CN103045691B - 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 hydrolysis on the lignocellulose biomass, wherein reaction kettles of the N-stage hydrolysis are connected end to end, one of the reaction kettle is designed as a first stage and a final reaction kettle is designed as an N stage, a freshly prepared acid solution is added in the first stage reaction kettle, a final pentose solution obtained by hydrolysis is discharged from the N stage reaction kettle, final acid hydrolysis residues obtained by acid hydrolysis are discharged from the first stage reaction kettle, and new materials are loaded on the first stage reaction kettle, the first stage hydrolysis reaction time is 1-4 hours, the subsequent hydrolysis reaction time is reduced by 0.25-1.5 hours 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; and (c) treating the enzymatic hydrolysis residues produced in 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, take lignocellulose biomass as raw material production ethanol, will greatly solve the mankind's energy problem, but still exist in this respect a lot of technical barriers not yet to solve.At present, take lignocellulose biomass in raw material production ethanol process, the first problem running into is that hemicellulose, Mierocrystalline cellulose and xylogen are failed to fully utilize well, the Technology of existing processing biomass, mainly with degraded carbohydrate, obtaining ethanol is greatly object, can not extract simultaneously and obtain high purity, highly active xylogen, often xylogen 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.
As disclosed a kind of combined pretreatment method and system thereof of lignocellulose biomass in CN100564667C, after being pulverized, lignocellulose biomass packs in circulating reaction still, and inject diluted acid, opening recycle pump is to carry out circulating reaction at 50 ℃-200 ℃ in temperature, reaction finish after by the hydrolyzed solution obtaining; After remaining lignocellulose rinses in circulating reaction still, put into ball mill and add alkali lye and carry out ball milling, further except delignification, ball milling complete except after alkali for follow-up enzymolysis, obtain ethanol.This patent adopts an acidolysis to remove hemicellulose can cause two disadvantageous effects, on the one hand, if want, remove as much as possible hemicellulose and need adopt higher temperature and/or long reaction times, cause like this pentose of hydrolysis in early stage under the reaction times of comparatively high temps and/or length, 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 alkali lignin, 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, thereby can not recycle xylogen and 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 take 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, as support frame, surround and add set Mierocrystalline cellulose and hemicellulose, xylogen and hemicellulose spatially can hinder contacting of cellulosic molecule and enzyme, enzyme accessibility is poor, has increased the difficulty of enzymolysis.Therefore be necessary lignocellulose biomass to carry out effective pre-treatment, destroy the spatial obstacle of xylogen and hemicellulose, also to avoid pre-treatment to produce simultaneously and be unfavorable for the enzyme inhibitor (as furfural, acetic acid etc.) of enzymolysis, thereby be conducive to cellulosic enzymolysis; On the other hand, 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, by two-step approach, produce furfural, 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 time in hydrolytic reaction pots at different levels is identical, therefore large to xylogen and cellulosic destructive rate, and the enzyme inhibitors such as the furfural, acetic acid that generate 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 to overcome while fully utilizing Mierocrystalline cellulose, hemicellulose and xylogen in prior art, 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 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 N level acid hydrolytic reaction still, the acid solution that N level acid hydrolytic reaction still is discharged is final pentose solution, then take out the acid hydrolysis residue in first step acid hydrolytic reaction still, then pack new lignocellulose biomass raw material into, again 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 hydrolysis moves in circles and can realize the continuous hydrolysis of lignocellulose biomass,
Wherein, the time of first step hydrolysis reaction is 1-4 hour, and the time of hydrolysis reaction at different levels reduces 0.25-1.5 hour 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 solution and enzymolysis residue that main component is glucose;
(c) the described enzymolysis residue producing with alkaline solution treatment step (b), thus the alkali lignin in described enzymolysis residue extracted.
Further, the time of described first step hydrolysis reaction is 1.5-3 hour, and the time of hydrolysis reaction at different levels reduces 0.5-1 hour 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 of using, and for example acid can be one or more in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
The concentration of the acid-hydrolyzed temperature of described N level, pressure and acid solution is not particularly limited, can be the concentration that lignocellulose biomass carries out acid-hydrolyzed conventional temperature, pressure and acid solution, for example in the acid hydrolysis of described N level, the temperature of every grade of hydrolysis reaction is 100-150 ℃, and pressure is 0.1-0.47MPa.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, 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 concentration of preferably phosphoric acid is 1-20 % by weight.
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, wheat straw, rice straw, bagasse, cotton bavin, cotton seed hull, corn cob, straw, kaoliang stalk, broad-leaved wood and wood chip.
According to raw material condition, carry out pre-treatment, lignocellulose biomass raw material is cut or pulverized, then this stalk section is carried out to scrubbing dust collection.
Described 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.Take 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 ℃, 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) with alkaline solution, processing described enzymolysis residue 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.
At alkaline solution described in institute's step (i), process and carry out at 40-100 ℃.
In alkaline solution described in institute's step (i) is processed, liquid-solid volume ratio is 5: 1-20: 1.
Time in alkaline hydrolysis processing described in described step (i) 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 first N level hydrolysis, enzymolysis again, the operational path of last alkaline hydrolysis processing, and in hydrolytic process, adopted the method that reduces step by step to N order reaction still hydrolysis time from first step reactor (first step hydrolysis reaction be 1-4 hour, the time of hydrolysis reaction at different levels reduces 0.25-1.5 hour step by step subsequently), the method can adopt the different acid-hydrolyzed time according to the complexity of hemicellulose acidolysis and pentose damaed cordition, because the material in N order reaction still is new material, hemicellulose is more easily removed, therefore the time of hydrolysis reaction is shorter, in addition, in N order reaction still, the concentration of pentose is the highest, time of hydrolysis reaction is shorter 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, the time length of hydrolysis reaction is 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, also shortened in addition the working time of whole technique, improved production efficiency,
Adopt aforesaid method to make more than the later half cellulosic extraction yield of acidolysis 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, the present invention adopts is the acidolysis of first N level, the operational path of enzymolysis, last alkaline hydrolysis again, due to acidolysis complete after residue be subacidity, so do not need first acidolysis, the operational path of alkaline hydrolysis, last enzymolysis again, before enzymolysis, need substrate to neutralize, 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, the main component of enzymolysis residue is xylogen, therefore, extracts alkali lignin ratio be easier to alkaline solution, has reduced the consumption of alkaline solution, has also reduced the pollution to environment;
As can be seen here, by aforesaid method of the present invention, solved the problem of complex utilization of lignocellulose biomass in prior art, 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 time of the hydrolysis reaction of the first step described in the present invention is 1.5-3 hour, the time of hydrolysis reaction at different levels reduces 0.5-1 hour step by step subsequently, above-mentioned scope can guarantee under the higher prerequisite of hemicellulose extraction yield, lower to xylogen and cellulosic destructive rate, and the furfural generating and the enzyme inhibitors such as acetic acid are still less.
4, the present invention has adopted film device to separate and concentrated step in alkaline hydrolysis step, has improved the purity of alkali lignin, is conducive to produce high value-added product.
5, after the present invention concentrates wooden alkali solution, dilute with water, again concentrated, further reduced the ash oontent in alkali lignin solution, the content of however, residual base, has improved solid content, is more 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, because major part in enzymolysis residue is xylogen, so can, in the lower realization of lower temperature (40-100 ℃) to lignin extraction, 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, avoided that liquid-solid ratio is too little is unfavorable for that liquid-solid mixing is also unfavorable for the alkaline hydrolysis of xylogen, it is large that the too large follow-up alkali of liquid-solid ratio reclaims load, and the wastewater flow rate of generation is also large, uneconomic problem.
9, the condition of alkaline solution processing of the present invention adopts the liquid-solid ratio, alkali consumption, the temperature and time that are more preferably, and the activity of the alkali lignin finally obtaining is very high, and the xylogen therefore finally obtaining is particularly suitable for producing the products such as modified phenolic resins.
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, at substrate consumption, be 80-150g/L, the addition of cellulase is 10-15FPU/g Mierocrystalline cellulose, temperature is that 45-55 ℃, pH are that 4-6, mixing speed are 50-200rpm, enzymolysis transformation time is that under the condition of 2-7 days, enzymolysis transformation efficiency is the highest.
Accompanying drawing explanation
For content of the present invention is more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein:
Fig. 1 is the schematic diagram of technical process of the present invention;
Fig. 2 is the schematic flow sheet that alkaline solution of the present invention extracts alkali lignin;
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
By naming number, be that PenicilliumdecumbensPD-G3-08 Penicillium notatum seed liquor is linked in the fermentor tank that contains seed culture medium through 121 ℃ of sterilizing 30min and activates with the inoculum size of 5% (v/v), keep tank pressure 0.02-0.05MPa, air flow 0.5vvm, mixing speed 100-150rpm, 30 ℃ of cultivation 30-60 hour, the seed liquor after being activated.
Component in described seed culture medium and consumption are: get embodiment 1 acid hydrolysis residue 10-30g/L, wheat bran 20-50g/L, peptone 1-4g/L, ammonium sulfate 2-4g/L, all the other are water.
Component and consumption in described seed culture medium are preferably: acid hydrolysis residue 20g/L, wheat bran 40g/L, peptone 3g/L, ammonium sulfate 3g/L, all the other are water.
(B) prepare cellulase
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 ℃ of cultivation 80-136 hour, obtain fermented liquid.
In described fermention medium, each amounts of components is respectively: acid hydrolysis residue 30-50g/L, wheat bran 20-50g/L, Microcrystalline Cellulose or carboxymethyl cellulose 4-8g/L, ammonium sulfate 2-5g/L, potassium primary phosphate 2-4g/L, magnesium sulfate 0.4-0.6g/L, all the other are water, and the initial pH of substratum is 5.0-6.0.
In described fermention medium, each amounts of components is preferably: acid hydrolysis residue 45g/L, wheat bran 35g/L, Microcrystalline Cellulose 5g/L, ammonium sulfate 4g/L, potassium primary phosphate 3g/L, magnesium sulfate 0.6g/L, all the other are water, and the initial pH of substratum is 5.0-6.0.
The fermented liquid 8000rpm centrifuging and taking obtaining obtains supernatant liquor, must contain the crude enzyme liquid of cellulase, and this crude enzyme liquid can be directly used in cellulosic enzymolysis.
(2) test as follows the various performances of xylogen in following examples
The mensuration of content of lignin: comprise sour insoluble xylogen and sour solvable xylogen.Wherein the mensuration of sour insoluble xylogen adopts Klason method, according to GB GB/T2677.8-94, carries out; The solvable xylogen of acid carries out according to GB 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 alkali lignin solution: get 100g solution to be measured, at 105 ℃, dry 24 hours, be cooled to room temperature, weigh the quality of remaining solid, this total mass number is the percentage ratio of the solid content of solution.
The mensuration of alkali content in alkali lignin solution and recovery alkali lye: get 0.5-1g testing liquid, make indicator with phenolphthalein, the hydrochloric acid soln of 0.2M/L is made titration reagent, is titrated to terminal, calculates the content of however, residual base in solution according to consumed hydrochloric acid volumeter.
Following examples are participated in 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 for each embodiment, provides pressure data.
In following examples, outside specified otherwise, percentage composition used all represents weight percentage, i.e. " % " expression " % by weight ".
Embodiment 1
(1) N level 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 is 2.95% years old) smash, then 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 hydrolytic reaction pot of the second stage, the acid solution that second stage solution reaction kettle is discharged adds in third stage hydrolytic reaction pot, the acid solution that third stage reactor is discharged is final pentose solution, and take out the acid hydrolysis residue in first step hydrolytic reaction pot, then pack new corn cob raw material into, now using former first step hydrolytic reaction pot as new third stage reactor, using former second stage reactor as new first step reactor, former third stage reactor is as new second stage reactor, proceed hydrolysis reaction, so hydrolysis moves in circles and can realize the continuous acid hydrolysis of corn cob.
Wherein, the time of first step hydrolysis reaction is 1.5 hours, and the time of second stage hydrolysis reaction is 1.0 hours, the time of third stage hydrolysis reaction is 0.5 hour, every grade of acid-hydrolyzed temperature is that 130 ℃, pressure are 0.27MPa, and acid solution is phosphate aqueous solution, and the mass concentration of phosphoric acid solution is 10%; 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 1.0 × 10
3the water of kg is washed described acid hydrolysis residue, and water lotion and acid hydrolysis solution merge, and the weight that finally obtains acid hydrolysis residue is 1.73 × 10
3kg (water ratio is 65% left and right, and the over dry content of hemicellulose is 7.33%, and cellulosic over dry content is 52.61%, and the over dry content of xylogen is 34.86%), pentose solution 8.27 × 10
3kg, pentose concentration is 3.59%, the extraction yield of hemicellulose is 87%.
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 to the reaction times 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 all acid hydrolytic residue that step (1) obtains as cellulosic substrate, according to the cellulosic addition of 15FPU/g, add cellulase, cellulosic substrate consumption is 125g/L, in temperature, be that 48 ℃, pH are 5.0, under the condition of mixing speed 50rpm, enzymolysis transforms 2 days, and whole enzymolysis process, without pressurize, obtains 0.95 × 10
3kg enzymolysis residue (water ratio is 65% left and right), also obtains glucose solution, and quality is 4.84 × 10
3kg, concentration is 5.58%, cellulosic extraction yield is 72%.
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 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 ℃, 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 0.36 × 10
3kg alkaline hydrolysis residue (water ratio is 65% left and right) and 2.63 × 10
3kg alkali lignin solution, the alkali lignin content in solution is 7.41%, the extraction yield of alkali lignin is 77%.
The calculation formula of alkali lignin extraction yield 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
Raw material and method are with embodiment 1 step (1), and time 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 the extraction yield of acid-hydrolyzed time, hemicellulose, cellulosic rate of loss and xylogen is in Table 1.
Table 1
(2) cellulase hydrolysis
Get respectively all acid hydrolytic residue obtaining in comparative example 1A, comparative example 1B, comparative example 1C step (1), according to the method for embodiment 1 step (2), carry out cellulase hydrolysis, cellulosic extraction yield is in Table 2.
Table 2
| Mierocrystalline cellulose extraction yield | |
| Comparative example 1A | 58％ |
| Comparative example 1B | 60％ |
| Comparative example 1C | 40％ |
(3) alkaline solution extracts alkali lignin
Three kinds of enzymolysis residues getting respectively in comparative example 1A, comparative example 1B, comparative example 1C step (2) carry out alkaline hydrolysis processing, and method is with embodiment 1 step (3).The extraction yield of alkali lignin is in Table 3:
Table 3
Embodiment 2
(1) N level acid hydrolysis
Raw material and method are with embodiment 1 step (1), and difference is: the time of first step hydrolysis reaction is 3 hours, and the time of second stage hydrolysis reaction is 2 hours, and the time of third stage hydrolysis reaction is 1 hour, and every grade of acid-hydrolyzed temperature is 110 ℃; The weight that obtains acid hydrolysis residue is 1.66 × 10
3kg (water-content 65% left and right, the over dry content of hemicellulose is 6.44%, cellulosic over dry content is 52.9%, the over dry content of xylogen is 35.27%), pentose solution is 8.33 × 10
3kg, pentose concentration is 3.64%, the extraction yield of hemicellulose is 89%.
(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, according to the cellulosic addition of 10FPU/g, add cellulase, cellulosic substrate consumption is 150g/L, in temperature, be that 55 ℃, pH are 4, under the condition of mixing speed 200rpm, enzymolysis transforms 7 days, and whole enzymolysis process is without pressurize.Obtain 0.89 × 10
3kg enzymolysis residue (water ratio is 65% left and right) and 4.46 × 10
3kg glucose solution, concentration is 5.96%, cellulosic extraction rate reached 71%.
(3) alkaline solution extracts alkali lignin
Whole enzymolysis residues that the present embodiment step (2) is obtained mix with sodium hydroxide solution, and wherein liquid-solid volume ratio is 10: 1, and the concentration of sodium hydroxide is 6%, then be warming up to 70 ℃, 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 0.33 × 10
3kg alkaline hydrolysis residue (water ratio is 65% left and right) and 4.12 × 10
3kg alkali lignin solution; Alkali lignin solution with film device separate concentrated after, add 1.0 × 10
3the dilution of kg water, reconcentration, finally obtains 0.77 × 10
3the alkali lignin concentrated solution of kg, and reclaim 4.35 × 10
3kg alkali lye.The solid content of this concentrated solution is 25.8% after measured, and the alkali lignin content of concentrated solution is 24%, and the content of the however, residual base of concentrated solution is 0.6%, and the ash oontent of concentrated solution is 1.8%, and the extraction yield of alkali lignin is 73%; And the content of alkali is 3.5% in the alkali lye reclaiming, the rate of recovery of alkali is 81%.
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, method is with embodiment 2 steps (3), difference is: the temperature of alkaline hydrolysis is 170 ℃, and the rate of recovery of content, ash content and the alkali lye of the extraction yield of alkali lignin, the however, residual base of alkali lignin concentrated solution is in Table 4.
Table 4
Embodiment 3
(1) N level acid hydrolysis
Raw material and method are with embodiment 1 step (1), difference is, the time of first step hydrolysis reaction is 1 hour, and the time of second stage hydrolysis reaction is 0.75 hour, the time of third stage hydrolysis reaction is 0.5 hour, and the concentration of every grade of acid-hydrolyzed phosphoric acid is 15%; The weight that finally obtains acid hydrolysis residue is 1.80 × 10
3kg (water-content 65% left and right, the over dry content of hemicellulose is 10.27%, cellulosic over dry content is 50.74%, the over dry content of xylogen is 34.01%), pentose solution is 8.20 × 10
3kg, pentose concentration is 3.37%, the extraction yield of hemicellulose is 81%.
(2) cellulase hydrolysis
Above-mentioned acid hydrolysis residue is carried out to enzymolysis, method according to embodiment 1 step (2) is carried out cellulase hydrolysis, difference is: the condition of described enzymolysis is: cellulase is aforementioned Penicillium notatum (PenicilliumdecumbensPD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195) cultivate cellulase; Obtaining enzymolysis residue is 0.98 × 10
3kg (water ratio is 65% left and right) and 5.05 × 10
3kg glucose solution, concentration is 5.57%, cellulosic extraction rate reached 75%.
(3) alkaline solution extracts alkali lignin
Whole enzymolysis residues that the present embodiment step (2) is obtained, carry out alkaline solution processing according to the method for embodiment 2 steps (3), and difference is, liquid-solid volume ratio is 10: 1, the concentration of sodium hydroxide is 8%, and the temperature of alkaline solution is 40 ℃, and the time is 6 hours.Finally obtain 0.39 × 10
3kg alkaline hydrolysis residue (water ratio is 65% left and right) and 0.81 × 10
3kg alkali lignin concentrated solution, the solid content of this concentrated solution is 25.8% 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 0.7%, and the ash oontent of concentrated solution is 1.4%, the extraction yield of alkali lignin is 78%; And the content of alkali is 5.05% in the alkali lye reclaiming, the rate of recovery of alkali is 84%.
Comparative example 4
Get the acid hydrolysis residue that embodiment 3 steps (1) obtain, according to the method for embodiment 1 step (2), carry out cellulase hydrolysis, obtain glucose solution and enzymolysis residue, the quality of glucose solution is 5.05 × 10
3kg, concentration is 4.01%, cellulosic extraction rate reached 54%.
Embodiment 4
(1) N level acid hydrolysis
Technique and method be with embodiment 2 steps (1), and difference is, raw material is 1.11 × 10
3kg Wheat Straw (mass component composition: moisture 10.1%, Mierocrystalline cellulose 44%, hemicellulose 22.2%, xylogen 17%, other 6.7%), every grade of acid-hydrolyzed temperature is 100 ℃, acid solution is 1% sulphuric acid soln, the time of first step hydrolysis reaction is 4 hours, the time of second stage hydrolysis reaction is 2.5 hours, and the time of third stage hydrolysis reaction is 1 hour; 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%), pentose solution is 8.14 × 10
3kg, pentose concentration is 2.76%, hemicellulose extraction yield is 91%.
(2) cellulase hydrolysis
Get all acid hydrolytic residue obtaining in the present embodiment step (1) and carry out cellulase hydrolysis, the condition of described enzymolysis is: cellulase is above-mentioned Penicillium notatum (Penicillium decumbens PD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195) cultivate obtain cellulase, get whole residues that the described alkaline solution processing of the present embodiment step (2) obtains as cellulosic substrate, according to the cellulosic addition of 12FPU/g, add cellulase, cellulosic substrate consumption is 80g/L, in temperature, it is 45 ℃, pH is 6, under the condition of mixing speed 200rpm, enzymolysis transforms 5 days, whole enzymolysis process is without pressurize.Obtain 0.83 × 10
3kg enzymolysis residue (water ratio is 65% left and right) and 8.78 × 10
3kg glucose solution, concentration is 4.07%, cellulosic extraction rate reached 73%.
(3) alkaline solution extracts alkali lignin
Whole enzymolysis residues that the present embodiment step (2) is obtained, carry out alkaline solution processing according to the method for embodiment 2 steps (3), and difference is, liquid-solid volume ratio is 20: 1, the concentration of sodium hydroxide is 5%, and the temperature of alkaline solution is 100 ℃, and the time is 2 hours.Finally obtain 0.39 × 10
3kg alkaline hydrolysis residue (water ratio is 65% left and right) and 0.58 × 10
3kg alkali lignin concentrated solution, the solid content of this concentrated solution is 25.9% after measured, and the alkali lignin content of concentrated solution is 24.4%, and the content of the however, residual base of concentrated solution is 0.8%, and the ash oontent of concentrated solution is 1.5%, the extraction yield of alkali lignin is 75%; And the content of alkali is 3.14% in the alkali lye reclaiming, the rate of recovery of alkali is 77%.
Alternatively, can, by 10% sulphur acid for adjusting pH value to 3 for the alkali lignin solution obtaining, filter washing, the dry alkali lignin solid that obtains.
Comparative example 5
(1) N level acid hydrolysis
Method is with embodiment 4 steps (1), and time when difference is the 1st, 2 and 3 grades of acid hydrolysiss in reactor is identical numerical value, and the numerical value of the rate of loss of the extraction yield of hemicellulose, cellulosic rate of loss and xylogen is in Table 4.
Table 4
(2) cellulase hydrolysis
The all acid hydrolytic residue obtaining in this comparative example step (1) is carried out to cellulase hydrolysis according to the method for embodiment 4 steps (2), and Mierocrystalline cellulose extraction yield is in Table 5.
Table 5
| Mierocrystalline cellulose extraction yield | |
| Comparative example 5A | 60％ |
| Comparative example 5B | 67％ |
| Comparative example 5C | 48％ |
(3) alkaline solution extracts alkali lignin
Three kinds of enzymolysis residues getting this comparative example step (2), carry out alkaline hydrolysis processing according to the method for embodiment 4 steps (3).The rate of recovery of content, ash content and the alkali lye of the extraction yield of alkali lignin, the however, residual base of alkali lignin concentrated solution is in Table 6:
Table 6
Above in each embodiment, only take three grades of acid hydrolysiss as example.But according to the trend of test-results, acid hydrolysis progression is more, is more conducive to farthest extract hemicellulose.But from the angle of economy, the first step extract hemicellulose at most, the most obvious, the hemicelluloses that extract at different levels more backward less, more insignificant.From test, recognize equally, the hemicellulose that the later acid hydrolysis of Pyatyi can be extracted has lost industrial economic worth significantly, and high to xylogen and cellulosic destruction.Therefore in this case, preferably acid hydrolysis progression is 3-5 level.
Test case 1
In the phenol of 10kg, the alkali lignin concentrated solution that adds respectively 3kg embodiment 2 and comparative example 2,3 to obtain, is warming up to 70 ℃, adds the sodium hydroxide solution (mass percent concentration is 50) of 1kg, air distillation to 150 ℃, back flow reaction 90 minutes, is cooled to 70-80 ℃, adds 11kg (mass percent concentration is 37%) reaction 90 minutes, be cooled to 50 ℃, regulate pH to 6.5-7, vacuum hydro-extraction is to viscosity 9000cp/25 ℃ left and right, discharging.The alkali lignin concentrated solution that finally can be obtained by embodiment 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/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 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 8 Different Alkali lignin liquor
In the resol product that three kinds of Different Alkali lignin liquors obtain, the content of phenol and formaldehyde raises gradually, illustrate the alkali lignin solution that adds not only with formaldehyde between the activity of reacting die down gradually, but also affected reacting to each other of phenol and formaldehyde.The first alkali lignin solution is the alkali lignin solution that the present invention obtains, and the content of its however, residual base and ash oontent are all lower, does not substantially affect reacting between alkali lignin and phenol and formaldehyde; The second alkali lignin solution is 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 the activity during with formaldehyde reaction weakens greatly.
The lignin liquor of 25% left and right that industrial soda xylogen (Gaotang, Shandong polynary xylogen company limited) is made into if directly use, synthesis technique and method are constant, method according to test case 1 is prepared modified phenolic resins, regulate after pH value, only at the bottom of bottle, there is a small amount of resin to produce, see that on the whole alkali lignin solution does not participate in reaction, after decompression dehydration, at the bottom of bottle, find that there is alkali lignin precipitation, cannot obtain alkali lignin modified novolac resin.
In sum, the alkali lignin solution that known the present invention obtains has higher activity, can be in order to prepare the products such as modified phenolic resins.
In each embodiment, only with amplitudes such as times, be reduced to example 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 (13)
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 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 N level acid hydrolytic reaction still, the acid solution that N level acid hydrolytic reaction still is discharged is final pentose solution, then take out the acid hydrolysis residue in first step acid hydrolytic reaction still, then pack new lignocellulose biomass raw material into, again 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 hydrolysis moves in circles and can realize the continuous hydrolysis of lignocellulose biomass, wherein, the time of first step hydrolysis reaction is 1-4 hour, and the time of hydrolysis reaction at different levels reduces 0.25-1.5 hour step by step subsequently, and N is more than or equal to 2 integer,
(b) with cellulase, acid hydrolysis residue described in step (a) is carried out to enzymolysis, obtain solution and enzymolysis residue that main component is glucose;
(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 time of described first step hydrolysis reaction is 1.5-3 hour, the time of hydrolysis reaction at different levels reduces 0.5-1 hour step by step subsequently.
3. according to the method described in claim 2, it is characterized in that: the integer that described N is 3-5.
4. according to the method described in any one in claim 1-3, 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 CCTCCM2011195.
5. method according to claim 4, it is characterized in that: the condition of described cellulase hydrolysis is: substrate consumption is 80-150g/L, the addition of cellulase is 10-15FPU/g Mierocrystalline cellulose, temperature is that 45-55 ℃, pH are that 4-6, mixing speed are 50-200rpm, and enzymolysis transformation time is 2-7 days.
6. method according to claim 5, is characterized in that: the concrete steps of described step (c) are:
(I) processes described enzymolysis residue with alkaline solution, makes lignin dissolution in enzymolysis residue 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.
7. according to the method described in claim 6, 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.
8. according to the method described in claim 6 or 7, 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.
9. method according to claim 8, is characterized in that: in described step (III), be also included in the concentrated step that obtains described alkali lignin solution afterwards or recycle alkaline solution wherein simultaneously.
10. method according to claim 9, is characterized in that: at alkaline hydrolysis described in described step (I), process and carry out at 40-100 ℃.
11. according to the method described in claim 9 or 10, it is characterized in that: in alkaline hydrolysis described in described step (I) is processed, liquid-solid volume ratio is 5:1-20:1.
12. methods according to claim 11, is characterized in that: the time of described (I) step process is 1-6 hour.
13. methods according to claim 12, is characterized in that: in described alkaline hydrolysis processing, the concentration of alkaline solution is 5-8 % by weight.
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