CN1557913A - 有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺 - Google Patents
有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺 Download PDFInfo
- Publication number
- CN1557913A CN1557913A CNA2004100006979A CN200410000697A CN1557913A CN 1557913 A CN1557913 A CN 1557913A CN A2004100006979 A CNA2004100006979 A CN A2004100006979A CN 200410000697 A CN200410000697 A CN 200410000697A CN 1557913 A CN1557913 A CN 1557913A
- Authority
- CN
- China
- Prior art keywords
- oil
- grease
- lipase
- reaction
- reaction system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 50
- 239000004519 grease Substances 0.000 title claims description 46
- 108090001060 Lipase Proteins 0.000 title claims description 22
- 239000004367 Lipase Substances 0.000 title claims description 22
- 102000004882 Lipase Human genes 0.000 title claims description 22
- 235000019421 lipase Nutrition 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000002283 diesel fuel Substances 0.000 title abstract description 5
- 239000000758 substrate Substances 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 108090000790 Enzymes Proteins 0.000 claims abstract description 15
- 102000004190 Enzymes Human genes 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 14
- 238000006911 enzymatic reaction Methods 0.000 claims abstract description 14
- 235000011187 glycerol Nutrition 0.000 claims abstract description 11
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 125000002252 acyl group Chemical group 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000012429 reaction media Substances 0.000 claims abstract description 6
- 239000002551 biofuel Substances 0.000 claims description 34
- 239000003921 oil Substances 0.000 claims description 31
- 235000019198 oils Nutrition 0.000 claims description 31
- 239000003225 biodiesel Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 15
- 108010048733 Lipozyme Proteins 0.000 claims description 12
- 108010084311 Novozyme 435 Proteins 0.000 claims description 11
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000005456 glyceride group Chemical group 0.000 claims description 9
- FCCDDURTIIUXBY-UHFFFAOYSA-N lipoamide Chemical compound NC(=O)CCCCC1CCSS1 FCCDDURTIIUXBY-UHFFFAOYSA-N 0.000 claims description 9
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 8
- -1 alcohol ester Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 210000000582 semen Anatomy 0.000 claims description 8
- 235000012424 soybean oil Nutrition 0.000 claims description 8
- 239000003549 soybean oil Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000012075 bio-oil Substances 0.000 claims description 6
- 239000008157 edible vegetable oil Substances 0.000 claims description 6
- 235000021323 fish oil Nutrition 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 102000004895 Lipoproteins Human genes 0.000 claims description 5
- 108090001030 Lipoproteins Proteins 0.000 claims description 5
- 241001465754 Metazoa Species 0.000 claims description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 241000269319 Squalius cephalus Species 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 5
- 239000008158 vegetable oil Substances 0.000 claims description 5
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 4
- 241000195493 Cryptophyta Species 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 235000019483 Peanut oil Nutrition 0.000 claims description 3
- 239000000312 peanut oil Substances 0.000 claims description 3
- 108010079522 solysime Proteins 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 6
- 230000002255 enzymatic effect Effects 0.000 description 5
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- 108010093096 Immobilized Enzymes Proteins 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241001661345 Moesziomyces antarcticus Species 0.000 description 1
- 241000235403 Rhizomucor miehei Species 0.000 description 1
- 241000223258 Thermomyces lanuginosus Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002646 long chain fatty acid esters Chemical class 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/649—Biodiesel, i.e. fatty acid alkyl esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/62—Carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
- C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis
-
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Zoology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Microbiology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Fats And Perfumes (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Enzymes And Modification Thereof (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
Abstract
本发明公开了属于生物油脂合成领域的利用有机溶剂作为反应介质的一种有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺。该工艺是以短链醇ROH作为反应酰基受体，用一些对酶反应活性没有负面影响的相对亲水的有机溶剂作为反应介质，利用生物酶催化油脂原料进行转酯反应合成生物柴油。将短链醇、油脂和脂肪酶装入具塞三角瓶中或酶反应器中混合均匀，置于可自动控温的往复摇床中或适于酶催化反应的各种生化反应器中加热反应后，油脂原料几乎可完全转化生成生物柴油和副产物甘油，生物柴油得率达94％以上。这些新型有机介质反应体系可以促进甲醇等短链醇在油脂中的溶解，并且可以部分溶解副产物甘油，从而可显著提高酶反应活性、缩短酶促反应时间并延长酶的使用寿命。
Description
技术领域
本发明属于生物油脂合成领域，特别涉及利用有机溶剂作为反应介质的一种有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺。
背景技术
油脂工业的新前景-生物柴油是由生物油脂原料通过转酯反应生成的长链脂肪酸酯类物质，是一种新型的无污染可再生能源，被称为生物柴油。其燃烧性能可以与传统的石油系柴油媲美，由于生物柴油燃烧后发动机排放出的尾气里有害物质比传统石化柴油降低了50％。目前生物柴油的研究和应用已经受到了广泛的关注。
目前生物柴油主要是用化学法生产，即用动植物油脂和一些低碳醇(甲醇或乙醇)在碱或者酸性催化剂作用下进行转酯反应，生成相应的脂肪酸甲酯或乙酯。化学法制备生物柴油存在如下一些不可避免的缺点：①油脂原料中的游离脂肪酸和水严重影响反应的进行；②甲醇在油脂中溶解性不好，易导致乳化液的形成从而使得后续处理过程复杂；③工艺要求甲醇用量大大超过反应摩尔比，过量甲醇的蒸发回流增大过程能耗。
由于利用生物酶法合成生物柴油具有反应条件温和、无污染物排放、油脂原料中的游离脂肪酸和少量水不影响酶促反应等优点，符合绿色化学的发展方向，因而日益受到人们的重视。
但同化学方法相比，生物酶法也存在如下一些亟待解决的问题。在[Shimada Yujiet al.Enzymatic alcoholysis for biodiesel fuel production and applicationof the reaction to oil processing，Journal of Molecular Catalysis B：Enzymatic，2002，17：133-142]文献中报道：甲醇、乙醇等短链醇在油脂原料中的溶解性较差，不利于反应的进行；其次，过量醇的存在会导致脂肪酶严重失活，故在利用生物酶法生产生物柴油的工艺过程中，多采用分批加入短链醇的方式以缓解其对酶的毒害作用。这种方式操作繁琐，反应时间较长；另外，以短链醇作为反应的酰基受体，反应过程中有副产物甘油产生，亲水性的甘油容易附着在固定化酶内孔及外表面，从而对酶的活性位点形成“屏蔽”，严重影响酶反应活性；而且，同化学方法相比，酶法合成生物柴油的得率相对较低。为改善以上情况，一些学者尝试采用有机溶剂反应体系合成生物柴油，文献[Shimada Yuji et al.Enzymatic alcoholysis for biodiesel fuel production and application ofthe reaction to oil processing，Journal of Molecular Catalysis B：Enzymatic，2002，17：133-142]报道：采用一些疏水性较强的有机溶剂如己烷、环己烷、石油醚等作为反应介质。这些疏水性有机溶剂可以很好的溶解油脂，在一定程度上能促进反应的进行；但由于这些疏水性较强的有机溶剂并不能有效溶解甲醇等低碳醇以及副产物甘油，故对酶反应活性、酶的使用寿命以及生物柴油得率等并未有明显改善。
发明内容
本发明的目的在于提出一种有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺。该工艺是以短链醇ROH作为反应酰基受体，用一些对酶反应活性没有负面影响的相对亲水的有机溶剂作为反应介质，利用生物酶催化油脂原料进行转酯反应合成生物柴油。其特征在于：将醇脂摩尔比为3∶1～6∶1的短链醇和油脂、油脂体积20-200％的有机溶剂和油脂质量2~30％的脂肪酶，装入具塞三角瓶中混合均匀，置于可自动控温的往复摇床中加热至20℃～60℃，反应5-24小时后，油脂原料可完全转化生成生物柴油和副产物甘油。
所述相对亲水的有机溶剂为叔丁醇、1，4-二氧六环或短链脂肪酸酯RCOOR’，其中R和R’为具有1-4个碳原子的烷基。
所述脂肪酶为微生物脂肪酶，包括Lipozyme TL，Lipozyme RM，Novozym 435或它们的混合物
所述油脂为生物油脂包括植物油脂、动物油脂、废食用油或炼油脚料。
所述植物油脂为蓖麻油、菜籽油、大豆油、花生油、玉米油、棉子油、米糠油或藻类油脂。
所述动物油脂为鱼油、猪油。
所述短链醇ROH中R为具有1-5个碳原子的烷基。
所述短链醇为甲醇、乙醇、丙醇、丁醇或戊醇。
本发明的有益效果是提高了酶反应活性、延长了酶的使用寿命并显著提高了生物柴油得率。这些新型有机介质反应体系可以促进甲醇等短链醇在油脂中的溶解，有效降低短链醇对酶反应活性的负面影响；其次，在这种有机介质反应体系中，可以一次性加入反应所需低碳醇，从而可显著缩短酶促反应时间、提高生物柴油得率，生物柴油得率达94％以上；另外，这些相对亲水的有机溶剂在一定程度上可以部分溶解甘油，可以有效降低反应物低碳醇以及副产物甘油对酶反应活性的负面影响、显著提高酶反应活性，有效改善甘油对固定化酶孔径的“屏蔽”状况，提高酶反应活性并延长酶的使用寿命。
具体实施方式
本发明提出一种有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺。该工艺是以短链醇ROH(R为具有1-5个碳原子的烷基)作为反应酰基受体，用一些对酶反应活性没有负面影响的相对亲水的有机溶剂叔丁醇、1，4-二氧六环或短链脂肪酸酯RCOOR’(R和R’为具有1-4个碳原子的烷基)作为反应介质，利用生物酶催化油脂原料进行转酯反应合成生物柴油。其工艺是将醇脂摩尔比为3∶1～6∶1的短链醇和油脂、油脂体积20-200％的有机溶剂和油脂质量2~30％的脂肪酶，装入具塞三角瓶中或适于酶催化反应的各种生化反应器中混合均匀，置于可自动控温的往复摇床中加热至20℃～60℃，反应5-24小时后，油脂原料可完全转化生成生物柴油和副产物甘油。
所述脂肪酶为微生物脂肪酶，包括Lipozyme TL，Lipozyme RM，Novozym 435或它们的混合物
上述油脂为生物油脂包括植物油脂(蓖麻油、菜籽油、大豆油、花生油、玉米油、棉子油、米糠油或藻类油脂)、动物油脂(鱼油、猪油)、废食用油或炼油脚料。上述短链醇为甲醇、乙醇、丙醇、丁醇或戊醇。
下面通过实施例来进一步说明本发明。
实施例1
将摩尔比为4∶1的甲醇和菜籽油(菜籽油9.65g)和基于油脂体积100％的叔丁醇，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至40℃后，加入油脂质量10％的固定化脂肪酶Novozym 435开始反应，经6小时后生产出生物柴油9.64g，生物柴油得率约为100％。
实施例2
将摩尔比为3∶1的甲醇和大豆油(大豆油9.65g)和基于油脂体积20％的叔丁醇，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至20℃后，加入油脂质量2％的固定化脂肪酶Novozym 435开始反应，经24小时后生产出生物柴油9.17g，生物柴油得率为95％。
实施例3
将摩尔比为5∶1的乙醇和棉籽油(棉籽油9.65g)、基于油脂体积200％的甲酸甲酯，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至60℃后，加入基于油脂质量10％的固定化脂肪酶Novozym 435开始反应，经12小时后生产出生物柴油9.1g，生物柴油得率为94％。
实施例4
将摩尔比为3∶1的丁醇和废食用油(废食用油9.65g)、基于油脂体积80％的叔丁醇，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至40℃后，加入基于油脂质量10％的固定化脂肪酶Novozym 435开始反应，经7小时后生产出生物柴油9.65g，生物柴油得率为100％。
实施例5
将摩尔比为4∶1的甲醇和猪油(猪油9.65g)、基于油脂体积100％的1，4-二氧六环，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至50℃后，加入基于油脂质量20％的固定化脂肪酶Novozym 435开始反应，经10小时后生产出生物柴油9.46g，生物柴油得率为98％。
实施例6
将摩尔比为3∶1的甲醇和大豆油(大豆油9.65g)、基于油脂体积50％的叔丁醇，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至40℃后，加入基于油脂质量20％的固定化脂肪酶Lipozyme TL开始反应，经10小时后生产出生物柴油9.1g，生物柴油得率为94％。
实施例7
将摩尔比为4∶1的戊醇和菜籽油(菜籽油9.65g)、基于油脂体积100％的丁酸丁酯，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至50℃后，加入基于油脂质量30％的固定化脂肪酶Lipozyme TL开始反应，经8小时后生产出生物柴油9.17g，生物柴油得率为95％。
实施例8
将摩尔比为3∶1的乙醇和棉籽油(棉籽油9.65g)、基于油脂体积80％的叔丁醇，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至40℃后，加入基于油脂质量20％的固定化脂肪酶Lipozyme RM开始反应，经10小时后生产出生物柴油9.1g，生物柴油得率为94％。
实施例9
将摩尔比为3∶1的甲醇和鱼油(鱼油9.65g)、基于油脂体积50％的1，4-二氧六环，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至50℃后，加入基于油脂质量2％的固定化脂肪酶Novozym 435和10％的Lipozyme TL开始反应，经18小时后生产出生物柴油9.46g，生物柴油得率为98％。
实施例10
将摩尔比为4∶1的乙醇和米糠油(米糠油9.65g)、基于油脂体积150％的叔丁醇，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至40℃后，加入基于油脂质量2％的固定化脂肪酶Novozym 435和10％的Lipozyme RM开始反应，经10小时后生产出生物柴油9.36g，生物柴油得率为97％。
实施例11：
将实施例1中反应后的脂肪酶直接滤出用于下一批次反应，其他反应条件同实施例1，如此将脂肪酶连续回用10次。在第10个反应批次中，反应6小时可生产出生物柴油9.62g，生物柴油得率仍高达99％。
根据上述实施例，以叔丁醇、1，4-二氧六环、短链脂肪酸酯RCOOR’(R、R’为具有1-4个碳原子数的烷基)作为有机介质反应体系，短链醇ROH(R为具有1-5个碳原子数的烷基)作为反应酰基受体时，在适宜的温度范围下加入油脂质量2％～30％的固定化脂肪酶Novozym 435(来源于Candida antarctica)、LipozymeRM(来源于Rhizomucor miehei)或Lipozyme TL(来源于Thermomyceslanuginosus)，不同生物油脂原料(蓖麻油、菜籽油、棉籽油、废食用油、大豆油、鱼油、猪油、炼油下脚料、藻类油脂等)都能被高效转化生成生物柴油。短链醇与油脂最优的反应摩尔比为3∶1～5∶1，最优的有机溶剂添加量为基于油脂体积的50％-100％，最优的反应温度为30℃～50℃。
Claims (8)
1.一种有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺，该工艺是以短链醇ROH作为反应酰基受体，用一些对酶反应活性没有负面影响的相对亲水的有机溶剂作为反应介质，利用生物酶催化油脂原料进行转酯反应合成生物柴油；其特征在于：将醇脂摩尔比为3∶1～6∶1的短链醇和油脂、油脂体积20-200％的有机溶剂和油脂质量2~30％的脂肪酶，装入具塞三角瓶中或各种酶反应器中混合均匀，置于可自动控温的往复摇床中或适于酶催化反应的各种生化反应器中进行加热至20℃～60℃，反应5-24小时后，油脂原料可完全转化生成生物柴油和副产物甘油。
2.根据权利要求1所述有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺，其特征在于：所述相对亲水的有机溶剂为叔丁醇、1，4-二氧六环或短链脂肪酸酯RCOOR’，其中R和R’为具有1-4个碳原子的烷基。
3.根据权利要求1所述有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺，其特征在于：所述脂肪酶为微生物脂肪酶，包括Lipozyme TL，Lipozyme RM，Novozym 435或它们的混合物。
4.根据权利要求1所述有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺，其特征在于：所述油脂为生物油脂包括植物油脂、动物油脂、废食用油或炼油脚料。
5.根据权利要求4所述有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺，其特征在于：所述植物油脂为蓖麻油、菜籽油、大豆油、花生油、玉米油、棉子油、米糠油或藻类油脂。
6.根据权利要求4所述有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺，其特征在于：所述动物油脂为鱼油、猪油。
7.根据权利要求1所述有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺，其特征在于：所述短链醇ROH中R为具有1-5个碳原子的烷基。
8.根据权利要求1所述有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺，其特征在于：所述短链醇为甲醇、乙醇、丙醇、丁醇或戊醇。
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100006979A CN1238469C (zh) | 2004-01-16 | 2004-01-16 | 有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺 |
| DE602004023761T DE602004023761D1 (de) | 2004-01-16 | 2004-11-29 | Neues verfahren zur herstellung von biodiesel aus ölen und fetten unter lipasekatalyse in einem organischen medium als reaktionssystem |
| CA2553653A CA2553653C (en) | 2004-01-16 | 2004-11-29 | A process for producing biodiesel from renewable oil under lipase catalysis in an organic medium reaction system |
| AT04797388T ATE446353T1 (de) | 2004-01-16 | 2004-11-29 | Neues verfahren zur herstellung von biodiesel aus ölen und fetten unter lipasekatalyse in einem organischen medium als reaktionssystem |
| PCT/CN2004/001372 WO2005075615A1 (fr) | 2004-01-16 | 2004-11-29 | Nouveau procede de production de biodiesel a partir d'huiles et de graisses catalysees par lipase dans un systeme de reaction a milieu organique |
| EP04797388A EP1705238B1 (en) | 2004-01-16 | 2004-11-29 | A new process for producing biodiesel from oils and fats catalyzed by lipase in organic medium reaction system |
| BRPI0418062A BRPI0418062B1 (pt) | 2004-01-16 | 2004-11-29 | processo para a produção de biodiesel a partir de óleo renovável na presença de catálise por lipase em um sistema de reação em meio orgânico |
| US10/597,123 US7550278B2 (en) | 2004-01-16 | 2004-11-29 | Process for producing biodiesel from renewable oil under lipase catalysis in an organic medium reaction system |
| HK06114093.1A HK1094229A1 (en) | 2004-01-16 | 2006-12-22 | A new process for producing biodiesel from oils and fats catalyzed by lipase in organic medium reaction system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100006979A CN1238469C (zh) | 2004-01-16 | 2004-01-16 | 有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1557913A true CN1557913A (zh) | 2004-12-29 |
| CN1238469C CN1238469C (zh) | 2006-01-25 |
Family
ID=34350467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100006979A Expired - Fee Related CN1238469C (zh) | 2004-01-16 | 2004-01-16 | 有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US7550278B2 (zh) |
| EP (1) | EP1705238B1 (zh) |
| CN (1) | CN1238469C (zh) |
| AT (1) | ATE446353T1 (zh) |
| BR (1) | BRPI0418062B1 (zh) |
| CA (1) | CA2553653C (zh) |
| DE (1) | DE602004023761D1 (zh) |
| HK (1) | HK1094229A1 (zh) |
| WO (1) | WO2005075615A1 (zh) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100375781C (zh) * | 2005-11-09 | 2008-03-19 | 中国科学院广州能源研究所 | 一种生产生物柴油的方法 |
| CN100404643C (zh) * | 2006-07-07 | 2008-07-23 | 清华大学 | 有机介质反应体系中微生物细胞转化油脂生产生物柴油的工艺 |
| CN1928116B (zh) * | 2006-08-25 | 2010-07-21 | 江南大学 | 一种非水相中脂肪酶合成酶活力的快速测定方法 |
| CN101838670A (zh) * | 2010-06-11 | 2010-09-22 | 贵州师范大学 | 制备生物柴油的方法 |
| CN101358216B (zh) * | 2008-08-06 | 2011-11-09 | 清华大学 | 一种利用膜在线脱水的酶法制备生物柴油工艺 |
| CN101215233B (zh) * | 2008-01-09 | 2012-05-23 | 江门市江海区嘉诺化工发展有限公司 | 脂肪酸甲酯生产工艺 |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE602006020837D1 (de) * | 2005-01-10 | 2011-05-05 | Novozymes As | Verfahren zur herstellung von fettsäurealkylestern aus triglyceriden und alkoholen unter verwendung einer kombination zweier lipolytischer enzyme |
| AU2005327879B2 (en) * | 2005-02-17 | 2011-03-03 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Liquid bio-fuel mixture and method and device for producing said mixture |
| ES2289943B1 (es) * | 2006-07-21 | 2008-12-16 | Universidad De Cordoba | Procedimiento de produccion de biodiesel mediante el uso de lipasa pancreatica de cerdo como biocatalizador enzimatico. |
| CN100455656C (zh) * | 2006-10-26 | 2009-01-28 | 中国农业科学院油料作物研究所 | 胞内分泌脂肪酶型全细胞催化剂的制备方法 |
| SG10201509864QA (en) | 2007-06-01 | 2015-12-30 | Solazyme Inc | Production of oil in microorganisms |
| US7790429B2 (en) | 2007-11-28 | 2010-09-07 | Transbiodiesel Ltd. | Robust multi-enzyme preparation for the synthesis of fatty acid alkyl esters |
| US8617866B2 (en) | 2007-11-28 | 2013-12-31 | Sobhi Basheer | Robust multi-enzyme preparation for the synthesis of fatty acid alkyl esters |
| KR100956414B1 (ko) | 2008-02-25 | 2010-05-06 | 한국신발피혁연구소 | 플레싱 스크랩으로부터 바이오디젤의 제조방법 |
| CN101235351B (zh) * | 2008-02-27 | 2012-07-18 | 浙江大学 | 一种固定化酶膜反应器及其制备和用其生产生物柴油的方法 |
| JP6066463B2 (ja) * | 2008-04-09 | 2017-01-25 | テラヴィア ホールディングス， インコーポレイテッド | 微生物バイオマス及び微生物油の直接的化学修飾 |
| CN102144035B (zh) * | 2008-07-08 | 2014-10-08 | 科技研究局 | 通过酶促水解及随后的化学/酶促酯化生产生物柴油 |
| EP2189535A1 (en) | 2008-11-21 | 2010-05-26 | Centre National de la Recherche Scientifique | Use of ionic liquids for implementing a process for the preparation of biodiesel |
| EP2370554B1 (en) * | 2008-11-28 | 2019-05-15 | Corbion Biotech, Inc. | Manufacturing of tailored oils in recombinant heterotrophic microorganisms |
| CN101418322B (zh) * | 2008-12-11 | 2011-09-14 | 清华大学 | 膜回收脂肪酶催化可再生油脂制备生物柴油的方法 |
| EP2455484B1 (en) * | 2009-07-17 | 2018-12-05 | Korea Advanced Institute of Science and Technology | Method for producing fatty acid alkyl esters using microorganisms having oil-producing ability |
| KR20110035612A (ko) * | 2009-09-30 | 2011-04-06 | 한국생산기술연구원 | 액체 이산화탄소 상태에서 효소적 바이오 디젤 제조방법 |
| GB2478137A (en) * | 2010-02-25 | 2011-08-31 | Hycagen Ltd | Biodiesel compositions |
| AU2011257982B2 (en) | 2010-05-28 | 2017-05-25 | Corbion Biotech, Inc. | Tailored oils produced from recombinant heterotrophic microorganisms |
| SG10201509035WA (en) | 2010-11-03 | 2015-12-30 | Solazyme Inc | Microbial Oils With Lowered Pour Points, Dielectric Fluids Produced Therefrom, And Related Methods |
| KR101964965B1 (ko) | 2011-02-02 | 2019-04-03 | 테라비아 홀딩스 인코포레이티드 | 재조합 유지성 미생물로부터 생산된 맞춤 오일 |
| BR112013028621A2 (pt) | 2011-05-06 | 2016-11-29 | Solazyme Inc | "microalgas oleaginosas recombinantes, método para produzir biomassa de microalga ou um produto produzido da biomassa, e método para produzir uma composição lipídica de microalga". |
| RU2491325C1 (ru) * | 2012-02-28 | 2013-08-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Омский государственный аграрный университет имени П.А. Столыпина" | Способ переработки жира в жидкое топливо |
| CN103305559B (zh) * | 2012-03-12 | 2015-07-22 | 广州市名花香料有限公司 | 一种天然风味脂肪酸酯的制备方法 |
| BR112014025719A8 (pt) | 2012-04-18 | 2017-10-03 | Solazyme Inc | Óleos customizados |
| MX369685B (es) | 2013-10-04 | 2019-11-19 | Terravia Holdings Inc | Aceites adaptables. |
| EP3620517A3 (en) | 2014-07-10 | 2020-07-29 | Corbion Biotech, Inc. | Ketoacyl acp synthase genes and uses thereof |
| CN112368375A (zh) | 2018-04-26 | 2021-02-12 | 巴斯夫欧洲公司 | 脂肪酶 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3004591C2 (de) * | 1980-02-08 | 1983-11-24 | Hellmut Dipl.-Ing. 7300 Esslingen Mueller | Auslegersystem für Radialbohrmaschinen |
| JPH11263750A (ja) * | 1998-03-16 | 1999-09-28 | Osaka City | 長鎖不飽和脂肪酸メントールエステルおよび酵素法によるその製造方法 |
| JP3891759B2 (ja) * | 2000-07-04 | 2007-03-14 | 三菱化学株式会社 | 電子写真感光体 |
| JP3837466B2 (ja) * | 2001-02-06 | 2006-10-25 | 独立行政法人酒類総合研究所 | バイオディーゼル（モノアルキルエステル）の製造方法 |
| TW491890B (en) | 2001-04-20 | 2002-06-21 | Wen-Teng Wu | Process for preparing lower alkyl fatty acid esters and in particular biodiesel |
| US6398707B1 (en) * | 2001-05-31 | 2002-06-04 | Wen-Teng Wu | Method of preparing lower alkyl fatty acids esters and in particular biodiesel |
-
2004
- 2004-01-16 CN CNB2004100006979A patent/CN1238469C/zh not_active Expired - Fee Related
- 2004-11-29 EP EP04797388A patent/EP1705238B1/en not_active Not-in-force
- 2004-11-29 AT AT04797388T patent/ATE446353T1/de not_active IP Right Cessation
- 2004-11-29 US US10/597,123 patent/US7550278B2/en active Active
- 2004-11-29 CA CA2553653A patent/CA2553653C/en not_active Expired - Fee Related
- 2004-11-29 BR BRPI0418062A patent/BRPI0418062B1/pt not_active IP Right Cessation
- 2004-11-29 WO PCT/CN2004/001372 patent/WO2005075615A1/zh active Application Filing
- 2004-11-29 DE DE602004023761T patent/DE602004023761D1/de active Active
-
2006
- 2006-12-22 HK HK06114093.1A patent/HK1094229A1/xx not_active IP Right Cessation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100375781C (zh) * | 2005-11-09 | 2008-03-19 | 中国科学院广州能源研究所 | 一种生产生物柴油的方法 |
| CN100404643C (zh) * | 2006-07-07 | 2008-07-23 | 清华大学 | 有机介质反应体系中微生物细胞转化油脂生产生物柴油的工艺 |
| CN1928116B (zh) * | 2006-08-25 | 2010-07-21 | 江南大学 | 一种非水相中脂肪酶合成酶活力的快速测定方法 |
| CN101215233B (zh) * | 2008-01-09 | 2012-05-23 | 江门市江海区嘉诺化工发展有限公司 | 脂肪酸甲酯生产工艺 |
| CN101358216B (zh) * | 2008-08-06 | 2011-11-09 | 清华大学 | 一种利用膜在线脱水的酶法制备生物柴油工艺 |
| CN101838670A (zh) * | 2010-06-11 | 2010-09-22 | 贵州师范大学 | 制备生物柴油的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2553653C (en) | 2011-06-28 |
| DE602004023761D1 (de) | 2009-12-03 |
| BRPI0418062B1 (pt) | 2016-06-28 |
| CN1238469C (zh) | 2006-01-25 |
| ATE446353T1 (de) | 2009-11-15 |
| US7550278B2 (en) | 2009-06-23 |
| EP1705238A1 (en) | 2006-09-27 |
| HK1094229A1 (en) | 2007-03-23 |
| WO2005075615A1 (fr) | 2005-08-18 |
| EP1705238B1 (en) | 2009-10-21 |
| EP1705238A4 (en) | 2007-04-11 |
| CA2553653A1 (en) | 2005-08-18 |
| BRPI0418062A (pt) | 2007-04-17 |
| US20080038804A1 (en) | 2008-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1238469C (zh) | 有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺 | |
| US9249437B2 (en) | Process for preparing biodiesel from renewable oil and fat catalyzed by lipase with online dehydration | |
| CA2829990C (en) | Method for preparing biodiesel | |
| Wang et al. | Microorganisms-promoted biodiesel production from biomass: A review | |
| CN101418322B (zh) | 膜回收脂肪酶催化可再生油脂制备生物柴油的方法 | |
| CN101225415A (zh) | 有机介质体系中酶法制备甘油二酯的工艺 | |
| CN1282729C (zh) | 一种不同脂肪酶相结合生产生物柴油的工艺 | |
| US7473791B2 (en) | Method for synthesizing biodiesel from renewable oils | |
| CN101343551A (zh) | 以乙酸甲酯为酰基受体的生物柴油制备方法 | |
| CN100347271C (zh) | 微生物细胞催化脂肪酸及含酸油脂生产生物柴油的方法 | |
| CN1190471C (zh) | 一种利用油脂原料合成生物柴油的方法 | |
| CN100404643C (zh) | 有机介质反应体系中微生物细胞转化油脂生产生物柴油的工艺 | |
| CN101358216B (zh) | 一种利用膜在线脱水的酶法制备生物柴油工艺 | |
| CN101381614B (zh) | 一种回收非固定化脂肪酶催化油脂制备生物柴油工艺 | |
| CN101250424A (zh) | 有机介质中通过补加短链醇提高生物柴油得率的酶法工艺 | |
| CN111073915A (zh) | 一种酶法高效制备生物柴油的方法 | |
| CN1844331A (zh) | 利用油脂原料生产生物柴油的方法 | |
| CN1730613A (zh) | 生物催化高酸值油脂进行酯交换反应生产生物柴油的方法 | |
| CN101381710A (zh) | 利用离心技术回收生物柴油制备中非固定化脂肪酶的工艺 | |
| Sharma et al. | Enzymatic transesterification of waste cooking oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060125 Termination date: 20220116 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |