CN102060812A - Method for preparing epoxy fatty acid methyl ester - Google Patents
Method for preparing epoxy fatty acid methyl ester Download PDFInfo
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- CN102060812A CN102060812A CN 201010608227 CN201010608227A CN102060812A CN 102060812 A CN102060812 A CN 102060812A CN 201010608227 CN201010608227 CN 201010608227 CN 201010608227 A CN201010608227 A CN 201010608227A CN 102060812 A CN102060812 A CN 102060812A
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- methyl ester
- acid methyl
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Abstract
The invention relates to an improved method for preparing epoxy fatty acid methyl ester, which is characterized in that a solid catalyst or a sodium bisulfate solid catalyst obtained by mixing 30-90 parts of sodium bisulfate, 10-50 parts of ferric sulfate and 0-20 parts of calcium sulfate is adopted in an epoxidation reaction. By using the solid catalyst, when catalytic activity of the solid catalyst corresponds to that of sulfuric acid, the reaction condition is temperate; the production safety is good; the obtained product has high epoxy value which can reach more than 3.5; the epoxidation temperature is reduced to a certain degree, for example, the reaction temperature can be reduced by about 10 DEG C; and because too high temperature is needless, the fatty acid eater is not easy to be carbonized; the obtained product has light and bright color and luster and can be directly used for a light-color product without a decolorization process; the yield is also enhanced; and particularly the corrosivity to equipment is greatly reduced, thereby reducing equipment investment, maintainance and replacement. Meanwhile, the solid catalyst is simpler than a liquid catalyst in use and recovery aspects and is friendly to environment.
Description
Technical field
The present invention is to the improvement of preparation epoxy aliphatic acid methyl ester method, relates in particular to a kind of employing complex vitriolate and makes Preparation of Catalyst epoxy aliphatic acid methyl ester method.
Background technology
Epoxy aliphatic acid methyl ester can substitute dioctyl phthalate (DOP) (DOP) effectively becomes a kind of non-toxic plasticizer.Be widely used in processing industries such as agricultural, film, cable, leatheroid, case, cultural goods, also can be used as the tensio-active agent and the dispersion agent of rubber item tenderizer and epoxy coating and Resins, epoxy etc.Its synthetic main employing has solvent method and solventless method.Solvent method brings pollution, long, big, the poor product quality of three wastes processing of Production Flow Chart to environment, is replaced by solventless method substantially.Solventless method mainly be with fatty acid ester, formic acid under the concentrated sulfuric acid catalyst effect with hydrogen peroxide in room temperature ~ 70 ℃ following stoichiometric number hour, reaction finishes the back and obtains product with alkali cleaning washing, drying, for example Chinese patent CN1966497 is described.Make the deficiency of Preparation of Catalyst epoxy aliphatic acid methyl ester with the vitriol oil, liquid vitriol oil severe corrosive, uses all inconveniently, and serious to equipment corrosion at storage, therefore will adopt the corrosion resisting alloy preparation that costs an arm and a leg, and equipment investment cost is higher; Secondly, the easy carbonization of fatty acid ester causes product colour darker in reaction process; Besides, phenomenon that the reaction fast speed is fast to be taken place easily " pot overflows ", production security is poor.
Chinese patent CN101235021 discloses the agent of employing heteropolyacid liquid phase catalysis, though reduced the corrosion of catalyzer to equipment, but contain heavy metal in the heteropolyacid liquid phase catalysis agent, can cause product heavy metal contamination, the wrapping material that can not be used for food, medicine, and the auxiliary agent of toy and home decoration material; Secondly, the heteropolyacid catalyst preparation is complicated, and technical process is long, the cost costliness.
Chinese patent CN101284821 epoxy aliphatic acid methyl ester preparation method adopts ionic-liquid catalyst.Ionic liquid is a hydrophilic salts, can produce inorganic solution in the epoxidation process, reduce its catalytic effect, thereby the gained oxirane value is lower.
Chinese patent CN101139328 novel process for synthesizing epoxy aliphatic acid methyl ester adopts magnetic catalyst.Magnetic catalyst its objective is the solution catalyst separating, but prepares more complicated equally, the cost height.
Chinese patent CN101591588 epoxy soybean oil or epoxyfatty acid first (second) ester preparation method adopt organic rhenium oxide to make catalyzer, and urea peroxide provides oxygen source, do not use protonic acid and carboxylic acid to transmit Sauerstoffatom.This legal system is equipped with complicated cost height.
By above-mentioned prior art as can be known, the preparation epoxy aliphatic acid methyl ester, technological line is basic identical, all is to adopt fatty acid ester, formic acid (organic acid) to carry out epoxidation reaction with hydrogen peroxide under catalyst action.Therefore catalyzer is selected, but becomes preparation epoxy aliphatic acid methyl ester changing factor, it and preparation cost, and equipment requirements, product quality etc. directly are related, and therefore select more economically, help improving the quality catalyzer and are pursued by people.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, provides a kind of not only speed of response fast, product oxirane value height, and also little to equipment corrosion, the epoxy aliphatic acid methyl ester preparation method that preparation cost is low.
The object of the invention realizes, the main improvement is through a large amount of test and Selection, composite solid catalyzer or sodium pyrosulfate solid catalyst that employing is made up of sodium pyrosulfate, ferric sulfate, calcium sulfate, the concentrated sulfuric acid catalyst that replaces prior art to use, thereby overcome the deficiencies in the prior art, realize the object of the invention.Specifically, epoxy aliphatic acid methyl ester preparation method of the present invention, comprise fatty acid ester and hydrogen peroxide, formic acid and/or acetate, epoxidation reaction under catalyst, it is characterized in that said catalyzer for by sodium pyrosulfate, ferric sulfate, calcium sulfate by 30-90 part: 10-50 part: 0-20 part is mixed gained solid catalyst or sodium pyrosulfate solid catalyst.
Among the present invention.
Ester fat acid ester, same as the prior art, be meant the alcohol reaction gained ester fat acid ester that comprises acid of carbon atom 8-24 ester fat and 1-8 carbon, for example can be ester fatty acid methyl esters, ester fat acetoacetic ester, ester fat acid butyl ester, the misery ester of ester fat.Wherein be preferably and adopt the ester fatty acid methyl esters, for example iodine value is greater than 80 fatty acid methyl esters (biofuel), products obtained therefrom oxirane value height, quality product height.
Solid catalyst, sodium pyrosulfate, ferric sulfate, calcium sulfate mixing composite catalyst are relatively selected in test, or the sodium pyrosulfate solid catalyst, wherein are preferably three kinds of blended composite catalysts, have better catalytic efficiency.
Epoxidation reaction, basic identical with existing preparation epoxy aliphatic acid methyl ester epoxidation reaction (particularly sulfuric acid epoxidation), by ester fat acid ester, hydrogen peroxide, formic acid and/or the acetate epoxidation reaction under catalyst, raw material and catalyst levels, also similar substantially with prior art, for example ester fat acid ester is 100 parts, hydrogen peroxide (concentration is 30%-60wt%) 30-60 part, formic acid and/or acetate 2-30 part, catalyzer 0.5-5 part, in room temperature ~ 70 ℃, reaction times 0.1-10h, atmospheric pressure or under pressure reaction.The aftertreatment of products therefrom also with existing identical, for example with the epoxy aliphatic acid methyl ester alkali cleaning twice that makes, washes twice, drying or vacuum-drying.Wherein the better consumption of catalyzer is 0.5-1.5 part.In epoxidation reaction, the hydrogen peroxide concentration height helps obtaining the high product of oxirane value, but reaction low concentration fierceness, control is difficulty relatively.
With common chemical reaction, the interval value that the present invention provides not is the accurate end value of mathematical concept, and the association that is test and Selection is when interval, and suitably departing from end value is not cannot.
Epoxy aliphatic acid methyl ester preparation method of the present invention, with respect to prior art, owing to adopt solid catalyst (sodium pyrosulfate or sodium pyrosulfate and ferric sulfate and calcium sulfate composite catalyst), substitute concentrated sulfuric acid catalyst, at catalytic activity and sulfuric acid mutually instantly, the reaction conditions gentleness, production security is good, and has reduced the epoxidation temperature to a certain extent, for example can reduce about 10 ℃ of temperature of reaction, owing to do not need too high-temperature, fatty acid ester is difficult for carbonization, and the products obtained therefrom lighter color is bright, can be directly used in light goods, and the processing of needn't decolouring, yield also has raising.Particularly greatly reduce, thereby reduced facility investment and maintain and replace equipment corrosion.Simultaneously solid catalyst use and reclaim simple than liquid type, environmental friendliness.The inventive method is simple, easy handling, and products therefrom oxirane value height can reach more than 3.5, and the reaction times is short, both can reduce the preparation energy, can reduce preparation cost again.
Below in conjunction with several specific embodiments; essence of the present invention is further understood in exemplary illustration and help; but the embodiment detail only is for the present invention is described; do not represent the present invention to conceive whole technical schemes down; therefore should not be construed as the total technical scheme of the present invention is limited; some are In the view of the technician; the unsubstantiality that does not depart from the present invention's design increases and/or change; for example simple the change or replacement of technical characterictic to have same or similar technique effect all belongs to protection domain of the present invention.
Embodiment
Embodiment 1: with the formic acid of 100g fatty acid methyl ester, 4g and the complex vitriolate of 2g (sodium pyrosulfate: ferric sulfate: the thorough mixing of calcium sulfate=60:30:10).Stirring is warming up to 60 ℃, the hydrogen peroxide of the 30wt% of Dropwise 5 0g, per 10 seconds one.Be incubated 2 hours, stopped reaction, static layering is told the catalyzer of lower floor, and adding yellow soda ash in the upper organic phase, to be washed till pH value be 6.5-7.5, and drying obtains epoxy aliphatic acid methyl ester, and yield 99% records product oxirane value 4.0.
Embodiment 2: with the formic acid of 100g fatty acid methyl ester, 10g and the complex vitriolate of 2g (sodium pyrosulfate: ferric sulfate: the thorough mixing of calcium sulfate=70:25:5).Stirring is warming up to 65 ℃, the hydrogen peroxide of the 30wt% of Dropwise 5 0g, per 10 seconds one.Be incubated 3 hours, record product oxirane value 4.4.Stopped reaction is removed catalyzer, obtains epoxy aliphatic acid methyl ester after alkali cleaning washing, the vacuum-drying, yield 101%.
Embodiment 3: with the formic acid of 100g fatty acid methyl ester, 8g and the complex vitriolate of 2g (sodium pyrosulfate: ferric sulfate: the thorough mixing of calcium sulfate=60:25:15).Stirring is warming up to 60 ℃, drips the hydrogen peroxide of the 30wt% of 40g, per 10 seconds one.Be incubated 4 hours, record product oxirane value 3.9.Stopped reaction is removed catalyzer, obtains epoxy aliphatic acid methyl ester after alkali cleaning washing, the vacuum-drying, yield 98%.
Embodiment 4: with the formic acid of 100g fatty acid methyl ester, 8g and the complex vitriolate of 0.5g (sodium pyrosulfate: ferric sulfate: the thorough mixing of calcium sulfate=35:45:20).Stirring is warming up to 55 ℃, drips 50% the hydrogen peroxide of 30g, per 10 seconds one.Be incubated 3 hours, record product oxirane value 3.3.Stopped reaction is removed catalyzer, obtains epoxy aliphatic acid methyl ester after alkali cleaning washing, the vacuum-drying, yield 97%.
Embodiment 5: with the acetate of 100g fatty acid methyl ester, 20g and the complex vitriolate of 1g (sodium pyrosulfate: ferric sulfate: the thorough mixing of calcium sulfate=50:35:15).Stirring is warming up to 65 ℃, 30% the hydrogen peroxide of Dropwise 5 0g, per 10 seconds one.Be incubated 4 hours, record product oxirane value 3.9.Stopped reaction is removed catalyzer, obtains epoxy aliphatic acid methyl ester after alkali cleaning washing, the vacuum-drying, yield 98%.
Embodiment 6: with the acetate of 100g fatty acid methyl ester, 28g and the complex vitriolate of 3g (sodium pyrosulfate: ferric sulfate: the thorough mixing of calcium sulfate=70:25:5).Stirring is warming up to 65 ℃, drips 30% the hydrogen peroxide of 60g, per 10 seconds one.Be incubated 4 hours, record product oxirane value 4.4.Stopped reaction is removed catalyzer, obtains epoxy aliphatic acid methyl ester after alkali cleaning washing, the vacuum-drying, yield 102%.
Embodiment 7: with the formic acid of 100g fatty acid butyl ester, 10g and the complex vitriolate of 2g (sodium pyrosulfate: ferric sulfate: the thorough mixing of calcium sulfate=80:20:0).Stirring is warming up to 70 ℃, 30% the hydrogen peroxide of Dropwise 5 0g, per 10 seconds one.Be incubated 4 hours, record product oxirane value 3.2.Stopped reaction is removed catalyzer, obtains epoxy aliphatic acid methyl ester after alkali cleaning washing, the vacuum-drying, yield 97%.
Embodiment 8: with the formic acid of 100g lipid acid monooctyl ester, 10g and the sodium pyrosulfate thorough mixing of 5g.Stirring is warming up to 55 ℃, drips 50% the hydrogen peroxide of 30g, per 10 seconds one.Be incubated 4 hours, record product oxirane value 3.0.Stopped reaction is removed catalyzer, obtains epoxy aliphatic acid methyl ester after alkali cleaning washing, the vacuum-drying, yield 97%.
By embodiment, temperature of reaction improves, hydrogen peroxide concentration improves, catalyst levels adds, and helps fast reaction speed, improves oxirane value.
Comparative example: with the formic acid of 100g fatty acid methyl ester, 4g and the 98wt% vitriol oil thorough mixing of 0.1g.Stirring is warming up to 70 ℃, the hydrogen peroxide of the 30wt% of Dropwise 5 0g, per 10 seconds one.Be incubated 4 hours, record product oxirane value 4.0.Stopped reaction is removed catalyzer, obtains epoxy aliphatic acid methyl ester after alkali cleaning washing, the vacuum-drying, and yield 98%, color slightly are deeper than embodiment 1.
To those skilled in the art; under this patent design and specific embodiment enlightenment; some distortion that can directly derive or associate from this patent disclosure and general knowledge; those of ordinary skills will recognize also can adopt additive method; or the substituting of known technology commonly used in the prior art; and the equivalence of feature changes or modification; mutual various combination between feature; for example raw material can also adopt fatty-acid ethyl ester; fatty acid butyl ester; the lipid acid monooctyl ester; the change of hydrogen peroxide concentration; or the like unsubstantiality change; can be employed equally; can both realize this patent representation function and effect, launch for example no longer one by one to describe in detail, all belong to this patent protection domain.
Claims (4)
1. epoxy aliphatic acid methyl ester preparation method, comprise fatty acid ester and hydrogen peroxide, formic acid and/or acetate, epoxidation reaction under catalyst, it is characterized in that said catalyzer for by sodium pyrosulfate, ferric sulfate, calcium sulfate by 30-90 part: 10-50 part: 0-20 part is mixed gained solid catalyst or sodium pyrosulfate solid catalyst.
2. according to the described epoxy aliphatic acid methyl ester preparation method of claim 1, it is characterized in that mixed catalyst consumption 0.5-1.5 part.
3. according to claim 1 or 2 described epoxy aliphatic acid methyl ester preparation methods, it is characterized in that fatty acid ester is a fatty acid methyl ester.
4. according to the described epoxy aliphatic acid methyl ester preparation method of claim 3, it is characterized in that the fatty acid methyl ester iodine value is greater than 80.
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| CN2010106082276A CN102060812B (en) | 2010-12-28 | 2010-12-28 | Method for preparing epoxy fatty acid methyl ester |
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| CN2010106082276A CN102060812B (en) | 2010-12-28 | 2010-12-28 | Method for preparing epoxy fatty acid methyl ester |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103045323A (en) * | 2012-12-11 | 2013-04-17 | 福建达安能源实业有限责任公司 | Preparation method for environment-friendly lubricant through oxosynthesis of hexadecanoic acid methyl ester epoxy |
| CN103111332A (en) * | 2013-03-05 | 2013-05-22 | 安徽天意环保科技有限公司 | Catalyst for preparation of epoxy plasticizers |
| CN104557796A (en) * | 2015-01-21 | 2015-04-29 | 吴俊荣 | Preparation method of epoxidized fatty acid methyl ester |
| CN104592171A (en) * | 2015-01-21 | 2015-05-06 | 吴俊荣 | Production method of epoxy fatty acid methyl ester |
| US10093636B2 (en) | 2016-08-05 | 2018-10-09 | Cpc Corporation, Taiwan | Method for synthesizing bio-plasticizers using acidic ionic liquids as catalysts |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919905A (en) * | 2006-09-04 | 2007-02-28 | 罗春妹 | Preparation method of nontoxic plasticizer |
| CN101774985A (en) * | 2010-02-05 | 2010-07-14 | 江苏工业学院 | Method for preparing epoxidized methyl acetorieinoleate |
-
2010
- 2010-12-28 CN CN2010106082276A patent/CN102060812B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919905A (en) * | 2006-09-04 | 2007-02-28 | 罗春妹 | Preparation method of nontoxic plasticizer |
| CN101774985A (en) * | 2010-02-05 | 2010-07-14 | 江苏工业学院 | Method for preparing epoxidized methyl acetorieinoleate |
Non-Patent Citations (1)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 20100815 杨华 脂肪酸甲酯环氧化反应及催化体系研究 第4.2.1,4.2.2和4.3.3.2节 1,3,4 , 第8期 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103045323A (en) * | 2012-12-11 | 2013-04-17 | 福建达安能源实业有限责任公司 | Preparation method for environment-friendly lubricant through oxosynthesis of hexadecanoic acid methyl ester epoxy |
| CN103111332A (en) * | 2013-03-05 | 2013-05-22 | 安徽天意环保科技有限公司 | Catalyst for preparation of epoxy plasticizers |
| CN104557796A (en) * | 2015-01-21 | 2015-04-29 | 吴俊荣 | Preparation method of epoxidized fatty acid methyl ester |
| CN104592171A (en) * | 2015-01-21 | 2015-05-06 | 吴俊荣 | Production method of epoxy fatty acid methyl ester |
| CN104557796B (en) * | 2015-01-21 | 2016-06-29 | 吴俊荣 | The preparation method of epoxy aliphatic acid methyl ester |
| US10093636B2 (en) | 2016-08-05 | 2018-10-09 | Cpc Corporation, Taiwan | Method for synthesizing bio-plasticizers using acidic ionic liquids as catalysts |
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| CN102060812B (en) | 2012-07-25 |
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