CN103408508A - Method for producing epichlorohydrin by utilizing chloropropene - Google Patents
Method for producing epichlorohydrin by utilizing chloropropene Download PDFInfo
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- CN103408508A CN103408508A CN2013102714302A CN201310271430A CN103408508A CN 103408508 A CN103408508 A CN 103408508A CN 2013102714302 A CN2013102714302 A CN 2013102714302A CN 201310271430 A CN201310271430 A CN 201310271430A CN 103408508 A CN103408508 A CN 103408508A
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Abstract
The invention relates to a method for preparing epichlorohydrin, and mainly the method can be used for solving the problems of low conversion rate of chloropropene and product epichlorohydrin hydrolysis in the process of epichlorohydrin producing process in the prior art. The method adopts peroxyacetic acid and chloropropene as raw materials, and comprises the following steps of: heating to a reaction temperature, and strongly stirring to react; pumping the reacting liquid into an external circulating dehydration system filled with a dehydrating agent at a certain flowing speed to circularly dehydrate. According to the method, the conversion rate of chloropropene is improved, the dosage of peroxyacetic acid is reduced, and low-energy consumption, simple and quick continuous production can be realized, and the yield of the reaction product epichlorohydrin is more than 92 percent.
Description
Technical field
The present invention relates to a kind of method of utilizing propenyl chloride and Peracetic Acid 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 epoxy resin, 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 also used 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 is mainly 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.
In recent years, the technique for preparing epoxy chloropropane with organic peracid epoxidation propenyl chloride is because reaction preference is high, reaction conditions gentleness, the advantage such as pollution-free become domestic and international epoxy chloropropane produce in a kind of method of novelty.At present the research of the method rarely had to report, only having HOII P NL7609148 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 by acetaldehyde in air through the metal Co catalyzed oxidation, then pass in peracetic acid soln and obtain epoxy chloropropane.But the method finally also needs to remove metal ion wherein through ion exchange resin, has increased postprocessing working procedures and process costs.But in this reaction, Peracetic Acid is produced under sulfuric acid catalysis by acetic acid and hydrogen peroxide, this step reaction is a reversible reaction, when the main reaction propenyl chloride has consumed the Peracetic Acid in the system, it is reduced into to acetic acid.Although being conducive to peroxidation, the rising of acetic acid concentration carries out to positive dirction, but the water in reaction system is but in constantly accumulation, the existence of water not only is unfavorable for the generation of Peracetic Acid, and then affect the process of main reaction, in system, too much water can cause product epoxy chloropropane generation hydrolysis reaction simultaneously, has reduced process recovery ratio.
Summary of the invention
Technical purpose of the present invention is to provide a kind of method of producing epoxy chloropropane by propenyl chloride and Peracetic Acid, make the water produced in reaction process effectively to be removed, and the loss that improves reaction conversion ratio and product epoxy chloropropane, realize less energy-consumption, simply, produce continuously rapidly, in the reaction product obtained, the transformation efficiency of epoxy chloropropane is greater than 92%, 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 reactor by propenyl chloride and the Peracetic Acid that mole proportioning is mixed, be heated to temperature of reaction, the violent stirring reaction, will react feed liquid and pump in the outer circulation water scavenging system that loads water-removal agent and circulate and dewater with certain flow rate in reaction process.The frequent pressure fractionating of reaction mixture, can obtain highly purified epoxy chloropropane.
Mole proportioning of propenyl chloride of the present invention and Peracetic Acid is 1:1～1:10.
Temperature of reaction of the present invention is 30～90 ℃.
Reaction times of the present invention is 1～8 h.
Water-removal agent of the present invention comprises molecular sieve, Calcium Chloride Powder Anhydrous, anhydrous sodium sulphate or anhydrous magnesium sulfate;
The external circulating system of filling water-removal agent of the present invention, external circulating system wherein be a filling water-removal agent except water column, perhaps two and above filling water-removal agent except the water column series combination, or two and above filling water-removal agent except the water column parallel combination.
The beneficial effect of the epoxy chloropropane production method that the present invention proposes is:
(1) external circulating system of the filling water-removal agent of the present invention's design, not only water-removal agent is cheap, change, regenerate and be convenient, and water-removal agent can not introduced to reaction system, therefore the epoxy chloropropane crude product obtained by present method directly normal pressure fractionation obtains the epoxy chloropropane sterling, the technique environmental protection, can be widely used in the industry of fine chemicals and industrial chemicals etc.
(2) external circulating system of the filling water-removal agent of the present invention's design, can design arbitrarily size, quantity and the array mode except water column according to the throughput of reactor, and select different water-removal agents, to meet continuously, to remove efficiently the requirement of the water that reaction system generates.
(3) the inventive method makes the water produced in reaction process effectively to be removed, and improves the loss of reaction conversion ratio and product epoxy chloropropane, has strengthened product yield.
The accompanying drawing explanation
Fig. 1 structural representation of the present invention
Being labeled as in Fig. 1: 1, agitator; 2, reactor; 3, pump; 4, outer circulation water scavenging system; 5, condenser; 6, holding tank.
Embodiment
Embodiment 1
The outer circulation water scavenging system of the present embodiment is the water column that removes of single filling water-removal agent, and except water column is of a size of 1.6 m * internal diameter 0.15 m, the filling rate of water-removal agent is 80%.
Reaction substrate 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.
By propenyl chloride 38.3 g(0.5 mol) and 40% peroxide acetate aqueous solution 95.06 g(0.5 mol) pump in reactor 2, be heated to 90 ℃ of temperature of reaction, violent stirring reaction, will react feed liquid and pass into the outer circulation water scavenging system 4 that loads anhydrous sodium sulphate and return in reactor 2 in reaction process.After reacting 8 h, stop, the frequent pressure fractionating of mixture, collect the cut of 118 ℃, obtains highly purified epoxy chloropropane 44.23 g, yield 95.6%.
The outer circulation water scavenging system of the present embodiment is the combinations except water column series connection of two filling water-removal agents, every column dimension 1.6 m that dewater * internal diameter 0.15 m wherein, and the filling rate of water-removal agent is 75%.
Reaction substrate and product method for qualitative and quantitative detection and operation are all identical with embodiment 1, and the implementation step that changes water-removal agent and each operating parameters is as follows:
By propenyl chloride 38.3 g(0.5 mol) and 40% peroxide acetate aqueous solution 285.18 g(1.5 mol) pump in reactor 2, be heated to 70 ℃ of temperature of reaction, violent stirring reaction, will react feed liquid and pass into the outer circulation water scavenging system 4 that loads molecular sieve and return in reactor 2 in reaction process.After reacting 6 h, stop, the frequent pressure fractionating of mixture, collect the cut of 118 ℃, obtains highly purified epoxy chloropropane 43.58 g, yield 94.2%.
The outer circulation water scavenging system of the present embodiment be two filling water-removal agents except the combinations of water column parallel connection, every column dimension 1.6 m that dewater * internal diameter 0.15 m wherein, the filling rate of water-removal agent is 85%.
Reaction substrate and product method for qualitative and quantitative detection and operation are all identical with embodiment 1, and the implementation step that changes water-removal agent and each operating parameters is as follows:
By propenyl chloride 38.3 g(0.5 mol) and 40% peroxide acetate aqueous solution 665.44 g(3.5 mol) pump in reactor 2, be heated to 50 ℃ of temperature of reaction, violent stirring reaction, will react feed liquid and pass into the outer circulation water scavenging system 4 that loads Calcium Chloride Powder Anhydrous and return in reactor 2 in reaction process.After reacting 3 h, stop, the frequent pressure fractionating of mixture, collect the cut of 118 ℃, obtains highly purified epoxy chloropropane 43.35 g, yield 93.7%.
The outer circulation water scavenging system of the present embodiment be three filling water-removal agents except the combinations of water column parallel connection, every column dimension 1.6 m that dewater * internal diameter 0.15 m wherein, the filling rate of water-removal agent is 70%.
Reaction substrate and product method for qualitative and quantitative detection and operation are all identical with embodiment 1, and the implementation step that changes water-removal agent and each operating parameters is as follows:
By propenyl chloride 38.3 g(0.5 mol) and 40% peroxide acetate aqueous solution 950.63 g(5.0 mol) pump in reactor 2, be heated to 30 ℃ of temperature of reaction, violent stirring reaction, will react feed liquid and pass into the outer circulation water scavenging system 4 that loads anhydrous magnesium sulfate and return in reactor 2 in reaction process.After reacting 1 h, stop, the frequent pressure fractionating of mixture, collect the cut of 118 ℃, obtains highly purified epoxy chloropropane 44.18 g, yield 95.5%.
Claims (6)
1. method of utilizing propenyl chloride and Peracetic Acid to produce epoxy chloropropane, it is characterized in that: will pump in reactor by propenyl chloride and the Peracetic Acid that mole proportioning is mixed, be heated to temperature of reaction, the violent stirring reaction, in reaction process, will react feed liquid pumps in the outer circulation water scavenging system that loads water-removal agent and circulates and dewater with certain flow rate, the frequent pressure fractionating of reaction mixture, can obtain highly purified epoxy chloropropane.
2. a kind of method of utilizing propenyl chloride and Peracetic Acid to produce epoxy chloropropane according to claim 1, is characterized in that mole proportioning of propenyl chloride and Peracetic Acid is 1:1～1:10.
3. a kind of method of utilizing propenyl chloride and Peracetic Acid to produce epoxy chloropropane according to claim 1, is characterized in that described temperature of reaction is 30～90 ℃.
4. a kind of method of utilizing propenyl chloride and Peracetic Acid to produce epoxy chloropropane according to claim 1, is characterized in that the described reaction times is 1～8 h.
5. a kind of method of utilizing propenyl chloride and Peracetic Acid to produce epoxy chloropropane according to claim 1, the external circulating system that it is characterized in that described filling water-removal agent, external circulating system wherein is the water column that removes of a filling water-removal agent, perhaps two and above filling water-removal agent except the water column series combination, or two and above filling water-removal agent except the water column parallel combination.
6. according to claim 1 and 6 a kind of described methods of utilizing propenyl chloride and Peracetic Acid to produce epoxy chloropropane, it is characterized in that described water-removal agent comprises molecular sieve, Calcium Chloride Powder Anhydrous, anhydrous sodium sulphate or anhydrous magnesium sulfate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2013102714302A CN103408508A (en) | 2013-07-01 | 2013-07-01 | Method for producing epichlorohydrin by utilizing chloropropene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2013102714302A CN103408508A (en) | 2013-07-01 | 2013-07-01 | Method for producing epichlorohydrin by utilizing chloropropene |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0061393A1 (en) * | 1981-03-24 | 1982-09-29 | Elf Atochem S.A. | Continuous process for the preparation of propylene oxide |
| US4424391A (en) * | 1979-05-10 | 1984-01-03 | Solvay & Cie | Process for the manufacture of olefine oxides |
| CN101255099A (en) * | 2008-04-03 | 2008-09-03 | 南京工业大学 | Method for producing dichloropropanol by using glycerin |
| CN102295569A (en) * | 2011-07-04 | 2011-12-28 | 南京工业大学 | Method for preparing (S)-metoprolol succinate |
-
2013
- 2013-07-01 CN CN2013102714302A patent/CN103408508A/en active Pending
Patent Citations (4)
| 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 |
| EP0061393A1 (en) * | 1981-03-24 | 1982-09-29 | Elf Atochem S.A. | Continuous process for the preparation of propylene oxide |
| CN101255099A (en) * | 2008-04-03 | 2008-09-03 | 南京工业大学 | Method for producing dichloropropanol by using glycerin |
| CN102295569A (en) * | 2011-07-04 | 2011-12-28 | 南京工业大学 | Method for preparing (S)-metoprolol succinate |
Non-Patent Citations (1)
| Title |
|---|
| 杨涛 等: "异戊烯酸甲酯催化合成新工艺", 《精细石油化工》, vol. 26, no. 6, 30 November 2009 (2009-11-30) * |
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Application publication date: 20131127 |