CN104531807B - A kind of method of efficiently saccharifying draft energy-source plant - Google Patents
A kind of method of efficiently saccharifying draft energy-source plant Download PDFInfo
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- CN104531807B CN104531807B CN201410812247.3A CN201410812247A CN104531807B CN 104531807 B CN104531807 B CN 104531807B CN 201410812247 A CN201410812247 A CN 201410812247A CN 104531807 B CN104531807 B CN 104531807B
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Abstract
The invention discloses a kind of method of efficiently saccharifying draft energy-source plant, comprise the following steps：A, not pretreated draft energy-source plant raw material and cellulase be added in enzymolysis liquid, pH4.8 is digested at 50 DEG C, separation of solid and liquid, obtains Production With Residue of Enzymatic Hydrolysis I and enzymolysis liquid glucose I；The Production With Residue of Enzymatic Hydrolysis I that b, step a are obtained is in the pH containing boric acid or borate in 4~6 hydro-thermal cushioning liquid, after hydrothermal pretreatment, separation of solid and liquid obtains pretreatment slag and pre-processes liquid glucose；The pretreatment slag that c, step b are obtained, repeat step a obtains Production With Residue of Enzymatic Hydrolysis II and enzymolysis liquid glucose II；The repeat step b of Production With Residue of Enzymatic Hydrolysis II that d, step c are obtained, untill sugared concentration is not further added by obtained pretreatment liquid glucose.The present invention reduces water consumption in preprocessing process on the basis of raw material saccharic composition high efficiente callback utilization, reduces energy consumption, and effectively improves sugared concentration in pretreatment fluid and enzymolysis liquid, in order to which subsequent transformation is utilized.
Description
Technical field：
The present invention relates to biomass energy trans-utilization technical field, and in particular to a kind of efficiently saccharifying draft energy-source plant
Method.
Background technology：
The non-renewable and its a large amount of consumption of fossil fuel causes the continuous deterioration of energy resource supply and ecological environment, causes
The concern of the environmentally friendly type regenerative resource research and development of people.In this context, the wood fibre based on " sugared platform "
Plain biolobic material refining, the fuels and chemicals research to produce alternative oil product is increasingly subject to pay attention to.It is being referred to as
The 21 century of " sugar is economic " development in science and technology, the polysaccharide component (cellulose and hemicellulose) in lignocellulose biomass is degraded
It is to promote important foundation and the guarantee of realizing " sugar is economical " for the sugared intermediate such as Soluble Monosaccharide or oligosaccharide.
The means of current biomass by hydrolyzation saccharification mainly have two kinds of mineral acid hydrolysis and cellulose hydrolyzation, cellulase water
Solution is with its reaction condition is gentle, product is single advantage, it has also become the important development direction of manufacturing sugar by biomass.But because of wood fibre
The netted embedding shadow of the fine and close and complicated space three-dimensional structure of plain biolobic material, cellulose crystallite and hemicellulose and lignin
Ring, DIRECT UTILIZATION OF CELLULOSE enzyme hydrolysis it is less efficient.Therefore, before enzymatic saccharification, generally requiring to break wood by pretreatment
Matter cellulose compact texture, to increase subsequent enzymatic hydrolysis efficiency.
Compared with the preprocess methods such as traditional acid-base method, ammonia fiber explosion, hydrothermal pretreatment process is cheap using green
Reaction medium, with cost is low, efficiency high, environmental protection, to the more low advantage of equipment requirement, it has also become the research of preprocessing technical field
Focus.However, hydrothermal pretreatment energy consumption is higher, biomass sugar chemical conversion is raised originally, therefore, developing efficient biomass
Method for saccharifying, it is significant to improving the sugared Technical Economy times of lignocellulosic production.
Draft energy-source plant is considered as one of most promising Biomass Energy Resources, is referred to through special plantation,
A class herbaceous plant to provide energy source raw material, including Chinese pennisetum, napier grass, switchgrass, awns genus crop etc..Due to the draft energy
Plant structure relative loose, rich in cellulose and hemicellulose, content of lignin is low, and draft energy-source plant is a kind of good
Biomass mash goods.
The enzymatic saccharification patent of presently relevant hydrothermal pretreatment has：CN101818217 provides one kind with low-concentration metallic
The method of hemi-cellulose components in ionic catalysis, hydro-thermal saccharification biomass；CN101613728 discloses a kind of pre- with alkaline hydro-thermal
The straw pulp fiber efficiently saccharifying method of processing；CN101586136 discloses a kind of using two steps segmentation alternating temperature hydrothermal pretreatment
The method of sugar product in mode, high efficiente callback lignocellulose-like biomass；CN103993053 discloses a kind of wood fibre
The high temperature liquid water that plain biolobic material component is efficiently utilized-ammonia process two-step method technique；CN104073533 provides a kind of water
Pyrohydrolysis liquid is recycled, hydrolysis residue ultrasonically treated low power consuming pyrohydrolysis biomass pretreatment method and its device；
CN102174594 is provided after a kind of biomass water Grape berry, is added surfactant, is used batch feeding mode of action, with
The method for improving the sugared concentration of enzymolysis liquid.
In above-mentioned existing method, hydrothermal pretreatment is carried out mostly under low concentration of substrate, unit raw material high energy consumption；Pretreatment
During saccharic composition be lost in, reduce raw material saccharic composition utilization；Detoxification treatment is needed after pretreatment, is required with meeting enzymolysis；Need many
Step pretreatment can be only achieved efficient enzymolysis；Hydrolyzate sugar concentration is limited, limits subsequent transformation and the deficiency such as utilizes all to constrain wood
The promotion and application of matter cellulose series biomass saccharification technology.
The content of the invention：
The purpose of the present invention is to overcome shortcoming and deficiency present in prior art there is provided a kind of efficiently saccharifying draft energy
The method of plant, using draft energy-source plant as raw material, using enzymolysis coupling cushioning liquid hydrothermal pretreatment mode, efficiently saccharifying is former
Cellulose and hemi-cellulose components in material.
The present invention is achieved by the following technical programs：
A kind of method of efficiently saccharifying draft energy-source plant, this method comprises the following steps：
A, not pretreated draft energy-source plant raw material and cellulase by granularity after crushing less than 1cm are added to enzyme
Solve in liquid, pH4.8, at 50 DEG C after enzymolysis 24-96h, separation of solid and liquid obtains Production With Residue of Enzymatic Hydrolysis I and enzymolysis liquid glucose I；The enzymolysis raw material
Mass-volume concentration be 10%~30%g/mL；The cellulase consumption is 10~30FPU/g celluloses；
The Production With Residue of Enzymatic Hydrolysis I that b, step a are obtained the pH containing boric acid or borate for 4~6 hydro-thermal cushioning liquid in 100~
After 180 DEG C of 10~60min of hydrothermal pretreatment, separation of solid and liquid obtains pretreatment slag and pre-processes liquid glucose；The matter of the Production With Residue of Enzymatic Hydrolysis I
Amount volumetric concentration is 10~30%g/mL；The hydrothermal pretreatment environment is inert atmosphere, and pressure is 2-4MPa；
After the pretreatment slag that c, step b are obtained, addition cellulase, it is with enzymolysis liquid described in step a or enzymolysis liquid glucose I
Medium, repeat step a continues to digest, and separation of solid and liquid obtains Production With Residue of Enzymatic Hydrolysis II and enzymolysis liquid glucose II；
The repeat step b of Production With Residue of Enzymatic Hydrolysis II that d, step c are obtained, until in obtained pretreatment liquid glucose sugared concentration be not further added by for
Only.
Enzymolysis liquid glucose I that the step a and step c are obtained, enzymolysis liquid glucose II are used as enzymolysis medium circulation, to enter one
Step improves sugared concentration in enzymolysis liquid.
The pretreatment liquid glucose obtained in step b can be used for the hydrothermal pretreatment of next round, be disappeared with being enriched with sugar and reducing water
Consumption.
One or more of the draft energy-source plant in Chinese pennisetum, napier grass, switchgrass, awns genus crop.
The pH containing boric acid or borate is selected from potassium dihydrogen phosphate-phosphoric acid hydrogen two for 4~6 hydro-thermal cushioning liquid
Any of potassium-boric acid, phosphoric acid-sodium phosphate-Boratex, citric acid-sodium citrate-boric acid.
The separation of solid and liquid is selected from any of centrifugation, press filtration separation or sedimentation separation.
Main sugar component is glucose, xylose, xylo-oligosaccharide, cellobiose in the enzymolysis liquid glucose and pretreatment liquid glucose
The water-soluble hexose that is produced Deng cellulose and hemi-cellulose components hydrolysis and saccharification in raw material, pentose, oligomeric hexose and
Oligomeric pentose.
Beneficial effects of the present invention are as follows：
(1) using first digest pre-process afterwards by the way of reduce needed for pretreated feedstock amount, and then reduction water and energy consumption；
(2) pretreatment liquid glucose and enzymolysis liquid glucose are recycled, sugar that can be in enrichment solution, are utilized with sharp subsequent transformation；
(3) step b can avoid pretreatment liquid glucose from following with cushioning liquid hydrothermal pretreatment while pre-processing intensity is kept
Continuous acidifying during ring use, and then soluble sugar degraded consumption caused by acid is reduced, be conducive to improving sugar in solution dense
Degree；
(4) acid hydro-thermal cushioning liquid is in circulation preprocessing process, and the oligosaccharide in energy constantly hydrating solution is improved molten
Monosaccharide concentration in liquid；
(5) hydro-thermal cushioning liquid mesoboric acid or borate can be conducive to the steady of sugar with the hydroxyl ligand complex in glycan molecule
Fixed enrichment；
(6) residual toxicity material is few in pretreatment slag, and contained pH value of solution is approached with pH needed for enzymolysis, therefore pretreatment slag need not
Detoxification, is added after enzymolysis liquid and enzyme, you can directly digested；
(7) enzyme is recycled with enzymolysis liquid glucose, can be effectively improved enzyme service efficiency, be reduced cost.
In a word, the present invention couples cushioning liquid hydrothermal pretreatment side afterwards using draft energy-source plant as raw material using first digesting
The method of cellulose and hemi-cellulose components in formula, efficiently saccharifying raw material.Raw material of the present invention is easy to get, and is pre-processed afterwards by first digesting
The simple process recycled with hydrolyzate, on the basis of raw material saccharic composition high efficiente callback utilization, is reduced in preprocessing process
Water consumption, reduces energy consumption, and can effectively improve sugared concentration in pretreatment fluid and enzymolysis liquid, in order to which subsequent transformation is utilized.This hair
It is bright environmentally friendly, efficient, the efficient utilization of fibre fractionation in draft energy-source plant can be realized, sugar loss is few, rate of recovery height.
Embodiment：
Further illustrated the following is to the present invention, rather than limitation of the present invention.
Embodiment 1：
Using Chinese pennisetum as raw material, granularity is crushed to less than 1cm, is placed in enzyme digestion reaction device, by enzymolysis raw material
Mass-volume concentration is that 10%g/mL adds enzymolysis liquid, and cellulase is added with the ratio of 20FPU/g celluloses, in pH4.8, temperature
Under conditions of 50 DEG C of degree after enzymolysis 24h, separation of solid and liquid collects Production With Residue of Enzymatic Hydrolysis and enzymolysis liquid glucose；Production With Residue of Enzymatic Hydrolysis is placed in hydrothermal pretreatment
It is the hydro-thermal cushioning liquid (phosphoric acid-sodium phosphate-boric acid that 10%g/mL adds that pH is 5 by mass-volume concentration in reaction unit
Sodium) after stir, in 180 DEG C, 4MPa nitrogen atmospheres, react 10min, separation of solid and liquid collects pretreatment residue and pre- place
Manage liquid glucose；Pretreatment residue is placed in enzyme digestion reaction device, added by the mass-volume concentration of enzymolysis raw material for 10%g/mL
Above-mentioned enzymolysis liquid glucose, cellulase is added with the ratio of 20FPU/g celluloses, is digested under conditions of pH4.8, temperature 50 C
After 48h, separation of solid and liquid.Now, saccharification of cellulose utilization rate is 90% in raw material, wherein, contained water-soluble grape in enzymolysis liquid glucose
Sugared and oligomeric hexose accounts for 83% of glucose total amount contained by raw material, in pretreatment hydrolysis sugar liquid contained aqueous glucose and it is oligomeric oneself
Sugar accounts for 7% of glucose total amount contained by raw material.Hemicellulose saccharification utilization rate is 93% in raw material, wherein, institute in enzymolysis liquid glucose
35% of xylose total amount contained by raw material is accounted for containing water-soluble xylose and oligomeric pentose, water-soluble xylose contained by hydrolysis sugar liquid is pre-processed and low
Poly-pentose accounts for 58% of xylose total amount contained by raw material.
Embodiment 2：
Using Chinese pennisetum as raw material, granularity is crushed to less than 1cm, is placed in enzyme digestion reaction device, by enzymolysis raw material
Mass-volume concentration is that 10%g/mL adds enzymolysis liquid, and cellulase is added with the ratio of 30FPU/g celluloses, in pH4.8, temperature
Under conditions of 50 DEG C of degree after enzymolysis 24h, separation of solid and liquid collects enzymolysis liquid glucose, and be recycled and be used in enzymolysis process.It is circulated throughout
Pretreatment of raw material condition, enzymatic hydrolysis condition and result are digested in journey as shown in the table, enzymolysis liquid glucose is digested after 4 uses
Concentration of glucose reaches 203.7g/L in liquid glucose, and xylose concentration reaches 47.8g/L.
Sugared change in concentration in enzymolysis liquid glucose after table 1 is recycled
Embodiment 3：
Enzymolysis processing reference implementation example 1, the change for investigating pretreatment liquid glucose access times in hydrothermal pretreatment reaction is brought
Pretreatment sugar concentration change.
It is the hydro-thermal cushioning liquid that 10%g/mL adds that pH is 5 by mass-volume concentration in hydrothermal pretreatment reaction unit
Stirred after (potassium dihydrogen phosphate-dipotassium hydrogen phosphate-boric acid), in 100 DEG C, 2MPa nitrogen atmospheres, react 60min, solid-liquid
Separation, collects pretreatment liquid glucose, and be recycled and be used in pretreatment.Recycling condition and result are as shown in the table, pre- place
Liquid glucose is managed after 3 uses, total xylose concentration reaches 115.1g/L in pretreatment liquid glucose, and xylose concentration reaches 37.1g/L,
Concentration of glucose reaches 16.8g/L.
Table 2 recycles sugared change in concentration in pretreatment liquid glucose
Note：Total xylose concentration is that xylose concentration and xylo-oligosaccharide complete hydrolysis produce xylose concentration sum in table.
Claims (4)
1. a kind of method of efficiently saccharifying draft energy-source plant, it is characterised in that this method comprises the following steps：
A, not pretreated draft energy-source plant raw material and cellulase by granularity after crushing less than 1cm are added to enzymolysis liquid
In, pH4.8, at 50 DEG C after enzymolysis 24-96h, separation of solid and liquid obtains Production With Residue of Enzymatic Hydrolysis I and enzymolysis liquid glucose I；The matter of the enzymolysis raw material
Amount volumetric concentration is 10%~30%g/mL；The cellulase consumption is 10~30FPU/g celluloses；The draft energy is planted
One or more of the thing in Chinese pennisetum, napier grass, switchgrass, awns genus crop；
The Production With Residue of Enzymatic Hydrolysis I that b, step a are obtained is in 4~6 hydro-thermal cushioning liquid 100~180 in the pH containing boric acid or borate
After DEG C 10~60min of hydrothermal pretreatment, separation of solid and liquid obtains pretreatment slag and pre-processes liquid glucose；The mass body of the Production With Residue of Enzymatic Hydrolysis I
Product concentration is 10~30%g/mL；The hydrothermal pretreatment environment is inert atmosphere, and pressure is 2-4MPa；It is described containing boric acid or
The pH of borate is selected from potassium dihydrogen phosphate-dipotassium hydrogen phosphate-boric acid, phosphoric acid-sodium phosphate-boric acid for 4~6 hydro-thermal cushioning liquid
Any of sodium, citric acid-sodium citrate-boric acid；
It is Jie with enzymolysis liquid described in step a or enzymolysis liquid glucose I after the pretreatment slag that c, step b are obtained, addition cellulase
Matter, repeat step a continues to digest, and separation of solid and liquid obtains Production With Residue of Enzymatic Hydrolysis II and enzymolysis liquid glucose II；
The repeat step b of Production With Residue of Enzymatic Hydrolysis II that d, step c are obtained, untill sugared concentration is not further added by obtained pretreatment liquid glucose.
2. the method for efficiently saccharifying draft energy-source plant according to claim 1, it is characterised in that the step a and step
Enzymolysis liquid glucose I that rapid c is obtained, enzymolysis liquid glucose II are used as enzymolysis medium circulation.
3. the method for efficiently saccharifying draft energy-source plant according to claim 1 or 2, it is characterised in that obtained in step b
Pretreatment liquid glucose be used for next round hydrothermal pretreatment.
4. the method for efficiently saccharifying draft energy-source plant according to claim 1 or 2, it is characterised in that the solid-liquid point
From selected from any of centrifugation, press filtration separation or sedimentation separation.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101932695A (en) * | 2008-01-04 | 2010-12-29 | 托莱多大学 | Methods for fermentation of xylose and hexose sugars |
| CN102605020A (en) * | 2012-03-29 | 2012-07-25 | 天津大学 | Method for improving lignocellulose enzymolysis and saccharification efficiency |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101932695A (en) * | 2008-01-04 | 2010-12-29 | 托莱多大学 | Methods for fermentation of xylose and hexose sugars |
| CN102605020A (en) * | 2012-03-29 | 2012-07-25 | 天津大学 | Method for improving lignocellulose enzymolysis and saccharification efficiency |
Non-Patent Citations (2)
| Title |
|---|
| Interactions between boric acid derivatives and saccharides inaqueous media:Structures and stabilities of resulting esters;Joop A. Peters;《Corordination Chemistry Reviews》;20140123;第268卷(第1期);第1-22页 * |
| 木质纤维素类生物质高温液态水预处理技术;余强等;《化工进展》;20101105;第29卷(第11期);第2177-2182页 * |
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