CN1208305C - Method for producing diglyceride - Google Patents
Method for producing diglyceride Download PDFInfo
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- CN1208305C CN1208305C CN 03113862 CN03113862A CN1208305C CN 1208305 C CN1208305 C CN 1208305C CN 03113862 CN03113862 CN 03113862 CN 03113862 A CN03113862 A CN 03113862A CN 1208305 C CN1208305 C CN 1208305C
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Abstract
The present invention relates to a production method of diglyceride. Lower alcohol is mixed with triglyceride, and then, reacts under the action of immobilized lipase; the reaction product is separated to obtain diglyceride; simultaneously, by-product of fatty acid lower alcohol ester is obtained; the lower alcohol is monohydric alcohol with the C atomicity less than 3; the triglyceride is refined animal oil, vegetable oil, microorganism microbe lipin or the mixture; the immobilized lipase is lipase fixed on a carrier by methods of physical adsorption, covalent cross-linking, etc. The present invention uses the triglyceride and the lower alcohol as substrates to synthesize diglyceride; simultaneously, by-product-fatty acid lower alcohol ester is produced. The method has the advantages of rapid reaction, easy separation of the product and by-product value lifting.
Description
Technical field
The present invention relates to the method for synthetic triglyceride, particularly reaction substrate adopts the production method of the triglyceride of lower alcohol and triglyceride level.
Background technology
Triglyceride is a kind of the fat mols with two fatty acid chains, and the overwhelming majority is a triglyceride level in the natural fats and oils, only contains a small amount of triglyceride, usually less than 5%.Triglyceride and triglyceride level have very big difference in intravital absorption of humans and animals and metabolic process.The metabolism of triglyceride level at first is to generate mono-glycerides and free fatty acids through the digestive ferment effect based on steapsase, then through intestinal villi absorb enter human body after, major part synthetic glycerine three esters again very, therefore, excessive edible glycerol three esters can make blood fat raise, thereby are detrimental to health.The metabolism of triglyceride is through digestive ferment effect generation glycerine and free fatty acids based on steapsase, and the two changes into energy in human body, so triglyceride do not have the effect of rising blood fat, and it is a kind of healthy grease.In addition, triglyceride can absorb by other approach outside small intestine, can alleviate the enteron aisle burden, especially is fit to some patient's supplementing energy and indispensable fatty acid purposes.Triglyceride has very important potential using value, as healthy oils, medical auxiliary materials, makeup auxiliary material, medicinal intermediates etc.
The enzyme process of common triglyceride is synthetic to be to adopt following method: a. triglyceride level and glycerine carry out glycerolysis reaction; B. glycerine and fatty acid esterification reaction; C. the hydrolysis of triglyceride level.Method a and b exist that reaction substrate viscosity is big, speed of response is slow, the by product free fatty acids is many and problem such as separation difficulty, make the production cost of triglyceride raise; Method c exists that reaction is wayward, by product many and shortcoming such as separation difficulty, not too is fit to industrial applications.
Summary of the invention
The objective of the invention is to the problem at the prior art existence, a kind of production method of triglyceride is provided, is substrate with triglyceride level and lower alcohol, and synthetic triglyceride is produced by product lipid acid low-carbon-ester simultaneously; This method is swift in response, product is easy to separate, and can promote by product value.
The lipid acid low-carbon-ester has almost and the same performance of hydro carbons diesel oil usually, and some aspect also is better than hydro carbons diesel oil, can be used as a kind of diesel oil substitute, claims biofuel.Compare with the hydro carbons diesel oil in oil source, biofuel is a kind of renewable resources, has huge potential using value in energy problem in the future.
The production method of triglyceride of the present invention be will lower alcohol and triglyceride level mix the back and under the immobilized lipase effect, react, with reaction product separate triglyceride, obtain by product lipid acid low-carbon-ester simultaneously.
Described immobilized lipase can directly join in lower alcohol and the triglyceride mixture and react, concrete grammar comprises: lower alcohol and triglyceride level are mixed back adding immobilized lipase, reacted 1～10 hour, product separates the acquisition triglyceride through underpressure distillation or molecular distillation, obtains by product lipid acid low-carbon-ester simultaneously; The mol ratio of described lower alcohol and triglyceride level is 0.3～1.5: 1, and the immobilized lipase enzyme dosage is 1～10% weight of reaction substrate consumption.
Also lower alcohol and triglyceride level can be mixed the back by the column reactor of immobilized lipase is housed, the residence time of substrate in post was not less than 5 minutes, and product separates the acquisition triglyceride through molecular distillation, obtains by product lipid acid low-carbon-ester simultaneously; The mol ratio of described lower alcohol and triglyceride level is 0.3～1.0: 1.
Described lower alcohol is meant the C atomicity less than 3 monohydroxy-alcohol, for example methyl alcohol, ethanol, propyl alcohol one or more mixtures wherein.
Described triglyceride level can adopt refining microbial oil and animal and plant grease, as Rice pollard oil, soya-bean oil, Oleum Gossypii semen, rape oil, sunflower oil, Semen Maydis oil, fish oil one or more mixtures wherein.
Described immobilized lipase is meant by methods such as physical adsorption, covalent cross-linkings and is fixed on lipase on the carrier, comprise that the root enzyme belongs to lipase, Aspergillus lipase, a hair enzyme belongs to lipase, bacterium lipase or steapsase, for example products such as the Lipozyme IM of Novozymes company, Novozyme 435.
The present invention compared with prior art has following advantage:
1) solves the excessive problem of substrate viscosity in the common triglyceride production well;
2) lower alcohol and triglyceride level have good consistency, obviously improve reaction efficiency;
3) reaction generates triglyceride and biofuel simultaneously, and the two separates as easy as rolling off a log and all has than higher value;
4) reduced the production cost of triglyceride;
5) reaction can be carried out in anhydrous system, and the inactivation of enzyme and loss loss speed reduce.
Embodiment
Embodiment 1
In the stirred reactor of controlled temperate zone, add the 1000g purified soyabean oil, the soybean oil free fatty acids is 0.1%, at the uniform velocity stream adds 50g methyl alcohol, stirring makes itself and grease fully miscible, add 10gLipozyme RM IM (Novozymes company product) simultaneously, methyl alcohol added in 15 hours, and above mixture is in 55 ℃ of reactions under 300 rev/mins the stirring velocity after 20 hours, filtered and recycled immobilized lipase recycling.Reaction product removes methyl alcohol and glycerine through washing, centrifugal, removes residual methanol through 110 ℃ of underpressure distillation again, carries out molecular distillation 0.5Pa, 150 ℃ then, obtains fatty acid methyl ester and glyceride fraction respectively.Fatty acid methyl ester can be used as biofuel and uses, and it is edible that glyceride fraction can be used as healthy grease.The quality percentage composition of each composition is as follows in the glyceride fraction: triglyceride level 28.1%, triglyceride are 60.9%, mono-glycerides 11.5%, free fatty acids 0.5%.Further molecular distillation can obtain containing triglyceride greater than 85% glyceryl ester under 0.5Pa, 193 ℃ of molecule conditions.
Embodiment 2
Add 1000g refining rape oil and soya-bean oil mixture in proportion in the stirred reactor of controlled temperate zone, free lipid acid is 0.15% in the grease, add 18g methyl alcohol again, stir and make it fully miscible, add 50g Novozyme 435 (Novozymes company product) again, the following 50 ℃ of reactions of 300 rev/mins stirring velocity are after 8 hours, and the filtered and recycled immobilized lipase reuses.Reaction product removes methyl alcohol and glycerine through washing, centrifugal, removes residual methanol through 110 ℃ of underpressure distillation again, carries out molecular distillation 0.5Pa, 146 ℃ then, obtains fatty acid methyl ester and glyceride fraction.Fatty acid methyl ester can be used as biofuel and uses, and it is edible that glyceride fraction can be used as healthy grease.The quality percentage composition of each composition is as follows in the glyceride fraction: triglyceride level 78.8%, triglyceride are 18.8%, and mono-glycerides is 2.1%, free fatty acids 0.3%.Further molecular distillation can obtain containing triglyceride greater than 65% glyceryl ester under 0.5Pa, 195 ℃ of molecule conditions.
Embodiment 3
In the stirred reactor of controlled temperate zone, add 1000g refining mortierella sp oil, mortierella sp oil free fatty acids is 0.5%, add 100g Novozyme 435 (Novozymes company product) again, all uniform flow adds the 75g dehydrated alcohol continuously, finish in 2 hours, the stream added-time fully stirs and makes itself and reaction system miscible rapidly, and 45 ℃ of reactions are after 2.5 hours, and the filtered and recycled immobilized lipase reuses.Reaction product removes ethanol and glycerine through washing, centrifugal, removes residual ethanol through 110 ℃ of underpressure distillation again, carries out molecular distillation 0.5Pa, 150 ℃ then, obtains fatty-acid ethyl ester and glyceride fraction.Fatty-acid ethyl ester can be used as biofuel and uses, and it is edible that glyceride fraction can be used as healthy grease.The quality percentage composition of each composition is as follows in the glyceride fraction: triglyceride level 25.2%, triglyceride are 68.6%, and mono-glycerides is 5.6%, free fatty acids 0.6%.Further molecular distillation can obtain containing triglyceride greater than 85% glyceryl ester under 0.5Pa, 195 ℃ of molecule conditions.
Embodiment 4
Add in the stirred reactor of controlled temperate zone 1000g refining sunflower seed oil and fish oil etc. the quality mixture, free lipid acid is 0.1% in the above-mentioned grease, add 30g Novozyme 435 (Novozymes company product) again, all uniform flow adds 63g anhydrous methanol and alcoholic acid mixture continuously, and wherein methyl alcohol 45 restrains, ethanol 18 grams, finish in 6 hours, the stream added-time fully stirs and makes itself and reaction system miscible rapidly, and 55 ℃ of reactions are after 8 hours, and the filtered and recycled immobilized lipase reuses.Reaction product removes methyl alcohol, ethanol and glycerine through washing, centrifugal, removes residual methanol and ethanol through 110 ℃ of underpressure distillation again, carries out molecular distillation 0.5Pa, 143 ℃ then, obtains fatty acid methyl ester, ethyl ester and glyceride fraction.Fatty acid methyl ester and ethyl ester can be used as biofuel and use, and it is edible that glyceride fraction can be used as healthy grease.The quality percentage composition of each composition is as follows in the glyceride fraction: triglyceride level 11.5%, triglyceride are 74.1%, and mono-glycerides is 14.2%, free fatty acids 0.2%.Further molecular distillation can obtain containing triglyceride greater than 85% glyceryl ester under 0.5Pa, 193 ℃ of molecule conditions.
Embodiment 5
1000 gram particulate state immobilized lipase Lipozyme TL IM (Novozymes company product), evenly load in the filling bed type reactor, rape oil, methyl alcohol mix by 20: 1 mass ratio in advance, be continuously pumped into this reactor through peristaltic pump, the flow velocity of rape oil, carbinol mixture is 1Kg/hr, the residence time of substrate in column reactor is about 1 hour, and temperature of reaction is 50 ℃.Reaction product removes methyl alcohol and glycerine through washing, centrifugal, removes residual methanol through 110 ℃ of underpressure distillation again, carries out molecular distillation 0.5Pa, 140 ℃ then, obtains fatty acid methyl ester and glyceride fraction.Fatty acid methyl ester can be used as biofuel and uses, and it is edible that glyceride fraction can be used as healthy grease.The quality percentage composition of each composition is as follows in the glyceride fraction: triglyceride level 31.3%, triglyceride are 62.9%, and mono-glycerides is 5.1%, free fatty acids 0.7%.Further molecular distillation can obtain containing triglyceride greater than 85% glyceryl ester under 0.5Pa, 190 ℃ of molecule conditions.
Embodiment 6
1000 gram particulate state immobilized lipase Novozyme, 435 (Novozymes company products), evenly load in the filling bed type reactor, soybean oil, ethanol mix by 25: 1 mass ratio in advance, be continuously pumped into this reactor through peristaltic pump, the flow velocity of soybean oil, alcohol mixture is 2Kg/hr, the residence time of substrate in column reactor is about 0.5 hour, and temperature of reaction is 55 ℃.Reaction product removes ethanol and glycerine through washing, centrifugal, removes residual ethanol through 110 ℃ of underpressure distillation again, carries out molecular distillation 0.5Pa, 150 ℃ then, obtains fatty-acid ethyl ester and glyceride fraction.Fatty-acid ethyl ester can be used as biofuel and uses, and it is edible that glyceride fraction can be used as healthy grease.The quality percentage composition of each composition is as follows in the glyceride fraction: triglyceride level 77.8%, triglyceride are 19.8%, and mono-glycerides is 2.1%, free fatty acids 0.3%.Further molecular distillation can obtain containing triglyceride greater than 55% glyceryl ester under 0.5Pa, 190 ℃ of molecule conditions.
Claims (7)
1, a kind of production method of triglyceride, it is characterized in that be will lower alcohol and triglyceride level mix the back and under the immobilized lipase effect, react, with reaction product separate triglyceride, obtain by product lipid acid low-carbon-ester simultaneously; Described lower alcohol is meant that lower alcohol is meant that the C atomicity is less than 3 monohydroxy-alcohol, described triglyceride level is refined animal, vegetables oil, microbial oil or their mixture, and described immobilized lipase is to be fixed on lipase on the carrier by methods such as physical adsorption, covalent cross-linkings.
2, the production method of triglyceride according to claim 1, it is characterized in that lower alcohol and triglyceride level are mixed back adding immobilized lipase, reacted 1～10 hour, product obtains triglyceride, by product lipid acid low-carbon-ester respectively through underpressure distillation or molecular distillation separation; The mol ratio of described lower alcohol and triglyceride level is 0.3～1.5: 1; The immobilized lipase enzyme dosage is 1～10% weight of reaction substrate.
3, the production method of triglyceride according to claim 1, it is characterized in that lower alcohol and triglyceride level are mixed the back by the column reactor of immobilized lipase is housed, the residence time of substrate in post was not less than 5 minutes, product separates the acquisition triglyceride through molecular distillation, obtains by product lipid acid low-carbon-ester simultaneously; The mol ratio of described lower alcohol and triglyceride level is 0.3～1.0: 1.
4, according to the production method of claim 1 or 2 or 3 described triglycerides, the mol ratio that it is characterized in that described lower alcohol and triglyceride level is 1: 1.
5, the production method of triglyceride according to claim 4 is characterized in that described lower alcohol is wherein one or more mixtures of methyl alcohol, ethanol, propyl alcohol.
6, the production method of triglyceride according to claim 4 is characterized in that described triglyceride level is wherein one or more mixtures of Rice pollard oil, soya-bean oil, Oleum Gossypii semen, rape oil, sweet oil, sunflower oil, Semen Maydis oil, microbial oil, fish oil.
7, the production method of triglyceride according to claim 5 is characterized in that described triglyceride level is wherein one or more mixtures of Rice pollard oil, soya-bean oil, Oleum Gossypii semen, rape oil, sweet oil, sunflower oil, Semen Maydis oil, microbial oil, fish oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03113862 CN1208305C (en) | 2003-03-06 | 2003-03-06 | Method for producing diglyceride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03113862 CN1208305C (en) | 2003-03-06 | 2003-03-06 | Method for producing diglyceride |
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| CN1438308A CN1438308A (en) | 2003-08-27 |
| CN1208305C true CN1208305C (en) | 2005-06-29 |
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| CN 03113862 Expired - Fee Related CN1208305C (en) | 2003-03-06 | 2003-03-06 | Method for producing diglyceride |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376541C (en) * | 2004-02-16 | 2008-03-26 | 东莞新宝精化有限公司 | Preparation process of diglyceride |
| CN1884564B (en) * | 2006-05-31 | 2010-09-08 | 东莞新宝精化有限公司 | Process for the production of diglyceride using holoenzyme |
| US20120052538A1 (en) * | 2009-04-06 | 2012-03-01 | Novozymes A/S | Triglycerides with high content of unsaturated fatty acids |
| CN102268464B (en) * | 2010-06-02 | 2013-05-01 | 河南工业大学 | Method for producing diglyceride with rice bran oil of high acid value |
| CN102432459B (en) * | 2010-09-29 | 2014-12-03 | 中国石油化工股份有限公司 | Purifying method of dihydroxy alcohol ester compound |
| CN102191134A (en) * | 2011-04-02 | 2011-09-21 | 大连理工大学 | Preparation method of partial glyceride |
| CN102531892A (en) * | 2012-01-05 | 2012-07-04 | 河南工业大学 | Method for preparing diacylglycerol |
| CN103361387B (en) * | 2013-07-25 | 2014-12-03 | 华南理工大学 | Production method for coproducing unsaturated monoglyceride by using diglyceride enzyme method |
| CN104630296A (en) * | 2015-03-09 | 2015-05-20 | 杭州铎海科技有限公司 | Method for preparing 1,3-diglyceride through enzymolysis |
| CN105441494B (en) * | 2016-01-05 | 2019-01-29 | 江南大学 | A kind of method of enzymatic clarification 1,2- diglyceride |
| CN108003021B (en) * | 2017-12-01 | 2019-08-06 | 广东省禾基生物科技有限公司 | A kind of preparation method of low polarity grease |
| CN109602011A (en) * | 2019-02-18 | 2019-04-12 | 广东省农业科学院蚕业与农产品加工研究所 | A kind of modified silkworm chrysalis grease and preparation method thereof |
| CN114540438A (en) * | 2022-02-23 | 2022-05-27 | 鹤岗萃元科技产业发展有限公司 | Method for producing diglyceride oil by recycling special grease deep processing byproducts |
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2003
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Owner name: DONGGUAN XINBAO REFINEMENT CO., LTD. Free format text: FORMER OWNER: SOUTH CHINA UNIVERSITY OF TECHNOLOGY Effective date: 20050812 |
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Effective date of registration: 20050812 Address after: 523000 Guangdong province Dongguan city Changping Town Road Xinbao Industrial Zone Patentee after: Dongguan Xinbao Fine Chemical Co., Ltd. Address before: 510640 No. five, 381 mountain road, Guangzhou, Guangdong, Tianhe District Patentee before: South China University of Technology |
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Effective date of registration: 20150928 Address after: Huang Dongshan 522000 Qishan Avenue in Guangdong province Jieyang city Rongcheng District East Ring Road South City Jinfeng Garden Garden Shop No. 24 Patentee after: Guangdong long run renewable resources Co., Ltd. Address before: 523000 Guangdong province Dongguan city Changping Town Road Xinbao Industrial Zone Patentee before: Dongguan Xinbao Fine Chemical Co., Ltd. |
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