CN103351366A - Method for continuous production of epoxy chloropropane through reaction-separation coupling - Google Patents
Method for continuous production of epoxy chloropropane through reaction-separation coupling Download PDFInfo
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- CN103351366A CN103351366A CN2013102713831A CN201310271383A CN103351366A CN 103351366 A CN103351366 A CN 103351366A CN 2013102713831 A CN2013102713831 A CN 2013102713831A CN 201310271383 A CN201310271383 A CN 201310271383A CN 103351366 A CN103351366 A CN 103351366A
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Abstract
The invention relates to a preparation method for epoxy chloropropane and mainly aims to overcome the problems of a low conversion rate of chloropropene and difficult separation of the product epoxy chloropropane during production of epoxy chloropropane in the prior art. According to the method, chloropropene and peroxybenzoic acid mixed according to a molar ratio are pumped into a reaction vessel and heated to a reaction temperature, a violent reaction with stirring is carried out, a reaction solution is injected to a primary rectifying tower in the process of reaction, the light components consisting of chloropropene and peroxybenzoic acid at the top of the primary rectifying tower flow back to the reaction vessel after condensation, heavy components at the bottom of the primary rectifying tower are pumped into a secondary rectifying tower for secondary rectification, the light component epoxy chloropropane at the top of the secondary rectifying tower undergoes condensation by a condenser at tower top and collection so as to obtain a high purity product, and the heavy component benzoic acid is collected at the bottom of the secondary rectifying tower. The method provided by the invention increases the conversion rate of chloropropene, realizes low-energy consumption, easy, rapid and continuous production and enables yield of the reaction product epoxy chloropropane to be greater than 90%.
Description
Technical field
The present invention relates to a kind of method of utilizing propenyl chloride and benzoyl hydroperoxide to produce epoxy chloropropane, relate to the technology of preparing of epoxy chloropropane in chemical field.
Background technology
Epoxy chloropropane is a kind of important Organic Chemicals and fine chemical product, mainly for the production of Resins, epoxy, strengthen resin, water treatment resin, synthetic glycerine (account for demand 10%～15%) and elastomerics etc., on a small quantity for the preparation of epoxypropyl ethers and ester class.Simultaneously, the sealing material that also uses for the production of coating, tackiness agent, strongthener and cast material, production automotive industry and aircraft industry and oil way flexible pipe and for the production of the raw material of chemical stabilizer, chemical fuel and water conditioner etc.
The production technique of epoxy chloropropane mainly is propylene high-temperature chlorination process and allyl acetate method at present.Wherein the propylene high-temperature chlorination process is the classical way of industrial production epoxy chloropropane, accounts for more than 90% of global epoxy chloropropane aggregated capacity.Its technical process comprises that mainly the propylene high-temperature chlorination prepares propenyl chloride; The reaction process such as propenyl chloride hypochlorination synthesizing dichloropropanol and dichlorohydrine saponification synthesizing epoxy chloropropane.The shortcoming of this method is need to just can obtain the final product epoxy chloropropane through three-step reaction from raw material propylene, and process is longer, and energy consumption is large, and by product is many, and product yield is low.
The advantages such as in recent years, the technique for preparing epoxy chloropropane with organic peracid epoxidation propenyl chloride is high owing to reaction preference, and reaction conditions is gentle, and is pollution-free become the method for a kind of novelty in the domestic and international epoxy chloropropane production.At present the research of the method rarely had report, wherein only having HOII P NL 7609148 in 1977 to disclose a kind of Peracetic Acid of utilizing comes the epoxidation propenyl chloride to produce the method for epoxy chloropropane, this patent be with acetaldehyde in air through the metal Co catalyzed oxidation, pass into again and obtain epoxy chloropropane in the peracetic acid soln.But the method also needs to remove wherein metal ion through ion exchange resin at last, has increased postprocessing working procedures and process costs.But in these reactions, reaction product epoxy chloropropane and phenylformic acid be constantly accumulation in system, and this is unfavorable for that reaction carries out to positive dirction, has affected the transformation efficiency of reaction, has caused difficulty also for simultaneously the separation of product.
Summary of the invention
Technical purpose of the present invention provides a kind of method of producing epoxy chloropropane by propenyl chloride and benzoyl hydroperoxide, so that the product in the reaction process can side by side be separated, improved the yield of reaction conversion ratio and product epoxy chloropropane, realize less energy-consumption, simply, produce continuously rapidly, the transformation efficiency of epoxy chloropropane is greater than 90% in the reaction product that obtains, and the reaction substrate utilization ratio obviously improves.
For realizing technical purpose of the present invention, technical scheme of the present invention is: will pump in the reactor by propenyl chloride and the benzoyl hydroperoxide that the mole proportioning is mixed, be heated to temperature of reaction, the violent stirring reaction, in the reaction process reaction solution injected the one-level rectifying tower, light constituent propenyl chloride and the benzoyl hydroperoxide of rectifying tower top are back in the reactor after condensation, recombinate at the bottom of the tower to divide to be pumped to and carry out secondary rectifying in the two-stage rectification tower, the light constituent epoxy chloropropane of cat head is collected to get high purity product after the overhead condenser condensation, a restructuring minute phenylformic acid is collected at the bottom of tower.
The mole proportioning of propenyl chloride of the present invention and Peracetic Acid is 1:1～1:5.
Temperature of reaction of the present invention is 45～80 ℃.
Reaction times of the present invention is 1～4 h.
The beneficial effect of the epoxy chloropropane production method that the present invention proposes is: epoxy chloropropane and phenylformic acid that reaction generates can be separated from reaction system in time by the two-stage rectification device among the present invention, and be obtained highly purified principal product epoxy chloropropane by the two-stage rectification tower is separable.
Description of drawings
Fig. 1 structural representation of the present invention
Being labeled as among Fig. 1: 1, collector at the bottom of reactor, 2, agitator, 3, one-level rectifying tower, 4, overhead condenser, 5, two-stage rectification tower, 6, the tower.
Embodiment
Embodiment 1
The reaction substrate of the present embodiment and product method for qualitative and quantitative detection are: adopt SE-54(30 m * 0.25 mm * 0.5 μ m) quartz capillary column, 200 ℃ of temperature of vaporization chamber; 130 ℃ of column temperatures; 260 ℃ of fid detector temperature; Carrier gas: high-purity N
2Column flow rate: 0.66 mL/min; Splitting ratio: 60:1.
With propenyl chloride 38.26 g(0.5 mol) and benzoyl hydroperoxide 69.06 g(0.5 mol) pump in the reactor 1, be heated to 80 ℃ of temperature of reaction, violent stirring is reacted 2.5 h, in the reaction process reaction solution injected one-level rectifying tower 3, light constituent propenyl chloride and the benzoyl hydroperoxide on rectifying tower 3 tops are back to after condensation in the reactor 1, recombinate at the bottom of the tower to divide to be pumped to and carry out secondary rectifying in the two-stage rectification tower 5, the light constituent epoxy chloropropane of cat head is collected to get high purity product epoxy chloropropane 43.21 g, yield 93.4% after overhead condenser 4 condensations.。
Embodiment 2
Reaction substrate and product method for qualitative and quantitative detection and operation are all identical with embodiment 1, and the implementation step that changes reactant mole proportioning and each operating parameters is as follows:
With propenyl chloride 38.26 g(0.5 mol) and benzoyl hydroperoxide 207.18 g(1.5 mol) pump in the reactor 1, be heated to 60 ℃ of temperature of reaction, violent stirring is reacted 1 h, in the reaction process reaction solution injected one-level rectifying tower 3, light constituent propenyl chloride and the benzoyl hydroperoxide on rectifying tower 3 tops are back to after condensation in the reactor 1, recombinate at the bottom of the tower to divide to be pumped to and carry out secondary rectifying in the two-stage rectification tower 5, the light constituent epoxy chloropropane of cat head is collected to get high purity product epoxy chloropropane 42.42 g, yield 91.7% after overhead condenser 4 condensations.。
Embodiment 3
Reaction substrate and product method for qualitative and quantitative detection and operation are all identical with embodiment 1, and the implementation step that changes reactant mole proportioning and each operating parameters is as follows:
With propenyl chloride 38.26 g(0.5 mol) and benzoyl hydroperoxide 345.30 g(2.5 mol) pump in the reactor 1, be heated to 45 ℃ of temperature of reaction, violent stirring is reacted 4 h, in the reaction process reaction solution injected one-level rectifying tower 3, light constituent propenyl chloride and the benzoyl hydroperoxide on rectifying tower 3 tops are back to after condensation in the reactor 1, recombinate at the bottom of the tower to divide to be pumped to and carry out secondary rectifying in the two-stage rectification tower 5, the light constituent epoxy chloropropane of cat head is collected to get high purity product epoxy chloropropane 44.78 g, yield 96.8% after overhead condenser 4 condensations.
Claims (4)
1. method of utilizing propenyl chloride and benzoyl hydroperoxide to produce epoxy chloropropane, it is characterized in that: will pump in the reactor by propenyl chloride and the benzoyl hydroperoxide that the mole proportioning is mixed, be heated to temperature of reaction, the violent stirring reaction, in the reaction process reaction solution injected the one-level rectifying tower, light constituent propenyl chloride and the benzoyl hydroperoxide of rectifying tower top are back in the reactor after condensation, recombinate at the bottom of the tower to divide to be pumped to and carry out secondary rectifying in the two-stage rectification tower, the light constituent epoxy chloropropane of cat head is collected to get high purity product after the overhead condenser condensation, a restructuring minute phenylformic acid is collected at the bottom of tower.
2. a kind of method of utilizing propenyl chloride and benzoyl hydroperoxide to produce epoxy chloropropane according to claim 1 is characterized in that the mole proportioning of propenyl chloride and Peracetic Acid is 1:1～1:5.
3. a kind of method of utilizing propenyl chloride and benzoyl hydroperoxide to produce epoxy chloropropane according to claim 1 is characterized in that described temperature of reaction is 45～80 ℃.
4. a kind of method of utilizing propenyl chloride and benzoyl hydroperoxide to produce epoxy chloropropane according to claim 1 is characterized in that the described reaction times is 1～4 h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310271383.1A CN103351366B (en) | 2013-07-01 | 2013-07-01 | Method for continuous production of epoxy chloropropane through reaction-separation coupling |
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| CN201310271383.1A CN103351366B (en) | 2013-07-01 | 2013-07-01 | Method for continuous production of epoxy chloropropane through reaction-separation coupling |
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| CN103351366A true CN103351366A (en) | 2013-10-16 |
| CN103351366B CN103351366B (en) | 2015-06-24 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110872216A (en) * | 2019-12-06 | 2020-03-10 | 南京恒道医药科技有限公司 | Method and device for producing (2-chloro-5-iodophenyl) -4-fluorobenzyl ketone by reaction separation coupling |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4424391A (en) * | 1979-05-10 | 1984-01-03 | Solvay & Cie | Process for the manufacture of olefine oxides |
| CN102372683A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing epichlorohydrin through chloropropene epoxidation |
| CN103159703A (en) * | 2011-12-16 | 2013-06-19 | 中国科学院大连化学物理研究所 | Method of continuously producing epichlorohydrin by directly epoxidizing chloropropene |
-
2013
- 2013-07-01 CN CN201310271383.1A patent/CN103351366B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4424391A (en) * | 1979-05-10 | 1984-01-03 | Solvay & Cie | Process for the manufacture of olefine oxides |
| CN102372683A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing epichlorohydrin through chloropropene epoxidation |
| CN103159703A (en) * | 2011-12-16 | 2013-06-19 | 中国科学院大连化学物理研究所 | Method of continuously producing epichlorohydrin by directly epoxidizing chloropropene |
Non-Patent Citations (1)
| Title |
|---|
| 王星 等: "环氧氯丙烷生产方法综述", 《广东科技》, no. 6, 31 March 2011 (2011-03-31) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110872216A (en) * | 2019-12-06 | 2020-03-10 | 南京恒道医药科技有限公司 | Method and device for producing (2-chloro-5-iodophenyl) -4-fluorobenzyl ketone by reaction separation coupling |
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