阅读说明：本技术 气相异构化制备z-1-r-3,3,3-三氟丙烯的方法 (Method for preparing Z-1-R-3,3, 3-trifluoropropene by gas phase isomerization ) 是由 张呈平 郭勤 贾晓卿 权恒道 于 2021-04-22 设计创作，主要内容包括：本发明公开了一种气相异构化制备Z-1-R-3,3,3-三氟丙烯的方法,即：在异构化催化剂存在下,E-1-R-3,3,3-三氟丙烯(R=氯、氟、-CF-3或-CF-2CF-3)于气相条件下发生异构化反应,得到Z-1-R-3,3,3-三氟丙烯(R=氯、氟、-CF-3或-CF-2CF-3),其中,异构化催化剂是由前驱体无水金属氯化物经活化试剂含氟的卤代饱和烃或卤代不饱和烃活化得到。本发明提供的技术方法不仅原料容易获取、转化率高、选择性高,而且易实现气相连续制备Z-1-R-3,3,3-三氟丙烯。(The invention discloses a method for preparing Z-1-R-3,3, 3-trifluoropropene by gas phase isomerization, which comprises the following steps: E-1-R-3,3, 3-trifluoropropene (R = chloro, fluoro, -CF) in the presence of an isomerization catalyst 3 or-CF 2 CF 3 ) Isomerization reaction is carried out under the gas phase condition to obtain Z-1-R-3,3, 3-trifluoropropene (R = chlorine, fluorine, -CF) 3 or-CF 2 CF 3 ) Wherein, the isomerization catalyst is obtained by activating a precursor anhydrous metal chloride by halogenated saturated hydrocarbon or halogenated unsaturated hydrocarbon containing fluorine of an activating reagent. The technical method provided by the invention not only has the advantages of easy acquisition of raw materials, high conversion rate and high selectivity, but also is easy to realize the gas-phase continuous preparation of Z-1-R-3,3, 3-trifluoropropene.)

1. AA process for the preparation of Z-1-R-3,3, 3-trifluoropropene by gas phase isomerization, wherein R = chloro, fluoro, -CF₃or-CF₂CF₃The method is characterized in that: in the presence of an isomerization catalyst, E-1-R-3,3, 3-trifluoropropene is subjected to isomerization reaction under the gas phase condition to obtain Z-1-R-3,3, 3-trifluoropropene, wherein the isomerization catalyst is MF_pCl_m-pWherein M is +2 or +3, p is greater than zero and less than M, and M is a +2 or +3 valent metal ion;

the isomerization catalyst is MF_pCl_m-pThe preparation method comprises the following steps: from a precursor of anhydrous metal chloride MCl_mHalogenated saturated hydrocarbon containing fluorine or halogenated unsaturated hydrocarbon containing fluorine by activating reagent C_nH_xF_yCl_zActivation results, wherein y is greater than zero, x, z are both greater than or equal to zero, n is greater than or equal to 1 and less than or equal to 10, 2n +2= x + y + z or 2n-2= x + y + z or 2n = x + y + z.

2. The method of claim 1, wherein: the precursor is any one or more of aluminum chloride, zinc chloride, chromium chloride, ferric chloride, nickel chloride, cobalt chloride, copper chloride, gallium chloride and indium chloride.

3. The method of claim 2, wherein: the activating reagent contains fluorine-containing halogenated saturated hydrocarbon which is one or more of trifluoromethane, trifluoromonochloromethane, difluorodichloromethane, chlorodifluoromethane, dichlorofluoromethane, chloropentafluoroethane, 2, 2-dichloro-1, 1, 1-trifluoroethane, 1-chloro-1, 2,2, 2-tetrafluoroethane, 1-chloro-2, 2, 2-trifluoroethane, 2-chloro-1, 1,1, 2-tetrafluoropropane, 3-chloro-1, 1,1, 3-tetrafluoropropane and 2, 3-dichloro-1, 1, 1-trifluoropropane; the halogenated unsaturated hydrocarbon of the activating reagent is one or more of octafluorocyclopentene, 1,3,3,4,4,5, 5-heptafluorocyclopentene, 3,3,4,4,5, 5-hexafluorocyclopentene, 1-chloro-heptafluorocyclopentene, 1, 3-dichlorohexachlorocyclopentene, 1, 4-dichlorohexachlorocyclopentene, 1, 2-dichlorohexafluorocyclopentene, 1,2, 3-trichloropentafluorocyclopentene, 1,2, 4-trichloropentafluorocyclopentene, 1,3, 3-trichloropentafluorocyclopentene, 1,4, 4-trichloropentafluorocyclopentene, hexafluorocyclopentene, decafluorocyclohexene, hexafluorobutadiene, hexafluoro-2-butyne, tetrafluoropropadiene, trifluoropropylene, tetrafluoropropyne, 3, 3-trifluoropropyne and hexafluoropropene.

4. The method of claim 3, wherein: the activation method comprises the following steps: placing anhydrous metal chloride and fluorine-containing halogenated saturated hydrocarbon or halogenated unsaturated hydrocarbon into a closed reactor for reaction, wherein the mass ratio of the anhydrous metal chloride to the fluorine-containing halogenated saturated hydrocarbon or halogenated unsaturated hydrocarbon is 1: 1 to 5, the reaction temperature is 10 to 150 ℃, and the reaction time is 7 to 20 hours; or

Placing granular anhydrous metal chloride into a tubular reactor, continuously introducing fluorine-containing halogenated saturated hydrocarbon or halogenated unsaturated hydrocarbon for activation treatment, wherein the contact time of the fluorine-containing halogenated saturated hydrocarbon or halogenated unsaturated hydrocarbon is 5-100 s, performing segmented activation, activating at 50-150 ℃ for 4-20 hours, activating at 150-350 ℃ for 4-20 hours, stopping introducing an activating reagent, and cooling to room temperature under the protection of nitrogen to prepare the isomerization catalyst.

5. The method of claim 1, wherein: the isomerization reaction conditions are as follows: in the presence of an isomerization catalyst, the reaction pressure is 0.1-0.5MPa, the reaction temperature is 100-500 ℃, and the contact time of E-1-R-3,3, 3-trifluoropropene and the catalyst is 1-60 s.

6. The method of claim 5, wherein: the isomerization reaction conditions are as follows: in the presence of an isomerization catalyst, the reaction pressure is 0.1-0.5MPa, the reaction temperature is 100-350 ℃, and the contact time of E-1-R-3,3, 3-trifluoropropene and the catalyst is 1-30 s.

7. The method according to any one of claims 1 to 4, wherein: wherein M is +3 metal ions of aluminum or iron, and the activating reagent is fluorine-containing olefin.

8. The method of claim 7The method is characterized in that: the isomerization catalyst MF_pCl_m-pWherein the ratio of p to m is greater than 1: 2.

9. the method of claim 8, wherein: the isomerization catalyst MF_pCl_m-pWherein the ratio of p to m is greater than or equal to 13: 15.

Technical Field

The invention relates to a method for preparing Z-1-R-3,3, 3-trifluoropropene (R = chlorine, fluorine, -CF) by gas phase isomerization₃or-CF₂CF₃) Method (2)In particular to a compound prepared from E-1-R-3,3, 3-trifluoropropene (R = chlorine, fluorine, -CF)₃or-CF₂CF₃) The raw material is subjected to isomerization reaction under the action of an isomerization catalyst to obtain Z-1-R-3,3, 3-trifluoropropene.

Background

Z-1-chloro-3, 3, 3-trifluoropropene is an important refrigerant, a high-temperature heat pump working medium, a foaming agent, a cleaning agent and a fumigant, and is also an important raw material for preparing a pharmaceutical intermediate trifluoropropionic acid.

Since Z-1-chloro-3, 3, 3-trifluoropropene has a higher energy than E-1-chloro-3, 3, 3-trifluoropropene and is less stable than E-1-chloro-3, 3, 3-trifluoropropene, the main products are E-1-chloro-3, 3, 3-trifluoropropene in dehydrochlorination of 1, 1-dichloro-3, 3, 3-trifluoropropane (US 2015/45590), dehydrofluorination of 1-chloro-1, 3, 3-tetrafluoropropane (US 10118879 and US 2014/5446), addition of 3,3, 3-trifluoropropyne to HCl (US 9000239B 2), fluorination of 1,1,1,3, 3-pentachloropropane to HF (CN 104039745B, EP2341040a1 and US 2011/201853), and the like, z-1-chloro-3, 3, 3-trifluoropropene is a by-product and is much less abundant than E-1-chloro-3, 3, 3-trifluoropropene, so none of the above methods fall into an ideal route for the synthesis of Z-1-chloro-3, 3, 3-trifluoropropene.

Currently, Z-1-chloro-3, 3, 3-trifluoropropene is generally synthesized by isomerization of E-1-chloro-3, 3, 3-trifluoropropene. US9000239B2 reports 2-chloro-3, 3, 3-trifluoropropene over CrF at 350 ℃₃The isomerization reaction is catalyzed to obtain HCFO-1233zd (E) and HCFO-1233zd (Z), wherein the conversion rate of 2-chloro-3, 3, 3-trifluoropropene is 50.1%, the selectivity of HCFO-1233zd (E) is 64.9%, and the selectivity of HCFO-1233zd (Z) is 32.3%, see reaction (1). AlF is reported in patent CN102245548B₃As a catalyst, the yield of HCFO-1233zd (Z) was 10.8% at 300 ℃; fluorinated Cr is also reported₂O₃As a catalyst, when the catalyst was operated at 250 ℃ for 10 hours, the conversion of HCFO-1233zd (E) was 9.59%, the selectivity of HCFO-1233zd (Z) was 90.6%, and when the catalyst was operated at 300 ℃ for 10 hours, the conversion of HCFO-1233zd (E) was 12.55%, and the selectivity of HCFO-1233zd (Z) was 80.6%, see reaction (2). In patent CN 104603089B, Cl is reported₂In the presence of HCFO-1233zd (E) isomerization to HCFO-1233zd (Z) at "350 deg.C, Cl₂A flow rate of 2.6ml/min, a HCFO-1233zd (E) flow rate of 0.75ml/min, and a contact time of 1.70s ", a conversion of HCFO-1233zd (E) of 12.4%, and a selectivity of HCFO-1233zd (Z) of 90.7%; at "temperature 450 ℃ Cl₂The flow rate was 0.4ml/min, the HCFO-1233zd (E) flow rate was 1.27ml/min, and the contact time was 0.87s ", the HCFO-1233zd (E) conversion was 16.79%, and the HCFO-1233zd (Z) selectivity was 91.4%, see reaction (3).

Reaction (1)

Reaction (2)

Reaction (3)

The above isomerization route has the following problems: the raw material 2-chloro-3, 3, 3-trifluoropropene used in the reaction (1) is not easy to obtain; reaction (2) with AlF₃Or fluorinated Cr₂O₃Catalyzing isomerization of HCFO-1233zd (E) to HCFO-1233zd (Z), with the disadvantage of lower selectivity for HCFO-1233zd (Z); reaction (3) adopts chlorine gas to generate Cl free radical to promote the isomerization of HCFO-1233zd (E), and has the defect of poor selectivity of HCFO-1233zd (Z).

Disclosure of Invention

The technical problem to be solved by the invention is to solve the defects in the background technology and provide a method which is easy to obtain raw materials, high in conversion rate and high in selectivity and can easily realize the gas-phase continuous preparation of Z-1-R-3,3, 3-trifluoropropene (R = chlorine, fluorine, -CF)₃or-CF₂CF₃) The method of (1).

A process for the preparation of Z-1-R-3,3, 3-trifluoropropene by gas phase isomerization wherein R = chloro, fluoro, -CF₃or-CF₂CF₃The method is characterized in that: in the presence of an isomerization catalyst, E-1-R-3,3, 3-trifluoropropene is introduced into gasCarrying out isomerization reaction under the phase condition to obtain Z-1-R-3,3, 3-trifluoropropene, wherein the isomerization catalyst is MF_pCl_m-pWherein M is +2 or +3, p is greater than zero and less than M, and M is a +2 or +3 valent metal ion.

The isomerization catalyst MF_pCl_m-pThe preparation method comprises the following steps: from a precursor of anhydrous metal chloride MCl_mHalogenated saturated hydrocarbon containing fluorine or halogenated unsaturated hydrocarbon containing fluorine by activating reagent C_nH_xF_yCl_zActivation, wherein y is greater than zero, x, z are both greater than or equal to zero, n is greater than or equal to 1 and less than or equal to 10, 2n +2= x + y + z or 2n-2= x + y + z or 2n = x + y + z.

The reactions that occur during activation are as follows:

the precursor is any one or more of aluminum chloride, zinc chloride, chromium chloride, ferric chloride, nickel chloride, cobalt chloride, copper chloride, gallium chloride and indium chloride.

The activating reagent contains fluorine-containing halogenated saturated hydrocarbon which is one or more of trifluoromethane, trifluoromonochloromethane, difluorodichloromethane, chlorodifluoromethane, dichlorofluoromethane, chloropentafluoroethane, 2, 2-dichloro-1, 1, 1-trifluoroethane, 1-chloro-1, 2,2, 2-tetrafluoroethane, 1-chloro-2, 2, 2-trifluoroethane, 2-chloro-1, 1,1, 2-tetrafluoropropane, 3-chloro-1, 1,1, 3-tetrafluoropropane and 2, 3-dichloro-1, 1, 1-trifluoropropane; the halogenated unsaturated hydrocarbon of the activating reagent is one or more of octafluorocyclopentene, 1,3,3,4,4,5, 5-heptafluorocyclopentene, 3,3,4,4,5, 5-hexafluorocyclopentene, 1-chloro-heptafluorocyclopentene, 1, 3-dichlorohexachlorocyclopentene, 1, 4-dichlorohexachlorocyclopentene, 1, 2-dichlorohexafluorocyclopentene, 1,2, 3-trichloropentafluorocyclopentene, 1,2, 4-trichloropentafluorocyclopentene, 1,3, 3-trichloropentafluorocyclopentene, 1,4, 4-trichloropentafluorocyclopentene, hexafluorocyclopentene, decafluorocyclohexene, hexafluorobutadiene, hexafluoro-2-butyne, tetrafluoropropadiene, trifluoropropylene, tetrafluoropropyne, 3, 3-trifluoropropyne and hexafluoropropene.

The activation method comprises the following steps: placing anhydrous metal chloride and fluorine-containing halogenated saturated hydrocarbon or halogenated unsaturated hydrocarbon into a closed reactor for reaction, wherein the mass ratio of the anhydrous metal chloride to the fluorine-containing halogenated saturated hydrocarbon or halogenated unsaturated hydrocarbon is 1: 1-5, the reaction temperature is 10-150 ℃, and the reaction time is 7-20 hours; or

Placing granular anhydrous metal chloride into a tubular reactor, continuously introducing fluorine-containing halogenated saturated hydrocarbon or halogenated unsaturated hydrocarbon for activation treatment, wherein the contact time of the fluorine-containing halogenated saturated hydrocarbon or halogenated unsaturated hydrocarbon is 5-100 s, performing segmented activation, activating at 50-150 ℃ for 4-20 hours, activating at 150-350 ℃ for 4-20 hours, stopping introducing an activating reagent, and cooling to room temperature under the protection of nitrogen to prepare the isomerization catalyst.

The isomerization reaction conditions are as follows: in the presence of an isomerization catalyst, the reaction pressure is 0.1-0.5MPa, the reaction temperature is 100-500 ℃, and the contact time of E-1-R-3,3, 3-trifluoropropene and the catalyst is 1-60 s.

The isomerization reaction conditions are as follows: in the presence of an isomerization catalyst, the reaction pressure is 0.1-0.5MPa, the reaction temperature is 100-350 ℃, and the contact time of E-1-R-3,3, 3-trifluoropropene and the catalyst is 1-30 s.

Preferably: wherein M is +3 metal ions of aluminum or iron, and the activating reagent is fluorine-containing olefin.

The isomerization catalyst MF_pCl_m-pWherein the ratio of p to m is greater than 1: 2.

the isomerization catalyst MF_pCl_m-pWherein the ratio of p to m is greater than or equal to 13: 15.

in the invention, fluorine-containing halogenated saturated hydrocarbon or halogenated unsaturated hydrocarbon is used as an activating reagent in the activation process of the catalyst, and the material flow from the reactor after the activation treatment contains the raw material C_nH_xF_yCl_zAnd reaction product C_nH_xF_{y- p}Cl_z+pCan be treated by a separation apparatus such as an acid removal column, a drying column, a separation column to obtain a raw material C_nH_xF_yCl_zAnd product C_nH_xF_y-pCl_z+pThe raw material can be recycled to the reactor for continuous use, and the product C_nH_xF_y-pCl_z+pMay be useful intermediates in the fluorine process, may be sold or used as intermediates in the production of other high value added products, and may be recycled to the reactor for use as an activating reagent until C_nH_xF_y-pCl_z+pNo fluorine, i.e. y = p.

The isomerization reaction of the invention takes E-1-R-3,3, 3-trifluoropropene as a raw material, and Z-1-R-3,3, 3-trifluoropropene is obtained through gas phase isomerization reaction. The main reaction is as follows:

the invention can be carried out at normal pressure or under elevated pressure. The preferred pressure of the invention is 0.1-0.5 MPa.

The invention provides a preparation method of Z-1-R-3,3, 3-trifluoropropene. After the reaction is finished, the mixture containing the E-1-R-3,3, 3-trifluoropropene and the Z-1-R-3,3, 3-trifluoropropene is subjected to post-treatment such as separation, initial acid treatment, drying and the like, so that a corresponding product can be obtained: Z-1-R-3,3, 3-trifluoropropene. Wherein the boiling point of E-1-chloro-3, 3, 3-trifluoropropene is 19 ℃ (760 mmHg), the boiling point of Z-1-chloro-3, 3, 3-trifluoropropene is 38 ℃ (760 mmHg), the boiling point of E-1,3,3, 3-tetrafluoropropene is-19 ℃ (760 mmHg), the boiling point of Z-1,3,3, 3-tetrafluoropropene is 9 ℃ (760 mmHg), the boiling point of E-1,1,1,4,4, 4-hexafluoro-2-butene is 8 ℃ (760 mmHg), the boiling point of Z-1,1,1,4, 4-hexafluoro-2-butene is 33.3 ℃ (760 mmHg), the boiling point of E-1,1,1,4,4,5,5, 5-octafluoro-2-pentene is 29 to 30 ℃ (760 mmHg), the boiling point of Z-1,1,1,4,4,5,5, 5-octafluoro-2-pentene is 48 ℃ (760 mmHg).

The raw material E-1-R-3,3, 3-trifluoropropene of the invention is easily available, such as: the E-1-chloro-3, 3, 3-trifluoropropene can be prepared according to the methods provided by Chinese patents CN100361944C and CN102211974B, namely, the telomerization reaction of carbon tetrachloride and chloroethylene is carried out to obtain HCC-240 fa; then obtaining the E-1-chloro-3, 3, 3-trifluoropropene through fluorine-chlorine exchange reaction and dehydrochlorination reaction.

The invention has the advantages that: the technical method provided by the invention has the advantages of easily obtained raw materials, high conversion rate, high selectivity and easily controlled reaction; the reaction mixture is distilled and purified, the product is obtained at the tower bottom and can be further purified, and the raw material at the tower top can be recycled to the reactor, so that the continuous large-scale production of the Z-1-chloro-3, 3, 3-trifluoropropene is realized.

Drawings

FIG. 1 Process flow diagram for the continuous preparation of Z-1-R-3,3, 3-trifluoropropene

The reference numerals in fig. 1 have the following meanings. Pipeline: 1.2, 4, 6 and 7; a first reactor: 3; a first distillation column: 5.

Detailed Description

The invention is described in further detail below with reference to the accompanying drawings.

The present invention is described in further detail with reference to fig. 1. But not to limit the invention. Fresh E-1-R-3,3, 3-trifluoropropene enters a first reactor 3 filled with a catalyst through a pipeline 1 and a pipeline 6 to be recycled together with the E-1-R-3,3, 3-trifluoropropene for reaction through a pipeline 2, a reaction product flows through a pipeline 4 to enter a first distillation tower 5 for pressure distillation, the pressure is controlled between 0.1 and 2.5MPa, the tower top component of the first distillation tower 5 is the E-1-R-3,3, 3-trifluoropropene, the tower top component can be recycled to the first reactor 3 for continuous reaction and conversion into the Z-1-R-3,3, 3-trifluoropropene, the tower bottom component is a Z-1-R-3,3, 3-trifluoropropene crude product, is led out through a pipeline 7 and is rectified, Drying and deacidifying to obtain the high-purity Z-1-R-3,3, 3-trifluoropropene.

An analytical instrument: shimadzu GC-2010, column model InterCap 1 (i.d. 0.25 mm; length 60 m; J & W Scientific Inc.).

GC analysis method: the temperature of the detector is 240 ℃, the temperature of the vaporization chamber is 150 ℃, the initial temperature of the column is 40 ℃, the temperature is kept for 10 minutes, the temperature is raised to 240 ℃ at the rate of 20 ℃/min, and the temperature is kept for 10 minutes.

The present invention will be described in more detail with reference to the following examples, which are not intended to limit the scope of the present invention.

Example 1

Preparation of catalystPreparing: a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of anhydrous aluminum chloride, and 1,3,3,4,4,5, 5-heptafluorocyclopentene was introduced thereinto to activate the reaction mixture under the following conditions: the contact time of the 1,3,3,4,4,5, 5-heptafluorocyclopentene is 60s, the catalyst is firstly activated for 10 hours at the temperature of 50 ℃, then activated for 10 hours at the temperature of 300 ℃, the introduction of an activating reagent is stopped, the temperature is reduced to room temperature under the protection of nitrogen, the isomerization catalyst is prepared, and the catalyst component is AlCl through XRF elemental analysis_0.1F_2.9 。

A tubular reactor of 30cm length having an inner diameter of 1/2 inches was charged with 10mL of the isomerization catalyst prepared above. The reaction conditions are as follows: the temperature of the reaction is raised to 100 ℃, the contact time of the E-1-chloro-3, 3, 3-trifluoropropene is 30s, and the reaction pressure is 0.1 MPa. After 10h of operation, the reaction product was collected and heated, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 11.9%, and the selectivity of Z-1-chloro-3, 3, 3-trifluoropropene was 99.9%.

Example 2

The same as in example 1, except that the temperature of the isomerization reaction was changed to 200 ℃, the reaction results were: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 15.3%, and the selectivity of Z-1-chloro-3, 3, 3-trifluoropropene was 99.9%.

Example 3

The same as in example 1, except that the temperature of the isomerization reaction was changed to 300 ℃, the results were: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 17.4%, and the selectivity of Z-1-chloro-3, 3, 3-trifluoropropene was 99.8%.

Example 4

The same as in example 1, except that the temperature of the isomerization reaction was changed to 400 ℃, the results were: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 23.6%, the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 91.4%, and the selectivity for 3,3, 3-trifluoropropyne was 8.5%.

Example 5

The same as in example 1, except that the temperature of the isomerization reaction was changed to 500 ℃, the results were: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 31.6%, the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 75.8%, and the selectivity for 3,3, 3-trifluoropropyne was 24.2%.

Example 6

The same as in example 1, except that the contact time for the isomerization reaction was changed to 1s, the reaction temperature was changed to 300 ℃, and the results were: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 11.3%, and the selectivity of Z-1-chloro-3, 3, 3-trifluoropropene was 100%.

Example 7

The same as in example 1, except that the contact time for the isomerization reaction was changed to 10s, the reaction temperature was changed to 300 ℃, and the results were: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 13.5%, and the selectivity of Z-1-chloro-3, 3, 3-trifluoropropene was 99.9%.

Example 8

The same as in example 1, except that the contact time for the isomerization reaction was changed to 60s, the reaction temperature was changed to 300 ℃, and the results were: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 18.1%, and the selectivity of Z-1-chloro-3, 3, 3-trifluoropropene was 96.1%.

Example 9

The same as in example 1, except that the reaction pressure of the isomerization reaction was changed to 0.3MPa, the reaction temperature was changed to 300 ℃, and the reaction results were: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 15.7%, and the selectivity of Z-1-chloro-3, 3, 3-trifluoropropene was 99.2%.

Example 10

The same as in example 1, except that the reaction pressure of the isomerization reaction was changed to 0.5MPa, the reaction temperature was changed to 300 ℃, and the results were as follows: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 13.2%, and the selectivity of Z-1-chloro-3, 3, 3-trifluoropropene was 98.5%.

Example 11

The isomerization catalyst prepared in the same manner as in example 1 except that the activating reagent 1,3,3,4,4,5, 5-heptafluorocyclopentene was changed to 1, 3-dichlorohexachlorocyclopentene in an equivalent amount was analyzed by XRF element and had a composition of AlCl_0.2F_2.8The method is used for the isomerization reaction of E-1-chloro-3, 3, 3-trifluoropropene, the reaction conditions are the same, and the reaction result is as follows: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 16.8%, and the selectivity of Z-1-chloro-3, 3, 3-trifluoropropene was 99.9%.

Example 12

The isomerization catalyst prepared as in example 1 except that aluminum chloride was changed to ferric chloride had a composition of FeCl as analyzed by XRF elemental analysis_0.4F_2.6The method is used for the isomerization reaction of E-1-chloro-3, 3, 3-trifluoropropene, the reaction conditions are the same, and the reaction result is as follows: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 15.2%, and the selectivity of Z-1-chloro-3, 3, 3-trifluoropropene was 99.9%.

Example 13

Preparation of the catalyst: putting aluminum chloride and 1,3,3,4,4,5, 5-heptafluorocyclopentene into a 500mL autoclave for reaction, wherein the mass ratio of the aluminum chloride (1mol) to the 1,3,3,4,4,5, 5-heptafluorocyclopentene (3mol) is 1:3, the reaction temperature is 25 ℃, the reaction time is 18 hours, after the reaction is finished, filtering and drying materials in a reaction system to obtain an isomerization catalyst, and the composition of the isomerization catalyst is AlCl after XRF elemental analysis_0.04F_2.96 。

A tubular reactor of 30cm length having an inner diameter of 1/2 inches was charged with 10mL of the isomerization catalyst prepared above. The reaction conditions are as follows: the temperature of the reaction is increased to 300 ℃, the contact time of the E-1-chloro-3, 3, 3-trifluoropropene is 30s, and the reaction pressure is 0.1 MPa. After 10h of operation, the reaction product was collected and heated, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 17.6%, and the selectivity of Z-1-chloro-3, 3, 3-trifluoropropene was 99.9%.

Example 14

The same as in example 1, except that the temperature of the isomerization reaction was changed to 350 ℃ and the raw material of the isomerization reaction was changed to E-1,3,3, 3-tetrafluoropropene, the reaction results were: the conversion of E-1,3,3, 3-tetrafluoropropene was 24.3% and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 99.9%.

Example 15

Similar to example 1, except that the temperature of the isomerization reaction was changed to 250 ℃, the raw material for the isomerization reaction was changed to E-1,1,1,4,4, 4-hexafluoro-2-butene, and the conversion of E-1,1,1,4,4, 4-hexafluoro-2-butene was 67.4% and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 99.9%.