WO2004081158A1 - Obtention de biogazole par synthese d'huiles et de graisses - Google Patents

Obtention de biogazole par synthese d'huiles et de graisses Download PDF

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Publication number
WO2004081158A1
WO2004081158A1 PCT/CN2004/000051 CN2004000051W WO2004081158A1 WO 2004081158 A1 WO2004081158 A1 WO 2004081158A1 CN 2004000051 W CN2004000051 W CN 2004000051W WO 2004081158 A1 WO2004081158 A1 WO 2004081158A1
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biodiesel
oil
fatty acid
low
reaction
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PCT/CN2004/000051
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English (en)
French (fr)
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Wei Du
Yuanyuan Xu
Dehua Liu
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Tsinghua University
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Priority to US10/549,336 priority Critical patent/US7473791B2/en
Publication of WO2004081158A1 publication Critical patent/WO2004081158A1/zh

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    • 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
    • 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
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • 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

Definitions

  • the invention belongs to the field of bio-oil synthesis, and particularly provides a method for synthesizing bio-diesel by using oil and fat raw materials. Background technique
  • the long-chain fatty acid esters produced by the transesterification of bio-oil raw materials are a new type of pollution-free renewable energy source, called biodiesel, whose combustion performance is comparable to traditional petroleum-based diesel. Due to the 50% reduction of harmful substances in the exhaust gas emitted by the engine after the combustion of biodiesel compared to traditional petrochemical diesel, the research and application of biodiesel has received extensive attention (Hideki Fuloida et al., Biodiesel fuel production by transesterification of oils, J Biosci. Bioeng., 2001, 92 (5): 405-416).
  • biodiesel is mainly produced by chemical methods, that is, trans-esterification reaction using animal and vegetable oils and fats and some low-carbon alcohols (methanol or ethanol) under the action of alkali or acid catalysts to generate corresponding fatty acid methyl esters or ethyl esters.
  • the chemical method for preparing biodiesel has the following unavoidable shortcomings: 1 Free fatty acids and water in the oil and fat materials seriously affect the progress of the reaction; 2 Methanol has poor solubility in oils and fats, which easily leads to the formation of emulsions and complicates subsequent processing. ; 3 The process requires that the amount of methanol greatly exceeds the molar ratio of the reaction, and the evaporation and reflux of excess methanol increases the energy consumption of the reaction process.
  • biodiesel has the advantages of mild reaction conditions, no pollutant discharge, free fatty acids and small amounts of water in the oil and fat raw materials, and does not affect the enzymatic reaction, which is the development direction of green-combined chemistry, and therefore it has attracted increasing attention.
  • Yomi Watanabe et al. Continuous production of biodiesel fuel from vegetable oil using immobilized Candida antarctica lipase, JAOCS, 2000, 7 (4): 355-358 In the currently reported production process of using bioenzyme to prepare biodiesel, some low-carbon alcohols such as methanol, ethanol and other low-carbon alcohols are mainly used as acyl acceptors for the reaction.
  • An object of the present invention is to provide a method for synthesizing biodiesel by using a fat and oil raw material.
  • the method uses a low-carbon fatty acid ester RCOOR 'as an acyl acceptor to transform a renewable bio-oil and fat raw material into biodiesel, wherein R and R' Is an alkyl group having 1 to 4 carbon atoms.
  • the separated by-product triglyceride is further reacted with a low-carbon alcohol ROH to obtain the above-mentioned low-carbon fatty acid ester, and the generated low-carbon fatty acid ester can be recycled for use in biodiesel. synthesis.
  • a low-carbon fatty acid ester is used as an acyl acceptor, and a bio-enzyme is used to catalyze a trans-esterification reaction of a fat and oil raw material to synthesize biodiesel.
  • These low-carbon fatty acid esters are miscible with oils and fats and have no negative effect on the enzyme reactivity.
  • the molar ratio of low-carbon fatty acid ester to fat is 3: 1 ⁇ 20: 1. After 4 ⁇ 20 hours of reaction, biodiesel is produced. During the reaction, no by-product glycerol was formed, and the by-products were triglycerides. These triglycerides had no negative effect on the enzyme reaction activity.
  • Fig. 1 is a process flow chart of the present invention for synthesizing biodiesel from a bio-oil raw material, in which a low-carbon fatty acid ester is used as an acyl acceptor to synthesize biodiesel. detailed description
  • the low-carbon fatty acid ester is selected from methyl acetate, ethyl acetate, methyl formate, ethyl formate, methyl propionate, and mixtures thereof.
  • the said lipase is a lipase derived from Candida antarctica or Rhizomucor miehei. Novozym 435, Lipozyme RM or mixtures thereof are preferred.
  • the fats and oils are biological fats and oils, such as castor oil, rapeseed oil, soybean oil, peanut oil, corn oil, cottonseed oil, waste food fats and other vegetable fats, fish oil, lard and other animal fats and algae fats.
  • the molar ratio of low-carbon fatty acid esters to fats and oils is 3: 1 to 20: 1, preferably 4: 1 to 14: 1.
  • the reaction of low-carbon fatty acid esters with oils and fats can be carried out in a reciprocating shaker with automatic temperature control.
  • the reaction temperature is 20 ° ( ⁇ 60 ° C, preferably 30 ° C to 50 ° C).
  • the amount of lipase in the present invention is 5-30% of the mass of fat and oil, and the reaction time is 4-20 hours.
  • Biodiesel and tri-oligocarbonate are produced as a by-product.
  • the present invention uses low-carbon fatty acid esters that are not toxic to enzyme activity to replace low-carbon alcohols as direct acyl acceptors for the production of biodiesel.
  • the reaction conditions are mild and the reaction process is simple and easy to control; moreover, the reaction process No by-product glycerol was produced, and the by-product was triglyceride.
  • Tri-oligocarbonate does not clog the pore size of the immobilized enzyme and does not have any negative effect on the activity of the immobilized enzyme.
  • the lipase can be directly recycled after being filtered out, and the lipase can still maintain high catalytic activity during recovery.
  • the separated by-product triglyceride can be further reacted with low-carbon alcohol to obtain the above-mentioned low-carbon Fatty acid esters (this step is easy to carry out under normal conditions).
  • the low-carbon fatty acid esters can be recycled for biodiesel synthesis.
  • the raw materials of the entire process are still oils and fats and relatively low-cost low-carbon alcohols, but the low-carbon fatty acid esters that directly participate in the enzyme reaction effectively avoid the low-carbon fatty acids.
  • the negative effects of carbon alcohol and by-product glycerol on enzyme activity greatly extend the life of the enzyme. Examples
  • Example 1 The present invention is further explained by the following examples, but the present invention is not limited to these examples.
  • Example 1 The present invention is further explained by the following examples, but the present invention is not limited to these examples.
  • Ethyl propionate and soybean oil (soy oil 9.7g) with a molar ratio of 12: 1 were put into a triangle bottle with a stopper and mixed uniformly, and then heated to 40 ° C in a reciprocating shaker with automatic temperature control. After adding 30% of the fat mass based on the immobilized lipase Novozym 435, the reaction was started. After 12 hours, 8.7g of biodiesel was produced, and the yield of biodiesel was 90%.
  • Methyl acetate and rapeseed oil (rapeseed oil: 9.7g) in a molar ratio of 12: 1 were mixed into a conical flask with a stopper and heated in a reciprocating shaker with automatic temperature control and heated to 40 ° C. Then, 30% of the fat mass based on the immobilized lipase Novozym 435 was added to start the reaction. After 7 hours, 9.3 g of biodiesel was produced, and the biodiesel yield was 96%.
  • Methyl acetate and waste edible oil (9.7g) with a molar ratio of 12: 1 were put into a triangle bottle with a stopper and mixed uniformly, and then heated in a reciprocating shaker with automatic temperature control to 40 Then, 30% of the fat mass based on the immobilized lipase Novozym 435 was added to start the reaction. After 12 hours, 8.5 g of biodiesel was produced, and the biodiesel yield was 88%.
  • Example 22 The lipase after the reaction in Example 2 was directly filtered out for the next batch of reactions, and other reaction conditions were the same as those in Example 2. Thus, the lipase was reused continuously 10 times. In the 10th reaction batch, 9.2g of biodiesel was produced in 6 hours of reaction, and the yield of biodiesel was still as high as 95%. It can be seen that the lipase showed good operational stability in the new process.
  • Methanol with a molar ratio of 3: 2 and the by-product glyceryl triacetate in Example 2 were put into a stoppered Erlenmeyer flask and mixed well, and placed in a reciprocating shaker with automatic temperature control and heated to
  • a low-carbon fatty acid ester is used as an acyl acceptor, and an immobilized lipase derived from Candida antarctica or Rhizomorcor miehei (Novozym 435) is added at a temperature range of 5% to 30% of the fat mass at a suitable temperature range Or Lipozyme RM), different bio-oil materials (castor oil, rapeseed oil, cottonseed oil, waste edible oil, soybean oil, fish oil, lard, algae oil, etc.) can be effectively converted into biodiesel.
  • the byproduct triglyceride can be further reacted with a low-carbon alcohol to obtain the above-mentioned low-carbon fatty acid ester, and the generated low-carbon fatty acid ester can be recycled for biodiesel synthesis.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Description

利用油脂原料合成生物柴油的方法 技术领域
本发明属于生物油料合成领域,特别是提供了一种利用油脂原料 合成生物柴油的方法。 背景技术
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 (Hideki Fuloida等人， Biodiesel fuel production by transesterification of oils, J. Biosci. Bioeng., 2001，92(5):405-416)。
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 增大反应过程的能耗。
由于利用生物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并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 (Yomi Watanabe 等人， Continuous production of biodiesel fuel from vegetable oil using immobilized Candida antarctica lipase, JAOCS, 2000, 7(4): 355-358)。 在目前所报道的利用生物酶法制备生物柴油的生产工艺中，主要是利 用一些低碳醇如甲醇、乙醇等低碳醇作为反应的酰基受体。直接利用 这些低碳醇作为反应的酰基受体生产生物柴油， 存在如下一些问题： 这些低碳醇对酶分子有毒性， 从而影响酶的使用寿命； 而且， 直接用 这些低碳醇作为反应的酰基受体生产生物柴油，反应过程中有副产物 甘油产生，副产物甘油很容易堵塞固定化酶的孔径，严重影响酶反应 活性 ( Yuji Shimada等人, Enzymatic alcoholysis for biodiesel fuel production and application of the reaction to oil processing, Journal of Molecular Catalysis B: Enzymatic, 2002, 17: 133-142)。 发明内容
本发明的目的在于提供了一种利用油脂原料合成生物柴油的方 法， 该方法以低碳脂肪酸酯 RCOOR'为酰基受体,将可再生的生物油 脂原料转化生成生物柴油,其中 R和 R'为具有 1一 4个碳原子的烷基。 在本发明的方法中，分离后的副产物三低碳酸甘油酯进一步与低碳醇 ROH反应， 又可得到上述的低碳脂肪酸酯， 生成的低碳脂肪酸酯可 循环用于生物柴油的合成。
在本发明中， 以低碳脂肪酸酯作为酰基受体，利用生物酶催化油 脂原料进行转酯反应合成生物柴油。这些低碳脂肪酸酯与油脂互溶且 对酶反应活性没有负面影响。低碳脂肪酸酯与油脂的摩尔比为 3 : 1〜 20： 1 , 经 4〜20小时反应后， 即生产出生物柴油。 反应过程中没有 副产物甘油生成，生成的副产物为三低碳酸甘油酯，这些三低碳酸甘 油酯对酶反应活性没有负面作用。分离后的副产物三低碳酸甘油酯进 一步与低碳醇反应又可得到上述低碳脂肪酸酯，这些三低碳酸甘油酯 与低碳醇互溶，该步反应在常规反应条件下容易进行，生成的低碳脂 肪酸酯可循环用于生物柴油的合成。 附图说明
图 1 是本发明利用生物油脂原料合成生物柴油的工艺流程图，其 中以低碳脂肪酸酯作为酰基受体合成生物柴油。 具体实施方式
在本发明中， 所述的低碳脂肪酸酯选自乙酸甲酯、 乙酸乙酯、 甲酸甲酯、 甲酸乙酯、 丙酸甲酯， 以及它们的混合物。
所述的月旨肪酶为来源于 Candida antarctica或来源于 Rhizomucor miehei的脂肪酶。优选 Novozym 435、 Lipozyme RM或它们的混合物。
所述油脂为生物油脂， 如蓖麻油、 菜籽油、 大豆油、花生油、 玉 米油、棉子油、废食用油脂及其它植物油脂、鱼油、猪油及其它动物 油脂及藻类油脂等。
低碳脂肪酸酯与油脂的摩尔比为 3: 1〜20: 1， 优选为 4: 1〜14: 1。 低碳脂肪酸酯与油脂的反应可以在可自动控温的往复摇床中进 行， 反应温度为 20° (〜 60°C， 优选 30°C〜50°C。
本发明中脂肪酶的用量为油脂质量的 5~30%， 反应时间为 4〜20 小时， 生产出生物柴油和副产物三低碳酸甘油酯。
如附图 1 所示， 本发明利用对酶活性没有毒性的低碳脂肪酸酯 代替低碳醇直接作为反应的酰基受体生产生物柴油， 反应条件温和、 反应过程简单易控； 而且， 反应过程中没有副产物甘油产生， 生成的 副产物为三低碳酸甘油酯。 三低碳酸甘油酯不会堵塞固定化酶孔径， 对固定化酶活性没有任何负面作用。反应后将脂肪酶滤出后可直接循 环回用，在回复利用中脂肪酶仍可保持高的催化活性；分离后的副产 物三低碳酸甘油酯进一步与低碳醇反应又可得到上述低碳脂肪酸酯 (该步反应在常规条件下就容易进行）， 生成的低碳脂肪酸酯可循环 用于生物柴油的合成。整个工艺的原料仍然是油脂和价格比较低廉的 低碳醇，但直接参与酶反应的是低碳脂肪酸酯，从而有效地避开了低 碳醇和副产物甘油对酶活性的负面作用， 大大延长了酶的使用寿命。 实施例
下面通过实施例来进一步说明本发明，但是本发明不限于这些实 施例。 实施例 1
将摩尔比为 3 : 1的乙酸甲酯和大豆油 （大豆油 9.7g) 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 3CTC后， 加入基于油脂质量 30%的固定化脂肪酶 Novozym 435开始反应，经 4 小时后生产出生物柴油 8.5g， 生物柴油得率为 88%。 实施例 2
将摩尔比为 12: 1的乙酸甲酯和大豆油（大豆油 9.7g)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°C后， 加入基于油脂质量 30%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 9.2g， 生物柴油得率为 95%。 实施例 3
将摩尔比为 20: 1的乙酸甲酯和大豆油（大豆油 9.7g)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 30°C后， 加入基于油脂质量 30%的固定化脂肪酶 NovoZym 435开始反应，经 8 小时后生产出生物柴油 8.7g， 生物柴油得率为 90%。 实施例 4
将摩尔比为 12: 1的乙酸甲酯和大豆油（大豆油 9.7g)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 30°C后， 加入基于油脂质量 30%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 9.2g， 生物柴油得率为 95%。 实施例 5
将摩尔比为 12: 1的乙酸甲酯和大豆油（大豆油 9.7g)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°C后， 加入基于油脂质量 30%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 8.7g， 生物柴油得率为 90%。 实施例 6
将摩尔比为 12: 1的乙酸甲酯和大豆油（大豆油 9.7g)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°C后， 加入基于油脂质量 5%的固定化脂肪酶 Novozym 435开始反应，经 15 小时后生产出生物柴油 9.2g， 生物柴油得率为 95%。 实施例 Ί
将摩尔比为 12: 1的乙酸乙酯和大豆油（大豆油 9.7g)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°C后， 加入基于油脂质量 30%的固定化脂肪酶 Novozym 435开始反应，经 8 小时后生产出生物柴油 9.2g， 生物柴油得率为 95%。 实施例 8
将摩尔比为 12: 1的甲酸甲酯和大豆油（大豆油 9.7g)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 C后， 加入基于油脂质量 30%的固定化脂肪酶 Novozym 435开始反应，经 9 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 12: 1的丙酸乙酯和大豆油（大豆油 9.7g)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 °C后， 加入基于油脂质量 30%的固定化脂肪酶 Novozym 435幵始反应， 经 12小时后生产出生物柴油 8.7g， 生物柴油得率为 90%。 实施例 10
将摩尔比为 12: 1的乙酸甲酯和棉籽油（棉籽油为 9.7g)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 4(TC 后， 加入基于油脂质量 30%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 8.9g， 生物柴油得率为 92%。 实施例 11
将摩尔比为 12: 1的乙酸甲酯和菜籽油（菜籽油为 9.7g)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°C 后， 加入基于油脂质量 30%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 9.3g， 生物柴油得率为 96%。 实施例 12
将摩尔比为 12: 1的乙酸甲酯和藻类油脂（藻类油 9.7g)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°C 后， 加入基于油脂质量 30%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 8.9g， 生物柴油得率为 92%。 实施例 13
将摩尔比为 12: 1的乙酸甲酯和废食用油（废食用油 9.7g)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 30%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 8.5g， 生物柴油得率为 88%。 实施例 14
将摩尔比为 12: 1的乙酸甲酯和猪油（猪油 9.7g)装入具塞三角 瓶中混合均勾， 并置于可自动控温的往复摇床中加热至 50°C后， 加 入基于油脂质量 30%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 8.7g， 生物柴油得率为 90%。 实施例 15
将摩尔比为 12: 1的乙酸甲酯和大豆油（大豆油 9.7g)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°C后， 加入基于油脂质量 30%的固定化脂肪酶 Lipozyme RM开始反应， 经 12小时后生产出生物柴油 8.2g， 生物柴油得率为 85%。 实施例 16
将摩尔比为 12: 1的乙酸乙酯和棉籽油（棉籽油 9.7g)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°C后， 加入基于油脂质量 30%的固定化脂肪酶 Lipozyme RM开始反应， 经 14小时后生产出生物柴油 8.1g， 生物柴油得率为 84%。 实施例 17
将摩尔比为 12: 1的甲酸甲酯和废食用油（废食用油 9.7g)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 °C后，加入基于油脂质量 5%的固定化脂肪酶 Lipozyme RM幵始反应， 经 20小时后生产出生物柴油 7.7g, 生物柴油得率为 80% 将摩尔比为 10: 1的丁酸甲酯和猪油（猪油 9.7g)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°C后， 加 入基于油脂质量 30%的固定化脂肪酶 Novozym 435开始反应， 经 15 小时后生产出生物柴油 8.7g， 生物柴油得率为 89%。 实施例 19
将摩尔比为 14: 1的乙酸丁酯和大豆油（大豆油 9.7g)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 3(TC后， 加入基于油脂质量 20%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 9.0g， 生物柴油得率为 91%。 实施例 20
将摩尔比为 10: 1的丁酸丁酯和大豆油（大豆油 9.7g)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°C后， 加入基于油脂质量 5%的固定化脂肪酶 Novozym 435和 15%的脂肪酶 Lipozyme RM开始反应， 经 15小时后生产出生物柴油 8.9g， 生物柴 油得率为 92%。 实施例 21
将实施例 2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 2， 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 9.2g， 生物柴油得率仍高达 95% 可见， 脂肪酶在该新工艺中表现出较好的操作稳定性。 实施例 22
将摩尔比为 3 : 2的甲醇与实施例 2中的副产物三乙酸甘油酯装 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
8 40°C后， 加入基于三乙酸甘油脂质量 0.6%的 NaOH开始反应， 经 4 小时反应后， 99%的甲醇转化生成乙酸甲酯， 生成的乙酸甲酯经简单 蒸熘后可直接循环用于生物柴油的合成。 根据上述实施例， 以低碳脂肪酸酯作为酰基受体，在适宜的温度 范围下加入油脂质量 5%〜30%的来源于 Candida antarctica或来源于 Rhizomucor miehei的固定化月旨肪酶（Novozym 435或 Lipozyme RM)， 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、 藻类油脂等)都能被有效转化生成生物柴油。 副产物三 低碳酸甘油酯进一步与低碳醇反应又可得到上述低碳脂肪酸酯，生成 的低碳脂肪酸酯可循环用于生物柴油的合成。

Claims

权利要求
1、 一种利用油脂原料合成生物柴油的方法， 其特征在于： 以低 碳脂肪酸酯 RCOOR'作为酰基受体，其中 R和 R'为具有 1一 4个碳原 子的烷基，利用生物酶催化生物油脂进行转酯反应，其中低碳脂肪酸 酯与油脂的摩尔比为 3:1〜20:1； 将副产物三低碳酸甘油酯进一步与 低碳醇 ROH反应又可得到上述的低碳脂肪酸酯，生成的低碳脂肪酸 酯可循环用于生物柴油的合成。
2、 根据权利要求 1所述的方法， 其中反应温度为 20°C〜60°C。
3、 根据权利要求 2所述的方法， 其中反应温度为 30°C〜5(TC
4、 根据权利要求 1所述的方法， 其中反应时间为 4〜20小时。
5、 根据权利要求 1所述的方法， 其中脂肪酶的用量为油脂质量 的 5—30%。
6、 根据权利要求 1所述的方法， 其中低碳脂肪酸酯与油脂的摩 尔比为 4: 1~14:1。
7、 根据权利要求 1所述的方法， 其特征在于： 所述低碳脂肪酸 酯选自乙酸甲酯、 乙酸乙酯、 甲酸甲酯、 甲酸乙酯、丙酸甲酯、丙酸 乙酯、 丁酸甲酯、 甲酸丁酯， 以及它们的混合物。
8、 根据权利要求 1所述的方法， 其特征在于： 所述脂肪酶来源 于 Candida antarctica禾口 /或 Rhizomucor mieheL
9、，根据权利要求 8所述的方法， 其特征在于， 所述的脂肪酶选 自 Novozym 435、 Lipozyme RM， 以及它们的混合物。
10、根据权利要求 1所述的方法， 其特征在于： 所述油脂选自蓖 麻油、 菜籽油、 大豆油、 鱼油、 猪油、 废食用油、 藻类油脂， 以及它 们的混合物。
PCT/CN2004/000051 2003-03-13 2004-01-15 Obtention de biogazole par synthese d'huiles et de graisses WO2004081158A1 (fr)

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