CN101993423A - Method for producing epoxy chloropropane - Google Patents
Method for producing epoxy chloropropane Download PDFInfo
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- CN101993423A CN101993423A CN2010105227066A CN201010522706A CN101993423A CN 101993423 A CN101993423 A CN 101993423A CN 2010105227066 A CN2010105227066 A CN 2010105227066A CN 201010522706 A CN201010522706 A CN 201010522706A CN 101993423 A CN101993423 A CN 101993423A
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- hydrogen peroxide
- epoxy chloropropane
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Abstract
The invention relates to a method for producing epoxy chloropropane by a phase transfer method, which comprises the following steps of: adding 3-chloropropene serving as a raw material and a catalyst into a reactor, stirring, heating to the bubble point temperature of between 44 and 46 DEG C, adding hydrogen peroxide serving as an oxidant, and reacting at the bubble point temperature, wherein reaction heat in the reaction process is taken away through organic steam condensation and reflow; the catalyst is quaternary ammonium phosphotungstate; the reaction time is 1 hour; and the mass ratio of the 3-chloropropene to 50 percent hydrogen peroxide to the catalyst is 1:0.3:0.11. Other solvents are not added in the reaction; the hydrogen peroxide is added at the temperature of between 44 and 46 DEG C, so that the epoxidation reaction is further promoted, and the conversion rate of the epoxidation reaction is improved; meanwhile, the increase of organic steam partial pressure is facilitated, gaseous oxygen is diluted, and the blasting danger of a gaseous phase of the reactor is effectively reduced.
Description
Technical field
The present invention relates to a kind of production method of epoxy chloropropane, particularly relate to a kind of method that adopts phase transfer method to produce epoxy chloropropane.
Background technology
Epoxy chloropropane is a kind of important Organic Chemicals and fine chemical product, and purposes is very extensive.Traditional epichlorohydrin production process mainly is propylene high-temperature chlorination process and allyl acetate method, has the governing problem that a large amount of " three wastes " pollute in the water discharge process under the saponification.Propelling along with the strategy of sustainable development, green synthetic route with epoxy chloropropane of industrial value becomes the focus of research in the industry, present research mainly concentrates on the exploration of the direct epoxidation technique route of propenyl chloride, adopting HTS or Lin Wusuanyan as catalyzer, is the epoxidation reaction that oxygenant carries out propenyl chloride with the hydrogen peroxide.
The direct epoxidation system epoxy chloropropane of phase transfer method propenyl chloride and hydrogen peroxide technology is arisen at the historic moment under this environment just.Adopt phosphotungstic acid quaternary as catalyzer, be oxygenant with the hydrogen peroxide, successfully solved the problem that traditional technology produces a large amount of waste water, and tool has high conversion and selectivity very much.Yet under the effect of catalyzer, invalid decomposition takes place in a part of hydrogen peroxide in reaction process, has not only reduced the transformation efficiency of reaction, and easily makes the reactor gas phase form the mixed gas with explosion hazard.Therefore, reduce the invalid decomposition amount of hydrogen peroxide, reducing gas phase phase oxygen concn is to produce the major issue that epoxy chloropropane technology is faced at present.
Summary of the invention
The technical problem to be solved in the present invention is, a kind of method that adopts phase transfer method to produce epoxy chloropropane is provided, under the bubble point temperature that this method provides, reacts, can reduce the invalid decomposition amount of hydrogen peroxide, improve the transformation efficiency of epoxidation reaction, reduce gas phase phase oxygen concn.
A kind of method that adopts phase transfer method to produce epoxy chloropropane, with the chlorallylene is raw material, hydrogen peroxide is an oxygenant, add chlorallylene and catalyzer in the reactor earlier, stirring is warming up to bubble point temperature, adds hydrogen peroxide again, reacts under bubble point temperature, behind about 44 ℃～46 ℃ of the initial reaction temperature, the reaction heat of reaction process is taken away by the organic steam condensing reflux.
Wherein, catalyzer is a phosphotungstic acid quaternary.
Preferably, at the uniform velocity add hydrogen peroxide and react, reinforced time 0.5h, the reaction times is 1h.The charging mass ratio is a propenyl chloride: 50% (mass ratio) hydrogen peroxide: catalyzer is 1: 0.3: 0.11.
Do not add any other solvent in the reaction.
The present invention adds hydrogen peroxide again under about 44 ℃～46 ℃ of bubble point temperature, react under bubble point temperature, has avoided that chlorallylene, catalyzer and hydrogen peroxide are at room temperature added reactor together and has reacted.
Because the decomposition reaction competing reaction each other of epoxidation reaction and hydrogen peroxide, helped the generation of decomposing hydrogen dioxide solution reaction in the past being warming up to bubble point temperature, yet the speed of reaction of epoxidation reaction is extremely low, and effective oxygenizement is not played in a large amount of decomposition of hydrogen peroxide.Take method of the present invention, owing to do not add hydrogen peroxide in the temperature-rise period, can avoid hydrogen peroxide that invalid decomposition takes place on the one hand, discharge a large amount of oxygen to gas phase formation and fire danger; On the other hand, near 44 ℃～46 ℃, the reaction rate accelerates of epoxidation reaction, add hydrogen peroxide this moment again, given full play to its oxygenizement, further promoted the carrying out of epoxidation reaction, improve the transformation efficiency of epoxidation reaction, simultaneously, help improving the organic steam dividing potential drop, gas phase oxygen is played diluting effect, effectively reduce the danger that fires of reactor gas phase.Can not obtain these beneficial technical effects and under other temperature, add hydrogen peroxide.
Embodiment
A kind of method that adopts phase transfer method to produce epoxy chloropropane, with the chlorallylene is raw material, phosphotungstic acid quaternary is a catalyzer, and hydrogen peroxide is an oxygenant, adds chlorallylene and catalyzer in the reactor earlier, stirring is warming up to bubble point temperature, after about 44 ℃～46 ℃, add hydrogen peroxide again, under bubble point temperature, react, the reaction heat of reaction process is taken away by the organic steam condensing reflux, and the reaction times is 1h.
Do not add any other solvent in the reaction.
Embodiment one
Chlorallylene, catalyzer are added earlier in the reactor, stir and be warming up to bubble point temperature, after about 44 ℃, at the uniform velocity add hydrogen peroxide again and react, reinforced time 0.5h, total reaction time 1h, the reaction heat of reaction process is taken away by the organic steam condensing reflux.The charging mass ratio, propenyl chloride: 50% hydrogen peroxide: catalyzer is 1: 0.3: 0.11.
The reaction process oxygen concentration of gas phase is up to 4.4%, and the propenyl chloride transformation efficiency is 41.6%, and the invalid rate of decomposition of hydrogen peroxide is 1.4%.
Embodiment two
Chlorallylene, catalyzer are added earlier in the reactor, stir and be warming up to bubble point temperature, after about 46 ℃, at the uniform velocity add hydrogen peroxide again and react, reinforced time 1h, total reaction time 1.5h, the reaction heat of reaction process is taken away by the organic steam condensing reflux.The charging mass ratio, propenyl chloride: 50% hydrogen peroxide: catalyzer is 1: 0.3: 0.11.
The reaction process oxygen concentration of gas phase is up to 1.9%, and the propenyl chloride transformation efficiency is 41.4%, and the invalid rate of decomposition of hydrogen peroxide is 1.8%.
Embodiment three:
Under the room temperature chlorallylene, catalyzer, hydrogen peroxide are added in the reactor simultaneously, stir and be warming up to bubble point temperature, about 44 ℃～46 ℃, reaction times 1h.The charging mass ratio, propenyl chloride: 50% hydrogen peroxide: catalyzer is 1: 0.3: 0.11.
The reaction process oxygen concentration of gas phase is up to 22.8%, and the propenyl chloride transformation efficiency is 40.6%, and the invalid rate of decomposition of hydrogen peroxide is 3.8%.
Claims (5)
1. method that adopts phase transfer method to produce epoxy chloropropane, with the chlorallylene is raw material, hydrogen peroxide is an oxygenant, it is characterized in that, chlorallylene and catalyzer are added earlier in the reactor, after stirring is warming up to bubble point temperature, add hydrogen peroxide again, react under bubble point temperature, initial reaction temperature is 44 ℃～46 ℃, and the reaction heat of reaction process is taken away by the organic steam condensing reflux.
2. produce the method for epoxy chloropropane according to claim 1, it is characterized in that, catalyzer is a phosphotungstic acid quaternary.
3. as the method for production epoxy chloropropane as described in the claim 2, it is characterized in that, at the uniform velocity add hydrogen peroxide and react, reinforced time 0.5h, the reaction times is 1h.
4. as the method for production epoxy chloropropane as described in the claim 3, it is characterized in that the charging mass ratio is a propenyl chloride: 50% hydrogen peroxide: catalyzer is 1: 0.3: 0.11.
As claim 1-4 arbitrary as described in the method for production epoxy chloropropane, it is characterized in that, do not add any other solvent in the reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105227066A CN101993423A (en) | 2010-10-27 | 2010-10-27 | Method for producing epoxy chloropropane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105227066A CN101993423A (en) | 2010-10-27 | 2010-10-27 | Method for producing epoxy chloropropane |
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| CN101993423A true CN101993423A (en) | 2011-03-30 |
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| CN2010105227066A Pending CN101993423A (en) | 2010-10-27 | 2010-10-27 | Method for producing epoxy chloropropane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8481765B2 (en) | 2008-03-17 | 2013-07-09 | Momentive Specialty Chemicals Inc. | Method for the production of epichlorohydrin |
| US8729282B2 (en) | 2008-08-01 | 2014-05-20 | Momentive Specialty Chemicals Inc. | Process for the manufacture of a 1,2-epoxide |
| US8802873B2 (en) | 2008-08-01 | 2014-08-12 | Momentive Specialty Chemicals Inc. | Process for the manufacture of epichlorohydrin |
| CN109776456A (en) * | 2019-02-26 | 2019-05-21 | 山东凯泰科技股份有限公司 | A kind of starting method for establishing concentration gradient for realizing directly production ECH continuous production commercial run using phase transfer catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900071A (en) * | 2005-07-21 | 2007-01-24 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane |
| CN101205220A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Preparation method of methyl epichlorohydrin |
| CN101279961A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for preparing epoxy chloropropane by epoxidation of propylene chloride |
| CN101279958A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for preparing epoxy chloropropane by epoxidation of propylene chloride |
| CN101992125A (en) * | 2009-08-13 | 2011-03-30 | 中国石油化工集团公司 | Method for regenerating heteropoly acid quaternary ammonium salt catalyst |
-
2010
- 2010-10-27 CN CN2010105227066A patent/CN101993423A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900071A (en) * | 2005-07-21 | 2007-01-24 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane |
| CN101205220A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Preparation method of methyl epichlorohydrin |
| CN101279961A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for preparing epoxy chloropropane by epoxidation of propylene chloride |
| CN101279958A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for preparing epoxy chloropropane by epoxidation of propylene chloride |
| CN101992125A (en) * | 2009-08-13 | 2011-03-30 | 中国石油化工集团公司 | Method for regenerating heteropoly acid quaternary ammonium salt catalyst |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8481765B2 (en) | 2008-03-17 | 2013-07-09 | Momentive Specialty Chemicals Inc. | Method for the production of epichlorohydrin |
| US8729282B2 (en) | 2008-08-01 | 2014-05-20 | Momentive Specialty Chemicals Inc. | Process for the manufacture of a 1,2-epoxide |
| US8802873B2 (en) | 2008-08-01 | 2014-08-12 | Momentive Specialty Chemicals Inc. | Process for the manufacture of epichlorohydrin |
| CN109776456A (en) * | 2019-02-26 | 2019-05-21 | 山东凯泰科技股份有限公司 | A kind of starting method for establishing concentration gradient for realizing directly production ECH continuous production commercial run using phase transfer catalyst |
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Application publication date: 20110330 |