[go: up one dir, main page]

CN112811975B - Method for preparing Z-1-R-3,3, 3-trifluoropropene by gas phase isomerization - Google Patents

Method for preparing Z-1-R-3,3, 3-trifluoropropene by gas phase isomerization Download PDF

Info

Publication number
CN112811975B
CN112811975B CN202110433904.3A CN202110433904A CN112811975B CN 112811975 B CN112811975 B CN 112811975B CN 202110433904 A CN202110433904 A CN 202110433904A CN 112811975 B CN112811975 B CN 112811975B
Authority
CN
China
Prior art keywords
trifluoropropene
reaction
isomerization
chloro
catalyst
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.)
Active
Application number
CN202110433904.3A
Other languages
Chinese (zh)
Other versions
CN112811975A (en
Inventor
张呈平
郭勤
贾晓卿
权恒道
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.)
Quanzhou Yuji New Material Technology Co.,Ltd.
Original Assignee
Quanzhou Yuji New Material Technology Co ltd
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 Quanzhou Yuji New Material Technology Co ltd filed Critical Quanzhou Yuji New Material Technology Co ltd
Priority to CN202110433904.3A priority Critical patent/CN112811975B/en
Publication of CN112811975A publication Critical patent/CN112811975A/en
Application granted granted Critical
Publication of CN112811975B publication Critical patent/CN112811975B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

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 catalyst3or-CF2CF3) Isomerization reaction is carried out under the gas phase condition to obtain Z-1-R-3,3, 3-trifluoropropene (R = chlorine, fluorine, -CF)3or-CF2CF3) 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.

Description

Method for preparing Z-1-R-3,3, 3-trifluoropropene by gas phase isomerization
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) In particular to a method of preparing a compound of (1-R-3, 3, 3-trifluoropropene) (R = chloro, fluoro, -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), HCFO-1233zd (Z) is isomerized at a temperature of 350 deg.C in the presence of 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).
Figure DEST_PATH_IMAGE001
Reaction (1)
Figure 544293DEST_PATH_IMAGE002
Reaction (2)
Figure DEST_PATH_IMAGE003
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 subjected to isomerization reaction under the gas phase condition to obtain Z-1-R-3,3, 3-trifluoropropene, wherein the isomerization catalyst is MFpClm-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 MFpClm-pThe preparation method comprises the following steps: from a precursor of anhydrous metal chloride MClmHalogenated saturated hydrocarbon containing fluorine or halogenated unsaturated hydrocarbon containing fluorine by activating reagent CnHxFyClzActivation, 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:
Figure DEST_PATH_IMAGE005
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 MFpClm-pWherein the ratio of p to m is greater than 1: 2.
the isomerization catalyst MFpClm-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 CnHxFyClzAnd reaction product CnHxFy- pClz+pCan be treated by a separation apparatus such as an acid removal column, a drying column, a separation column to obtain a raw material CnHxFyClzAnd product CnHxFy-pClz+pThe raw material can be recycled to the reactor for continuous use, and the product CnHxFy-pClz+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 CnHxFy-pClz+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:
Figure DEST_PATH_IMAGE007
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 the catalyst: 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 analysis0.1F2.9 。
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 AlCl0.2F2.8The 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 analysis0.4F2.6The 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: aluminum chloride and 1,3,3,4,4,5, 5-heptafluorocyclopentene are placed in a 500mL autoclave for reaction, 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 ℃, and the reaction is carried outThe time is 18 hours, after the reaction is finished, materials in the reaction system are filtered and dried to obtain an isomerization catalyst, and the composition of the isomerization catalyst is AlCl after XRF element analysis0.04F2.96 。
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%.

Claims (3)

1. Method for preparing Z-1-R-3,3, 3-trifluoropropene by gas phase isomerization, wherein R = -CF3The 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 AlCl0.1F2.9；
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 activation treatment is firstly carried out for 10 hours at the temperature of 50 ℃, then the activation treatment is carried out for 10 hours at the temperature of 300 ℃, the introduction of the activation reagent is stopped, the reaction is carried out, and the reaction is carried out in the presence of the catalystCooling to room temperature under the protection of nitrogen to prepare an isomerization catalyst, and analyzing XRF element to obtain the catalyst with AlCl0.1F2.9。
2. 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.
3. The method of claim 2, 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.
CN202110433904.3A 2021-04-22 2021-04-22 Method for preparing Z-1-R-3,3, 3-trifluoropropene by gas phase isomerization Active CN112811975B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110433904.3A CN112811975B (en) 2021-04-22 2021-04-22 Method for preparing Z-1-R-3,3, 3-trifluoropropene by gas phase isomerization

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110433904.3A CN112811975B (en) 2021-04-22 2021-04-22 Method for preparing Z-1-R-3,3, 3-trifluoropropene by gas phase isomerization

Publications (2)

Publication Number Publication Date
CN112811975A CN112811975A (en) 2021-05-18
CN112811975B true CN112811975B (en) 2021-07-30

Family

ID=75862523

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110433904.3A Active CN112811975B (en) 2021-04-22 2021-04-22 Method for preparing Z-1-R-3,3, 3-trifluoropropene by gas phase isomerization

Country Status (1)

Country Link
CN (1) CN112811975B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114316909B (en) * 2022-03-03 2022-06-24 北京宇极科技发展有限公司 Fluorine-containing heat transfer fluid and preparation method and application thereof
CN114853563B (en) * 2022-06-27 2024-06-28 山东华安新材料有限公司 Preparation method of 2-chloro-1, 1-difluoroethane
CN115382560B9 (en) * 2022-10-27 2023-04-28 北京宇极科技发展有限公司 Block aluminum chloride catalyst, preparation method and application
CN116037120B (en) * 2023-03-31 2023-07-14 北京宇极科技发展有限公司 Preparation method of positive and negative isomer of 1, 4-hexafluoro-2-butene
CN116143585B (en) * 2023-04-04 2023-07-14 北京宇极科技发展有限公司 Method for preparing hydrohaloolefine and method for preparing fluorine-containing alkyne

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1051904A (en) * 1989-10-16 1991-06-05 纳幕尔杜邦公司 The preparation method of chlorine fluorine propane
CN1067879A (en) * 1991-06-14 1993-01-13 大金工业株式会社 Process for preparing fluorinated compounds
CN101796003A (en) * 2007-08-16 2010-08-04 纳幕尔杜邦公司 Catalytic isomerization between E and Z isomers of 1,2,3,3,3 pentafluoropropene using aluminum catalyst
CN102245548A (en) * 2008-12-12 2011-11-16 霍尼韦尔国际公司 Isomerization of 1-chloro-3, 3, 3-trifluoropropene
CN105189421A (en) * 2013-03-14 2015-12-23 霍尼韦尔国际公司 Method to produce cis 1-chloro-3,3,3-trifluoropropene
CN111925274A (en) * 2020-09-17 2020-11-13 北京宇极科技发展有限公司 Preparation method of Z-1-chloro-3, 3, 3-trifluoropropene

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7795482B2 (en) * 2007-07-03 2010-09-14 E. I. Du Pont De Nemours And Company Method of hydrodechlorination to produce dihydrofluorinated olefins
US8530709B2 (en) * 2010-05-21 2013-09-10 Honeywell International Inc. Process for the production of fluorinated alkenes
GB2519572B (en) * 2013-10-25 2015-12-30 Mexichem Amanco Holding Sa Process for isomerising (hydro)(halo)fluoroalkenes
WO2017027323A1 (en) * 2015-08-07 2017-02-16 The Chemours Company Fc, Llc Catalytic isomerization of z-1,1,1,4,4,4-hexafluoro-2-butene to e-1,1,1,4,4,4-hexafluoro-2-butene
CN108727155B (en) * 2018-06-19 2021-01-01 北京宇极科技发展有限公司 Preparation method of E-1,1,1,4,4, 4-hexafluoro-2-butene
JP7710375B2 (en) * 2019-04-18 2025-07-18 ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー Lewis acid catalyzed synthesis of 1,2-bis(perfluoroalkyl)ethylenes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1051904A (en) * 1989-10-16 1991-06-05 纳幕尔杜邦公司 The preparation method of chlorine fluorine propane
CN1067879A (en) * 1991-06-14 1993-01-13 大金工业株式会社 Process for preparing fluorinated compounds
CN101796003A (en) * 2007-08-16 2010-08-04 纳幕尔杜邦公司 Catalytic isomerization between E and Z isomers of 1,2,3,3,3 pentafluoropropene using aluminum catalyst
CN102245548A (en) * 2008-12-12 2011-11-16 霍尼韦尔国际公司 Isomerization of 1-chloro-3, 3, 3-trifluoropropene
CN105189421A (en) * 2013-03-14 2015-12-23 霍尼韦尔国际公司 Method to produce cis 1-chloro-3,3,3-trifluoropropene
CN111925274A (en) * 2020-09-17 2020-11-13 北京宇极科技发展有限公司 Preparation method of Z-1-chloro-3, 3, 3-trifluoropropene

Also Published As

Publication number Publication date
CN112811975A (en) 2021-05-18

Similar Documents

Publication Publication Date Title
CN112811975B (en) Method for preparing Z-1-R-3,3, 3-trifluoropropene by gas phase isomerization
JP5143011B2 (en) Method for producing fluorinated organic compound
CN111925274B (en) Preparation method of Z-1-chloro-3, 3, 3-trifluoropropene
JP5498381B2 (en) Method for producing a fluorinated organic compound
EP2178814B1 (en) Method for producing fluorinated olefins
CN101868435B (en) Processes for synthesis of fluorinated olefins
EP2736864B1 (en) Process for preparing 2,3,3,3-tetrafluoropropene
JP6107467B2 (en) Process for producing 1-chloro-3,3,3-trifluoropropene
TW200920721A (en) Preparation of halogen and hydrogen containing alkenes over metal fluoride catalysts
US20130150632A1 (en) Process for cis-1-chloro-3,3,3-trifluoropropene
KR20160091937A (en) Hydrochloric acid purification process
JP5715177B2 (en) Method for producing fluorinated organic compound
CN112723985B (en) Preparation method of E-1-halo-3, 3, 3-trifluoropropene
KR20140077958A (en) Process for producing 2,3,3,3-tetrafluoropropene
CN108033871A (en) The preparation of 1,3,3,3- tetrafluoropropenes
KR20140071456A (en) Process for producing 2,3,3,3-tetrafluoropropene
CN116037117A (en) Initiator, fluorination catalyst and preparation method of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene
JP5713015B2 (en) Method for producing 1,1-dichloro-2,2,3,3,3-pentafluoropropane
JP6015543B2 (en) (E) Process for producing 1-chloro-3,3,3-trifluoropropene
CN112811973B (en) Preparation method of E-1,3,3, 3-tetrafluoropropene
WO2023171275A1 (en) Halogenated alkene production method
JP7609062B2 (en) Method for producing hydrochlorofluorocarbons, method for producing 1-chloro-2,3,3-trifluoropropene, method for producing 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20210601

Address after: 362000 west side of 11 / F, youth building, 288 Tian'an North Road, Fengze District, Quanzhou City, Fujian Province

Applicant after: Quanzhou Yuji New Material Technology Co.,Ltd.

Address before: 100081 room 02, 15 / F, building 6, courtyard A2, Xisanhuan North Road, Haidian District, Beijing

Applicant before: BEIJING YUJI SCIENCE AND TECHNOLOGY Co.,Ltd.

GR01 Patent grant
GR01 Patent grant