CN101358216B - Bio diesel oil preparation technique using enzyme method membrane on-line dehydration - Google Patents
Bio diesel oil preparation technique using enzyme method membrane on-line dehydration Download PDFInfo
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- CN101358216B CN101358216B CN2008101178434A CN200810117843A CN101358216B CN 101358216 B CN101358216 B CN 101358216B CN 2008101178434 A CN2008101178434 A CN 2008101178434A CN 200810117843 A CN200810117843 A CN 200810117843A CN 101358216 B CN101358216 B CN 101358216B
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- 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
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
A process for preparing biodiesel by utilizing the enzymatic method of membrane online dehydration belongs to the field of biological and chemical synthesis. During the reaction of preparing the biodiesel by enzymatic grease with tertiary butyl alcohol as the reaction medium, volatilizable gases in the reaction system are directly used as the circulation dynamic force of the liquid in a reactor; the by-product water produced during the reaction is carried out from the enzyme reactor by the volatilizable gas and passes through a water-permselective membrane device so as to realize the online separation of the by-product water; the volatilizable gases such as the tertiary butyl alcohol and short chain alcohol still return to the enzyme reactor after passing through the membrane device and the circulation continues. The transmission of the membrane to water is more than 90 percent; the transmission of the membrane to the tertiary butyl alcohol is below 5 percent. The process for preparing biodiesel by utilizing the enzymatic method of membrane online dehydration has the advantage that the enzymatic reaction efficiency as well as the yield of the biodiesel are greatly improved, and is significant for the continuous production of preparing the biodiesel by the industrial enzymatic method.
Description
Technical field
The invention belongs to the synthetic field of biochemical industry, particularly a kind of process for preparing biodiesel by enzyme technology of utilizing membrane on-line dehydration as reaction medium, utilizes film to carry out the enzymatic preparing biodiesel from lipid of online dehydration with the trimethyl carbinol.
Background technology
Biofuel is by the long chain fatty acid ester class material of bio-oil raw material by the transesterification reaction generation, is a kind of novel pollution-free renewable energy source, is called as biofuel.Its combustionproperty can be that diesel oil matches in excellence or beauty with traditional oil, and research of biofuel at present and application have been subjected to widely to be paid close attention to.Biofuel mainly is to use chemical method production at present, promptly uses animal-plant oil and some low-carbon alcohol (methyl alcohol or ethanol) to carry out transesterification reaction under alkali or an acidic catalyst effect, generates corresponding fatty acid methyl ester or ethyl ester.Chemical method prepares biofuel and has the following inevitable shortcoming: 1. free fatty acids in the glyceride stock and water have a strong impact on the carrying out of reaction; 2. methyl alcohol solvability in grease is bad, thereby easily causes the formation of emulsion to make the subsequent processes complexity; 3. the processing requirement methanol usage substantially exceeds the reaction mol ratio, the evaporation backflow increase process energy consumption of excessive methanol.
Because free fatty acids and the less water of utilizing the biological enzyme biodiesel synthesis to have in reaction conditions gentleness, non-pollutant discharge, the glyceride stock do not influence advantages such as enzymatic reaction, meet the developing direction of Green Chemistry, thereby are subject to people's attention day by day.But compare with chemical method, also there is the following problem demanding prompt solution in biological enzyme.At [Shimada Yuji et al.Enzymatic alcoholysis for biodiesel fuel production andapplication of the reaction to oil processing, Journal of Molecular CatalysisB:Enzymatic, 2002,17:133-142] to report in the document: the solvability of short chain alcohol such as methyl alcohol, ethanol in glyceride stock is relatively poor, is unfavorable for the carrying out that reacts; Secondly, the existence of alcohol excess can cause the serious inactivation of lipase, so in the technological process of utilizing biological enzyme production biofuel, many employings add the mode of short chain alcohol to alleviate its toxic action to enzyme in batches.This mode complex operation, the reaction times is longer; In addition, with the acyl acceptor of short chain alcohol as reaction, have by-product glycerin to produce in the reaction process, hydrophilic glycerine is easily attached to immobilized enzyme endoporus and outside surface, thereby the avtive spot of enzyme is formed " shielding ", has a strong impact on activity of enzyme reaction; For improving above situation, some scholars attempt adopting organic solvent reaction system biodiesel synthesis, document [Shimada Yuji et al.Enzymatic alcoholysis for biodiesel fuel production and application of thereaction to oil processing, Journal of Molecular Catalysis B:Enzymatic, 2002,17:133-142] report: adopt stronger organic solvent of some hydrophobicitys such as hexane, hexanaphthene, sherwood oil etc. as reaction medium.These hydrophobic organic solvents can well dissolve grease, can promote the carrying out that reacts to a certain extent; But because the stronger organic solvent of these hydrophobicitys can not effectively dissolve low-carbon alcohol and by-product glycerins such as methyl alcohol, so work-ing life of activity of enzyme reaction, enzyme and bio-diesel yield etc. are not had clear improvement.
This seminar once proposed to utilize the moderate organic solvent trimethyl carbinol of hydrophobicity to be used for the preparation of biofuel as reaction medium, and reactant grease and short chain alcohol and by-product glycerin can both effectively be dissolved in trimethyl carbinol system.Trimethyl carbinol reaction medium system has fundamentally been removed short chain alcohol such as reactant methanol or ethanol and the by-product glycerin toxic side effect to enzyme, relevant patent has obtained Chinese invention patent mandate (ZL200410000697.9), international patent application has entered the U.S., European Union, a plurality of countries such as Brazil.On this basis, this seminar has further proposed the lipase of different catalytic performances is used in combination the preparation (authorized ZL200510011623.X) that is used for biofuel.For promoting the industrialization of relevant achievement, this seminar is further according to the feature that balances each other of trimethyl carbinol medium system, invented a kind of Airlift circulating reactor (authorized ZL200510070863.7) of needing no foreign gas, directly with in the system with the force of circulation of volatilization gas (being mainly the trimethyl carbinol and methyl alcohol) as liquid in the reactor, save external source of the gas, significantly reduced the loss of material.Above-mentioned patent achievement is successful implementation on the ton industrialized scale.
Compare with traditional chemical technology, one of remarkable advantage of biological enzyme is to have glyceride stock suitability widely, promptly can carry out the preparation of biofuel by the different glyceride stocks of catalysis.But, when utilizing some low-quality high acid value greases, have water byproduct in the reaction process and generate for the feedstock production biofuel.The existence of too much water will have obvious negative effect to reaction in the system, cause bio-diesel yield sharply to descend; And, be fixed on the immobilized lipase disintegration easily in Aquo System on the silica-gel carrier, it is serious to cause enzyme to run off.So, when being the feedstock production biofuel, how to realize that online dehydration all is extremely important to the operational stability that improves bio-diesel yield and prolongation enzyme with the low-quality grease of high acid value.
Summary of the invention
The purpose of this invention is to provide a kind of process for preparing biodiesel by enzyme technology of utilizing membrane on-line dehydration, solved when being the feedstock production biofuel, how to have realized the problem of online dehydration improving bio-diesel yield and prolonging the operational stability of enzyme with the low-quality grease of high acid value.
The present invention is with in the reaction process of the trimethyl carbinol as the enzymatic preparing biodiesel from lipid of reaction medium, directly with volatile gas in the reaction system as the force of circulation of liquid in the reactor, the water byproduct that generates in the reaction process is carried out secretly the film device of back by alternative permeate water by above-mentioned volatile gas from enzyme reactor, thereby realizes the ON-LINE SEPARATION of water byproduct; Behind the film device, the volatile gas trimethyl carbinol and short chain alcohol are still got back in the enzyme reactor, and so circulation is carried out.Fig. 1 is seen in technical process.
Described film is selective permeation water, be difficult to see through the selective membrane of the trimethyl carbinol and short chain alcohol.Film is 90%-98% to the transmitance of water, is 0-5% to the transmitance of the trimethyl carbinol and short chain alcohol.
Described film is a metallic membrane, mineral membranes such as organic membrane or ceramic membrane.
Described volatile gas is the trimethyl carbinol and reaction acyl acceptor short chain alcohol, and described short chain alcohol is methyl alcohol, ethanol, propyl alcohol or butanols.
The invention has the beneficial effects as follows to have significantly improved enzymatic reaction efficient and bio-diesel yield that the continuity production of industrialization process for preparing biodiesel by enzyme is had particularly important meaning.
Description of drawings
Fig. 1 is the process for preparing biodiesel by enzyme synoptic diagram of the online dehydration of membrane sepn.
Embodiment
Embodiment 1
Mol ratio be housed be 4: 1 methyl alcohol and rapic acid carburetion (acid value is 120) in the Airlift circulating reactor, and based on the trimethyl carbinol of grease volume 60%, temperature is controlled at 50 ℃, be equipped with based on the immobilized lipase Lipozyme TL of oil quality 3% with based on the immobilized lipase Novozym 435 of oil quality 2%, the volatile gas trimethyl carbinol and methyl alcohol are as the force of circulation of liquid in the reactor, carry out the water that generates in real time in the reaction process secretly ceramic membrane by an alternative permeate water, and then get back to enzyme reactor, so circulation is carried out.Transmitance by water behind the film device can reach 90%, and the transmitance of the trimethyl carbinol and methyl alcohol is 5%.Reacted 5 hours, bio-diesel yield reaches more than 90%.
Embodiment 2
Mol ratio be housed be 5: 1 ethanol and soybean acidified oil (acid value is 60) in the Airlift circulating reactor, and based on the trimethyl carbinol of grease volume 80%, temperature is controlled at 50 ℃, be equipped with based on the immobilized lipase Lipozyme TL of oil quality 3% with based on the immobilized lipase Novozym 435 of oil quality 2%, the volatile gas trimethyl carbinol and methyl alcohol are as the force of circulation of liquid in the reactor, carry out the water that generates in real time in the reaction process secretly ceramic membrane by an alternative permeate water, and then get back to enzyme reactor, so circulation is carried out.Transmitance by water behind the film device can reach 92%, and the trimethyl carbinol and alcoholic acid transmitance are 1%.Reacted 6 hours, bio-diesel yield reaches more than 90%.
Embodiment 3
Mol ratio be housed be 6: 1 propyl alcohol and soybean acidified oil (acid value is 100) in the Airlift circulating reactor, and based on the trimethyl carbinol of grease volume 60%, temperature is controlled at 50 ℃, be equipped with based on the immobilized lipase Lipozyme TL of oil quality 3% with based on the immobilized lipase Novozym 435 of oil quality 2%, the volatile gas trimethyl carbinol and methyl alcohol are as the force of circulation of liquid in the reactor, carry out the water that generates in real time in the reaction process secretly organic membrane by an alternative permeate water, and then get back to enzyme reactor, so circulation is carried out.Transmitance by water behind the film device can reach 98%, sees through the trimethyl carbinol and propyl alcohol hardly.Reacted 5 hours, bio-diesel yield reaches more than 90%.
Embodiment 4
Mol ratio be housed be 5: 1 butanols and soybean acidified oil (acid value is 180) in the Airlift circulating reactor, and based on the trimethyl carbinol of grease volume 80%, temperature is controlled at 50 ℃, be equipped with based on the immobilized lipase Lipozyme TL of oil quality 3% with based on the immobilized lipase Novozym 435 of oil quality 2%, the volatile gas trimethyl carbinol and methyl alcohol are as the force of circulation of liquid in the reactor, carry out the water that generates in real time in the reaction process secretly metallic membrane by an alternative permeate water, and then get back to enzyme reactor, so circulation is carried out.Transmitance by water behind the film device can reach 95%, does not see through the trimethyl carbinol and butanols.Reacted 8 hours, bio-diesel yield reaches more than 90%.
Embodiment 5
The embodiment that carries out continuously of reaction: mol ratio is housed is 5: 1 methyl alcohol and soybean acidified oil (15 liters of soybean acidified oils in 28 liters of Airlift circulating reactors, acid value is 180), the trimethyl carbinol based on oil quality 60% is housed, and based on the immobilized lipase Lipozyme TL of oil quality 2% with based on the immobilized lipase Novozym 435 of oil quality 2%, with the volatile gas trimethyl carbinol and methyl alcohol force of circulation as liquid in the reactor, carry out the water that generates in real time in the reaction process secretly ceramic membrane by an alternative permeate water, and then get back to enzyme reactor, so circulation is carried out.(stock liquid composition proportioning is simultaneously to inject new stock liquid continuously in the reactor; Mol ratio be 5: 1 methyl alcohol and soybean acidified oil and based on the trimethyl carbinol of oil quality 60%), flow velocity is 5L/h, reaction solution is with the continuous outflow reactor of 5L/h, bio-diesel yield reaches more than 90%.
Claims (6)
1. process for preparing biodiesel by enzyme technology of utilizing membrane on-line dehydration, it is characterized in that, in the reaction process of the trimethyl carbinol as the enzymatic preparing biodiesel from lipid of reaction medium, directly with volatile gas in the reaction system as the force of circulation of liquid in the reactor, the water byproduct that generates in the reaction process is carried out secretly the film device of back by alternative permeate water by above-mentioned volatile gas from enzyme reactor, thereby realizes the ON-LINE SEPARATION of water byproduct; Behind the film device, the volatile gas trimethyl carbinol and short chain alcohol are still got back in the enzyme reactor, and so circulation is carried out;
Described short chain alcohol is methyl alcohol, ethanol, propyl alcohol or butanols.
2. according to the described technology of claim 1, it is characterized in that described film is metallic membrane, organic membrane or ceramic membrane.
3. according to the described technology of claim 1, it is characterized in that described film is selective permeation water, be difficult to see through the selective membrane of the trimethyl carbinol and short chain alcohol.
4. according to the described technology of claim 3, it is characterized in that described film is 90%-98% to the transmitance of water, is 0-5% to the transmitance of the trimethyl carbinol and short chain alcohol.
5. according to the described technology of claim 1, it is characterized in that described volatile gas is the trimethyl carbinol.
6. according to the described technology of claim 1, it is characterized in that the transesterification reaction in the described enzyme reactor is rhythmic reaction or successive reaction.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008101178434A CN101358216B (en) | 2008-08-06 | 2008-08-06 | Bio diesel oil preparation technique using enzyme method membrane on-line dehydration |
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| CN2008101178434A CN101358216B (en) | 2008-08-06 | 2008-08-06 | Bio diesel oil preparation technique using enzyme method membrane on-line dehydration |
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| CN101358216B true CN101358216B (en) | 2011-11-09 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676304B (en) * | 2011-03-15 | 2013-06-19 | 清华大学 | Preparation method for biodiesel fuel |
| CN102559789A (en) * | 2012-02-07 | 2012-07-11 | 清华大学 | Method for preparing biodiesel from grease catalyzed by phosphatidase and lipase |
| CN103131735B (en) * | 2012-12-28 | 2014-09-03 | 清华大学 | Method of improving enzymatic oil and fat preparation biodiesel productivity |
| CN116333822A (en) * | 2021-12-23 | 2023-06-27 | 中国石油天然气股份有限公司 | Method for preparing biodiesel by reaction extraction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1453332A (en) * | 2003-04-24 | 2003-11-05 | 华南理工大学 | Biologically catalystic process of converting fat into ester to produce biological diesel oil |
| CN1557913A (en) * | 2004-01-16 | 2004-12-29 | �廪��ѧ | Novel process for preparing biological diesel oil from grease catalyzed by lipase in the reaction system with organic substrate as medium |
| CN1706932A (en) * | 2005-05-20 | 2005-12-14 | 清华大学 | Airlift circulating reactor needing no foreign gas |
| CN101113360A (en) * | 2006-07-27 | 2008-01-30 | 上海中油企业集团有限公司 | Method for producing biodiesel by waste oil ester biological process |
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- 2008-08-06 CN CN2008101178434A patent/CN101358216B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1453332A (en) * | 2003-04-24 | 2003-11-05 | 华南理工大学 | Biologically catalystic process of converting fat into ester to produce biological diesel oil |
| CN1557913A (en) * | 2004-01-16 | 2004-12-29 | �廪��ѧ | Novel process for preparing biological diesel oil from grease catalyzed by lipase in the reaction system with organic substrate as medium |
| CN1706932A (en) * | 2005-05-20 | 2005-12-14 | 清华大学 | Airlift circulating reactor needing no foreign gas |
| CN101113360A (en) * | 2006-07-27 | 2008-01-30 | 上海中油企业集团有限公司 | Method for producing biodiesel by waste oil ester biological process |
Non-Patent Citations (1)
| Title |
|---|
| Lucilia Domingues et al..Studies of a pervaporation reactor:kinetics and equilibrium shift in benzyl alcohol acetylation.《Chemical Engineering Science》.1999,第54卷 * |
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Effective date of registration: 20081212 Address after: Beijing 100084-82 mailbox code: 100084 Applicant after: Tsinghua University Co-applicant after: Hunan Hainabaichuan Biological Engineering Co., Ltd. Address before: Beijing 100084-82 mailbox Zip code: 100084 Applicant before: Tsinghua University |
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