CN101270375A - Technique for preparing 1,3-diglyceride with enzyme in tert-butanol system - Google Patents
Technique for preparing 1,3-diglyceride with enzyme in tert-butanol system Download PDFInfo
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- CN101270375A CN101270375A CNA2008101122551A CN200810112255A CN101270375A CN 101270375 A CN101270375 A CN 101270375A CN A2008101122551 A CNA2008101122551 A CN A2008101122551A CN 200810112255 A CN200810112255 A CN 200810112255A CN 101270375 A CN101270375 A CN 101270375A
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- lipase
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 12
- 108090000790 Enzymes Proteins 0.000 title claims description 12
- 102000004190 Enzymes Human genes 0.000 title claims description 12
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims abstract description 35
- 125000002252 acyl group Chemical group 0.000 claims abstract description 26
- 238000005516 engineering process Methods 0.000 claims abstract description 23
- 108090001060 Lipase Proteins 0.000 claims abstract description 22
- 239000004367 Lipase Substances 0.000 claims abstract description 22
- 102000004882 Lipase Human genes 0.000 claims abstract description 22
- 235000019421 lipase Nutrition 0.000 claims abstract description 22
- 239000003921 oil Substances 0.000 claims abstract description 19
- 235000019198 oils Nutrition 0.000 claims abstract description 19
- 150000002148 esters Chemical class 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 12
- 229930195729 fatty acid Natural products 0.000 claims abstract description 12
- 239000000194 fatty acid Substances 0.000 claims abstract description 12
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 9
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000008158 vegetable oil Substances 0.000 claims abstract description 5
- 238000006911 enzymatic reaction Methods 0.000 claims abstract description 3
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 claims description 91
- 239000000203 mixture Substances 0.000 claims description 44
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 34
- 150000002632 lipids Chemical group 0.000 claims description 27
- 230000009466 transformation Effects 0.000 claims description 17
- 235000011187 glycerol Nutrition 0.000 claims description 15
- 235000019197 fats Nutrition 0.000 claims description 8
- 239000004519 grease Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 241000223258 Thermomyces lanuginosus Species 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 239000010773 plant oil Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 102000004895 Lipoproteins Human genes 0.000 claims description 4
- 108090001030 Lipoproteins Proteins 0.000 claims description 4
- 241001465754 Metazoa Species 0.000 claims description 4
- 239000012075 bio-oil Substances 0.000 claims description 4
- 210000000582 semen Anatomy 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 241001661345 Moesziomyces antarcticus Species 0.000 claims description 3
- 241000235403 Rhizomucor miehei Species 0.000 claims description 3
- 235000009508 confectionery Nutrition 0.000 claims description 3
- 235000021588 free fatty acids Nutrition 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 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 2
- 241001048891 Jatropha curcas Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 241001494479 Pecora Species 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 241000269319 Squalius cephalus Species 0.000 claims description 2
- 244000248162 Xanthoceras sorbifolium Species 0.000 claims description 2
- 235000009240 Xanthoceras sorbifolium Nutrition 0.000 claims description 2
- 235000014121 butter Nutrition 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 239000008157 edible vegetable oil Substances 0.000 claims description 2
- 235000021323 fish oil Nutrition 0.000 claims description 2
- 230000000813 microbial effect Effects 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 241000235527 Rhizopus Species 0.000 claims 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002255 enzymatic effect Effects 0.000 abstract description 6
- 239000012429 reaction media Substances 0.000 abstract description 4
- 239000000370 acceptor Substances 0.000 abstract 4
- 235000019737 Animal fat Nutrition 0.000 abstract 1
- 239000000413 hydrolysate Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 108010048733 Lipozyme Proteins 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 108010084311 Novozyme 435 Proteins 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940085633 glyceryl linolenate Drugs 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000001079 digestive effect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 241000209094 Oryza Species 0.000 description 1
- 240000005384 Rhizopus oryzae Species 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- -1 pentyl ester Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses an enzymatic preparation process of 1, 3-diglyceride in tert-butyl alcohol system and belongs to the field of preparation technology of diglyceride. The process procedure is carried out as follows: monoglyceride of acyl acceptors and acyl donors in the molar ratio of 1:0.5 to 1:3, tert-butyl alcohol with 20 to 200 percent by weight of monoglyceride of accyl acceptors and lipase with 2 to 20 percent by weight of monoglyceride of accyl acceptors are loaded in any biochemical reactor of being suitable for enzyme reaction and well-mixed, the temperature is controlled at 30 to 65 DEG C, the reaction time is controlled at 1 to 12 hours, then the conversion rate of monoglyceride of acyl acceptors to diglyceride reaches 70 to 90 percent and the concentration of 1, 3-diglyceride in diglyceride reaches over 75 percent. The acyl donors are fatty acid, short chain ester of fatty acid, monoglyceride, triglyceride, animal fat and vegetable oils or incomplete hydrolysate of oils. The enzymatic preparation process of 1, 3-diglyceride in tert-butyl alcohol system has the advantages that tert-butyl alcohol is used as reaction medium, the reaction system is a homogeneous system, and the enzymatic conversion efficiency is high.
Description
Technical field
The invention belongs to the triglyceride preparing technical field, provide enzyme process efficient production 1 in a kind of medium system especially, the technology of 3-triglyceride.
Background technology
Triglyceride is a kind of fat mols with two fatty acid chains, and two kinds of isomerss are arranged, promptly 1, and 2-triglyceride and 1,3-triglyceride.Discovering in recent years, 1, the 3-triglyceride is in the intravital absorption metabolic way of people and triglyceride level and 1, the difference of 2-triglyceride.Triglyceride level and 1,2-triglyceride are through digestive ferment digestion back generation mono-glycerides and free fatty acids, after the two absorption enters blood, and major part synthetic glycerine three esters again very.And 1, the 3-triglyceride generates glycerine and free fatty acids after the digestive ferment effect, and the two changes into energy in vivo.Therefore, eat and contain 1, the grease of 3-triglyceride has the effect that prevents weight increase, and 1, the 3-triglyceride demonstrates good commercial exploitation prospect.
Esterification and transesterify are the important method of producing triglyceride, and this method employing glycerine or glyceryl ester are with the derivatives reaction of lipid acid or lipid acid, and by chemical catalysis or enzyme catalysis, can obtain with the triglyceride is the product of main component.Compare with chemical catalysis, lipase-catalyzed have in reaction conditions gentleness, the reaction process advantages such as non-pollutant discharge and later separation purifying be easy, so, utilizing biological enzyme synthetic triglyceride especially 1, the research of 3-triglyceride just more and more is subjected to people's attention in recent years.
Utilizing biological enzyme to prepare in the report of triglyceride, all adopt glycerine basically as reaction substrate.Glycerine is a kind of highly hydrophilic material, and in the enzymatic conversion process, glycerine is very easily attached to the lipase surface, and the avtive spot formation " shielding " to enzyme has a strong impact on mass transfer and Enzymatic transformation efficient.The present invention proposes to utilize the trimethyl carbinol as reaction medium; replace glycerine with mono-glycerides, utilize lipase-catalyzed mono-glycerides and other acry radical donor (to comprise mono-glycerides, lipid acid; fatty acid short-chain ester and triglyceride level) between transesterification reaction come efficient production 1, the novel process of 3-triglyceride.In trimethyl carbinol system, except immobilized lipase, reactant can effectively be dissolved in trimethyl carbinol system, and reaction is a homogeneous system.Trimethyl carbinol system can effectively solve glycerine in the traditional technology influences mass transfer attached to the enzyme surface problem; And, utilize mono-glycerides as a reaction substrate wherein, can obtain more high-load 1, the 3-triglyceride.This invention has better industrial application prospect.
Summary of the invention
The object of the present invention is to provide enzyme process efficient production 1 in a kind of medium system; the technology of 3-triglyceride; with the trimethyl carbinol as reaction medium; (refer to that the same lipid acid of a hydroxyl in the glycerol molecule forms ester with monoglyceride; the hereinafter referred mono-glycerides) is a substrate wherein; by the transesterification reaction of lipase-catalyzed mono-glycerides and other acry radical donor, High-efficient Production 1,3-triglyceride.
The present invention proposes to utilize lipase-catalyzed mono-glycerides preparation 1, the technology of 3-triglyceride in trimethyl carbinol system.Wherein mono-glycerides is an acyl acceptor, and acry radical donor can be mono-glycerides, lipid acid, fatty acid short-chain ester or triglyceride level, under lipase-catalyzed, and High-efficient Production 1, the technology of 3-triglyceride.Processing step is:
With mol ratio is that (acry radical donor can be lipid acid R-COOH for 1: 0.5～1: 3 mono-glycerides and acry radical donor; fatty acid short-chain ester RCOOR '; mono-glycerides; triglyceride level; animal-plant oil or fat hydrolysis thing); adding is based on the trimethyl carbinol of acyl acceptor mono-glycerides quality 20～200%; adding is based on the lipase of acyl acceptor mono-glycerides quality 2～20%; pack into together and mix in any biochemical reactor that is suitable for enzyme reaction; temperature is controlled at 30～65 ℃; reacted 1～12 hour; the acyl acceptor mono-glycerides reaches 70～95% to the transformation efficiency of product triglyceride; in these triglycerides 1, the content of 3-triglyceride reaches more than 75%.
Lipase can be certain single fat enzyme, also can be the combination of different performance lipase, comprises the lipase with position specific and has 1, the lipase of 3-position specific;
Described lipase comprises the lipase that derives from Candida antarctica, Thermomyces lanuginosus, Rhizomucormiehei, Rhizopus oryza.
Described mono-glycerides is the ester that the same lipid acid R-COOH of a hydroxyl in the glycerol molecule forms, and wherein R is the alkyl chain of 10～22 carbon atoms.
Described acyl acceptor mono-glycerides and acry radical donor mono-glycerides can be the corresponding mono-glycerides of certain single fat acid, also can be the mixture of the mono-glycerides of two or more different lipid acid correspondences.
Described acyl acceptor mono-glycerides is 1 (3)-mono-glycerides, 2-mono-glycerides, or the mixture of 1 (3)-mono-glycerides and 2-mono-glycerides.
Described acry radical donor mono-glycerides is 1 (3)-mono-glycerides, 2-mono-glycerides, or the mixture of 1 (3)-mono-glycerides and 2-mono-glycerides.
Described acry radical donor lipid acid R '-COOH can be a certain single fat acid, also can be the mixture of lipid acid more than a kind.Wherein R ' is the alkyl chain of 10～22 carbon atoms.
Described acry radical donor fatty acid short-chain ester RCOOR ' can be a certain single ester, also can be the mixture of several short-chain esters.Wherein R is the alkyl chain of 10～22 carbon atoms, and R ' is the alkyl chain of 1-5 carbon atom.
Described acry radical donor triglyceride level is a bio-oil, and bio-oil comprises one or more the mixture in Vegetable oil lipoprotein, animal grease, microbial oil, waste edible oil, the oil refining pin material.
Described acry radical donor Vegetable oil lipoprotein is Viscotrol C, rapeseed oil, soybean oil, peanut oil, Semen Maydis oil, Oleum Gossypii semen, Rice pollard oil, barbadosnut seed oil or shinyleaf yellowhorn oil.
Described acry radical donor animal grease is fish oil, lard, butter or sheep oil.Described acry radical donor is the incomplete hydrolyzate of various animal-plant oil, is lipid acid, mono-glycerides, two sweet esters, the mixture of triglyceride and glycerine.
The above acry radical donor can use separately, also can two or more mixing, use as acry radical donor;
The invention has the beneficial effects as follows and adopt the trimethyl carbinol as reaction medium, reaction system is a homogeneous system, Enzymatic transformation efficient height.In addition, adopt mono-glycerides as acyl acceptor, the negative effect of when having avoided glycerine enzyme having been lived as acyl acceptor, and, can obtain more high-load 1, the 3-triglyceride.With in the past be that substrate is compared by the mode that esterification or transesterify prepare triglyceride with glycerine, this method has better prospects for commercial application.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1
With mol ratio is 1: 1 mono-glycerides (1 (3)-olein) and oleic acid, based on the trimethyl carbinol of mono-glycerides quality 100%, and based on the water-retaining agent of oleic acid quality 100%
Molecular sieve, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 50 ℃ after, adding is based on the immobilized lipase Novozym435 (deriving from Candida antarctica) of mono-glycerides quality 5%, reacted 2 hours, mono-glycerides is 80% to the transformation efficiency of triglyceride, wherein 1, and the 3-triglyceride accounts for 80%.
Embodiment 2
With mol ratio 1: 0.5 mono-glycerides (being the mixture of 1 (3)-stearin and 2-olein) and fatty acid methyl ester, and based on the trimethyl carbinol of mono-glycerides quality 80%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 50 ℃ after, adding is based on the immobilized lipase Lipozyme TL IM (deriving from Thermomyces lanuginosu) of mono-glycerides quality 10%, reacted 5 hours, mono-glycerides reaches 70% to the transformation efficiency of triglyceride, wherein 1, the 3-triglyceride accounts for 85%.
Embodiment 3
Mono-glycerides (mixture of 1 (3)-olein and 2-olein) with two parts of equivalent; and based on the trimethyl carbinol of acyl acceptor mono-glycerides quality 200%; pack into and mix in the tool plug triangular flask; and place can be temperature automatically controlled reciprocal shaking table be heated to 60 ℃ after; adding is based on the immobilized lipase LipozymeRM IM (deriving from Rhizomucor miehei) of acyl acceptor mono-glycerides quality 10%; reacted 12 hours; the acyl acceptor mono-glycerides reaches 85% to the transformation efficiency of triglyceride; wherein 1, the 3-triglyceride accounts for 80%.
Embodiment 4
With mol ratio 1: 1 mono-glycerides (mixture of 1 (3)-olein and 1-palmitin) and soybean oil, and based on the trimethyl carbinol of mono-glycerides quality 70%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 50 ℃ after, adding was reacted 10 hours based on the immobilized lipase Novozym435 of mono-glycerides quality 10%, and mono-glycerides reaches 80% to the transformation efficiency of triglyceride, wherein 1, the 3-triglyceride accounts for 75%.
Embodiment 5
With mol ratio is 1: 3 mono-glycerides (mixture of 1 (3)-laurin and 2-laurin) and lipid acid (mixture of oleic acid and palmitinic acid), based on the water-retaining agent of lipid acid acid quality 100%
Molecular sieve, and based on the trimethyl carbinol of mono-glycerides quality 100%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 30 ℃ after, adding was reacted 1 hour based on the immobilized lipase Lipozyme TL IM of mono-glycerides quality 2%, and mono-glycerides reaches 80% to the transformation efficiency of triglyceride, wherein 1, the 3-triglyceride accounts for 85%.
Embodiment 6
It with mol ratio mono-glycerides (1 (3)-olein of 1: 2,1 (3)-glyceryl linoleate, the 2-olein, the mixture of 2-glyceryl linoleate) and curcas oil, and based on the trimethyl carbinol of mono-glycerides quality 150%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 35 ℃ after, adding is based on the immobilized lipase Lipozyme TL IM of mono-glycerides quality 6%,, reacting 10 hours, mono-glycerides reaches 70% to the transformation efficiency of triglyceride, wherein 1, the 3-triglyceride accounts for 70%.
Embodiment 7
Mono-glycerides (1 (3)-olein with two parts of equivalent, 1 (3)-glyceryl linoleate, 1 (3)-glyceryl linolenate, the 2-olein, the mixture of 2-glyceryl linoleate and 2-glyceryl linolenate), and based on the trimethyl carbinol of mono-glycerides quality 150%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 45 ℃ after, adding was reacted 2 hours based on the immobilized lipase Novozym 435 of a mono-glycerides quality 3% and 6% immobilized lipase Lipozyme TL IM, and mono-glycerides reaches 90% to the transformation efficiency of triglyceride, wherein 1, the 3-triglyceride accounts for 78%.
Embodiment 8
With mol ratio is 1: 2 mono-glycerides (1 (3)-olein, the mixture of 2-glyceryl linoleate and 1 (3)-glyceryl linolenate) and acidifying oil, based on the water-retaining agent of lipid acid acid quality 100% in the acidifying oil
Molecular sieve, and based on the trimethyl carbinol of mono-glycerides quality 100%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 50 ℃ after, adding was reacted 2 hours based on the immobilized lipase Novo 435 of mono-glycerides quality 2% and 4% immobilized lipase Lipozyme RM IM, and mono-glycerides reaches 90% to the transformation efficiency of triglyceride, wherein 1, the 3-triglyceride accounts for 80%.
Embodiment 9
It with mol ratio mono-glycerides (1 (3)-olein of 1: 3,1 (3)-glyceryl linoleate, the mixture of 2-stearin and 1 (3)-20 carbon fatty acid glyceryl ester) and lard, and based on the trimethyl carbinol of mono-glycerides quality 150%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 60 ℃ after, adding is based on the immobilized lipase LipozymeTLIM of mono-glycerides quality 3% and 4% immobilized lipase LipozymeRM IM, reacted 10 hours, mono-glycerides reaches 90% to the transformation efficiency of triglyceride, wherein 1, the 3-triglyceride accounts for 75%.
Embodiment 10
It with mol ratio mono-glycerides (1 (3)-olein of 1: 3,1 (3)-glyceryl linoleate, the mixture of 1 (3)-stearin and 2-20 carbon fatty acid glyceryl ester) and waste grease (mixture of animal oil and vegetables oil), and based on the trimethyl carbinol of mono-glycerides quality 120%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 60 ℃ after, adding is based on the immobilized lipase Lipozyme TL IM of mono-glycerides quality 3% and 4% immobilized lipase Lipozyme RM IM, reacted 10 hours, mono-glycerides reaches 88% to the transformation efficiency of triglyceride, wherein 1, the 3-triglyceride accounts for 78%.
Embodiment 11
With mol ratio 1: 0.5 mono-glycerides (being the mixture of 1 (3)-palmitin and 2-olein) and fatty-acid ethyl ester, and based on the trimethyl carbinol of mono-glycerides quality 60%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 50 ℃ after, adding is based on the immobilized lipase Lipozyme TL IM (deriving from Thermomyces lanuginosu) of mono-glycerides quality 10%, reacted 5 hours, mono-glycerides reaches 75% to the transformation efficiency of triglyceride, wherein 1, the 3-triglyceride accounts for 90%.
Embodiment 12
With mol ratio 1: 1 mono-glycerides (being the mixture of 1 (3)-stearin and 2-olein) and lipid acid pentyl ester, and based on the trimethyl carbinol of mono-glycerides quality 40%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 50 ℃ after, adding is based on the immobilized lipase Lipozyme TL IM (deriving from Thermomyces lanuginosu) of mono-glycerides quality 10%, reacted 5 hours, mono-glycerides reaches 78% to the transformation efficiency of triglyceride, wherein 1, the 3-triglyceride accounts for 88%.
Embodiment 13
With mol ratio is that 1: 2.5 acyl acceptor mono-glycerides (is 1 (3)-olein; 1 (3)-glyceryl linoleate; the mixture of 1 (3)-stearin and 2-20 carbon fatty acid glyceryl ester) and the incomplete hydrolyzate of grease (be mainly lipid acid; mono-glycerides; two sweet esters; the mixture of triglyceride and glycerine, wherein the content of mono-glycerides is 40% in the fat hydrolysis thing), based on the water-retaining agent of lipid acid acid quality 60% in the incomplete hydrolyzate of grease
Molecular sieve; and based on the trimethyl carbinol of acyl acceptor mono-glycerides quality 120%; pack into and mix in the tool plug triangular flask; and place can be temperature automatically controlled reciprocal shaking table be heated to 60 ℃ after; adding was reacted 10 hours based on the immobilized lipase Lipozyme TL IM of acyl acceptor mono-glycerides quality 3% and 4% immobilized lipase Lipozyme RM IM, and the acyl acceptor mono-glycerides reaches 88% to the transformation efficiency of triglyceride; wherein 1, the 3-triglyceride accounts for 78%.
Claims (15)
1, enzyme process preparation 1 in a kind of trimethyl carbinol medium system, the technology of 3-triglyceride, it is characterized in that: the acyl acceptor mono-glycerides and the acry radical donor that with mol ratio are 1: 0.5～1: 3, adding is based on the trimethyl carbinol of acyl acceptor mono-glycerides quality 20～200%, lipase based on acyl acceptor mono-glycerides quality 2～20%, pack into together and mix in any biochemical reactor that is suitable for enzyme reaction, temperature is controlled at 30～65 ℃, reacted 1～12 hour, the acyl acceptor mono-glycerides reaches 70～90% to the transformation efficiency of triglyceride, in the triglyceride that generates 1, the content of 3-triglyceride reaches more than 75%; Described acry radical donor is lipid acid R-COOH, fatty acid short-chain ester RCOOR ', mono-glycerides, triglyceride level, animal-plant oil or greasy incomplete hydrolyzate; Acry radical donor is a lipid acid or when containing the oil substances of lipid acid, is added with in the reaction system based on free fatty acids quality 60-100%'s
Molecular sieve is carried out online dewatering as water-retaining agent.
According to the described technology of claim 1, it is characterized in that 2, described mono-glycerides is the ester that a hydroxyl in the glycerol molecule and a lipid acid R-COOH form, wherein R is the alkyl chain of 10～22 carbon atoms.
3. according to the described technology of claim 1, it is characterized in that described acyl acceptor mono-glycerides and acry radical donor mono-glycerides are the corresponding mono-glycerides of certain single fat acid, perhaps are the mixture of the mono-glycerides of two or more different lipid acid correspondences.
According to the described technology of claim 1, it is characterized in that 4, described acyl acceptor mono-glycerides is 1 (3)-mono-glycerides or 2-mono-glycerides, or the mixture of 1 (3)-mono-glycerides and 2-mono-glycerides.
According to the described technology of claim 1, it is characterized in that 5, described acry radical donor mono-glycerides is 1 (3)-mono-glycerides or 2-mono-glycerides, or the mixture of 1 (3)-mono-glycerides and 2-mono-glycerides.
According to the described technology of claim 1, it is characterized in that 6, described lipase comprises the lipase that derives from Candida antarctica, Thermomyces lanuginosus, Rhizomucor miehei or Rhizopus.oryzae.
According to the described technology of claim 1, it is characterized in that 7, described lipase uses separately, perhaps is used in combination for multiple lipase.
8. according to the described technology of claim 1, it is characterized in that described lipase comprises the lipase with position specific or has 1, the lipase of 3-position specific.
9. according to the described technology of claim 1, it is characterized in that described acry radical donor lipid acid R '-COOH is a certain single fat acid, the perhaps mixture of lipid acid more than a kind, wherein R ' is the alkyl chain of 10～22 carbon atoms.
10. according to the described technology of claim 1; it is characterized in that described acry radical donor fatty acid short-chain ester RCOOR ' is a certain single ester, perhaps is the mixture of several short-chain esters; wherein R is the alkyl carbon chain of 10～22 carbon atoms, and R ' is the alkyl chain of 1-5 carbon atom.
11. according to the described technology of claim 1; it is characterized in that; described acry radical donor triglyceride level is a bio-oil, and described bio-oil comprises one or more the mixture in Vegetable oil lipoprotein, animal grease, microbial oil, waste edible oil, the oil refining pin material.
12., it is characterized in that described Vegetable oil lipoprotein is Viscotrol C, rapeseed oil, soybean oil, peanut oil, Semen Maydis oil, Oleum Gossypii semen, Rice pollard oil, barbadosnut seed oil or shinyleaf yellowhorn oil according to the described technology of claim 11; Described animal grease is fish oil, lard, butter or sheep oil.
13, technology according to claim 1, described acry radical donor are the incomplete hydrolyzate of various animal-plant oil, and the incomplete hydrolyzate of various animal-plant oil is a lipid acid, mono-glycerides, two sweet esters, the mixture of triglyceride or glycerine.
14, technology according to claim 1, described different acyl donor uses separately, and perhaps two or more mixing is used as acry radical donor.
15, technology according to claim 1, acry radical donor are lipid acid or when containing the oil substances of lipid acid, take alternate manner to carry out online dewatering in the reaction process, and described alternate manner is carried out online dewatering and comprised that film dewaters or vaccum dewatering.
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