CN103382415A - Production method of epoxidized fatty acid methyl ester/epoxidized soybean oil - Google Patents
Production method of epoxidized fatty acid methyl ester/epoxidized soybean oil Download PDFInfo
- Publication number
- CN103382415A CN103382415A CN2013100133691A CN201310013369A CN103382415A CN 103382415 A CN103382415 A CN 103382415A CN 2013100133691 A CN2013100133691 A CN 2013100133691A CN 201310013369 A CN201310013369 A CN 201310013369A CN 103382415 A CN103382415 A CN 103382415A
- Authority
- CN
- China
- Prior art keywords
- soybean oil
- methyl ester
- acid methyl
- hydrogen peroxide
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 235000012424 soybean oil Nutrition 0.000 title claims abstract description 45
- 239000003549 soybean oil Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 235000019387 fatty acid methyl ester Nutrition 0.000 title claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 62
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000004593 Epoxy Substances 0.000 claims abstract description 49
- 235000019253 formic acid Nutrition 0.000 claims abstract description 26
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 150000004702 methyl esters Chemical class 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- 125000001931 aliphatic group Chemical group 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract 1
- 239000004902 Softening Agent Substances 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
Abstract
The invention relates to a production method of epoxidized fatty acid methyl ester/epoxidized soybean oil. The production method concretely comprises the following technological steps: (1) taking one of soybean oil and fatty acid methyl ester, formic acid and hydrogen peroxide and preheating them to 90+/-2 DEG C; and (2) adding preheated soybean oil, formic acid and hydrogen peroxide into a pipeline reactor to react until the end of the reaction. According to the invention, by the utilization of the pipeline reactor, the technical bias that a high concentration of hydrogen peroxide cannot be used in a traditional epoxidized soybean oil production technology is overcome; by the use of 70% high concentration of hydrogen peroxide in the production process, the reaction time is greatly shortened, and the yield is substantially raised. In addition, by the use of a high concentration of hydrogen peroxide and a high proportion of formic acid, the reaction speed is fast, side reaction is less, epoxy value of the produced epoxidized soybean oil/epoxidized fatty acid methyl ester is remarkably raised, color is obviously improved, and transparency is better.
Description
Technical field
The present invention relates to a kind of production method of epoxy aliphatic acid methyl ester/epoxy soybean oil.
Background technology
Epoxy soybean oil is a kind of most popular nontoxic polyvinyl chloride softening agent stablizer of holding concurrently.Have good thermostability and light stability, water tolerance and oil-proofness are also good, can give the good physical strength of goods, weathering resistance and electrical property, and nontoxicity, are the chemical technology auxiliary agents that is used for packaging material for food of international population.The epoxy aliphatic acid methyl ester softening agent not only can replace the DOP softening agent to produce PVC product nontoxic, environmental protection wholly or in part, be used for food product pack, medical article material, toy and water supply line etc., simultaneously also as celluosic resin and elastomeric non-toxic plasticizer and tenderizer, in the processing of goods, adding epoxy aliphatic acid methyl ester can obviously improve the physicals of goods and extend digestion time, with metal(lic)stabilizer and used times such as barium, cadmium, zinc, good synergy is arranged.In addition, because it also has good oilness, consistency and dispersion performance, go back useful as surfactants and application of dispersant in production industries such as epoxy coating and epoxy resin
The most of raw material that adopts of the production process of at present domestic epoxy methyl esters/epoxy soybean oil adds reactor, be heated to drip hydrogen peroxide behind 50 ℃ of left and right, and the concentration of hydrogen peroxide is the raw material of 25～50%, 10 cubes, about 8 hours reaction times, because the reaction times is long, in reaction process side reaction is more, so the product oxirane value is not high, epoxy soybean oil 6.3 left and right, epoxy methyl esters 3.8 left and right, product color is poor partially yellow.
Summary of the invention
The objective of the invention is to solve above-mentioned deficiency, the production method of short, quantity-produced epoxy aliphatic acid methyl ester/epoxy soybean oil of a kind of reaction times is provided.
The technical scheme that realizes the object of the invention is a kind of production method of epoxy aliphatic acid methyl ester/epoxy soybean oil, specifically comprises following processing step: one of get in soybean oil and fatty acid methyl ester (1), formic acid, hydrogen peroxide are preheated to 90 ± 2 ℃; (2) will add through soybean oil, formic acid and the hydrogen peroxide of preheating pipeline reactor internal reaction to reaction to finish.
The production method of above-mentioned epoxy aliphatic acid methyl ester/epoxy soybean oil, the concentration of described hydrogen peroxide are 70%.
The production method of above-mentioned epoxy aliphatic acid methyl ester/epoxy soybean oil, the add-on of described formic acid are 6% of raw material total amount.
The production method of above-mentioned epoxy aliphatic acid methyl ester/epoxy soybean oil, the internal diameter of described pipeline reactor are 25 ~ 50mm.
The production method of above-mentioned epoxy aliphatic acid methyl ester/epoxy soybean oil, step (2) will be for adding the pipeline reactor internal reaction 10 minutes through soybean oil, formic acid and the hydrogen peroxide of preheating.
The production method of above-mentioned epoxy aliphatic acid methyl ester/epoxy soybean oil: described step (1) one of is got in soybean oil and fatty acid methyl ester, formic acid, hydrogen peroxide are preheated to 90 ℃.
The production method of above-mentioned epoxy aliphatic acid methyl ester/epoxy soybean oil, described step (2) for volume pump with one of in soybean oil and fatty acid methyl ester, formic acid, hydrogen peroxide adds in pipeline reactor simultaneously.
The production method of above-mentioned epoxy aliphatic acid methyl ester/epoxy soybean oil, described pipeline reactor periphery has water-cooling jacket.
Reaction principle of the present invention is that hydrogen peroxide and formic acid reaction generate peroxyformic acid, and peroxyformic acid reacts with soybean oil again.
Reaction equation:
HCOOH+H
2O
2→HCOOOH+H
2O
The present invention has positive effect: (1) utilizes pipeline reactor to overcome the technology prejudice that can not adopt the high density hydrogen peroxide in traditional epoxy soybean oil production technique, use 70% high density hydrogen peroxide in production process, reaction times significantly shortens, and output significantly improves; (2) adopt hydrogen peroxide and a high proportion of formic acid of high density, speed of response is very fast, and side reaction is less, and the epoxy soybean oil of producing/epoxy aliphatic acid methyl ester oxirane value significantly improves, the color and luster aspect be improved significantly, its transparency is better.
Embodiment
(embodiment 1)
(1) getting 5 cubes of soybean oil, formic acid, the concentration of 200 kilograms is that 2 cubes, 70% hydrogen peroxide is preheated to 88 ℃ in tank; (2) use volume pump with 2.5m
3It is the pipeline reactor internal reaction 20 minutes of 25mm that the speed of/h will add simultaneously through soybean oil, formic acid and the hydrogen peroxide of preheating internal diameter, then charging again, successive reaction production.
(embodiment 2)
(1) getting 5 cubes of soybean oil, formic acid, the concentration of 200 kilograms is that 2 cubes, 70% hydrogen peroxide is preheated to 90 ℃ in tank; (2) use volume pump with 2.5m
3It is the pipeline reactor internal reaction 10 minutes of 25mm that the speed of/h will add simultaneously through soybean oil, formic acid and the hydrogen peroxide of preheating internal diameter, then charging again, successive reaction production.
(embodiment 3)
(1) getting 5 cubes of fatty acid methyl esters, formic acid, the concentration of 200 kilograms is that 2 cubes, 70% hydrogen peroxide is preheated to 92 ℃ in tank; (2) use volume pump with 2.5m
3It is the pipeline reactor internal reaction 15 minutes of 50mm that the speed of/h will add simultaneously through fatty acid methyl ester, formic acid and the hydrogen peroxide of preheating internal diameter, then charging again, successive reaction production.
(embodiment 4)
(1) getting 5 cubes of fatty acid methyl esters, formic acid, the concentration of 200 kilograms is that 2 cubes, 70% hydrogen peroxide is preheated to 92 ℃ in tank; (2) use volume pump with 2.5m
3It is the pipeline reactor internal reaction 15 minutes of 50mm that the speed of/h will add simultaneously through fatty acid methyl ester, formic acid and the hydrogen peroxide of preheating internal diameter, and the outer wall of pipeline reactor has water-cooling jacket, then charging again, successive reaction production.
This handicraft product compares with the Q/JAHG002 standard
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. the production method of an epoxy aliphatic acid methyl ester/epoxy soybean oil specifically comprises following processing step: one of get in soybean oil and fatty acid methyl ester (1), formic acid, hydrogen peroxide are preheated to 90 ± 2 ℃; (2) will add through soybean oil, formic acid and the hydrogen peroxide of preheating pipeline reactor internal reaction to reaction to finish.
2. the production method of epoxy aliphatic acid methyl ester/epoxy soybean oil according to claim 1, it is characterized in that: the concentration of described hydrogen peroxide is 70%.
3. the production method of epoxy aliphatic acid methyl ester/epoxy soybean oil according to claim 1, it is characterized in that: the add-on of described formic acid is 6% of raw material total amount.
4. the production method of epoxy aliphatic acid methyl ester/epoxy soybean oil according to claim 1, it is characterized in that: the internal diameter of described pipeline reactor is 25 ~ 50mm.
5. the production method of epoxy aliphatic acid methyl ester/epoxy soybean oil according to claim 4, it is characterized in that: step (2) will be for adding the pipeline reactor internal reaction 10 minutes through soybean oil, formic acid and the hydrogen peroxide of preheating.
6. the production method of epoxy aliphatic acid methyl ester/epoxy soybean oil according to claim 1 is characterized in that: described step (1) one of is got in soybean oil and fatty acid methyl ester, formic acid, hydrogen peroxide are preheated to 90 ℃.
7. the production method of epoxy aliphatic acid methyl ester/epoxy soybean oil according to claim 1 is characterized in that: described step (2) for volume pump with one of in soybean oil and fatty acid methyl ester, formic acid, hydrogen peroxide adds in pipeline reactor simultaneously.
8. the production method of epoxy aliphatic acid methyl ester/epoxy soybean oil according to claim 1 is characterized in that: described pipeline reactor periphery has water-cooling jacket.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310013369.1A CN103382415B (en) | 2013-01-14 | 2013-01-14 | Production method of epoxidized fatty acid methyl ester/epoxidized soybean oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310013369.1A CN103382415B (en) | 2013-01-14 | 2013-01-14 | Production method of epoxidized fatty acid methyl ester/epoxidized soybean oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103382415A true CN103382415A (en) | 2013-11-06 |
| CN103382415B CN103382415B (en) | 2014-09-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310013369.1A Expired - Fee Related CN103382415B (en) | 2013-01-14 | 2013-01-14 | Production method of epoxidized fatty acid methyl ester/epoxidized soybean oil |
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| Country | Link |
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| CN (1) | CN103382415B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865508A (en) * | 2014-03-07 | 2014-06-18 | 荆州市国洋化工有限公司 | Plasticizer for displacing oil during oilfield exploitation |
| CN104086513A (en) * | 2014-07-10 | 2014-10-08 | 江南大学 | Method for preparing epoxy soybean oil by utilizing high-concentration oxydol reaction heat |
| CN104560407A (en) * | 2015-01-06 | 2015-04-29 | 中山联成化学工业有限公司 | Method for preparing epoxy plasticizer |
| CN104892548A (en) * | 2015-06-25 | 2015-09-09 | 中国石油大学(华东) | Preparation method of novel green environmental-protection epoxidized soybean oil |
| CN105018236A (en) * | 2014-04-28 | 2015-11-04 | 南通海珥玛植物油脂有限公司 | Epoxidized soybean oil production deacidification process |
| CN106749105A (en) * | 2016-12-21 | 2017-05-31 | 北京昊业同宇科技有限公司 | The preparation technology of epoxy aliphatic acid methyl ester |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016396A (en) * | 2007-02-15 | 2007-08-15 | 宜兴市三联化工厂 | Method of preparing polyvinylchloride composite processing auxiliary agent |
| CN101613639A (en) * | 2009-07-20 | 2009-12-30 | 河南工业大学 | The preparation method of epoxidized oil under ultrasound condition |
| CN101891713A (en) * | 2010-07-09 | 2010-11-24 | 南京工业大学 | Method for preparing epoxidized fatty acid methyl ester |
| CN102703225A (en) * | 2012-06-11 | 2012-10-03 | 刘忠 | Epoxidized soybean oil plasticizer and production method thereof |
| CN102864021A (en) * | 2012-09-26 | 2013-01-09 | 山东吉青化工有限公司 | Epoxidation vegetable oil preparation method |
| CN103305347A (en) * | 2013-07-03 | 2013-09-18 | 江南大学 | Method for preparing environment-friendly plasticizer by high concentration hydrogen peroxide epoxidized oil |
-
2013
- 2013-01-14 CN CN201310013369.1A patent/CN103382415B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016396A (en) * | 2007-02-15 | 2007-08-15 | 宜兴市三联化工厂 | Method of preparing polyvinylchloride composite processing auxiliary agent |
| CN101613639A (en) * | 2009-07-20 | 2009-12-30 | 河南工业大学 | The preparation method of epoxidized oil under ultrasound condition |
| CN101891713A (en) * | 2010-07-09 | 2010-11-24 | 南京工业大学 | Method for preparing epoxidized fatty acid methyl ester |
| CN102703225A (en) * | 2012-06-11 | 2012-10-03 | 刘忠 | Epoxidized soybean oil plasticizer and production method thereof |
| CN102864021A (en) * | 2012-09-26 | 2013-01-09 | 山东吉青化工有限公司 | Epoxidation vegetable oil preparation method |
| CN103305347A (en) * | 2013-07-03 | 2013-09-18 | 江南大学 | Method for preparing environment-friendly plasticizer by high concentration hydrogen peroxide epoxidized oil |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865508A (en) * | 2014-03-07 | 2014-06-18 | 荆州市国洋化工有限公司 | Plasticizer for displacing oil during oilfield exploitation |
| CN103865508B (en) * | 2014-03-07 | 2017-03-15 | 湖北国洋科技有限公司 | A kind of plasticizer for the oilfield exploitation displacement of reservoir oil |
| CN105018236A (en) * | 2014-04-28 | 2015-11-04 | 南通海珥玛植物油脂有限公司 | Epoxidized soybean oil production deacidification process |
| CN105018236B (en) * | 2014-04-28 | 2019-05-24 | 南通海珥玛科技股份有限公司 | A kind of epoxidized soybean oil production deacidification technique |
| CN104086513A (en) * | 2014-07-10 | 2014-10-08 | 江南大学 | Method for preparing epoxy soybean oil by utilizing high-concentration oxydol reaction heat |
| CN104560407A (en) * | 2015-01-06 | 2015-04-29 | 中山联成化学工业有限公司 | Method for preparing epoxy plasticizer |
| CN104560407B (en) * | 2015-01-06 | 2017-08-25 | 中山联成化学工业有限公司 | A kind of preparation method of epoxy plasticiser |
| CN104892548A (en) * | 2015-06-25 | 2015-09-09 | 中国石油大学(华东) | Preparation method of novel green environmental-protection epoxidized soybean oil |
| CN104892548B (en) * | 2015-06-25 | 2017-04-12 | 中国石油大学(华东) | Preparation method of novel epoxidized soybean oil |
| CN106749105A (en) * | 2016-12-21 | 2017-05-31 | 北京昊业同宇科技有限公司 | The preparation technology of epoxy aliphatic acid methyl ester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103382415B (en) | 2014-09-03 |
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| C56 | Change in the name or address of the patentee |
Owner name: JIANGSU YUEDA KATE NEW ENERGY CO., LTD. Free format text: FORMER NAME: JIANGSU KAT NEW ENERGY CO., LTD. |
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| CP03 | Change of name, title or address |
Address after: Wujin District of Jiangsu city in Changzhou province 213116 Zheng Lu Wu Shun Cheng Industrial Park Road No. 1 Patentee after: Jiangsu Kate New Energy Co., Ltd. Address before: 213102 Jiangsu city of Changzhou province Qi Jian Lu ditch East No. 200 Patentee before: Jiangsu Kate New Energy Co., Ltd. |
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Granted publication date: 20140903 Termination date: 20190114 |
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