CN107338274A - A kind of method for preparing fatty glyceride - Google Patents
A kind of method for preparing fatty glyceride Download PDFInfo
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- CN107338274A CN107338274A CN201710700407.9A CN201710700407A CN107338274A CN 107338274 A CN107338274 A CN 107338274A CN 201710700407 A CN201710700407 A CN 201710700407A CN 107338274 A CN107338274 A CN 107338274A
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- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
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- C12P7/6454—Glycerides by esterification
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Abstract
The invention discloses a kind of method for preparing fatty glyceride, comprise the following steps：(1) it is (1~5) by mass ratio：1 glycerine and free fatty mixing, add free-fat enzyme, the water of reactant gross mass 1%~6% of reactant gross mass 0.1%~2%, 2~4h of stirring reaction at 30~60 DEG C；(2) centrifuge the oil phase in above-mentioned reaction and glycerine phase, glycerine mutually retain recycling, oil phase is through dewater treatment；(3) immobilized lipase of oil phase gross mass 1~5% is added into the oil phase after above-mentioned dehydration, high vacuum reacts 4~8h at 45~65 DEG C, that is, obtains fatty glyceride.The two-step method lactate synthesis fatty glyceride used in the present invention, makes the conversion ratio of aliphatic acid in final product improve the conversion ratio of aliphatic acid more than 98%, reduce purification procedures, has good economic value and the value of environmental protection.
Description
Technical field
The present invention relates to a kind of method of synthctic fat acid glyceride.
Background technology
Glyceride is most important lipid components in humans and animals diet, especially in vegetable fat and animal fat,
The content of glyceride is typically larger than 90%, even above 99%.Free fatty is widely present in various greases, common
In the crude oil of animal and plant fat, the content of free fatty can reach 1%~5%, can be reached in some high acid value greases
To more than 25%.In course of oil processing, free fatty can be separated as accessory substance, and this just produces substantial amounts of day
The free-fat acid product of right animal and plant fat.Free-fat Acidity is unstable, typically has caused by process not
Good smell, it is impossible to used as animal feed or human food's raw material.Therefore, suitable process is developed, by aliphatic acid
It is the important topic that people pay close attention to for a long time to change into glyceride.
The synthetic method of fatty glyceride mainly has two kinds of chemical method and enzyme process, and chemical method is to be existed using chemical catalyst
Using glycerine and aliphatic acid as substrate synthetic glyceride under high temperature, its reaction efficiency is high, but because its reaction temperature is high, catalyst
Residual, gradually substituted by enzyme law catalysis synthesis the shortcomings of inapplicable unsaturated fatty acid ester.
In a kind of preparation method for the ester type PUFA of high-purity glycerol three that CN102994580A is announced, with immobilized lipase
Catalysis polyunsaturated fatty acid prepares glyceride with glycerine esterification, and the esterification yield of aliphatic acid only up to reach 86.4%.Zhong Nan
Capital etc., enzyme process esterified fatty acid synthesizes with glycerine utilizes fixed lipase catalyzed glycerine and fatty acid ester in 1,3-DAG
Change prepares diglyceride, and conversion rate of fatty acid is no more than 78%.
When free-fat enzymatic aliphatic acid carries out esterification with glycerine, because lipase can be dispersed in oil phase
With on the interface of glycerine phase so that its catalytic efficiency is very high, and esterification can be rapidly achieved poised state.It is but free
Lipase needs a certain amount of moisture to maintain its molecular structure and catalytic efficiency in reaction system, and water is in esterification
Product, the presence and accumulation of water can cause esterification to be offset to back reaction direction, so the ester using free-fat enzymatic
When change reaction reaches poised state, the esterification yield of aliphatic acid is relatively low, generally between 50~70%.
When immobilized lipase is catalyzed aliphatic acid with glycerine progress esterification in solvent-free system, dehydration can be passed through
The modes such as the addition of processing and increase glycerine improve the esterification yield of aliphatic acid, reach the purpose for improving conversion rate of fatty acid.But
It is that the catalytic efficiency of lipase can be produced and had a strong impact in the presence of the too low and excessive glycerine of moisture.It is particularly excessive
Glycerine can greatly limit the package action of immobilised enzymes the mass-transfer efficiency of esterification system, extend esterification and reach
The time (about 24h) required to balance, reduce the production efficiency of enzymatic esterification technique.
The content of the invention
The present invention is low for conversion rate of fatty acid present in existing enzymatic esterification method, and esterification reaches flat
The shortcomings that long the time required to weighing apparatus, there is provided a kind of method that catalysis prepares fatty glyceride.Free-fat enzyme pair is used first
System using glycerine and aliphatic acid as substrate carries out first step esterification, and most fatty acid ester is turned into glyceride；Point
From second step esterification is carried out by immobilized lipase in the anhydrous system of high vacuum after the oil phase in reaction system, enter one
Step improves the conversion ratio of aliphatic acid.The present invention substantially increases the reaction efficiency of aliphatic acid and glycerine esterification synthetic glyceride, contracting
The short reaction time；The conversion ratio of aliphatic acid is improved, the esterification yield of reaction has been reached more than 99%.Reduce last point
Separating process, the economic value of products therefrom improve.
The present invention is achieved through the following technical solutions to achieve the above object：
A kind of method for preparing fatty glyceride, comprises the following steps：
(1) by mass ratio (1~5)：1 glycerine and free fatty mixing, adds reactant gross mass 0.1%~2%
Free-fat enzyme, the water of reactant gross mass 1%~6%, 2~4h of stirring reaction at 30~60 DEG C；
(2) centrifuge the oil phase and glycerine phase in above-mentioned reaction, glycerine mutually retains recycling, oil phase through dehydration at
Reason；
(3) immobilized lipase of oil phase gross mass 1~5% is added into the oil phase after above-mentioned dehydration, at 45~65 DEG C
High vacuum reacts 4~8h, that is, obtains fatty glyceride.
The mass ratio of free fatty and glycerine described in step (1) is 1:1~1:3, the addition of free-fat enzyme is
The 0.1%~2% of substrate gross mass, water addition are 2%~5%.
Step (1) described reaction temperature is 30~55 DEG C, and the reaction time is 3~4h.
The temperature of step (3) high vacuum reaction is 45~60 DEG C, and the time is 3~5h, and vacuum is less than 200Pa.
Immobilized lipase described in step (3) is the immobilized lipase without glyceride acyl group position specific.
The immobilized lipase is Novozym 435.
Free-fat enzyme described in step (1) is from root enzyme category, aspergillus, hair enzyme category, bacterium, saccharomycete and pancreas fat
Mixture more than one or both of fat enzyme.
The free-fat enzyme be Lipozyme TL 100L lipase orCALB L lipase.
Take in a kind of method of the above-mentioned ester of synthetic glycerine three and be first catalyzed by free-fat enzyme in the environment of high glycerine
Reaction, dissociate in solvent-free system lipase-catalyzed aliphatic acid and the high efficiency of glycerine esterification reaction are made full use of, by system
Aliphatic acid be esterified on glycerine group.The oil phase in reaction system, i.e. triglyceride (TAG), diglyceride is then demultiplex out
(DAG), monoglyceride (MAG), the mixture of free fatty (FFA), glycerine and moisture and free-fat in system have been reclaimed
Enzyme.By the oil phase catalytic esterification under condition of high vacuum degree of the lipase through immobilization again, due in now system without water
In the presence of so esterification substantially increases the esterification yield of reaction, reacts complete in optimal conditions to reaction positive direction skew
Esterification yield >=98% afterwards, TAG >=38%, DAG >=50%, MAG≤5% in product, FFA≤1%, this product can pass through letter
Used after single refining process processing directly as oil and fat product.
Relative to prior art, the beneficial effects of the present invention are：
(1) present invention uses two-step method lactate synthesis fatty glyceride, by two kinds of lipase under the conditions of each
Joint esterification, only need 5~10h to react and finish, greatly reduce reaction time, efficiency high.
(2) present invention improves the esterification yield of aliphatic acid, and more than 98% is all glyceride in reaction product, reduces separation
Purification step, this product can be used as oil and fat product by simple refinery practice and use, and save production cost.
Embodiment
Introduce the implementation of the present invention in more detail by the following examples.
Embodiment 1 (two step enzyme methods)
It is raw material to take the fatty acid by-products in deep sea fish oil processing, and wherein content of fatty acid is 99.5%, in its fat
DHA is 20% in acid, EPA content 22%.Take this aliphatic acid 100g to be mixed in 100g glycerine in reaction vessel, add 4g's
It is placed in 50 DEG C of glycerol baths and is stirring after Lipozyme TL 100L (from the lipase for dredging cotton like thermophilic hyphomycete) and 5g water
Lower reaction 2h is mixed, it is 62% that liquid chromatographic detection, which obtains this reaction esterification yield,.The oil phase and glycerine phase in above-mentioned reaction are centrifuged,
Glycerine mutually retains recycling, and oil phase is through dewater treatment；Take above-mentioned oil phase 100g to be placed in reaction vessel, add 1.6g
Novozym435 lipase (lipase for deriving from antarctic candida), is placed in 55 DEG C of constant temperature blender with magnetic force,
Reaction product is obtained under 100pa vacuum states after stirring reaction 5h, liquid chromatographic detection obtains, and now in product, TAG contents are
41.73%, DAG53.76%, MAG3.85%, FFA0.65%；The esterification yield of aliphatic acid is 99.35%.
Embodiment 2 (two step enzyme methods)
It is reaction raw materials to take the deodorization effluent in soybean oil deodorization refining process, and wherein content of fatty acid is 91.3%,
The compound 500g, glycerine 600g, water 11g are taken,L (lipase for deriving from antarctic candida)
5g, 50 DEG C of stirring reaction 4h in reactor are placed in after mixing, it is 59% that liquid chromatographic detection, which obtains this reaction esterification yield,.Centrifuge
Oil phase and glycerine phase, glycerine in above-mentioned reaction mutually retain recycling, and oil phase is through dewater treatment；Above-mentioned oil sample 300g is taken to add
The 10g lipase of Novozym 435 obtains reaction product under 100Pa vacuum after stirring reaction 4h, liquid chromatographic detection obtains, this
When product in, TAG contents are that 41.5%, DAG contents are 52.27%, MAG3.51%, FFA, 2.74%；The esterification yield of aliphatic acid
For 97.26%.
Embodiment 3 (two step enzyme methods)
Take soybean oil refinement by-product acids carburetion, wherein content of fatty acid be 51.5%, content of triglyceride 48.3%,
Compound 500g is taken, glycerine 250g, water 11g, Lipozyme TL 100L lipase 5g, 45 DEG C are placed in reactor after mixing
Stirring reaction 4h.Centrifuge the oil phase and glycerine phase in above-mentioned reaction, glycerine mutually retains recycling, oil phase through dehydration at
Reason；Take above-mentioned oil sample 400g to add 8g Novozym435 lipase and obtain reaction production after stirring reaction 4h under 100Pa vacuum
Thing, liquid chromatographic detection obtain, and now in product, TAG contents are that 66.5%, DAG contents are that 30.27%, MAG contents are
2.09%, FFA content are 1.14%；The esterification yield of aliphatic acid is 97.78%.
Comparative example 1 (step enzyme method)
It is raw material to take the fatty acid by-products in deep sea fish oil processing, and wherein content of fatty acid is 99.5%, in its fat
DHA is 20% in acid, EPA content 22%.Take this aliphatic acid 100g to be mixed in 100g glycerine in reaction vessel, add 1.6g
Novozym435 lipase, it is placed in 55 DEG C of constant temperature blender with magnetic force, under 100pa vacuum states after stirring reaction 24h
To reaction product, the conversion ratio that liquid chromatographic detection obtains aliphatic acid is 86.18%, and now in product, TAG contents are 32.10%,
DAG43.96%, MAG10.11%, FFA13.82%.
Comparative example 2 (step enzyme method)
Take oleic acid 100g to be mixed in 100g glycerine in reaction vessel, add 1.6g Novozym435 lipase, be placed in 55
DEG C constant temperature blender with magnetic force in, reaction product, liquid chromatographic detection are obtained after stirring reaction 24h under 100pa vacuum states
The conversion ratio of aliphatic acid is 87.14%, now TAG contents are 33.51%, DAG42.78%, MAG10.84% in product,
FFA12.86%.Esterification yield is low, it is necessary to which more than 24h can be only achieved balance when this method is catalyzed 10h；Efficiency is low.
Claims (8)
- A kind of 1. method for preparing fatty glyceride, it is characterised in that comprise the following steps：(1) it is (1~5) by mass ratio：1 glycerine and free fatty mixing, addition reactant gross mass 0.1%~2% The water of free-fat enzyme, reactant gross mass 1%~6%, 2~4h of stirring reaction at 30~60 DEG C；(2) centrifuge the oil phase in above-mentioned reaction and glycerine phase, glycerine mutually retain recycling, oil phase is through dewater treatment；(3) immobilized lipase of oil phase gross mass 1~5% is added into the oil phase after above-mentioned dehydration, Gao Zhen at 45~65 DEG C Sky 4~8h of reaction, that is, obtain fatty glyceride.
- 2. according to the method for claim 1, it is characterised in that the quality of free fatty and glycerine described in step (1) Than for 1:1~1:3, the addition of free-fat enzyme is the 0.1%~2% of substrate gross mass, and water addition is 2%~5%.
- 3. according to the method for claim 2, it is characterised in that step (1) described reaction temperature is 30~55 DEG C, during reaction Between be 3~4h.
- 4. according to the method described in claim 1 or 2 or 3, it is characterised in that the temperature of step (3) high vacuum reaction for 45~ 60 DEG C, the time is 3~5h, and vacuum is less than 200Pa.
- 5. according to the method for claim 4, it is characterised in that immobilized lipase described in step (3) is without glyceride The immobilized lipase of acyl group position specific.
- 6. according to the method for claim 5, it is characterised in that the immobilized lipase is Novozym 435.
- 7. according to the method described in claim 1 or 2 or 3, it is characterised in that free-fat enzyme described in step (1) is source Mixture more than one or both of root enzyme category, aspergillus, hair enzyme category, bacterium, saccharomycete and pancreatic lipase.
- 8. according to the method for claim 7, it is characterised in that the free-fat enzyme is Lipozyme TL 100L fat Enzyme orCALB L lipase.
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| CN201710700407.9A CN107338274A (en) | 2017-08-16 | 2017-08-16 | A kind of method for preparing fatty glyceride |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108531522A (en) * | 2018-03-09 | 2018-09-14 | 华南理工大学 | A kind of method of enzyme law catalysis synthesis monoglyceride |
| CN108795999A (en) * | 2018-07-04 | 2018-11-13 | 嘉必优生物技术（武汉）股份有限公司 | A kind of preparation method of three saturated fatty acid glycerides |
| CN110511966A (en) * | 2019-08-16 | 2019-11-29 | 杭州信泓科技有限公司 | The preparation method of short-chain fat acid glyceride |
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| EP0093602A2 (en) * | 1982-04-30 | 1983-11-09 | Unilever N.V. | Interesterification with a lipase enzyme as an interesterification catalyst |
| CN105420300A (en) * | 2015-12-09 | 2016-03-23 | 华南理工大学 | Method for preparing glyceride type polyunsaturated fatty acids |
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2017
- 2017-08-16 CN CN201710700407.9A patent/CN107338274A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0093602A2 (en) * | 1982-04-30 | 1983-11-09 | Unilever N.V. | Interesterification with a lipase enzyme as an interesterification catalyst |
| CN105420300A (en) * | 2015-12-09 | 2016-03-23 | 华南理工大学 | Method for preparing glyceride type polyunsaturated fatty acids |
Non-Patent Citations (4)
| Title |
|---|
| DAOMING LI 等: "Preparation of Highly Pure n‑3 PUFA‑Enriched Triacylglycerols by Two‑Step Enzymatic Reactions Combined with Molecular Distillation", 《JOURNAL OF THE AMERICAN OIL CHEMISTS SOCIETY》 * |
| 全文琴: "ω-3多不饱和脂肪酸甘油酯富集的研究", 《中国优秀硕士学位论文全文数据库基础科学辑》 * |
| 朱东奇 等: "两步酶法合成富含EPA/DHA甘油酯的研究", 《中国油脂》 * |
| 王伟东: "《微生物学》", 31 August 2015, 中国农业大学出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108531522A (en) * | 2018-03-09 | 2018-09-14 | 华南理工大学 | A kind of method of enzyme law catalysis synthesis monoglyceride |
| CN108531522B (en) * | 2018-03-09 | 2021-09-21 | 华南理工大学 | Method for synthesizing monoglyceride by enzymatic catalysis |
| CN108795999A (en) * | 2018-07-04 | 2018-11-13 | 嘉必优生物技术（武汉）股份有限公司 | A kind of preparation method of three saturated fatty acid glycerides |
| CN108795999B (en) * | 2018-07-04 | 2021-01-05 | 嘉必优生物技术（武汉）股份有限公司 | Preparation method of tri-saturated fatty acid glyceride |
| CN110511966A (en) * | 2019-08-16 | 2019-11-29 | 杭州信泓科技有限公司 | The preparation method of short-chain fat acid glyceride |
| 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 |
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