CN103045692B - 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 N-stage acid hydrolysis on the lignocellulose biomass, wherein the first stage hydrolysis reaction temperature is 100-150 DEG C, the subsequent hydrolysis reaction temperature is reduced by 5-25 DEG C stage by stage, and N is an integer larger than or equal to 2; (b) performing enzymatic hydrolysis on the acid hydrolysis residues in the step (a) by using cellulose, so that a glucose solution and enzymatic hydrolysis residues are obtained; (c) treating the enzymatic hydrolysis residues produced by the step (b) with an alkali solution, so that lignin in the enzymatic hydrolysis residues can be extracted. The above method realizes maximized resource utilization of the 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, the mainly raw material using starch based (corn, cassava etc.) and carbohydrate (sugarcane, beet etc.) as fermentation of world's alcohol production.Adopt microbial 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, therefore find new raw material imperative.Scientist is more cheap sight trend of purchasing cost, the lignocellulose biomass widely of originating now.
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 exceedes 2,000 hundred million tons, and therefore Wooden Biomass is renewable resources abundant, the most cheap on the earth.
If can, taking 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, taking 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, obtaining ethanol mainly with degraded carbohydrate is greatly object, can not extract simultaneously and obtain high purity, highly active xylogen, often xylogen is removed to object as one, simultaneously in double cellulosic utilization, also there is the shortcoming that generates a lot of cellulase inhibitors, finally also can affect the productive rate of ethanol.
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 DEG C-200 DEG C 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.This patent adopts an acidolysis to remove hemicellulose can cause two disadvantageous effects, on the one hand, need adopt higher temperature and/or long reaction times if want as far as possible hemicelluloses of removing more, cause like this pentose of hydrolysis in early stage under comparatively high temps, easily to produce the cellulase inhibitors such as furfural and acetic acid, thereby reduce enzymolysis transformation efficiency; On the other hand, if do not adopt higher temperature and/or long reaction times, after acidolysis, in residue, contain more hemicellulose, be unfavorable for that alkaline solution extracts xylogen, if wanting 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 its xylogen to remove to produce high value-added product, therefore, technique scheme can not be taken into account the comprehensive utilization of Mierocrystalline cellulose, hemicellulose and xylogen simultaneously.
Running into the low conversion rate that another problem is cellulase hydrolysis in the process of raw material production ethanol taking lignocellulose biomass, cause the high cost (accounting for the 40-50% of total cost of production) of enzymolysis, 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, surround and add set Mierocrystalline cellulose and hemicellulose as support frame, 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, in cellulosic molecule, with the intermolecular hydrogen bond that exists, aggregated structure complexity and degree of crystallinity are high, and cellulase is low to crystalline cellulose enzymatic reaction vigour, therefore, in order to improve the transformation efficiency of cellulase hydrolysis, need to improve the vigor of enzyme.
The system and method that utilizes agriculture and forestry organic waste material to produce furfural is disclosed in CN101130530B, produce furfural by two-step approach, comprise hydrolysis system and dehydration Distallation systm, wherein hydrolysis system comprises the N level acid hydrolytic reaction still that mutual head and the tail connect, and agriculture and forestry organic waste material continuous hydrolysis is generated to pentose solution.The shortcoming that above-mentioned N level acid hydrolysis system exists is, because hydrolysis temperature in hydrolytic reaction pots at different levels is identical, therefore large to xylogen and cellulosic destructive rate, and the enzyme inhibitors such as furfural, acetic acid generating is more, is unfavorable for the comprehensive utilization of lignocellulose biomass.
Summary of the invention
For this reason, technical problem to be solved by this invention is while overcoming the comprehensive utilization Mierocrystalline cellulose that exists in prior art, hemicellulose and xylogen, can not obtain highly active xylogen, higher hemicellulose and the problem of Mierocrystalline cellulose extraction yield simultaneously, thereby propose a kind of method of comprehensive utilization of lignocellulose biomass.
For achieving the above object, the invention provides a kind of method of comprehensive utilization of lignocellulose biomass, comprise the following steps:
(a) lignocellulose biomass is carried out to the acid hydrolysis of N level, the acid-hydrolyzed reactor of N level is end to end, one of them reactor is made as to the first step, last is made as N level, the acid solution of new preparation adds in first step acid hydrolytic reaction still, the acid solution that first step acid hydrolytic reaction still is discharged adds in the acid hydrolytic reaction still of the second stage, the acid solution of discharging in the acid hydrolytic reaction still of the second stage adds in third stage acid hydrolytic reaction still, order successively, until the acid solution that N-1 level acid hydrolytic reaction still is discharged adds in N level acid hydrolytic reaction still, the acid solution that N level acid hydrolytic reaction still is discharged is final pentose solution, take out the acid hydrolysis residue in first step acid hydrolytic reaction still, then pack new lignocellulose biomass raw material into, then using first step acid hydrolytic reaction still as N level acid hydrolytic reaction still, using second stage acid hydrolytic reaction still as first step acid hydrolytic reaction still, third stage acid hydrolytic reaction still is as second stage acid hydrolytic reaction still, until N level acid hydrolytic reaction still is as N-1 level acid hydrolytic reaction still, reaction is again hydrolyzed, so move in circles and can realize the hydrolysis to lignocellulose biomass,
Wherein, the acid-hydrolyzed temperature of the first step is 100-150 DEG C, and every grade is reduced 5-25 DEG C step by step subsequently, and N is more than or equal to 2 integer;
(b) use cellulase to carry out enzymolysis to acid hydrolysis residue described in step (a), obtain glucose solution and enzymolysis residue;
(c) the described enzymolysis residue producing with alkaline solution treatment step (b), thus the alkali lignin in described enzymolysis residue extracted.
The acid-hydrolyzed temperature of the described first step is 120-140 DEG C, and every grade is reduced 10-20 DEG C step by step subsequently.
There is no particular limitation for the kind of described acid solution, can be that lignocellulose biomass carries out the acid-hydrolyzed conventional acid using, for example, in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid one or more.
Concentration and the time of the acid-hydrolyzed acid solution of described N level are not particularly limited, it can be concentration and the time that lignocellulose biomass carries out acid-hydrolyzed conventional acid solution, for example in the acid hydrolysis of described N level, the concentration of the acid solution of every grade of hydrolysis reaction is that (as the acid of selecting is strong acid to 0.5-30 % by weight, lower (as the acid of selecting is strong acid to the concentration of acid solution, 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, be about 5-30 % by weight), the time of every grade of hydrolysis reaction in the acid hydrolysis of described N level (being the residence time of acid solution in reactor) is 0.25-2 hour.The preferred 1-20 % by weight of concentration of phosphoric acid.
The integer that is chosen as 3-5 that described N is comparatively desirable above.
Described lignocellulose biomass can be one or more of maize 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 this stalk section is carried out to scrubbing dust collection.
Described cellulase is to cultivate by a penicillium cellulase obtaining, this Penicillium notatum Classification And Nomenclature is Penicillium decumbens PD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center (being called for short CCTCC), depositary institution address: Wuhan University's preservation center.The numbering of registering on the books is CCTCC M 2011195, and preservation date is on June 13rd, 2011.Taking this bacterial strain as the cellulosic bacterial strain of enzymolysis.
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 DEG C, 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.
The concrete steps of described step (c) are:
(i) processing described enzymolysis residue with alkaline solution makes lignin dissolution wherein in alkaline solution;
(ii) then filter, wash and obtain solid and liquid;
(iii) by the separation of gained liquid process film device, the concentrated alkali lignin solution that obtains;
In described step (iii), also comprise the described concentrated alkali lignin solution dilute with water again obtaining, and then concentrated step.
In described step (iii), also comprise the alkali lignin solution process neutralization obtaining, filter and be dried, obtain the step of 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.
Described alkaline solution is processed and is carried out at 40-100 DEG C.
In described alkaline solution processing, liquid-solid volume ratio is 5: 1-20: 1.
The time of described alkaline hydrolysis processing is 1-6 hour.
In described alkaline solution processing, the concentration of alkaline solution is 5-8 % by weight.
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 has adopted the acidolysis of first N level, enzymolysis again, the operational path of last alkaline hydrolysis, and (the acid-hydrolyzed temperature of the first step is 100-150 DEG C in acidolysis process, to have adopted the method reducing step by step to N order reaction still temperature from first step reactor, every grade is reduced 5-25 DEG C step by step subsequently), because the material in N order reaction still is new material, hemicellulose is more easily removed, therefore the lower acid solution of working concentration, in addition, in N order reaction still, the concentration of pentose is the highest, adopt lower acid concentration, can prevent from generating furfural and acetic acid, thereby reduce furfural and the restraining effect of acetic acid to cellulase, and for the material in first step reactor, remove remaining hemicellulose more difficult, adopt higher acid concentration to be conducive to farthest extract hemicellulose, adopt technique scheme can farthest extract hemicellulose, destroy as little as possible xylogen and Mierocrystalline cellulose simultaneously, keep the activity of xylogen, owing to having reduced sour usage quantity, also saved cost in addition, and reduced the pollution to environment,
Adopt aforesaid method to make to be hydrolyzed more than later half cellulosic extraction yield can reach 90 % by weight, cellulosic rate of loss is less than 19 % by weight, and the rate of loss of xylogen is less than 18 % by weight; In addition, because the structure of xylogen is not destroyed, so the activity of the xylogen extracting through alkaline solution is higher, can be directly as the raw material of producing other high value added product (as resol); On the other hand, because the enzyme inhibitor generating in acidolysis process is less, also improved cellulosic extraction yield;
In addition, what the present invention adopted is the acidolysis of first N level, 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 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, solve the problem of complex utilization of the lignocellulose biomass of prior art by aforesaid method of the present invention, made the utilization of resources reach maximization.
2, the preferred 3-5 level of described N level, it is both economical within the scope of this that (equipment investment is few, easy and simple to handle) can obtain again high hemicellulose extraction yield, and to xylogen and cellulosic destructive rate minimum (the more multipair xylogen of progression and cellulosic destructive rate are larger).
3. the preferred 120-140 DEG C of the acid-hydrolyzed temperature of the first step in the present invention, every grade of preferred 10-20 DEG C of temperature reducing step by step subsequently, above-mentioned scope can ensure under the higher prerequisite of hemicellulose extraction yield, lower to xylogen and cellulosic destructive rate, and the enzyme inhibitors such as furfural and acetic acid generating is still less.
4, the present invention has adopted film device to separate and concentrated step in alkaline hydrolysis process, has improved the purity of alkali lignin, is conducive to produce high value-added product.
5, the present invention dilutes wooden alkali solution with water, again concentrated, has further reduced the ash oontent in alkali lignin solution, and remaining alkali content, has improved solid content, is conducive to use xylogen to produce high value-added product.
6, 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.
7, realize lignin extraction because the alkaline solution treatment temp (40-100 DEG C) lower is lower, further protect the activity of xylogen.
8, the present invention adopts liquid-solid volume ratio in alkaline solution to be relatively applicable to extracting xylogen, avoid 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.
9, the condition of alkaline solution processing of the present invention adopts liquid-solid ratio, alkali consumption, temperature and time, the activity of the alkali lignin finally obtaining is very high.
10, cellulase of the present invention is to cultivate by a penicillium cellulase obtaining, 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.
What 11. the present invention were used cultivates by Penicillium notatum the cellulase obtaining, be 80-150g/L at substrate consumption, the addition of cellulase is 10-15FPU/g Mierocrystalline cellulose, and temperature is that 45-55 DEG C, pH are that 4-6, mixing speed are 50-200rpm, and enzymolysis transformation time is that 2-7 days enzymolysis transformation efficiencys are the highest.
Brief description of the drawings
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 alkali lignin;
Fig. 3 is N level acidolysis equipment schematic diagram used.
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
Be that Penicillium decumbens PD-G3-08 Penicillium notatum seed liquor is linked in the fermentor tank that contains seed culture medium through 121 DEG C of sterilizing 30min and activates with the inoculum size of 5% (v/v) by naming number, 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 activation.
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
Step (A) is obtained to seed liquor to be accessed with the inoculum size of 10% (v/v) in the 5L fermentor tank that 3L fermention medium is housed of sterilizing, in fermenting process, add defoamer 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 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, 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 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 DEG C, 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 can be referring to Fig. 1 and Fig. 2 and Fig. 3.
In following examples, pressure corresponding to acid hydrolysis temperature is the pressure of saturated vapor, therefore no longer provides pressure data for each embodiment.
In following examples, outside specified otherwise, percentage composition used all represents weight percentage, i.e. " % " expression " % by weight ".
Embodiment 1
(1) N level acid hydrolysis
In the present embodiment: employing be three grades of acid hydrolysiss, first by corn cob (mass component composition: moisture 6.12%, Mierocrystalline cellulose 35.19%, hemicellulose 32.1%, xylogen 23.7%, other 2.95%, lower same) smash, wash dedusting with water.First reactor is made as to the first step, last is made as the third stage, the acid solution of newly preparation is added in first step hydrolytic reaction pot, the acid solution that first step acid hydrolytic reaction still is discharged adds in the acid hydrolytic reaction still of the second stage, the acid solution that second stage acid hydrolytic reaction still is discharged adds in third stage acid hydrolytic reaction still, the solution of discharging in third stage acid hydrolytic reaction still is final pentose solution, then the acid hydrolysis residue in first step acid hydrolytic reaction still is discharged, and pack new corn cob raw material into, set it as third stage acid hydrolytic reaction still, using former second stage acid hydrolytic reaction still as first step acid hydrolytic reaction still, using former third stage acid hydrolytic reaction still as second stage acid hydrolytic reaction still, carry out again acid hydrolytic reaction, so hydrolysis moves in circles and can realize the continuous hydrolysis of lignocellulose biomass,
Wherein, the acid-hydrolyzed temperature of the first step is 140 DEG C, and the acid-hydrolyzed temperature in the second stage is 120 DEG C, and the acid-hydrolyzed temperature of the third stage is 100 DEG C; Every grade of acid-hydrolyzed time is 1 hour, and acid solution is phosphate aqueous solution, and the concentration of phosphoric acid solution is 10%, and liquid-solid ratio is 8: 1 (mass ratio of new preparating acid solution and over dry corn cob raw material, lower together), by aforesaid method to 1.06 × 10
3the corn cob raw material that kg is new carries out after continuous acid hydrolysis processing, uses 1 × 10
3the water of kg is washed described acid hydrolysis residue, and water lotion and acid hydrolysis solution merge, and finally obtaining pentose solution is 8.29 × 10
3kg, pentose concentration is 3.66%, the weight that obtains acid hydrolysis residue is 1.71 × 10
3kg (water ratio is 65% left and right, and the over dry content of hemicellulose is 6.27%, and cellulosic over dry content is 53.06%, and the over dry content of xylogen is 35.42%).The extraction yield of hemicellulose is 89%,
The calculation formula of hemicellulose extraction yield is as follows:
Extraction yield %=(concentration of the quality × pentose of pentose solution)/(content of hemicellulose in corn cob quality × corn cob) × 100% of hemicellulose.
In this step, relate to the variation of acid concentrations at different levels, the selection of other parameters, is determined according to conventional factor in corresponding reaction process by adopted acid.Each embodiment, in acid hydrolysis step, all adopts identical parameter to choose mode below.
(2) cellulase hydrolysis
The condition of described enzymolysis is: cellulase is commercially available cellulase (jade of the He family Bioisystech Co., Ltd, 4w unit), get the described all acid hydrolytic residue of step (1) as cellulosic substrate, add cellulase according to the cellulosic addition of 15FPU/g, cellulosic substrate consumption is 125g/L, be in temperature that 48 DEG C, pH are 5.0, under the condition of mixing speed 50rpm, enzymolysis transforms 2 days, and whole enzymolysis process, without pressurize, obtains 0.96 × 10
3kg enzymolysis residue (water ratio is 65% left and right), also obtains the solution that main component is glucose, and quality is 4.79 × 10
3kg, concentration is 4.99%, cellulosic extraction yield is 70%.
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%.
It is existing technique that glucose solution is produced ethanol, does not repeat them here, and following examples are same.
(3) alkaline solution extracts alkali alkali lignin
The whole enzymolysis residues that obtain in the present embodiment step (2) are mixed with sodium hydroxide solution, and wherein liquid-solid volume ratio is 5: 1, and the concentration of sodium hydroxide is 6%, then be warming up to 70 DEG C, through the boiling alkaline hydrolysis of 1 hour, separate and obtain alkaline hydrolysis residue and alkali lignin solution, with 1 × 10
3kg water cleans described alkaline hydrolysis residue, and scavenging solution and described alkali lignin solution merge; Finally obtain 0.40 × 10
3kg alkaline hydrolysis residue (water ratio is 65% left and right) and 2.61 × 10
3kg alkali lignin solution; Alkali lignin content in alkali lignin solution is 7.45%, and the extraction yield of alkali lignin is 77%.
The extraction yield formula of alkali lignin is as follows:
Alkali lignin extraction yield %=(content of lignin in quality × alkali lignin solution of alkali lignin solution)/(content of xylogen in corn cob quality × corn cob) × 100%
Comparative example 1
(1) N level acid hydrolysis
Method is with embodiment 1 step (1), and temperature when difference is the 1st, 2 and 3 grades of acid hydrolysiss is identical numerical value, and the numerical value of the rate of loss of hemicellulose extraction yield, cellulosic rate of loss and xylogen is in table 1:
Table 1
(2) cellulase hydrolysis
Get respectively three kinds of acid hydrolysis residues in comparative example 1A, comparative example 1B, comparative example 1C step (1), carry out cellulase hydrolysis, method is with embodiment 1 step (2), and cellulosic extraction yield is in table 2:
Table 2
| Cellulosic extraction yield | |
| Embodiment 1 | 70％ |
| Comparative example 1A | 60％ |
| Comparative example 1B | 73％ |
| Comparative example 1C | 51％ |
(3) alkaline solution extracts alkali alkali lignin
Get respectively three kinds of enzymolysis residues in comparative example 1A, comparative example 1B, comparative example 1C step (2), method is with embodiment 1 step (3), alkali lignin extraction yield table 3.
Table 3
| Alkali lignin extraction yield | |
| Comparative example 1A | 67％ |
| Comparative example 1B | 80％ |
| Comparative example 1C | 81％ |
Embodiment 2
(1) N level acid hydrolysis
Raw material and method be with embodiment 1 step (1), and difference is, the acid-hydrolyzed temperature of the first step is 135 DEG C, and the acid-hydrolyzed temperature in the second stage is 120 DEG C, and the acid-hydrolyzed temperature of the third stage is 105 DEG C; The weight that finally obtains acid hydrolysis residue is 1.79 × 10
3kg (water-content 65% left and right, the over dry content of hemicellulose is 8.69%, cellulosic over dry content is 51.9%, the over dry content of xylogen is 34.4%), final pentose solution is 8.21 × 10
3kg, pentose concentration is 3.49%, the extraction yield of hemicellulose is 84%.
(2) 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 (1) obtains as cellulosic substrate, add cellulase according to the cellulosic addition of 10FPU/g, cellulosic substrate consumption is 150g/L, be in temperature that 55 DEG C, pH are 4, under the condition of mixing speed 200rpm, enzymolysis transforms 7 days, and whole enzymolysis process is without pressurize.Obtain 1.02 × 10
3kg enzymolysis residue (water ratio is 65% left and right), also obtains the solution of glucose, and quality is 4.81 × 10
3kg, concentration is 5.10%, cellulosic extraction rate reached 72%.
(3) alkaline solution extracts alkali alkali lignin
The whole enzymolysis residues that obtain in the present embodiment step (2) are mixed with sodium hydroxide solution, and wherein liquid-solid volume ratio is 5: 1, and the concentration of sodium hydroxide is 6%, then be warming up to 70 DEG C, through the boiling alkaline hydrolysis of 1 hour, separate and obtain alkaline hydrolysis residue and alkali lignin solution, with 1 × 10
3kg water cleans described alkaline hydrolysis residue, and scavenging solution and described alkali lignin solution merge; Finally obtain 0.46 × 10
3kg alkaline hydrolysis residue (water ratio is 65% left and right) and 4.48 × 10
3kg alkali lignin solution; Liquid with film device separate concentrated after, add 1 × 10
3the dilution of kg water, reconcentration, finally obtains 0.79 × 10
3the alkali lignin concentrated solution of kg, and reclaim 4.68 × 10
3kg alkali lye.The solid content of this concentrated solution is 26.4% after measured, and alkali lignin content is 24.9%, and the content of however, residual base is 0.7%, and ash oontent is 1.5%, and in the alkali lye obtaining, the content of alkali is 3.76%, and the rate of recovery of alkali is 82%; Alkali lignin extraction yield is 78%.
Comparative example 2
The enzymolysis residue of getting in embodiment 2 steps (2) carries out alkaline hydrolysis, method is with embodiment 2 steps (3), difference is: there is no thin up, concentrated step again, the rate of recovery table 4 of content, ash content and the alkali lye of the extraction yield of alkali lignin, the however, residual base of alkali lignin concentrated solution.
Comparative example 3
The enzymolysis residue of getting in embodiment 2 steps (2) carries out alkaline hydrolysis processing, method is with embodiment 2 steps (3), difference is: the temperature of alkaline hydrolysis processing is 170 DEG C, the rate of recovery table 4 of content, ash content and the alkali lye of the extraction yield of alkali lignin, the however, residual base of alkali lignin concentrated solution:
Table 4
Embodiment 3
(1) N level acid hydrolysis
Raw material and method are with embodiment 1 step (1), difference is, in every order reaction still, the concentration of phosphoric acid solution is 15%, every grade of acid-hydrolyzed time is 2 hours, the acid-hydrolyzed temperature of the first step is 100 DEG C, the acid-hydrolyzed temperature in the second stage is 95 DEG C, and the acid-hydrolyzed temperature of the third stage is 90 DEG C; The weight that finally obtains acid hydrolysis residue is 1.83 × 10
3kg (water-content 65% left and right, the over dry content of hemicellulose is 10.65%, cellulosic over dry content is 50.56%, the over dry content of xylogen is 33.89%), final pentose solution is 8.17 × 10
3kg, pentose concentration is 3.34%, the extraction yield of hemicellulose is 80%.
(2) cellulase hydrolysis alcohol prepared by fermenting
By all acid hydrolytic residue obtaining in the present embodiment step (1), method according to embodiment 1 step (2) is carried out cellulase hydrolysis, difference is: cellulase is that 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 M 2011195) cultivate obtain cellulase, obtain 1.01 × 10
3kg enzymolysis residue (water ratio is 65% left and right), also obtains the solution of glucose, and quality is 5.12 × 10
3kg, concentration is 5.12%, cellulosic extraction yield is 77%.
(3) alkaline solution extracts alkali alkali lignin
The whole enzymolysis residues that obtain in the present embodiment step (2) and sodium hydroxide solution are mixed, wherein liquid-solid volume ratio is 10: 1, and the concentration of sodium hydroxide is 8%, is then warming up to 40 DEG C, separate and obtain alkaline hydrolysis residue and alkali lignin solution through the boiling alkaline hydrolysis of 6 hours, with 1 × 10
3kg water cleans described alkaline hydrolysis residue, and scavenging solution and described alkali lignin solution merge; Finally obtain 0.699 × 10
3kg alkaline hydrolysis residue (water ratio is 65% left and right) and 5.16 × 10
3the alkali lignin solution of kg; Liquid with film device separate concentrated after, add 1.0 × 10
3the dilution of kg water, reconcentration, finally obtains 0.83 × 10
3the alkali lignin concentrated solution of kg, and reclaim 5.34 × 10
3kg alkali lye.The solid content of this concentrated solution is 25.3% after measured, and alkali lignin content is 23.9%, and the content of however, residual base is 0.7%, and ash oontent is 1.4%; And in the alkali lye obtaining, the content of alkali is 5.56%, the rate of recovery of alkali is 84%.Alkali lignin extraction yield is 78%.
Comparative example 4
Get the acid hydrolysis residue arriving in embodiment 3 steps (1), method according to embodiment 3 steps (2) is carried out cellulase hydrolysis, difference is, cellulase is commercially available cellulase (jade of the He family Bioisystech Co., Ltd, 4w unit), obtain the solution of glucose, quality is 5.12 × 10
3kg, concentration is 3.53%, cellulosic extraction yield is 53%.
Embodiment 4
(1) N level acid hydrolysis
Raw material, technique and method are with embodiment 1 step (1), and difference is: acid solution is sulphuric acid soln, and concentration is 1%; Every grade of acid-hydrolyzed time is 1.5 hours; The acid-hydrolyzed temperature of the first step is 120 DEG C, and the acid-hydrolyzed temperature in the second stage is 110 DEG C, and the acid-hydrolyzed temperature of the third stage is 100 DEG C, and the acid-hydrolyzed temperature of the fourth stage is 90 DEG C, and the acid-hydrolyzed temperature of level V is 80 DEG C.The weight that finally obtains acid hydrolysis residue is 1.77 × 10
3kg (water-content 65% left and right, the over dry content of hemicellulose is 5.5%, cellulosic over dry content is 53.75%, the over dry content of xylogen is 35.68%), final pentose solution is 8.23 × 10
3kg, pentose concentration is 3.73%, the extraction yield of hemicellulose is 90%.
(2) 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 M 2011195) cultivate obtain cellulase, get all acid hydrolytic residue that step (1) obtains as cellulosic substrate, add cellulase according to the cellulosic addition of 12FPU/g, cellulosic substrate consumption is 80g/L, it is 45 DEG C in temperature, pH is 6, under the condition of mixing speed 200rpm, enzymolysis transforms 5 days, whole enzymolysis process is without pressurize, obtain 0.99 × 10
3kg enzymolysis residue (water ratio is 65% left and right), also obtains the solution that main component is glucose, and quality is 8.37 × 10
3kg, concentration is 2.97%, cellulosic extraction rate reached 73%.
(3) alkaline solution extracts alkali alkali lignin
By the enzymolysis residue obtaining in above-mentioned steps (2), carry out alkaline hydrolysis processing according to the method for embodiment 2 steps (3), difference is, liquid-solid ratio is 20: 1, the concentration of sodium hydroxide is 5%, and the temperature of alkaline solution processing is 100 DEG C, and the time is 2 hours.Finally obtain 0.41 × 10
3kg alkaline hydrolysis residue (water ratio is 65% left and right) and 0.78 × 10
3kg alkali lignin concentrated solution, and reclaim 8.07 × 10
3kg alkali lye.The solid content of this concentrated solution is 26.9% after measured, and the alkali lignin content of concentrated solution is 25.7%, and the content of the however, residual base of concentrated solution is 0.6%, and the ash oontent of concentrated solution is 1.2%; And in the alkali lye obtaining, the content of alkali is 3%, the rate of recovery of alkali is 70%.The extraction yield of alkali lignin is 80%.
Embodiment 5
(1) N level acid hydrolysis
Technique and method be with embodiment 2 steps (1), and difference is, raw material is 1.11 × 10
3the Wheat Straw of kg (mass component composition: moisture 10.1%, Mierocrystalline cellulose 44%, hemicellulose 22.2%, xylogen 17%, other 6.7%), acid solution is 0.8% sulfuric acid, the acid-hydrolyzed temperature of the first step is 150 DEG C, the acid-hydrolyzed temperature in the second stage is 125 DEG C, and the acid-hydrolyzed temperature of the third stage is 100 DEG C.The weight that finally obtains acid hydrolysis residue is 1.86 × 10
3kg (water-content 65% left and right, the over dry content of hemicellulose is 3.42%, cellulosic over dry content is 61.17%, the over dry content of xylogen is 23.96%), final pentose solution is 8.14 × 10
3kg, pentose concentration is in 2.76% left and right, and hemicellulose extraction yield is 91%
(2) cellulase hydrolysis
Get the acid hydrolysis residue that the present embodiment step (1) obtains, according to the method for embodiment 1 step (2) is carried out to cellulase hydrolysis, obtain 0.87 × 10
3kg enzymolysis residue (water ratio is 65% left and right), also obtains the solution that main component is glucose, and quality is 5.2 × 10
3kg, concentration is 3.37%, cellulosic extraction yield is 71%.
(3) alkaline solution extracts alkali lignin
Get the whole enzymolysis residues that obtain in above-mentioned steps (2), identical with embodiment 2 steps (3) processing method.Finally obtain 0.46 × 10
3kg alkaline hydrolysis residue and 0.58 × 10
3the alkali lignin concentrated solution of kg, and reclaim 2.78 × 10
3kg alkali lye.The solid content of this concentrated solution is 26.1% 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 0.6%, and the ash oontent of concentrated solution is 1.7%; And the rate of recovery of alkali is 87%.Alkali lignin solution extraction yield is 75%.
Alternatively, can, by 10% sulphur acid for adjusting pH value to 3 for the alkali lignin solution obtaining, filter the alkali lignin solid that washing obtains.
Comparative example 5
(1) N level acid hydrolysis
Method is with embodiment 5 steps (1), and difference is that the 1st, 2 and 3 grades of acid-hydrolyzed temperature are identical numerical value, and the numerical value of the rate of loss of the extraction yield of acid-hydrolyzed temperature, hemicellulose, cellulosic rate of loss and xylogen is in table 5.
Table 5
(2) cellulase hydrolysis
Get respectively three kinds of acid hydrolysis residues in comparative example 5A, comparative example 5B, comparative example 5C step (1), carry out cellulase hydrolysis, method is with embodiment 5 steps (2), and cellulosic extraction yield is in table 6:
Table 6
| Cellulosic extraction yield | |
| Comparative example 5A | 55％ |
| Comparative example 5B | 74％ |
| Comparative example 5C | 52％ |
(3) alkaline solution extracts alkali alkali lignin
Get respectively three kinds of enzymolysis residues in comparative example 5A, comparative example 5B, comparative example 5C step (2), method is with embodiment 5 steps (3), the rate of recovery table 7 of content, ash content and the alkali lye of the however, residual base of alkali lignin extraction yield, alkali lignin concentrated solution
Table 7
Test case 1
In the phenol of 10Kg, the alkali lignin concentrated solution that adds respectively 30Kg embodiment 2, comparative example 2 and 3 to obtain, is warming up to 70 DEG C, adds the sodium hydroxide solution (mass percent concentration is 50) of 1Kg, air distillation to 150 DEG C, back flow reaction 90 minutes, is cooled to 70-80 DEG C, adds 11Kg formaldehyde (mass percent concentration is 37%) reaction 90 minutes, be cooled to 50 DEG C, regulate pH to 6.5-7, vacuum hydro-extraction is to viscosity 9000cp/25 DEG C left and right, discharging.The alkali lignin concentrated solution that finally can be obtained by embodiment 2 and comparative example 2,3 makes respectively lignin modification resol, and its performance index are tested by the following method, and property indices is listed in table 8:
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 HG5 1342.
The mensuration of the free aldehyde of resol: carry out according to HG5 1343.
The mensuration of phenolic resin gel time: carry out according to HG5 1338.
The mensuration of water-content in resol: carry out according to HG5 1341.
The mensuration of resol pH value: carry out according to HG/T 2501.
The performance index of the modified phenolic resins of table 8 Different Alkali xylogen concentrated solution
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 directly to concentrate the alkali lignin solution obtaining, and without water washing, the content of however, residual base and ash oontent are all higher, have 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 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.
In each embodiment, be only reduced to example with amplitudes such as temperature above, but according to principle of the present invention and experiment test, the amplitude such as non-reduces also can realize object of the present invention, does not repeat them here.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also giving exhaustive to all embodiments.And the apparent variation of being extended out thus or variation are still among the protection domain in the invention.
Claims (12)
1. a method of comprehensive utilization for lignocellulose biomass, is characterized in that comprising the following steps:
(a) lignocellulose biomass is carried out to the acid hydrolysis of N level, the acid-hydrolyzed reactor of N level is end to end, one of them reactor is made as to the first step, last is made as N level, the acid solution of new preparation adds in first step acid hydrolytic reaction still, the acid solution that first step acid hydrolytic reaction still is discharged adds in the acid hydrolytic reaction still of the second stage, the acid solution of discharging in the acid hydrolytic reaction still of the second stage adds in third stage acid hydrolytic reaction still, order successively, until the acid solution that N-1 level acid hydrolytic reaction still is discharged adds in N level acid hydrolytic reaction still, the acid solution that N level acid hydrolytic reaction still is discharged is final pentose solution, take out the acid hydrolysis residue in first step acid hydrolytic reaction still, then pack new lignocellulose biomass raw material into, then using first step acid hydrolytic reaction still as N level acid hydrolytic reaction still, using second stage acid hydrolytic reaction still as first step acid hydrolytic reaction still, third stage acid hydrolytic reaction still is as second stage acid hydrolytic reaction still, until N level acid hydrolytic reaction still is as N-1 level acid hydrolytic reaction still, reaction is again hydrolyzed, so move in circles and can realize the hydrolysis to lignocellulose biomass, wherein, the acid-hydrolyzed temperature of the first step is 100-150 DEG C, and every grade is reduced 5-25 DEG C step by step subsequently, the integer that described N is 2-5,
(b) use cellulase to carry out enzymolysis to acid hydrolysis residue described in step (a), obtain glucose solution and enzymolysis residue;
(c) the described enzymolysis residue producing with alkaline solution treatment step (b), thus the alkali lignin in described enzymolysis residue extracted.
2. according to the method described in claim 1, it is characterized in that: the acid-hydrolyzed temperature of the first step is 120-140 DEG C, every grade is reduced 10-20 DEG C step by step subsequently.
3. according to the method described in any one in claim 1 or 2, it is characterized in that: described cellulase is to cultivate by a penicillium cellulase obtaining, and 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.
4. method according to claim 3, 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 DEG C, pH are that 4-6, mixing speed are 50-200rpm, and enzymolysis transformation time is 2-7 days.
5. method according to claim 4, is characterized in that: the concrete steps of described step (c) are: (I) processes described enzymolysis residue with alkaline solution makes lignin dissolution wherein in alkaline solution; (II) then filter, wash and obtain solid and liquid; (III) is by the separation of gained liquid process film device, the concentrated alkali lignin solution that obtains.
6. according to the method described in claim 5, it is characterized in that: in described step (III), also comprise the described concentrated alkali lignin solution dilute with water again obtaining, and then concentrated step.
7. according to the method described in claim 5 or 6, it is characterized in that: in described step (III), also comprise the alkali lignin solution process neutralization obtaining, filter and be dried, obtain the step of alkali lignin solid.
8. method according to claim 7, 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.
9. method according to claim 8, is characterized in that: described alkaline solution is processed and carried out at 40-100 DEG C.
10. the method described in any one according to Claim 8 or 9, is characterized in that: described alkaline solution process in liquid-solid volume ratio be 5:1-20:1.
11. methods according to claim 10, is characterized in that: in described alkaline solution processing, the concentration of alkaline solution is 5-8 % by weight.
12. methods according to claim 11, is characterized in that: the time of described alkaline solution processing is 1-6 hour.
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