CN101279958A - Method for preparing epoxy chloropropane by epoxidation of propylene chloride - Google Patents

Method for preparing epoxy chloropropane by epoxidation of propylene chloride Download PDF

Info

Publication number
CN101279958A
CN101279958A CNA2007100390801A CN200710039080A CN101279958A CN 101279958 A CN101279958 A CN 101279958A CN A2007100390801 A CNA2007100390801 A CN A2007100390801A CN 200710039080 A CN200710039080 A CN 200710039080A CN 101279958 A CN101279958 A CN 101279958A
Authority
CN
China
Prior art keywords
reaction
catalyzer
epoxidation
chloropropene
hydrogen peroxide
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
Application number
CNA2007100390801A
Other languages
Chinese (zh)
Other versions
CN101279958B (en
Inventor
丁琳
陈璐
高焕新
金国杰
杨洪云
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN2007100390801A priority Critical patent/CN101279958B/en
Publication of CN101279958A publication Critical patent/CN101279958A/en
Application granted granted Critical
Publication of CN101279958B publication Critical patent/CN101279958B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a method to prepare epoxy chloropropane through the epoxidation of chloropropene, mainly solving the problems of complex operation and large energy consumption during the separation process in prior art which introduces a large amount of solvent carbinol during the preparation of propylene oxide. The method takes peroxide and chloropropene as material and ti-si molecular sieveTS-1 as catalyzer, and the materials contact with the catalyzer to produce epoxy chloropropane; wherein the mol ratio of chloropropene to peroxide is 1-100:1; the weight ratio of peroxide to catalyzer is 0.2-200:1; the temperature for the reaction is 25-100 DEG C, the absolute pressure for the reaction is between normal pressure and is 0.2MPa and the reaction lasts for 0.1-48h. The method solves above problems and is applicable to the industrial production of preparing epoxy chloropropane through the epoxidation of propylene.

Description

The method of preparing epichlorohydrin by chloropropene epoxidation
Technical field
The present invention relates to a kind of method of preparing epichlorohydrin by chloropropene epoxidation.
Background technology
Epoxy chloropropane (claim Epicholorohydrin again, English name epichlorohydrin is called for short ECH) is a kind of important Organic Chemicals and intermediate, and it is widely used in producing and making Resins, epoxy, synthetic glycerine and chlorohydrin rubber etc.In epoxy compounds, the output of epoxy chloropropane is only second to oxyethane and propylene oxide and occupies the 3rd.
The industrial production of epoxy chloropropane mainly contains two kinds of approach at present, a kind of is chlorohydrination, it is the method from the synthetic ECH of the indirect epoxidation of propenyl chloride (the propylene high-temperature chlorination is produced), synthetic route is longer, at first be that time chlorination reaction generation hypochlorous acid takes place the chlorine G﹠W, hypochlorous acid and propenyl chloride carry out addition reaction and generate dichlorohydrine, and adduct is under alkaline condition then, and the dechlorination closed loop makes ECH.Another kind then is the allyl acetate method, and it makes vinylcarbinol or ester from propylene through allyl oxidation, produces ECH by dechlorination cyclisation under chlorination, the alkaline condition again.These two kinds of methods prepare in the process of epoxy chloropropane all can produce a large amount of chlorine-contained wastewaters, causes the serious environmental pollution problem.
Patent CN03121153.4 has described the method that titanium molecular sieve catalysis propenyl chloride and hydrogen peroxide dilute aqueous soln epoxidation prepare epoxy chloropropane.Document (Applied catalysisi A:138 (1996) P27) discloses a kind of with H 2O 2Being oxygenant, is catalyzer with the HTS, is solvent with methyl alcohol, carries out the method for preparing epichlorohydrin by chloropropene epoxidation.45 ℃ of chloro propylene epoxidation temperature of reaction, normal pressure, the transformation efficiency of hydrogen peroxide can reach more than 90%, and the selectivity of epoxy chloropropane also surpasses 90%.Yet, because the introducing of a large amount of methanol solvates has increased the complicacy of operation, and has increased separating energy consumption.
Summary of the invention
Technical problem to be solved by this invention be in the prior art preparation epoxy chloropropane because the introducing of a large amount of methanol solvates, complicated operation, the problem that separating energy consumption is big provides a kind of method of new preparing epichlorohydrin by chloropropene epoxidation.With this method prepare epoxy chloropropane have simple to operate, the characteristics that the later separation energy consumption is little.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of preparing epichlorohydrin by chloropropene epoxidation, with hydrogen peroxide and propenyl chloride is reaction raw materials, with the titanium-silicon molecular sieve TS-1 is catalyzer, reaction raw materials and catalyzer contact reacts generate epoxy chloropropane, wherein the mol ratio of propenyl chloride and hydrogen peroxide is 1～100: 1, the weight ratio of hydrogen peroxide and catalyzer is 0.2～200: 1, temperature of reaction is 25～100 ℃, the reaction absolute pressure is normal pressure～0.2MPa, and the reaction times is 0.1～48 hour.
In the technique scheme, used catalyst Ti-si molecular sieves TS-1 preferred version is for wherein silicon-dioxide and titanium dioxide mol ratio are SiO 2: TiO 2=10～200.The temperature of reaction preferable range is 30～80 ℃, and the reaction times preferable range is 0.2～24 hour.The weight ratio preferable range of hydrogen peroxide and catalyzer is 1～100: 1, and the mol ratio preferable range of propenyl chloride and hydrogen peroxide is 2～20: 1.Hydrogen peroxide weight percent concentration preferable range is 1～80%, and more preferably scope is 10～40%.
The preparation process of titanium-silicon molecular sieve TS-1 is as follows among the present invention: with trivalent titanium compound, tetraethyl titanate or tetrabutyl titanate is the titanium source, with tetraethyl orthosilicate or silicon sol is the silicon source, quaternary ammonium hydroxide, quaternary ammonium salt are or/and organic amine is a template, by the hydrothermal method synthesis of titanium silicon molecular sieve.The mol ratio of each material is in the molecular sieve precursor: SiO 2/ TiO 2Be 10～200; OH -/ SiO 2Be 0.03～0.6; H 2O/SiO 2Be 60～100; Template/SiO 2Be 0.2～0.50, above-mentioned reaction mixture is warming up to 70～90 ℃ earlier also to be continued to stir 0.5～5 hour, and crystallization is after 1～3 day under 120～200 ℃ of temperature then, and collection, fractional crystallization product from reaction mixture wash then and dry.In air, behind the calcination crystallized product certain hour, get HTS.
Because propenyl chloride is excessive greatly, be reaction solvent directly promptly in the reaction system of the present invention, improved propenyl chloride concentration on the one hand, thereby accelerated speed of response, improved production efficiency with the reaction raw materials propenyl chloride.Can simplify reaction system on the other hand, simplify reacted separated from solvent process, reduce separating energy consumption, obtain better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
In 1000 milliliters of stainless steel reactors, add 400 gram propenyl chlorides, 10 gram SiO 2/ TiO 2Mol ratio be 80 titanium-silicon molecular sieve TS-1 as catalyzer, normal pressure is heated to 40 ℃, adds 60 grams, 30 weight %H then 2O 2, under agitation reacting 1 hour, reaction result sees Table 1.
[embodiment 2]
In 1000 milliliters of stainless steel reactors, add 400 gram propenyl chlorides, 20 gram SiO 2/ TiO 2Mol ratio be 100 titanium-silicon molecular sieve TS-1 as catalyzer, normal pressure is heated to 60 ℃, adds 120 grams, 30 weight %H then 2O 2, under agitation reacting 1 hour, reaction result sees Table 1.
[embodiment 3]
In 1000 milliliters of stainless steel reactors, add 400 gram propenyl chlorides, 30 gram SiO 2/ TiO 2Mol ratio be 80 titanium-silicon molecular sieve TS-1 as catalyzer, normal pressure is heated to 45 ℃, adds 36 grams, 50 weight %H then 2O 2, under agitation reacting 0.5 hour, reaction result sees Table 1.
[embodiment 4]
In 1000 milliliters of stainless steel reactors, add 400 gram propenyl chlorides, 10 gram SiO 2/ TiO 2Mol ratio be 75 titanium-silicon molecular sieve TS-1 as catalyzer, normal pressure is heated to 45 ℃, adds 150 grams, 30 weight %H then 2O 2, under agitation reacting 10 hours, reaction result sees Table 1.
[embodiment 5]
In 1000 milliliters of stainless steel reactors, add 400 gram propenyl chlorides, 6.0 gram SiO 2/ TiO 2Mol ratio be 60 titanium-silicon molecular sieve TS-1 as catalyzer, normal pressure is heated to 45 ℃, adds 150 grams, 30 weight %H then 2O 2, under agitation reacting 1 hour, reaction result sees Table 1.
[embodiment 6]
In 1000 milliliters of stainless steel reactors, add 400 gram propenyl chlorides, 5.0 gram SiO 2/ TiO 2Mol ratio be 40 titanium-silicon molecular sieve TS-1 as catalyzer, normal pressure is heated to 30 ℃, adds 150 grams, 30 weight %H then 2O 2, under agitation reacting 10 hours, reaction result sees Table 1.
[embodiment 7]
In 1000 milliliters of stainless steel reactors, add 400 gram propenyl chlorides, 1.0 gram SiO 2/ TiO 2Mol ratio be 20 titanium-silicon molecular sieve TS-1 as catalyzer, normal pressure is heated to 40 ℃, adds 180 grams, 40 weight %H then 2O 2, under agitation reacting 20 hours, reaction result sees Table 1.
[embodiment 8]
In 1000 milliliters of stainless steel reactors, add 400 gram propenyl chlorides, 0.5 gram SiO 2/ TiO 2Mol ratio be 20 titanium-silicon molecular sieve TS-1 as catalyzer, normal pressure is heated to 50 ℃, adds 120 grams, 30 weight %H then 2O 2, under agitation reacting 20 hours, reaction result sees Table 1.
[comparative example 1]
In 1000 milliliters of stainless steel reactors, add 200 gram propenyl chlorides and 300 gram chloroforms, 50.0 grams, 30 weight %H 2O 2, 5 the gram titanium-silicon molecular sieve TS-1 catalysts, normal pressure, 40 ℃, the reaction 20 hours, reaction result sees Table 1.
[comparative example 2]
In 1000 milliliters of stainless steel reactors, add 200 gram propenyl chlorides and 200 gram methyl alcohol, 50.0 grams, 30 weight %H 2O 2, 6 the gram titanium-silicon molecular sieve TS-1 catalysts, normal pressure, 40 ℃, the reaction 20 hours, reaction result sees Table 1.
Table 1
Embodiment H 2O 2Transformation efficiency % The selectivity % of propylene oxide
Embodiment 1 97.28％ 97.31％
Embodiment 2 98.80％ 92.24％
Embodiment 3 97.96％ 95.97％
Embodiment 4 98.78％ 93.23％
Embodiment 5 95.72％ 92.26％
Embodiment 6 96.46％ 95.91％
Embodiment 7 95.72％ 98.76％
Embodiment 8 95.46％ 94.17％
Comparative example 1 81.43％ 83.76％
Comparative example 2 88.78％ 87.85％

Claims (8)

1. the method for a preparing epichlorohydrin by chloropropene epoxidation, with hydrogen peroxide and propenyl chloride is reaction raw materials, with the titanium-silicon molecular sieve TS-1 is catalyzer, reaction raw materials and catalyzer contact reacts generate epoxy chloropropane, wherein the mol ratio of propenyl chloride and hydrogen peroxide is 1～100: 1, and the weight ratio of hydrogen peroxide and catalyzer is 0.2～200: 1, and temperature of reaction is 25～100 ℃, the reaction absolute pressure is normal pressure～0.2MPa, and the reaction times is 0.1～48 hour.
2. according to the method for the described preparing epichlorohydrin by chloropropene epoxidation of claim 1, it is characterized in that in the described titanium-silicon molecular sieve TS-1 that silicon-dioxide and titanium dioxide mol ratio are SiO 2: TiO 2=10～200.
3. according to the method for the described preparing epichlorohydrin by chloropropene epoxidation of claim 1, it is characterized in that 30～80 ℃ of temperature of reaction.
4. according to the method for the described preparing epichlorohydrin by chloropropene epoxidation of claim 1, it is characterized in that 0.2～24 hour reaction times.
5. according to the method for the described preparing epichlorohydrin by chloropropene epoxidation of claim 1, the weight ratio that it is characterized in that hydrogen peroxide and catalyzer is 1～100: 1.
6. according to the method for the described preparing epichlorohydrin by chloropropene epoxidation of claim 1, the mol ratio that it is characterized in that propenyl chloride and hydrogen peroxide is 2～20: 1.
7. according to the method for the described preparing epichlorohydrin by chloropropene epoxidation of claim 1, the weight percent concentration that it is characterized in that hydrogen peroxide is 1～80%.
8. according to the method for the described preparing epichlorohydrin by chloropropene epoxidation of claim 7, the weight percent concentration that it is characterized in that hydrogen peroxide is 10～40%.
CN2007100390801A 2007-04-04 2007-04-04 Method for preparing epoxy chloropropane by epoxidation of propylene chloride Active CN101279958B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2007100390801A CN101279958B (en) 2007-04-04 2007-04-04 Method for preparing epoxy chloropropane by epoxidation of propylene chloride

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2007100390801A CN101279958B (en) 2007-04-04 2007-04-04 Method for preparing epoxy chloropropane by epoxidation of propylene chloride

Publications (2)

Publication Number Publication Date
CN101279958A true CN101279958A (en) 2008-10-08
CN101279958B CN101279958B (en) 2011-01-19

Family

ID=40012650

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2007100390801A Active CN101279958B (en) 2007-04-04 2007-04-04 Method for preparing epoxy chloropropane by epoxidation of propylene chloride

Country Status (1)

Country Link
CN (1) CN101279958B (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101993423A (en) * 2010-10-27 2011-03-30 中国石油化工股份有限公司 Method for producing epoxy chloropropane
CN101747297B (en) * 2008-12-22 2011-11-02 中国石油化工股份有限公司 Method for continuously producing epoxy chloropropane
US8735612B2 (en) 2010-03-25 2014-05-27 Dow Global Technologies, Inc. Pretreated epoxidation catalyst and a process for producing an olefin therewith
US8754246B2 (en) 2011-02-04 2014-06-17 Dow Global Technologies, Llc Separating phases of a mixture
TWI473795B (en) * 2009-08-05 2015-02-21 Dow Global Technologies Llc Process for producing an oxirane
US8980780B2 (en) 2011-02-04 2015-03-17 Dow Global Technologies Llc Regenerating a titanium silicalite catalyst
CN105272947A (en) * 2014-07-24 2016-01-27 中国石油化工股份有限公司 Continuous epichlorohydrin production method
CN105272948A (en) * 2014-07-24 2016-01-27 中国石油化工股份有限公司 Epichlorohydrin preparation method
CN105315240A (en) * 2014-07-24 2016-02-10 中国石油化工股份有限公司 Method used for producing epoxy chloropropane
US9498762B2 (en) 2011-02-04 2016-11-22 Blue Cube Ip Llc System and process for producing an oxirane
CN112375047A (en) * 2020-11-25 2021-02-19 江苏扬农化工集团有限公司 Synthetic method of epichlorohydrin
CN112742472A (en) * 2021-01-19 2021-05-04 中国科学院大连化学物理研究所 Preparation method of epoxidation catalyst with high activity and low byproduct
CN116514741A (en) * 2023-07-04 2023-08-01 山东民基新材料科技有限公司 Process for producing epoxy chloropropane by utilizing micro-interface reaction

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2846965B1 (en) * 2002-11-12 2006-10-13 PROCESS FOR THE PRODUCTION OF 1,2-EPOXY-3-CHLOROPROPANE
CN1275952C (en) * 2003-03-28 2006-09-20 中国石油化工股份有限公司 Production method of epoxy chloropropane

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747297B (en) * 2008-12-22 2011-11-02 中国石油化工股份有限公司 Method for continuously producing epoxy chloropropane
TWI473795B (en) * 2009-08-05 2015-02-21 Dow Global Technologies Llc Process for producing an oxirane
US8981132B2 (en) 2010-03-25 2015-03-17 Dow Global Technologies Llc Pretreated epoxidation catalyst and a process for producing an olefin therewith
US8735612B2 (en) 2010-03-25 2014-05-27 Dow Global Technologies, Inc. Pretreated epoxidation catalyst and a process for producing an olefin therewith
CN101993423A (en) * 2010-10-27 2011-03-30 中国石油化工股份有限公司 Method for producing epoxy chloropropane
US9498762B2 (en) 2011-02-04 2016-11-22 Blue Cube Ip Llc System and process for producing an oxirane
US8754246B2 (en) 2011-02-04 2014-06-17 Dow Global Technologies, Llc Separating phases of a mixture
US8980780B2 (en) 2011-02-04 2015-03-17 Dow Global Technologies Llc Regenerating a titanium silicalite catalyst
CN105272947B (en) * 2014-07-24 2018-07-17 中国石油化工股份有限公司 The method of continuous production epoxychloropropane
CN105315240A (en) * 2014-07-24 2016-02-10 中国石油化工股份有限公司 Method used for producing epoxy chloropropane
CN105272948A (en) * 2014-07-24 2016-01-27 中国石油化工股份有限公司 Epichlorohydrin preparation method
CN105272948B (en) * 2014-07-24 2018-04-06 中国石油化工股份有限公司 The method for preparing epoxychloropropane
CN105272947A (en) * 2014-07-24 2016-01-27 中国石油化工股份有限公司 Continuous epichlorohydrin production method
CN105315240B (en) * 2014-07-24 2019-01-25 中国石油化工股份有限公司 The method for producing epoxychloropropane
CN112375047A (en) * 2020-11-25 2021-02-19 江苏扬农化工集团有限公司 Synthetic method of epichlorohydrin
CN112375047B (en) * 2020-11-25 2023-07-28 江苏扬农化工集团有限公司 Synthetic method of epoxy chloropropane
CN112742472A (en) * 2021-01-19 2021-05-04 中国科学院大连化学物理研究所 Preparation method of epoxidation catalyst with high activity and low byproduct
CN112742472B (en) * 2021-01-19 2022-03-15 中国科学院大连化学物理研究所 Preparation method of epoxidation catalyst with high activity and low byproduct
CN116514741A (en) * 2023-07-04 2023-08-01 山东民基新材料科技有限公司 Process for producing epoxy chloropropane by utilizing micro-interface reaction
CN116514741B (en) * 2023-07-04 2023-09-26 山东民基新材料科技有限公司 Process for producing epoxy chloropropane by utilizing micro-interface reaction

Also Published As

Publication number Publication date
CN101279958B (en) 2011-01-19

Similar Documents

Publication Publication Date Title
CN101279958B (en) Method for preparing epoxy chloropropane by epoxidation of propylene chloride
CN101172970A (en) Method for producing epoxychloropropane
CN110203947B (en) Preparation method of titanium-silicon molecular sieve Ti-MWW
CN101279961B (en) Method for preparing epoxy chloropropane by epoxidation of propylene chloride
CN105367520B (en) The method for preparing expoxy propane
CN103818924B (en) Preparation method of titanium-silicon molecular sieve and application
WO2001070710A1 (en) Process for producing propylene oxide
CN102145300A (en) Microsphere TS-1 catalyst and preparation method of microsphere TS-1 catalyst
CN104528759A (en) Preparation method of TS-1 titanium silicalite molecular sieve
CN106517236A (en) Preparation method of titanium silicalite molecular sieve
CN102010293A (en) Method for catalyzing and synthesizing 1, 2-pentanediol by using titanium silicalite
CN107999124B (en) Core-shell structure Ti-MWW @ Si molecular sieve and preparation and application thereof
CN110357835B (en) Preparation method of epichlorohydrin
CN101279957B (en) Method for preparing epoxypropane by epoxidation of propene
CN114436757A (en) Method, system and application for treating hydrogenolysis product of alpha, alpha-dimethyl benzyl alcohol
CN103818921B (en) A kind of method using composite mould plate agent to prepare TS-1 molecular sieve
CN102464632B (en) Method for preparing epoxy chloropropane
CN101591024A (en) A kind of method of modifying of HTS
CN105315237B (en) The synthetic method of the butylene of 3,4 epoxy 1
CN104098532A (en) Method for preparing epoxybutane through butene epoxidation
CN112408414B (en) Preparation method and application of thin-layer nanosheet type hierarchical pore TS-1 molecular sieve catalyst
CN110437178A (en) A kind of method of green high-efficient synthesizing epoxypropane
CN102731253B (en) Method capable of inhibiting generation of cyclic ether alcohol and used for preparing glycol by catalytic conversion of cellulose
CN105315236B (en) The method for producing 3,4- epoxy-1-butylene
CN116514741B (en) Process for producing epoxy chloropropane by utilizing micro-interface reaction

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant