CN105567758A - Method for preparing epoxy fatty acid methyl ester - Google Patents
Method for preparing epoxy fatty acid methyl ester Download PDFInfo
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- CN105567758A CN105567758A CN201610020676.6A CN201610020676A CN105567758A CN 105567758 A CN105567758 A CN 105567758A CN 201610020676 A CN201610020676 A CN 201610020676A CN 105567758 A CN105567758 A CN 105567758A
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
- C12P17/02—Oxygen as only ring hetero atoms
Abstract
The invention belongs to the field of biochemical engineering, and discloses a method for preparing epoxy fatty acid methyl ester. The method comprises the following steps that 1, esterase serves as a catalyst, ethyl acetate serves as a reaction assistant, and fatty acid methyl ester and hydrogen peroxide are subjected to an epoxidation reaction; 2, the reaction product is separated, an oil phase is recycled, and epoxy fatty acid methyl ester is obtained. A catalyzing process adopted in the method is mild in reaction condition, and no side effect occurs. The reaction product is single in ingredient and easy to separate and purify. Meanwhile, the yield of epoxy fatty acid methyl ester is increased, and the content of free fatty acid in epoxy fatty acid methyl ester is reduced.
Description
Technical field
The present invention relates to a kind of method of epoxidized fatty acid methyl esters.
Background technology
Fatty acid methyl ester is a kind of very important chemical intermediate.But a large amount of carbon-carbon double bonds causes its oxidative stability poor, therefore, carry out the dissimilar fatty acid methyl ester derivatives of generation such as sulfonation neutralization, hydrogenation, ethoxylation and transesterify to receive much concern to its double bond, these product clean environment firendlies can be widely used in daily cosmetics, washing composition and plastics processing industry etc.Epoxidized fatty acid methyl esters can add in industrial copolymer material, strengthens the plasticity of polymkeric substance.European Union and U.S. polyvinyl chloride (PVC) toxicity research to traditional dioctyl phthalate (DOP) (DOP) and dibutyl phthalate (DBP) softening agent finds, DOP can cause and organizes hepatic disease and canceration, upset the danger such as internal secretion, European Union and FDA (FDA) forbid 6 kinds of softening agent such as the toy for children of less than 3 years old and goods use DOP.And epoxidized fatty acid methyl esters is as polyvinyl chloride (PVC) resin plasticizer, compare with dibutyl phthalate (DBP) with traditional dioctyl phthalate (DOP) (DOP), there is the advantages such as nontoxic, fast light, heat-resistant stability is good, therefore may be used for the aspects such as food product pack, toy for children, medical article material.At present, China's production non-neighboring benzene class environment-friendly plasticizer kind that is nontoxic, environmental protection is relatively deficient, and related application is little.Current plasticising better performances that to take soybean oil as the epoxy soybean oil of raw material be and belong to that environment-protecting asepsis is renewable prepares fluidizer, but epoxy soybean oil molecular weight is comparatively large, viscosity is large and plastic pvc consistency is poor, can only add as auxiliary material and improve plasticising performance, generally add 1% ~ 3% at polyvinyl chloride resin.Relatively epoxy soybean oil and epoxy aliphatic acid methyl ester, epoxy aliphatic acid methyl ester in the plastic addition, up to 10% ~ 30%, can substitute the plastics that DOP produces asepsis environment-protecting completely.Meanwhile, epoxy aliphatic acid methyl ester has good oilness, consistency and dispersiveness, can be used as tensio-active agent and dispersion agent, also can be used in epoxy coating and epoxy resin.So epoxy aliphatic acid methyl ester is a kind of application industrial processes articles for use widely.
The existing main production of epoxy aliphatic acid methyl ester is: (1) adopts peroxy acid or derivative directly to add in grease, opens carbon-carbon double bond and carries out epoxidation.But it is unstable that existing problems are organic acids, explosive, complex process, difficult separated product; (2) original position epoxidation.The problems such as it is synchronously carry out that this technical process control peroxy acid produces with epoxidation, does not accumulate peroxy acid, improves the security of production, but there is aftertreatment difficulty, unstable products formation open loop; (3) excessive metalcatalyzing method is utilized.Adopt quaternary ammonium salt phosphor-tungstic heteropoly acid phase-transfer catalyst to obtain higher epoxidation value product, select reaction lowered temperature reclamation catalyzer, reduce spent acid discharge simultaneously; But reactive chemistry reagent is too much, the discharge of phosphorus can bring environment water pollution problem [Yang Hua, fatty acid methyl ester epoxidation reaction and catalyst system research].(4) biological catalysis.This technique mainly utilizes zymin catalysis to form epoxidation product.
Owing to using the Production Flow Chart of solvent long in the technique of chemical method synthesizing epoxy fatty acid methyl ester, environment is vulnerable to pollute, and is substantially eliminated at present.Recent most study be exactly mineral acid catalysis method in solvent-free system, using sulfuric acid, phosphoric acid etc. as fatty acid methyl ester epoxidation catalyst, although the reaction times is short, oxirane value is high, but aftertreatment bothers, industry produces a large amount of spent acid solution, be unfavorable for environmental protection, also there is the problems such as reaction stability difference, equipment corrosion, the direction awaiting preparing to biological enzyme is improved further.Enzyme catalysis fatty acid methyl ester epoxidation has the advantage of highly selective, specificity, high yield, and can reduce open loop to greatest extent.But the catalyzer used in existing enzymatic process is lipase, and generally carry out in toluene, dimethylbenzene, normal hexane equal solvent, sometimes also need to add stearic acid or other lipid acid carrier as oxygen.When utilizing lipase-catalyzed fatty acid methyl ester to carry out epoxidation, fatty acid methyl ester self can be produced lipid acid by lipase hydrolysis, and lipid acid generates peroxide lipid acid, as the carrier of oxygen with hydroperoxidation again.First ester hydrolysis is the side reaction in lipase-catalyzed epoxidation process, obtain the epoxidized fatty acid methyl esters of low acid value, and need to carry out depickling process to epoxidation reaction product, this just extends technical process, adds production cost.
Summary of the invention
Many for the side reaction of existing fatty acid methyl ester epoxidation technique, product acid value, the shortcoming that epoxy methyl esters yield is low, the invention provides a kind of method that enzyme process prepares epoxidized fatty acid methyl esters, with longer chain fatty acid methyl esters (C16 ~ C22) and hydrogen peroxide for raw material, ethyl acetate is reaction promoter, prepares epoxy aliphatic acid methyl ester by esterase catalyzed epoxidation reaction.The acid value of the epoxy aliphatic acid methyl ester obtained by this technique is at below 1mgKOH/g, and the yield of epoxy aliphatic acid methyl ester can reach more than 98%.
For achieving the above object, technical scheme is as follows in the present invention:
A preparation method for epoxidized fatty acid methyl esters, comprises the steps:
(1) take esterase as catalyzer, fatty acid methyl ester and hydrogen peroxide, as reaction promoter, are carried out epoxidation reaction by ethyl acetate;
(2) reaction product isolated, reclaims oil phase, namely obtains epoxy aliphatic acid methyl ester.
The carbonatoms of the fatty acid acyl of step (1) described fatty acid methyl ester is 16 ~ 22.
Described hydrogen peroxide is 5% ~ 10% of fatty acid methyl ester quality.
The described ethyl acetate addition of step (1) is 1% ~ 5% of fatty acid methyl ester quality.
The addition of described esterase is 1% ~ 10% of fatty acid methyl ester quality.
Step (1) described esterase is one or more the mixture in AFEST, PestE and EstE1.
The temperature of step (1) described epoxidation reaction is 40 DEG C ~ 60 DEG C, more than agitation condition 400rpm, reaction times 24h ~ 48h.
The temperature of described epoxidation reaction is 50 DEG C ~ 60 DEG C.
Step (2) described sepn process is natural layering, reclaims oil phase, and ethyl acetate is reclaimed in underpressure distillation, obtains epoxy aliphatic acid methyl ester.
Esterase is a kind of special Acyl-hydrolase, can be hydrolyzed the acyl glyceride that chain length is less than 10, is widely used in the fields such as food, medicine, makeup and papermaking.[K.E.Jaege，B.W.Dijkstra,M.T.Bacterialbiocatalysts:Molecularbiology,three-dimensionalstructures,andbiotechnologicalapplicationsoflipases[J].ANNUALREVIEWOFMICROBIOLOGY1999；53:315-351]。Esterase of the present invention is that hormone-sensitive lipase family derives from PyrobaculumCalidifontis (PestE), the EstE1 esterase of ArchaeoglobusFulgidus (AFEST) and grand genomic source.Contriver study discovery utilize esterase for catalyst longer chain fatty acid methyl esters contact with hydrogen peroxide time, there is not hydrolysis reaction in fatty acid methyl ester; After adding ethyl acetate, fatty acid methyl ester can realize epoxidation, obtains the epoxy aliphatic acid methyl ester that free fatty acid content is extremely low, and then defines the present invention.
Compared with prior art, beneficial effect of the present invention is:
(1) the present invention take esterase as catalyzer, catalyze fatty acid methyl esters carries out epoxidation, avoid the generation of the side reactions such as fatty acid methyl ester hydrolysis, make product more single, only need carry out the epoxy aliphatic acid methyl ester product that simple separation and purification can obtain low acid value.Improve the yield of epoxy aliphatic acid methyl ester simultaneously, reduce the free fatty acid content in epoxy aliphatic acid methyl ester.
(2) choosing ethyl acetate had been both reaction promoter, improve the transformation efficiency of fatty acid methyl ester, and was beneficial to the Separation and Recovery of reaction product.
Embodiment
Introduce enforcement of the present invention in more detail by the following examples.In the described embodiment, all per-cent all in mass.Esterase used in the present invention, its protein sequence number is announced (http://www.rcsb.org/pdb/home/home.do) by Protein Data Bank: the esterase (AFEST deriving from ArchaeoglobusFulgidus, PDBID:1JJI_A), derive from the esterase (PestE of PyrobaculumCalidifontis, PDBID:3ZWQ_A), the esterase (EstE1, PDBID:2C7B_B) in grand genomic library source, applicant provides to society.
Embodiment 1
In reaction vessel, add Witconol 2301 300g, ethyl acetate 15g, esterase AFEST3g, start to add hydrogen peroxide (content of hydrogen peroxide 30%) after mixing and start epoxidation reaction, in 2h, at the uniform velocity drip 100g hydrogen peroxide.The temperature controlling reaction system is 60 DEG C, and stirring velocity is 400rpm.After sustained reaction 24h, stop stirring termination ring oxidizing reaction, reaction mixture sat 5min is carried out layering, reclaim upper organic phase.The ethyl acetate in organic phase is reclaimed in underpressure distillation, namely obtains epoxyoleic acid methyl esters.Product after testing, its epoxyoleic acid methyl ester content is 98.2%, and acid number is 0.3mgKOH/g.
Embodiment 2
In reaction vessel, add methyl soyate 300g, ethyl acetate 3g, 3g esterase EstE1, start to add hydrogen peroxide (content of hydrogen peroxide 30%) after mixing and start epoxidation reaction, in 2h, at the uniform velocity drip 100g hydrogen peroxide.The temperature controlling reaction system is 50 DEG C, and stirring velocity is 400rpm.After sustained reaction 24h, stop stirring termination ring oxidizing reaction, reaction mixture sat 5min is carried out layering, reclaim upper organic phase.The ethyl acetate in organic phase is reclaimed in underpressure distillation, namely obtains epoxy soybean soyate.Product after testing, its epoxidised soybean oil fatty acid methyl ester is 83.5%, and acid number is 0.26mgKOH/g.
Embodiment 3
In reaction vessel, add methyl soyate 300g, ethyl acetate 15g, 3g esterase PestE, start to add hydrogen peroxide (content of hydrogen peroxide 30%) after mixing and start epoxidation reaction, in 2h, at the uniform velocity drip 50g hydrogen peroxide.The temperature controlling reaction system is 40 DEG C, and stirring velocity is 400rpm.After sustained reaction 24h, stop stirring termination ring oxidizing reaction, reaction mixture sat 5min is carried out layering, reclaim upper organic phase.The ethyl acetate in organic phase is reclaimed in underpressure distillation, namely obtains epoxy aliphatic acid methyl ester.Product after testing, its epoxidized fatty acid methyl ester content is 91.7%, and acid number is 0.26mgKOH/g.
Embodiment 4
Methyl soyate 300g is added in reaction vessel, ethyl acetate 10g, the each 1.5g of esterase PestE and AFEST, starts to add hydrogen peroxide (content of hydrogen peroxide 30%) and starts epoxidation reaction, in 2h, at the uniform velocity drip 50g hydrogen peroxide after mixing.The temperature controlling reaction system is 50 DEG C, and stirring velocity is 400rpm.After sustained reaction 48h, stop stirring termination ring oxidizing reaction, reaction mixture sat 5min is carried out layering, reclaim upper organic phase.The ethyl acetate in organic phase is reclaimed in underpressure distillation, namely obtains epoxy aliphatic acid methyl ester.Product after testing, its epoxidized fatty acid methyl ester content is 89.5%, and acid number is 0.23mgKOH/g.
Comparative example 1
In reaction vessel, add Witconol 2301 300g, start to add hydrogen peroxide (content of hydrogen peroxide 30%) after ethyl acetate 15g, 3g lipase LipaseCALB mixes and start epoxidation reaction, in 2h, at the uniform velocity drip 100g hydrogen peroxide.The temperature controlling reaction system is 40 DEG C, and stirring velocity is 400rpm.After sustained reaction 24h, stop stirring termination ring oxidizing reaction, reaction mixture sat 5min is carried out layering, reclaim upper organic phase.The ethyl acetate in organic phase is reclaimed in underpressure distillation, namely obtains epoxyoleic acid methyl esters.Product after testing, its epoxidized fatty acid methyl ester content is 98.2%, and acid number is 5.4mgKOH/g.
Comparative example 2
In reaction vessel, add Witconol 2301 300g, 3g esterase PestE, start to add hydrogen peroxide (content of hydrogen peroxide 30%) after mixing and start epoxidation reaction, in 2h, at the uniform velocity drip 100g hydrogen peroxide.The temperature controlling reaction system is 40 DEG C, and stirring velocity is 400rpm.After sustained reaction 24h, stop stirring termination ring oxidizing reaction, reaction mixture sat 5min is carried out layering, reclaim upper organic phase.The ethyl acetate in organic phase is reclaimed in underpressure distillation, namely obtains epoxy aliphatic acid methyl ester.Product after testing, its epoxidized fatty acid methyl ester content is 2.7%, and acid number is 0.5mgKOH/g.
Claims (9)
1. a preparation method for epoxidized fatty acid methyl esters, is characterized in that, comprises the steps:
(1) take esterase as catalyzer, fatty acid methyl ester and hydrogen peroxide, as reaction promoter, are carried out epoxidation reaction by ethyl acetate;
(2) reaction product isolated, reclaims oil phase, namely obtains epoxy aliphatic acid methyl ester.
2. preparation method according to claim 1, is characterized in that, the carbonatoms of the fatty acid acyl of step (1) described fatty acid methyl ester is 16 ~ 22.
3. preparation method according to claim 2, is characterized in that, described hydrogen peroxide is 5% ~ 10% of fatty acid methyl ester quality.
4. the preparation method according to claim 1 or 2 or 3, is characterized in that, the described ethyl acetate addition of step (1) is 1% ~ 5% of fatty acid methyl ester quality.
5. the preparation method according to claim 1 or 2 or 3, is characterized in that, the addition of described esterase is 1% ~ 10% of fatty acid methyl ester quality.
6. the preparation method according to claim 1 or 2 or 3, is characterized in that, step (1) described esterase is one or more the mixture in AFEST, PestE and EstE1.
7. the preparation method according to claim 1 or 2 or 3, is characterized in that, the temperature of step (1) described epoxidation reaction is 40 DEG C ~ 60 DEG C, more than agitation condition 400rpm, reaction times 24h ~ 48h.
8. preparation method according to claim 7, is characterized in that, the temperature of described epoxidation reaction is 50 DEG C ~ 60 DEG C.
9. the preparation method according to claim 1 or 2 or 3, is characterized in that, step (2) described sepn process is natural layering, reclaims oil phase, and ethyl acetate is reclaimed in underpressure distillation, obtains epoxy aliphatic acid methyl ester.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106754818A (en) * | 2016-12-02 | 2017-05-31 | 华南理工大学 | A kind of thermostable esterases mutant and its preparation method and application |
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| CN103088082A (en) * | 2013-01-16 | 2013-05-08 | 闭美娥 | Method for preparing epoxidized fatty acid methyl ester through lipase catalysis |
| CN104326911A (en) * | 2014-09-16 | 2015-02-04 | 浙江恒丰新材料有限公司 | Method for preparing polyol from waste grease and application thereof |
| CN104894178A (en) * | 2015-05-12 | 2015-09-09 | 华南理工大学 | Method for preparing epoxidized fatty acid methyl ester |
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| CN103088082A (en) * | 2013-01-16 | 2013-05-08 | 闭美娥 | Method for preparing epoxidized fatty acid methyl ester through lipase catalysis |
| CN104326911A (en) * | 2014-09-16 | 2015-02-04 | 浙江恒丰新材料有限公司 | Method for preparing polyol from waste grease and application thereof |
| CN104894178A (en) * | 2015-05-12 | 2015-09-09 | 华南理工大学 | Method for preparing epoxidized fatty acid methyl ester |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106754818A (en) * | 2016-12-02 | 2017-05-31 | 华南理工大学 | A kind of thermostable esterases mutant and its preparation method and application |
| CN106754818B (en) * | 2016-12-02 | 2020-04-28 | 华南理工大学 | Heat-resistant esterase mutant and preparation method and application thereof |
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