CN103740471A - Method for preparing epoxy resin fatty acid short-chained alcohol ester in biological catalytic method - Google Patents
Method for preparing epoxy resin fatty acid short-chained alcohol ester in biological catalytic method Download PDFInfo
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- CN103740471A CN103740471A CN201410001434.3A CN201410001434A CN103740471A CN 103740471 A CN103740471 A CN 103740471A CN 201410001434 A CN201410001434 A CN 201410001434A CN 103740471 A CN103740471 A CN 103740471A
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Abstract
The invention provides a method for preparing epoxy resin fatty acid short-chained alcohol ester in a biological catalytic method. The method is characterized by comprising the following steps: preparing a reaction liquid with 82 to 90 percent of fatty acid short-chained alcohol ester by adopting fatty acid or biological oil such as vegetable oil, animal oil, catering waste oil and the like as raw materials and adopting lipase as a catalyst, and adding hydrogen peroxide and biological catalyst after roughly separating the reaction liquid to catalyzing the reaction liquid to generate the epoxy resin fatty acid short-chained alcohol ester. The process is an environment-friendly epoxy resin fatty acid short-chained alcohol ester production process. Compared with the traditional epoxy resin fatty acid short-chained alcohol ester production process, the preparation process has the characteristics such as wide raw material applicable range, convenience in flow operation, less raw material consumption, high product conversion rate, low production cost, strong environmental friendliness and the like.
Description
Technical field
The present invention relates to biochemical industry and material engineering, specifically a kind ofly utilize Biocatalysis method catalysis grease and short chain alcohol and hydrogen peroxide reaction under solvent-free or solvent system, prepare the method for epoxyfatty acid short chain alcohol ester.
Background technology
Epoxyfatty acid short chain alcohol ester is as epoxy plasticiser, ternary oxygen ring not only has plastification, and can absorb rapidly the chlorination oxygen that polyvinyl chloride discharges because of the Degradation of light and heat, thereby stop polyvinyl chloride to continue to decompose the effect of having played stablizer, have good synergy with the metal(lic)stabilizers such as barium, zinc, cadmium used time, can reduce the consumption of organic metal salt, and reduce product cost.Simultaneously, the epoxy-functional wherein containing is because polarity and ring strain have very high reactive behavior, can be used as much as the synthetic polyurethane of the reactions such as intermediate generation open loop, polymerization, polyester, epoxy resin, alcohol polyimide resin etc., because it also has good dispersion performance, oilness and consistency, also can directly be used as dispersion agent, the lubricant of coating.Therefore, epoxyfatty acid is extremely widely used in the fields such as plastics industry, coatings industry, novel high polymer material and rubber industry.
Epoxyfatty acid short chain alcohol ester is owing to having the more polar group such as short chain alcohol ester group and epoxy group(ing), join and in macromolecular material, show the characteristic that consistency is good, transport property is little, volatility is low, can be used for replacing traditional softening agent completely and produce plastic prod nontoxic, environmental protection, these products can be used on the high articles for use of the hygienic requirements such as food product pack, toy, medical article material and water supply line.
Prepare at present the main applied chemistry method of epoxyfatty acid short chain alcohol ester both at home and abroad, the achievement in research of report is more, and wherein the optimization of processing condition and the selection of catalyzer are the emphasis of research.Chemical method catalyzes and synthesizes the cruel method of epoxyfatty acid and is divided into again traditional mineral acid catalysis method, ion-exchange resin catalyzed method and metal catalytic method etc. according to the kind difference of used catalyst.But in chemical method synthesizing epoxy short chain alcohol ester process, all need formic acid or acetic acid as oxygen carrier, therefore side reaction easily occurs and produce poisonous by product, not only cause deterioration in quality, also easily surrounding environment is polluted.Therefore, do not use the enzyme catalysis epoxidation of formic acid or acetic acid can not only improve the difficult by product that produces of selectivity, epoxide stabilization, reaction conditions is gentle and environmentally friendly, and product does not have toxicity.
The present invention adopts biocatalysis two-step approach to produce epoxyfatty acid short chain alcohol ester, and the optimization by for reaction conditions, has improved reaction conversion ratio, has reduced the generation of byproduct of reaction, has reduced the impact of reaction for environment.This reaction process is simple, has good stability, and the cost that makes thing catalyse two-step method produce epoxyfatty acid short chain alcohol ester significantly reduces.
Summary of the invention
The object of this invention is to provide a kind of method of utilizing biocatalysis synthesizing epoxy lipid acid short chain alcohol ester.
Epoxyfatty acid short chain alcohol ester production method provided by the present invention is first with biological catalyst fcc raw material grease and short chain alcohol pre-esterification reactor under 32-55 ℃ of condition, enzyme addition 0.1%-10%, reaction times 30h; Then add the hydrogen peroxide based on the heavy 30%-60% quality of oil, continue reaction 24h, after reaction finishes, then through fractionation by distillation, obtain the epoxyfatty acid short chain alcohol ester of oxirane value 4.0%-6.0%.
In biocatalysis process, the catalyzer using is immobilized lipase, lipase powder, lipase liquid and lipase fermentation liquid, and lipase derives from microorganism or animal; Hydrogen peroxide refers to that massfraction is the superoxol of 30%-50%.
In described method, stock oil is lipid acid or bio-oil.Bio-oil comprises Vegetable oil lipoprotein, animal grease, microbial oil, discards food oils Huo You factory oil refining pin material.
Reaction adopts stirring reactor.The reaction the first step adopts biological catalyst synthetic fatty acid short chain alcohol ester reaction solution, can use solvent system, or solvent-free system, and the solvent that uses comprises sherwood oil, toluene, normal hexane, hexanaphthene, ethyl acetate.
Effect of the present invention is: adopt biocatalytic reaction, obtained new epoxyfatty acid short chain alcohol ester production technique path, this path has effectively reduced the impact that the problems such as traditional chemical catalytic production epoxyfatty acid short chain alcohol ester high energy consumption, environmental pollution are large are produced for epoxyfatty acid short chain alcohol ester.
The epoxyfatty acid short chain alcohol ester product lighter color after separation and purification being obtained by the present invention, clear, quality product is high, and cost is low, thereby provides a kind of new method for the suitability for industrialized production of epoxyfatty acid short chain alcohol ester.
Embodiment
Method in following embodiment, if no special instructions, is ordinary method.Enforcement below can make professional and technical personnel more understand the present invention, but does not limit in any form the present invention.
Example 1: the acid number 124.7mgKOH/g sewer oil of take is raw material, use stirring reactor, sewer oil 20kg feeds intake at every turn, the short chain alcohol that adds theoretical molar ratio, add water 2kg, immobilized lipase 1.5kg(enzyme activity is 20000U/g), 37 ℃ of temperature of reaction, obtain the enzymic catalytic reaction liquid that lipid acid short chain alcohol ester content is 81.5%-85.5%, then divide and evenly add 30% hydrogen peroxide 10kg altogether for ten times, every two hours add hydrogen peroxide one time, 40 ℃ of coreaction 24h, reaction finishes rear centrifugation and goes out enzyme and unreacted hydrogen peroxide, obtain epoxyfatty acid short chain alcohol ester crude product, after rectifying separation, obtaining epoxyfatty acid short chain alcohol ester product, oxirane value is at 4.0-5.0%.
Example 2: take acidification oil as raw material, use stirring reactor, acidification oil 10kg feeds intake at every turn, the short chain alcohol that adds theoretical molar ratio, sherwood oil is made solvent 20L, add water 1kg, immobilized lipase 1.5kg(enzyme activity is 20000U/g), 38 ℃ of temperature of reaction, obtain the enzymic catalytic reaction liquid that lipid acid short chain alcohol ester content is 83.4%-88.2%, then divide and evenly add 50% hydrogen peroxide 3kg altogether for ten times, every two hours add hydrogen peroxide one time, 40 ℃ of coreaction 24h, reaction finishes rear standing separation and goes out enzyme and unreacted hydrogen peroxide, boil off solvent, obtain epoxyfatty acid short chain alcohol ester crude product, after rectifying separation, obtaining epoxyfatty acid short chain alcohol ester product, oxirane value is at 4.0-6.0%.
Example 3: take sewer oil as raw material, use stirring reactor, sewer oil 10kg feeds intake, the short chain alcohol that adds theoretical molar ratio, oil weighs 2% lipase powder, sherwood oil is made solvent 10L, add water 0.4kg, 37 ℃ of temperature of reaction, stirring reaction 30h, short chain alcohol is divided 10 times and is added, every 3h, add once, finally obtain the enzymic catalytic reaction liquid that lipid acid short chain alcohol ester content is 82.4%-87.2%, then divide and evenly add 50% hydrogen peroxide 3kg altogether for ten times, every two hours add hydrogen peroxide one time, 40 ℃ of coreaction 24h, reaction finishes rear standing separation and goes out enzyme and unreacted hydrogen peroxide, boil off solvent, obtain epoxyfatty acid short chain alcohol ester crude product, after rectifying separation, obtaining epoxyfatty acid short chain alcohol ester product, oxirane value is at 4.0-6.0%.
Example 4: take soybean oil as raw material, use stirring reactor, the soybean oil that feeds intake 10kg, the short chain alcohol that adds theoretical molar ratio, toluene is made solvent 10L, oil weighs 3% lipase powder, add water 0.4kg, 39 ℃ of temperature of reaction, stirring reaction 30h, short chain alcohol is divided 10 times and is added, every 3h, add once, finally obtain the enzymic catalytic reaction liquid that lipid acid short chain alcohol ester content is 83.4%-88.2%, then divide and evenly add 50% hydrogen peroxide 3kg altogether for ten times, every two hours add hydrogen peroxide one time, 39 ℃ of coreaction 24h, reaction finishes rear standing separation and goes out enzyme and unreacted hydrogen peroxide, boil off solvent, obtain epoxyfatty acid short chain alcohol ester crude product, after rectifying separation, obtaining epoxyfatty acid short chain alcohol ester product, oxirane value is at 4.0-6.0%.
Example 5: take vegetable seed as raw material, use stirring reactor, the soybean oil that feeds intake 10kg, the short chain alcohol that adds theoretical molar ratio, toluene is made solvent 10L, oil weighs 3% lipase powder, add water 0.4kg, 39 ℃ of temperature of reaction, stirring reaction 30h, short chain alcohol is divided 10 times and is added, every 3h, add once, finally obtain the enzymic catalytic reaction liquid that lipid acid short chain alcohol ester content is 82.6%-90.2%, then divide and evenly add 50% hydrogen peroxide 3kg altogether for ten times, every two hours add hydrogen peroxide one time, 39 ℃ of coreaction 24h, reaction finishes rear standing separation and goes out enzyme and unreacted hydrogen peroxide, boil off solvent, obtain epoxyfatty acid short chain alcohol ester crude product, after rectifying separation, obtaining epoxyfatty acid short chain alcohol ester product, oxirane value is at 4.0-6.0%.
Example 6: take soybean oil as raw material, use stirring reactor, sewer oil 20kg feeds intake at every turn, the short chain alcohol that adds theoretical molar ratio, add water 2kg, immobilized lipase 1.5kg(enzyme activity is 20000U/g), 37 ℃ of temperature of reaction, obtain the enzymic catalytic reaction liquid that lipid acid short chain alcohol ester content is 84.5%-91.5%, then divide and evenly add 30% hydrogen peroxide 10kg altogether for ten times, every two hours add hydrogen peroxide one time, 40 ℃ of coreaction 24h, reaction finishes rear centrifugation and goes out enzyme and unreacted hydrogen peroxide, obtain epoxyfatty acid short chain alcohol ester product, oxirane value is at 4.0-6.0%.
Example 7: take lard as raw material, use stirring reactor, the soybean oil that feeds intake 10kg, the short chain alcohol that adds theoretical molar ratio, ethyl acetate is made solvent 10L, oil weighs 3% lipase powder, add water 0.4kg, 39 ℃ of temperature of reaction, stirring reaction 30h, short chain alcohol is divided 10 times and is added, every 3h, add once, finally obtain the enzymic catalytic reaction liquid that lipid acid short chain alcohol ester content is 81.6%-86.2%, then divide and evenly add 50% hydrogen peroxide 3kg altogether for ten times, every two hours add hydrogen peroxide one time, 39 ℃ of coreaction 24h, reaction finishes rear standing separation and goes out enzyme and unreacted hydrogen peroxide, boil off solvent, obtain epoxyfatty acid short chain alcohol ester crude product, after rectifying separation, obtaining epoxyfatty acid short chain alcohol ester product, oxirane value is at 4.0-5.0%.
Claims (8)
1. a method of utilizing biocatalysis to produce epoxyfatty acid short chain alcohol ester, it is characterized in that adopting lipid acid or bio-oil as vegetables oil, animal oil, waste cooking oil etc. be raw material production epoxyfatty acid short chain alcohol ester, Catalytic processes process comprises: biocatalysis esterification, two steps of biocatalysis epoxidation reaction, and detailed process and operating parameters are:
(1) biocatalysis esterification biocatalysis esterification completes in stirring reactor, it is characterized in that: adopt stirring reactor reaction, that biological catalyst is directly added in the stirring reactor that stock oil after pre-treatment is housed and carries out biocatalytic reaction, short chain alcohol adds several times, consumption is 1-1.5 times of theoretical reaction mol ratio, temperature of reaction is 32-55 ℃, reaction times is 35-40 hour, reaction can adopt solvent or solvent-free system, and in the reaction solution obtaining after biocatalysis esterification, lipid acid short chain alcohol ester content is 85%-97%;
(2) biocatalysis epoxidation reaction biocatalysis epoxidation reaction refers to that the short chain alcohol ester to obtaining after biocatalysis esterification carries out biocatalysis epoxidation, it is characterized in that: complete after biocatalysis esterification, in reaction solution, amount in batches and add based on the heavy 30%-50% hydrogen peroxide of oil, temperature of reaction 30-55 ℃, reaction times is 24h, and the epoxyfatty acid short chain alcohol ester oxirane value obtaining after biocatalysis epoxidation reaction is 4.0%-6.0%.
2. technique according to claim 1, adopt Biocatalysis method to produce epoxyfatty acid short chain alcohol ester, it is characterized in that first using biological catalyst to carry out esterification, then adopt biological catalyst to carry out epoxidation, two reaction process complete in same reactor, are finally isolated to epoxyfatty acid short chain alcohol ester product.
3. technique according to claim 1, it is characterized in that: described stock oil is lipid acid or bio-oil, bio-oil comprises Vegetable oil lipoprotein, animal grease, microbial oil, discards food oils Huo You factory oil refining pin material, and lipid acid comprises the unsaturated fatty acidss such as oleic acid, linolic acid, linolenic acid, Zoomeric acid.
4. technique according to claim 1, it is characterized in that the first step catalyzed reaction biological catalyst used is immobilized lipase, lipase powder, lipase liquid or lipase fermentation liquid, the 0.1%-10% that enzyme dosage is weight of oil, described biological catalyst lipase derives from microorganism or animal.
5. technique according to claim 1, is characterized in that: the superoxol that the hydrogen peroxide that second step biocatalysis epoxidation is used is 20-80% for massfraction.
6. technique according to claim 1, is characterized in that: reaction adopts stirring reactor, and it can single-stage batch operation, also can plural serial stage operate continuously.
7. technique according to claim 1, is characterized in that: whole biocatalysis process can be used solvent system, or solvent-free system, and the solvent that uses comprises sherwood oil, toluene, normal hexane, hexanaphthene, ethyl acetate.
8. technique according to claim 1, is characterized in that: it is methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol that reaction adopts short chain alcohol.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105543302A (en) * | 2016-01-25 | 2016-05-04 | 华南理工大学 | Preparing method for epoxy fatty glyceride |
| CN105693887A (en) * | 2016-03-08 | 2016-06-22 | 华南理工大学 | Preparation method of epoxidised polybutadiene |
| CN105861581A (en) * | 2016-05-10 | 2016-08-17 | 北京化工大学 | Method using biological catalyzing to synthesize epoxy oleic acid |
| CN106086094A (en) * | 2016-06-16 | 2016-11-09 | 江南大学 | A kind of method of enzymatic continuous synthesis geranyl propionate in organic phase |
| CN110669254A (en) * | 2019-11-06 | 2020-01-10 | 东莞深圳清华大学研究院创新中心 | Method for preparing epoxy plasticizer from waste grease |
| CN111073735A (en) * | 2019-10-23 | 2020-04-28 | 北京化工大学 | Method for preparing low-pour-point biological lubricating oil from green modified plant-based derived oil |
| CN111253995A (en) * | 2020-02-28 | 2020-06-09 | 上海壹萨化学科技有限公司 | Animal and vegetable oil high-pressure hydrolysis epoxidation modified additive for metal working fluid |
| CN113025369A (en) * | 2021-04-18 | 2021-06-25 | 重庆工商大学 | Method for preparing hydrocarbon fuel from dining and drinking waste oil |
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2014
- 2014-01-02 CN CN201410001434.3A patent/CN103740471A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105543302A (en) * | 2016-01-25 | 2016-05-04 | 华南理工大学 | Preparing method for epoxy fatty glyceride |
| CN105543302B (en) * | 2016-01-25 | 2020-08-18 | 华南理工大学 | Preparation method of epoxy fatty glyceride |
| CN105693887A (en) * | 2016-03-08 | 2016-06-22 | 华南理工大学 | Preparation method of epoxidised polybutadiene |
| CN105861581A (en) * | 2016-05-10 | 2016-08-17 | 北京化工大学 | Method using biological catalyzing to synthesize epoxy oleic acid |
| CN106086094A (en) * | 2016-06-16 | 2016-11-09 | 江南大学 | A kind of method of enzymatic continuous synthesis geranyl propionate in organic phase |
| CN106086094B (en) * | 2016-06-16 | 2019-11-08 | 江南大学 | A method of the continuous propionic acid synthesized geraniol ester of enzymatic in organic phase |
| CN111073735A (en) * | 2019-10-23 | 2020-04-28 | 北京化工大学 | Method for preparing low-pour-point biological lubricating oil from green modified plant-based derived oil |
| CN111073735B (en) * | 2019-10-23 | 2021-04-02 | 北京化工大学 | Method for preparing low-pour-point biological lubricating oil from green modified plant-based derived oil |
| CN110669254A (en) * | 2019-11-06 | 2020-01-10 | 东莞深圳清华大学研究院创新中心 | Method for preparing epoxy plasticizer from waste grease |
| WO2021088136A1 (en) * | 2019-11-06 | 2021-05-14 | 东莞深圳清华大学研究院创新中心 | Method for preparing epoxy plasticizer from waste oils and fats |
| CN111253995A (en) * | 2020-02-28 | 2020-06-09 | 上海壹萨化学科技有限公司 | Animal and vegetable oil high-pressure hydrolysis epoxidation modified additive for metal working fluid |
| CN113025369A (en) * | 2021-04-18 | 2021-06-25 | 重庆工商大学 | Method for preparing hydrocarbon fuel from dining and drinking waste oil |
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