CN102174593A - Process for producing high-concentration ethanol by coupling lignocellulose fermentation and membrane separation - Google Patents
Process for producing high-concentration ethanol by coupling lignocellulose fermentation and membrane separation Download PDFInfo
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- CN102174593A CN102174593A CN2011100560419A CN201110056041A CN102174593A CN 102174593 A CN102174593 A CN 102174593A CN 2011100560419 A CN2011100560419 A CN 2011100560419A CN 201110056041 A CN201110056041 A CN 201110056041A CN 102174593 A CN102174593 A CN 102174593A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention relates to a process for producing high-concentration ethanol by coupling lignocellulose fermentation and membrane separation. By the method, lignocellulose substrate, hydrolase and enzymolysis product can be separated, recycle of the hydrolase and concentration of the enzymolysis sugar product are realized, the ethanol serving as a fermentation product can be separated in situ, and concentration of the ethanol is realized at the same time. Ultra-filtration, nano-filtration and permeating evaporation are organically combined and used in the process, so the enzymolysis efficiency and the fermentation efficiency of the ethanol are improved, the enzymolysis cost and the separation energy consumption of the ethanol are reduced, the water consumption in the production process is saved, and the production cost of producing the ethanol fuel by using lignocellulose is greatly reduced.
Description
Invention field
The present invention relates to a kind of technology of lignocellulose fermentative preparation high concentration ethanol, relate in particular to the technology that high concentration ethanol is produced in using membrane separating technology and lignocellulose fermentation coupling.
Background technology
Along with the exhaustion day by day of fossil energy and increasing the weight of day by day of environmental pollution, seek and greatly develop the important component part that renewable energy technologies has become the national energy development strategy.By occurring in nature wide material sources, cheap renewable lignocellulosic materials for fuel ethanol, be a kind of high-end clean energy technology, substituting aspect the fossil energy, placed high hopes by various countries.But, up to the present also very high by the production cost of lignocellulosic materials for fuel ethanol, cause and can't compete mutually with traditional fossil energy.The process of bio-transformation lignocellulosic materials for fuel ethanol comprises that pre-treatment, enzymic hydrolysis, microbial fermentation and product separate four steps.Wherein, in the enzymic hydrolysis process, exist serious product and suppress phenomenon, cause the concentration of hydrolysate glucose not high, be difficult to directly carry out ethanol fermentation as substrate, and because the cost height of cellulase needs cellulase is reclaimed after enzymic hydrolysis finishes; On the other hand, in the ethanol fermentation process, tunning ethanol can produce feedback inhibition to fermenting process, has reduced fermentation efficiency, has influenced the economy of ethanol fermentation.Therefore, reduce the cellulase hydrolysis cost, improve the fermentation efficiency of alcohol fuel, reducing the alcoholic acid separating energy consumption is lignocellulose fermentative production of ethanol urgent problem.
Summary of the invention
The object of the invention is to provide a kind of technology of lignocellulose fermentative production high concentration ethanol, this technology can not only be separated lignocellulose substrate, lytic enzyme and enzymolysis product, realize the recycle of lytic enzyme and concentrating of enzymolysis sugar product, can also original position isolate tunning ethanol, realize that simultaneously alcoholic acid concentrates.This technology organically combines ultrafiltration, nanofiltration and infiltration evaporation and uses, enzymolysis efficiency and alcoholic acid fermentation efficiency have been improved, reduced enzymolysis cost and alcoholic acid separating energy consumption, and saved the water consumption in the production process, greatly reduced production cost by lignocellulosic materials for fuel ethanol.
The invention provides the technology that high concentration ethanol is produced in a kind of lignocellulose fermentation and membrane sepn coupling, it is characterized in that technological process is as follows:
(1) saccharification of lignocellulose: pretreated lignocellulose is hydrolyzed enzymic hydrolysis in hydrolytic decomposition pot, produces the enzymolysis solution that contains glucose;
(2) ultra-filtration filters: enzymolysis solution to hyperfiltration membrane assembly, obtains containing the trapped fluid and the liquid that sees through that contains glucose of lytic enzyme through pump delivery, and trapped fluid returns hydrolytic decomposition pot;
(3) nanofiltration is filtered: ultrafiltration sees through liquid and concentrates the concentrated solution that obtains containing high concentration glucose through nanofiltration;
(4) ethanol fermentation: with nanofiltration concentrated solution preparation substratum, microbe inoculation fermentative production of ethanol;
(5) infiltration evaporation separates: ethanol fermentation liquid to the infiltration evaporation membrane separation assemblies, is collected the ethanolic soln that obtains high density through pump delivery in condenser.
The bottom of used hydrolytic decomposition pot is equipped with filter separator in the lignocellulose saccharifying of the present invention, and it can be stainless steel filtering net or porous plate.
Enzymolysis solution in the ultra-filtration filters process of the present invention filters through accurate filter, and the molecular weight cut-off of used ultra-filtration membrane is 5000～50000 dalton, and mould material is polyethersulfone, polysulfones, polyvinylidene difluoride (PVDF), polyacrylonitrile, polymeric amide or inorganic ceramic.
The molecular weight cut-off of used nanofiltration membrane is 90～300 dalton in the nanofiltration filtration procedure of the present invention; Its membrane module form is rolling, tubular type or plate and frame organic membrane assembly or tubular type inorganic membrane assembly; Organic nanofiltration membrane material is cellulose acetate, SPSF, polymeric amide, polyethersulfone, sulfonated polyether sulfone, poly-piperazine or polyvinyl alcohol; Inorganic nanofiltration membrane material is a pottery.
Used infiltrating and vaporizing membrane is compound hybrid organic-inorganic film in the infiltration evaporation sepn process of the present invention; Its membrane module form is rolling, tubular type, plate and frame or tubular fibre formula.The material of the supporting layer of compound hybrid organic-inorganic film can be inorganic Al
2O
3, ZrO
2, Ti O
2Or SiO
2In a kind of; Or organic polysulfones or polyacrylonitrile; The material of active layer is the silicon rubber that is filled with molecular sieve, poly-trimethyl silicane propine, polypropylene, polyhutadiene, polyvinylidene difluoride (PVDF) or tetrafluoroethylene.
Lignocellulose of the present invention can be stalk, careless class and deciduous tree or the acerose wood chip of various farm crop such as wheat stalk, maize straw, bagasse.The pretreatment process of lignocellulose adopts physics and chemistry pre-treatment such as Chemical Pretreatment such as conventional diluted acid or steam explosion to get final product.The hydrolysis temperature of lignocellulose is 45～50 ℃, and the temperature of ethanol fermentation is 35～37 ℃.Preferred ethanol fermentation microorganism is a yeast saccharomyces cerevisiae.
Lignocellulose fermentation provided by the invention organically combines ultrafiltration, nanofiltration and infiltration evaporation with the technology that high concentration ethanol is produced in the membrane sepn coupling, realized recycling of lytic enzyme, and avoided the restraining effect of enzymolysis product, and then improved enzymolysis efficiency the lignocellulose enzymolysis; Realize concentrating of glucose in the enzymolysis solution, improved the concentration of glucose substrate in the fermention medium, be easy to improve ethanol fermentation efficient; Realized the separation of tunning alcoholic acid original position, reduced the restraining effect of ethanol, improved ethanol fermentation intensity, and realized that simultaneously alcoholic acid concentrates, and has reduced follow-up alcoholic acid separation costs organism of fermentation.Technology provided by the invention concentrates and the technology and the membrane sepn process close-coupled such as fermentation of alcohol fuel glucose in the enzymic hydrolysis of lignocellulose, the hydrolyzed solution, saved energy consumption and the water consumption in the production process, reduced production cost by lignocellulosic materials for fuel ethanol.
Description of drawings
Fig. 1 is the process flow diagram that high concentration ethanol is produced in lignocellulose fermentation and membrane sepn coupling.
Reference numeral
1. hydrolytic decomposition pot 2. valves 3. fresh feed pumps 4. inlet pressure gauges 5. accurate filters 6. delivery gauges 7. ultrafiltration modules 8. valves 9. receivers 10. fresh feed pumps 11. nanofiltration assemblies 12. valves 13. valves 14. fermentor tanks 15. fresh feed pumps 16. infiltration evaporation assemblies 17. condensers 18. vacuum pumps
Embodiment
The present invention will be further described below in conjunction with embodiment, and theme protection domain involved in the present invention is not limited only to these embodiment.
Embodiment 1: step is as follows:
(1) ratio in 5% (w/v) adds bagasse, cellulase and the beta-glucosidase that diluted acid is handled in hydrolytic decomposition pot 1, and cellulase and beta-glucoside enzyme dosage are respectively 20IU/g substrate and 20IU/g substrate.PH is adjusted into 4.8,50 ℃ of following hydrolysis 12h.The filter separator of hydrolytic decomposition pot bottom is a stainless steel filtering net.
(2) Open valve 2 and fresh feed pump 3, enzymolysis solution is 10000 daltonian tubular type polymeric amide ultrafiltration modules 7 through entering molecular weight cut-off behind the accurate filter 5, and the lytic enzyme of holding back returns hydrolytic decomposition pot 1 and continues hydrolysis, and the liquid that sees through that obtains enters receiver 9.Simultaneously adding entry, pretreated bagasse and lytic enzyme (5IU/g substrate) and regulate pH in hydrolytic decomposition pot 1 is 4.8, and liquid volume and concentration of substrate in the hydrolytic decomposition pot 1 are remained unchanged.Treat that the liquid volume in the receiver 9 reaches at 70% o'clock, valve-off 2 and fresh feed pump 3 stop ultrafiltration.
(3) to see through liquid be 90 daltonian flat polyamide nanofiltration membrane modules 11 through fresh feed pump 10 pressurization backs by molecular weight cut-off to the ultrafiltration in the receiver 9, returns hydrolytic decomposition pot 1, shut-down operation when glucose concn reaches 80g/L in receiver through liquid.
(4) Open valve 13, make the high concentration glucose solution in the receiver 9 enter fermentor tank 14, the preparation fermention medium, the inoculation yeast saccharomyces cerevisiae, when alcohol concn reaches 20g/L in the fermented liquid, open fresh feed pump 15 and vacuum pump 18, fermented liquid is pumped into the board-like infiltration vaporization membrane module 16 of the silicon rubber that is filled with zeolite molecular sieve, the ethanol that fermentation produces in the fermentor tank 14 enters condenser 17 through infiltrating and vaporizing membrane and is collected, and the fermented liquid of holding back returns fermentor tank 14.Shut-down operation behind the fermentation separation coupling 12h, the alcohol concn of collecting in condenser 17 reaches 236g/L.
Embodiment 2: step is as follows:
(1) ratio in 8% (w/v) adds the pretreated wheat stalk of diluted alkaline, cellulase and beta-glucosidase in hydrolytic decomposition pot 1, and cellulase and beta-glucoside enzyme dosage are respectively 20IU/g substrate and 20IU/g substrate.PH is adjusted into 4.8,50 ℃ of following hydrolysis 12h.The filter separator of hydrolytic decomposition pot bottom is a porous plate.
(2) Open valve 2 and fresh feed pump 3, enzymolysis solution is 5000 daltonian flat polyethersulfone ultrafiltration modules 7 through entering molecular weight cut-off behind the accurate filter 5, and the lytic enzyme of holding back returns hydrolytic decomposition pot 1 and continues hydrolysis, and the liquid that sees through that obtains enters receiver 9.Simultaneously adding entry, pretreated wheat stalk and lytic enzyme (5IU/g substrate) and regulate pH in hydrolytic decomposition pot 1 is 4.8, and liquid volume and concentration of substrate in the hydrolytic decomposition pot 1 are remained unchanged.Treat that the liquid volume in the receiver 9 reaches at 70% o'clock, valve-off 2 and fresh feed pump 3 stop ultrafiltration.
(3) to see through liquid be 90 daltonian rolling polyether sulfone filtering membrane modules 11 through fresh feed pump 10 pressurization backs by molecular weight cut-off to the ultrafiltration in the receiver 9, returns hydrolytic decomposition pot 1, shut-down operation when glucose concn reaches 150g/L in receiver through liquid.
(4) Open valve 13, make the high concentration glucose solution in the receiver 9 enter fermentor tank 14, the preparation fermention medium, the inoculation yeast saccharomyces cerevisiae, when alcohol concn reaches 20g/L in the fermented liquid, open fresh feed pump 15 and vacuum pump 18, fermented liquid is pumped into the polyvinylidene difluoride (PVDF) tubular type infiltration vaporization membrane module 16 that is filled with zeolite molecular sieve, the ethanol that fermentation produces in the fermentor tank 14 enters condenser 17 through infiltrating and vaporizing membrane and is collected, and the fermented liquid of holding back returns fermentor tank 14.Shut-down operation behind the fermentation separation coupling 12h.In fermentor tank 14 stream add separate with infiltration evaporation obtain see through the isopyknic nanofiltration concentrated solution of liquid phase, continue fermentation 6h, when the ethanol volume in the fermentor tank 14 reaches 20g/L once more, ferment once more and separate coupling operation 12h, in condenser 17, collect penetrating fluid, and stop coupling operation, and add the nanofiltration concentrated solution that equates with infiltration evaporation penetrating fluid volume once more, so repetitive operation four times is to fermentation ends.Alcohol concn reaches 435g/L in the penetrating fluid that collection obtains in condenser 17.
Embodiment 3: step is as follows:
(1) ratio in 6% (w/v) adds the pretreated straw of steam explosion, cellulase and beta-glucosidase in hydrolytic decomposition pot 1, and cellulase and beta-glucoside enzyme dosage are respectively 20IU/g substrate and 20IU/g substrate.PH is adjusted into 4.8,50 ℃ of following hydrolysis 12h.The filter separator of hydrolytic decomposition pot bottom is a porous plate.
(2) Open valve 2 and fresh feed pump 3, enzymolysis solution is 10000 daltonian tubular fibre polyethersulfone ultrafiltration modules 7 through entering molecular weight cut-off behind the accurate filter 5, and the lytic enzyme of holding back returns hydrolytic decomposition pot 1 and continues hydrolysis, and the liquid that sees through that obtains enters receiver 9.Simultaneously adding entry, pretreated straw and lytic enzyme (5IU/g substrate) and regulate pH in hydrolytic decomposition pot 1 is 4.8, and liquid volume and concentration of substrate in the hydrolytic decomposition pot 1 are remained unchanged.Treat that the liquid volume in the receiver 9 reaches at 70% o'clock, valve-off 2 and fresh feed pump 3 stop ultrafiltration.
(3) to see through liquid be 150 daltonian tubular type polyamide nanofiltration membrane modules 11 through fresh feed pump 10 pressurization backs by molecular weight cut-off to the ultrafiltration in the receiver 9, returns hydrolytic decomposition pot 1, shut-down operation when glucose concn reaches 100g/L in receiver through liquid.
(4) Open valve 13, make the high concentration glucose solution in the receiver 9 enter fermentor tank 14, the preparation fermention medium, the inoculation yeast saccharomyces cerevisiae, when alcohol concn reaches 20g/L in the fermented liquid, open fresh feed pump 15 and vacuum pump 18, fermented liquid is pumped into the silicon rubber rolling infiltration evaporation assembly 16 that is filled with zeolite molecular sieve, the ethanol that fermentation produces in the fermentor tank 14 enters condenser 17 through infiltrating and vaporizing membrane and is collected, and the fermented liquid of holding back returns fermentor tank 14.Shut-down operation behind the fermentation separation coupling 12h.Alcohol concn reaches 342g/L in the penetrating fluid that collection obtains in condenser 17.
Claims (8)
1. a lignocellulose fermentation is coupled with membrane sepn and produces the technology of high concentration ethanol, it is characterized in that this technology may further comprise the steps:
(1) saccharification of lignocellulose: pretreated lignocellulose is hydrolyzed enzymic hydrolysis in hydrolytic decomposition pot, produces the enzymolysis solution that contains glucose;
(2) ultra-filtration filters: enzymolysis solution to hyperfiltration membrane assembly, obtains containing the trapped fluid and the liquid that sees through that contains glucose of lytic enzyme through pump delivery, and trapped fluid returns hydrolytic decomposition pot;
(3) nanofiltration is filtered: ultrafiltration sees through liquid and concentrates the concentrated solution that obtains containing high concentration glucose through nanofiltration;
(4) ethanol fermentation: with nanofiltration concentrated solution preparation substratum, microbe inoculation fermentative production of ethanol;
(5) infiltration evaporation separates: ethanol fermentation liquid to the infiltration evaporation membrane separation assemblies, is collected the ethanolic soln that obtains high density through pump delivery in condenser.
2. according to the technology described in the claim 1, it is characterized in that the bottom of hydrolytic decomposition pot is equipped with filter separator described in the step (1).
3. according to the technology described in the claim 2, it is characterized in that filter separator can be stainless steel filtering net or porous plate.
4. according to the technology described in the claim 1, it is characterized in that the enzymolysis solution described in the step (2) filters through accurate filter.
5. according to the technology described in the claim 1, it is characterized in that the molecular weight cut-off of ultra-filtration membrane is 5000～50000 dalton described in the step (2), mould material is polyethersulfone, polysulfones, polyvinylidene difluoride (PVDF), polyacrylonitrile, polymeric amide or inorganic ceramic.
6. according to the technology described in the claim 1, it is characterized in that the molecular weight cut-off of nanofiltration membrane is 90～300 dalton described in the step (3); Its membrane module form is rolling, tubular type or plate and frame organic membrane assembly or tubular type inorganic membrane assembly; Organic nanofiltration membrane material is cellulose acetate, SPSF, polymeric amide, polyethersulfone, sulfonated polyether sulfone, poly-piperazine or polyvinyl alcohol; Inorganic nanofiltration membrane material is a pottery.
7. according to the technology described in the claim 1, it is characterized in that infiltrating and vaporizing membrane is compound hybrid organic-inorganic film described in the step (5); Its membrane module form is rolling, tubular type, plate and frame or tubular fibre formula.
8. according to the technology described in the claim 7, it is characterized in that the material of the supporting layer of compound hybrid organic-inorganic film can be inorganic Al
2O
3, ZrO
2, TiO
2Or SiO
2In a kind of; Or organic polysulfones or polyacrylonitrile; The material of active layer is the silicon rubber that is filled with molecular sieve, poly-trimethyl silicane propine, polypropylene, polyhutadiene, polyvinylidene difluoride (PVDF) or tetrafluoroethylene.
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Cited By (7)
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|---|---|---|---|---|
| CN102839229A (en) * | 2012-09-14 | 2012-12-26 | 武汉工程大学 | Method for increasing reducing sugar yield by coupling of membrane separation and lignocellulose acid hydrolysis |
| CN102899358A (en) * | 2012-09-03 | 2013-01-30 | Acs农化系统有限公司 | Volatile organic product preparation method |
| EP2596852A1 (en) * | 2011-11-28 | 2013-05-29 | Annikki GmbH | Method for the regeneration of an aqueous solution containing lignin |
| CN103911466A (en) * | 2012-12-28 | 2014-07-09 | 川崎重工业株式会社 | Condensed saccharification liquid production method |
| CN103923949A (en) * | 2014-03-13 | 2014-07-16 | 中国石油集团东北炼化工程有限公司吉林设计院 | Method and apparatus for producing ethanol through synchronous saccharification and fermentation of lignocellulose |
| CN107904265A (en) * | 2017-12-21 | 2018-04-13 | 北京首钢朗泽新能源科技有限公司 | The utilization technique and device of product in a kind of legal system alcohol that ferments |
| CN111057724A (en) * | 2019-12-10 | 2020-04-24 | 河北经贸大学 | Method for producing ethanol by fermentation of lignocellulose |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2596852A1 (en) * | 2011-11-28 | 2013-05-29 | Annikki GmbH | Method for the regeneration of an aqueous solution containing lignin |
| WO2013079280A1 (en) * | 2011-11-28 | 2013-06-06 | Annikki Gmbh | Method for reprocessing an aqueous solution containing lignin |
| JP2015504363A (en) * | 2011-11-28 | 2015-02-12 | アニッキ ゲーエムベーハーＡｎｎｉｋｋｉ Ｇｍｂｈ | Method for preparing an aqueous solution containing lignin |
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| CN102899358A (en) * | 2012-09-03 | 2013-01-30 | Acs农化系统有限公司 | Volatile organic product preparation method |
| CN102839229A (en) * | 2012-09-14 | 2012-12-26 | 武汉工程大学 | Method for increasing reducing sugar yield by coupling of membrane separation and lignocellulose acid hydrolysis |
| CN103911466A (en) * | 2012-12-28 | 2014-07-09 | 川崎重工业株式会社 | Condensed saccharification liquid production method |
| CN103923949A (en) * | 2014-03-13 | 2014-07-16 | 中国石油集团东北炼化工程有限公司吉林设计院 | Method and apparatus for producing ethanol through synchronous saccharification and fermentation of lignocellulose |
| CN107904265A (en) * | 2017-12-21 | 2018-04-13 | 北京首钢朗泽新能源科技有限公司 | The utilization technique and device of product in a kind of legal system alcohol that ferments |
| CN111057724A (en) * | 2019-12-10 | 2020-04-24 | 河北经贸大学 | Method for producing ethanol by fermentation of lignocellulose |
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Application publication date: 20110907 |