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CN111116342B - Method for preparing hexafluoroacetone through isomerization of hexafluoropropylene oxide - Google Patents

Method for preparing hexafluoroacetone through isomerization of hexafluoropropylene oxide Download PDF

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CN111116342B
CN111116342B CN201911318644.4A CN201911318644A CN111116342B CN 111116342 B CN111116342 B CN 111116342B CN 201911318644 A CN201911318644 A CN 201911318644A CN 111116342 B CN111116342 B CN 111116342B
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reaction
introducing
hexafluoroacetone
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hexafluoropropylene oxide
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CN111116342A (en
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陈爽
徐雅硕
王博
张志君
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Tianjin Changlu Chemical New Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/58Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention belongs to the field of fluoride preparation, and particularly relates to a method for preparing hexafluoroacetone through hexafluoropropylene oxide isomerization. The method specifically comprises the following steps: filling a catalyst into a reactor, and introducing reaction raw material gas hexafluoropropylene oxide for reaction, wherein the reaction pressure is normal pressure, the reaction temperature is 0-200 ℃, and the reaction space velocity is 100-‑1And introducing the product into ionized water after the reaction is finished, thus obtaining hexafluoroacetone hydrate. According to the method of the present invention, high purity hexafluoroacetone can be obtained by isomerizing hexafluoropropylene oxide, by-products are hardly formed, selectivity is high, the reaction can be carried out at low temperature and normal pressure, and requirements on reaction conditions are low. Meanwhile, the catalyst used in the invention is simple to prepare, the raw materials are easy to obtain, and the catalyst is easy to form and produce in a large scale.

Description

Method for preparing hexafluoroacetone by isomerizing hexafluoropropylene oxide
Technical Field
The invention belongs to the field of fluoride preparation, and particularly relates to a method for preparing hexafluoroacetone through hexafluoropropylene oxide isomerization.
Background
Hexafluoroacetone (CF3COCF3, HFA for short) is a fluorine-containing fine chemical which has a wide range of uses. First reported in the literature, trials were successful in 1957 in the 60's of the 20 th century by Allied Chemical and Du Pont, USA. Due to the strong electron withdrawing property of 2-CF 3 groups, the physical and chemical properties of HFA are greatly different from those of acetone, and the HFA also has unique physical and chemical properties. Hexafluoroacetone is used in the fields of medicines, agricultural chemicals, synthetic materials and the like, and particularly can be used as a raw material for synthesizing high molecular materials in special fields, wherein hexafluoroacetone is used as a raw material of a high-grade solvent, namely hexafluoropropanol, and a monomer of a high-performance fluorine-containing elastomer in a large industrial application.
The preparation technology of hexafluoroacetone mainly comprises an octafluoroisobutylene oxidation method, a hexafluoropropylene oxide rearrangement method, a hexafluoropropylene catalytic oxidation method, a hexachloroacetone high-temperature gas phase catalytic fluorination method and a 2-chlorohexafluoropropane oxidation method. In the prior art, hexafluoropropylene oxide is used as a raw material, hexafluoroacetone is generated through molecular rearrangement isomerization, and solid Lewis acid such as Al2O3, Cr2O3, AlCl3 and the like can be used as a catalyst of the reaction, which is also a main industrial method for producing HFA at present. US patent 4238416 uses fluorinated Al2O3 or Al2O3-SiO2 as catalyst, which has high HFPO conversion rate, but the exothermic reaction is severe, and needs to introduce inert gas and oxygen, which has high requirements for temperature and pressure. Japanese patents JP58062130 and JP58062131 have examined a series of fluorinated Al2O3, Cr2O3, Al2O3-SiO2 catalysts, but with a high number of reaction by-products. U.S. patent US2004186322, which uses TiO2 as a catalyst and US6933413, which uses SnO2 as a catalyst, achieves higher yields but still requires higher reaction temperatures. The catalyst reported in the Chinese patent CN1899692A can be composed of Cr2O3, AlF3, TiO2, graphite or metal powder, and can react at normal temperature and normal pressure, but the catalyst has more components and is complex to prepare.
Therefore, a catalyst which has high activity, high stability and simple preparation at low temperature and normal pressure is needed to be suitable for preparing hexafluoroacetone by the catalytic isomerization of hexafluoropropylene oxide.
Disclosure of Invention
The invention aims to provide a method for preparing hexafluoroacetone by isomerizing hexafluoropropylene oxide.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing hexafluoroacetone by isomerizing hexafluoropropylene oxide adopts the following reaction formula (I):
Figure BDA0002326548110000021
the method specifically comprises the following steps: filling a catalyst into a reactor, and introducing reaction raw material gas hexafluoropropylene oxide for reaction, wherein the reaction pressure is normal pressure, the reaction temperature is 0-200 ℃, and the reaction space velocity is 100--1And introducing the product into ionized water after the reaction is finished, thus obtaining hexafluoroacetone hydrate.
Preferably, the reaction temperature is 20-100 ℃, and the reaction space velocity is 150--1
Preferably, the reaction space velocity is 300h-1
Wherein, the catalyst is prepared by the following method: silicon is mixedZSM-5 molecular sieve with aluminum ratio of 50 is dried in a baking oven at 120 ℃ for 4 hours, 10g of the molecular sieve is put into a tube furnace, N2 is introduced, the temperature is raised to 350 ℃, CHClF is introduced2The gas flow is 30ml/min, fluorination is carried out for 4 hours, and N2 is introduced to be cooled to room temperature. Tabletting to 20-40 mesh.
Compared with the prior art, the invention has the beneficial effects that:
according to the method of the present invention, high purity hexafluoroacetone can be obtained by isomerizing hexafluoropropylene oxide, by-products are hardly formed, selectivity is high, the reaction can be carried out at low temperature and normal pressure, and requirements on reaction conditions are low. Meanwhile, the catalyst used in the invention is simple to prepare, the raw materials are easy to obtain, and the catalyst is easy to form and produce in a large scale.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the following preferred embodiments.
The embodiment is as follows: preparation of the catalyst: drying a ZSM-5 molecular sieve (the silica-alumina ratio is 50) in an oven at 120 ℃ for 4 hours, taking 10g of the molecular sieve, putting the molecular sieve into a tube furnace, introducing N2, heating to 350 ℃, introducing R22 gas at the flow rate of 30ml/min, fluorinating for 4 hours, and introducing N2, and cooling to room temperature. Tabletting to obtain 20-40 mesh powder as catalyst.
And (3) preparing hexafluoroacetone by catalytic isomerization of hexafluoropropylene oxide: the reaction test is carried out in a fixed bed reactor, a stainless steel reaction tube (with the inner diameter of 10mm and the length of 300mm) is filled with 5.0ml (20-40 meshes) of catalyst, the reaction temperature is 20 ℃, 60 ℃, 100 ℃, 150 ℃, 200 ℃, the operation pressure is normal pressure, and the reaction space velocity is 300h < -1 >. And analyzing and measuring the reaction product by adopting a gas chromatography analysis method, and then introducing the reaction product into deionized water to absorb and generate hexafluoroacetone hydrate. The reaction results are shown in table 1.
Wherein, the comparative catalyst is TiO2 prepared by US2004186322 as the catalyst;
TABLE 1
Figure BDA0002326548110000031
As can be seen from table 1, according to the process of the present invention, high-purity hexafluoroacetone can be obtained by isomerizing hexafluoropropylene oxide, by-products are hardly formed, selectivity is high, the reaction can be carried out at low temperature and normal pressure, and the requirements on reaction conditions are low.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.

Claims (1)

1. A method for preparing hexafluoroacetone by isomerizing hexafluoropropylene oxide is characterized by adopting the following reaction formula (I):
Figure DEST_PATH_IMAGE001
the method specifically comprises the following steps: filling a catalyst into a reactor, and introducing reaction raw material gas hexafluoropropylene oxide for reaction, wherein the reaction pressure is normal pressure, the reaction temperature is 60 ℃, and the reaction space velocity is 300h-1Introducing the product into ionized water after the reaction is finished, and obtaining hexafluoroacetone hydrate;
wherein, the catalyst is prepared by the following method: drying a ZSM-5 molecular sieve with a silicon-aluminum ratio of 50 in an oven at 120 ℃ for 4 hours, taking 10g of the molecular sieve, putting the molecular sieve into a tube furnace, introducing N2, heating to 350 ℃, introducing CHClF2 gas with the flow of 30ml/min, fluorinating for 4 hours, and introducing N2, and cooling to room temperature; tabletting to 20-40 mesh.
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CN116532133B (en) * 2023-03-24 2025-05-27 湖南有色郴州氟化学有限公司 Method for preparing hexafluoroacetone by isomerization of hexafluoropropylene oxide

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4238416A (en) * 1976-08-21 1980-12-09 Daikin Kogyo Co., Ltd. Method for isomerization of fluorinated epoxy compounds
SU859348A2 (en) * 1979-08-10 1981-08-30 Предприятие П/Я Г-4567 Method of producing hexafluoroacetone
US4705904A (en) * 1984-02-14 1987-11-10 Allied Corporation Vapor phase synthesis of hexafluoroisobutylene
RU2152923C2 (en) * 1996-03-14 2000-07-20 АООТ "Кирово-Чепецкий химический комбинат им.Б.П.Константинова" Method of preparing hexafluoroacetone
CN1899692A (en) * 2006-07-25 2007-01-24 浙江蓝天环保高科技股份有限公司 Catalyst for preparing hexafloroacetone by isomerization method and its preparing method and use
CN101036882A (en) * 2007-04-13 2007-09-19 上海泰卓科技有限公司 Catalyzer of the Epoxide including fluorin isomerization and the preparing method and application

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE345321T1 (en) * 2001-07-19 2006-12-15 Daikin Ind Ltd METHOD FOR PRODUCING HEXAFLUOROCACETONE AND ITS HYDRATE

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4238416A (en) * 1976-08-21 1980-12-09 Daikin Kogyo Co., Ltd. Method for isomerization of fluorinated epoxy compounds
SU859348A2 (en) * 1979-08-10 1981-08-30 Предприятие П/Я Г-4567 Method of producing hexafluoroacetone
US4705904A (en) * 1984-02-14 1987-11-10 Allied Corporation Vapor phase synthesis of hexafluoroisobutylene
RU2152923C2 (en) * 1996-03-14 2000-07-20 АООТ "Кирово-Чепецкий химический комбинат им.Б.П.Константинова" Method of preparing hexafluoroacetone
CN1899692A (en) * 2006-07-25 2007-01-24 浙江蓝天环保高科技股份有限公司 Catalyst for preparing hexafloroacetone by isomerization method and its preparing method and use
CN101036882A (en) * 2007-04-13 2007-09-19 上海泰卓科技有限公司 Catalyzer of the Epoxide including fluorin isomerization and the preparing method and application

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