CN103045698B - Method for comprehensively utilizing lignocellulose biomass - Google Patents
Method for comprehensively utilizing lignocellulose biomass Download PDFInfo
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Abstract
A method for comprehensively utilizing lignocellulose biomass comprises the following steps that: (a) the lignocellulose biomass is subjected to acid hydrolysis so as to obtain a pentose solution and acid hydrolytic residues; (b) cellulase is used for the enzymolysis of the acid hydrolytic residues, so that glucose solution and enzymatic residues are obtained, the cellulose is the cellulose which is obtained through culturing penicillium, the penicillium has a classification name of Penicilliumdecumbens PD-G3-08, is preserved in the China center for type culture collection (CCTCC) in the Wuhan university and has a preservation number of CCTCC M 2011195; (c) aqueous alkali is used to treat the enzymatic residues so as to extract lignin in the enzymatic residues and obtain alkaline hydrolytic residues; and (d) the alkaline hydrolytic residues are subjected to enzymolysis of the step (b) again or the alkaline hydrolytic residues and the new acid hydrolytic residues are merged and then are subjected to enzymolysis of the step (b) again, steps (c) and (d) are then carried out sequentially, operations are repeated, lignin is further extracted and cellulose enzymolysis is further carried out. By the method, the maximum utilization of the lignocellulose biomass resource is realized.
Description
Technical field
The present invention relates to a kind of method that fully utilizes lignocellulose biomass, specifically a kind of method that fully utilizes Mierocrystalline cellulose in lignocellulose biomass, hemicellulose and xylogen.
Background technology
Day by day serious along with the increasingly exhausted and environmental pollution of fossil fuel resource, utilizes the substitute that the renewable energy resources are petroleum chemicals to become further important.And alcohol fuel is the principal mode of the material of biomass liquid energy, it is also the most probable substitute of fossil oil.At present, the mainly raw material using starch based (corn, cassava etc.) and carbohydrate (sugarcane, beet etc.) as fermentation of world's alcohol production.Adopt microbial method fermentative production of ethanol technology maturation, but high raw materials cost is restricted the industrial application of grain fermentative production of ethanol, exist simultaneously with people strive grain and grain strive etc. drawback, and cause provision price Continued, therefore find new raw material imperative.Scientist is more cheap sight trend of purchasing cost, the lignocellulose biomass widely of originating now.
Lignocellulose biomass exists with the form of plant materials, main component is Mierocrystalline cellulose, hemicellulose and xylogen, wherein, Mierocrystalline cellulose accounts for 40% left and right, hemicellulose accounts for 25% left and right, xylogen accounts for 20% left and right, and the lignocellulose biomass total amount being generated by photosynthesis every year on the earth exceedes 2,000 hundred million tons, and therefore Wooden Biomass is renewable resources abundant, the most cheap on the earth.
If can, taking lignocellulose biomass as raw material production ethanol, will greatly solve the mankind's energy problem, but still exist in this respect a lot of technical barriers not yet to solve.At present, taking lignocellulose biomass in raw material production ethanol process, the first problem running into is that hemicellulose, Mierocrystalline cellulose and xylogen are failed to fully utilize well, the Technology of existing processing biomass, obtaining ethanol mainly with degraded carbohydrate is greatly object, can not extract simultaneously and obtain high purity, highly active xylogen, often xylogen be removed to object as one; Another greatest problem is the low conversion rate of cellulase hydrolysis, the high cost (accounting for the 40-50% of total cost of production) of enzymolysis, and production cost is too high, cannot really realize industrialization.The reason of the low conversion rate of cellulase hydrolysis is: hemicellulose is combined between Mierocrystalline cellulose and xylogen as molecule tamanori on the one hand, and the reticulated structure that xylogen has, surround and add set Mierocrystalline cellulose and hemicellulose as support frame, xylogen and hemicellulose spatially can hinder contacting of cellulosic molecule and enzyme, enzyme accessibility is poor, has increased the difficulty of enzymolysis.Therefore be necessary lignocellulose biomass to carry out effective pre-treatment, destroy the spatial obstacle of xylogen and hemicellulose, also to avoid pre-treatment to produce simultaneously and be unfavorable for the enzyme inhibitor (as furfural, acetic acid etc.) of enzymolysis, thereby be conducive to cellulosic enzymolysis; On the other hand, cellulase is low to crystalline cellulose enzymatic reaction vigour, therefore, in order to improve the transformation efficiency of cellulase hydrolysis, need to improve the vigor of cellulase.
Summary of the invention
For this reason, technical problem to be solved by this invention is to overcome prior art in the time of comprehensive utilization hemicellulose, xylogen and Mierocrystalline cellulose, the problem of and cellulase hydrolysis low conversion rate low to the utilization ratio of xylogen, thus a kind of method of comprehensive utilization of lignocellulose biomass has been proposed.
For achieving the above object, the invention provides a kind of method of comprehensive utilization of lignocellulose biomass, it is characterized in that comprising the following steps:
(a) lignocellulose biomass is carried out to acid hydrolysis, after separation, obtain pentose solution and acid hydrolysis residue;
(b) use cellulase to carry out enzymolysis to described acid hydrolysis residue, obtain glucose solution and enzymolysis residue, described cellulase is to cultivate by a penicillium cellulase obtaining, this Penicillium notatum Classification And Nomenclature is Penicillium decumbens PD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195;
(c) process described enzymolysis residue with alkaline solution, extract xylogen wherein and obtain 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.
There is no particular limitation for the kind of described acid solution, can be that lignocellulose biomass carries out the acid-hydrolyzed conventional acid using, and for example acid can be one or more in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
Described acid-hydrolyzed temperature is 100-150 DEG C, time is 0.5-3 hour, while carrying out described acid hydrolysis, the concentration of acid solution is that (as the acid of selecting is strong acid to 0.5-30 % by weight, the concentration of acid solution is lower, is about 0.5-5 % by weight, as the acid of selecting is weak acid, the concentration of acid solution is higher, is about 5-30 % by weight).The concentration of preferably phosphoric acid is 1-20 % by weight.
Described acid solution phosphoric acid solution, the concentration of phosphoric acid solution is 1-20 % by weight.
Described lignocellulose biomass can be one or more of maize straw, wheat straw, rice straw, bagasse, cotton bavin, cotton seed hull, corn cob, straw, kaoliang stalk, broad-leaved wood and wood chip.
Carry out pre-treatment according to raw material condition, lignocellulose biomass raw material is cut or pulverized, then this stalk section is carried out to scrubbing dust collection.
The condition of described cellulase hydrolysis is: substrate consumption is 80-150g/L, and the addition of cellulase is 10-15FPU/g Mierocrystalline cellulose, and temperature is that 45-55 DEG C, pH are that 4-6, mixing speed are 50-200rpm, and enzymolysis transformation time is 2-7 days.
After cellulase hydrolysis saccharification, can adopt the method for well known to a person skilled in the art, fermentative production of ethanol.
Described alkaline solution is processed and is carried out at 40-100 DEG C.
In described alkaline solution processing, liquid-solid volume ratio is 5: 1-20: 1.
In described alkaline solution processing, the concentration of alkaline solution is 0.8-5 % by weight.
The time of described alkaline solution processing 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 first acid hydrolysis, the operational path of enzymolysis, last alkaline hydrolysis again, because cellulase used is to cultivate by a penicillium cellulase obtaining, this Penicillium notatum Classification And Nomenclature is Penicillium decumbens PD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195, the cellulase that adopts this Penicillium notatum to produce has higher vigor, has improved the extraction yield of cellulase hydrolysis; The present invention adopts circulation technology respectively Mierocrystalline cellulose, xylogen to be replaced to extraction process simultaneously, improve 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, further protection xylogen and Mierocrystalline cellulose are not destroyed, thereby can make xylogen and cellulosic utilization maximize; In addition, first 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 the first acidolysis of picture, 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,, owing to having adopted the technique of first acidolysis, rear enzymolysis, last alkaline hydrolysis, so the main component of the residue obtaining after enzymolysis is xylogen, 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. what the present invention was used cultivates by Penicillium notatum the cellulase obtaining, be 80-150g/L at substrate consumption, the addition of cellulase is 10-15FPU/g Mierocrystalline cellulose, temperature is that 45-55 DEG C, pH are that 4-6, mixing speed are 50-200rpm, under the enzymolysis conversion condition of 2-7 days, enzymolysis transformation efficiency is the highest.
3. the temperature of reacting in acid hydrolysis described in is 100-150 DEG C, time is 0.5-3 hour, under this temperature and time, can be by hydrolysis of hemicellulose more thorough, can stop again under acidic conditions high temperature and reaction times long to xylogen and cellulosic destruction.
4, acid hydrolysis of the present invention acid used is phosphoric acid solution, and the concentration of phosphoric acid solution is 1-20 % by weight, has avoided to greatest extent destruction xylogen and Mierocrystalline cellulose, and due to phosphoric acid corrosion a little less than, therefore, maintenance of the equipment is simple, duration of service is long.
5. the condition of alkaline solution processing of the present invention adopts liquid-solid ratio, alkali consumption, temperature and time, the activity that finally obtains alkali lignin is very high.
Brief description of the drawings
For content of the present invention is more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the schematic diagram of technical process of the present invention.
Embodiment
Below will by specific embodiment, the invention will be further described.
The self-control cellulase that following examples are used is cultivated and is obtained by Penicillium notatum, and concrete cultural method is:
(A) bacterial classification multiplication culture
Be that Penicillium decumbens PD-G3-08 Penicillium notatum seed liquor is linked in the fermentor tank that contains seed culture medium through 121 DEG C of sterilizing 30min and activates with the inoculum size of 5% (v/v) by naming number, keep tank pressure 0.02-0.05MPa, air flow 0.5vvm, mixing speed 100-150rpm, 30 DEG C of cultivation 30-60 hour, obtain the seed liquor after activation.
Component in described seed culture medium and consumption are: get embodiment 1 acid hydrolysis residue 10-30g/L, wheat bran 20-50g/L, peptone 1-4g/L, ammonium sulfate 2-4g/L, all the other are water.
Component and consumption in described seed culture medium are preferably: acid hydrolysis residue 20g/L, wheat bran 40g/L, peptone 3g/L, ammonium sulfate 3g/L, all the other are water.
(B) prepare cellulase
Step (A) is obtained to seed liquor to be accessed with the inoculum size of 10% (v/v) in the 5L fermentor tank that 3L fermention medium is housed of sterilizing, in fermenting process, add defoamer control foaming, keep tank pressure 0.02-0.05MPa, air flow 0.5-0.6vvm, mixing speed 100-150rpm, 30 DEG C of cultivation 80-136 hour, obtain fermented liquid.
In described fermention medium, each amounts of components is respectively: acid hydrolysis residue 30-50g/L, wheat bran 20-50g/L, Microcrystalline Cellulose or carboxymethyl cellulose 4-8g/L, ammonium sulfate 2-5g/L, potassium primary phosphate 2-4g/L, magnesium sulfate 0.4-0.6g/L, all the other are water, and the initial pH of substratum is 5.0-6.0.
In described fermention medium, each amounts of components is preferably: acid hydrolysis residue 45g/L, wheat bran 35g/L, Microcrystalline Cellulose 5g/L, ammonium sulfate 4g/L, potassium primary phosphate 3g/L, magnesium sulfate 0.6g/L, all the other are water, and the initial pH of substratum is 5.0-6.0.
The fermented liquid 8000rpm centrifuging and taking obtaining obtains supernatant liquor, must contain the crude enzyme liquid of cellulase, and this crude enzyme liquid can be directly used in cellulosic enzymolysis.
(2) test as follows the various performances of xylogen in following examples
The mensuration of content of lignin: comprise sour insoluble xylogen and sour solvable xylogen.Wherein the mensuration of sour insoluble xylogen adopts Klason method, carries out according to GB GB/T2677.8-94; The solvable xylogen of acid carries out according to GB GB 10337-89.
The mensuration of moisture: carry out according to GB/T 2667.3-93.
Following examples are participated in Fig. 1.
In following examples, pressure corresponding to acid hydrolysis temperature is the pressure of saturated vapor, therefore no longer provides pressure data for each embodiment.
In embodiments of the invention, except indicating, percentage composition used is all expressed as weight percentage, i.e. " % " expression " % by weight ".
Embodiment 1
(1) acid hydrolysis
By 10.6kg corn cob (mass component composition: moisture 6.12%, Mierocrystalline cellulose 35.19%, hemicellulose 32.1%, xylogen 23.7%, other is 2.95% years old, lower same) smash, wash dedusting with water, then be hydrolyzed with 80kg phosphoric acid solution, the mass concentration of phosphoric acid solution is 10%, acid-hydrolyzed temperature is 120 DEG C, time is 1 hour, acid hydrolysis residue and pentose solution that rear separation obtains are hydrolyzed, clean described acid hydrolysis residue with 10kg water, scavenging solution and described pentose solution merge, (water content is 65% left and right finally to obtain 19.64kg acid hydrolysis residue, the over dry content of hemicellulose is 15.87%, the over dry content of xylogen is 31.75%, cellulosic over dry content is 47.81%) and 80.34kg pentose solution, the concentration of pentose solution is 2.89%, the extraction yield of hemicellulose is 68%.
The calculation formula of hemicellulose extraction yield is as follows:
Extraction yield %=(concentration of the quality × pentose of pentose solution)/(content of hemicellulose in corn cob quality × corn cob) × 100% of hemicellulose.
(2) cellulase hydrolysis
The condition of described enzymolysis is: cellulase is above-mentioned Penicillium notatum (Penicillium decumbensPD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195) cultivate obtain cellulase, the all acid hydrolytic residue that the present embodiment step (1) is obtained is as cellulosic substrate, add cellulase according to the cellulosic addition of 15FPU/g, cellulosic substrate consumption is 125g/L, it is 48 DEG C in temperature, pH is 5.0, under the condition of mixing speed 50rpm, enzymolysis transforms 2 days, whole enzymolysis process is without pressurize, obtain glucose solution, quality is 54.99kg, concentration is 2.93%, cellulosic extraction yield is 43%.
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, wherein liquid-solid volume ratio is 5: 1, the concentration of sodium hydroxide is 3%, then be warming up to 70 DEG C, through the boiling alkaline hydrolysis of 1 hour, separation obtains alkaline hydrolysis residue and alkali lignin solution, cleans described alkaline hydrolysis residue with 10kg water, and scavenging solution and described alkali lignin solution merge; Final 29.92kg alkali lignin solution and the 11.65kg alkaline hydrolysis residue (water ratio is 65% left and right) of obtaining, in solution, alkali lignin content is 3.72%, the extraction yield of alkali lignin is 44%.
Alkali lignin extraction yield %=(content of lignin in quality × alkali lignin solution of alkali lignin solution)/(content of xylogen in corn cob quality × corn cob) × 100%
(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 32.63kg glucose solution, the concentration of glucose solution is 3.56%, and cellulosic extraction yield is 31% 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 of alkali lignin solution is 16.41kg, and the alkali lignin content in solution is 4.78%, and the extraction yield of alkali lignin is 31% for the second time.
In sum, the extraction yield of hemicellulose is 68%, and cellulosic total extraction yield is 74%, and total extraction yield of alkali lignin is 75%.
Embodiment 2
(1) acid hydrolysis
10.6kg corn cob is smashed, wash dedusting with water, then be hydrolyzed with 80kg phosphoric acid solution, the mass concentration of phosphoric acid solution is 20%, acid-hydrolyzed temperature is 100 DEG C, time is 0.5 hour, acid hydrolysis residue and pentose solution that rear separation obtains are hydrolyzed, clean described acid hydrolysis residue with 10kg water, scavenging solution and described pentose solution merge, (water content is 65% left and right finally to obtain 19.35kg acid hydrolysis residue, the over dry content of hemicellulose is 15.10%, the over dry content of xylogen is 31.79%, cellulosic over dry content is 48.47%) and 80.63kg pentose solution, the concentration of pentose solution is 2.96%, the extraction yield of hemicellulose is 70%.
(2) cellulase hydrolysis
Get step (1) and obtain all acid hydrolytic residue as cellulosic substrate, carry out cellulase hydrolysis, the condition of described enzymolysis is: cellulase is above-mentioned Penicillium notatum (Penicillium decumbensPD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M 2011195) cultivate obtain cellulase, add cellulase according to the cellulosic addition of 10FPU/g, cellulosic substrate consumption is 150g/L, it is 55 DEG C in temperature, pH is 4, under the condition of mixing speed 200rpm, enzymolysis transforms 7 days, whole enzymolysis process obtains glucose solution without pressurize, quality is 51.92kg, concentration is 3.18%, cellulosic extraction rate reached 44%.
(3) alkaline solution extracts alkali lignin
Whole enzymolysis residues that above-mentioned steps (2) is obtained mix with sodium hydroxide solution, wherein liquid-solid volume ratio is 10: 1, the concentration of sodium hydroxide is 5%, then be warming up to 40 DEG C, through the boiling alkaline hydrolysis of 6 hours, separation obtains alkaline hydrolysis residue and alkali lignin solution, cleans described alkaline hydrolysis residue with 10kg water, and scavenging solution and described alkali lignin solution merge; Finally obtain 11.12kg alkaline hydrolysis residue (water ratio is about 65%) and 55.25kg alkali lignin solution; Alkali lignin content in solution is 2.1%, and alkali lignin extraction yield 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 29.8kg glucose solution, the concentration of glucose solution is 4.15%, and cellulosic extraction yield is 33% 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 of alkali lignin solution is 28.41kg, and the alkali lignin content in solution is 2.22%, and the extraction yield of alkali lignin is 25% for the second time.
In sum, the extraction yield of hemicellulose is 70%, and cellulosic total extraction yield is 77%, and total extraction yield of alkali lignin is 71%.
Embodiment 3
(1) acid hydrolysis
10.6kg corn cob is smashed, wash dedusting with water, then be hydrolyzed with 80kg phosphoric acid solution, the mass concentration of phosphoric acid solution is 5%, acid-hydrolyzed temperature is 150 DEG C, time is 1 hour, acid hydrolysis residue and pentose solution that rear separation obtains are hydrolyzed, clean described acid hydrolysis residue with 10kg water, scavenging solution and described pentose solution merge, (water content is 65% left and right finally to obtain 20.02kg acid hydrolysis residue, the over dry content of hemicellulose is 16.05%, the over dry content of xylogen is 31.5%, cellulosic over dry content is 47.97%) and 79.96kg pentose solution, the concentration of pentose solution is 2.86%, the extraction yield of hemicellulose is 67%.
(2) cellulase hydrolysis
Get the described acid hydrolysis residue of step (1) as cellulosic substrate, carry out cellulase hydrolysis, the condition of described enzymolysis is: cellulase is above-mentioned Penicillium notatum (Penicillium decumbens PD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M2011195) cultivate obtain cellulase, add cellulase according to the cellulosic addition of 12FPU/g, cellulosic substrate consumption is 80g/L, it is 55 DEG C in temperature, pH is 4, mixing speed is under the condition of 100rpm, enzymolysis transforms 2 days, whole enzymolysis process is without pressurize, obtain glucose solution, quality is 94.6kg, concentration is 1.86%, cellulosic extraction yield is 47%.
(3) alkaline solution extracts alkali lignin
Whole enzymolysis residues that above-mentioned steps (2) is obtained mix with sodium hydroxide solution, wherein liquid-solid volume ratio is 20: 1, the concentration of sodium hydroxide is 0.8%, then be warming up to 100 DEG C, through the boiling alkaline hydrolysis of 2 hours, separation obtains alkaline hydrolysis residue and alkali lignin solution, cleans described alkaline hydrolysis residue with 10kg water, and scavenging solution and described alkali lignin solution merge; Finally obtain 11.47kg alkaline hydrolysis residue (water ratio is about 65%) and 108.7kg alkali lignin solution; Alkali lignin content in solution is 1.07%, and alkali lignin extraction yield is 46%.
(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 completing, enzymolysis processing carries out again the alkaline hydrolysis processing of step (3), 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 process 106kg corn cob, the extraction yield that finally obtains the hemicellulose of corn cob is 67%, and cellulosic total extraction yield is 79%, and total extraction yield of xylogen is 73%.
Embodiment 4
(1) acid hydrolysis
First by Wheat Straw (the mass component composition: moisture 10.1% that is 11.12kg, Mierocrystalline cellulose 44%, hemicellulose 22.2%, xylogen 17%, other is 6.7% years old) smash, wash dedusting with water, then be hydrolyzed with sulphuric acid soln, the mass concentration of sulphuric acid soln is 0.5%, carrying out acid-hydrolyzed temperature is 130 DEG C, pressure is 0.27MPa, time is 3 hours, be hydrolyzed that rear separation obtains, after the acid hydrolysis residue that acid hydrolysis residue and pentose solution obtain cleans with 10kg water, then scavenging solution and pentose solution merge, (water content is 65% left and right finally to obtain 21.87kg acid hydrolysis residue, the over dry content of hemicellulose is 11.61%, the over dry content of xylogen is 22.03%, cellulosic over dry content is 56.63%) and 78.1kg pentose solution, pentose concentration is 2.02%, the extraction yield of hemicellulose is 64%.
(2) cellulase hydrolysis
Get the described acid hydrolysis residue of step (1) as cellulosic substrate, carry out cellulase hydrolysis, the condition of described enzymolysis is: cellulase is above-mentioned Penicillium notatum (Penicillium decumbens PD-G3-08, be preserved in Wuhan University's Chinese Typical Representative culture collection center, its deposit number is CCTCC M2011195) cultivate obtain cellulase, add cellulase according to the cellulosic addition of 15FPU/g, cellulosic substrate consumption is 125g/L, it is 48 DEG C in temperature, pH is 5.0, under the condition of mixing speed 50rpm, enzymolysis transforms 2 days, whole enzymolysis process is without pressurize, obtain glucose solution, quality is 61.4kg, concentration is 3.68%, cellulosic extraction yield is 46%.
(3) alkaline solution extracts alkali lignin
Whole enzymolysis residues that above-mentioned steps (2) is obtained mix with sodium hydroxide solution, wherein liquid-solid volume ratio is 5: 1, the concentration of sodium hydroxide is 3%, then be warming up to 70 DEG C, through the boiling alkaline hydrolysis of 1 hour, separation obtains alkaline hydrolysis residue and alkali lignin solution, cleans described alkaline hydrolysis residue with 10kg water, and scavenging solution and described alkali lignin solution merge; Finally obtain 12.91kg alkaline hydrolysis residue (water ratio is about 65%) and 29.52kg alkali lignin solution; Alkali lignin content in solution is 2.75%, and alkali lignin extraction yield is 43%;
(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 36.14kg glucose solution, the concentration of glucose solution is 4.06%, and cellulosic extraction yield is 30% 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 of alkali lignin solution is 16.04kg, and the alkali lignin content in solution is 3.18%, and the extraction yield of alkali lignin is 27% for the second time.
In sum, the extraction yield of hemicellulose is 64%, and cellulosic total extraction yield is 76%, and total extraction yield of alkali lignin is 70%.
Found through experiments, when acid solution adopts the weak acid that concentration expressed in percentage by weight is 30%, less to xylogen and cellulosic destruction, can realize object of the present invention.And the concentration of phosphoric acid solution is while being 1%, also can realize the present invention, just needed time of acid hydrolysis and temperature of reaction need corresponding increase.
Comparative example 1
Technique and method are with embodiment 1, 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 the circular treatment of step (3) and (4), obtaining quality is the glucose solution that 54.9kg, concentration are 2.25%, and cellulosic extraction yield is 33%.
Comparative example 2
Technique and method are with embodiment 2, 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 the circular treatment of step (3) and (4), obtaining quality is the glucose solution that 51.9kg, concentration are 2.17%, and cellulosic extraction yield is 30%.
Comparative example 3
Technique and method are with embodiment 4, difference is: 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 the circular treatment of step (3) and (4), obtaining quality is the glucose solution that 61.2kg, concentration are 2.32%, and cellulosic extraction yield is 29%.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also giving exhaustive to all embodiments.And the apparent variation of being extended out thus or variation are still among the protection domain in the invention.
Claims (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 acid hydrolysis, obtain pentose solution and acid hydrolysis residue after separation, the acid solution adopting when described acid hydrolysis is phosphoric acid solution, and concentration is 1-20 % by weight;
(b) use cellulase to carry out enzymolysis to described acid hydrolysis residue, obtain glucose solution and enzymolysis residue, described cellulase is to cultivate by a penicillium cellulase obtaining, and this Penicillium notatum Classification And Nomenclature is
penicillium decumbenspD-G3-08, has been preserved in Wuhan University's Chinese Typical Representative culture collection center, and its deposit number is CCTCC M 2011195;
(c) process described enzymolysis residue with alkaline solution, extract xylogen wherein and obtain 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, is characterized in that: described acid-hydrolyzed temperature is 100-150 DEG C, and the time is 0.5-3 hour.
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 DEG C, pH are that 4-6, mixing speed are 50-200rpm, and enzymolysis transformation time is 2-7 days.
4. method according to claim 3, is characterized in that: described alkaline solution is processed and carried out at 40-100 DEG C.
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. according to the method described in any one in claim 3-5, it is characterized in that: in described alkaline solution processing, the concentration of alkaline solution is 0.8-5 % by weight.
7. method according to claim 6, is characterized in that: the time of described alkaline solution processing is 1-6 hour.
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| CN1157853A (en) * | 1996-11-13 | 1997-08-27 | 山东大学 | Preparing method of high active cellulase |
| CN1339585A (en) * | 2000-08-21 | 2002-03-13 | 中国科学院化工冶金研究所 | Process for producing high activity cellulase by solid fermentation of steam puffed stalk |
| CN101619332A (en) * | 2009-08-13 | 2010-01-06 | 安徽丰原发酵技术工程研究有限公司 | Method for efficiently saccharifying bagasse |
| CN102061267A (en) * | 2010-11-26 | 2011-05-18 | 东北林业大学 | Engonus fungus with high enzyme activity and high capacity of efficiently degrading straw cellulose in northeast China region |
| CN102153763A (en) * | 2010-09-27 | 2011-08-17 | 天津大学 | Lignocellulose acid/alkali coupling pretreatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1157853A (en) * | 1996-11-13 | 1997-08-27 | 山东大学 | Preparing method of high active cellulase |
| CN1339585A (en) * | 2000-08-21 | 2002-03-13 | 中国科学院化工冶金研究所 | Process for producing high activity cellulase by solid fermentation of steam puffed stalk |
| CN101619332A (en) * | 2009-08-13 | 2010-01-06 | 安徽丰原发酵技术工程研究有限公司 | Method for efficiently saccharifying bagasse |
| CN102153763A (en) * | 2010-09-27 | 2011-08-17 | 天津大学 | Lignocellulose acid/alkali coupling pretreatment method |
| CN102061267A (en) * | 2010-11-26 | 2011-05-18 | 东北林业大学 | Engonus fungus with high enzyme activity and high capacity of efficiently degrading straw cellulose in northeast China region |
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