CN103305559B - Preparation method for natural flavor fatty acid ester - Google Patents
Preparation method for natural flavor fatty acid ester Download PDFInfo
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- CN103305559B CN103305559B CN201210062497.0A CN201210062497A CN103305559B CN 103305559 B CN103305559 B CN 103305559B CN 201210062497 A CN201210062497 A CN 201210062497A CN 103305559 B CN103305559 B CN 103305559B
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Abstract
The invention discloses a method for continuous preparation of natural flavor fatty acid ester. Grease is converted into flavor fatty acid ester through enzymatic transesterification with lipase used as a catalyst and one or more selected from the group consisting of coconut oil rich in low and medium carbon chain fatty glyceride (no more than C14), natural cream, Brazilian palm oil and palm kernel oil as a substrate. Alcohol used in transesterification is micro-molecular alcohol like ethanol, butanol, isobutanol and isoamyl alcohol; immobilized lipase is filled in a packed-column reactor; under the condition of continuous operation, the reaction substrate and the micro-molecular alcohol continuously flow through the lipase packed-column reactor to synthesize fatty acid ester; and an obtained reaction mixture is purified by using molecular distillation technology so as to obtain high-purity flavor fatty acid ester, i.e., mixed low and medium carbon chain fatty acid ester.
Description
Technical field
The invention belongs to flavour of food products chemistry and biological technical field, be specifically related to a kind of preparation method of natural flavor fatty acid ester.By the method for continuous reaction production natural flavor fatty acid ester in the reaction pillar that immobilized lipase is housed, and molecular distillation technique is utilized to purify from reaction mixture this flavour substances.
Background technology
Food flavour spices is the class additive that in foodstuff additive, quantity at most, use face is the widest in food, is the important component part of foodstuff additive.The at present production of food flavour, spices mainly synthetic and extracting from natural animal-plant in the world.Along with the raising of living standards of the people, and the enhancing of back to nature consciousness, the demand of people to natural spices increases day by day.The fragrance material of natural extract, due to the restriction by raw material sources, cannot meet the needs of people.
It is adopt the biological approach simulation natural animal-plant metabolic processes such as microbial project, enzyme engineering, cell engineering, genetic modification engineering that biotechnology produces perfume (or spice), produce flavor compounds, and these compounds are defined as " natural " by many state food regulations such as Europe and the U.S..Therefore, use biotechnology to produce flavor compounds or essence base-material, become the focus of Chinese scholars research.
Short-chain aliphatic ester is the very important aromatic compound of a class, in natural fruit fragrance, can be widely used in the perfuming of the industry such as food, medicine.The fatty acid ester used in current food flavor(ing) field of perfumery mostly is synthetic perfume, enzyme process produces the natural product that aromatic ester is not only considered to high-quality, and enzymic catalytic reaction has efficient, single-minded, the advantage such as reaction conditions is gentle, energy consumption is low, it is little to pollute, easy control simple to operate, thus has incomparable superiority.
The synthesis of the more lipase-catalyzed aromatic esters of the commercialization of 13 different sourcess of the report such as Langrand of France, wherein come from Mucor, aspergillus niger, candiyeast, head mold microbial lipase the most applicablely catalyze and synthesize short chain aromatic ester in organic solvent.The C. J in Taiwan. Shich etc. have studied the optimal conditions with the lipase-catalyzed butyric acid spiceleaf alcohol ester from candiyeast.The D. Y. Kwon etc. of Korea S reports and uses 20 kinds of lipase-catalyzed racemic methyl butyric acid synthesizing apple fragrant substance 2-methylbutyric methyl esters enantiomorphs in organic solvent.Result shows: immobilized lipase IM20, lipase A P and lipase FAP-15 are right
(S)the compound display of 2-methylbutyric methyl esters goes out higher enzymic activity and mapping is selected active.Gondola R. Gandolfi etc. reports use
rhizopus oryzaethe synthesis of dry mycelium catalysis distinct fragrance ester selectively in organic phase.The C. H. Lee etc. of Britain reports and comes from
burkholderia cepacia, Rhizozopus miehi, Candida antarcticawith
candida rugosathe impact that in lipase-catalyzed esterification, water-activity and fatty acid selectivity are fixed.Liu Guangye etc. report the synthesis of Monascus fulginosus lyolipase catalysis ethyl hexanoate.The synthesis of the lipase-catalyzed oleic acid oleic alcohol ester of institute of microbiology of Chinese Academy of Sciences Zhang Junyong 14 kinds of different sourcess, wherein the strongest with the lipase-catalyzed ability of candiyeast 1619.Xu Yan reports the research that microbial lipase synthesizes short chain aromatic ester in normal heptane.Gao Xiugong etc. report pseudomonas fat non-aqueous enzymatic catalysis butyric acid and the esterified by butyl alcohol character of reacting.Result shows: in organic phase, the katalysis of enzyme needs certain moisture, and the suitableeest water-content is difference to some extent because of the difference of solvent; In organic solvent, the thermostability of enzyme comparatively significantly improves in the aqueous solution; Close in the suitableeest effect pH value and the aqueous solution.
Result of study both domestic and external shows: can catalyze and synthesize multiple aromatic ester with the microbial lipase of different sources, and the catalytic activity of microbial lipase and thermostability are comparatively significantly improved in the aqueous solution in organic phase.Adopting lipase direct enzyme to turn into industrial production aromatic ester is a kind of selection very well, potentially contaminated and harm when can avoid chemosynthesis.
Summary of the invention
The present invention aims to provide a kind of continuous production method of natural flavor fatty acid ester.Immobilized lipase is as biological catalyst, to be rich in the Oleum Cocois of middle low carbon chain glycerin fatty acid ester, natural cream, babassu oil, palm-kernel oil for zymolyte, be fatty-acid ethyl ester by the adipose conversion existed with sweet three ester-formins, fatty acid butyl ester, lipid acid isobutyl ester or lipid acid isopentyl ester.The product obtained except containing except these fatty acid esters, also containing as the glycerol mono fatty acid ester of middle converted product and diglyceride, and residual small molecular alcohol and fatty acid triglyceride.Then by molecular distillation obtain the higher flavor fatty acid ester of purity namely mix in low carbon chain fatty acid ester.
The object of the invention is achieved through the following technical solutions:
A preparation method for natural flavor fatty acid ester, comprises the following steps:
1. the filling of immobilized enzyme reaction column: reactor body is a cylindrical stainless steel column, reactor jacket layer connects circulator bath, make to maintain required temperature of reaction in post, be placed in by immobilized enzyme in post, the bottom of reaction column and top are all padded a small amount of glass fibre and are run off to prevent enzyme.
2. the continuous production of flavor fatty acid ester: first substrate oil is preheated to corresponding temperature of reaction, add small molecular alcohol, mechanical stirring mixes, use constant flow pump with certain flow rate by its input reactor bottom inlet simultaneously, adjustment flow velocity, make retention time (reactant is average retention time in packed column) be 10min, start esterification.
3. molecular distillation purifying: adopt two-stage tandem molecular distillation method to carry out purifying to the reaction product of collecting.First order molecular distillation removing small molecular alcohol wherein, distillation residuum enters secondary molecules distiller as raw material, distill out the fatty acid ester of middle low carbon chain, distillation residuum is the macromole impurity such as residual tri-glyceride, middle converted product diglyceride, glycerol mono fatty acid ester.By fractional distillation so, the fatty acid ester of middle low carbon chain and small molecular alcohol remaining in system are reached with the macromole such as tri-glyceride, diglyceride impurity and is separated preferably.
Described temperature of reaction is 35 DEG C ~ 50 DEG C; Described immobilized enzyme comprises antarctic candidia lipase, Candida lipalytica Lipase, root miehei lipase.
Described substrate grease separation is from Oleum Cocois, natural cream, babassu oil, palm-kernel oil and arbitrary combination thereof.
Described small molecular alcohol comprises ethanol, butanols, isopropylcarbinol or primary isoamyl alcohol.Its consumption is 0.05 ~ 0.3 equivalent to the molar ratio of lipid acid.
The inlet amount of described first order molecular distillation is 0.5 ~ 1.0L/h, and distillation temperature is 40 ~ 50 DEG C, and pressure (absolute pressure) is 100 ~ 150Pa, and the inlet amount of secondary molecules distillation is 1.5 ~ 2.5L/h, and distillation temperature is 90 ~ 105 DEG C, and pressure (absolute pressure) is 5 ~ 20 Pa.
The inventive method has following characteristics:
1. adopt immobilized enzyme packed column reactor production flavor fatty acid ester, achieve the continuous production of flavor fatty acid ester.
2. molecular distillation method is adopted to purify to reactant, can operate at lower temperature and higher vacuum tightness, residence time of material is short, avoid oxidation during esters of polyunsaturated fatty acids pyrogenic distillation, and the impurity such as residual small molecular alcohol and sweet three esters of macromole can be removed.
Embodiment
Following embodiment sets forth the present invention further.
Embodiment one
The immobilized enzyme packed column reactor interior diameter adopted is 3cm, length 20cm.Be placed in post by 60g immobilized candida antarctica lipase, enzyme used is lived as 11087Plu/g, and the bottom of reaction column and top are all padded a small amount of glass fibre and run off to prevent enzyme.10kg Oleum Cocois is joined in thermostatic mixer, and heated constant temperature is to 35 DEG C, add 0.15kg dehydrated alcohol, be uniformly mixed, inputted reaction column bottom inlet with constant flow pump with certain flow rate simultaneously, adjustment flow velocity, retention time is made to be 10min, reactor jacket layer connects circulator bath, makes to maintain 35 DEG C in post, carries out transesterification reaction.The reaction mixture of gained adopts series connection secondary molecules distillation method purifying, and the inlet amount of first order molecular distillation is 0.5L/h, and distillation temperature is 40 ~ 45 DEG C, pressure (absolute pressure) is 100Pa, the inlet amount of secondary molecules distillation is 1.5L/h, and distillation temperature is 90 ~ 95 DEG C, and pressure (absolute pressure) is 10Pa.Collect the overhead product of secondary distillation.
Embodiment two
The structure of reactor and size identical with embodiment 1, be placed in post by 60g immobilized candida antarctica lipase, enzyme used is lived as 11087Plu/g, and the bottom of reaction column and top are all padded a small amount of glass fibre and run off to prevent enzyme.10kg palm-kernel oil is joined in thermostatic mixer, and heated constant temperature is to 45 DEG C, add 0.2kg isopropylcarbinol, be uniformly mixed, inputted reaction column bottom inlet with constant flow pump with certain flow rate simultaneously, adjustment flow velocity, retention time is made to be 10min, reactor jacket layer connects circulator bath, makes to maintain 45 DEG C in post, carries out transesterification reaction.The reaction mixture of gained adopts series connection secondary molecules distillation method purifying, and the inlet amount of first order molecular distillation is 1.0L/h, and distillation temperature is 40 ~ 45 DEG C, pressure (absolute pressure) is 100Pa, the inlet amount of secondary molecules distillation is 1.5L/h, and distillation temperature is 95 ~ 100 DEG C, and pressure (absolute pressure) is 15Pa.Collect the overhead product of secondary distillation.
Embodiment three
The structure of reactor and size identical with embodiment 1, be placed in post by 60g immobilized candida antarctica lipase, enzyme used is lived as 11087Plu/g, and the bottom of reaction column and top are all padded a small amount of glass fibre and run off to prevent enzyme.8k Oleum Cocois and 2kg anhydrous butter oil are joined in thermostatic mixer, and heated constant temperature is to 50 DEG C, add 0.25kg butanols, be uniformly mixed, inputted reaction column bottom inlet with constant flow pump with certain flow rate simultaneously, adjustment flow velocity, retention time is made to be 10min, reactor jacket layer connects circulator bath, makes to maintain 50 DEG C in post, carries out esterification.The reaction mixture of gained adopts series connection secondary molecules distillation method purifying, and the inlet amount of first order molecular distillation is 1.0L/h, and distillation temperature is 40 ~ 45 DEG C, pressure (absolute pressure) is 150Pa, the inlet amount of secondary molecules distillation is 2.5L/h, and distillation temperature is 90 ~ 95 DEG C, and pressure (absolute pressure) is 20Pa.Collect the overhead product of secondary distillation.
Claims (2)
1. the continuous production method of a natural flavor fatty acid ester, it is characterized in that comprising the following steps: the 1. filling of immobilized enzyme reaction column: reactor body is a cylindrical stainless steel column, reactor jacket layer connects circulator bath, make in post, to maintain required temperature of reaction, harden monitoring is placed in post, and the bottom of reaction column and top are all padded a small amount of glass fibre and are run off to prevent enzyme, 2. the continuous production of flavor fatty acid ester: first by fuel oil preheating extremely corresponding temperature of reaction, add small molecular alcohol, mechanical stirring mixes, use constant flow pump with certain flow rate input reactor bottom inlet simultaneously, adjustment flow velocity, makes retention time be 10min, starts esterification, described stock oil is selected from Oleum Cocois, natural cream, babassu oil, palm-kernel oil and arbitrary combination thereof, described small molecular alcohol is ethanol, butanols or primary isoamyl alcohol, and its consumption is 0.05 ~ 0.3 equivalent to the molar ratio of lipid acid, 3. molecular distillation purifying: adopt two-stage tandem molecular distillation method to carry out purifying to the reaction product of collecting, first order molecular distillation removing small molecular alcohol wherein, distillation residuum enters secondary molecules distiller as raw material, distill out the fatty acid ester of middle low carbon chain, distillation residuum is residual tri-glyceride, middle converted product diglyceride, the macromole impurity such as glycerol mono fatty acid ester, by fractional distillation so, by small molecular alcohol remaining in the fatty acid ester of middle low carbon chain and system and tri-glyceride, the macromolecule impurities such as diglyceride reach good separation, the inlet amount of described first order molecular distillation is 0.5 ~ 1.0L/h, and distillation temperature is 45 ~ 50 DEG C, and pressure is 100 ~ 150Pa, the inlet amount of secondary molecules distillation is 1.5 ~ 2.5L/h, and distillation temperature is 90 ~ 105 DEG C, and pressure is 5 ~ 20Pa.
2. the continuous production method of a kind of natural flavor fatty acid ester according to claim 1, is characterized in that, described temperature of reaction is 35 DEG C ~ 50 DEG C; Described immobilized enzyme comprises antarctic candidia lipase, Candida lipalytica Lipase, root miehei lipase.
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| CN104642996A (en) * | 2015-03-17 | 2015-05-27 | 王婧婧 | Banana essence formula for dairy product |
| CN104643003A (en) * | 2015-03-17 | 2015-05-27 | 王婧婧 | Apple essence formula for dairy product |
| CN106916631A (en) * | 2015-12-28 | 2017-07-04 | 丰益(上海)生物技术研发中心有限公司 | Fat or oil composition, human milk fat substituted thing and preparation method thereof |
| CN106753755A (en) * | 2017-01-23 | 2017-05-31 | 石狮市华宝海洋生物医药有限公司 | A kind of preparation technology of isoamyl ester type fish oil |
| CN107115889A (en) * | 2017-04-27 | 2017-09-01 | 河北工业大学 | A kind of reactive distillation enzymatic filler and its coating method and application |
| CN107043794A (en) * | 2017-06-12 | 2017-08-15 | 浙江工业大学 | A kind of method that enzymatic safflower oil alcoholysis prepares fatty-acid ethyl ester |
| CN110511966B (en) * | 2019-08-16 | 2021-03-23 | 杭州信泓科技有限公司 | Preparation method of short-chain fatty glyceride |
| CN114231571B (en) * | 2021-12-29 | 2024-02-06 | 赞宇科技集团股份有限公司 | Production method for synthesizing monoglyceride stearate by immobilized composite lipase catalysis |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284998A (en) * | 2008-05-06 | 2008-10-15 | 西北大学 | Process for preparing biodiesel by coupling catalytic reaction and separation process |
| CN101631857A (en) * | 2007-01-08 | 2010-01-20 | 转换生物柴油有限公司 | Immobilized interfacial enzymes of improved and stabilized activity |
| CN101896614A (en) * | 2007-12-14 | 2010-11-24 | 关西化学机械制作株式会社 | Utilize the production of the continous way biodiesel fuel of enzyme process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101631857A (en) * | 2007-01-08 | 2010-01-20 | 转换生物柴油有限公司 | Immobilized interfacial enzymes of improved and stabilized activity |
| CN101896614A (en) * | 2007-12-14 | 2010-11-24 | 关西化学机械制作株式会社 | Utilize the production of the continous way biodiesel fuel of enzyme process |
| CN101284998A (en) * | 2008-05-06 | 2008-10-15 | 西北大学 | Process for preparing biodiesel by coupling catalytic reaction and separation process |
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