CN104561149A - Method for preparing epoxidized soybean oil by using lipase catalysis - Google Patents
Method for preparing epoxidized soybean oil by using lipase catalysis Download PDFInfo
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- 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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Abstract
The invention discloses a method for preparing epoxidized soybean oil by using lipase catalysis. The method comprises the following steps: uniformly mixing the following components in parts by weight: 150-250 parts of soybean oil, 1-3 parts of organic acid, 1-3 parts of a surfactant and 3-8 parts of lipase, stirring and heating to the temperature of 20-22 DEG C; adding 10-14 weight parts of urea hydrogen peroxide, reacting for 5-8 hours, sampling, centrifuging, performing alkali wash, washing, and finally performing calcium chloride drying, thereby obtaining the epoxidized soybean oil product. According to the method disclosed by the invention, the urea hydrogen peroxide serves as an oxygen source, and the epoxidized soybean oil is prepared by using a lipase catalysis reaction, so that high epoxy value is obtained from the reaction, the enzyme maintains high activity and is difficult to inactivate, the reaction conditions are mild, the energy consumption is low, the catalytic reaction is high in specificity, byproducts are difficult to produce, and the product is high in purity and environment-friendly.
Description
Technical field
The present invention relates to the preparing technical field of epoxy soybean oil, be specifically related to a kind of be oxygen source with urea hydrogen peroxide, utilize the lipase-catalyzed method preparing epoxy soybean oil.
Background technology
Plant oil based softening agent utilizes crude vegetal, carries out structural transformation by functional group reactions glyceryl ester, to improve the object of vegetables oil and PVC consistency.The achievement in research mainly epoxidation grease of current this respect.Epoxy soybean oil is domestic and international Application and Development a kind of epoxy plasticizer comparatively early, is widely used in PVC field.Sustained production increases in recent years, is only second to phthalic acid and fatty group dibasic acid, accounts for the 3rd of consumption at the consumption of U.S.'s epoxy plasticizer.Epoxy soybean oil not only has plastification to PVC, and the active chlorine atom of degrading out because of light and heat can be absorbed rapidly, play stable effect, its in goods water tolerance and oil-proofness good, the PVC product of its plasticising has the performances such as fast light, hot, anti-aging, shock-resistant, folding.With in soft, the boardy product of epoxy soybean oil plasticising, not only can improve the price of goods, and corresponding raising is all had to the processing characteristics of PVC product and physicals.
The research of epoxidized vegetable oil both domestic and external comprises epoxy soybean oil, oleum lini, Rice pollard oil, sunflower seed oil, Viscotrol C, Oleum Gossypii semen, Sunflower Receptacle wet goods.China's epoxidized vegetable oil class softening agent is mainly based on epoxy soybean oil, and other kinds such as epoxidized linseed oil, epoxy cottonseed oil etc. are not well developed.Because China's oil resource enriches, kind is more, particularly the output of soybean oil is in the prostatitis of countries in the world, therefore Speeding Up The Advancement of technology is answered by domestic production enterprise, improve synthesis technique, production equipment, the reduction production cost of suitability for industrialized production epoxy soybean oil, to meet the demand of plastic working industry.Also large quantifier elimination has been carried out abroad for plant oil based.Be wherein the GrindstedSoft-N-Safe of vegetables oil synthesis with main raw material by Danish company, this softening agent has been listed in the leading product of softening agent by European Union, go through to use in food association area, the U.S. also formally comes into operation the beginning of the year this softening agent product.
The conventional epoxy method of Vegetable oil lipoprotein can be divided into solvent method and solventless method.Solvent method due to solvent for use be benzene, environment vulnerable to pollution, and Production Flow Chart is long, equipment is many, three-protection design amount is large, poor product quality, is therefore substantially eliminated.Solventless method Production Flow Chart is short, and temperature of reaction is low, and the reaction times is short, and by product is few, and quality product is high, substantially the production technique of replace solvents method.
Oxygen source the most frequently used in chemical method and enzyme process is aqueous hydrogen peroxide solution.But utilize aqueous hydrogen peroxide solution easily to cause ring-opening reaction in chemical method, easily enzyme deactivation is caused in enzyme process reaction, and the oxygen level of aqueous hydrogen peroxide solution is low, poor stability, the release rate of hydrogen peroxide is too fast besides, be difficult to control, cause severe reaction conditions, easily produce by product, epoxidation reaction poor effect, awaits further improvement.In recent years, have been reported and utilize urea hydrogen peroxide to substitute aqueous hydrogen peroxide solution to provide oxygen source in the epoxidation.Compared to other inorganic peroxides, the oxygen level of urea hydrogen peroxide is higher, stability is higher, action time is longer, substitutes the epoxidation that aqueous hydrogen peroxide solution is applied to fatty acid ester can improve the selectivity of reaction and the stability of enzyme with urea hydrogen peroxide.Application number be 201210512531.X to patent discloses a kind of take crude oil of soybean as the method for raw material production epoxy soybean oil, the method uses acid as catalyzer, urea peroxide is as a kind of oxygen source, epoxy soybean oil is obtained by reacting under the reaction conditions of 50 ~ 100 DEG C, this reaction due to temperature of reaction high, long reaction time, causes severe reaction conditions, production energy consumption is high, is unfavorable for commercial scale production.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of lipase-catalyzed method preparing epoxy soybean oil, and the method reaction conditions is gentle, and production energy consumption is low, and catalyzed reaction high specificity, not easily produces by product, to eliminate defect in above-mentioned background technology.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of lipase-catalyzed method preparing epoxy soybean oil, comprise the following steps: soybean oil, organic acid, tensio-active agent and the lipase ratio of weight and number according to 150 ~ 250 parts: 1 ~ 3 part: 1 ~ 3 part: 3 ~ 8 parts is mixed, stirring is warming up to 20 ~ 22 DEG C, then urea hydrogen peroxide 10 ~ 14 weight part is added, after reaction 5 ~ 8h, sampling, then centrifugal, alkali cleaning washes, and last calcium chloride drying obtains epoxy soybean oil production.
As preferred a kind of technical scheme, described organic acid is at least one in stearic acid and palmitinic acid.
As preferred a kind of technical scheme, described soybean oil is crude oil of soybean.
As preferred a kind of technical scheme, described tensio-active agent is at least one in polysorbas20, polysorbate40, polysorbate60, tween 80, span 20, sorbester p18, sorbester p17, tartrate and Seignette salt.
As preferred a kind of technical scheme, the urea hydrogen peroxide used in the preparation method of described epoxy soybean oil is adopted and is prepared with the following method: be in the superoxol of 25 ~ 50% in mass concentration, add the stablizer EDTA of 0.1 ~ 0.3wt%, start stirring, after it dissolves completely, add urea, the mol ratio of described urea and hydrogen peroxide is 1:1 ~ 1.2, under constantly stirring, be heated to 30 ~ 35 DEG C, treat that urea dissolves completely, insulation reaction 20 ~ 30min, then be cooled to less than-5 DEG C and carry out crystallization 4 ~ 6h, white crystal is obtained after suction filtration, dry 2h at 50 ~ 80 DEG C, obtain described urea hydrogen peroxide.
As preferred a kind of technical scheme, the washing after described centrifugal, alkali cleaning comprises at least three washings.
As preferred a kind of technical scheme, described lipase is candiyeast 99-125 lipase.
Lipase is one of important industrial enzyme agent kind, can the reaction such as catalysis solution fat, transesterify, Lipase absobed, is widely used in the industry such as fats and oils processing, food, medicine, daily use chemicals.
Soybean oil contains more unsaturated double-bond, under the existence of lipase, and organic acid and H
2o
2reaction generates peroxide organic acid, and peroxide organic acid reacts with the unsaturated double-bond in epoxy soybean oil immediately, generates epoxy soybean oil.Principal reaction can be expressed as:
(1) epoxy agent preparation feedback
(2) epoxy reaction
Owing to have employed technique scheme, the invention has the beneficial effects as follows:
The lipase-catalyzed method preparing epoxy soybean oil of the present invention, by soybean oil, organic acid, tensio-active agent and lipase mix according to the ratio of weight and number of 150 ~ 250 parts: 1 ~ 3 part: 1 ~ 3 part: 3 ~ 8 parts, stirring is warming up to 20 ~ 22 DEG C, then urea hydrogen peroxide 10 ~ 14 weight part is added, after reaction 5 ~ 8h, sampling, centrifugal, then alkali cleaning washes, last calcium chloride drying obtains epoxy soybean oil production, reaction is catalyzer with lipase, reaction just can be carried out under the temperature condition of 20 ~ 22 DEG C, reaction conditions is gentle, energy consumption is low, catalyzed reaction high specificity, not easily produce by product, product purity is high, environmentally friendly.
Enzymic catalytic reaction, compared with acid catalyzed reaction of the prior art, has the advantage that the specificity of selectivity and reaction is strong, therefore there will not be the by product of over oxidation.But because epoxy soybean oil itself is a kind of mixture, therefore generally detect data and directly can not demonstrate this point.Only just reaction itself, the reaction of acid catalysis epoxy soybean oil after 6 hours oxirane value starts to decline, in 4 ~ 6 hours, even can be reduced to 0; Even and if enzymatic product continues to maintain reaction conditions 24 hours, oxirane value also can not reduce, can the selectivity of the specificity of indirect proof enzymic catalytic reaction and product high.
The present invention adds urea hydrogen peroxide as oxygen source, makes reaction obtain higher oxirane value and can make the activity that enzyme keeps higher, not easy in inactivation.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Be in the superoxol of 30% in mass concentration, add the stablizer EDTA of 0.15wt%, start stirring, after it dissolves completely, add urea, the mol ratio of described urea and hydrogen peroxide is 1:1.1, under constantly stirring, be heated to 32 DEG C, treat that urea dissolves completely, insulation reaction 25min, then be cooled to-5 DEG C and carry out crystallization 4h, obtain white crystal after suction filtration, at 50 DEG C, dry 2h, obtains urea hydrogen peroxide.
Embodiment 2
Be in the superoxol of 40% in mass concentration, add the stablizer EDTA of 0.25wt%, start stirring, after it dissolves completely, add urea, the mol ratio of described urea and hydrogen peroxide is 1:1.1, under constantly stirring, be heated to 35 DEG C, treat that urea dissolves completely, insulation reaction 30min, then be cooled to-5 DEG C and carry out crystallization 5h, obtain white crystal after suction filtration, at 60 DEG C, dry 2h, obtains urea hydrogen peroxide.
Embodiment 3
By 200g crude oil of soybean, 1g stearic acid, 1g palmitinic acid, 1g polysorbas20,1g sorbester p17, mix with 5g lipase, stirring is warming up to 20 DEG C, then urea hydrogen peroxide 10g is added, after reaction 5h, sampling, centrifugal, alkali cleaning and three washings, last calcium chloride drying obtains epoxy soybean oil production.
Embodiment 4
By 180g crude oil of soybean, 1.5g stearic acid, 1g span 20,0.5g tartrate, and 4g lipase mixes, and stirs and is warming up to 22 DEG C, then urea hydrogen peroxide 12g is added, after reaction 6h, sampling, centrifugal, alkali cleaning and three washings, last calcium chloride drying obtains epoxy soybean oil production.
Embodiment 5
Adopt candiyeast 99-125 lipase, by 220g crude oil of soybean, 1g stearic acid, 1.5g palmitinic acid, 1g polysorbate40,1g sorbester p17,1g tartrate, mix with 6g lipase, stirring is warming up to 22 DEG C, then the urea hydrogen peroxide 14g that embodiment 1 prepares is added, after reaction 5.5h, sampling, centrifugal, alkali cleaning and three washings, last calcium chloride drying obtains epoxy soybean oil production.
Embodiment 6
Be in the superoxol of 45% in mass concentration, add the stablizer EDTA of 0.3wt%, start stirring, after it dissolves completely, add urea, the mol ratio of described urea and hydrogen peroxide is 1:1.2, under constantly stirring, be heated to 33 DEG C, treat that urea dissolves completely, insulation reaction 25min, then be cooled to less than-5 DEG C and carry out crystallization 4h, obtain white crystal after suction filtration, at 55 DEG C, dry 2h, obtains urea hydrogen peroxide.
Adopt candiyeast 99-125 lipase, by 150g crude oil of soybean, 0.5g stearic acid, 0.5g palmitinic acid, 0.8g sorbester p18,0.5g Seignette salt, mix with 4g lipase, stirring is warming up to 20 DEG C, then the above-mentioned urea hydrogen peroxide 12g prepared is added, after reaction 5h, sampling, then centrifugal, alkali cleaning and three washings wash, and last calcium chloride drying obtains epoxy soybean oil production.
The performance index of the epoxy soybean oil production that above embodiment 3-6 prepares are in table 1.
Table 1
| Project | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Color and luster | 40B | 35B | 30B | 25B |
| Oxirane value | 5.5 | 5.8 | 6.0 | 6.2 |
| Acid number | 1.0mgKOH/g | 0.8mgKOH/g | 0.6mgKOH/g | 0.5mgKOH/g |
Claims (6)
1. the lipase-catalyzed method preparing epoxy soybean oil, it is characterized in that comprising the following steps: soybean oil, organic acid, tensio-active agent and the lipase ratio of weight and number according to 150 ~ 250 parts: 1 ~ 3 part: 1 ~ 3 part: 3 ~ 8 parts is mixed, stirring is warming up to 20 ~ 22 DEG C, then urea hydrogen peroxide 10 ~ 14 weight part is added, after reaction 5 ~ 8h, then centrifugal, alkali cleaning washes, and final drying obtains epoxy soybean oil production.
2. the lipase-catalyzed method preparing epoxy soybean oil as claimed in claim 1, is characterized in that: described organic acid is at least one in stearic acid and palmitinic acid.
3. the lipase-catalyzed method preparing epoxy soybean oil as claimed in claim 1, is characterized in that: described soybean oil is crude oil of soybean.
4. the lipase-catalyzed method preparing epoxy soybean oil as claimed in claim 1, is characterized in that: described tensio-active agent is at least one in polysorbas20, polysorbate40, polysorbate60, tween 80, span 20, sorbester p18, sorbester p17, tartrate and Seignette salt.
5. the lipase-catalyzed method preparing epoxy soybean oil as described in any one of Claims 1-4, it is characterized in that described urea hydrogen peroxide is adopted to prepare with the following method: be in the superoxol of 25 ~ 50% in mass concentration, add the stablizer EDTA of 0.1 ~ 0.3wt%, start stirring, after it dissolves completely, add urea, the mol ratio of described urea and hydrogen peroxide is 1:1 ~ 1.2, under constantly stirring, be heated to 30 ~ 35 DEG C, treat that urea dissolves completely, insulation reaction 20 ~ 30min, then be cooled to less than-5 DEG C and carry out crystallization 4 ~ 6h, white crystal is obtained after suction filtration, dry at 50 ~ 80 DEG C, obtain described urea hydrogen peroxide.
6. the lipase-catalyzed method preparing epoxy soybean oil as claimed in claim 5, is characterized in that: the washing after described centrifugal, alkali cleaning comprises at least three washings.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105062695A (en) * | 2015-07-08 | 2015-11-18 | 中国科学院嘉兴材料与化工技术工程中心 | Method for preparing environment-friendly flexibilizer by use of normal-temperature plasma |
| CN105693887A (en) * | 2016-03-08 | 2016-06-22 | 华南理工大学 | Preparation method of epoxidised polybutadiene |
| CN114058650A (en) * | 2021-11-16 | 2022-02-18 | 北京化工大学 | Method for preparing epoxy vegetable oil by double-enzyme coupling reaction system |
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| CN102864021A (en) * | 2012-09-26 | 2013-01-09 | 山东吉青化工有限公司 | Epoxidation vegetable oil preparation method |
| CN103088082A (en) * | 2013-01-16 | 2013-05-08 | 闭美娥 | Method for preparing epoxidized fatty acid methyl ester through lipase catalysis |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102864021A (en) * | 2012-09-26 | 2013-01-09 | 山东吉青化工有限公司 | Epoxidation vegetable oil preparation method |
| CN103088082A (en) * | 2013-01-16 | 2013-05-08 | 闭美娥 | Method for preparing epoxidized fatty acid methyl ester through lipase catalysis |
Non-Patent Citations (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105062695A (en) * | 2015-07-08 | 2015-11-18 | 中国科学院嘉兴材料与化工技术工程中心 | Method for preparing environment-friendly flexibilizer by use of normal-temperature plasma |
| CN105693887A (en) * | 2016-03-08 | 2016-06-22 | 华南理工大学 | Preparation method of epoxidised polybutadiene |
| CN114058650A (en) * | 2021-11-16 | 2022-02-18 | 北京化工大学 | Method for preparing epoxy vegetable oil by double-enzyme coupling reaction system |
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Application publication date: 20150429 |