CN103045693A - 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 reaction kettles of the N-stage acid 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) treating the acid hydrolysis residues by using an alkali solution, so that alkali lignin is extracted; and (c) performing enzymatic hydrolysis on the alkali hydrolysis residues obtained by alkali hydrolysis treatment in the step (b) by using cellulase, so that a solution with glucose as a main component is obtained. 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 the lignocellulose biomass, hemicellulose and xylogen.
Background technology
Day by day serious along with the increasingly exhausted and environmental pollution of fossil fuel resource utilizes the renewable energy resources to become further important for the substitute of petroleum chemicals.And alcohol fuel is the principal mode of the material of biomass liquid energy, also is the most probable substitute of fossil oil.At present, world's alcohol production is mainly with starch based (corn, cassava etc.) and carbohydrate (sugarcane, the beet etc.) raw material as fermentation.Adopt microbial method fermentative production of ethanol technology maturation, but high raw materials cost is restricted the industrial application of grain fermentative production of ethanol, simultaneously existence strives grain with the people and grain is striven the drawbacks such as ground, and causes the provision price Continued, and it is imperative therefore to seek new raw material.Scientist invests more cheap, the widely lignocellulose biomass of originating of cost to sight now.
Lignocellulose biomass exists with the form of plant materials, main component is Mierocrystalline cellulose, hemicellulose and xylogen, wherein, Mierocrystalline cellulose accounts for about 40%, hemicellulose accounts for about 25%, xylogen accounts for about 20%, and the annual lignocellulose biomass total amount that is generated by photosynthesis surpasses 2,000 hundred million tons on the earth, so lignocellulose biomass is renewable resources abundant, the most cheap on the earth.
If can take lignocellulose biomass as raw material production ethanol, will greatly solve human energy problem, but still exist in this respect a lot of technical barriers not yet to solve.At present, take lignocellulose biomass in the raw material production ethanol process, the first problem that runs into is that hemicellulose, Mierocrystalline cellulose and xylogen are failed to fully utilize well, the existing Technology of processing biomass, obtaining ethanol mainly with the degraded carbohydrate greatly is purpose, can not extract simultaneously and obtain high purity, highly active xylogen, often xylogen is removed object as one, simultaneously in double cellulosic utilization, also there is the shortcoming that generates a lot of cellulase inhibitors, finally also can affects the productive rate of ethanol.
Such as combined pretreatment method and the system thereof that in CN100564667C, discloses a kind of lignocellulose biomass, in the circulating reaction still of packing into after the lignocellulose biomass pulverizing, and injection diluted acid, opening recycle pump is to carry out circulating reaction under 50 ℃-200 ℃ in temperature, after reaction finishes with the hydrolyzed solution that obtains; In the circulating reaction still after the remaining lignocellulose flushing, put into ball mill and add alkali lye and carry out ball milling, further except delignification, ball milling is complete except being used for follow-up enzymolysis behind the alkali, obtains 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 to remove as much as possible hemicellulose, 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 the enzymolysis transformation efficiency; On the other hand, if do not adopt higher temperature and/or long reaction times, then contain more hemicellulose after the acidolysis in the residue, be unfavorable for that alkaline solution extracts alkali lignin, if wanting dissolved lignin as much as possible just needs to improve the temperature of alkali concn, alkaline purification and prolong 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.
Run into the low conversion rate that another problem is cellulase hydrolysis in take lignocellulose biomass as the process of raw material production ethanol, cause the high cost (accounting for the 40-50% of total cost of production) of enzymolysis, production cost is too high, can't really realize industrialization.The reason of the low conversion rate of cellulase hydrolysis is: hemicellulose is combined between Mierocrystalline cellulose and the xylogen as the molecule tamanori on the one hand, and the reticulated structure that xylogen has, surround and add set Mierocrystalline cellulose and hemicellulose as support frame, xylogen and hemicellulose spatially can hinder contacting of cellulosic molecule and enzyme, the enzyme accessibility is poor, has increased the difficulty of enzymolysis.Therefore be necessary lignocellulose biomass is carried out effective pre-treatment, destroy the spatial obstacle of xylogen and hemicellulose, also to avoid simultaneously pre-treatment to produce and be unfavorable for the enzyme inhibitor (such as furfural, acetic acid etc.) of enzymolysis, thereby be conducive to cellulosic enzymolysis; On the other hand, with the intermolecular hydrogen bond that exists, aggregated structure complexity and degree of crystallinity are high in the cellulosic molecule, and cellulase is low to crystalline cellulose enzymatic reaction vigour, therefore, in order to improve the transformation efficiency of cellulase hydrolysis, need to improve enzyme activity.
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 the agriculture and forestry organic waste material continuous hydrolysis is generated pentose solution.The shortcoming that above-mentioned N level acid hydrolysis system exists is, because hydrolysis time is identical in the hydrolytic reaction pots at different levels, therefore large to xylogen and cellulosic destructive rate, and the enzyme inhibitorss such as the furfural that generates, acetic acid are more, are unfavorable for the comprehensive utilization of lignocellulose biomass.
Summary of the invention
For this reason, technical problem to be solved by this invention is when overcoming the comprehensive utilization Mierocrystalline cellulose that exists in the prior art, hemicellulose and xylogen, can not obtain simultaneously highly active xylogen, higher hemicellulose and the problem of Mierocrystalline cellulose extraction yield, thereby propose a kind of method of lignocellulose biomass comprehensive utilization.
For achieving the above object, the invention provides a kind of method of comprehensive utilization of lignocellulose biomass, may further comprise the steps:
(a) lignocellulose biomass is carried out the acid hydrolysis of N level, the acid-hydrolyzed reactor of N level is end to end, one of them reactor is made as the first step, last is made as the 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 the third stage acid hydrolytic reaction still, successively sequentially, 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 the first step acid hydrolytic reaction still, the lignocellulose biomass raw material of then packing into new, again with first step acid hydrolytic reaction still as N level acid hydrolytic reaction still, with the second acid hydrolysis order 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, the reaction that is hydrolyzed again so 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 the integer more than or equal to 2;
(b) process described acid hydrolysis residue with alkaline solution, thereby extract alkali lignin;
(c) use cellulase that alkaline solution described in the step (b) is processed the alkaline hydrolysis residue that obtains and carry out enzymolysis, obtain the solution that main component is glucose.
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.Hydrolysis time is the residence time of acid solution in reactor herein.
There is no particular limitation for the kind of described acid solution, can be that lignocellulose biomass carries out the acid-hydrolyzed conventional acid of using, and for example acid can be in sulfuric acid, hydrochloric acid, nitric acid and the phosphoric acid one or more.
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 the temperature of every grade of hydrolysis reaction is 100-150 ℃ in the acid hydrolysis of described N level, and pressure is 0.1-0.47MPa.For example the concentration of the acid solution of every grade of hydrolysis reaction is that (as the acid of selecting is strong acid to the 0.5-30 % by weight in the acid hydrolysis of described N level, then the concentration of acid solution is lower, be about the 0.5-5 % by weight, as the acid of selecting is weak acid, then the concentration of acid solution is higher, be about 5-30%), the concentration of preferably phosphoric acid is the 1-20 % by weight.
Described N is the integer of 3-5.
Described lignocellulose biomass can be one or more of maize straw, wheat straw, rice straw, bagasse, cotton bavin, cotton seed hull, corn cob, straw, kaoliang stalk, broad-leaved wood and wood chip.
Carry out pre-treatment according to raw material condition, the lignocellulose biomass raw material is cut or pulverizes, then this stalk section is carried out scrubbing dust collection.
The concrete steps of described step (b) are:
(i) processing described acid hydrolysis residue through alkaline solution makes wherein lignin dissolution in alkaline solution;
(ii) then filter, wash and obtain solid and liquid;
(iii) with the separation of gained liquid process film device, the concentrated alkali lignin solution that obtains;
Also comprise again dilute with water of the described concentrated alkali lignin solution that obtains in the described step (iii), and then concentrated step.
Comprise also in the described step (iii) that the alkali lignin solution that will obtain through neutralization, filtration and dry, obtains the step of alkali lignin solid.
Also be included in the concentrated step that obtains after the described alkali lignin solution or recycle simultaneously alkaline solution wherein in the described step (iii).
Described alkaline solution is processed and is carried out under 40-100 ℃.
Liquid-solid volume ratio was 5 during described alkaline solution was processed: 1-20: 1.
The concentration of alkaline solution is the 5-8 % by weight.
The time that described alkaline solution is processed is 1-6 hour.
Various alkali may be used to the present invention, include but not limited to aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, ammoniacal liquor etc.But according to some preferred embodiment, alkaline solution is the aqueous solution of sodium hydroxide.
Described cellulase is for being cultivated the cellulase that obtains by a penicillium, this Penicillium notatum Classification And Nomenclature is that Classification And Nomenclature is Penicillium decumbens PD-G3-08, be preserved in Wuhan University Chinese Typical Representative culture collection center (being called for short CCTCC), depositary institution address: Wuhan University preservation center.The numbering of registering on the books is CCTCC M 2011195, and preservation date is on June 13rd, 2011.The cellulosic bacterial strain take this bacterial strain as enzymolysis.
The condition of described cellulase hydrolysis is: the substrate consumption is 80-150g/L, and the addition of cellulase is the 10-15FPU/g Mierocrystalline cellulose, and temperature is that 45-55 ℃, pH are that 4-6, mixing speed are 50-200rpm, and the enzymolysis transformation time is 2-7 days.
Technique scheme of the present invention compared with prior art has the following advantages:
1, the present invention has adopted the acid hydrolysis of first N level, alkaline hydrolysis again, the operational path of last enzymolysis, and in the acid hydrolysis process, adopted the method that reduces step by step to the N order reaction still acid hydrolytic reaction 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 hydrolysis time with the pentose damaed cordition according to the complexity of hemicellulose acidolysis, because the material in the N order reaction still is new material, hemicellulose is more easily removed, therefore the time of hydrolysis reaction short getting final product, in addition, the concentration of pentose is the highest in the N order reaction still, the time of hydrolysis reaction weak point can prevent from generating furfural and acetic acid, thereby reduce furfural and acetic acid to the restraining effect of cellulase; And for the material in the first step reactor, remove relatively difficulty of remaining hemicellulose, 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 so that the later half cellulosic extraction yield of acidolysis can reach more than 85 % by weight, cellulosic rate of loss is less than 20 % by weight, and the rate of loss of xylogen is less than 20 % by weight; In addition, because the structure of xylogen is not destroyed, so the activity of the xylogen that the process alkaline solution extracts is higher, can be directly as the raw material of producing other high value added product (such as resol); Hemicellulose owing to the overwhelming majority is extracted simultaneously, extracted by alkaline solution through most xylogen behind the alkaline hydrolysis, thereby eliminated cellulosic spatial obstacle, made the easier contact Mierocrystalline cellulose of cellulase, improved cellulosic extraction yield, reduced the usage quantity of cellulase, shortened enzymolysis time, reduced production cost, on the other hand, because the enzyme inhibitor that generates in the acidolysis process is less, has also improved cellulosic extraction yield; This shows, solved the problem of complex utilization of the lignocellulose biomass of prior art by aforesaid method of the present invention, make the utilization of resources reach maximization.
2, the preferred 3-5 level of described N level, it is both economical in this scope 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 (progression is more larger to xylogen and cellulosic destructive rate).
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 enzyme inhibitorss such as the furfural that generates and acetic acid are still less.
4, the present invention has adopted film device to separate and concentrated step in the alkaline hydrolysis process, has improved the purity of alkali lignin, is conducive to produce high value-added product.
5, the present invention concentrates the wooden solution with water dilution of alkali again, has further reduced the ash oontent in the alkali lignin solution, and the content of however, residual base has improved solid content, is more conducive to use xylogen to produce high value-added product.
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, owing to major part in hydrolytic residue is xylogen, so can in the lower realization of lower alkaline solution treatment temp (40-100 ℃) to lignin extraction, further protect the activity of xylogen.
8, the present invention adopts the relatively more suitable xylogen that extracts of liquid-solid volume ratio in the alkaline solution, avoided that liquid-solid ratio is too little to be unfavorable for that liquid-solid mixing also is unfavorable for the alkaline hydrolysis of xylogen, it is large that the too large follow-up alkali of liquid-solid ratio reclaims load, and the wastewater flow rate of generation is also large, uneconomic problem.
9, liquid-solid ratio, alkali consumption, the temperature and time of the condition employing of alkaline solution processing of the present invention, the activity of the alkali lignin that finally obtains is very high.
10, cellulase of the present invention is for being cultivated the cellulase that obtains by a penicillium, this Penicillium notatum Classification And Nomenclature is Penicillium decumbens PD-G3-08, be preserved in Wuhan University Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195, adopt the cellulase of this Penicillium notatum production to have higher vigor, further improved the extraction yield of cellulase hydrolysis.
11. what the present invention was used cultivates the cellulase that obtains by Penicillium notatum, be 80-150g/L at the substrate consumption, the addition of cellulase is the 10-15FPU/g Mierocrystalline cellulose, temperature is that 45-55 ℃, pH are that 4-6, mixing speed are 50-200rpm, under 2-7 days the condition of enzymolysis conversion, the enzymolysis transformation efficiency is the highest.
Description of drawings
For content of the present invention is more likely to be clearly understood, the below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein:
Fig. 1 is the synoptic 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 the used equipment synoptic diagram of N level acidolysis.
Embodiment
The below will the invention will be further described by specific embodiment.
(1) the employed self-control cellulase of following examples is cultivated by Penicillium notatum and is obtained, and concrete cultural method is:
(A) bacterial classification multiplication culture
To be Penicillium decumbens PD-G3-08 Penicillium notatum seed liquor with the inoculum size of 5% (v/v) be linked in the fermentor tank that contains seed culture medium through 121 ℃ of sterilization 30min activates with naming number, keep tank pressure 0.02-0.05MPa, air flow 0.5vvm, mixing speed 100-150rpm, 30 ℃ to cultivate the seed liquor after obtaining activating 30-60 hour.
Component in the described seed culture medium and consumption are: get embodiment 1 acid hydrolysis residue 10-30g/L, wheat bran 20-50g/L, peptone 1-4g/L, ammonium sulfate 2-4g/L, all the other are water.
Component and consumption in the described seed culture medium are preferably: acid hydrolysis residue 20g/L, wheat bran 40g/L, peptone 3g/L, ammonium sulfate 3g/L, all the other are water.
(B) preparation cellulase
The inoculum size of step (A) acquisition seed liquor with 10% (v/v) accessed in the 5L fermentor tank that the 3L fermention medium is housed of having sterilized, add defoamer control foaming in the fermenting process, keep tank pressure 0.02-0.05MPa, air flow 0.5-0.6vvm, mixing speed 100-150rpm, 30 ℃ to cultivate 80-136 hour, obtain fermented liquid.
Each amounts of components is respectively in the described fermention medium: acid hydrolysis residue 30-50g/L, wheat bran 20-50g/L, Microcrystalline Cellulose or carboxymethyl cellulose 4-8g/L, ammonium sulfate 2-5g/L, potassium primary phosphate 2-4g/L, sal epsom 0.4-0.6g/L, all the other are water, and the initial pH of substratum is 5.0-6.0.
Each amounts of components is preferably in the described fermention medium: acid hydrolysis residue 45g/L, wheat bran 35g/L, Microcrystalline Cellulose 5g/L, ammonium sulfate 4g/L, potassium primary phosphate 3g/L, sal epsom 0.6g/L, all the other are water, and the initial pH of substratum is 5.0-6.0.
The fermented liquid 8000rpm centrifuging and taking that obtains gets supernatant liquor, namely gets the crude enzyme liquid that contains cellulase, and this crude enzyme liquid can be directly used in cellulosic enzymolysis.
(2) test as follows the various performances of the xylogen that following examples obtain
The mensuration of content of lignin: comprise sour insoluble xylogen and sour solvable xylogen.Wherein the mensuration of sour insoluble xylogen adopts the Klason method, carries out according to GB GB/T2677.8-94; The solvable xylogen of acid carries out according to GB GB10337-89.
The mensuration of ash oontent: carry out according to GB/T2667.2-93.
The mensuration of moisture: carry out according to GB/T2667.3-93.
The mensuration of solid content in the alkali lignin solution: get 100g solution to be measured, under 105 ℃, dried by the fire 24 hours, be cooled to room temperature, the quality of weighing remaining solid, this total mass number is the percentage ratio of the solid content of solution.
The mensuration of alkali content in alkali lignin solution and the recovery alkali lye: get the 0.5-1g testing liquid, make indicator with phenolphthalein, the hydrochloric acid soln of 0.2M/L is made titration reagent, is titrated to terminal point, calculates the content of however, residual base in the solution according to the hydrochloric acid volumeter that consumes.
Following examples are referring to Fig. 1, Fig. 2 and Fig. 3.
Pressure corresponding to acid hydrolysis temperature is the pressure of saturated vapor in following examples, therefore no longer provides pressure data for each embodiment.
In following examples, except specified otherwise was arranged, used percentage composition all represented weight percentage, i.e. " % " expression " % by weight ".
Embodiment 1
(1) N level acid hydrolysis
In the present embodiment: employing be three grades of acid hydrolysiss, at first with corn cob (mass component forms: moisture 6.12%, Mierocrystalline cellulose 35.19%, hemicellulose 32.01%, xylogen 23.7%, other 2.95%, lower with) smash, wash dedusting with water.One of them reactor is made as the first step, last is made as the third stage, then the acid solution that will newly prepare adds in the 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 the third stage hydrolytic reaction pot, the acid solution that third stage reactor is discharged is final pentose solution, then take out the acid-hydrolyzed residue in the first step hydrolytic reaction pot, the corn cob raw material of then packing into new, again with former first step hydrolytic reaction pot as third stage reactor, with former second stage reactor as first step reactor, with former third stage reactor as second stage reactor, the reaction that is hydrolyzed again, 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, the mass concentration 10% of phosphoric acid solution; Liquid-solid ratio is 8: 1 (mass ratio of new preparating acid solution and over dry corn cob raw material, lower same), by aforesaid method to 1.06 * 10
3The corn cob raw material that kg is new uses 1.0 * 10 after carrying out continuous acid hydrolysis processing
3The water of kg is washed described acid hydrolysis residue, and water lotion and acid hydrolysis solution merge, and finally obtain pentose solution 8.27 * 10
3Kg, pentose concentration is 3.59%,, the weight that obtains the acid hydrolysis residue is 1.73 * 10
3Kg (water ratio is about 65%, 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%); The extraction yield of hemicellulose is 87%.
The calculation formula of hemicellulose extraction yield is as follows:
The extraction yield %=of hemicellulose (pentose solution quality * pentose solution concentration)/(content of hemicellulose in corn cob quality * corn cob) * 100%
(2) alkaline solution extracts alkali lignin
The all acid hydrolytic residue that obtains in the present embodiment step (1) is 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 ℃, boiling alkali through 1 hour is molten, separates to 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 1.15 * 10
3Kg alkaline hydrolysis residue (water ratio is about 65%) and 3.47 * 10
3Kg alkali lignin solution, the content of alkali lignin is 5.46% in the alkali lignin solution; Then the extraction yield of alkali lignin is 75%;
The calculation formula of alkali lignin extraction yield is as follows:
Alkali lignin extraction yield %=(the alkali lignin content in the quality of alkali lignin solution * alkali lignin solution)/(content of xylogen in corn cob quality * corn cob) * 100%
(3) cellulase hydrolysis
The condition of described enzymolysis is: cellulase is commercially available cellulase (jade of the He family Bioisystech Co., Ltd, 4w unit), get the described alkaline solution of step (2) and process whole alkaline hydrolysis residues of obtaining as cellulosic substrate, add cellulase according to the cellulosic addition of 15FPU/g, the cellulosic substrate consumption is 125g/L, be in temperature that 48 ℃, pH are 5.0, under the condition of mixing speed 50rpm, enzymolysis transforms 2 days, whole enzymolysis process need not pressurize, obtain the solution that main component is glucose, quality is 3.23 * 10
3Kg, concentration is 8.82%, then cellulosic extraction yield is 76%.
The formula of Mierocrystalline cellulose extraction yield is as follows:
Cellulosic extraction yield %=(concentration of the quality * glucose solution of glucose solution)/(cellulosic content in corn cob quality * corn cob) * 100%
Glucose solution is produced the technique of ethanol for existing technique, does not repeat them here, and other embodiment is identical.
Comparative Examples 1
(1) N level acid hydrolysis
Method is with embodiment 1 step (1), and difference is that the 1st, 2 times during with 3 grades of acid hydrolysiss are identical, and then the numerical value of the rate of loss of the extraction yield of hemicellulose, cellulosic rate of loss and xylogen sees Table 1:
Table 1
(2) alkaline solution extracts alkali lignin
Three kinds of acid hydrolysis residues getting in this comparative example step (1) carry out the alkaline solution processing, and method is with embodiment 1 step (2).Then the extraction yield of alkali lignin sees Table 2:
Table 2
| The extraction yield of alkali lignin | |
| Comparative Examples 1A | 65％ |
| Comparative Examples 1B | 71％ |
| Comparative Examples 1C | 67％ |
(3) cellulase hydrolysis
Three kinds of alkaline solutions getting in this comparative example step (2) are processed the residue that obtains, and carry out cellulase hydrolysis, and method is with embodiment 3 steps (3), and cellulosic extraction yield sees Table 3:
Table 3
| Cellulosic extraction yield | |
| Comparative Examples 1A | 62％ |
| Comparative Examples 1B | 67％ |
| Comparative Examples 1C | 58％ |
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 the acid hydrolysis residue is 1.66 * 10
3Kg (about water-content 65%, the over dry content of hemicellulose is 6.44%, and cellulosic over dry content is 52.9%, and the over dry content of xylogen is 35.27%), pentose solution is 8.33 * 10
3Kg, pentose concentration is 3.64%, then the extraction yield of hemicellulose is 89%.
(2) alkaline solution extracts alkali lignin
The acid hydrolysis residue that obtains in the present embodiment step (1) is mixed 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 1 hour boiling alkaline hydrolysis, separate obtaining 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 1.10 * 10
3Kg alkaline hydrolysis residue (water ratio is about 65%) and 6.31 * 10
3Kg alkali lignin solution; Alkali lignin solution with film device separate concentrated after, add 1.0 * 10
3The dilution of kg water, reconcentration obtains 0.77 * 10 at last
3The alkali lignin concentrated solution of kg, and reclaim 6.54 * 10
3Kg alkali lye.The solid content of this concentrated solution is 25.5% after measured, and alkali lignin content is 24%, and the content of however, residual base is 0.7%, and ash oontent is 1.5%, and in the resulting alkali lye, the content of alkali is 4.38%, and the rate of recovery of alkali is 82%; Then the extraction yield of alkali lignin is 73%.
(3) cellulase hydrolysis
The condition of described enzymolysis is: cellulase is commercially available cellulase (jade of the He family Bioisystech Co., Ltd, 4w unit), get the described alkaline solution of step (2) and process whole residues of obtaining as cellulosic substrate, add cellulase according to the cellulosic addition of 10FPU/g, the cellulosic substrate consumption is 150g/L, be in temperature that 55 ℃, pH are 4, under the condition of mixing speed 200rpm, enzymolysis transforms 7 days, and whole enzymolysis process need not pressurize.Obtain the solution that main component is glucose, quality is 2.94 * 10
3Kg, concentration is 9.57%, then cellulosic extraction rate reached 75%.
Comparative Examples 2
The acid hydrolysis residue of getting in embodiment 2 steps (1) carries out the alkaline solution processing, method is with embodiment 2 steps (2), difference is: liquid separates with film device does not have thin up after concentrated, concentrated step again, and the rate of recovery of content, ash content and the alkali lye of the however, residual base of the extraction yield of alkali lignin, alkali lignin concentrated solution sees Table 4.
Comparative Examples 3
The acid hydrolysis residue of getting in embodiment 2 steps (1) carries out the alkaline solution processing, method is with embodiment 2 steps (2), difference is: the temperature that alkaline solution is processed is 170 ℃, and then the rate of recovery of content, ash content and the alkali lye of the however, residual base of the extraction yield of alkali lignin, alkali lignin concentrated solution sees Table 4:
Table 4
Embodiment 3
(1) N level acid hydrolysis
Raw material and method are with embodiment 1 step (1), difference is that 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 the acid hydrolysis residue is 1.80 * 10
3Kg (about water-content 65%, the over dry content of hemicellulose is 10.27%, and cellulosic over dry content is 50.74%, and the over dry content of xylogen is 34.01%), pentose solution is 8.20 * 10
3Kg, pentose concentration is 3.37%, then the extraction yield of hemicellulose is 81%.
(2) alkaline solution extracts alkali lignin
Get all acid hydrolytic residue that obtains in the present embodiment step (1), carry out alkaline solution according to embodiment 2 steps (2) processing method and process, difference is, liquid-solid volume ratio is 20: 1, the concentration of sodium hydroxide is 8%, and the temperature that alkaline solution is processed is 40 ℃, and the time is 6 hours.Obtain at last 1.27 * 10
3Kg alkaline hydrolysis residue (water ratio is about 65%) and 0.725 * 10
3Kg alkali lignin concentrated solution, and reclaim 13.25 * 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 24.4%, and the content of the however, residual base of concentrated solution is 0.6%, and the ash oontent of concentrated solution is 1.4%; And the content of alkali is 6.4% in the alkali lye that reclaims, and the rate of recovery of alkali is 84%; Then the extraction yield of alkali lignin is 70%.
(3) cellulase hydrolysis
Get present embodiment step (2) alkaline solution and process the whole alkaline hydrolysis residues that obtain, method according to embodiment 1 step (3) is carried out cellulase hydrolysis, difference is: cellulase is above-mentioned Penicillium notatum (Penicillium decumbens PD-G3-08, its deposit number is CCTCC M 2011195) cultivate obtain cellulase, obtain the solution that main component is glucose, quality is 3.57 * 10
3Kg, concentration is 8.18%, cellulosic extraction yield is 78%.
Comparative Examples 4
Get the residue that the alkaline solution processing obtains in embodiment 3 steps (2), carry out cellulase hydrolysis according to the method for embodiment 1 step (3), finally obtain the solution that main component is glucose, quality is 3.57 * 10
3Kg, concentration is 5.98%, then cellulosic extraction yield is 57%.
Embodiment 4
(1) N level acid hydrolysis
Technique and method are with embodiment 2 steps (1), and difference is that raw material is 1.11 * 10
3The kg Wheat Straw (mass component forms: 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 the acid hydrolysis residue is 1.86 * 10
3Kg (about water-content 65%, the over dry content of hemicellulose is 3.42%, and cellulosic over dry content is 61.17%, and the over dry content of xylogen is 23.96%), pentose solution is 8.14 * 10
3Kg, pentose concentration is 2.76%, then the hemicellulose extraction yield is 91%.
(2) alkaline solution extracts alkali lignin
With the acid hydrolysis residue that obtains in the present embodiment step (1), carry out alkaline solution according to the method for embodiment 2 steps (2) and process, difference is: the temperature that alkaline solution is processed is 100 ℃, and the time is 2 hours, the concentration of potassium hydroxide is 5%, and liquid-solid volume ratio is 20: 1.Obtain at last 1.42 * 10
3Kg alkaline hydrolysis residue (water ratio is about 65%) and 0.57 * 10
3Kg alkali lignin concentrated solution, and reclaim 13.67 * 10
3Kg alkali lye.The solid content of this concentrated solution is 26% after measured, and the alkali lignin content of concentrated solution is 24.5%, and the content of the however, residual base of concentrated solution is 0.70%, and the ash oontent of concentrated solution is 1.50%; The content of alkali is 3.9% in the alkali lye that reclaims, and the rate of recovery of alkali is 82%; The extraction yield of alkali lignin is 74%.
Alternatively, with the alkali lignin concentrated solution that obtains, the sulphur acid for adjusting pH value to 3 with 10% filters, and washing and drying obtain the alkali lignin solid.
(3) cellulase hydrolysis
The condition of described enzymolysis is: cellulase is above-mentioned Penicillium notatum (Penicillium decumbens PD-G3-08, be preserved in Wuhan University Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195) cultivate obtain cellulase; get the described alkaline solution of present embodiment step (2) and process whole residues of obtaining as cellulosic substrate; add cellulase according to the cellulosic addition of 12FPU/g; the cellulosic substrate consumption is 80g/L; be 45 ℃ in temperature; pH is 6; under the condition of mixing speed 200rpm; enzymolysis transforms 5 days, and whole enzymolysis process need not pressurize.Obtain the solution that main component is glucose, quality is 6.73 * 10
3Kg, concentration is 5.17%, then cellulosic extraction rate reached 71%.
More than among each embodiment, only take three grades of acid hydrolysiss as example.But according to the trend of test-results, acid hydrolysis progression is more, more is conducive to farthest extract hemicellulose.Yet 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 that the hemicellulose that the later acid hydrolysis of Pyatyi can be extracted has lost industrial economic worth significantly equally, and high to xylogen and cellulosic destruction.Therefore more excellent acid hydrolysis progression is the 3-5 level in this case.
Comparative Examples 5
(1) N level acid hydrolysis
Method is with embodiment 4 steps (1), and difference is that the 1st, 2 hydrolysis times during with 3 grades of acid hydrolysiss are identical, and then the numerical value of the rate of loss of the extraction yield of hemicellulose, cellulosic rate of loss and xylogen sees Table 5:
Table 5
(2) alkaline solution extracts alkali lignin
Three kinds of acid hydrolysis residues getting in this comparative example step (1) carry out the alkaline solution processing, and method is with embodiment 4 steps (2).The rate of recovery table 6 of the content of the however, residual base of the extraction yield of alkali lignin, alkali lignin concentrated solution, ash content and alkali lye:
Table 6
(3) cellulase hydrolysis
Three kinds of alkaline solutions getting in this comparative example step (2) are processed the residue that obtains, and carry out cellulase hydrolysis, and method is with embodiment 4 steps (3), and cellulosic extraction yield sees Table 7:
Table 7
| Cellulosic extraction yield | |
| Comparative Examples 5A | 60％ |
| Comparative Examples 5B | 66％ |
| Comparative Examples 5C | 54％ |
Test case 1
In the phenol of 10Kg, add respectively the alkali lignin solution that 30Kg embodiment 2 and Comparative Examples 2,3 obtain, be warming up to 70 ℃, add the sodium hydroxide solution (mass percent concentration is 50) of 1Kg, air distillation to 150 ℃, back flow reaction 90 minutes is cooled to 70-80 ℃, adds 11Kg formaldehyde (mass percent concentration is 37%) reaction 90 minutes, be cooled to 50 ℃, regulate PH to 6.5-7, vacuum hydro-extraction is to about viscosity 9000cp/25 ℃, discharging.Finally can make respectively lignin modification resol by the wooden concentrated solution of alkali that embodiment 2 and Comparative Examples 2,3 obtain, 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 the resol: carry out according to HG51341.
The mensuration of resol pH value: carry out according to HG/T2501.
The performance index of the modified phenolic resins of table 8 Different Alkali lignin liquor
The content of phenol and formaldehyde raises gradually in the resol product that three kinds of Different Alkali lignin liquors obtain, and the alkali lignin solution that adds is described not only and the activity of reacting between formaldehyde dies down gradually, but also has affected reacting to each other of phenol and formaldehyde.The first alkali lignin solution is the alkali lignin solution that the present invention obtains, and the content of its however, residual base and ash oontent are all lower, does not basically affect the reaction between alkali lignin and phenol and the formaldehyde; The second alkali lignin solution is for directly concentrating the alkali lignin solution that obtains, and without water washing, the content of however, residual base and ash oontent are all higher, have affected the reaction between alkali lignin and phenol and the formaldehyde; And having passed through a high temperature steaming process in the third alkali lignin solution, some active groups of xylogen are damaged under hot conditions, thereby the activity during with formaldehyde reaction weakens greatly.
If about 25% the lignin liquor that uses directly that industrial soda xylogen (the polynary xylogen in Gaotang, Shandong company limited) is made into, synthesis technique and method are constant, method according to test case 1 prepares modified phenolic resins, after regulating the pH value, only at the bottom of bottle, there is a small amount of resin to produce, sees that on the whole alkali lignin solution does not participate in reaction, behind the decompression dehydration, finding at the bottom of bottle has the alkali lignin precipitation, can't obtain alkali lignin modified novolac resin.
In sum, the alkali lignin solution that obtains of the present invention has higher activity as can be known, can be in order to prepare the products such as modified phenolic resins.
In addition, more than among each embodiment, only be reduced to example with amplitudes such as times, but according to principle of the present invention and experiment test, the amplitude such as non-reduces and also can realize not repeating them here purpose of the present invention.
Obviously, above-described embodiment only is for example clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give all embodiments exhaustive.And the apparent variation of being extended out thus or change still are among the protection domain of the invention.
Claims (13)
1. the method for comprehensive utilization of a lignocellulose biomass is characterized in that may further comprise the steps:
(a) lignocellulose biomass is carried out the acid hydrolysis of N level, the acid-hydrolyzed reactor of N level is end to end, one of them reactor is made as the first step, last is made as the 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 the third stage acid hydrolytic reaction still, successively sequentially, 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 the first step acid hydrolytic reaction still, the lignocellulose biomass raw material of then packing into new, again with first step acid hydrolytic reaction still as N level acid hydrolytic reaction still, with second stage acid hydrolysis order 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, the reaction that is hydrolyzed again so 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 the integer more than or equal to 2;
(b) process described acid hydrolysis residue with alkaline solution, thereby extract alkali lignin;
(c) use cellulase that alkaline solution described in the step (b) is processed the alkaline hydrolysis residue that obtains and carry out enzymolysis, obtain the solution that main component is glucose.
2. method according to 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. method according to claim 1 and 2, it is characterized in that: described N is the integer of 3-5.
4. the described method of any one according to claim 1-3 is characterized in that: the concrete steps of described step (b) are:
(i) processing described acid hydrolysis residue through alkaline solution makes wherein lignin dissolution in alkaline solution;
(ii) then filter, wash and obtain solid and liquid;
(iii) with the separation of gained liquid process film device, the concentrated alkali lignin solution that obtains.
5. method according to claim 4 is characterized in that: also comprise again dilute with water of the described concentrated alkali lignin solution that obtains in the described step (iii), and then concentrated step.
6. according to claim 4 or 5 described methods, it is characterized in that: also comprise in the described step (iii) the alkali lignin solution that will obtain through neutralization, filter and dry, obtain the step of alkali lignin solid.
7. the described method of any one according to claim 1-6 is characterized in that: also be included in the concentrated step that obtains after the described alkali lignin solution or recycle simultaneously alkaline solution wherein in the described step (iii).
8. the described method of any one according to claim 1-7 is characterized in that: described alkaline solution is processed and is carried out under 40-100 ℃.
9. the described method of any one according to claim 1-8 is characterized in that: liquid-solid volume ratio was 5 during described alkaline solution was processed: 1-20: 1.
10. the described method of any one according to claim 1-9 is characterized in that: the concentration of alkaline solution was the 5-8 % by weight during described alkaline solution was processed.
11. the described method of any one according to claim 1-10 is characterized in that: the time that described alkaline solution is processed is 1-6 hour.
12. the described method of any one according to claim 1-11, it is characterized in that: described cellulase is for being cultivated the cellulase that obtains by a penicillium, this Penicillium notatum Classification And Nomenclature is Penicillium decumbens PD-G3-08, be preserved in Wuhan University Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195.
13. the described method of any one according to claim 1-12, it is characterized in that: the condition of described cellulase hydrolysis is: the substrate consumption is 80-150g/L, the addition of cellulase is the 10-15FPU/g Mierocrystalline cellulose, temperature is that 45-55 ℃, pH are that 4-6, mixing speed are 50-200rpm, and the enzymolysis transformation time is 2-7 days.
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