CN103045688B - Comprehensive utilization method of lignocellulose biomass - Google Patents
Comprehensive utilization method of lignocellulose biomass Download PDFInfo
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Abstract
A comprehensive utilization method of lignocellulose biomass comprises the following steps: (a) performing acid hydrolysis of the lignocellulose biomass, separating to obtain a pentose solution and acid hydrolysis residues; b) performing enzymatic hydrolysis of the acid hydrolysis residues in step (a) by using cellulase, then performing fermentation to produce ethanol, wherein the cellulase is obtained by culturing a strain of penicillium which has a classification name of Penicillium decumbens PD-G3-08, and is preserved in Wuhan University China Center for Type Culture Collection with a preservation number of CCTCC M 2011195; (c) processing the fermentation residues produced in step (b) by using an alkaline solution so as to extract lignin from the fermentation residues; (d) after step (c) is complete, returning to step (b) to perform enzymatic hydrolysis and fermentation by using residues obtained after alkaline solution processing as enzymatic hydrolysis raw materials, and then performing steps (c) and (d). The method realizes the maximum resource utilization of lignocellulose biomass.
Description
Technical field
The present invention relates to a kind of method that fully utilizes lignocellulose biomass, specifically a kind of method that fully utilizes Mierocrystalline cellulose in lignocellulose biomass, hemicellulose and xylogen.
Background technology
Day by day serious along with the increasingly exhausted and environmental pollution of fossil fuel resource, utilizes the substitute that the renewable energy resources are petroleum chemicals to become further important.And alcohol fuel is the principal mode of the material of biomass liquid energy, it is also the most probable substitute of fossil oil.At present, world's alcohol production is mainly usingd starch based (corn, cassava etc.) and carbohydrate (sugarcane, the beet etc.) raw material as fermentation.Adopt microbial method method fermentative production of ethanol technology maturation, but high raw materials cost is restricted the industrial application of grain fermentative production of ethanol, exist simultaneously with people strive grain and grain strive etc. drawback, and cause provision price Continued, so it is imperative to find new raw material.Present scientist is more cheap sight trend of purchasing cost, the 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 40% left and right, hemicellulose accounts for 25% left and right, xylogen accounts for 20% left and right, and the lignocellulose biomass total amount being generated by photosynthesis every year on the earth surpasses 2,000 hundred million tons, so 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 mankind's energy problem, but still exist in this respect a lot of technical barriers not yet to solve.At present, take lignocellulose biomass in raw material production ethanol process, the first problem running into is that hemicellulose, Mierocrystalline cellulose and xylogen are failed to fully utilize well, the Technology of existing processing biomass, mainly with degraded carbohydrate, obtaining ethanol is greatly object, can not extract simultaneously and obtain high purity, highly active xylogen, often xylogen be removed to object as one; Another problem is the low conversion rate of cellulase hydrolysis, the high cost of enzymolysis (accounting for the 40-50% of total cost of production), and production cost is too high, cannot really 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, as support frame, surround and add set Mierocrystalline cellulose and hemicellulose, xylogen and hemicellulose spatially can hinder contacting of cellulosic molecule and enzyme, enzyme accessibility is poor, has increased the difficulty of enzymolysis.Therefore be necessary lignocellulose biomass to carry out effective pre-treatment, destroy the spatial obstacle of xylogen and hemicellulose, also to avoid pre-treatment to produce simultaneously and be unfavorable for the enzyme inhibitor (as furfural, acetic acid etc.) of enzymolysis, thereby 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, need to improve enzyme activity.
A kind of combined pretreatment method and system thereof of lignocellulose biomass are disclosed in CN100564667C, after being pulverized, lignocellulose biomass packs in circulating reaction still, and inject diluted acid, opening recycle pump is to carry out circulating reaction at 50 ℃-200 ℃ in temperature, reaction finish after by the hydrolyzed solution obtaining; After remaining lignocellulose rinses in circulating reaction still, put into ball mill and add alkali lye and carry out ball milling, further except delignification, ball milling complete except after alkali for follow-up enzymolysis, obtain ethanol.If the shortcoming that above-mentioned technique exists is to want dissolved lignin as much as possible just need to improve the temperature of alkali concn, alkaline purification and extend the time of alkaline purification, cause the active part of xylogen to be damaged, can not utilize it to produce high value-added product.
Summary of the invention
For this reason, technical problem to be solved by this invention be overcome in prior art, exist in comprehensive utilization when Mierocrystalline cellulose, hemicellulose and xylogen, can not obtain the problem of the extraction yield of high reactivity, highly purified xylogen and higher Mierocrystalline cellulose and hemicellulose simultaneously, thereby propose a kind of method of lignocellulose biomass comprehensive utilization.
A kind of method that the present invention proposes lignocellulose biomass comprehensive utilization, is characterized in that comprising the following steps:
(a) lignocellulose biomass is carried out to acid hydrolysis, after separation, obtain pentose solution and acid hydrolysis residue;
(b) use cellulase to carry out enzymolysis to described acid hydrolysis residue, obtain glucose solution and enzymolysis residue;
(c) with alkaline solution, process described enzymolysis residue, comprise
(i) with alkaline solution, processing described enzymolysis residue makes lignin dissolution wherein in alkaline solution;
(ii) then filter, wash and obtain liquid and alkaline hydrolysis residue;
(iii) by separated, the concentrated alkali lignin solution that obtains of gained liquid process film device;
(d) described alkaline hydrolysis residue is returned step (b) carry out enzymolysis processing or described alkaline hydrolysis residue and new acid hydrolysis residue are merged after carry out again the enzymolysis processing of step (b), then carry out successively step (c) and (d), so circulation, thus further extract xylogen and carry out cellulase hydrolysis.
There is no particular limitation for the kind of described acid solution, can be that lignocellulose biomass carries out the acid-hydrolyzed conventional acid of using, and for example acid can be one or more in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
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.
According to raw material condition, carry out pre-treatment, lignocellulose biomass raw material is cut or pulverized, then this stalk section is carried out to scrubbing dust collection.
Described acid-hydrolyzed temperature is 100-150 ℃, time is 0.5-3 hour, while carrying out described acid hydrolysis, the concentration of acid solution is that (as the acid of selecting is strong acid to 0.5-30 % by weight, and lower (as the acid of selecting is strong acid to the concentration of acid solution, and the concentration of acid solution is lower, be about 0.5-5 % by weight, as the acid of selecting is weak acid, the concentration of acid solution is higher, is about 5-30%).
Described acid solution is when containing phosphorus aqueous acid, and in the described aqueous solution, the concentration of phosphoric acid is 1-20 % by weight.
Described cellulase is for being cultivated the cellulase obtaining by a penicillium, this Penicillium notatum Classification And Nomenclature is Penicillium decumbens PD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195.
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 that 45-55 ℃, pH are that 4-6, mixing speed are 50-200rpm, and enzymolysis transformation time is 2-7 days.
After cellulase hydrolysis saccharification, can adopt the method for well known to a person skilled in the art, fermentative production of ethanol.
In described step (iii), also comprise the described concentrated alkali lignin solution obtaining dilute with water again, and then concentrated step.
In described step (iii), also comprise the alkali lignin solution process neutralization obtaining, filter and be dried, obtain alkali lignin solid.
In described step (iii), be also included in the concentrated step that obtains described alkali lignin solution afterwards or recycle alkaline solution wherein simultaneously.
At alkaline solution described in institute's step (i), process and carry out at 40-100 ℃.
In alkaline solution described in institute's step (i) is processed, liquid-solid volume ratio is 5: 1-20: 1.
The time of processing at alkaline solution described in institute's step (i) is 1-6 hour.
In the described alkaline solution of institute step (i) is processed, the concentration expressed in percentage by weight of alkaline solution is 0.8-5%.
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, the aqueous solution that alkaline solution is sodium hydroxide.
Technique scheme of the present invention compared with prior art has the following advantages:
1, the present invention adopts first acidolysis, enzymolysis again, the technique of last alkaline hydrolysis is extracted respectively hemicellulose, Mierocrystalline cellulose and xylogen, and by being set between enzymolysis and alkaline hydrolysis, circulation technology respectively Mierocrystalline cellulose, xylogen are replaced to extraction process, improved on the one hand the extraction yield of Mierocrystalline cellulose and xylogen, can weaken by this method on the other hand acidolysis, alkaline hydrolysis treatment condition, thereby further protect xylogen and Mierocrystalline cellulose not to be destroyed, can make xylogen and cellulosic utilization maximize; In addition, the present invention adopts alkaline solution to process hydrolytic residue and carries out membrane sepn, concentrated to obtaining liquid, has improved the purity of alkali lignin, is conducive to use xylogen to produce high value-added product, as resol; In addition, the first acidolysis that the present invention adopts, enzymolysis again, the operational path of last alkaline hydrolysis, due to acidolysis complete after residue be subacidity, so do not need to need substrate to neutralize before enzymolysis the operational path of the last enzymolysis of alkaline hydrolysis again as first acidolysis in prior art, make its pH value reach 4-6, therefore, simplify production technique, reduced the pollution to environment; Secondly, due to the technique of alkaline hydrolysis again after having adopted enzymolysis to complete, so the main component in enzymolysis residue is xylogen, therefore, alkaline solution extracts alkali lignin ratio and is easier to, and has reduced the consumption of alkaline solution, has reduced the pollution to environment;
As can be seen here, aforesaid method of the present invention has solved the problem of complex utilization of the lignocellulose biomass of prior art, makes the utilization of resources reach maximization.
2, the temperature of described acid hydrolytic reaction is 100-150 ℃, and the time is 0.5-3 hour, can be by hydrolysis of hemicellulose under this temperature and time more thorough, can stop again under acidic conditions high temperature and reaction times long to xylogen and cellulosic destruction.
3, acid hydrolysis of the present invention acid used is phosphoric acid solution, and the concentration of phosphoric acid solution is 1-20 % by weight, has avoided to greatest extent destruction xylogen and Mierocrystalline cellulose, and due to phosphoric acid corrosion a little less than, therefore, maintenance of the equipment is simple, duration of service is long.
4, the present invention is by the wooden solution with water dilution of alkali, again concentrated, has further reduced the ash oontent in alkali lignin solution, and the content of however, residual base, has improved solid content, is more conducive to use xylogen to produce high value-added product.
5, the present invention adopt concentrated obtain described alkali lignin solution after or recycling alkaline solution wherein simultaneously, spent caustic solution has obtained recycling, does not pollute the environment.
6, because major part in hydrolytic residue is xylogen, so can, in the lower realization of lower alkaline solution treatment temp (40-100 ℃) to lignin extraction, further protect the activity of xylogen.
7, the present invention adopts liquid-solid volume ratio in alkaline solution to be relatively applicable to extracting xylogen, avoided that liquid-solid ratio is too little is unfavorable for that liquid-solid mixing is also unfavorable for the alkaline hydrolysis of xylogen, it is large that the too large follow-up alkali of liquid-solid ratio reclaims load, and the wastewater flow rate of generation is also large, uneconomic problem.
8, the condition that alkaline solution of the present invention is processed adopts liquid-solid ratio, alkali consumption, the temperature and time being more preferably, and the activity of the alkali lignin finally obtaining is very high, and the xylogen therefore finally obtaining is particularly suitable for the xylogen of modified phenolic resins.
9, cellulase of the present invention is for being cultivated the cellulase obtaining by a penicillium, this Penicillium notatum Classification And Nomenclature is Penicillium decumbens PD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195, the cellulase that adopts this Penicillium notatum to produce has higher vigor, has further improved the extraction yield of cellulase hydrolysis.
10. what the present invention was used cultivates by Penicillium notatum the cellulase obtaining, at substrate consumption, be 80-150g/L, the addition of cellulase is 10-15FPU/g Mierocrystalline cellulose, temperature is that 45-55 ℃, pH are that 4-6, mixing speed are 50-200rpm, under the enzymolysis conversion condition of 2-7 days, enzymolysis transformation efficiency is the highest.
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 schematic diagram of technical process of the present invention;
Fig. 2 is the schematic flow sheet that alkaline solution of the present invention extracts alkali lignin.
Embodiment
Below will by specific embodiment, the invention will be further described.
(1) the self-control cellulase that following examples are used is cultivated and is obtained by Penicillium notatum, and concrete cultural method is:
(A) bacterial classification multiplication culture
By naming number, being Penicillium decumbens PD-G3-08 Penicillium notatum seed liquor is linked in the fermentor tank that contains seed culture medium through 121 ℃ of sterilizing 30min and activates with the inoculum size of 5% (v/v), keep tank pressure 0.02-0.05MPa, air flow 0.5vvm, mixing speed 100-150rpm, 30 ℃ of cultivation 30-60 hour, the seed liquor after being activated.
Component in described seed culture medium and consumption are: get embodiment 1 acid hydrolysis residue 10-30g/L, wheat bran 20-50g/L, peptone 1-4g/L, ammonium sulfate 2-4g/L, all the other are water.
Component and consumption in described seed culture medium are preferably: acid hydrolysis residue 20g/L, wheat bran 40g/L, peptone 3g/L, ammonium sulfate 3g/L, all the other are water.
(B) prepare cellulase
Inoculum size by step (A) acquisition seed liquor with 10% (v/v) accesses in the 5L fermentor tank that 3L fermention medium is housed of sterilizing, in fermenting process, add defoamer and control foaming, keep tank pressure 0.02-0.05MPa, air flow 0.5-0.6vvm, mixing speed 100-150rpm, 30 ℃ 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 obtaining obtains supernatant liquor, must contain the crude enzyme liquid of cellulase, and this crude enzyme liquid can be directly used in cellulosic enzymolysis.
(2) test as follows the various performances of xylogen in following examples
The mensuration of content of lignin: comprise sour insoluble xylogen and sour solvable xylogen.Wherein the mensuration of sour insoluble xylogen adopts Klason method, according to GB GB/T2677.8-94, carries out; The solvable xylogen of acid carries out according to GB GB 10337-89.
The mensuration of ash oontent: carry out according to GB/T 2667.2-93.
The mensuration of moisture: carry out according to GB/T 2667.3-93.
The mensuration of solid content in alkali lignin solution: get 100g solution to be measured, at 105 ℃, dry 24 hours, be cooled to room temperature, weigh the quality of remaining solid, this total mass number is the percentage ratio of the solid content of solution.
The mensuration of alkali content in alkali lignin solution and recovery alkali lye: get 0.5-1g testing liquid, make indicator with phenolphthalein, the hydrochloric acid soln of 0.2M/L is made titration reagent, is titrated to terminal, calculates the content of however, residual base in solution according to consumed hydrochloric acid volumeter.
Following examples see figures.1.and.2.
In following examples, pressure corresponding to acid hydrolysis temperature is the pressure of saturated vapor, therefore no longer for each embodiment, provides data.
In following examples, except having 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 with 80kg phosphoric acid solution, be hydrolyzed, the mass concentration of phosphoric acid solution is 10%, acid-hydrolyzed temperature is 120 ℃, time is 1 hour, acid hydrolysis residue and pentose solution that rear separation obtains have been hydrolyzed, with 10kg water, clean described acid hydrolysis residue, scavenging solution and described pentose solution merge, (water content is 65% left and right 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%.The extraction yield of hemicellulose is 68%.
The calculation formula of hemicellulose extraction yield is as follows:
The extraction yield %=of hemicellulose (pentose solution quality * pentose solution concentration)/(content of hemicellulose in corn cob quality * corn cob) * 100%
(2) cellulase hydrolysis
The condition of described enzymolysis is: cellulase is commercially available cellulase (,4w unit of jade of the He family Bioisystech Co., Ltd), the all acid hydrolytic residue that the present embodiment step (1) is obtained is as cellulosic substrate, according to the cellulosic addition of 15FPU/g, add cellulase, cellulosic substrate consumption is 125g/L, in temperature, be that 45 ℃, pH are 5.0, under the condition of mixing speed 50rpm, enzymolysis transforms 2 days, and whole enzymolysis process is without pressurize.Obtain 15.57kg enzymolysis residue (water ratio is 65% left and right), also obtain glucose solution, quality is 54.99kg, and concentration is 2.59%, and cellulosic extraction yield is 38%.
The formula of Mierocrystalline cellulose extraction yield is as follows:
Cellulosic extraction yield %=(concentration of the quality * glucose solution of glucose solution)/(cellulosic content in corn cob quality * corn cob) * 100%
The technique that glucose solution is produced ethanol is existing technique, does not repeat them here, and other embodiment is identical.
(3) alkaline solution extracts alkali lignin
Whole enzymolysis residues that above-mentioned steps (2) is obtained mix with sodium hydroxide solution, wherein liquid-solid volume ratio is 5: 1, the concentration of sodium hydroxide is 3%, then be warming up to 70 ℃, boiling alkaline hydrolysis through 1 hour, separation obtains alkaline hydrolysis residue and alkali lignin solution, with 10kg water, cleans described alkaline hydrolysis residue, and scavenging solution and described alkali lignin solution merge; Finally obtain 12.19kg alkaline hydrolysis residue (water ratio is about 65%) and 30.51kg alkali lignin solution; Alkali lignin solution with film device carry out separation concentrated after, add the dilution of 10kg water, reconcentration, finally obtains the alkali lignin concentrated solution of 4.69kg, and reclaims 35.82kg alkali lye.The solid content of this concentrated solution is 25.3% after measured, and alkali lignin content is 23.6%, and the content of however, residual base is 0.8%, and ash oontent is 1.7%, and in resulting alkali lye, the content of alkali is 1.83%, and the rate of recovery of alkali is 80%; The extraction yield of alkali lignin is 44%.
Alkali lignin extraction yield %=(content of lignin in the quality * concentrated solution of alkali lignin concentrated solution)/(content of xylogen in corn cob quality * corn cob) * 100%
(4) circular treatment
Whole alkaline hydrolysis residues that step (3) is obtained return to step (2) and carry out enzymolysis for the second time, and enzymolysis processing is identical with the condition of enzymolysis processing step in the present embodiment (2) Suo Shu for the second time; Obtain 8.66kg enzymolysis residue (water ratio is 65% left and right) and 34.13kg glucose solution for the second time, the concentration of glucose solution is 3.62%; Cellulosic extraction yield is 33% for the second time;
The described residue of enzymolysis is for the second time carried out to alkaline hydrolysis for the second time, and the condition of alkaline hydrolysis is identical with the condition of alkaline hydrolysis described in step in the present embodiment (3) for the second time; The quality of alkali lignin concentrated solution is 3.32kg, and the alkali lignin content in alkali lignin concentrated solution is 23.6%, and the extraction yield of alkali lignin is 31% for the second time.
In sum, the extraction yield of hemicellulose is 68%, and cellulosic total extraction yield is 71%, and total extraction yield of alkali lignin is 75%.
Embodiment 2
(1) acid hydrolysis
10.6kg corn cob is smashed, wash dedusting with water, then with 80kg phosphoric acid solution, be hydrolyzed, the mass concentration of phosphoric acid solution is 20%, acid-hydrolyzed temperature is 100 ℃, time is 0.5 hour, acid hydrolysis residue and pentose solution that rear separation obtains have been hydrolyzed, with 10kg water, clean described acid hydrolysis residue, scavenging solution and described pentose solution merge, (water content is 65% left and right 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%.The extraction yield of hemicellulose is 70%.
(2) cellulase hydrolysis alcohol prepared by fermenting
Get step (1) and obtain all acid hydrolytic residue as cellulosic substrate, carry out cellulase hydrolysis, the condition of described enzymolysis is: cellulase is commercially available cellulase (,4w unit of jade of the He family Bioisystech Co., Ltd), according to the cellulosic addition of 10FPU/g, add cellulase, cellulosic substrate consumption is 150g/L, in temperature, be that 55 ℃, pH are 4, under the condition of mixing speed 200rpm, enzymolysis transforms 7 days, whole enzymolysis process is without pressurize.Obtain 15.39kg enzymolysis residue (water ratio is 65% left and right), also obtain glucose solution, quality is 51.92kg, and concentration is 2.67%, cellulosic extraction rate reached 37%.
(3) alkaline solution extracts alkali lignin
By the whole enzymolysis residues that obtain in the present embodiment step (2) according to embodiment 1 step (3) processing method, difference is, liquid-solid volume ratio is 20: 1, and the concentration of sodium hydroxide is 0.8%, the temperature that alkaline solution is processed is 100 ℃, and the time is 2 hours.Finally obtain 11.79kg alkaline hydrolysis residue (water ratio is 65% left and right) and 4.85kg alkali lignin concentrated solution, and reclaim 116.48kg alkali lye.The solid content of this concentrated solution is 25.9% after measured, and the alkali lignin content of concentrated solution is 24.5%, and the content of the however, residual base of concentrated solution is 0.4%, and the ash oontent of concentrated solution is 1.4%; And the content of alkali is 0.52% in the alkali lye reclaiming, the rate of recovery of alkali is 70%.The extraction yield of alkali lignin is 47%.
(4) circular treatment
Whole alkaline hydrolysis residues that step (3) is obtained return to step (2) and carry out enzymolysis for the second time, and enzymolysis processing is identical with the condition of enzymolysis processing the present embodiment step (2) Suo Shu for the second time; Obtain 8.26kg enzymolysis residue (water ratio is 65% left and right) and 31.64kg glucose solution for the second time, the concentration of glucose solution is 3.91%; Cellulosic extraction yield is 33% for the second time;
The described residue of enzymolysis is for the second time carried out to alkaline hydrolysis for the second time, and the condition of alkaline hydrolysis is identical with the condition of alkaline hydrolysis described in step in the present embodiment (3) for the second time; The quality of alkali lignin concentrated solution is 2.99kg, and the alkali lignin content in alkali lignin concentrated solution is 24.5%, and the extraction yield of alkali lignin is 29% for the second time.
In sum, the extraction yield of hemicellulose is 70%, and cellulosic total extraction yield is 70%, and total extraction yield of alkali lignin is 76%
Embodiment 3
(1) acid hydrolysis
10.6kg corn cob is smashed, wash dedusting with water, then with 80kg phosphoric acid solution, be hydrolyzed, the mass concentration of phosphoric acid solution is 5%, acid-hydrolyzed temperature is 150 ℃, time is 1 hour, acid hydrolysis residue and pentose solution that rear separation obtains have been hydrolyzed, with 10kg water, clean described acid hydrolysis residue, scavenging solution and described pentose solution merge, (water content is 65% left and right 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%.The extraction yield of hemicellulose is 67%.
(2) cellulase hydrolysis
Get the described acid hydrolysis residue of step (1) as cellulosic substrate, carry out cellulase hydrolysis, the condition of described enzymolysis is: cellulase is above-mentioned Penicillium notatum (Penicillium decumbens PD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M2011195) cultivate obtain cellulase, according to the cellulosic addition of 12FPU/g, add cellulase, cellulosic substrate consumption is 80g/L, in temperature, it is 55 ℃, pH is 6, mixing speed is under the condition of 100rpm, enzymolysis transforms 2 days, whole enzymolysis process is without pressurize.The enzymolysis residue obtaining is 15.31kg (water content is 65% left and right), obtains glucose solution, and quality is 94.61kg, and concentration is 1.74%, and cellulosic extraction yield is 44%.
(3) alkaline solution extracts alkali lignin
By the whole enzymolysis residues that obtain in the present embodiment step (2), according to embodiment 1 step (3) processing method, difference is, liquid-solid volume ratio is 10: 1, and the concentration of sodium hydroxide is 5%, and the temperature that alkaline solution is processed is 40 ℃, and the time is 6 hours.Finally obtain 11.79kg alkaline hydrolysis residue (water ratio is 65% left and right) and 4.75kg alkali lignin concentrated solution, and reclaim 62.42kg alkali lye.The solid content of this concentrated solution is 26% after measured, and the alkali lignin content of concentrated solution is 24.4%, and the content of the however, residual base of concentrated solution is 0.8%, and the ash oontent of concentrated solution is 1.6%; And the content of alkali is 3.52% in the alkali lye reclaiming, the rate of recovery of alkali is 82%.Alkali lignin extraction yield is 46%.
(4) circular treatment
Whole alkaline hydrolysis residues in step (3) are returned in step (2), after merging with new acid hydrolysis residue (another batch of acid hydrolysis residue that corn cob obtains after step acid hydrolysis), carry out again enzymolysis processing, after enzymolysis processing completes, carrying out the alkaline hydrolysis of step (3) processes again, and then alkaline hydrolysis residue is returned in step (2), again merge with new acid hydrolysis residue, so can form circular treatment.
Adopt aforesaid method to process 106kg corn cob, the extraction yield that finally obtains the hemicellulose of corn cob is 67%, and cellulosic total extraction yield is 75%, and total extraction yield of xylogen is 71%.
Embodiment 4
(1) acid hydrolysis
First by the Wheat Straw that is 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 with sulphuric acid soln, be hydrolyzed, the mass concentration of sulphuric acid soln is 0.5%, carrying out acid-hydrolyzed temperature is 130 ℃, pressure is 0.27MPa, time is 3 hours, be hydrolyzed that rear separation obtains, after the acid hydrolysis residue that acid hydrolysis residue and pentose solution obtain cleans with 10kg water, then scavenging solution and pentose solution merge, (water content is 65% left and right 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 concentration is 2.02%, hemicellulose extraction yield is 64%.
(2) cellulase hydrolysis
Get the described acid hydrolysis residue of step (1) as cellulosic substrate, carry out cellulase hydrolysis, the condition of described enzymolysis is: cellulase is above-mentioned Penicillium notatum (Penicillium decumbens PD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M2011195) cultivate obtain cellulase, according to the cellulosic addition of 15FPU/g, add cellulase, cellulosic substrate consumption is 125g/L, in temperature, it is 48 ℃, pH is 5.0, under the condition of mixing speed 50rpm, enzymolysis transforms 2 days, whole enzymolysis process is without pressurize.Obtain 16kg enzymolysis residue (water ratio is 65% left and right), obtain glucose solution, quality is 61.24kg, and concentration is 3.36%, and cellulosic extraction yield is 42%.
(3) alkaline solution extracts alkali lignin
The whole enzymolysis residues that obtain in the present embodiment step (2) are carried out to alkaline hydrolysis according to the processing method of embodiment 1 step (3); Finally obtain the alkali lignin concentrated solution of 13.47kg alkaline hydrolysis residue (water ratio is 65% left and right) and 3.3kg, and reclaim 36.83kg alkali lye.The solid content of this alkali lignin concentrated solution is 26.2% after measured, and alkali lignin content is 24.6%, and the content of however, residual base is 0.8%, and ash oontent is 1.6%; And the content of alkali is 1.69% in the alkali lye reclaiming, and the rate of recovery of alkali is 74%, and the extraction yield of alkali lignin is 43%.
Alternatively, 10% sulphur acid for adjusting pH value to 3 for the alkali lignin concentrated solution obtaining can be filtered to washing and the dry alkali lignin solid that obtains.
(4) circular treatment
Whole alkaline hydrolysis residues that step (3) is obtained return to step (2) and carry out enzymolysis for the second time, and enzymolysis processing is identical with the condition of enzymolysis processing the present embodiment step (2) Suo Shu for the second time; Obtain 8.99kg enzymolysis residue (water ratio is 65% left and right) and 37.71kg glucose solution for the second time, the concentration of glucose solution is 4.15%; Cellulosic extraction yield is 32% for the second time.
The described residue of enzymolysis is for the second time carried out to alkaline hydrolysis for the second time, and the condition of alkaline hydrolysis is identical with the condition of alkaline hydrolysis described in step in the present embodiment (3) for the second time; The quality of alkali lignin concentrated solution is 2.12kg, and the alkali lignin content in alkali lignin concentrated solution is 24.1%, and the extraction yield of alkali lignin is 27% for the second time.
In sum, the extraction yield of hemicellulose is 64%, and cellulosic total extraction yield is 74%, and total extraction yield of alkali lignin is 70%.
Found through experiments, when acid solution adopts the weak acid that concentration expressed in percentage by weight is 30%, less to xylogen and cellulosic destruction, can realize object of the present invention.And the concentration of phosphoric acid solution is while being 1%, also can realize the present invention, just needed time of acid hydrolysis and temperature of reaction need corresponding increase.
Comparative example 1
The enzymolysis residue of getting in embodiment 1 step (2) carries out alkaline solution processing, method is with embodiment 1 step (3), difference is: liquid with film device carry out there is no thin up after separated concentrated, concentrated step, the rate of recovery table 1 of content, ash oontent and the alkali lye of the however, residual base of the extraction yield of alkali lignin, alkali lignin concentrated solution again.
Comparative example 2
The acid hydrolysis residue of getting in embodiment 1 step (2) carries out alkaline solution processing, method is with embodiment 1 step (3), difference is: the temperature that alkaline solution is processed is 170 ℃, the rate of recovery table 1 of content, ash content and the alkali lye of the however, residual base of alkali lignin extraction yield, alkali lignin concentrated solution.
Table 1
Comparative example 3
Technique and method are with embodiment 3, difference is that step (3) cellulase hydrolysis cellulase used is commercially available cellulase (,4w unit of jade of the He family Bioisystech Co., Ltd), only carry out primary fiber element enzymolysis, do not carry out step (3) and step (4), obtaining quality is the glucose solution that 94.61kg, concentration are 1.23%.Cellulosic extraction yield is 31%.
Comparative example 4
Technique and method are with embodiment 4, difference is: step (3) cellulase hydrolysis cellulase used is commercially available cellulase (,4w unit of jade of the He family Bioisystech Co., Ltd), only carry out primary fiber element enzymolysis, do not carry out step (3) and (4), obtaining quality is the glucose solution that 61.3kg, concentration are 2.24%.Cellulosic extraction yield is 28%.
Test case 1
In the phenol of 10Kg, the alkali lignin concentrated solution that adds respectively 30Kg embodiment 1 and comparative example 1,2 to obtain, is warming up to 70 ℃, adds the sodium hydroxide solution (mass percent concentration is 50%) of 1Kg, air distillation to 150 ℃, back flow reaction 90 minutes, is cooled to 70-80 ℃, adds 11Kg formaldehyde (mass percent concentration is 37%) to react 90 minutes, be cooled to 50 ℃, regulate pH to 6.5-7, vacuum hydro-extraction is to viscosity 9000cp/25 ℃ left and right, discharging.The alkali lignin concentrated solution that finally can be obtained by embodiment 1 and comparative example 1,2 makes respectively lignin modification resol, and its performance index are tested by the following method, and property indices is listed in table 2
The mensuration of resol solid content: carry out according to HG/T 2711.
The mensuration of the viscosity of resol: carry out according to HG/T 2712.
The mensuration of resol free phenol: carry out according to HG51342.
The mensuration of the free aldehyde of resol: carry out according to HG51343.
The mensuration of phenolic resin gel time: carry out according to HG51338.
The mensuration of water-content in resol: carry out according to HG51341.
The mensuration of resol pH value: carry out according to HG/T 2501.
The performance index of the modified phenolic resins of table 2 Different Alkali lignin liquor
In the resol product that three kinds of Different Alkali lignin liquors obtain, the content of phenol and formaldehyde raises gradually, illustrate the alkali lignin solution that adds not only with formaldehyde between the activity of reacting die down gradually, but also affected reacting to each other of phenol and formaldehyde.The first alkali lignin solution is the alkali lignin solution that the present invention obtains, and the content of its however, residual base and ash oontent are all lower, does not substantially affect reacting between alkali lignin and phenol and formaldehyde; The second alkali lignin solution is the direct concentrated alkali lignin solution obtaining, and without water washing, the content of however, residual base and ash oontent are all higher, has affected reacting between alkali lignin and phenol and formaldehyde; And in the third alkali lignin solution, having passed through a high temperature steaming process, some active groups of xylogen are damaged under hot conditions, thereby the activity during with formaldehyde reaction weakens greatly.
The lignin liquor of 25% left and right that industrial soda xylogen (Gaotang, Shandong polynary xylogen company limited) is made into if directly use, synthesis technique and method are constant, method according to test case 1 is prepared modified phenolic resins, regulate after pH value, only at the bottom of bottle, there is a small amount of resin to produce, see that on the whole alkali lignin solution does not participate in reaction, after decompression dehydration, at the bottom of bottle, find that there is alkali lignin precipitation, cannot obtain alkali lignin modified novolac resin.
In sum, the alkali lignin solution that known the present invention obtains has higher activity, can be in order to prepare the products such as modified phenolic resins.
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 exhaustive without also giving all embodiments.And the apparent variation of being extended out thus or change are still among the protection domain in the invention.
Claims (1)
1. a method of comprehensive utilization for lignocellulose biomass, is characterized in that comprising the following steps:
(a) lignocellulose biomass is carried out to acid hydrolysis, after separation, obtain pentose solution and acid hydrolysis residue;
(b) use cellulase to carry out enzymolysis to described acid hydrolysis residue, obtain glucose solution and enzymolysis residue; (c) with alkaline solution, process described enzymolysis residue, comprise
(I) processes described enzymolysis residue with alkaline solution makes lignin dissolution wherein in alkaline solution;
(II) then filter, wash and obtain liquid and alkaline hydrolysis residue;
(III) is by separated, the concentrated alkali lignin solution that obtains of gained liquid process film device;
(d) described alkaline hydrolysis residue is returned step (b) carry out enzymolysis processing or described alkaline hydrolysis residue and new acid hydrolysis residue are merged after carry out again the enzymolysis processing of step (b), then carry out successively step (c) and (d), so circulation, thus further extract xylogen 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 ℃, the time is 0.5-3 hour.
3, according to the method described in claim 1 or 2, it is characterized in that: while carrying out described acid hydrolysis, the concentration of acid solution is 0.5-30 % by weight.
4, method according to claim 3, is characterized in that: described acid solution is for containing phosphorus aqueous acid, and in the described aqueous solution, the concentration of phosphoric acid is 1-20 % by weight.
5, method according to claim 4, is characterized in that: described cellulase is for being cultivated the cellulase obtaining by a penicillium, this Penicillium notatum Classification And Nomenclature is
penicillium decumbenspD-G3-08, has been preserved in Wuhan University's Chinese Typical Representative culture collection center, and its deposit number is CCTCC M 2011195.
6, method according to claim 5, 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 that 45-55 ℃, pH are that 4-6, mixing speed are 50-200rpm, and enzymolysis transformation time is 2-7 days.
7, method according to claim 6, is characterized in that: in described step (III), also comprises the described concentrated alkali lignin solution obtaining dilute with water again, and then concentrated step.
8, method according to claim 7, is characterized in that: in described step (III), also comprise the alkali lignin solution process neutralization obtaining, filter and be dried, obtain alkali lignin solid.
9, method according to claim 8, is characterized in that: in described step (III), be also included in the concentrated step that obtains described alkali lignin solution afterwards or recycle alkaline solution wherein simultaneously.
10, method according to claim 9, is characterized in that: at alkaline solution described in institute's step (I), process and carry out at 40-100 ℃.
11, method according to claim 10, is characterized in that: in alkaline solution described in institute's step (I) is processed, liquid-solid volume ratio is 5:1-20:1.
12, method according to claim 11, is characterized in that: the time of processing at alkaline solution described in institute's step (I) is 1-6 hour.
13, method according to claim 12, is characterized in that: in the described alkaline solution of institute's step (I) is processed, the concentration expressed in percentage by weight of alkaline solution is 0.8-5%.
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