CN116874345A - Method for the gas phase continuous production of E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene - Google Patents

Method for the gas phase continuous production of E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene Download PDF

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CN116874345A
CN116874345A CN202311143584.3A CN202311143584A CN116874345A CN 116874345 A CN116874345 A CN 116874345A CN 202311143584 A CN202311143584 A CN 202311143584A CN 116874345 A CN116874345 A CN 116874345A
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trifluoromethyl
pent
ene
reaction
gas phase
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张呈平
董利
李瑞涛
权恒道
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Quanzhou Yuji New Material Technology Co ltd
Beijing Yuji Science and Technology Co Ltd
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Quanzhou Yuji New Material Technology Co ltd
Beijing Yuji Science and Technology Co Ltd
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    • 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
    • C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
    • 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
    • B01J27/13—Platinum group metals
    • 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
    • B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • 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

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Abstract

The application discloses a method for continuously preparing E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene in a gas phase, the method comprises the steps of carrying out first gas phase hydrogenation reaction, first gas phase dehydrofluorination reaction, second gas phase dehydrofluorination reaction, third gas phase dehydrofluorination reaction and fourth gas phase dehydrofluorination reaction on 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene the second gas phase hydrogenation reaction and the second gas phase dehydrofluorination reaction to obtain E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene, the application takes 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene as raw material the single-pass yield of synthesizing E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene is high, the raw materials are easy to obtain and can be obtained by the market.

Description

Method for the gas phase continuous production of E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene
Technical Field
The application relates to the technical field of hydrofluoroolefins, in particular to a method for continuously preparing E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene by using a gas phase.
Background
E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene is a typical hydrofluoroolefin, has the characteristics of environmental friendliness and excellent application performance in the field of chlorofluorocarbon substitutes, and is considered to be one of ideal chlorofluorocarbon substitutes. At present, the published literature reports that the synthesis method of E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene is less, and mainly comprises the following steps:
(1) The first synthetic route: starting materials of 2, 2-dichloro-1, 3-hexafluoropropane and 3, 3-trifluoropropene
Patent WO 2021150801A 1 reports starting from 2, 2-dichloro-1, 3-hexafluoropropane and 3, 3-trifluoropropene the raw materials are reacted in two steps to synthesize E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene. Firstly, a catalyst consisting of tributyl phosphate and ferric chloride catalyzes 2, 2-dichloro-1, 3-hexafluoropropane and 3, 3-trifluoropropene to react, reacting at 150 ℃ for 12 hours to obtain 2, 4-dichloro-1, 5-hexafluoro-2- (trifluoromethyl) pentane with the yield of 31%; secondly, the ratio of the amounts of the substances HF to 2, 4-dichloro-1, 5-hexafluoro-2- (trifluoromethyl) pentane in the presence of a chromium-based catalyst is 15:1, under the condition of 325 ℃ and 10 s of contact time, E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene is obtained, the conversion of 2, 4-dichloro-1, 5-hexafluoro-2- (trifluoromethyl) pentane was 90%, the selectivity of E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene is only 15-20%, whereas the selectivity of the subfluorinated intermediate E-4-chloro-1, 5-hexafluoro-4- (trifluoromethyl) pent-2-ene is 55-60%.
(2) The second synthetic route: hexafluoropropylene and 1, 3-tetrafluoropropene are used as raw materials
Patent application WO2021150801 A1 reports a method for synthesizing E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene by a one-step reaction using hexafluoropropylene and 1, 3-tetrafluoropropene as raw materials. Adding antimony pentafluoride bulk catalyst into a closed vibrating tube to catalyze hexafluoropropylene and 1, 3-tetrafluoropropene to react for 12 hours at 50 ℃, the reaction gave E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene in a yield of 50%.
The above route for the synthesis of E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene has the following problems: (1) The yield of the two-step reaction of the first synthetic route is very low, and the catalyst in the first step reaction is difficult to recycle, so that a large amount of solid waste is generated, and the environment is easy to be polluted; (2) The second route belongs to an intermittent process, the reaction time is longer, the yield of the target product is low, and the bulk catalyst antimony pentafluoride is difficult to recycle.
Disclosure of Invention
Aiming at the technical problems, the application provides the preparation method for producing E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene in a large scale, which has the advantages of easily available raw materials, high single-pass yield, high catalyst activity and easiness in realizing gas phase continuous mass production.
The specific technical scheme of the application is as follows:
1. a process for the vapor phase continuous preparation of E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene comprising:
1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene is subjected to a first gas phase hydrogenation reaction, a first gas phase dehydrofluorination reaction the second gas phase hydrogenation reaction and the second gas phase dehydrofluorination reaction to obtain E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene.
2. The method according to item 1, wherein, the 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) group pent-2-ene is E-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene and/or Z-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene.
3. The method according to item 1 or 2, wherein, the first gas phase hydrogenation reaction is to react 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene and hydrogen in the presence of the reaction is carried out in the presence of a hydrogenation catalyst to obtain 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane.
4. The method according to item 3, wherein,
the reaction pressure of the first gas phase reaction is 0.1-2MPa; and/or
The reaction temperature is 50-250 ℃; and/or
The ratio of the amount of the substances of the 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene and the hydrogen is 1:1-15; and/or
The contact time is 1-100s.
5. The method according to item 3, wherein, the first gas phase dehydrofluorination reaction is carried out in the presence of a dehydrofluorination catalyst for 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane the reaction is carried out to obtain 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and/or 1,2,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene.
6. The process according to item 5, wherein the reaction pressure of the first gas phase dehydrofluorination reaction is from 0.1 to 2MPa; and/or
The reaction temperature is 250-500 ℃; and/or
The contact time is 1-100s.
7. The method according to item 5, wherein, the second gas phase hydrogenation reaction is 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and/or 1,2,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene reacting with hydrogen in the presence of a hydrogenation catalyst to obtain 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane or/and 1,2,4, 5-octafluoro-2- (trifluoromethyl) pentane.
8. The process according to item 7, wherein the reaction pressure of the second gas-phase hydrogenation reaction is 0.1 to 2MPa; and/or
The reaction temperature is 50-250 ℃; and/or
1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene or/and 1,2,4, 5-octa the ratio of the amount of the fluorine-4- (trifluoromethyl) pent-2-ene to the amount of the hydrogen gas is 1:1-15; and/or
The contact time is 1-100s.
9. The method according to item 7, wherein, the second gas phase dehydrofluorination reaction is the 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane or/and 1,2,4, 5-octafluoro-2- (tri-fluoromethyl) pentane fluoromethyl) pentane in the presence of a dehydrofluorination catalyst to give E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene.
10. The process according to item 9, wherein the reaction pressure of the second gas phase dehydrofluorination reaction is from 0.1 to 2MPa; and/or
The reaction temperature is 250-500 ℃; and/or
The contact time is 1-100s.
11. The process according to item 3, wherein the hydrogenation catalyst contains an active ingredient and a carrier, preferably the active ingredient is palladium or platinum;
preferably, the carrier is selected from CrF 3 、FeF 3 、CoF 2 、NiF 2 、ZnF 2 、MgF 2 、CaF 2 、BaF 2 、SrF 2 、AlF 3 、GaF 3 And InF 3 One of the following;
preferably, the active component accounts for 0.1 to 5 percent of the hydrogenation catalyst, and the carrier accounts for 95 to 99.9 percent of the hydrogenation catalyst.
12. The method of item 5, wherein the dehydrofluorination catalyst is selected from one of metal fluorides or metal oxyfluorides of Cr, fe, co, ni, zn, mg, ca, ba, sr, al, ga and In.
ADVANTAGEOUS EFFECTS OF INVENTION
The application takes 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene as raw material the single-pass yield of the synthesized E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene is high.
The application adopts 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene as raw material, the raw material is easy to obtain, and the raw material can be obtained by market.
The application adopts a gas phase continuous method to prepare E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene, and the materials with incomplete reaction are independently circulated through a gas phase independent circulation process, the initial raw material can be almost completely converted into E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene, finally, the product E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene is extracted from the process system, so that liquid waste and waste gas are not generated, and green production is realized.
Drawings
FIG. 1 is a process flow diagram for the preparation of E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene, wherein 1,2,3, 5, 7, 8, 10, 11, 13, 14, 16, 17, 19, 20, 21, 22, 24, 26, 27, 29, 30, 32, 33, 35, 36, 38 and 39 are lines, 4-first reactor, 9-second reactor, 23-third reactor, 28-fourth reactor, 6-first distillation column, 12-first HF adsorption column, 15-first HF analysis column, 18-second distillation column, 25-third distillation column, 31-second HF adsorption column, 34-second HF analysis column, 37-fourth distillation column.
Detailed Description
The application is described in detail below in connection with the embodiments described. While specific embodiments of the application are shown, it should be understood that the application may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the application to those skilled in the art.
It should be noted that certain terms are used throughout the description and claims to refer to particular components. Those of skill in the art will understand that a person may refer to the same component by different names. The specification and claims do not identify differences in terms of components, but rather differences in terms of the functionality of the components. As referred to throughout the specification and claims, the terms "include" or "comprising" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. The description hereinafter sets forth a preferred embodiment for practicing the application, but is not intended to limit the scope of the application, as the description proceeds with reference to the general principles of the description. The scope of the application is defined by the appended claims.
The application provides a method for continuously preparing E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene in a gas phase, which comprises the following steps:
1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene is subjected to a first gas phase hydrogenation reaction, a first gas phase dehydrofluorination reaction the second gas phase hydrogenation reaction and the second gas phase dehydrofluorination reaction to obtain E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene.
The application adopts 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene as the raw material raw materials are used for preparing E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene, the raw materials are easy to obtain, can be obtained by a commercial method, and have high single-pass yield.
The application adopts 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene, and the product yield is high after two hydrogenation reactions and two dehydrofluorination reactions, and liquid waste and waste gas are not generated, thus green production can be realized.
In some embodiments of the present application, in some embodiments, the 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) group pent-2-ene is E-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene and/or Z-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene.
The application can be used with E-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene or Z-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene is subjected to a first gas phase addition reaction, E-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene and Z-1, 2,3,4,5 may also be used the mixture of nonafluoro-4- (trifluoromethyl) pent-2-ene is subjected to a first gas phase addition reaction, the present application is not limited in terms of the ratio of the two, and may be conventionally selected as required.
In some embodiments of the present invention, in some embodiments, the first gas phase hydrogenation reaction is to react 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene with hydrogen the reaction is carried out in the presence of a hydrogenation catalyst to obtain 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane. In some embodiments, the first gas phase hydrogenation reaction has a reaction pressure of from 0.1 to 2MPa, preferably from 0.1 to 0.5MPa; and/or the reaction temperature is 50-250 ℃, preferably 100-200 ℃; and/or the ratio of the amount of said 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene to the amount of hydrogen is from 1:1 to 15, preferably from 1:5 to 15; and/or the contact time is 1 to 100s, preferably 10 to 60s.
The first gas phase hydrogenation reaction refers to the reaction of 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene and hydrogen in the presence of the addition reaction is carried out in the presence of a hydrogenation catalyst to give 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane.
In the first gas phase hydrogenation reaction, the reaction pressure may be, for example, 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1.0 MPa, 1.1 MPa, 1.2 MPa, 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 1.9 MPa, 2MPa, etc.
The reaction temperature may be 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, etc.
The ratio of the amounts of the substances of the 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene to the hydrogen (n) 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene :n Hydrogen gas ) May be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, etc.
The contact time was 1s, 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, 100s, etc.
In the present application, in the first gas phase hydrogenation reaction, the contact time is the residence time of 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene with hydrogen in the hydrogenation catalyst bed, i.e., the reaction time.
In some embodiments of the present application, in some embodiments, the first gas phase dehydrofluorination reaction is carried out in the presence of a dehydrofluorination catalyst for 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane the reaction is carried out to obtain 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and/or 1,2,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene. In some embodiments, the reaction pressure of the first gas phase dehydrofluorination reaction is from 0.1 to 2MPa, preferably from 0.1 to 0.5MPa; and/or the reaction temperature is 250-500 ℃, preferably 350-450 ℃; and/or the contact time is from 1 to 100s, preferably from 20 to 100s.
In the present application, the first gas phase dehydrofluorination reaction is to subject 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane to an elimination reaction in the presence of a dehydrofluorination catalyst to dehydrofluorinate, thus obtaining 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and/or 1,2,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene.
In the first gas phase dehydrofluorination reaction, the reaction pressure may be 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1.0 MPa, 1.1 MPa, 1.2 MPa, 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 1.9 MPa, 2 MPa, etc.
The reaction temperature may be 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, etc.
The contact time was 1s, 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, 100s, etc.
In the present application, for the first gaseous phase dehydrofluorination reaction, the contact time refers to the residence time of 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane in the dehydrofluorination catalyst bed, i.e., the reaction time.
In some embodiments of the present invention, in some embodiments, the second gas phase hydrogenation reaction is 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and/or 1,2,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene reacting with hydrogen in the presence of a hydrogenation catalyst to obtain 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane or/and 1,2,4, 5-octafluoro-2- (trifluoromethyl) pentane. In some embodiments, the second gas phase hydrogenation reaction has a reaction pressure of from 0.1 to 2MPa, preferably from 0.1 to 0.5MPa; and/or the reaction temperature is 50-250 ℃, preferably 100-200 ℃; and/or 1,3,4, 5-octafluoro-4- (trifluoro) methyl) pent-2-ene or/and 1,2,4, 5-the ratio of the amount of the octafluoro-4- (trifluoromethyl) pent-2-ene to the amount of the substance of hydrogen is 1:1-15, preferably 1:5-10; and/or the contact time is 1 to 100s, preferably 10 to 60s.
In the second gas-phase hydrogenation reaction, 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and +. or 1,2,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene with the hydrogen is subjected to addition reaction to obtain 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane or/and 1,2,4, 5-octafluoro-2- (trifluoromethyl) pentane.
In the second gas-phase hydrogenation reaction, the reaction pressure may be 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1.0 MPa, 1.1 MPa, 1.2 MPa, 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 1.9 MPa, 2MPa, etc.
The reaction temperature may be 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, etc.
The 1,3,4, 5-octafluoro-4- (trifluoro) methyl) pent-2-ene or/and 1,2,4,5 ratio of the amount of substance of octafluoro-4- (trifluoromethyl) pent-2-en to hydrogen (n) 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene or +. and 1,2,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene :n Hydrogen gas ) May be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, etc.
The contact time was 1s, 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, 100s, etc.
In the present application, for the second gas phase hydrogenation reaction, the contact time refers to 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene or/and 1,2,4,5 the residence time of the octafluoro-4- (trifluoromethyl) pent-2-ene and hydrogen in the hydrogenation catalyst bed, i.e. the reaction time.
In some embodiments of the present application, in some embodiments, the second gas phase dehydrofluorination reaction is the 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane or/and 1,2,4, 5-octafluoro-2- (tri-fluoromethyl) pentane fluoromethyl) pentane in the presence of a dehydrofluorination catalyst to give E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene. In some embodiments, the second vapor phase dehydrofluorination reaction has a reaction pressure of from 0.1 MPa to 2MPa; and/or the reaction temperature is 250-500 ℃, preferably 250-400 ℃; and/or the contact time is from 1 to 100s, preferably from 20 to 100s.
In the present application, the second vapor phase dehydrofluorination reaction is in the presence of a dehydrofluorination catalyst, 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane or/and 1,2,4, 5-octafluoro-2- (trifluoromethyl) pentane the reaction was eliminated to remove hydrogen fluoride to give E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene.
In the second dehydrofluorination reaction, the reaction pressure may be 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1.0 MPa, 1.1 MPa, 1.2 MPa, 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 1.9 MPa, 2 MPa, etc.
The reaction temperature may be 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, etc.
The contact time was 1s, 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, 100s, etc.
In the second dehydrofluorination reaction, the contact time was 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane or/and the residence time of 1,2,4, 5-octafluoro-2- (trifluoromethyl) pentane in the dehydrofluorination catalyst bed, i.e., the reaction time.
In the present application, the present application is not limited in any way with respect to the hydrogenation catalyst and the dehydrofluorination catalyst, and it may be catalyzed according to a catalyst commonly used in the art, preferably, the hydrogenation catalyst may comprise an active ingredient and a carrier, preferably, the active ingredient is palladium or platinum;
preferably, the carrier is selected from CrF 3 、FeF 3 、CoF 2 、NiF 2 、ZnF 2 、MgF 2 、CaF 2 、BaF 2 、SrF 2 、AlF 3 、GaF 3 And InF 3 One of the following;
preferably, the active component accounts for 0.1 to 5 percent of the hydrogenation catalyst, and the carrier accounts for 95 to 99.9 percent of the hydrogenation catalyst.
The dehydrofluorination catalyst may be one of a metal fluoride or metal oxyfluoride of Cr, fe, co, ni, zn, mg, ca, ba, sr, al, ga and In.
In the present application, the present application is not limited in any way with respect to the preparation methods of the hydrogenation catalyst and the dehydrofluorination catalyst, and it may be prepared according to the conventional methods in the art, for example, the preparation methods of the hydrogenation catalyst include:
dissolving metal salt of the active ingredient, and adjusting the pH value to obtain an impregnating solution;
dripping the impregnating liquid into a carrier to obtain a catalyst precursor;
roasting and activating the catalyst precursor to obtain the hydrogenation catalyst.
Preferably, the active ingredient is palladium or platinum, and preferably, the metal salt of the active ingredient can be any one or more of palladium nitrate, palladium acetate, palladium chloride, platinum nitrate, platinum acetate, platinum chloride and chloroplatinic acid.
In some embodiments, the metal salt of the active ingredient is dissolved in water and the pH is adjusted with an acid solution, preferably dilute hydrochloric acid, such that the pH is 4-6, resulting in an impregnation solution.
In some embodiments, the impregnation is carried out dropwise to the support, preferably for a period of time of from 1 to 5 hours, and the catalyst precursor is obtained by filtration and drying.
In some embodiments, the carrier is CrF 3 、FeF 3 、CoF 2 、NiF 2 、ZnF 2 、MgF 2 、CaF 2 、BaF 2 、SrF 2 、AlF 3 、GaF 3 And InF 3 One of them.
The method for preparing the carrier is not limited in any way, and the carrier can be prepared according to a conventional method in the art, for example, by the following method:
dissolving metal salt, dripping a precipitator for precipitation, filtering, drying, and performing compression molding to obtain a carrier precursor;
and drying, roasting and activating the carrier precursor to obtain the carrier.
In some embodiments, the metal salt is dissolved in water and a precipitant is added to precipitate, preferably the precipitant includes at least one or more of ammonia, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, but is not limited to; ammonia is preferred.
In some embodiments, the metal salt is dissolved in water, then a precipitant is added dropwise to precipitate the metal ions completely, the pH value is adjusted to 7.0-9.0, the metal ions are fully precipitated under stirring, the metal salt is aged for 12-36 hours, the formed slurry is filtered, then the formed slurry is dried at 100-250 ℃ for 6-24 hours, the solid is crushed, and the solid is pressed and molded to obtain the carrier precursor.
In some embodiments, the support precursor is calcined at 300-500 ℃ for 6-24 hours under nitrogen atmosphere, and then activated at 200-400 ℃ for 6-24 hours with a mixed gas of hydrogen fluoride and nitrogen in a molar ratio of 1:2, to obtain the support.
In some embodiments, the catalyst precursor is dried under nitrogen protection, then calcined and then activated to provide the hydrogenation catalyst, preferably at a temperature of 100-200 ℃ for 5-10 hours, then calcined at a temperature of 250-350 ℃ for 5-10 hours, and then activated at a molar ratio of nitrogen to hydrogen of 4:1 for 8-20 hours at 200-300 ℃ to provide the hydrogenation catalyst.
In some embodiments, the hydrogenation catalyst is prepared by the following method:
dissolving soluble salt of noble metal in water, and regulating the pH value of the solution to 4-6 by using dilute hydrochloric acid to obtain impregnating solution, wherein the soluble salt of noble metal is any one or more of palladium nitrate, palladium acetate, palladium chloride, platinum nitrate, platinum acetate, platinum chloride and chloroplatinic acid;
dropwise adding the impregnating solution to the carrier under normal pressure and room temperature, maintaining impregnation for 1-5 hours after the dropwise adding is finished, and filtering and drying to obtain a catalyst precursor; drying the catalyst precursor for 5-10 hours at 100-200 ℃ under the protection of nitrogen, then heating to 250-350 ℃ for roasting for 5-10 hours, and activating for 8-20 hours at 200-300 ℃ by using mixed gas of nitrogen and hydrogen with the mol ratio of 4:1 to obtain the hydrogenation catalyst.
In the present application, the present application is not limited in any way as to the preparation method of the dehydrofluorination catalyst, and it may be conventionally selected as required, for example, it can be prepared by the following method:
dissolving metal salt, dripping a precipitator for precipitation, filtering, pressing and forming to obtain a catalyst precursor;
roasting and activating the catalyst precursor to obtain the dehydrofluorination catalyst.
In some embodiments, the metal salt may be any one or more of a chloride, nitrate or acetate salt of Cr, fe, co, ni, zn, mg, al, ga or In, preferably a chloride salt;
preferably, the precipitant includes at least one or more than two of ammonia water, sodium hydroxide, potassium hydroxide, cesium hydroxide and rubidium hydroxide; preferably ammonia.
In some embodiments, after adding the precipitate, the pH is adjusted to 7-9 to allow the metal ions to precipitate sufficiently and aging, preferably for 12-36 hours, is performed, and then the catalyst precursor is obtained by filtration, drying, and compression molding.
In some embodiments, the catalyst precursor is calcined at 300-500 ℃ for 6-24 hours under nitrogen atmosphere, and then activated at 200-400 ℃ for 6-24 hours with a mixed gas of hydrogen fluoride and nitrogen in a molar ratio of 1:2, to produce the dehydrofluorination catalyst.
In some embodiments, the method of preparing the dehydrofluorination catalyst is as follows:
(1) Dissolving metal salt in water, then dripping a precipitator to completely precipitate metal ions, adjusting the pH value to 7.0-9.0, fully precipitating under the stirring condition, aging for 12-36 hours, filtering the formed slurry, drying for 6-24 hours at 100-250 ℃, crushing the solid, and compacting to obtain a catalyst precursor;
(2) Roasting the catalyst precursor obtained in the step (1) for 6-24 hours at 300-500 ℃ in a nitrogen atmosphere, and activating the catalyst precursor for 6-24 hours at 200-400 ℃ by using mixed gas consisting of hydrogen fluoride and nitrogen in a molar ratio of 1:2 to obtain the dehydrofluorination catalyst.
FIG. 1 is a flow chart of a process for preparing E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene according to the application, wherein 1, 2, 3, 5, 7, 8, 10, 11, 13, 14, 16, 17, 19, 20, 21, 22, 24, 26, 27, 29, 30, 32, 33, 35, 36, 38 and 39 are lines, 4-first reactor, 9-second reactor, 23-third reactor, 28-fourth reactor, 6-first distillation column, 12-first HF adsorption column, 15-first HF analysis column, 18-second distillation column, 25-third distillation column, 31-second HF adsorption column, 34-second HF analysis column, 37-fourth distillation column.
The reaction equation is prepared as follows:
。
the operation is as follows:
fresh E-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene or Z-1, 2,3,4,5 nine fluorine-4- (trifluoromethyl) pent-2-ene via line 1 with fresh hydrogen via line 2, -nonafluoro-4- (trifluoromethyl) pent-2-ene via line 1 with fresh hydrogen via line 2, together with the catalyst through a pipeline 3 into a first reactor 4 filled with hydrogenation catalyst for gas-phase hydrogenation reaction, the reaction product stream is 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane and unreacted E-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene or Z-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene and hydrogen, the reaction product flow through a pipeline 5 enters a first distillation tower 6 for separation; the overhead component of the first distillation column 6 was E-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene or Z-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene and hydrogen, the tower bottom component is 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane, and the tower top component is continuously recycled to the first reactor 4 for continuous reaction through pipelines 7 and 3; the bottom component of the first distillation column 6 is fed via line 8 together with 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane which is recycled via line 20 via line 11 to the second reactor 9 which is charged with a dehydrofluorination catalyst for the gas phase dehydrofluorination, the reaction product stream was 1, 3-tetrafluoro-2- (trifluoromethyl) -1-propene hydrogen fluoride and unreacted 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane, the reaction product flows through a pipeline 10 and enters a first HF adsorption column 12 filled with 98-100% sulfuric acid by mass percent for adsorption; the top component of the first HF adsorption column 12 is 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene 1,2,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane, via line 13 to a second distillation column 18 for separation; the tower bottom component of the first HF adsorption tower 12 enters a first HF analysis tower 15 for analysis through a pipeline 14; the tower bottom component of the first HF analysis tower 15 is sulfuric acid, the tower top component is HF, the tower bottom component is circulated to the HF adsorption tower through a pipeline 17 for continuous use, and the tower top component is dried and rectified subsequently to obtain high-purity hydrogen fluoride or is prepared into hydrofluoric acid with various concentrations for selling; the bottoms components of the second distillation column 18 are 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane, the tower top components are 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and 1,2,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene, the tower bottom components are recycled to the second reactor 9 through a pipeline 20 and a pipeline 11 for continuous reaction, the tower top components are 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and 1,2,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene, the tower bottom component is recycled to the second reactor 9 through a pipeline 20 and a pipeline 11 for continuous reaction, together with the hydrogenation catalyst via line 22 to a third reactor 23 filled with hydrogenation catalyst, the reaction product streams were 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane, 1,2,4, 5-octafluoro-2- (trifluoromethyl) pentane, unreacted 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene, 1,2,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and hydrogen, the reaction product stream is passed via line 24 to a third distillation column 25 for separation; the top component of the third distillation column 25 is 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene 1,2,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and hydrogen, the tower bottom component is 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane, 1,2,4, 5-octafluoro-2- (trifluoromethyl) pentane, and the tower top component is continuously recycled to the third reactor 23 for continuous reaction through the pipelines 26 and 22; the bottoms of the third distillation column 25 is fed via line 27 to a fourth reactor 28 packed with a dehydrofluorination catalyst via line 29 for vapor phase dehydrofluorination reaction with 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane and 1,2,4, 5-octafluoro-2- (trifluoromethyl) pentane recycled via line 39, the reaction product stream was E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene hydrogen fluoride, unreacted 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane, 1,2,4, 5-octafluoro-2- (trifluoromethyl) pentane, the reaction product flows through a pipeline 30 and enters a second HF adsorption column 31 filled with 98-100% sulfuric acid by mass percent for adsorption; the top component of the second HF adsorption column 31 is E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane and 1,2,4, 5-octafluoro-2- (trifluoromethyl) pentane, enters a fourth distillation column 37 via line 32 for separation; the tower bottom component of the second HF adsorption tower 31 enters a second HF analysis tower 34 for analysis through a pipeline 33; the tower bottom component of the second HF analysis tower 34 is sulfuric acid, the tower top component is HF, the tower bottom component is circulated to the second HF adsorption tower 31 through a pipeline 36 for continuous use, and the tower top component is dried and rectified subsequently to obtain high-purity hydrogen fluoride or is prepared into hydrofluoric acid with various concentrations for selling; the column bottoms of the fourth distillation column 37 were 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane and 1,2,4, 5-octafluoro-2- (trifluoromethyl) pentane, the tower top component is E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene, the bottoms fraction is recycled to the fourth reaction 28 via line 39 and line 29 for further reaction, and the overhead fraction is subsequently subjected to acid removal, water removal and rectification to give the desired product E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene.
The application adopts the method to prepare, and can recycle unreacted raw materials in each step and independently circulate, thus almost completely converting the raw materials into E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene, finally, the product E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene is extracted from the process system, so that liquid waste and waste gas are not generated, green production is realized, and the yield in each step is higher.
In addition, the hydrogenation catalyst and the dehydrofluorination catalyst used in the application have high activity and long service life, and the raw materials used in the application are raw materials which are easy to obtain.
Examples
The materials used in the test and the test methods are described generally and/or specifically in the examples which follow,% represents wt%, i.e. weight percent, unless otherwise specified. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Analytical instrument: the Shimadzu GC-2010 column was designated InterCap1 (i.d. 0.25. 0.25 mm; length 60 m; J & W Scientific Inc.).
Gas chromatography method: high purity helium and hydrogen fluoride are used as carrier gases. 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 increased to 240 ℃ at 20 ℃/min, and the temperature is kept for 10 minutes.
Preparation of the catalyst
1. Preparation of hydrogenation catalyst:
(1) Preparation of a hydrogenation catalyst support: dissolving chromium chloride in water, and adding dropwise concentrated ammonia waterPrecipitating, adjusting pH to 7.5, aging for 24 hours, washing with water, filtering, drying in a baking oven at 120 ℃ for 15 hours, crushing the obtained solid, tabletting and forming to obtain a precursor of the carrier, loading 10mL of the precursor of the carrier into a tube reactor made of Monel material with an inner diameter of 1/2 inch and a length of 30cm, introducing nitrogen, roasting for 12 hours at 350 ℃, wherein the space velocity of the nitrogen is 200h < -1 >, then cooling to 300 ℃, and simultaneously introducing the material with the mass ratio of 1:2, the total space velocity of the gas is 220h < -1 >, the activation is carried out for 12 hours, and the mixed gas is stopped to prepare the CrF 3 。
Other carriers may be prepared in place of other soluble metal salts.
(2) Preparing a hydrogenation catalyst by an impregnation method: according to the mass percentage of Pd and CrF3, the mass percentage of the catalyst is 2 percent: dissolving palladium chloride in 98% water, and regulating the pH value of the solution to 4-6 by using dilute hydrochloric acid to obtain an impregnating solution; dropwise adding the impregnating solution to the carrier under normal pressure and room temperature, maintaining impregnation for 4 hours after the dropwise adding is finished, and filtering and drying to obtain a catalyst precursor; drying the catalyst precursor for 8 hours at 120 ℃ under the protection of nitrogen, then heating to 300 ℃ for roasting for 8 hours, and activating for 14 hours at 250 ℃ by using mixed gas of nitrogen and hydrogen with the molar ratio of 4:1 to prepare the hydrogenation catalyst.
Other hydrogenation catalysts can be prepared by replacing the types and the contents of active metals and carriers.
2. Preparation of dehydrofluorination catalyst: dissolving chromium trichloride in water, dropwise adding concentrated ammonia water for precipitation, regulating the pH value to 7.5, aging for 24 hours, washing with water, filtering, drying the obtained solid in a baking oven at 120 ℃ for 15 hours, crushing, tabletting and forming to obtain a catalyst precursor, loading 10mL of the catalyst precursor into a tube reactor made of Monel with the inner diameter of 1/2 inch and the length of 30cm, introducing nitrogen, roasting for 12 hours at 350 ℃, wherein the nitrogen airspeed is 200h < -1 >, then cooling to 300 ℃, and simultaneously introducing the material with the mass ratio of 1:2, the total space velocity of the gas is 220h < -1 >, the mixed gas is activated for 12 hours, and the CrF3 is prepared.
Other dehydrofluorination catalysts may be prepared in place of other soluble metal salts.
The catalysts of the following examples were prepared as described above, and the catalysts of the comparative examples were all commercially available products.
Example 1
A tube reactor made of Inconel having an inner diameter of 1/2 inch and a length of 30cm was filled with 2% Pd/98% CrF 3 Catalyst 10mL. The reaction conditions are as follows: the reaction temperature was 50℃and the mass ratio of E-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene to hydrogen was 1:10, the contact time was 60s, the reaction pressure was 0.1MPa, and the operation was performed according to the flow chart of FIG. 1. After 10h of operation, the organic phase of the reaction product was subjected to GC analysis. The results are shown in Table 1.
Example 2
The same procedure as in example 1 was repeated except that the reaction temperature was changed to 100℃and the results are shown in Table 1.
Example 3
The same procedure as in example 1 was repeated except that the reaction temperature was changed to 150℃and the results are shown in Table 1.
Example 4
The same procedure as in example 1 was repeated except that the reaction temperature was changed to 200℃and the results were shown in Table 1.
Example 5
The same procedure as in example 1 was repeated except that the reaction temperature was changed to 250℃and the results are shown in Table 1.
Example 6
The same procedure as in example 3 was repeated except that the mass ratio of E-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene to hydrogen was changed to 1:1 and the results are shown in Table 1.
Example 7
The same procedure as in example 3 was repeated except that the mass ratio of E-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene to hydrogen was changed to 1:5, the results are shown in Table 1.
Example 8
The same procedure as in example 3 was repeated except that the mass ratio of E-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene to hydrogen was changed to 1:15, the results are shown in Table 1.
Example 9
The same procedure as in example 3 was followed except that the contact time was changed to 1s, and the results are shown in Table 1.
Example 10
The same procedure as in example 3 was followed except that the contact time was changed to 10s, and the results are shown in Table 1.
Example 11
The same procedure as in example 3 was followed except that the contact time was changed to 100s, and the results are shown in Table 1.
Example 12
The same procedure as in example 3 was repeated except that the reaction pressure was changed to 0.5MPa, and the results are shown in Table 1.
Example 13
The same procedure as in example 3 was repeated except that the reaction pressure was changed to 1.0MPa, and the results are shown in Table 1.
Example 14
The same procedure as in example 3 was repeated except that the reaction pressure was changed to 1.5MPa, and the results are shown in Table 1.
Example 15
The same procedure as in example 3 was repeated except that the reaction pressure was changed to 2.0MPa, and the results are shown in Table 1.
Example 16
The same procedure as in example 3 was followed except that the hydrogenation catalyst was changed to 0.1% Pd/99.9% CrF 3 The results are shown in Table 1.
Example 17
The same procedure as in example 3 was followed except that the hydrogenation catalyst was changed to 1% Pd/99% CrF 3 The results are shown in Table 1.
Example 18
The same procedure as in example 3 was followed except that the hydrogenation catalyst was changed to 4% Pd/96% CrF 3 The results are shown in Table 1.
Example 19
The same procedure as in example 3 was followed except that the hydrogenation catalyst was changed to 5% Pd/95% CrF 3 The results are shown in Table 1.
Example 20
The same procedure as in example 3 was followed except that the hydrogenation catalyst was changed to 2% Pd/98% AlF 3 The results are shown in Table 1.
Example 21
The same procedure as in example 3 was followed except that the hydrogenation catalyst was changed to 2% Pd/98% FeF 3 The results are shown in Table 1.
Example 22
The same procedure as in example 3 was followed except that the hydrogenation catalyst was changed to 2% Pd/98% MgF 2 The results are shown in Table 1.
Example 23
The same procedure as in example 3 was followed except that the hydrogenation catalyst was changed to 2% Pd/98% ZnF 2 The results are shown in Table 1.
Example 24
In the same manner as in example 3, except that E-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene was changed to Z-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene in an amount of the same, the results are shown in Table 1.
Comparative example 1
The same procedure as in example 3 was followed except that the hydrogenation catalyst was changed to commercially available 2% Pd/98% Al 2 O 3 The results are shown in Table 1.
TABLE 1
；/>
。
Example 25
A tubular reactor made of Inconel having an inner diameter of 1/2 inch and a length of 30cm was filled with CrF 3 Catalyst 10mL. The reaction conditions are as follows: the reaction temperature was 250℃and the contact time of 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane was 60s and the reaction pressure was 0.1MPa, and the procedure was followed in accordance with FIG. 1. After 10h of operation, the reaction product was washed with water, alkali and dried, and the organic phase was taken for GC analysis. The results are shown in Table 2.
Example 26
The same procedure as in example 25 was repeated except that the reaction temperature was changed to 300℃and the results were shown in Table 2.
Example 27
The same procedure as in example 25 was repeated except that the reaction temperature was changed to 350℃and the results are shown in Table 2.
Example 28
The same procedure as in example 25 was repeated except that the reaction temperature was changed to 400℃and the results are shown in Table 2.
Example 29
The same procedure as in example 25 was repeated except that the reaction temperature was changed to 450℃and the results were shown in Table 2.
Example 30
The same procedure as in example 25 was repeated except that the reaction temperature was changed to 500℃and the results are shown in Table 2.
Example 31
The same procedure as in example 27 was repeated except that the contact time was changed to 1s, and the results are shown in Table 2.
Example 32
The same procedure as in example 27 was repeated except that the contact time was changed to 20s, and the results are shown in Table 2.
Example 33
The same procedure as in example 27 was repeated except that the contact time was changed to 100s, and the results are shown in Table 2.
Example 34
The same procedure as in example 27 was repeated except that the reaction pressure was changed to 0.5MPa, and the results are shown in Table 2.
Example 35
The same procedure as in example 27 was conducted except that the reaction pressure was changed to 1.0MPa, and the results are shown in Table 2.
Example 36
The same procedure as in example 27 was repeated except that the reaction pressure was changed to 1.5MPa, and the results are shown in Table 2.
Example 37
The same procedure as in example 27 was repeated except that the reaction pressure was changed to 2.0MPa, and the results are shown in Table 2.
Example 38
The same procedure as in example 27 was repeated except that the dehydrofluorination catalyst was changed to FeF 3 The results are shown in Table 2.
Example 39
The same procedure as in example 27 was repeated except that the dehydrofluorination catalyst was changed to AlF 3 The results are shown in Table 2.
Example 40
The same procedure as in example 27 was repeated except that the dehydrofluorination catalyst was changed to CoF 2 The results are shown in Table 2.
Example 41
The same procedure as in example 27 was repeated except that the dehydrofluorination catalyst was changed to ZnF 2 The results are shown in Table 2.
Comparative example 2
The same procedure as in example 27 was followed except that the dehydrofluorination catalyst was changed to a commercially available CrF 3 The results are shown in Table 2.
TABLE 2
。
Example 42
A tube reactor made of Inconel having an inner diameter of 1/2 inch and a length of 30cm was filled with 10mL of 2% Pd/98% CrF3 catalyst. The reaction conditions are as follows: the reaction temperature was 50 ℃, and the mass ratio of 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene to hydrogen was 1:10, the contact time was 60s, the reaction pressure was 0.1MPa, and the operation was performed according to the flow chart of FIG. 1. After 10h of operation, the reaction product organic phase was subjected to GC analysis, and the results are shown in Table 3.
Example 43
The same procedure as in example 42 was repeated except that the reaction temperature was changed to 100℃and the results are shown in Table 3.
Example 44
The same procedure as in example 42 was repeated except that the reaction temperature was changed to 150℃and the results are shown in Table 3.
Example 45
The same procedure as in example 42 was repeated except that the reaction temperature was changed to 200℃and the results were shown in Table 3.
Example 46
The same procedure as in example 42 was repeated except that the reaction temperature was changed to 250℃and the results are shown in Table 3.
Example 47
The same procedure as in example 44 was repeated except that the ratio of the amounts of substances of 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and hydrogen was changed to 1:1 and the results are shown in Table 3.
Example 48
The same procedure as in example 44 was repeated except that the ratio of the amounts of substances of 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and hydrogen was changed to 1:5, the results are shown in Table 3.
Example 49
The same procedure as in example 44 was repeated except that the ratio of the amounts of substances of 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and hydrogen was changed to 1:15, the results are shown in Table 3.
Example 50
The same procedure as in example 44 was repeated except that the contact time was changed to 1s, and the results are shown in Table 3.
Example 51
The same procedure as in example 44 was repeated except that the contact time was changed to 10s, and the results are shown in Table 3.
Example 52
The same procedure as in example 44 was repeated except that the contact time was changed to 100s, and the results are shown in Table 3.
Example 53
The same procedure as in example 44 was repeated except that the reaction pressure was changed to 0.5MPa, and the results are shown in Table 3.
Example 54
The same procedure as in example 44 was repeated except that the reaction pressure was changed to 1.0MPa, and the results are shown in Table 3.
Example 55
The same procedure as in example 44 was repeated except that the reaction pressure was changed to 1.5MPa, and the results are shown in Table 3.
Example 56
The same procedure as in example 44 was repeated except that the reaction pressure was changed to 2.0MPa, and the results are shown in Table 3.
Example 57
The same procedure as in example 44 was followed except that the hydrogenation catalyst was changed to 0.1% Pd/99.9% CrF 3 The results are shown in Table 3.
Example 58
The same procedure as in example 44 was followed except that the hydrogenation catalyst was changed to 1% Pd/99% CrF 3 The results are shown in Table 3.
Example 59
The same procedure as in example 44 was followed except that the hydrogenation catalyst was changed to 4% Pd/96% CrF 3 The results are shown in Table 3.
Example 60
The same procedure as in example 44 was followed except that the hydrogenation catalyst was changed to 5% Pd/95% CrF 3 The results are shown in Table 3.
Example 61
The same procedure as in example 44 was followed except that the hydrogenation catalyst was changed to 2% Pd/98% AlF 3 The results are shown in Table 3.
Example 62
The same procedure as in example 44 was followed except that the hydrogenation catalyst was changed to 2% Pd/98% FeF 3 The results are shown in Table 3.
Example 63
The same procedure as in example 44 was followed except that the hydrogenation catalyst was changed to 2% Pd/98% MgF 2 The results are shown in Table 3.
Example 64
The same procedure as in example 44 was followed except that the hydrogenation catalyst was changed to 2% Pd/98% ZnF 2 The results are shown in Table 3.
Example 65
In the same manner as in example 44, except that E-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene was changed to Z-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene in an amount of the same, the results are shown in Table 3.
Comparative example 3
The same procedure as in example 44 was followed except that the hydrogenation catalyst was changed to commercially available 2% Pd/98% Al 2 O 3 The results are shown in Table 3.
TABLE 3 Table 3
；/>
。
And (3) table notes: the major product of example 65 was 1,2,4, 5-octafluoro-2- (trifluoromethyl) pentane, the "1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane selectivity" in the reaction results was replaced with "1, 2,4, 5-octafluoro-2- (trifluoromethyl) pentane selectivity".
Example 66
A tubular reactor made of Inconel having an inner diameter of 1/2 inch and a length of 30cm was filled with CrF 3 Catalyst 10mL. The reaction conditions are as follows: the reaction temperature was 250℃and the contact time of 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane was 60s and the reaction pressure was 0.1MPa, and the reaction mixture was operated according to the scheme of FIG. 1, and after 10 hours of operation, the reaction product was washed with water, alkali and dried, and the organic phase was taken for GC analysis. The results are shown in Table 4.
Example 67
The same procedure as in example 66 was repeated except that the reaction temperature was changed to 300℃and the results are shown in Table 4.
Example 68
The same procedure as in example 66 was repeated except that the reaction temperature was changed to 350℃and the results are shown in Table 4.
Example 69
The same procedure as in example 66 was repeated except that the reaction temperature was changed to 400℃and the results are shown in Table 4.
Example 70
The same procedure as in example 66 was repeated except that the reaction temperature was changed to 450℃and the results were shown in Table 4.
Example 71
The same procedure as in example 66 was repeated except that the reaction temperature was changed to 500℃and the results are shown in Table 4.
Example 72
The same procedure as in example 68 was repeated except that the contact time was changed to 1s, and the results are shown in Table 4.
Example 73
The same procedure as in example 68 was repeated except that the contact time was changed to 20s, and the results are shown in Table 4.
Example 74
The same procedure as in example 68 was repeated except that the contact time was changed to 100s, and the results are shown in Table 4.
Example 75
The same procedure as in example 68 was conducted except that the reaction pressure was changed to 0.5MPa, and the results are shown in Table 4.
Example 76
The same procedure as in example 68 was conducted except that the reaction pressure was changed to 1.0MPa, and the results are shown in Table 4.
Example 77
The same procedure as in example 68 was conducted except that the reaction pressure was changed to 1.5MPa, and the results are shown in Table 4.
Example 78
The same procedure as in example 68 was conducted except that the reaction pressure was changed to 2.0MPa, and the results are shown in Table 4.
Example 79
The same procedure as in example 68 was repeated except that the dehydrofluorination catalyst was changed to FeF 3 The results are shown in Table 4.
Example 80
The same procedure as in example 68 was repeated except that the dehydrofluorination catalyst was changed to AlF 3 The results are shown in Table 4.
Example 81
The same procedure as in example 68 was repeated except that the dehydrofluorination catalyst was changed to CoF 2 The results are shown in Table 4.
Example 82
The same procedure as in example 68 was repeated except that the dehydrofluorination catalyst was changed to ZnF 2 The results are shown in Table 4.
Example 83
The same procedures as in example 68 were repeated except that 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane was changed to 1,2,4, 5-octafluoro-2- (trifluoromethyl) pentane in the same amount as described in Table 4.
Comparative example 4
The same procedure as in example 68 was followed except that the dehydrofluorination catalyst was changed to a commercially available CrF 3 The results are shown in Table 4.
TABLE 4 Table 4
。/>
The above description is only a preferred embodiment of the present application, and is not intended to limit the application in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present application still fall within the protection scope of the technical solution of the present application.

Claims (13)

1. A process for the vapor phase continuous preparation of E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene comprising:
1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene is subjected to a first gas phase hydrogenation reaction, a first gas phase dehydrofluorination reaction the second gas phase hydrogenation reaction and the second gas phase dehydrofluorination reaction to obtain E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene.
2. The method of claim 1, wherein, the 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene is E-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene and/or Z-1, 2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene.
3. The method according to claim 1 or 2, wherein, the first gas phase hydrogenation reaction is to react 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene and hydrogen in the presence of the reaction is carried out in the presence of a hydrogenation catalyst to obtain 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane.
4. The method of claim 3, wherein,
the reaction pressure of the first gas phase reaction is 0.1-2MPa; and/or
The reaction temperature is 50-250 ℃; and/or
The ratio of the amount of the substances of the 1,2,3,4, 5-nonafluoro-4- (trifluoromethyl) pent-2-ene and the hydrogen is 1:1-15; and/or
The contact time is 1-100s.
5. The method of claim 3, wherein, the first gas phase dehydrofluorination reaction is carried out in the presence of a dehydrofluorination catalyst for 1,2,3,4, 5-nonafluoro-2- (trifluoromethyl) pentane the reaction is carried out to obtain 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and/or 1,2,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene.
6. The process according to claim 5, wherein the reaction pressure of the first gas phase dehydrofluorination reaction is from 0.1 to 2MPa; and/or
The reaction temperature is 250-500 ℃; and/or
The contact time is 1-100s.
7. The method of claim 5, wherein, the second gas phase hydrogenation reaction is 1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene and/or 1,2,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene reacting with hydrogen in the presence of a hydrogenation catalyst to obtain 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane or/and 1,2,4, 5-octafluoro-2- (trifluoromethyl) pentane.
8. The process of claim 7, wherein the second gas phase hydrogenation reaction has a reaction pressure of 0.1-2MPa; and/or
The reaction temperature is 50-250 ℃; and/or
1,3,4, 5-octafluoro-4- (trifluoromethyl) pent-2-ene or/and 1,2,4, 5-octa the ratio of the amount of the fluorine-4- (trifluoromethyl) pent-2-ene to the amount of the hydrogen gas is 1:1-15; and/or
The contact time is 1-100s.
9. The method of claim 7, wherein, the second gas phase dehydrofluorination reaction is the 1,1,1,2,3,5,5,5-octafluoro-2- (trifluoromethyl) pentane or/and 1,2,4, 5-octafluoro-2- (tri-fluoromethyl) pentane fluoromethyl) pentane in the presence of a dehydrofluorination catalyst to give E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene.
10. The process according to claim 9, wherein the reaction pressure of the second gas phase dehydrofluorination reaction is from 0.1 to 2MPa; and/or
The reaction temperature is 250-500 ℃; and/or
The contact time is 1-100s.
11. The process according to claim 3, wherein the hydrogenation catalyst comprises an active ingredient and a carrier, the active ingredient being palladium or platinum and the carrier being selected from CrF 3 、FeF 3 、CoF 2 、NiF 2 、ZnF 2 、MgF 2 、CaF 2 、BaF 2 、SrF 2 、AlF 3 、GaF 3 And InF 3 One of them.
12. The method of claim 11, wherein the carrier is selected from CrF 3 、FeF 3 、CoF 2 、NiF 2 、ZnF 2 、MgF 2 、CaF 2 、BaF 2 、SrF 2 、AlF 3 、GaF 3 And InF 3 One of them.
13. The method of claim 5 wherein the dehydrofluorination catalyst is selected from one of a metal fluoride or metal oxyfluoride of Cr, fe, co, ni, zn, mg, ca, ba, sr, al, ga and In.
CN202311143584.3A 2023-09-06 2023-09-06 Method for the gas phase continuous production of E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene Pending CN116874345A (en)

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CN101553453A (en) * 2006-10-27 2009-10-07 霍尼韦尔国际公司 Process for the manufacture of fluorinated olefins
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CN105622331A (en) * 2016-02-23 2016-06-01 常熟三爱富中昊化工新材料有限公司 Preparation method of fluorine-containing olefin
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CN115003648A (en) * 2020-01-23 2022-09-02 科慕埃弗西有限公司 (E) Synthesis of (E) -1, 1, 1, 4, 5, 5, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene
CN115417745A (en) * 2022-11-04 2022-12-02 北京宇极科技发展有限公司 Method for synthesizing hydrofluoroolefin

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007053697A2 (en) * 2005-11-01 2007-05-10 E. I. Du Pont De Nemours And Company Compositions comprising fluoroolefins and uses thereof
CN101553453A (en) * 2006-10-27 2009-10-07 霍尼韦尔国际公司 Process for the manufacture of fluorinated olefins
CN104945221A (en) * 2015-06-11 2015-09-30 浙江衢州巨新氟化工有限公司 Method for co-production of 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene
CN105622331A (en) * 2016-02-23 2016-06-01 常熟三爱富中昊化工新材料有限公司 Preparation method of fluorine-containing olefin
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