperature is 120 DEG C, time is 1 hour, acid hydrolysis residue and pentose solution that rear separation obtains are hydrolyzed, described acid hydrolysis residue is cleaned with 10kg water, scavenging solution and described pentose solution merge, (water content is about 65% finally to obtain 19.64kg acid hydrolysis residue, the over dry content of hemicellulose is 15.87%, the over dry content of xylogen is 31.75%, cellulosic over dry content is 47.81%) and 80.34kg pentose solution, the concentration of pentose solution is 2.89%.Then the extraction yield of hemicellulose is 68%.
The calculation formula of hemicellulose extraction yield is as follows:
The extraction yield %=(pentose solution quality × pentose solution concentration) of the hemicellulose/content of hemicellulose (in the corn cob quality × corn cob) × 100%.
(2) alkaline solution extracts alkali lignin
Mix obtaining all acid hydrolytic residue in the present embodiment step (1) with sodium hydroxide solution, liquid-solid volume ratio is 5: 1, the concentration of sodium hydroxide is 3%, be warming up to 70 DEG C, through the boiling alkaline hydrolysis of 1 hour, separation obtains alkaline hydrolysis residue and alkali lignin solution, cleans described alkaline hydrolysis residue with 10kg water, and scavenging solution and described alkali lignin solution merge; Finally obtain 16.62kg alkaline hydrolysis residue (water content is about 65%), the quality of alkali lignin solution is 34.62kg, and in alkali lignin solution, the content of alkali lignin is 2.85%, and alkali lignin extraction yield is 39%.
The formula of alkali lignin extraction yield is as follows:
The extraction yield %=of the alkali lignin content of xylogen (in the quality × alkali lignin solution of the alkali lignin solution)/content of xylogen (in the corn cob quality × corn cob) × 100%
(3) cellulase hydrolysis alcohol prepared by fermenting
The condition of described enzymolysis is: cellulase is above-mentioned penicillin (Penicillium decumbensPD-G3-08, be preserved in Wuhan University's China typical culture collection center, its deposit number is CCTCC M 2011195, lower same) cultivate the cellulase obtained, get whole residues that step (2) described alkaline solution treatment obtains as cellulosic substrate, cellulase is added according to the cellulosic addition of 15FPU/g, cellulosic substrate consumption is 150g/L, it is 48 DEG C in temperature, pH is 5.0, under the condition of mixing speed 50rpm, enzymolysis transforms 7 days, whole enzymolysis process is without the need to pressurize, finally obtaining enzymolysis residue is 11.48kg (water content is about 65%), also obtain glucose solution, quality is 44.6kg, concentration is 4.03%, cellulosic extraction rate reached 48%.
The formula of cellulosic extraction yield is as follows:
Cellulosic extraction yield %=(concentration of the quality × glucose solution of glucose solution)/(in corn cob quality × corn cob cellulosic content) × 100%
The technique that glucose solution produces ethanol is existing technique, and do not repeat them here, other embodiment is identical.
(4) circular treatment
Whole enzymolysis residues step (3) obtained return step (2) and carry out second time alkaline solution treatment, and second time alkaline solution treatment is identical with the condition of the alkaline solution treatment described in step in the present embodiment (2); Obtain 9.02kg second time alkaline hydrolysis residue (water ratio is about 65%) and 20.08kg alkali lignin solution, in alkali lignin solution, the content of alkali lignin is 4.28%; Then the extraction yield of second time alkali lignin is 34%;
Carry out second time enzymolysis to described second time alkaline hydrolysis residue, the condition of second time enzymolysis is identical with the condition of enzymolysis described in step in the present embodiment (3); Obtain that quality is 24.21kg, concentration is the glucose solution of 4.33%, then the cellulosic extraction yield of second time is 28%.
In sum, the extraction yield of the hemicellulose of corn cob is 68%, and the total extraction yield of Mierocrystalline cellulose is 76%, and total extraction yield of xylogen is 73%.
Embodiment 2
(1) acid hydrolysis
10.6kg corn cob is smashed, wash dedusting with water, then be hydrolyzed with 80kg phosphoric acid solution, the mass concentration of phosphoric acid solution is 20%, acid-hydrolyzed temperature is 100 DEG C, time is 0.5 hour, acid hydrolysis residue and pentose solution that rear separation obtains are hydrolyzed, described acid hydrolysis residue is cleaned with 10kg water, scavenging solution and described pentose solution merge, (water content is about 65% finally to obtain 19.35kg acid hydrolysis residue, the over dry content of hemicellulose is 15.10%, the over dry content of xylogen is 31.79%, cellulosic over dry content is 48.47%) and 80.63kg pentose solution, the concentration of pentose solution is 2.96%.Then the extraction yield of hemicellulose is 70%.
(2) alkaline solution extracts alkali lignin
The present embodiment step (1) is obtained all acid hydrolytic residue mix with sodium hydroxide solution, be 20: 1 according to liquid-solid volume ratio, the concentration of sodium hydroxide is 0.8%, be warming up to 100 DEG C, molten through the boiling alkali of 2 hours, separation obtains alkaline hydrolysis residue and alkali lignin solution, cleans described alkaline hydrolysis residue with 10kg water, and scavenging solution and described alkali lignin solution merge; Finally obtain 16.19kg alkaline hydrolysis residue (water ratio about 65%), the quality of alkali lignin solution is 136.05kg, and in alkali lignin solution, the content of alkali lignin is 0.76%, and alkali lignin extraction yield is 41%.
(3) cellulase hydrolysis
The condition of described enzymolysis is: cellulase is that the cellulase obtained cultivated by above-mentioned penicillin (Penicillium decumbensPD-G3-08), get residue 12.94kg that step (2) described alkaline solution treatment obtains as cellulosic substrate, cellulase is added according to the cellulosic addition of 10FPU/g, cellulosic substrate consumption is 125g/L, temperature be 45 DEG C, under pH is 6, mixing speed is the condition of 200rpm, enzymolysis transforms 4 days, and whole enzymolysis process is without the need to pressurize.The enzymolysis residue obtained is 11.15kg (water content is about 65%), and obtain glucose solution, quality is 45.33kg, and concentration is 3.89%, and cellulosic extraction yield is 47%.
(4) circular treatment
Whole enzymolysis residues step (3) obtained return step (2) and carry out second time alkaline solution treatment, and second time alkaline solution treatment is identical with the condition of the alkaline solution treatment described in step in the present embodiment (2); Obtain 8.63kg second time alkaline hydrolysis residue (water ratio is about 65%) and 78.36kg alkali lignin solution, in alkali lignin solution, the content of alkali lignin is 1.13%; Then the extraction yield of second time alkali lignin is 35%;
Carry out second time enzymolysis to described second time alkaline hydrolysis residue, the condition of second time enzymolysis is identical with the condition of enzymolysis described in step in the present embodiment (3); Obtain that quality is 24.16kg, concentration is the glucose solution of 4.19%, then the cellulosic extraction yield of second time is 27%.
In sum, the extraction yield of the hemicellulose of corn cob is 70%, and the total extraction yield of Mierocrystalline cellulose is 74%, and total extraction yield of xylogen is 76%.
Embodiment 3
(1) acid hydrolysis
10.6kg corn cob is smashed, wash dedusting with water, then be hydrolyzed with 80kg phosphoric acid solution, the mass concentration of phosphoric acid solution is 5%, acid-hydrolyzed temperature is 150 DEG C, time is 1 hour, acid hydrolysis residue and pentose solution that rear separation obtains are hydrolyzed, described acid hydrolysis residue is cleaned with 10kg water, scavenging solution and described pentose solution merge, (water content is about 65% finally to obtain 20.02kg acid hydrolysis residue, the over dry content of hemicellulose is 16.05%, the over dry content of xylogen is 31.5%, cellulosic over dry content is 47.97%) and 79.96kg pentose solution, the concentration of pentose solution is 2.86%.Then the extraction yield of hemicellulose is 67%.
(2) alkaline solution extracts alkali lignin
The present embodiment step (1) is obtained all acid hydrolytic residue mix with sodium hydroxide solution, be 10: 1 according to liquid-solid volume ratio, the concentration of sodium hydroxide is 5%, be warming up to 40 DEG C, molten through the boiling alkali of 6 hours, separation obtains alkaline hydrolysis residue and alkali lignin solution, cleans described alkaline hydrolysis residue with 10kg water, and scavenging solution and described alkali lignin solution merge; Finally obtain 17.15kg alkaline hydrolysis residue (water ratio about 65%), the quality of alkali lignin solution is 69.94kg, and in alkali lignin solution, the content of alkali lignin is 1.34%, and alkali lignin extraction yield is 37%.
(3) cellulase hydrolysis
The condition of described enzymolysis is: cellulase is that the cellulase obtained cultivated by above-mentioned penicillin (Penicillium decumbensPD-G3-08), get residue 12.94kg that step (2) described alkaline solution treatment obtains as cellulosic substrate, cellulase is added according to the cellulosic addition of 12FPU/g, cellulosic substrate consumption is 80g/L, temperature be 55 DEG C, under pH is 4, mixing speed is the condition of 100rpm, enzymolysis transforms 2 days, and whole enzymolysis process is without the need to pressurize.The enzymolysis residue obtained is 11.58kg (water ratio is about 65%), and obtain glucose solution, quality is 81.02kg, and concentration is 2.41%, and cellulosic extraction yield is 52%.
(4) circular treatment
Whole enzymolysis residues step (3) obtained return step (2) and carry out second time alkaline solution treatment, and second time alkaline solution treatment is identical with the condition of the alkaline solution treatment described in step in the present embodiment (2); Obtain 9.12kg second time alkaline hydrolysis residue (water ratio is about 65%) and 20.19kg alkali lignin solution, in alkali lignin solution, the content of alkali lignin is 4.26%; Then the extraction yield of second time alkali lignin is 34%;
Carry out second time enzymolysis to described second time alkaline hydrolysis residue, the condition of second time enzymolysis is identical with the condition of enzymolysis described in step in the present embodiment (3); Obtain that quality is 43.11kg, concentration is the glucose solution of 1.74%, then the cellulosic extraction yield of second time is 20%.
In sum, the extraction yield of the hemicellulose of corn cob is 67%, and the total extraction yield of Mierocrystalline cellulose is 72%, and total extraction yield of xylogen is 71%.
Embodiment 4
(1) acid hydrolysis
First by the Wheat Straw for 11.12kg, (mass component forms: moisture 10.1%, Mierocrystalline cellulose 44%, hemicellulose 22.2%, xylogen 17%, other is 6.7% years old) smash, wash dedusting with water, then be hydrolyzed with sulphuric acid soln, the mass concentration of sulphuric acid soln is 0.5%, carrying out acid-hydrolyzed temperature is 130 DEG C, pressure is 0.27MPa, time is 3 hours, be hydrolyzed that rear separation obtains, after the acid hydrolysis residue 10kg water cleaning that acid hydrolysis residue and pentose solution obtain, then scavenging solution and pentose solution merge, (water content is about 65% finally to obtain 21.87kg acid hydrolysis residue, the over dry content of hemicellulose is 11.61%, the over dry content of xylogen is 22.03%, cellulosic over dry content is 56.63%), pentose solution 78.1kg, pentose sugar concentration is 2.02%, hemicellulose extraction yield is 64%.
(2) alkaline solution extracts alkali lignin
The present embodiment step (1) is obtained whole acid hydrolysis residues mix with potassium hydroxide solution, liquid-solid volume ratio is 5: 1, the concentration of potassium hydroxide is 3.0%, be warming up to 70 DEG C, through the boiling alkaline hydrolysis of 1 hour, separation obtains alkaline hydrolysis residue and alkali lignin solution, cleans described alkaline hydrolysis residue with 10kg water, and scavenging solution and described alkali lignin solution merge; Finally obtain 19.72kg alkaline hydrolysis residue, the quality of alkali lignin solution is 36.21kg, and in alkali lignin solution, the content of alkali lignin is 1.88%, and alkali lignin extraction yield is 36%.
(3) cellulase hydrolysis
The condition of described enzymolysis is with embodiment 2 step (3).The enzymolysis residue obtained is 12.87kg (water content is about 65%), and obtain glucose solution, quality is 55.21kg, and concentration is 4.34%, and cellulosic extraction yield is 49%.
(4) circular treatment
Whole enzymolysis residues in step (3) are returned in step (2), alkaline solution treatment is again carried out again after merging with new acid hydrolysis residue (the acid hydrolysis residue that another batch of Wheat Straw obtains after acid hydrolysis), alkaline solution treatment completes, carry out step (3) cellulase hydrolysis again, and then enzymolysis residue is returned in step (2), again merge with new acid hydrolysis residue, so can form circular treatment.
Adopt aforesaid method to process 111.2kg wheat straw bar, the extraction yield finally obtaining hemicellulose is 64%, and cellulosic total extraction yield is 77%, and total extraction yield of xylogen is 78%.
Found through experiments, acid solution adopts concentration expressed in percentage by weight when being the weak acid of 30%, to xylogen and cellulosic destruction less, object of the present invention can be realized.And the concentration of phosphoric acid solution is when being 1%, also can realize the present invention, the time just required for acid hydrolysis and temperature of reaction need corresponding increase.
Comparative example 1
Technological process control is with embodiment 1, difference is that step (3) cellulase hydrolysis cellulase used is marketed cellulose enzyme (jade of the He family Bioisystech Co., Ltd, 4w unit), only carry out primary fiber element enzymolysis, do not carry out the circular treatment of step (4), obtain that quality is 46.51kg, concentration is the glucose solution of 2.58%.Cellulosic extraction yield is 32%.
Comparative example 2
Technological process control is with embodiment 2, difference is that step (3) cellulase hydrolysis cellulase used is marketed cellulose enzyme (jade of the He family Bioisystech Co., Ltd, 4w unit), only carry out primary fiber element enzymolysis, do not carry out the circular treatment of step (4), obtain that quality is 45.1kg, concentration is the glucose solution of 2.58%.Cellulosic extraction yield is 30%.
Comparative example 3
Technological process control is with embodiment 4, difference is: step (3) cellulase hydrolysis cellulase used is marketed cellulose enzyme (jade of the He family Bioisystech Co., Ltd, 4w unit), only carry out primary fiber element enzymolysis, do not carry out the circular treatment of step (4), obtain that quality is 55.11kg, concentration is the glucose solution of 2.75%.Cellulosic extraction yield is 31%.
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 (4)
1. a method of comprehensive utilization for lignocellulose biomass, is characterized in that the method comprises the following steps:
A () carries out acid hydrolysis to lignocellulose biomass, obtain pentose solution and acid hydrolysis residue after separation, and the acid solution adopted in acid hydrolysis is phosphoric acid solution, and the concentration of described phosphoric acid solution is 1-20 % by weight;
B () uses acid hydrolysis residue described in alkaline solution treatment at 40-100 DEG C, thus extract alkali lignin, and the concentration of described alkaline solution is 0.8-5 % by weight, and the time of alkaline solution treatment is 1-6 hour;
C () uses cellulase to carry out enzymolysis to the alkaline hydrolysis residue that alkaline solution treatment described in step (b) obtains and obtains glucose solution and enzymolysis residue;
Described cellulase is cultivate by a penicillium cellulase obtained, and this Penicillium notatum Classification And Nomenclature is
penicillium decumbenspD-G3-08, has been preserved in Wuhan University's China typical culture collection center, and its deposit number is CCTCC M 2011195; Wherein, the cultural method of described cellulase is:
(1) bacterial classification multiplication culture
By naming number be
penicillium decumbenspD-G3-08 Penicillium notatum seed liquor is linked into the inoculum size of percent by volume 5% and activates through containing in the fermentor tank of seed culture medium of 121 DEG C of sterilizing 30min, keep tank pressure 0.02-0.05MPa, air flow 0.5vvm, mixing speed 100-150rpm, 30 DEG C of cultivation 30-60 hour, obtain the seed liquor after activating;
Component in described seed culture medium and consumption are: acid hydrolysis residue 10-30g/L, wheat bran 20-50g/L in described step (b), peptone 1-4g/L, ammonium sulfate 2-4g/L, all the other are water;
(2) cellulase is prepared
What step (1) is obtained seed liquor accesses sterilizing with the inoculum size of percent by volume 10% is equipped with in the fermentor tank of 3L fermention medium, add defoamer in fermenting process and control foaming, keep tank pressure 0.02-0.05MPa, air flow 0.5-0.6vvm, mixing speed 100-150rpm, 30 DEG C of cultivation 80-136 hour, obtain fermented liquid;
In described fermention medium, each amounts of components is respectively: acid hydrolysis residue 30-50g/L, wheat bran 20-50g/L, Microcrystalline Cellulose or carboxymethyl cellulose 4-8g/L, ammonium sulfate 2-5g/L, potassium primary phosphate 2-4g/L, magnesium sulfate 0.4-0.6g/L, all the other are water, and the initial pH of substratum is 5.0-6.0;
The fermented liquid 8000rpm centrifuging and taking obtained obtains supernatant liquor, obtains the crude enzyme liquid containing described cellulase;
D () step (c) completes after, the described enzymolysis residue obtained is returned the alkaline solution treatment that step (b) is carried out alkaline solution treatment or carried out step (b) after described enzymolysis residue and new acid hydrolysis residue being merged again, then step (c) and (d) is carried out successively, circulation like this, thus extract xylogen further and carry out cellulase hydrolysis.
2. according to the method described in claim 1, it is characterized in that: described acid-hydrolyzed temperature is 100-150 DEG C, the time is 0. 5-3 hour.
3. method according to claim 2, is characterized in that: in described alkaline solution treatment, liquid-solid volume ratio is 5:1-20:1.
4. according to the method in claim 1-3 described in any one, it is characterized in that: the condition of described cellulase hydrolysis is: substrate consumption is 80-150g/L, the addition of cellulase is 10-15FPU/g Mierocrystalline cellulose, temperature is 45-55 DEG C, pH is 4-6, mixing speed is 50-200rpm, and enzymolysis transformation time is 2-7 days.
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