CN101736060B - Method for producing ethanol by using ionic liquid - Google Patents
Method for producing ethanol by using ionic liquid Download PDFInfo
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- CN101736060B CN101736060B CN2010100301284A CN201010030128A CN101736060B CN 101736060 B CN101736060 B CN 101736060B CN 2010100301284 A CN2010100301284 A CN 2010100301284A CN 201010030128 A CN201010030128 A CN 201010030128A CN 101736060 B CN101736060 B CN 101736060B
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- ionic liquid
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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 belongs to the technical field of ethanol fermentation industry, in particular to a method for producing ethanol by using ionic liquid. The method comprises the following steps of: dissolving and regenerating cellulosic raw materials through ionic liquid, fermenting ethanol in a mode of fermentation after saccarification or synchronous saccarification and fermentation, introducing inert gas in the fermentation process for gas stripping, absorbing tail gas by ionic liquid dissolved with cellulosic raw material and separating out cellulose; after solid-liquid separation, distilling the liquid phase to obtain ethanol and ionic liquid with high concentration, and redissolving the cellulosic raw materials by ionic liquid for recycling. The method producing ethanol by using ionic liquid has high production efficiency, low cost and more reasonable process.
Description
(1) technical field
The invention belongs to technical field of ethanol fermentation industry, particularly utilize ionic liquid to produce the alcoholic acid method.
(2) background technology
Ethanol is the main representative of biomass liquid energy material, also is the most probable substitute of fossil fuel.With starch based and saccharide compound is raw material, and adopting production of ethanol from microbial fermentation is a proven technique, but along with the energy and crisis in food, is difficult to satisfy demands of social development.Mierocrystalline cellulose is the abundantest organic substance of reserves on the earth, and plant is annual to be produced up to 1,550 hundred million tons of cellulose substances through photosynthesis.It is with low cost, wide material sources, and preparing ethanol with Mierocrystalline cellulose as fermentation raw material becomes inevitable trend.
Cellulose fermentation is produced ethanol and is generally included operations such as enzymatic saccharification, fermentation, separation.Because Mierocrystalline cellulose is complicated crystal structure, adheres to semicellulose and xylogen on every side, must be after pre-treatment, Mierocrystalline cellulose is just easily by enzymatic saccharification.Common pretreatment process has physics method (like mechanical disintegration, steam explosion etc.) and chemical method (like ozone method, acid system, alkaline process etc.), but all unsatisfactory.The ionic liquid pretreatment method that occurs recently receives publicity, and specifically is to utilize the ion liquid dissolving Mierocrystalline cellulose, adds entry afterwards or pure equal solvent comes out Cellulose precipitates, separates through means such as centrifugal, filtrations again.Regenerated cellulose percent crystallinity, the polymerization degree obviously descend, and enzymolysis speed significantly increases.But the ionic liquid price is higher, and the precipitation agent addition is big, and ionic liquid and precipitation agent association are strong, and it is high to reclaim energy consumption, and these have all caused application cost high.
The ethanol fermentation process is typical product process of inhibition, and separated in synchronization ethanol can improve ferment strength greatly in the process of fermentation.For this reason, vacuum fermentation, gas have occurred and put forward processes such as fermentation, absorption fermentation, extractive fermentation, wherein gas is proposed the easiest realization industriallization of fermentation.This process is to utilize fermentation byproduct CO
2Be carrier gas, the ethanol that shifts out in the beer on the throne, the ethanol that reclaims in the tail gas has methods such as cooling, absorption, absorption.But there is following problem in it: directly cool off the energy consumption height; Water absorbs then because the vapor-liquid equilibrium easy recovery is incomplete; Use charcoal absorption, also need desorb again, complex process.
(3) summary of the invention
The object of the present invention is to provide a kind of ionic liquid to produce the alcoholic acid method, thereby reclaim the many low defectives of production efficiency of problem to overcome existing method or cost height or ethanol.
The technical scheme that the present invention adopts is following:
Utilize ionic liquid to produce the alcoholic acid method; Cellulosic material carries out ethanol fermentation after ion liquid dissolving regeneration, feed rare gas element during the fermentation and carry out gas and carry; Gas is proposed the ionic liquid absorption that waste gas utilization is dissolved with cellulosic material, and cellulosic material is separated out; Ionic liquid to after absorbing carries out solid-liquid separation, and liquid phase obtains the ethanol and the ionic liquid of high density through distillation, and ionic liquid dissolving cellulos raw material again recycles.
Concrete, described rare gas element can adopt CO
2Or N
2
Can adopt first saccharification secondary fermentation or simultaneous saccharification and fermentation pattern to carry out ethanol fermentation.
In the method, the second alcohol and water of being taken out of by rare gas element gets in the ionic liquid, and Mierocrystalline cellulose is precipitated out; After the solid-liquid separation, Mierocrystalline cellulose can be used for fermentation, and liquid phase obtains the ethanol and the ionic liquid of high density through distillation, and ionic liquid can continue dissolving cellulos and recycle as absorption agent.
Intermediate ion liquid of the present invention had not only been made cellulosic pretreating agent but also had been made the absorption agent of tail gas.Separate out through ion liquid dissolving, the regenerated cellulose enzymolysis is easy, and enzymolysis speed is fast; Carry out gas in the fermenting process and carry, ferment strength is high; Gas is carried the second alcohol and water that shifts out and is absorbed through ionic liquid, and technology is simple, and it is high to compare the water assimilated efficiency, and reclaims more complete; In the process that absorbs, the Mierocrystalline cellulose that is dissolved in the ionic liquid is separated out, practiced thrift precipitation agent, technology is more reasonable, and cost is lower.
The present invention has following advantage with respect to prior art:
The ionic liquid that utilizes according to the invention produces that alcoholic acid method production efficiency is high, cost is low, and technology is more reasonable.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
The corn straw of 100 grams is crushed to 40 orders, adds ionic liquid 1-butyl-3-N-Methylimidazoleacetic salt [BMIM] [CH by 1: 10 mass ratio
3COO] in, soaked 2 hours down at 90 ℃, it is subsequent use to make absorption liquid.
Regenerated cellulose after ion liquid dissolving is separated out and water mixed configuration quality percentage are 20% mixing solutions; Add in the airlift reactor, after sterilization, add cellulase degradation, the enzyme add-on is the 100U/g substrate; In 55 ℃ of insulations 24 hours; Generate the cellulase hydrolysis thing, in this process, from the little logical CO of reactor bottom
2Stir.The cellulase hydrolysis thing is under 35 ℃, and aseptic access yeast saccharomyces cerevisiae, dry yeast addition are 1g/L, ferments 24 hours, generates ethanol, in this process, continues from the little logical CO of reactor bottom
2Stir; When the alcoholic acid volumetric concentration reaches 3～5% in the reactor drum, increase CO
2Air flow is 3VVM, carries out gas and proposes operation, CO
2Ethanol is shifted out from reactor drum, carry tail gas from the gas of reactor drum discharge and feed the ready absorption liquid, the second alcohol and water is absorbed by ionic liquid, and the Mierocrystalline cellulose that is dissolved in the ionic liquid is precipitated out.Carry out spinning, solid phase obtains regenerated cellulose, ferments as raw material, and it is 40% ethanolic soln and pure ionic liquid that the liquid phase that obtains obtains volumetric concentration through distillation, and ionic liquid uses with the stalk powder mixed cycle again.
Embodiment 2
The straw of 100g is crushed to 60 orders, adds 1-butyl-3-Methylimidazole thioglycolate salt [BMIM] [HSCH by 1: 10 mass ratio
2COO] in, soaked 2 hours down at 100 ℃, it is subsequent use to make absorption liquid.
Regenerated cellulose after ion liquid dissolving is separated out and water mixed configuration quality percentage are 20% mixing solutions; Add in the airlift reactor; After sterilization, add cellulase (the enzyme add-on is the 150U/g substrate) and yeast saccharomyces cerevisiae (the dry yeast addition is 1g/L); Under 37 ℃, carry out simultaneous saccharification and fermentation 48h, in this process, from the little logical N of reactor bottom
2Stir.When the alcoholic acid volumetric concentration reached 3～5% in the reactor drum, the increase air flow was 3VVM, carried out gas and proposed operation, N
2Ethanol is shifted out from reactor drum, carry tail gas from the gas of reactor drum discharge and feed the ready absorption liquid, the second alcohol and water is absorbed by ionic liquid, and the Mierocrystalline cellulose that is dissolved in the ionic liquid is precipitated out.Carry out spinning, solid phase obtains regenerated cellulose, ferments as raw material, and it is 35% ethanolic soln and pure ionic liquid that the liquid phase that obtains obtains volumetric concentration through distillation, and ionic liquid recycles with the straw powder again.
Claims (3)
1. utilize ionic liquid to produce the alcoholic acid method, it is characterized in that, cellulosic material is after ion liquid dissolving regeneration; Carry out ethanol fermentation; Feed rare gas element during the fermentation and carry out gas and carry, gas is carried the ionic liquid that waste gas utilization is dissolved with cellulosic material and is absorbed, and cellulosic material is separated out; Ionic liquid to after absorbing carries out solid-liquid separation, and liquid phase obtains the ethanol and the ionic liquid of high density through distillation, and ionic liquid dissolving cellulos raw material again recycles.
2. the ionic liquid that utilizes as claimed in claim 1 is produced the alcoholic acid method, it is characterized in that described rare gas element is CO
2Or N
2
3. according to claim 1 or claim 2 the ionic liquid that utilizes is produced the alcoholic acid method, it is characterized in that, adopts first saccharification secondary fermentation or simultaneous saccharification and fermentation pattern to carry out ethanol fermentation.
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| CN2010100301284A CN101736060B (en) | 2010-01-08 | 2010-01-08 | Method for producing ethanol by using ionic liquid |
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| CN2010100301284A CN101736060B (en) | 2010-01-08 | 2010-01-08 | Method for producing ethanol by using ionic liquid |
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| CN101736060A CN101736060A (en) | 2010-06-16 |
| CN101736060B true CN101736060B (en) | 2012-07-04 |
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| CN101871020B (en) * | 2010-07-14 | 2012-05-30 | 河南科技大学 | Method for preparing wood sugar, glucose and lignin with ionic liquid controllable hydrolytic wood fiber raw material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1442483A (en) * | 2003-04-15 | 2003-09-17 | 天津大学 | Method of preparing high concentration ethanol fermentation liquid by paddy rice raw material fermentation |
| CN1696296A (en) * | 2005-05-08 | 2005-11-16 | 天津大学 | Flash evaporation ferment method of synchronous gas stripping for producing ethanol |
| CN101298620A (en) * | 2007-05-10 | 2008-11-05 | 河南科技大学 | Method for preparing ethanol by one-step fermentation after ion liquid stage treatments from native cellulose material |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1442483A (en) * | 2003-04-15 | 2003-09-17 | 天津大学 | Method of preparing high concentration ethanol fermentation liquid by paddy rice raw material fermentation |
| CN1696296A (en) * | 2005-05-08 | 2005-11-16 | 天津大学 | Flash evaporation ferment method of synchronous gas stripping for producing ethanol |
| CN101298620A (en) * | 2007-05-10 | 2008-11-05 | 河南科技大学 | Method for preparing ethanol by one-step fermentation after ion liquid stage treatments from native cellulose material |
Non-Patent Citations (1)
| Title |
|---|
| 刘振等.离子液体预处理的纤维素酶解糖化.《应用化学》.2009,第26卷(第9期), * |
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