CN112375047B - Synthetic method of epoxy chloropropane - Google Patents
Synthetic method of epoxy chloropropane Download PDFInfo
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- CN112375047B CN112375047B CN202011337839.6A CN202011337839A CN112375047B CN 112375047 B CN112375047 B CN 112375047B CN 202011337839 A CN202011337839 A CN 202011337839A CN 112375047 B CN112375047 B CN 112375047B
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- epichlorohydrin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention relates to a synthetic method of epoxy chloropropane, which comprises the following steps of (1) dehydration: hydrogen peroxide and tertiary butanol are added into a dehydration kettle, heated to 80-85 ℃ and azeotroped to obtain hydrogen peroxide/tertiary butanol solution; (2) reaction: reacting hydrogen peroxide/tertiary butanol solution, 3-chloropropene and titanium silicalite molecular sieve catalyst TS-1 in a fixed bed epoxidation reactor to obtain epichlorohydrin synthetic solution; (3) separation: and (3) sequentially carrying out normal pressure distillation on the epichlorohydrin synthetic liquid to recover 3-chloropropene and negative pressure distillation to recover tert-butyl alcohol, and finally carrying out negative pressure distillation to obtain an epichlorohydrin product. The synthetic method of the epichlorohydrin does not generate 1, 2-epoxy-3-methoxy propane, improves the product content of the epichlorohydrin, simplifies the operation flow and reduces the energy consumption of the subsequent separation.
Description
Technical Field
The invention relates to a synthetic method of epichlorohydrin, in particular to a method for preparing epichlorohydrin by epoxidation of 3-chloropropene and hydrogen peroxide in tert-butyl alcohol solution.
Background
The epichlorohydrin is an important basic chemical raw material and is mainly applied to the production of various products such as epoxy resin, chlorohydrin rubber, glycerol, surfactant and the like. The current industrial production method of epoxy chloropropane is mainly prepared by the reaction of hydrogen peroxide and chloropropene under the catalysis of a titanium silicalite molecular sieve TS-1 serving as a catalyst in a methanol solvent, and because of the existence of methanol, the methanol can further react with epoxy chloropropane or 3-chloropropene to generate methyl ether impurities such as 1, 2-epoxy-3-methoxypropane, 1-chloro-3-methoxy-2-propanol and the like. Wherein, the boiling point difference between the 1, 2-epoxy-3-methoxypropane and the epichlorohydrin is 2 ℃ and is difficult to effectively separate, which can affect the quality of the epichlorohydrin product. Patent CN101747296A discloses a production method of epichlorohydrin, which adopts a methanol solvent, the hydrogen peroxide conversion rate is more than 98%, and the epichlorohydrin selectivity is 95-97%.
In addition, when methanol is used as a solvent, the post-treatment process of the reaction solution is complex and difficult. The separation process of epichlorohydrin proposed in the patent CN105585542B and the patent CN104003961B needs to separate methanol, chloropropene and epichlorohydrin through the processes of water washing and layering, oil layer water washing, water layer extraction, oil layer rectification, extraction Yu Shuiceng rectification and the like, and the methanol and the 1, 2-epoxy-3-methoxypropane in the oil phase are strictly controlled to be less than 100ppm, so that the content of the obtained epichlorohydrin can be ensured to reach 99.9%, and the separation energy consumption is increased.
Disclosure of Invention
The invention aims to solve the technical problems of low content of epichlorohydrin products, complex operation and high separation energy consumption caused by using a methanol solvent for preparing epichlorohydrin in the prior art, and provides a novel method for preparing epichlorohydrin by epoxidation of chloropropene.
The aim of the invention is realized by the following technical scheme:
(1) Dehydrating: hydrogen peroxide and tertiary butanol are added into a dehydration kettle, heated to 80-85 ℃ and azeotroped to obtain hydrogen peroxide/tertiary butanol solution;
(2) The reaction: reacting hydrogen peroxide/tertiary butanol solution, 3-chloropropene and titanium silicalite molecular sieve catalyst TS-1 in a fixed bed epoxidation reactor to obtain epichlorohydrin synthetic solution;
(3) Separating: and (3) sequentially carrying out normal pressure distillation on the epichlorohydrin synthetic liquid to recover 3-chloropropene and negative pressure distillation to recover tert-butyl alcohol, and finally carrying out negative pressure distillation to obtain an epichlorohydrin product.
In the reaction step (1), the preferred weight percentage concentration of the hydrogen peroxide is 30-70%; the preferred range of hydrogen peroxide/t-butanol solution water content is < 0.1%; the preferred range of molar ratio of tert-butanol to hydrogen peroxide in the hydrogen peroxide/tert-butanol solution is 1-3:1.
In the reaction step (2), the titanium silicalite molecular sieve catalyst TS-1 is prepared by the reaction of tetraethyl orthosilicate, tetrapropylammonium hydroxide, quaternary ammonium salt template agent, tetrabutyl titanate and isopropanol solution; the preferred range of the molar ratio of the 3-chloropropene to the hydrogen peroxide is 1-3:1; the reaction temperature is preferably in the range of 10 to 60 ℃.
In the reaction system, tertiary butanol is taken as a solvent, water in hydrogen peroxide is removed by utilizing azeotropy of tertiary butanol and water to form hydrogen peroxide/tertiary butanol solution, and then the hydrogen peroxide/tertiary butanol solution and 3-chloropropene are subjected to epoxidation reaction under the action of a titanium silicon catalyst to synthesize epoxy chloropropane, so that the method has the following technical effects:
(1) The tertiary butanol replaces methanol as a solvent, 1, 2-epoxy-3-methoxy propane is not generated, and the content of an epoxy chloropropane product is more than or equal to 99.99 percent;
(2) The hydrolysis probability of epoxy chloropropane is effectively reduced;
(3) The tertiary butanol and the epichlorohydrin are easy to separate, and the post-treatment flow is effectively simplified.
Detailed Description
The present invention will be further described with reference to the following specific embodiments for the purpose of illustrating the technical aspects and technical purposes of the present invention, but the present invention is not limited thereto.
The specific preparation process of the titanium-silicon molecular sieve catalyst TS-1 in the invention is as follows: 45.0g of tetraethyl orthosilicate and 56.0g of 25wt.% tetrapropylammonium hydroxide are stirred and mixed uniformly and then prehydrolyzed for 1h at 65 ℃, 4.25g of quaternary ammonium salt template agent is added, 18wt.% solution containing 4.4g of tetrabutyl titanate and 19.8g of isopropanol is continuously added dropwise after cooling to 0 ℃ for 30min, and the mixture is heated and heated to 85 ℃ for hydrolysis for 4h after the dropwise addition. And (5) carrying out hydrothermal crystallization for 48h at 180 ℃ after the completion of the preparation process to obtain TS-1 nano catalyst raw powder. Mixing 10g of TS-1 nano catalyst raw powder, 2g of alumina, 8g of 30% alumina sol, 0.5g of nonylphenol polyoxyethylene ether and 1g of water uniformly, repeatedly kneading and extruding the strips, drying at 150 ℃ for 4 hours, roasting at 600 ℃ for 12 hours, crushing the roasted catalyst, and sieving with a 200-mesh sieve to obtain the titanium-silicon molecular sieve catalyst TS-1.
[ example 1 ]
Dehydrating: 34g of 50% hydrogen peroxide and 88g of tertiary butanol are added into a dehydration bottle, stirring is started and the temperature is raised, a mixture of tertiary butanol and water is extracted into a water separator when the temperature is raised to 80 ℃, then 88g of tertiary butanol is dropwise added into the flask by opening a feed valve of a tertiary butanol dropping funnel for 30min, the temperature is kept for 30min after the dropwise addition, 182g of hydrogen peroxide tertiary butanol solution in the dehydration bottle is kept warm, the hydrogen peroxide concentration is about 9.5%, and the water content is 0.08%.
The reaction: 60g of 3-chloropropene is added into a water removal bottle to be uniformly mixed into a homogeneous solution, then mixed raw material liquid is pumped into a fixed bed tube bundle reactor with the height of 2m (containing self-made TS-1 nano molecular sieve catalyst) at a constant speed by a metering pump, and is fed from the bottom of the reactor, and is extracted from the top into a receiving bottle. The reaction solution contains 0.05% of hydrogen peroxide, 19.2% of epichlorohydrin, the reaction temperature is 30 ℃, the 3-chloro-1, 2-propanediol content is 0.08%, the hydrogen peroxide conversion rate is 99.2%, and the epichlorohydrin selectivity is 98.9%.
Separating: the reaction liquid in the bottle is subjected to normal pressure rectification, 3-chloropropene is recovered at the temperature of 44-46 ℃, then the reaction liquid is subjected to negative pressure rectification, tertiary butanol is recovered at the pressure of 12kPa and the temperature of 45-48 ℃, and the reaction liquid is continuously heated at the pressure of 7kPa, so that the epichlorohydrin with the content of 99.990 percent is obtained at the temperature of 54-56 ℃.
[ example 2 ]
Dehydrating: 68g of 50% hydrogen peroxide and 88g of tertiary butanol are added into a dehydration bottle, stirring is started and the temperature is raised, liquid is extracted into a water separator when the temperature is raised to 83 ℃, then 176g of tertiary butanol is dripped into the flask by opening a feeding valve of a tertiary butanol dripping funnel, the dripping time is 30min, the temperature is kept for 30min after the dripping is finished, 292g of hydrogen peroxide tertiary butanol solution in the dehydration bottle is kept warm, and the hydrogen peroxide concentration is about 11.5% and the water content is 0.09%.
The reaction: 150g of 3-chloropropene is added into a dehydration bottle and mixed uniformly to form a homogeneous solution. And then, a metering pump is used for pumping mixed raw material liquid into a fixed bed tube bundle reactor with the height of 2m (containing a self-made TS-1 nano molecular sieve catalyst) at a constant speed, feeding is carried out from the bottom of the reactor, and the mixed raw material liquid is extracted from the top into a receiving bottle. The reaction solution contains 0.06% of hydrogen peroxide, 21.1% of epichlorohydrin, the reaction temperature is 10 ℃, 0.04% of 3-chloro-1, 2-propanediol, the hydrogen peroxide conversion rate is 99.1%, and the epichlorohydrin selectivity is 99.1%.
Separating: the reaction liquid in the bottle is subjected to normal pressure rectification, 3-chloropropene is recovered at the temperature of 44-46 ℃, then the reaction liquid is subjected to negative pressure rectification, tertiary butanol is recovered at the pressure of 12kPa and the temperature of 45-48 ℃, and the reaction liquid is continuously heated at the pressure of 7kPa, and the epoxy chloropropane with the content of 99.992% is obtained at the temperature of 54-56 ℃.
[ example 3 ]
Dehydrating: 68g of 50% hydrogen peroxide and 88g of tertiary butanol are added into a dehydration bottle, stirring is started and the temperature is raised, liquid is extracted into a water separator when the temperature is raised to 85 ℃, then 220g of tertiary butanol is dripped into the flask by opening a feeding valve of a tertiary butanol dripping funnel, the dripping time is 30min, the temperature is kept for 30min after the dripping is finished, 343g of hydrogen peroxide tertiary butanol solution in the dehydration bottle is obtained after the temperature is kept, and the hydrogen peroxide concentration is about 10% and the water content is 0.1%.
The reaction: 140g of 3-chloropropene is added into a water removal bottle and mixed uniformly to form a homogeneous solution. And then, a metering pump is used for pumping mixed raw material liquid into a fixed bed tube bundle reactor with the height of 2m (containing a self-made TS-1 nano molecular sieve catalyst) at a constant speed, feeding is carried out from the bottom of the reactor, and the mixed raw material liquid is extracted from the top into a receiving bottle. The reaction solution contains 0.07% of hydrogen peroxide, 20.1% of epichlorohydrin, the reaction temperature is 60 ℃, 0.05% of 3-chloro-1, 2-propanediol, the hydrogen peroxide conversion rate is 99.0%, and the epichlorohydrin selectivity is 99.2%.
Separating: the reaction liquid in the bottle is subjected to normal pressure rectification, 3-chloropropene is recovered at the temperature of 44-46 ℃, then the reaction liquid is subjected to negative pressure rectification, tertiary butanol is recovered at the pressure of 12kPa and the temperature of 45-48 ℃, and the reaction liquid is continuously heated at the pressure of 7kPa, and the epoxy chloropropane with the content of 99.991% is obtained at the temperature of 54-56 ℃.
[ examples 4 to 8 ]
The procedure is as in example 1, and the effect of the reaction under different reaction conditions is examined
Comparative example 1
153g of 3-chloropropene, 195g of methanol and 68g of 50% hydrogen peroxide are added into a four-necked flask to be uniformly mixed, and then mixed raw material liquid is pumped into a fixed bed tube bundle reactor with the height of 2m (containing self-made TS-1 nano molecular sieve catalyst) at a constant speed by a metering pump, and is fed from the bottom of the reactor, and is extracted from the top into a receiving bottle. The reaction solution contains 0.08% of hydrogen peroxide, 20.1% of epichlorohydrin, 0.24% of 3-chloro-1, 2-propanediol, 0.14% of 1, 2-epoxy-3-methoxypropane, 0.92% of 1-chloro-3-methoxy-2-propanol, 99.0% of hydrogen peroxide conversion, 94.8% of epichlorohydrin selectivity and 99.75% of epichlorohydrin obtained after separation.
Claims (1)
1. A synthetic method of epoxy chloropropane comprises the following steps:
(1) Dehydrating: hydrogen peroxide and tertiary butanol are added into a dehydration kettle, heated to 80-85 ℃ and azeotroped to obtain hydrogen peroxide/tertiary butanol solution;
(2) The reaction: reacting hydrogen peroxide/tertiary butanol solution, 3-chloropropene and titanium silicalite molecular sieve catalyst TS-1 in a fixed bed epoxidation reactor to obtain epichlorohydrin synthetic solution;
(3) Separating: sequentially carrying out normal pressure distillation on the epichlorohydrin synthetic liquid to recover 3-chloropropene and negative pressure distillation to recover tert-butanol, and finally carrying out negative pressure distillation to obtain an epichlorohydrin product;
the preparation method is characterized in that the preparation process of the titanium-silicon molecular sieve catalyst TS-1 in the step (2) comprises the steps of uniformly stirring and mixing 45.0g of tetraethyl orthosilicate and 56.0g of 25wt.% tetrapropylammonium hydroxide, then prehydrolyzing for 1h at 65 ℃, adding 4.25g of quaternary ammonium salt template agent, cooling to 0 ℃, continuously dropwise adding 18wt.% of solution containing 4.4g of tetrabutyl titanate and 19.8g of isopropanol for 30min, continuously heating to 85 ℃ after dropwise adding, hydrolyzing for 4h, and finally performing hydrothermal crystallization for 48h at 180 ℃ to obtain TS-1 nano-catalyst raw powder, uniformly mixing 10g of TS-1 nano-catalyst raw powder, 2g of alumina, 8g of 30% alumina sol, 0.5g of nonylphenol polyoxyethylene ether and 1g of water, repeatedly kneading and extruding strips, drying for 4h at 150 ℃, roasting for 12h at 600 ℃, and sieving for 200 meshes to obtain the titanium-silicon molecular sieve catalyst TS-1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101486690A (en) * | 2009-02-24 | 2009-07-22 | 江苏扬农化工集团有限公司 | Production method of epoxy chloropropane by hydrogen peroxide method |
| JP2010100546A (en) * | 2008-10-22 | 2010-05-06 | Daiso Co Ltd | Method for epoxidizing olefin compound |
| CN101747296A (en) * | 2008-12-22 | 2010-06-23 | 中国石油化工股份有限公司 | Production method of epoxy chloropropane |
| CN103880783A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for preparing epoxypropane by catalyzing propylene epoxidation with phase-transfer catalyst under reaction control |
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2020
- 2020-11-25 CN CN202011337839.6A patent/CN112375047B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2010100546A (en) * | 2008-10-22 | 2010-05-06 | Daiso Co Ltd | Method for epoxidizing olefin compound |
| CN101747296A (en) * | 2008-12-22 | 2010-06-23 | 中国石油化工股份有限公司 | Production method of epoxy chloropropane |
| CN101486690A (en) * | 2009-02-24 | 2009-07-22 | 江苏扬农化工集团有限公司 | Production method of epoxy chloropropane by hydrogen peroxide method |
| CN103880783A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for preparing epoxypropane by catalyzing propylene epoxidation with phase-transfer catalyst under reaction control |
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