CN103045690B - 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 a reduced range of the concentration of an acid solution from a first-stage to an N-stage stage by stage is 10-40% that of the first-stage acid solution, and N is an integer larger than or equal to 2; (b) performing enzymatic hydrolysis on the acid hydrolysis residues in the step (a) by using cellulose, so that a glucose solution and enzymatic hydrolysis residues are obtained; (c) treating the enzymatic hydrolysis residues produced in the step (b) with an alkali solution, so that lignin in the enzymatic hydrolysis residues can be extracted and alkali hydrolysis residues are obtained; and (d) returning the alkali hydrolysis residues obtained by alkali hydrolysis treatment to the step (b) after the step (c) is finished so as to perform enzymatic hydrolysis, or firstly mixing the alkali hydrolysis residues with fresh acid hydrolysis residues and then carrying out the enzymatic hydrolysis of the step (b), performing the step (c) and the step (d) successively, repeating such process, and further extracting the lignin and performing cellulose enzymatic hydrolysis. 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, world's alcohol production is mainly usingd starch based (corn, cassava etc.) and carbohydrate (sugarcane, the beet etc.) raw material as fermentation.Adopt microbial method fermentative production of ethanol technology maturation, but high raw materials cost is restricted the industrial application of grain fermentative production of ethanol, exist simultaneously with people strive grain and grain strive etc. drawback, and cause provision price Continued, so it is imperative to find new raw material.Present scientist is more cheap sight trend of purchasing cost, the lignocellulose biomass widely of originating.
Lignocellulose biomass exists with the form of plant materials, main component is Mierocrystalline cellulose, hemicellulose and xylogen, wherein, Mierocrystalline cellulose accounts for 40% left and right, hemicellulose accounts for 25% left and right, xylogen accounts for 20% left and right, and the lignocellulose biomass total amount being generated by photosynthesis every year on the earth surpasses 2,000 hundred million tons, so Wooden Biomass is renewable resources abundant, the most cheap on the earth.
If can take lignocellulose biomass as raw material production ethanol, will greatly solve the mankind's energy problem, but still exist in this respect a lot of technical barriers not yet to solve.At present, take lignocellulose biomass in raw material production ethanol process, the first problem running into is that hemicellulose, Mierocrystalline cellulose and xylogen are failed to fully utilize well, the Technology of existing processing biomass, mainly with degraded carbohydrate, obtaining ethanol is greatly object, can not extract simultaneously and obtain high purity, highly active xylogen, often xylogen is removed to object as one, simultaneously in double cellulosic utilization, also there is the shortcoming that generates a lot of cellulase inhibitors, finally also can affect the productive rate of ethanol.
A kind of combined pretreatment method and system thereof of lignocellulose biomass are disclosed in CN100564667C, after being pulverized, lignocellulose biomass packs in circulating reaction still, and inject diluted acid, opening recycle pump is to carry out circulating reaction at 50 ℃-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 as far as possible hemicelluloses of removing, need adopt higher temperature and long reaction times more, cause like this pentose of hydrolysis in early stage under comparatively high temps, easily to produce the cellulase inhibitors such as furfural and acetic acid, thereby reduce enzymolysis transformation efficiency; On the other hand, if do not adopt higher temperature and long reaction times, owing to containing more hemicellulose in residue after acidolysis, be unfavorable for that alkaline solution extracts alkali lignin, if want, the concentration of alkali just need to improve in dissolved lignin as much as possible, the time of the temperature of alkaline purification and prolongation alkaline purification, cause the active part of xylogen to be damaged, can not utilize its xylogen to remove to produce high value-added product, therefore, technique scheme can not be taken into account the comprehensive utilization of Mierocrystalline cellulose, hemicellulose and xylogen simultaneously.
In the process of raw material production ethanol, run into the low conversion rate that another problem is cellulase hydrolysis 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 enzyme activity.
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, identical owing to being hydrolyzed concentration in hydrolytic reaction pots at different levels, therefore large to xylogen and cellulosic destructive rate, and the enzyme inhibitors such as the furfural generating, acetic acid 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 fiber productivity 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, regulate the concentration of the acid solution of first step acid hydrolytic reaction still discharge, then added in the acid hydrolytic reaction still of the second stage, regulate the concentration of the acid solution of second stage acid hydrolytic reaction still discharge, then added in third stage acid hydrolytic reaction still, successively sequentially, until regulate the concentration of the acid solution of N-1 level acid hydrolytic reaction still discharge, then added in N level acid hydrolytic reaction still, the acid solution that N level acid hydrolytic reaction still is discharged is final pentose solution, then the acid hydrolysis residue in first step acid hydrolytic reaction still is discharged, and pack new lignocellulose biomass raw material into, using it 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, carry out again acid hydrolytic reaction, so move in circles and can realize the continuous hydrolysis of lignocellulose biomass,
Wherein, the amplitude that the concentration of described acid solution reduces to N level step by step from the first step is the 10-40% of first step acid solutions, 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), obtaining main component is glucose solution and enzymolysis residue;
(c) the described enzymolysis residue producing with alkaline solution treatment step (b), thus the alkali lignin in described enzymolysis residue extracted;
(d) after step (c) completes, alkaline hydrolysis is processed to the alkaline hydrolysis residue obtain to be returned to step (b) and carries out enzymolysis processing or carry out the enzymolysis processing of step (b) by after described alkaline hydrolysis residue and new acid hydrolysis residue merging again, then carry out successively step (c) and (d), so circulation, further extracts xylogen and carries out cellulase hydrolysis.
There is no particular limitation for the kind of described acid solution, can be that lignocellulose biomass carries out the acid-hydrolyzed conventional acid of using, for example one or more in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
The acid-hydrolyzed temperature of described N level, pressure and time are not particularly limited, can be that lignocellulose biomass carries out acid-hydrolyzed conventional temperature, pressure and time, 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 the time (being the residence time of acid solution in reactor) of every grade of hydrolysis reaction is 0.25-2 hour in the acid hydrolysis of described N level again.
Above the comparatively desirable integer that is chosen as 3-5 of described N.
Described lignocellulose biomass can be one or more of maize straw, rice straw, bagasse, cotton bavin, cotton seed hull, corn cob, straw, kaoliang stalk, broad-leaved wood and wood chip.
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 for being cultivated the cellulase obtaining 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'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.
Described alkaline solution is processed and is carried out at 40-100 ℃.
In described alkaline solution processing, liquid-solid volume ratio is 5: 1-20: 1.
In described alkaline solution processing, the concentration of alkaline solution is 0.8-5 % by weight.
The time that described alkaline solution is processed is 1-6 hour.
Various alkali may be used to the present invention, includes but not limited to aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, ammoniacal liquor etc.But, according to some preferred embodiment, the aqueous solution that alkaline solution is sodium hydroxide.
Technique scheme of the present invention compared with prior art has the following advantages:
1, the present invention has adopted the acidolysis of first N level, enzymolysis again, the operational path of last alkaline hydrolysis, and the method that has adopted the concentration from first step reactor to N order reaction still acid solution to reduce step by step in hydrolytic process, the method can adopt according to the complexity of hemicellulose acidolysis and pentose damaed cordition the concentration of different acid solutions, because the material in N order reaction still is new material, hemicellulose is more easily removed, so lower acid solution of working concentration, in addition, in N order reaction still, the concentration of pentose is the highest, adopt lower acid concentration, can prevent from generating furfural and acetic acid, thereby reduce furfural and the restraining effect of acetic acid to cellulase, and for the material in first step reactor, remove remaining hemicellulose more difficult, adopt higher acid concentration to be conducive to farthest extract hemicellulose, adopt technique scheme can farthest extract hemicellulose, destroy as little as possible xylogen and Mierocrystalline cellulose simultaneously, keep the activity of xylogen, owing to having reduced sour usage quantity, also saved cost in addition, and reduced the pollution to environment, adopt aforesaid method to make to be hydrolyzed more than later half cellulosic extraction yield can reach 70 % by weight, cellulosic rate of loss is less than 7 % by weight, and the rate of loss of xylogen is less than 9 % 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,
The present invention adopts circulation technology respectively Mierocrystalline cellulose, xylogen to be replaced to extraction process simultaneously, improved on the one hand the extraction yield of Mierocrystalline cellulose and xylogen, can weaken by this method on the other hand the treatment condition of acidolysis, alkaline hydrolysis, thereby further protect xylogen and Mierocrystalline cellulose not to be destroyed, can make xylogen and cellulosic utilization maximize;
In addition, the first N level acidolysis that the present invention adopts, 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, and therefore, alkaline solution extracts alkali lignin ratio and is easier to, and has reduced the consumption of alkaline solution, has also reduced the pollution to environment;
As can be seen here, aforesaid method of the present invention has solved the problem of complex utilization of lignocellulose biomass in prior art, makes 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, because the temperature lower (40-100 ℃) is lower, realizes alkali lignin is extracted, further protect the activity of alkali lignin.
4, 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.
5, the condition that alkaline solution of the present invention is processed adopts liquid-solid ratio, alkali consumption, the temperature and time being more preferably, and the activity that finally obtains alkali lignin is very high.
6, cellulase of the present invention is for being cultivated the cellulase obtaining by a penicillium, this Penicillium notatum Classification And Nomenclature is Penicillium decumbens PD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195, the cellulase that adopts this Penicillium notatum to produce has higher vigor, has improved the extraction yield of cellulase hydrolysis.
7. what the present invention was used cultivates by Penicillium notatum the cellulase obtaining, at substrate consumption, be 80-150g/L, the addition of cellulase is 10-15FPU/g Mierocrystalline cellulose, temperature is that 45-55 ℃, pH are that 4-6, mixing speed are 50-200rpm, 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 acid hydrolysis 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
The Penicillium notatum seed liquor that by naming number is Penicillium decumbens PD-G3-08 is linked in the fermentor tank that contains seed culture medium through 121 ℃ of sterilizing 30min and activates with the inoculum size of 5% (v/v), keep tank pressure 0.02-0.05MPa, air flow 0.5vvm, mixing speed 100-150rpm, 30 ℃ of cultivation 30-60 hour, the seed liquor after being activated.
Component in described seed culture medium and consumption are: get embodiment 1 acid hydrolysis residue 10-30g/L, wheat bran 20-50g/L, peptone 1-4g/L, ammonium sulfate 2-4g/L, all the other are water.
Component and consumption in described seed culture medium are preferably: acid hydrolysis residue 20g/L, wheat bran 40g/L, peptone 3g/L, ammonium sulfate 3g/L, all the other are water.
(B) prepare cellulase
Inoculum size by step (A) acquisition seed liquor with 10% (v/v) accesses in the 5L fermentor tank that 3L fermention medium is housed of sterilizing, in fermenting process, add defoamer and control foaming, keep tank pressure 0.02-0.05MPa, air flow 0.5-0.6vvm, mixing speed 100-150rpm, 30 ℃ of cultivation 80-136 hour, obtain fermented liquid.
In described fermention medium, each amounts of components is respectively: acid hydrolysis residue 30-50g/L, wheat bran 20-50g/L, Microcrystalline Cellulose or carboxymethyl cellulose 4-8g/L, ammonium sulfate 2-5g/L, potassium primary phosphate 2-4g/L, magnesium sulfate 0.4-0.6g/L, all the other are water, and the initial pH of substratum is 5.0-6.0.
In described fermention medium, each amounts of components is preferably: acid hydrolysis residue 45g/L, wheat bran 35g/L, Microcrystalline Cellulose 5g/L, ammonium sulfate 4g/L, potassium primary phosphate 3g/L, magnesium sulfate 0.6g/L, all the other are water, and the initial pH of substratum is 5.0-6.0.
The fermented liquid 8000rpm centrifuging and taking obtaining obtains supernatant liquor, must contain the crude enzyme liquid of cellulase, and this crude enzyme liquid can be directly used in cellulosic enzymolysis
(2) test as follows the various performances of xylogen in following examples
The mensuration of content of lignin: comprise sour insoluble xylogen and sour solvable xylogen.Wherein the mensuration of sour insoluble xylogen adopts Klason method, according to GB GB/T2677.8-94, carries out; The solvable xylogen of acid carries out according to GB GB 10337-89.
The mensuration of moisture: carry out according to GB/T 2667.3-93.
Following examples are referring to Fig. 1, 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 embodiments of the invention, except dated, percentage composition used is all expressed as weight percentage, i.e. " % " expression " % by weight ".
Embodiment 1
(1) N level acid hydrolysis
In the present embodiment: employing be three grades of acid hydrolysiss, first by corn cob (mass component forms: moisture 6.12%, Mierocrystalline cellulose 35.19%, hemicellulose 32.1%, xylogen 23.7%, other 2.95%, lower with) smash, wash dedusting with water.One of them reactor is made as to the first step, last is made as the third stage, the acid solution of newly preparation is added in first step hydrolytic reaction pot, regulate the concentration of the acid solution of first step acid hydrolytic reaction still discharge, then added in the acid hydrolytic reaction still of the second stage, regulate the concentration of the acid solution of discharging in the acid hydrolytic reaction still of the second stage, then added in third stage acid hydrolytic reaction still, the solution that third stage acid hydrolytic reaction still is discharged is final pentose solution, then the acid hydrolysis residue in first step acid hydrolytic reaction still is discharged, and pack new corn cob raw material into, using it as third stage acid hydrolytic reaction still, using former second stage acid hydrolytic reaction still as first step acid hydrolytic reaction still, using former third stage acid hydrolytic reaction still as second stage acid hydrolytic reaction still, carry out again acid hydrolytic reaction, so move in circles and can realize the continuous hydrolysis of lignocellulose biomass,
Wherein, described acid solution is phosphoric acid solution; In first step acid hydrolytic reaction still, the concentration of phosphoric acid is 15%, in the acid hydrolytic reaction still of the second stage, the concentration of phosphoric acid is 10%, in third stage acid hydrolytic reaction still, the concentration of phosphoric acid is 5%, and the amplitude reducing step by step from the first step to the third stage is 33.3% of first step acid solutions; The time of every grade of acid hydrolytic reaction is 1.0 hours, and the temperature of every grade of acid hydrolytic reaction is 110 ℃, and liquid-solid ratio is 8: 1 (newly prepare the mass ratio of acid solution and over dry corn cob raw material, lower with), by aforesaid method to 1.06 * 10
3the corn cob raw material that kg is new carries out after continuous acid hydrolysis processing, uses 1 * 10
3the water of kg is washed described acid hydrolysis residue, and water lotion and acid hydrolysis solution merge, and the weight that finally obtains acid hydrolysis residue is 1.98 * 10
3kg (water ratio is 65% left and right, and the over dry content of hemicellulose is 11.77%, and cellulosic over dry content is 50.25%, and the over dry content of xylogen is 33.46%), pentose solution weight is 8.01 * 10
3kg, pentose concentration is 3.23%, the extraction yield of hemicellulose is 76%.
The calculation formula of hemicellulose extraction yield is as follows:
Hemicellulose extraction yield %=(concentration of the quality * pentose of pentose solution)/(content of hemicellulose in corn cob quality * corn cob) * 100%.
In this step, relate to the variation of acid concentrations at different levels, the selection of other parameters, is determined according to conventional factor in corresponding reaction process by adopted acid.Each embodiment, in acid hydrolysis step, all adopts identical parameter to choose mode below.
(2) cellulase hydrolysis
The condition of described enzymolysis is: cellulase is commercially available cellulase (jade of the He family Bioisystech Co., Ltd, 4w unit), the all acid hydrolytic residue that the present embodiment step (1) is obtained is as cellulosic substrate, according to the cellulosic addition of 15FPU/g, add cellulase, cellulosic substrate consumption is 125g/L, in temperature, be that 48 ℃, pH are 5.0, under the condition of mixing speed 50rpm, enzymolysis transforms 2 days, and whole enzymolysis process is without pressurize.Obtain 1.57 * 10
3kg enzymolysis residue (water ratio is 65% left and right) and 5.56 * 10
3kg glucose solution, the concentration of glucose solution is 2.63%, cellulosic extraction yield is 39%.
The calculation formula of Mierocrystalline cellulose extraction yield is as follows:
Cellulosic extraction yield %=(concentration of glucose solution quality * glucose solution)/(cellulosic content in corn cob quality * corn cob) * 100%.
The technique that glucose solution is produced ethanol is existing technique, does not repeat them here, and other embodiment is identical.
(3) alkaline solution extracts alkali lignin
Whole enzymolysis residues that the present embodiment step (2) is obtained mix with sodium hydroxide solution, and wherein liquid-solid volume ratio is 5: 1, and the concentration of sodium hydroxide is 3%, then be warming up to 70 ℃, through the boiling alkaline hydrolysis of 1 hour, separation obtained 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 1.18 * 10
3kg alkaline hydrolysis residue (water ratio is 65% left and right) and 3.12 * 10
3kg alkali lignin solution, the alkali lignin content in solution is 4.05%, the extraction yield of alkali lignin is 50%.
The calculation formula of alkali lignin extraction yield is as follows:
The extraction yield %=of alkali lignin (content of xylogen in quality * alkali lignin solution of alkali lignin solution)/(content of xylogen in corn cob quality * corn cob) * 100%.
(4) circular treatment
Whole alkaline hydrolysis residues that step (3) is obtained return to step (2) and carry out enzymolysis for the second time, and enzymolysis processing is identical with the condition of enzymolysis processing step in the present embodiment (2) Suo Shu for the second time; Obtain 6.94 * 10
3kg enzymolysis residue (water ratio is 65% left and right) and 3.29 * 10
3kg glucose solution, the concentration of glucose solution is 5.12%, cellulosic extraction yield is 45% for the second time;
The described residue of enzymolysis is for the second time carried out to alkaline hydrolysis for the second time, and the condition of alkaline hydrolysis is identical with the condition of alkaline hydrolysis described in step in the present embodiment (3) for the second time; The weight that obtains alkali lignin solution is 2.02 * 10
3kg, the alkali lignin content in solution is 4.5%, the extraction yield of alkali lignin is 36% for the second time.
In sum, the extraction yield of hemicellulose is 76%, and cellulosic total extraction yield is 84%, and total extraction yield of alkali lignin is 86%.
Embodiment 2
(1) N level acid hydrolysis
Technique and method are with embodiment 1 step (1), difference is: the time of every grade of acid hydrolytic reaction is 0.5 hour, in first step acid hydrolysis, the concentration of phosphoric acid solution is 20%, and in the acid hydrolysis of the second stage, the concentration of phosphoric acid solution is 12%, and in third stage acid hydrolysis, the concentration of phosphoric acid solution is 4%; The weight that finally obtains acid hydrolysis residue is 1.93 * 10
3kg (water-content 65% left and right, the over dry content of hemicellulose is 10.07%, cellulosic over dry content is 51.11%, the over dry content of xylogen is 34.17%), the weight of pentose solution is 8.06 * 10
3kg, pentose concentration is 3.38%, the extraction yield of hemicellulose is 80%.
(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 1.48 * 10
3kg enzymolysis residue (water ratio is 65% left and right) and 5.19 * 10
3kg glucose solution, the concentration of glucose solution is 3.03%, cellulosic extraction rate reached 42%.
(3) alkaline solution extracts alkali lignin
Whole enzymolysis residues that above-mentioned steps (2) is obtained mix with sodium hydroxide solution, and wherein liquid-solid volume ratio is 5: 1, and the concentration of sodium hydroxide is 3%, then be warming up to 70 ℃, through the boiling alkaline hydrolysis of 1 hour, separation obtained 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 1.08 * 10
3kg alkaline hydrolysis residue (water ratio is about 65%) and 3.03 * 10
3kg alkali lignin solution, in solution, the content of alkali lignin is 4.25%, the extraction yield of alkali lignin is 51%.
(4) circular treatment
Whole alkaline hydrolysis residues that step (3) is obtained return to step (2) and carry out enzymolysis for the second time, and enzymolysis processing is identical with the condition of enzymolysis processing the present embodiment step (2) Suo Shu for the second time; Obtain 0.62 * 10
3kg enzymolysis residue (water ratio is 65% left and right) and 2.91 * 10
3kg glucose solution, the concentration of glucose solution is 5.54%, cellulosic extraction yield is 43% for the second time.
The described residue of enzymolysis is for the second time carried out to alkaline hydrolysis for the second time, and the condition of alkaline hydrolysis is identical with the condition of alkaline hydrolysis described in step in the present embodiment (3) for the second time; The weight that obtains alkali lignin solution is 1.93 * 10
3kg, the alkali lignin content in solution is 4.45%, the extraction yield of alkali lignin is 34% for the second time.
In sum, the extraction yield of hemicellulose is 80%, and cellulosic total extraction yield is 85%, and total extraction yield of alkali lignin is 85%.
Embodiment 3
(1) N level acid hydrolysis
Technique and method be with embodiment 1 step (1), and difference is, the concentration of first step acid hydrolysis phosphoric acid is 10%, the concentration of second stage acid hydrolysis phosphoric acid is 8%, the concentration of third stage acid hydrolysis phosphoric acid is 6%, and every grade of acid-hydrolyzed time is 1.5 hours, and temperature is 120 ℃; The weight that finally obtains acid hydrolysis residue is 2.06 * 10
3kg (water-content is 65% left and right, and the over dry content of hemicellulose is 14.18%, and cellulosic over dry content is 48.84%, and the over dry content of xylogen is 32.62%), the weight of pentose solution is 7.94 * 10
3kg, pentose concentration is 3.01%, the extraction yield of hemicellulose is 70%.
(2) cellulase hydrolysis
By all acid hydrolytic residue obtaining in the present embodiment step (1), method according to embodiment 1 step (2) is carried out cellulase hydrolysis, difference is: cellulase is above-mentioned Penicillium notatum (Penicillium decumbens PD-G3-08, its deposit number is CCTCC M 2011195, lower same) cultivate the cellulase obtaining, obtain 1.46 * 10
3kg enzymolysis residue (water ratio is about 65%) and 5.77 * 10
3kg glucose solution, the concentration of glucose solution is 3.64%, cellulosic extraction yield is 56%.
(3) alkaline solution extracts alkali lignin
By the whole enzymolysis residues that obtain in the present embodiment step (2), according to embodiment 2 steps (3) processing method, difference is, liquid-solid volume ratio is 10: 1, and the concentration of sodium hydroxide is 5%, and the temperature that alkaline solution is processed is 40 ℃, and the time is 6 hours.Finally obtain 1.1 * 10
3kg alkaline hydrolysis residue (water ratio is 65% left and right) and 5.53 * 10
3kg alkali lignin solution, in solution, the content of alkali lignin is 2.1%, the extraction yield of alkali lignin is 46%.
(4) circular treatment
Whole alkaline hydrolysis residues that step (3) is obtained return to step (2) and carry out enzymolysis for the second time, and enzymolysis processing is identical with the condition of enzymolysis processing the present embodiment step (2) Suo Shu for the second time; Obtain 0.76 * 10
3kg enzymolysis residue (water ratio is 65% left and right) and 3.07 * 10
3kg glucose solution, the concentration of glucose solution is 3.9%, cellulosic extraction yield is 32% for the second time;
The described residue of enzymolysis is for the second time carried out to alkaline hydrolysis for the second time, and the condition of alkaline hydrolysis is identical with the condition of alkaline hydrolysis described in step in the present embodiment (3) for the second time; The quality that obtains alkali lignin solution is 3.4 * 10
3kg, the alkali lignin content in solution is 2.94%, the extraction yield of alkali lignin is 40% for the second time.
In sum, the extraction yield of hemicellulose is 70%, and cellulosic total extraction yield is 88%, and total extraction yield of alkali lignin is 86%.
Embodiment 4
(1) N level acid hydrolysis
1) N level acid hydrolysis
Method is with embodiment 1 step (1), difference is: the acid solution adopting is sulphuric acid soln, in first step acid hydrolysis, the concentration of sulfuric acid is 0.8%, in the acid hydrolysis of the second stage, the concentration of sulfuric acid is 0.72%, in third stage acid hydrolysis, the concentration of sulfuric acid is 0.64%, in fourth stage acid hydrolysis, the concentration of sulfuric acid is 0.56%, and in level V acid hydrolysis, the concentration of sulfuric acid is 0.48%.The weight that finally obtains acid hydrolysis residue is 2.0 * 10
3kg (water-content is 65% left and right, and the over dry content of hemicellulose is 10.71%, and cellulosic over dry content is 50.54%, and the over dry content of xylogen is 34.26%), the weight of pentose solution is 8.0 * 10
3kg, pentose concentration is 3.30%, the extraction yield of hemicellulose is 78%.
(2) cellulase hydrolysis
The condition of described enzymolysis is: cellulase is above-mentioned Penicillium notatum (Penicillium decumbens PD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195) cultivate obtain cellulase, get all acid hydrolytic residue that the present embodiment step (1) 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 1.42 * 10
3kg enzymolysis residue (water ratio is 65% left and right) and 9.45 * 10
3the solution of kg glucose, the concentration of glucose solution is 2.14%, cellulosic extraction rate reached 54%.
(3) alkaline solution extracts alkali lignin
By the enzymolysis residue obtaining in the present embodiment step (2), according to the method for embodiment 2 steps (3), carry out alkaline solution processing, difference is, liquid-solid volume ratio is 20: 1, the concentration of sodium hydroxide is 0.8%, and the temperature that alkaline solution is processed is 100 ℃, and the time is 2 hours.Finally obtain 1.05 * 10
3kg alkaline hydrolysis residue (water ratio is 65% left and right) and 10.4 * 10
3kg alkali lignin solution, in solution, the content of alkali lignin is 1.14%, the extraction yield of alkali lignin is 47%.
(4) circular treatment
Whole alkaline hydrolysis residues in step (3) are returned in step (2), after merging with new acid hydrolysis residue (another batch of acid hydrolysis residue that corn cob obtains after step acid hydrolysis), carry out again enzymolysis processing, after enzymolysis processing completes, carrying out the alkaline hydrolysis of step (3) processes again, and then alkaline hydrolysis residue is returned in step (2), again merge with new acid hydrolysis residue, so can form circular treatment.
Adopt aforesaid method to 10.6 * 10
3kg corn cob is processed, and the extraction yield that finally obtains hemicellulose is 78%, and cellulosic total extraction yield is 89%, and total extraction yield of xylogen is 86%.
Embodiment 5
(1) N level acid hydrolysis
Method is with embodiment 1 step (1), and difference is that raw material is 1.11 * 10
3kg Wheat Straw (mass component forms: moisture 10.1%, Mierocrystalline cellulose 44%, hemicellulose 22.2%, xylogen 17%, other 6.7%), the acid solution adopting is sulfuric acid, it is 1.0% that the first step is hydrolyzed sour concentration, it is 0.8% that the second stage is hydrolyzed sour concentration, and it is 0.6% that the third stage is hydrolyzed sour concentration.The weight that finally obtains acid hydrolysis residue is 2.19 * 10
3kg (water-content 65% left and right, the over dry content of hemicellulose is 8.36%, cellulosic over dry content is 58.99%, the over dry content of xylogen is 22.95%), pentose solution weight is 7.8 * 10
3kg, pentose concentration is 2.34%, the extraction yield of hemicellulose is 74%.
(2) cellulase hydrolysis
Get all acid hydrolytic residue that the present embodiment step (1) obtains, according to the method for embodiment 1 step (2), carry out cellulase hydrolysis, obtain 1.68 * 10
3kg enzymolysis residue (water ratio is 65% left and right) and 6.19 * 10
3kg glucose solution, the concentration of glucose solution is 3.01%, cellulosic extraction yield is 38%.
(3) alkaline solution extracts alkali lignin
The whole enzymolysis residues that obtain in the present embodiment step (2) are carried out to alkaline hydrolysis according to the processing method of embodiment 2 steps (3); Finally obtain 1.38 * 10
3kg alkaline hydrolysis residue (water ratio is 65% left and right) and 3.15 * 10
3kg alkali lignin solution, in solution, the content of alkali lignin is 2.94%, the extraction yield of alkali lignin is 49%.
Alternatively, 10% sulphur acid for adjusting pH value to 3 for the alkali lignin concentrated solution obtaining can be filtered to washing and the dry alkali lignin solid that obtains.
(4) circular treatment
Whole alkaline hydrolysis residues that step (3) is obtained return to step (2) and carry out enzymolysis for the second time, and enzymolysis processing is identical with the condition of enzymolysis processing the present embodiment step (2) Suo Shu for the second time; Obtain 0.75 * 10
3kg enzymolysis residue (water ratio is 65% left and right) and 3.86 * 10
3kg glucose solution, the concentration of glucose solution is 5.71%, cellulosic extraction yield is 45% for the second time.
The described residue of enzymolysis is for the second time carried out to alkaline hydrolysis for the second time, and the condition of alkaline hydrolysis is identical with the condition of alkaline hydrolysis described in step in the present embodiment (3) for the second time; The weight that obtains alkali lignin solution is 2.01 * 10
3kg, the alkali lignin content in solution is 3.29%, the extraction yield of alkali lignin is 35% for the second time.
In sum, the extraction yield of hemicellulose is 74%, and cellulosic total extraction yield is 83%, and total extraction yield of alkali lignin is 84%.
Comparative example 1
(1) N level acid hydrolysis
Method is with embodiment 1 step (1), and when difference is the 1st, 2 and 3 grades of acid hydrolysiss, the concentration of phosphoric acid 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 1:
Table 1
Comparative example 2
(1) N level acid hydrolysis
Method is with embodiment 5 steps (1), and when difference is the 1st, 2 and 3 grades of acid hydrolysiss, the concentration of sulfuric acid 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 2:
Table 2
Comparative example 3
Technique and method are with embodiment 3, difference is that step (3) cellulase hydrolysis cellulase used is commercially available cellulase (jade of the He family Bioisystech Co., Ltd, 4w unit), only carry out primary fiber element enzymolysis, do not carry out step (3) and step (4), obtaining weight is 5.77 * 10
3the glucose solution that kg, concentration are 2.40%, cellulosic extraction yield is 37%.
The amplitudes such as in each embodiment, only the amplitudes such as concentration with acid solution are reduced to example above, but according to principle of the present invention and experiment test, non-reduce 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 exhaustive without also giving all embodiments.And the apparent variation of being extended out thus or change are still among the protection domain in the invention.
Claims (7)
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, regulate the concentration of the acid solution of first step acid hydrolytic reaction still discharge, then added in the acid hydrolytic reaction still of the second stage, regulate the concentration of the acid solution of second stage acid hydrolytic reaction still discharge, then added in third stage acid hydrolytic reaction still, successively sequentially, until regulate the concentration of the acid solution of N-1 level acid hydrolytic reaction still discharge, then added in N level acid hydrolytic reaction still, the acid solution that N level acid hydrolytic reaction still is discharged is final pentose solution, then the acid hydrolysis residue in first step acid hydrolytic reaction still is discharged, and pack new lignocellulose biomass raw material into, using it 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, carry out again acid hydrolytic reaction, so move in circles and can realize the continuous hydrolysis of lignocellulose biomass, wherein, the amplitude that the concentration of described acid solution reduces to N level step by step from the first step is the 10-40% of first step acid solutions, the integer that N is 2-5,
(b) use cellulase to carry out enzymolysis to acid hydrolysis residue described in step (a), obtain as glucose solution and enzymolysis residue;
(c) the described enzymolysis residue producing with alkaline solution treatment step (b), extracts xylogen wherein and obtains alkaline hydrolysis residue;
(d) described alkaline hydrolysis residue is returned step (b) carry out enzymolysis processing or described alkaline hydrolysis residue and new acid hydrolysis residue are merged after carry out again the enzymolysis processing of step (b), then carry out successively step (c) and (d), so circulation, further extracts xylogen and carries out cellulase hydrolysis.
2. method according to claim 1, it is characterized in that: described cellulase is for being cultivated the cellulase obtaining by a penicillium, this Penicillium notatum Classification And Nomenclature is Penicillium decumbens PD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M2011195.
3. method according to claim 2, 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.
4. according to the method described in any one in claim 1-3, it is characterized in that: described alkaline solution is processed and carried out at 40-100 ℃.
5. method according to claim 4, is characterized in that: in described alkaline solution processing, liquid-solid volume ratio is 5: 1-20: 1.
6. method according to claim 5, is characterized in that: in described alkaline solution processing, the concentration of alkaline solution is 0.8-5 % by weight.
7. according to the method described in claim 5 or 6, it is characterized in that: the time that described alkaline solution is processed is 1-6 hour.
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| WO2010047358A1 (en) * | 2008-10-23 | 2010-04-29 | 独立行政法人科学技術振興機構 | Concentrated acid treatment unit, concentrated acid treatment method, plant resource phase separation type conversion device and conversion method |
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