CN103045680A - 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 of: (a) alkaline hydrolysis processing: (i) processing the lignocellulose biomass by an alkaline solution to dissolve the lignin in the alkaline solution; (ii) then performing filtration and washing to obtain alkaline hydrolysis residues and liquid; (iii) separating the obtained liquid by a membrane device, and concentrating to obtain an alkaline lignin solution; (b) acid hydrolysis: performing acid hydrolysis of the alkaline hydrolysis residues, separating to obtain a pentose solution and acid hydrolysis residues; (c) cellulose enzymatic hydrolysis: performing enzymatic hydrolysis of the acid hydrolysis residues by using cellulase produced by a penicillium (Penicillium decumbens PD-G3-08), and then performing fermentation to produce ethanol. 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 the 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 renewable energy resources to become further important for the substitute of petroleum chemicals.And alcohol fuel is the principal mode of the material of biomass liquid energy, also is the most probable substitute of fossil oil.At present, world's alcohol production is mainly with 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, simultaneously existence strives grain with the people and grain is striven the drawbacks such as ground, and causes the provision price Continued, therefore seeks new raw material imperative.Present scientist is more cheap sight trend of purchasing cost, the widely lignocellulose biomass 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 annual lignocellulose biomass total amount that is generated by photosynthesis surpasses 2,000 hundred million tons on the earth, 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 human energy problem, but still exist in this respect a lot of technical barriers not yet to solve.At present, take lignocellulose biomass in the process of raw material production ethanol, the problem that runs into is that the extraction yield of cellulase hydrolysis is low, causes the high cost (accounting for the 40-50% of total cost of production) of enzymolysis, production cost is too high, can't really realize industrialization.The reason that the extraction yield of cellulase hydrolysis is low is: hemicellulose is combined between Mierocrystalline cellulose and the xylogen as the molecule tamanori on the one hand, and the reticulated structure that xylogen has, surround and add set Mierocrystalline cellulose and hemicellulose as support frame, xylogen and hemicellulose spatially can hinder contacting of cellulosic molecule and enzyme, the enzyme accessibility is poor, has increased the difficulty of enzymolysis.Therefore be necessary lignocellulose biomass is carried out effective pre-treatment, destroy the spatial obstacle of xylogen and hemicellulose, also to avoid simultaneously pre-treatment to produce and be unfavorable for the enzyme inhibitor (such as furfural, acetic acid etc.) of enzymolysis, thereby be conducive to cellulosic enzymolysis; On the other hand, with the intermolecular hydrogen bond that exists, aggregated structure complexity and degree of crystallinity are high in the cellulosic molecule, cellulase is low to crystalline cellulose enzymatic reaction vigour, therefore, in order to improve the extraction yield of cellulase hydrolysis, need to adopt better pretreatment process or improve enzyme activity.
Take lignocellulose biomass in the raw material production ethanol process, another problem that runs into is that hemicellulose, Mierocrystalline cellulose and xylogen are failed well to fully utilize, process in the prior art the technique of biomass, obtaining alcoholic product mainly with the degraded carbohydrate greatly is purpose, high purity and the high reactivity that can not take into account xylogen extract and later use, often xylogen is removed object as one, cause the wasting of resources and environmental pollution, fail to reach the resource maximum using.
In prior art, publication number is to disclose in the patent documentation of CN101696427A a kind ofly to produce alcohol fuel and 2 with fibrous matter, the method of 3-butyleneglycol, by the alkaline process pre-treatment, hemicellulose enzymolysis technique, hemicellulose more than 45% is changed into hypotoxic Xylose, obtained simultaneously the Mierocrystalline cellulose residue of high cellulose content.Hemicellulose hydrolysate wherein obtains 2 through fermentation, the 3-butyleneglycol, the Mierocrystalline cellulose residue obtains alcohol fuel through fermentation, Mierocrystalline cellulose and hemicellulose finally change into Industrial products utilized, but the purpose of this technique is wherein Mierocrystalline cellulose and hemicellulose changed into alcohol fuel and 2, the 3-butyleneglycol, the pretreated purpose of alkaline process is to remove to greatest extent xylogen, with xylogen as removing thing, do not consider the quality problems such as purity of gained xylogen and the later use of xylogen, higher with alkali concn, activity destruction to xylogen is larger, so the method to the separation of three kinds of materials, has been ignored the extraction effect of xylogen, only Mierocrystalline cellulose and hemicellulose have been carried out effective industrial utilization, can not guarantee that xylogen can carry out effective industrial utilization.
It is a kind of for the method and apparatus of fractional separation based on lignocellulose biomass that publication number is that the Chinese patent literature of CN101725068A discloses, provide based on lignocellulose biomass, adding can dissolved lignin the first solvent be that basic solvent is from described biomass extraction xylogen, adding second solvent that can dissolve hemicellulose is acid solvent extraction wood sugar again, and then extraction remains in the Mierocrystalline cellulose in the biomass; Xylogen, Mierocrystalline cellulose, hemicellulose can both be separated, but when using dilute acid pretreatment in this technique, hemicellulose is not degraded to pentose, but exists with the form of oligopolymer; When using high concentrated acid, although the rate of recovery of pentose is high, the amount that generates furfural is relatively also high, and therefore, operating process is relatively harsher to the requirement of potential of hydrogen.Used concentration of lye is higher in the process of separating lignin simultaneously, and is larger to the activity destruction of xylogen, and the xylogen of separating can only perhaps be used as the phenol chemical by degradation treatment as the fuel of steam boiler or boiler of power plant, and value added is low.
Summary of the invention
For this reason, technical problem to be solved by this invention is to overcome Mierocrystalline cellulose in the prior art, hemicellulose and xylogen to fail to be fully utilized, and the low problem of the extraction yield of cellulase hydrolysis, thereby a kind of method of comprehensive utilization of lignocellulose biomass has been proposed.
For achieving the above object, the invention provides a kind of method of comprehensive utilization of lignocellulose biomass, it is characterized in that may further comprise the steps:
(a) alkaline hydrolysis is processed
(i) using alkaline solution to process described lignocellulose biomass makes wherein lignin dissolution in alkaline solution;
(ii) then filter, wash and obtain alkaline hydrolysis residue and liquid;
(iii) with the separation of gained liquid process film device, the concentrated alkali lignin solution that obtains;
(b) acid hydrolysis
Described alkaline hydrolysis residue is carried out acid hydrolysis, obtain pentose solution and acid hydrolysis residue after the separation;
(c) cellulase hydrolysis
Use cellulase that described acid hydrolysis residue is carried out enzymolysis, obtain the solution that main component is glucose.
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 in sulfuric acid, hydrochloric acid, nitric acid and the phosphoric acid one or more.
Described acid-hydrolyzed temperature is 100-150 ℃, time is 0.5-3 hour, when carrying out described acid hydrolysis, the concentration of acid solution is that (as the acid of selecting is strong acid to the 0.5-30 % by weight, then the concentration of acid solution is lower, is about the 0.5-5 % by weight, as the acid of selecting is weak acid, then the concentration of acid solution is higher, is about the 5-30 % by weight).
Described acid solution is phosphoric acid solution, and the concentration of phosphoric acid solution is the 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, the lignocellulose biomass raw material is cut or pulverizes, then this stalk section is carried out scrubbing dust collection.
Also comprise again dilute with water of the described concentrated alkali lignin solution that obtains in the described step (iii), and then concentrated step.
Also be included in the concentrated step that obtains after the described alkali lignin solution or recycle simultaneously alkaline solution wherein in the described step (iii).
Described step (iii) comprises that also the alkali lignin solution that will obtain through neutralization, filtration and dry, obtains the alkali lignin solid.
Carry out under 40-100 ℃ at alkaline hydrolysis described in institute's step (i).
Liquid-solid volume ratio is 5 in alkaline hydrolysis step described in institute's step (i): 1-20: 1.
The concentration of alkaline solution is the 5-8 % by weight in alkaline hydrolysis step described in institute's step (i).
The time of processing at alkaline solution described in institute's step (i) is 1-6 hour.
Various alkali may be used to the present invention, include 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.
Described cellulase is for being cultivated the cellulase that obtains by a penicillium, this Penicillium notatum Classification And Nomenclature is PenicilliumdecumbensPD-G3-08, be preserved in Wuhan University Chinese Typical Representative culture collection center, its deposit number is CCTCCM2011195, and preservation date is on June 13rd, 2011.
The condition of described cellulase hydrolysis is: the substrate consumption is 80-150g/L, and the addition of cellulase is the 10-15FPU/g Mierocrystalline cellulose, and temperature is that 45-55 ℃, pH are that 4-6, mixing speed are 50-200rpm, and the enzymolysis transformation time is 2-7 days.
After the cellulase hydrolysis saccharification, fermentation can be adopted the method for well known to a person skilled in the art, fermentative production of ethanol.
Technique scheme of the present invention compared with prior art has the following advantages:
1, the present invention has adopted first alkaline hydrolysis, and the operational path of cellulase hydrolysis is carried out in acid hydrolysis at last, wherein, adopt the alkaline hydrolysis treatment of lignocellulosic biomass, the liquid that obtains carries out membrane sepn, concentrated, improve the purity of alkali lignin, be conducive to use xylogen to produce high value-added product.
In the present invention, the cellulase that enzymolysis adopts Penicillium notatum (PenicilliumdecumbensPD-G3-08) to produce, this cellulase has higher vigor, has improved the extraction yield of cellulase hydrolysis.
This shows, improved on the one hand cellulosic extraction yield by aforesaid method of the present invention, on the other hand because the xylogen purity of extracting is higher, can be directly as the raw material of producing other Industrial products such as resol.Therefore, the inventive method has solved the problem of complex utilization of lignocellulose biomass in the prior art, makes the utilization of resources reach maximization.
2, the present invention adopts the dilution of alkali lignin solution with water, and is again concentrated, further reduced the ash content in the alkali lignin solution, and residual alkali content has improved solid content, is more conducive to use it to produce high value-added product.
3, 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.
4, owing to adopting alkaline solution in the lower extraction that realizes xylogen of lower temperature (40-100 ℃), reduced the destruction to xylogen.
5, the present invention adopts the relatively more suitable xylogen that extracts of liquid-solid volume ratio in the alkaline solution, avoided that liquid-solid ratio is too little to be unfavorable for that liquid-solid mixing also is 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.
6, the present invention adopts the alkaline hydrolysis treatment of lignocellulosic biomass, because liquid-solid ratio, alkali consumption, temperature and time that the condition of alkaline hydrolysis adopts, reduced the destruction of alkaline hydrolysis process to the xylogen activity, the applicant finds amazedly, and the xylogen that finally obtains is particularly suitable for producing modified phenolic resins.
7, in the present invention under the temperature of described acid hydrolytic reaction, time and the concentration, can be with hydrolysis of hemicellulose more thorough, can stop again high temperature under the acidic conditions, the reaction times is long and excessive concentration to cellulosic destruction.
8, the used acid of acid hydrolysis of the present invention is phosphoric acid solution, and the concentration of phosphoric acid solution is the 1-20 % by weight, uses the above-mentioned acid solution can the considerable damage Mierocrystalline cellulose, and since phosphoric acid corrosion a little less than, therefore, maintenance of the equipment is simple, duration of service is long.
What 9, the present invention was used cultivates the cellulase that obtains by Penicillium notatum, be 80-150g/L at the substrate consumption, the addition of cellulase is the 10-15FPU/g Mierocrystalline cellulose, temperature is that 45-55 ℃, pH are that 4-6, mixing speed are 50-200rpm, under 2-7 days the condition of enzymolysis conversion, the enzymolysis transformation efficiency is the highest.
Description of drawings
For content of the present invention is more likely to be clearly understood, the 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
The below will the invention will be further described by specific embodiment.
(1) the employed self-control cellulase of following examples is cultivated by Penicillium notatum and is obtained, and concrete cultural method is:
(A) bacterial classification multiplication culture
To be PenicilliumdecumbensPD-G3-08 Penicillium notatum seed liquor with the inoculum size of 5% (v/v) be linked in the fermentor tank that contains seed culture medium through 121 ℃ of sterilization 30min activates with naming number, keep tank pressure 0.02-0.05MPa, air flow 0.5vvm, mixing speed 100-150rpm, 30 ℃ to cultivate the seed liquor after obtaining activating 30-60 hour.
Component in the 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 the 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) preparation cellulase
The inoculum size of step (A) acquisition seed liquor with 10% (v/v) accessed in the 5L fermentor tank that the 3L fermention medium is housed of having sterilized, add defoamer control foaming in the fermenting process, keep tank pressure 0.02-0.05MPa, air flow 0.5-0.6vvm, mixing speed 100-150rpm, 30 ℃ to cultivate 80-136 hour, obtain fermented liquid.
Each amounts of components is respectively in the described fermention medium: 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, sal epsom 0.4-0.6g/L, all the other are water, and the initial pH of substratum is 5.0-6.0.
Each amounts of components is preferably in the described fermention medium: acid hydrolysis residue 45g/L, wheat bran 35g/L, Microcrystalline Cellulose 5g/L, ammonium sulfate 4g/L, potassium primary phosphate 3g/L, sal epsom 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 that obtains gets supernatant liquor, namely gets the crude enzyme liquid that contains 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 the Klason method, carries out according to GB GB/T2677.8-94; The solvable xylogen of acid carries out according to GB GB10337-89.
The mensuration of ash oontent: carry out according to GB/T2667.2-93.
The mensuration of moisture: carry out according to GB/T2667.3-93.
The mensuration of solid content in the alkali lignin solution: get 100g solution to be measured, under 105 ℃, dried by the fire 24 hours, be cooled to room temperature, the quality of weighing 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 the recovery alkali lye: get the 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 point, calculates the content of however, residual base in the solution according to the hydrochloric acid volumeter that consumes.
Following examples can be referring to Fig. 1 and Fig. 2.
Pressure corresponding to acid hydrolysis temperature is the pressure of saturated vapor in following examples, therefore no longer provides pressure data for each embodiment.
In following examples, except specified otherwise was arranged, used percentage composition all represented weight percentage, i.e. " % " expression " % by weight ".
Embodiment 1
(1) alkaline solution extracts alkali lignin
With the corn cob of 10.65kg (mass component forms: moisture 6.12%, Mierocrystalline cellulose 35.19%, hemicellulose 32.01%, xylogen 23.7%, other 2.95%, lower same) pulverize, then mix with alkaline solution, wherein liquid-solid volume ratio is 5: 1, the concentration of sodium hydroxide is 6%, then be warming up to 70 ℃, through 1 hour boiling alkaline hydrolysis, separate obtaining alkaline hydrolysis residue and alkali lignin solution, clean described alkaline hydrolysis residue with 10kg water, scavenging solution and described alkali lignin solution merge; Finally obtain 20.38kg alkaline hydrolysis residue (water ratio is about 65%) and 49.61kg alkali lignin solution; Alkali lignin solution with film device separate concentrated after, add the dilution of 10kg water, reconcentration obtains the alkali lignin concentrated solution of 6.29kg at last, and reclaims 53.32kg alkali lye.The solid content of this concentrated solution is 26.1% after measured, and alkali lignin content is 24.9%, and the content of however, residual base is 0.8%, and ash oontent is 1.2%, and in the resulting alkali lye, the content of alkali is 4.39%, and the rate of recovery of alkali is 78%.The extraction yield of alkali lignin is 62%;
The calculation formula of alkali lignin extraction yield is as follows:
The extraction yield %=of alkali lignin (content of xylogen in the quality of alkali lignin concentrated solution * alkali lignin concentrated solution)/(content of xylogen in corn cob quality * corn cob) * 100%.
(2) acid hydrolysis
Get whole alkaline hydrolysis residues that the alkaline solution processing obtains in the present embodiment (1), then the aqueous solution with phosphoric acid is hydrolyzed, liquid-solid ratio is 10: 1 (mass ratio of new preparating acid solution and over dry alkaline hydrolysis residue), the mass concentration of phosphoric acid solution is 15%, acid-hydrolyzed temperature is 120 ℃, time is 0.5 hour, separation obtained after hydrolysis was finished acid hydrolysis residue and pentose solution, clean described acid hydrolysis residue with 10kg water, scavenging solution and described pentose solution merge, obtain at last 12.91kg acid hydrolysis residue (water ratio is about 65%) and 75.55kg pentose solution, the concentration of pentose solution is 3.29%, and then the extraction yield of hemicellulose is 73%.
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%.
(3) cellulase hydrolysis
The condition of described enzymolysis is: cellulase is commercially available cellulase (jade of the He family Bioisystech Co., Ltd, 4w unit), get all acid hydrolytic residue that step (2) obtains as cellulosic substrate, add cellulase according to the cellulosic addition of 15FPU/g, the cellulosic substrate consumption is 125g/L, be in temperature that 45 ℃, pH are 6, under the condition of mixing speed 200rpm, enzymolysis transforms 4 days, whole enzymolysis process need not pressurize, obtain the solution that main component is glucose, quality is 36.15kg, concentration is 5.6%, and cellulosic extraction yield is 54%.
The calculation 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%
Glucose solution is produced the technique of ethanol for existing technique, does not repeat them here, and other embodiment is identical.
Embodiment 2
(1) alkaline solution extracts alkali lignin
Raw material is identical with embodiment 1 step (1) with method, and difference is, liquid-solid volume ratio is 20: 1, and the concentration of sodium hydroxide is 5%, and the temperature that alkaline solution is processed is 100 ℃, and the time is 2 hours.Obtain at last 19.29kg alkaline hydrolysis residue (water ratio is about 65%) and 6.75kg alkali lignin concentrated solution, and reclaim 203.9kg alkali lye.The solid content of this concentrated solution is 25.2% after measured, and the alkali lignin content of concentrated solution is 23.6%, and the content of the however, residual base of concentrated solution is 0.7%, and the ash oontent of concentrated solution is 1.6%; And the content of alkali is 4.02% in the alkali lye that reclaims, and the rate of recovery of alkali is 82%.The extraction yield of alkali lignin is 63%.
(2) acid hydrolysis
Get whole alkaline hydrolysis residues that the alkaline solution processing obtains in the present embodiment (1), then the aqueous solution with phosphoric acid is hydrolyzed, liquid-solid ratio is 10: 1 (mass ratio of new preparating acid solution and over dry alkaline hydrolysis residue), the mass concentration of phosphoric acid solution is 20%, acid-hydrolyzed temperature is 100 ℃, time is 1 hour, separation obtained after hydrolysis was finished acid hydrolysis residue and pentose solution, clean described acid hydrolysis residue with 10kg water, scavenging solution and described pentose solution merge, obtain at last 12.13kg acid hydrolysis residue (water ratio is about 65%) and 72.15kg pentose solution, the concentration of pentose solution is 3.21%, and the extraction yield of hemicellulose is 68%.
(3) cellulase hydrolysis
The condition of described enzymolysis is: cellulase is above-mentioned penicillin (Penicillium decumbens PD-G3-08, be preserved in Wuhan University Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195) cultivate the cellulase obtain; get all acid hydrolytic residue that the present embodiment step (2) obtains as cellulosic substrate; add cellulase according to the cellulosic addition of 15FPU/g; the cellulosic substrate consumption is 150g/L; be 48 ℃ in temperature; pH is 5.0; under the condition of mixing speed 50rpm; enzymolysis transforms 7 days; whole enzymolysis process need not pressurize; obtain the solution of glucose; quality is 32.56kg; concentration is 7.25%, and cellulosic extraction yield is 63%.
Embodiment 3
(1) alkaline solution extracts alkali lignin
Raw material is identical with embodiment 1 step (1) with method, and difference is, liquid-solid volume ratio is 10: 1, and the concentration of sodium hydroxide is 8%, and the temperature that alkaline solution is processed is 40 ℃, and the time is 6 hours.Obtain at last 21.47kg alkaline hydrolysis residue (water ratio is about 65%) and 5.98kg alkali lignin concentrated solution, and reclaim 97.87kg alkali lye.The solid content of this concentrated solution is 25.7% after measured, and the alkali lignin content 24.1% of concentrated solution, the content of the however, residual base of concentrated solution are 0.5%, and the ash oontent of concentrated solution is 1.6%; And the content of alkali is 6.95% in the alkali lye that reclaims, and the rate of recovery of alkali is 85%.The extraction yield of alkali lignin is 57%.
(2) acid hydrolysis
Get whole alkaline hydrolysis residues that the alkaline solution processing obtains in the present embodiment (1), then the aqueous solution with phosphoric acid is hydrolyzed, liquid-solid ratio is 10: 1 (mass ratio of new preparating acid solution and over dry alkaline hydrolysis residue), the mass concentration of phosphoric acid solution is 5%, acid-hydrolyzed temperature is 150 ℃, time is 2 hours, separation obtained after hydrolysis was finished acid hydrolysis residue and pentose solution, clean described acid hydrolysis residue with 10kg water, scavenging solution and described pentose solution merge, obtain at last 13.98kg acid hydrolysis residue (water ratio is about 65%) and 78.68kg pentose solution, the concentration of pentose solution is 3.29%, and the extraction yield of hemicellulose is 76%.
(3) cellulase hydrolysis
The condition of described enzymolysis is: cellulase is above-mentioned Penicillium notatum (Penicillium decumbens PD-G3-08, be preserved in Wuhan University Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195) cultivate obtain cellulase; get all acid hydrolytic residue that the present embodiment step (2) obtains as cellulosic substrate; add cellulase according to the cellulosic addition of 12FPU/g; the cellulosic substrate consumption is 80g/L; be 45 ℃ in temperature; pH is 6; under the condition of mixing speed 200rpm; enzymolysis transforms 2 days, and whole enzymolysis process need not pressurize; Obtain the solution of glucose, quality is 66.053kg, and concentration is 3.92%, cellulosic extraction rate reached 69%.
Embodiment 4
(1) alkaline solution extracts alkali lignin
Method is identical with embodiment 1 step (1), and difference is, raw material be the 11.12kg Wheat Straw (mass component forms: moisture 10.1%, Mierocrystalline cellulose 44%, hemicellulose 22.2%, xylogen 17%, other 6.7%).Obtain at last 21.12kg alkaline hydrolysis residue (water ratio is about 65%) and 4.63kg alkali lignin concentrated solution, and reclaim 60.97kg 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 0.7%, and the ash oontent of concentrated solution is 1.4%; And the content of alkali is 3.79% in the alkali lye that reclaims, and the rate of recovery of alkali is 77%.The extraction yield of alkali lignin is 60%.
Alternatively, can filter with the alkali lignin solution that obtains with 10% sulphur acid for adjusting pH value to 3, washing, drying obtain the alkali lignin solid.
(2) acid hydrolysis
Get whole alkaline hydrolysis residues that the alkaline solution processing obtains in the present embodiment (1), then the aqueous solution with sulfuric acid is hydrolyzed, liquid-solid ratio is 10: 1 (mass ratio of new preparating acid solution and over dry alkaline hydrolysis residue), the mass concentration of sulphuric acid soln is 0.5%, acid-hydrolyzed temperature is 120 ℃, time is 3 hours, separation obtained after hydrolysis was finished acid hydrolysis residue and pentose solution, clean described acid hydrolysis residue with 10kg water, scavenging solution and described pentose solution merge, obtain at last 15.65kg acid hydrolysis residue (water ratio is about 65%) and 75.65kg pentose solution, the concentration of pentose solution is 2.35%, and the extraction yield of hemicellulose is 72%.
(3) cellulase hydrolysis
The condition of described enzymolysis is: cellulase is commercially available cellulase (jade of the He family Bioisystech Co., Ltd, 4w unit), get all acid hydrolytic residue that step (2) obtains as cellulosic substrate, add cellulase according to the cellulosic addition of 10FPU/g, the cellulosic substrate consumption is 125g/L, be in temperature that 55 ℃, pH are 4, under the condition of mixing speed 100rpm, enzymolysis transforms 5 days, whole enzymolysis process need not pressurize, obtain the solution of glucose, quality is 43.83kg, concentration is 6.25%, and cellulosic extraction yield is 56%.
Found through experiments, acid solution adopts concentration expressed in percentage by weight when being 30% weak acid, and is less to xylogen and cellulosic destruction, can realize purpose of the present invention.And the concentration of phosphoric acid solution also can realize the present invention when being 1%, and just needed time of acid hydrolysis and temperature of reaction need corresponding increases.
Comparative Examples 1
Method is with embodiment 1 step (1), difference is: liquid separates with film device does not have thin up after concentrated, concentrated step again, and then the rate of recovery of content, ash oontent and the alkali lye of the however, residual base of the extraction yield of alkali lignin, alkali lignin concentrated solution sees Table 1.
Comparative Examples 2
Method is with embodiment 1 step (1), and difference is: the temperature that alkaline solution is processed is 170 ℃, and then the rate of recovery of content, ash oontent and the alkali lye of the however, residual base of alkali lignin extraction yield, alkali lignin concentrated solution sees Table 1.
Table 1
Comparative Examples 3
Get the acid hydrolysis residue that obtains in embodiment 2 steps (2), method according to embodiment 2 steps (3) is carried out cellulase hydrolysis, difference is, cellulase is commercially available cellulase (jade of the He family Bioisystech Co., Ltd, 4w unit), the quality of glucose solution is 32.5kg, concentration is 5.18%, and cellulosic extraction yield is 45%.
Comparative Examples 4
Get the acid hydrolysis residue that obtains in embodiment 3 steps (2), method according to embodiment 3 steps (3) is carried out cellulase hydrolysis, difference is, cellulase is commercially available cellulase (jade of the He family Bioisystech Co., Ltd, 4w unit), the quality of glucose solution is 66kg, concentration is 2.72%, and cellulosic extraction yield is 48%.
Test case 1
In the phenol of 10Kg, add respectively the alkali lignin concentrated solution that 30Kg embodiment 1 and Comparative Examples 1,2 obtain, be warming up to 70 ℃, add 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%) reaction 90 minutes, be cooled to 50 ℃, regulate PH to 6.5-7, vacuum hydro-extraction is to about viscosity 9000cp/25 ℃, discharging.Finally can make respectively lignin modification resol by the alkali lignin concentrated solution that embodiment 1 and Comparative Examples 1,2 obtain, 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/T2711.
The mensuration of the viscosity of resol: carry out according to HG/T2712.
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 the resol: carry out according to HG51341.
The mensuration of resol pH value: carry out according to HG/T2501.
The performance index of the modified phenolic resins of table 2 Different Alkali lignin liquor
The content of phenol and formaldehyde raises gradually in the resol product that three kinds of Different Alkali lignin liquors obtain, and the alkali lignin solution that adds is described not only and the activity of reacting between formaldehyde dies down gradually, but also has 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 basically affect the reaction between alkali lignin and phenol and the formaldehyde; The second alkali lignin solution is for directly concentrating the alkali lignin solution that obtains, and without water washing, the content of however, residual base and ash oontent are all higher, have affected the reaction between alkali lignin and phenol and the formaldehyde; And having passed through a high temperature steaming process in the third alkali lignin solution, some active groups of xylogen are damaged under hot conditions, thereby the activity during with formaldehyde reaction weakens greatly.
If about 25% the lignin liquor that uses directly that industrial soda xylogen (the polynary xylogen in Gaotang, Shandong company limited) is made into, synthesis technique and method are constant, method according to test case 1 prepares modified phenolic resins, after regulating the pH value, only at the bottom of bottle, there is a small amount of resin to produce, sees that on the whole alkali lignin solution does not participate in reaction, behind the decompression dehydration, finding at the bottom of bottle has the alkali lignin precipitation, can't obtain alkali lignin modified novolac resin.
In sum, the alkali lignin solution that obtains of the present invention has higher activity as can be known, can be in order to prepare the products such as modified phenolic resins.
Obviously, above-described embodiment only is for example clearly is described, and is not the 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 need not also can't give all embodiments exhaustive.And the apparent variation of being extended out thus or change still are among the protection domain of the invention.
Claims (12)
1. the method for comprehensive utilization of a lignocellulose biomass is characterized in that may further comprise the steps:
(a) alkaline hydrolysis is processed
(i) using alkaline solution to process described lignocellulose biomass makes wherein lignin dissolution in alkaline solution;
(ii) then filter, wash and obtain alkaline hydrolysis residue and liquid;
(iii) with the separation of gained liquid process film device, the concentrated alkali lignin solution that obtains;
(b) acid hydrolysis
Described alkaline hydrolysis residue is carried out acid hydrolysis, obtain pentose solution and acid hydrolysis residue after the separation;
(c) cellulase hydrolysis
Use cellulase that described acid hydrolysis residue is carried out enzymolysis, obtain the solution that main component is glucose.
2. method according to claim 1 is characterized in that: also comprises in the described step (iii) the described concentrated alkali lignin solution that obtains dilute with water again, and then concentrated step.
3. method according to claim 1 and 2 is characterized in that: also be included in the concentrated step that obtains after the described alkali lignin solution or recycle simultaneously alkaline solution wherein in the described step (iii).
4. the described method of any one according to claim 1-3 is characterized in that: described step (iii) comprises that also the alkali lignin solution that will obtain through neutralization, filtration and dry, obtains the alkali lignin solid.
5. the described method of any one according to claim 1-4 is characterized in that: carry out under 40-100 ℃ at alkaline hydrolysis described in institute's step (i).
6. the described method of any one according to claim 1-5 is characterized in that: liquid-solid volume ratio is 5 in alkaline hydrolysis step described in institute's step (i): 1-20: 1.
7. the described method of any one according to claim 1-6 is characterized in that: the concentration of alkaline solution is the 5-8 % by weight in institute's step (i).
8. the described method of any one according to claim 1-7 is characterized in that: the time of processing at alkaline solution described in institute's step (i) is 1-6 hour.
9. the described method of any one according to claim 1-8, it is characterized in that: described acid-hydrolyzed temperature is 100-150 ℃, and the time is 0.5-3 hour, and the concentration of acid solution is the 0.5-30 % by weight.
10. method according to claim 9, it is characterized in that: described acid solution is phosphoric acid solution, the concentration of phosphoric acid solution is the 1-20 % by weight.
11. the described method of any one according to claim 1-10, it is characterized in that described cellulase is for being cultivated the cellulase that obtains by a penicillium, this Penicillium notatum Classification And Nomenclature is PenicilliumdecumbensPD-G3-08, be preserved in Wuhan University Chinese Typical Representative culture collection center, its deposit number is CCTCCM2011195.
12. the described method of any one according to claim 1-11, it is characterized in that: the condition of described cellulase hydrolysis is: the substrate consumption is 80-150g/L, the addition of cellulase is the 10-15FPU/g Mierocrystalline cellulose, temperature is that 45-55 ℃, pH are that 4-6, mixing speed are 50-200rpm, and the enzymolysis transformation time is 2-7 days.
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| CN107245505B (en) * | 2017-07-20 | 2021-04-30 | 淮阴师范学院 | Multistage hydrolysis saccharification method for urban waste biomass resources |
| CN107502626A (en) * | 2017-08-23 | 2017-12-22 | 北京林业大学 | A kind of Application way of wood fibre residue |
| CN114763680A (en) * | 2021-01-15 | 2022-07-19 | 中国石油天然气股份有限公司 | Method for removing lignin from lignocellulosic feedstocks |
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