CN105567758B - A kind of method of epoxidized fatty acid methyl esters preparation - Google Patents
A kind of method of epoxidized fatty acid methyl esters preparation Download PDFInfo
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Abstract
The invention belongs to biological chemical fields, disclose a kind of preparation method of epoxidized fatty acid methyl esters, include the following steps: (1) using esterase as catalyst, ethyl acetate carries out epoxidation reaction as reaction promoter, by fatty acid methyl ester and hydrogen peroxide；(2) reaction product, oil recovery phase, i.e. acquisition epoxy aliphatic acid methyl ester are separated.The Catalytic processes mild condition that the present invention uses, does not have side reaction；Moreover, reaction product ingredient is single, easily separated purifying.The yield for improving epoxy aliphatic acid methyl ester simultaneously, reduces the free fatty acid content in epoxy aliphatic acid methyl ester.
Description
Technical field
The present invention relates to a kind of methods of epoxidized fatty acid methyl esters.
Background technique
Fatty acid methyl ester is a kind of highly important chemical intermediate.But a large amount of carbon-carbon double bond leads to its oxidation stability
Therefore difference carries out the generation different type fatty acid methyl ester such as sulfonation neutralization plus hydrogen, ethoxylation and transesterification to its double bond and spreads out
Biology is concerned, these product clean and environmental protections can be widely applied to daily cosmetics, detergent and plastics processing industry etc..Ring
Oxidation of fatty acids methyl esters can be added in industrial copolymer material, enhance the plasticity of polymer.European Union and the U.S. are to traditional
Polyvinyl chloride (PVC) toxicity research of dioctyl phthalate (DOP) and dibutyl phthalate (DBP) plasticizer hair
Existing, DOP can trigger tissue hepatic disease and canceration, upset danger, European Union and the U.S. Food and Drug Administration such as endocrine
(FDA) 3 years old toy for children and product below is forbidden to use 6 kinds of plasticizer such as DOP.And epoxidized fatty acid methyl esters is as polychlorostyrene
Ethylene (PVC) resin plasticizer, compared with traditional dioctyl phthalate (DOP) and dibutyl phthalate (DBP),
Have many advantages, such as that nontoxic, fast light, heat-resistant stability is good, therefore can be used for food packaging, toy for children, medical article material etc.
Aspect.Currently, China produces, nontoxic, environmentally friendly non-neighboring benzene class environment-friendly plasticizer kind is relatively deficient, and related application is seldom.With big
Soya-bean oil is that the epoxidized soybean oil of raw material is current plasticising better performances and belongs to and environment-protecting and non-poisonous renewable prepare plasticiser, but ring
Oxygen soybean oil molecular weight is larger, viscosity is poor with plastic pvc compatibility greatly, can only improve as auxiliary material addition and be plasticized performance, and one
As polyvinyl chloride resin add 1%~3%.Compare epoxidized soybean oil and epoxy aliphatic acid methyl ester, epoxy aliphatic acid methyl ester is in the plastic
Additive amount is up to 10%~30%, can substitute the plastic products of DOP production asepsis environment-protecting completely.Meanwhile epoxyfatty acid first
Ester have good lubricity, compatibility and dispersibility, can be used as surfactant and dispersing agent, it can also be used to epoxy coating and
In epoxy resin.So epoxy aliphatic acid methyl ester is a kind of very widely used industrial processes articles.
The existing main production of epoxy aliphatic acid methyl ester is: (1) it using peroxy acid or derivative is directly added into grease,
It opens carbon-carbon double bond and carries out epoxidation.But it is that organic acid is unstable there are problem, explosive, complex process, difficult separation product；
(2) epoxidation in situ.It is synchronous progress that the technical process control peroxy acid, which is generated with epoxidation, does not accumulate peroxy acid, improves
The safety of production, but there is the problems such as post-processing is difficult, and unstable products form open loop；(3) excessive metalcatalyzing method is utilized.
Higher epoxidation value product is obtained using quaternary ammonium salt phosphor-tungstic heteropoly acid phase transfer catalyst, selects reaction lowered temperature reclamation catalysis
Agent, while reducing spent acid discharge；But reactive chemistry reagent is excessive, and the discharge of phosphorus can bring environment water pollution problem [Yang Hua, rouge
Fatty acid methyl esters epoxidation reaction and catalyst system research].(4) biological catalysis.The technique mainly utilizes enzyme preparation to be catalyzed shape
At epoxidation product.
Due to using the production procedure of solvent long in the technique of chemical method synthesizing epoxy fatty acid methyl ester, environment is vulnerable to dirt
Dye, is eliminated substantially at present.Recent most study is exactly inorganic acid catalyzed process in solvent-free system, with sulfuric acid, phosphoric acid etc.
As fatty acid methyl ester epoxidation catalyst, although the reaction time is short, epoxide number is high, post-processing trouble, industry generates big
The problems such as amount acid pickle, is unfavorable for environmental protection, and poor, equipment that there is also reaction stabilities is corroded, up for what is prepared to biological enzyme
Direction is further improved.Enzymatic fatty acid methyl ester epoxidation has highly selective, specificity, the advantage of high yield, Er Qieneng
Open loop is reduced to the maximum extent.But catalyst used in existing enzymatic process be lipase, and generally toluene,
It is carried out in dimethylbenzene, n-hexane equal solvent, also needs to add the carrier of stearic acid or other fatty acid as oxygen sometimes.Utilize rouge
When fat enzymatic fatty acid methyl ester carries out epoxidation, fatty acid methyl ester itself can be generated fatty acid by lipase hydrolysis, fat
Acid generates peroxide fatty acid with hydroperoxidation again, the carrier as oxygen.First ester hydrolysis is lipase-catalyzed epoxidation
Side reaction in journey will obtain the epoxidized fatty acid methyl esters of low acid value, need to carry out depickling processing to epoxidation reaction product,
This just extends process flow, increases production cost.
Summary of the invention
More, the product acid value for existing fatty acid methyl ester epoxidation technique side reaction, the low disadvantage of epoxy methyl esters yield,
The present invention provides a kind of method that enzyme process prepares epoxidized fatty acid methyl esters, with long chain fatty acids methyl esters (C16~C22) and dioxygen
Water is raw material, and ethyl acetate is reaction promoter, prepares epoxy aliphatic acid methyl ester by esterase catalyzed epoxidation reaction.Pass through this
The acid value for the epoxy aliphatic acid methyl ester that technique obtains is in 1mgKOH/g hereinafter, the yield of epoxy aliphatic acid methyl ester can achieve 98%
More than.
To achieve the above object, technical solution is as follows by the present invention:
A kind of preparation method of epoxidized fatty acid methyl esters, includes the following steps:
(1) using esterase as catalyst, ethyl acetate carries out epoxy as reaction promoter, by fatty acid methyl ester and hydrogen peroxide
Change reaction；
(2) reaction product, oil recovery phase, i.e. acquisition epoxy aliphatic acid methyl ester are separated.
The carbon atom number of the fatty acid acyl of step (1) described fatty acid methyl ester is 16~22.
The hydrogen peroxide is the 5%~10% of fatty acid methyl ester quality.
Step (1) the ethyl acetate additive amount is the 1%~5% of fatty acid methyl ester quality.
The additive amount of the esterase is the 1%~10% of fatty acid methyl ester quality.
Step (1) esterase is the mixture of one or more of AFEST, PestE and EstE1.
The temperature of step (1) described epoxidation reaction is 40 DEG C~60 DEG C, stirring condition 400rpm or more, the reaction time
For 24 hours~48h.
The temperature of the epoxidation reaction is 50 DEG C~60 DEG C.
Step (2) separation process is natural layering, and oil recovery phase is evaporated under reduced pressure recycling ethyl acetate, obtains epoxy
Fatty acid methyl ester.
Esterase is a kind of special Acyl- hydrolase, can hydrolyze acyl glyceride of the chain length less than 10, be widely used in
The fields such as food, medicine, cosmetics and papermaking.[K.E.Jaege, B.W.Dijkstra, M.T.Bacterial
biocatalysts:Molecular biology,three-dimensional structures,and
biotechnological applications of lipases[J].ANNUAL REVIEW OF MICROBIOLOGY
1999；53:315-351].Esterase of the present invention is hormone-sensitive lipase family from Pyrobaculum
Calidifontis (PestE), the EstE1 esterase of Archaeoglobus Fulgidus (AFEST) and macro genomic source.Hair
When bright people's research discovery is contacted for catalyst long chain fatty acids methyl esters with hydrogen peroxide using esterase, fatty acid methyl ester does not occur
Hydrolysis；After adding ethyl acetate, epoxidation is may be implemented in fatty acid methyl ester, obtains the extremely low epoxy of free fatty acid content
Fatty acid methyl ester, and then form the present invention.
Compared with prior art, the beneficial effects of the present invention are:
(1) for the present invention using esterase as catalyst, catalysis fatty acid methyl ester carries out epoxidation, avoids the water of fatty acid methyl ester
The generation of the side reactions such as solution only need to simply be isolated and purified the epoxy that low acid value can be obtained so that product is more single
Fatty acid methyl ester product.The yield for improving epoxy aliphatic acid methyl ester simultaneously, reduces the free rouge in epoxy aliphatic acid methyl ester
Fat acid content.
(2) choosing ethyl acetate is both reaction promoter, improves the transformation efficiency of fatty acid methyl ester, and is conducive to reaction and produces
The separation and recovery of object.
Specific embodiment
Introduce implementation of the invention in more detail by the following examples.In the described embodiment, all percentages with
Quality meter.Esterase used in the present invention, protein sequence number by Protein Data Bank announce (http: //
Www.rcsb.org/pdb/home/home.do): from esterase (AFEST, the PDB of Archaeoglobus Fulgidus
ID:1JJI_A), from the esterase of Pyrobaculum Calidifontis (PestE, PDB ID:3ZWQ_A), macro genome
The esterase (EstE1, PDB ID:2C7B_B) in library source, applicant provide to society.
Embodiment 1
Methyl oleate 300g is added in the reaction vessel, ethyl acetate 15g, esterase AFEST 3g start after mixing
It adds hydrogen peroxide (content of hydrogen peroxide 30%) and starts epoxidation reaction, 100g hydrogen peroxide is at the uniform velocity added dropwise in 2h.Control reaction
The temperature of system is 60 DEG C, mixing speed 400rpm.Sustained response for 24 hours after, stop stirring terminate epoxidation reaction, will react
Mixture stands 5min and is layered, and recycles upper organic phase.Vacuum distillation recycles the ethyl acetate in organic phase to get ring is arrived
Oxygen methyl oleate.Product is detected, epoxyoleic acid methyl ester content is 98.2%, and acid value is 0.3mgKOH/g.
Embodiment 2
Methyl soyate 300g, ethyl acetate 3g, 3g esterase EstE1 are added in the reaction vessel, is uniformly mixed
After start add hydrogen peroxide (content of hydrogen peroxide 30%) start epoxidation reaction, 100g hydrogen peroxide is at the uniform velocity added dropwise in 2h.Control
The temperature of reaction system processed is 50 DEG C, mixing speed 400rpm.Sustained response for 24 hours after, stop stirring terminate epoxidation reaction,
Reaction mixture sat 5min is layered, upper organic phase is recycled.Ethyl acetate in vacuum distillation recycling organic phase, i.e.,
Obtain epoxy soybean soyate.Product is detected, epoxidised soybean oil fatty acid methyl ester is 83.5%, acid value
It is 0.26mgKOH/g.
Embodiment 3
Methyl soyate 300g, ethyl acetate 15g, 3g esterase PestE are added in the reaction vessel, is uniformly mixed
After start add hydrogen peroxide (content of hydrogen peroxide 30%) start epoxidation reaction, 50g hydrogen peroxide is at the uniform velocity added dropwise in 2h.Control
The temperature of reaction system is 40 DEG C, mixing speed 400rpm.Sustained response for 24 hours after, stop stirring terminate epoxidation reaction, will
Reaction mixture sat 5min is layered, and upper organic phase is recycled.Vacuum distillation recycling organic phase in ethyl acetate to get
To epoxy aliphatic acid methyl ester.Product is detected, epoxidized fatty acid methyl ester content is 91.7%, and acid value is 0.26mgKOH/g.
Embodiment 4
Methyl soyate 300g is added in the reaction vessel, ethyl acetate 10g, esterase PestE and AFEST are each
1.5g starts to add hydrogen peroxide (content of hydrogen peroxide 30%) beginning epoxidation reaction after mixing, at the uniform velocity be added dropwise in 2h
50g hydrogen peroxide.The temperature for controlling reaction system is 50 DEG C, mixing speed 400rpm.After sustained response 48h, stop stirring eventually
Reaction mixture sat 5min is layered by only epoxidation reaction, recycles upper organic phase.In vacuum distillation recycling organic phase
Ethyl acetate to get arrive epoxy aliphatic acid methyl ester.Product is detected, epoxidized fatty acid methyl ester content is 89.5%, acid
Value is 0.23mgKOH/g.
Comparative example 1
Methyl oleate 300g is added in the reaction vessel, ethyl acetate 15g, 3g lipase Lipase CALB are uniformly mixed
After start add hydrogen peroxide (content of hydrogen peroxide 30%) start epoxidation reaction, 100g hydrogen peroxide is at the uniform velocity added dropwise in 2h.Control
The temperature of reaction system processed is 40 DEG C, mixing speed 400rpm.Sustained response for 24 hours after, stop stirring terminate epoxidation reaction,
Reaction mixture sat 5min is layered, upper organic phase is recycled.Ethyl acetate in vacuum distillation recycling organic phase, i.e.,
Obtain epoxyoleic acid methyl esters.Product is detected, epoxidized fatty acid methyl ester content is 98.2%, and acid value is 5.4mgKOH/g.
Comparative example 2
Methyl oleate 300g, 3g esterase PestE are added in the reaction vessel, starts to add hydrogen peroxide (mistake after mixing
Aoxidize hydrogen content 30%) start epoxidation reaction, 100g hydrogen peroxide is at the uniform velocity added dropwise in 2h.The temperature for controlling reaction system is 40
DEG C, mixing speed 400rpm.Sustained response for 24 hours after, stop stirring terminate epoxidation reaction, by reaction mixture sat 5min
It is layered, recycles upper organic phase.Vacuum distillation recycles the ethyl acetate in organic phase to get epoxy aliphatic acid methyl ester is arrived.
Product is detected, epoxidized fatty acid methyl ester content is 2.7%, and acid value is 0.5mgKOH/g.
Claims (8)
1. a kind of preparation method of epoxidized fatty acid methyl esters, which comprises the steps of:
(1) using esterase as catalyst, ethyl acetate is anti-by fatty acid methyl ester and hydrogen peroxide progress epoxidation as reaction promoter
It answers；The esterase is the mixture of one or more of AFEST, PestE and EstE1；
(2) reaction product, oil recovery phase, i.e. acquisition epoxy aliphatic acid methyl ester are separated.
2. preparation method according to claim 1, which is characterized in that the fatty acid acyl of step (1) described fatty acid methyl ester
The carbon atom number of base is 16 ~ 22.
3. preparation method according to claim 2, which is characterized in that the hydrogen peroxide is the 5% of fatty acid methyl ester quality
~10%。
4. preparation method according to claim 1 or 2 or 3, which is characterized in that step (1) the ethyl acetate additive amount
It is the 1% ~ 5% of fatty acid methyl ester quality.
5. preparation method according to claim 1 or 2 or 3, which is characterized in that the additive amount of the esterase is fatty acid methyl
The 1% ~ 10% of ester quality.
6. preparation method according to claim 1 or 2 or 3, which is characterized in that the temperature of step (1) described epoxidation reaction
Degree be 40 °C ~ 60 °C, stirring condition 400rpm or more, the reaction time for 24 hours ~ 48h.
7. preparation method according to claim 6, which is characterized in that the temperature of the epoxidation reaction is 50 °C ~ 60 °C.
8. preparation method according to claim 1 or 2 or 3, which is characterized in that step (2) separation process is nature
Layering, oil recovery phase, vacuum distillation recycling ethyl acetate obtain epoxy aliphatic acid methyl ester.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 微生物酯酶产生菌的选育、菌株Bacillus sp.EB-87产酶特性及酶学性质的研究;李光伟;《中国优秀硕士学位论文全文数据库基础科学辑》;20020615(第1期);第1-2页第1.1节 |
| 脂肪酸甲酯环氧化反应及催化体系研究;杨华;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20100815(第8期);第21页第3.2.2节 |
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