CN117396453A

CN117396453A - Process for producing 1-chloro-2, 3-trifluoropropene

Info

Publication number: CN117396453A
Application number: CN202280038111.4A
Authority: CN
Inventors: 镰塚达也; 盐田英史; 河口聪史; 竹内优
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2021-06-04
Filing date: 2022-06-01
Publication date: 2024-01-12
Also published as: JPWO2022255397A1; WO2022255397A1

Abstract

A novel method for manufacturing 1233yd is provided. 1-chloro-2, 3-trifluoropropene is produced by contacting 1, 3-dichloro-2, 3-trifluoropropene with a metal salt and a 0-valent metal and then with an acid.

Description

Process for producing 1-chloro-2, 3-trifluoropropene

Technical Field

The present invention relates to a process for producing 1-chloro-2, 3-trifluoropropene.

Background

1-chloro-2, 3-trifluoropropene (chcl=cf-CHF) ₂ HCFO-1233yd, hereinafter also referred to as 1233yd. ) Is a low Global Warming Potential (GWP) and can be used forDetergents, refrigerants, blowing agents, solvents and aerosol use compounds.

As an example of the production of 1233yd, patent document 1 describes that, when 3-chloro-1, 2-tetrafluoropropane and hydrogen fluoride are introduced in a gaseous state into a hastelloy (hastelloy c) reaction tube filled with a chromium hydroxide catalyst under a nitrogen stream, a trace amount of 1233yd by-product is produced together with 1,2, 3-pentafluoropropane.

Prior art literature

Patent literature

Patent document 1: international publication No. 1994/014737

Disclosure of Invention

Technical problem to be solved by the invention

However, the reaction described in patent document 1 is not suitable for mass production on an industrial scale because the amount of 1233yd produced is very small as a by-product.

The invention aims to provide a novel 1233yd manufacturing method.

Means for solving the technical problems

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by the following constitution.

(1) A process for producing 1-chloro-2, 3-trifluoropropene, wherein 1, 3-dichloro-2, 3-trifluoropropene is contacted with a metal salt and a 0-valent metal and then contacted with an acid to produce 1-chloro-2, 3-trifluoropropene.

(2) The production method according to (1), wherein the metal atom contained in the metal salt is a copper atom, an iron atom, a cobalt atom or a nickel atom.

(3) The production method according to (1) or (2), wherein the metal salt is copper chloride.

(4) The production method according to any one of (1) to (3), wherein the 0-valent metal is zinc, magnesium, iron, cobalt or nickel.

(5) The production method according to (4), wherein the 0-valent metal is zinc.

(6) The production method according to any one of (1) to (5), wherein the acid is hydrogen chloride, sulfuric acid, nitric acid, acetic acid or phosphoric acid.

(7) The production method according to any one of (1) to (6), wherein a temperature at which the 1, 3-dichloro-2, 3-trifluoropropene is brought into contact with the metal salt and the 0-valent metal is 0 to 200 ℃.

(8) The production process according to any one of (1) to (7), wherein the production of 1-chloro-2, 3-trifluoropropene is carried out in a liquid phase.

(9) The production method according to (8), wherein the production of 1-chloro-2, 3-trifluoropropene is carried out in the presence of a solvent.

(10) The production process according to any one of (1) to (9), wherein 1, 3-dichloro-2, 3-trifluoropropene obtained by subjecting 1, 3-trichloro-1, 2-tetrafluoropropane to a defluorination reaction and a dechlorination reaction in an aprotic solvent is used as the 1, 3-dichloro-2, 3-trifluoropropene.

Effects of the invention

According to the present invention, a novel method for producing 1233yd can be provided.

Detailed Description

The terms in this specification have the following meanings.

1233yd exists in the geometric isomers Z and E depending on the position of the substituent on the double bond. In the case where a compound name or a compound abbreviation is used herein without particular description, at least one selected from the group consisting of a Z-form and an E-form is represented, and in the case where (E) or (Z) is added after the compound name or the compound abbreviation, the (E) form or the (Z) form of each compound is represented. For example, HCFO-1233yd (Z) represents the Z-body, and HCFO-1233yd (E) represents the E-body.

The method for producing 1233yd according to the present invention (hereinafter also referred to simply as "the method for producing the present invention") comprises reacting 1, 3-dichloro-2, 3-trifluoropropene (CF) ₂ Cl-cf=chcl, HCFO-1223yd, hereinafter also referred to as 1223 yd) with a metal salt and a 0-valent metal, followed by contact with an acid.

The detailed reason for obtaining 1233yd by the above-described production method is not clear, but it is presumed that 1233yd is obtained by bringing 1223yd into contact with a metal salt and a metal of valence 0 to form an intermediate for obtaining 1233yd, and then allowing an acid to act on the intermediate.

The materials and steps used are described below.

The materials and steps used in contacting 1223yd with the metal salt and the 0-valent metal in the production method of the present invention are described in detail below.

In the production method of the present invention, 1223yd was used as a raw material.

1223yd can be manufactured by a known method.

When 1223yd is used, impurities may be included. That is, the raw material of the production method of the present invention may include 1223yd, and for example, a composition including 1223yd and impurities may be used as the raw material.

Examples of the impurities include a raw material for producing 1223yd and by-products produced other than 1223yd when producing 1223yd.

For example, in the case of using 1, 3-trichloro-1, 2-tetrafluoropropane (hereinafter also referred to as 224 ca) described later to produce 1223yd, the resultant product may contain 1223yd, unreacted 224ca, and by-product 1, 3-dichloro-1, 2-tetrafluoropropane (234 cc). The product may be used as a raw material for the production method of the present invention.

In the case where the above-mentioned impurities are contained in the raw material, the impurities can be removed by known means such as distillation, extractive distillation, azeotropic distillation, membrane separation, double-layer separation, adsorption, and the like.

The inclusion of 1223yd as a main component in the raw material is preferable from the viewpoint of efficient production of 1233yd. The main component is 1223yd of 50 mass% or more, preferably 75 mass% or more, more preferably 80 mass% or more, still more preferably 90 mass% or more, and particularly preferably 95 mass% or more, based on the total mass of the raw materials. The upper limit is exemplified by 100 mass%.

In the case of using 1223yd produced by the above production method, the content of 224ca in the raw material is preferably 5 mass% or less, more preferably 3 mass% or less, and still more preferably 1 mass% or less, relative to the total mass of the raw material. By the above upper limit value or less, 1233yd can be efficiently produced without impeding the reaction of converting 1223yd into 1233yd.

Specific examples of the metal salt include halides, carbonates, hydroxides, and alkoxides. Among them, from the viewpoint of more excellent yield of 1233yd, a halide is preferable, and a metal chloride is more preferable.

Specific examples of the metal atom contained in the metal salt include transition metals, and more specifically, copper atoms, iron atoms, cobalt atoms, and nickel atoms are preferable. Among them, nickel atom and copper atom are preferable, and copper atom is more preferable, from the viewpoint of more excellent yield of 1233yd.

Specific examples of the metal salt include copper (I) chloride, copper (II) chloride, nickel (I) chloride and nickel (II) chloride.

The metal salts may be used in combination of 2 or more.

The metal salt may be used in the form of powder to improve reactivity, may be formed into a pellet, or may be supported on a carrier to be used as a metal salt supporting carrier.

Examples of the carrier include: the carbon material such as activated carbon, carbon black, and carbon fiber, and the oxide material such as alumina, silica, titania, zirconia, alkali metal oxide, and alkaline earth metal oxide are preferably selected from activated carbon, alumina, silica, zirconia, alkali metal oxide, and alkaline earth metal oxide. Among them, activated carbon, alumina and zirconia are more preferable because of their large specific surface area and easiness of supporting metal salts.

The average particle diameter (D50) of the powdery metal salt is 0.05 to 1000. Mu.m, preferably 0.1 to 500. Mu.m, more preferably 0.5 to 200. Mu.m.

As a method for forming the metal salt into a pellet, there may be mentioned a method of pulverizing the metal salt into a powder and forming the powder by a tablet press or the like.

As the granular metal salt, for example, a metal salt formed into a cylindrical shape having a diameter of about 3.0mm and a height of about 4.0mm can be used. If necessary, a binder may be mixed with the metal salt, and the mixture may be used as a metal salt composition containing the metal salt and the binder. The amount of the binder to be used is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 10 parts by mass or less, based on 100 parts by mass of the metal salt. In this case, the mixture of the metal salt and the binder may be formed into a pellet by a tablet press or the like.

Further, specific examples of the binder include graphite, carbon, cellulose, alumina, and silica.

The metal salt is preferably dried in advance in an inert atmosphere (for example, in a nitrogen stream) in order to enhance the reactivity. The metal salt may be dried in the same manner as described above in the state of being stored in the reactor, from the viewpoint of simplifying the operation and improving the operation efficiency.

The specific surface area of the metal salt depends on the kind of each metal salt, and generally, the smaller the specific surface area, the lower the conversion, the larger the selectivity, and the faster the degradation.

For example, in the case of using a metal salt without using the binder, the specific surface area of the metal salt is preferably 0.1 to 300m ² /g。

In the present specification, the specific surface area is a value measured by the BET method.

Specific examples of the 0-valent metal include transition metals and alkaline earth metals, and more specifically, zinc, magnesium, iron, cobalt, and nickel are preferable. Among them, zinc is preferable in view of more excellent yield of 1233yd.

The 0-valent metal may be used in combination of 2 or more.

The 0-valent metal may be used in powder form to improve reactivity, and may be used as a metal sheet or may be formed into a pellet form.

The average particle diameter (D50) of the powdery 0-valent metal is 0.05 to 1000. Mu.m, preferably 0.1 to 500. Mu.m, more preferably 0.5 to 200. Mu.m.

As a method for forming the 0-valent metal into a pellet, there can be mentioned a method of pulverizing the 0-valent metal into powder, and forming the powder by a tablet press or the like.

As the granular 0-valent metal, for example, a metal formed into a columnar shape having a diameter of about 3.0mm and a height of about 4.0mm can be used. If necessary, a binder may be mixed with the metal 0 to be used as a composition containing the metal 0 and the binder. The amount of the binder to be used is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 10 parts by mass or less, based on 100 parts by mass of the 0-valent metal. In this case, the mixture of the 0-valent metal and the binder may be formed into a pellet by a tablet press or the like.

In addition to the above 1223yd, metal salt, and 0 valent metal, a solvent may be present in the reaction system.

Specific examples of the preferable solvent include: aromatic hydrocarbons such as benzene, toluene, xylene, and benzene, aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, and cyclopentane, halogenated hydrocarbons such as chloroform, methylene chloride, and carbon tetrachloride, amides such as N, N-Dimethylformamide (DMF), dimethylacetamide, and N-methylpyrrolidone, sulfoxides such as dimethyl sulfoxide (DMSO), sulfones such as sulfolane, dimethyl ether (DME), diethyl ether, diisopropyl ether, diglyme, tetrahydrofuran (THF), ethers such as 1, 4-dioxane, and tert-butyl methyl ether, nitriles such as acetonitrile, esters such as methyl acetate, ethyl acetate, and propyl carbonate, ketones such as acetone, methyl ethyl ketone, and alcohols such as methanol, ethanol, and 2-propanol.

Among them, DMF, acetonitrile and DMSO are preferable from the viewpoint of more excellent yield of 1233yd.

The solvent may be used in combination of 2 or more.

The method of contacting 1223yd with the metal salt and the 0-valent metal is not particularly limited, and may be a method of adding the metal salt and the 0-valent metal to 1223yd in a liquid state to contact them, a method of contacting 1223yd in a liquid state with the metal salt and the 0-valent metal in the presence of a solvent, or a method of contacting 1223yd in a gaseous state by supplying it into a reactor filled with the metal salt and the 0-valent metal. From the standpoint of reactivity, a method of bringing 1223yd in a liquid state into contact with a metal salt and a 0-valent metal in the presence of a solvent is preferable.

When 1223yd is contacted with a metal salt and a 0-valent metal, these components may be contacted together, or 1223yd may be added in small amounts to a mixed system containing a metal salt and a 0-valent metal.

1223yd is preferably contacted with the metal salt and the metal of valence 0 while stirring.

The amount of the metal salt to be used is preferably 0.001 to 1.0 equivalent, more preferably 0.01 to 0.3 equivalent, to 1 equivalent of 1223yd, from the viewpoint of more excellent yield of 1233yd.

The amount of the 0-valent metal to be used is preferably 0.01 to 10 equivalents, more preferably 0.1 to 5 equivalents, and even more preferably 0.3 to 3 equivalents relative to 1 equivalent of 1223yd, from the viewpoint of more excellent yield of 1233yd.

When the solvent is used, the amount of the solvent to be used is preferably 1 to 1000% by mass, more preferably 10 to 750% by mass, relative to the amount of 1223yd to be used, from the viewpoint of more excellent yield of 1233yd and productivity.

The temperature at which 1223yd is contacted with the metal salt and the 0-valent metal is not particularly limited, but is preferably 0 to 200 ℃, more preferably 10 to 160 ℃ in view of shortening the production time.

The contact time of 1223yd with the metal salt and the 0-valent metal is not particularly limited, but in the case of reacting with 1223yd in a liquid state, it is preferably 0.01 to 100 hours, more preferably 0.1 to 50 hours in the case of batch type, from the viewpoint of more excellent yield of 1233yd and productivity. In the case of continuous, it is preferably 0.01 to 50 hours, more preferably 0.1 to 20 hours. The contact time was 1223yd with the metal salt and the 0 valent metal in the reactor in the case of batch type, and was 1223yd with the metal salt and the 0 valent metal in the case of continuous type.

The reactor pressure is preferably 0 to 30MPaG, more preferably 0 to 10MPaG, from the viewpoints of reactivity and easiness in obtaining a pressure-resistant reactor.

Then, an acid was added to a system (hereinafter also referred to as "front-stage reaction system") containing a reaction mixture obtained by contacting 1223yd with a metal salt and a 0-valent metal, and the product in the front-stage reaction system was contacted with the acid, thereby producing 1233yd. The materials and steps used in the reaction in this latter stage are described in detail below.

In addition, the weakly acidic pH buffer may be added to the pre-reaction system to change the components in the pre-reaction system before the acid is added to the pre-reaction system. By the action of the pH buffer, the yield of 1233yd may be increased. The conditions such as the contact time and the contact temperature of the components in the reaction system in the preceding stage with the pH buffer solution are not particularly limited.

Specific examples of the pH buffer include an acetate buffer composed of acetic acid as a weak acid and sodium acetate as a salt thereof.

Specific examples of the acid include organic acids and inorganic acids, and more specifically, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and phosphoric acid are preferable. Among them, hydrochloric acid is preferable in view of more excellent yield of 1233yd.

In the production method of the present invention, the method of contacting with an acid is not particularly limited, and examples thereof include a method of contacting a pre-stage reaction system with an acid dissolved in water, and a method of contacting a pre-stage reaction system with an acid in a gaseous state.

When the reaction system of the preceding stage is brought into contact with the acid, these components may be mixed together, the acid may be added to the reaction system of the preceding stage in small amounts, or the reaction system of the preceding stage may be added to the acid in small amounts, and the reaction system of the preceding stage may be brought into contact. From the viewpoint of suppressing the heat generation in the preceding reaction system, it is preferable to add the acid to the preceding reaction system in small amounts.

The amount of the acid to be used is preferably 0.01 to 10 equivalents, more preferably 0.1 to 5 equivalents, and even more preferably 0.3 to 3 equivalents relative to 1 equivalent of 1223yd.

The temperature at which the reaction system in the preceding stage is brought into contact with the acid is not particularly limited, but is preferably-40 to 100℃and more preferably-20 to 60℃in view of the more excellent yield of 1233yd.

The reaction pressure is preferably 0 to 30MPaG, more preferably 0 to 10MPaG, from the viewpoints of reactivity and easiness in obtaining a pressure-resistant reactor.

The contact time between the reaction system in the former stage and the acid is not particularly limited, but is preferably 0.001 to 100 hours, more preferably 0.002 to 50 hours in the case of the batch type, from the viewpoint of more excellent yield of 1233yd and productivity. In the case of continuous, it is preferably 0.001 to 50 hours, more preferably 0.002 to 20 hours. The contact time is the contact time between the reaction system in the preceding stage and the acid in the reactor in the case of batch-wise operation, and the residence time between the reaction system in the preceding stage and the acid in the reactor in the case of continuous operation.

The contacting of the reaction system of the former stage with the acid may be carried out in the presence of the above-mentioned solvent.

For example, in the case where the front-end reaction system contains a solvent, the front-end reaction system containing the solvent may be contacted with an acid.

By carrying out the above steps, 1233yd is obtained.

In addition, impurities may be contained in the product obtained by mixing the acid with the reaction system in the preceding stage.

Examples of the impurities include a production raw material of 1223yd, a production raw material of 1233yd (specifically, 1223 yd), by-products produced during the production of 1233yd except for 1233yd, metal salts, 0-valent metals, solvents, acids, and the like.

As a raw material for producing 1223yd, for example, in the case of producing 1223yd via 224ca, which will be described later, unreacted 224ca, by-products 1, 3-dichloro-1, 2-tetrafluoropropane (234 cc), 3-chloro-1, 2-tetrafluoropropane (244 ca) are contained.

In the case where the above-mentioned impurities are contained in the product, the impurities can be removed by a known method such as distillation, extractive distillation, azeotropic distillation, membrane separation, double layer separation, adsorption, or the like.

The 1233yd purified by the above known method sometimes contains impurities.

As the impurities, 1223yd, 234cc, 244ca, and the like may be contained.

The content of the above-mentioned impurities is preferably 10 mass% or less, more preferably 5 mass% or less, further preferably 1 mass% or less, particularly preferably 0.1 mass% or less, relative to the total amount of the purified product.

As the starting material 1223yd of the present invention, 1223yd obtained by subjecting 224ca to defluorination and dechlorination in an aprotic solvent is preferably used.

Defluorination and dechlorination of 224ca in aprotic solvents such as DMF and diglyme can inhibit the formation of 234cc as a by-product and increase the selectivity of 1223yd.

The reason for this is not clear, but it is considered that when 224ca is subjected to defluorination and dechlorination, a side reaction in which a hydrogen atom is bonded to the 3-carbon atom is less likely to occur after the chlorine atom bonded to the 3-carbon atom of 224ca is pulled out, and the selectivity of 1223yd is improved.

In addition, the defluorination reaction and the dechlorination reaction of 224ca were performed in a liquid phase reaction. The liquid phase reaction is 224ca in a liquid state.

The method of producing 224ca may be as described in Japanese patent No. 5413451.

As the aprotic solvent used in the defluorination reaction and the dechlorination reaction of 224ca, preferred solvents are: aromatic hydrocarbons such as benzene, toluene, xylene, benzene, aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, cyclopentane, halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, amides such as N, N-Dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone, sulfoxides such as Dimethylsulfoxide (DMSO), sulfones such as sulfolane, ethers such as dimethyl ether (DME), diethyl ether, diisopropyl ether, diglyme, tetrahydrofuran (THF), ethers such as 1, 4-dioxane, tert-butyl methyl ether, nitriles such as acetonitrile, nitriles such as methyl acetate, ethyl acetate, propionic acid ester such as acetone, methyl ethyl ketone, and the like. Among them, DMF, acetonitrile, and DMSO are preferable from the viewpoint of more excellent yield of 1233yd.

The content of the aprotic solvent is preferably 1 to 500% by mass, more preferably 10 to 250% by mass, relative to the content of 224ca.

One of preferable embodiments of the defluorination and the dechlorination is to subject 224ca to the defluorination and the dechlorination in the presence of at least one metal selected from the group consisting of alkaline earth metals and transition metals (hereinafter, collectively referred to as "specific metals").

Specific examples of the alkaline earth metal include magnesium, calcium, and strontium. Specific examples of the transition metal include zinc, copper and nickel. Among them, magnesium, zinc, copper, and nickel are preferable, and magnesium and zinc are more preferable from the viewpoint of reactivity.

In addition, the specific metal may be used in combination of 2 or more kinds.

The specific metal may be used in powder form to improve reactivity, and may be used as a metal sheet or may be formed into a pellet form.

The amount of the specific metal to be used is preferably 0.01 to 10 equivalents, more preferably 0.1 to 5 equivalents, and even more preferably 0.3 to 3 equivalents relative to 1 equivalent of 224ca, from the viewpoints of the reaction yield and the selectivity of 1223yd.

The reaction temperature in the defluorination reaction and the dechlorination reaction of 224ca (particularly, the reaction temperature in the presence of a specific metal) is preferably 0 to 250 ℃, more preferably 30 to 200 ℃, still more preferably 50 to 170 ℃ from the viewpoints of reactivity and selectivity of 1223yd.

The reaction pressure in step 3 is preferably 0 to 30MPaG, more preferably 0 to 10MPaG, from the viewpoints of reactivity and easiness in obtaining a pressure-resistant reactor.

The reaction time in step 3 (particularly in the presence of a specific metal) is preferably 0.1 to 100 hours, more preferably 1 to 30 hours in the case of batch. In the case of continuous, it is preferably 0.01 to 50 hours, more preferably 0.1 to 20 hours. The reaction time in the case of continuous is the residence time of the raw materials in the reactor.

As a method of carrying out the defluorination and the dechlorination of 224ca in the presence of the specific metal, a method of dispersing the specific metal in a powder state in an aprotic solvent may be mentioned.

One of the more preferable modes of the defluorination and the dechlorination in the above-mentioned method for producing 1223yd is to perform defluorination and the dechlorination of 224ca in the presence of an activator. In this mode, the above specific metal is preferably used in combination with an activator. That is, 224ca is preferably subjected to defluorination and dechlorination in the presence of the specific metal and the activator. In addition, the activated metal may be obtained by previously mixing the above specific metal and the activator. By using the activated metal, the same effect as in the case of using the above-mentioned specific metal and activator in combination can be obtained.

The activator may be used to activate the defluorination and dechlorination of 224ca, and examples thereof include metal chlorides (for example, zinc chloride when zinc is used and magnesium chloride when magnesium is used), 1, 2-dibromoethane, and hydrogen chloride. Among them, zinc chloride is preferable.

The activator may be used in combination of 2 or more kinds.

The amount of the activator to be used is preferably 0.001 to 10 equivalents, more preferably 0.01 to 2 equivalents, and even more preferably 0.01 to 1.5 equivalents relative to 1 equivalent of 224ca, from the viewpoints of reaction yield, selectivity of 1223yd, and economy.

The products obtained by the defluorination reaction and the dechlorination reaction of 224ca contain impurities in addition to the target 1223yd.

Specific examples of the impurities include unreacted 224ca and 234cc.

In the case where impurities are contained in the product, a treatment of separating 1223yd from the obtained product is preferably carried out. More specifically, the treatment of filtering the obtained product, and the treatment of distilling the obtained product to obtain a fraction mainly composed of 1223yd may be mentioned. Here, "using 1223yd as a main component" means that the mass of 1223yd in the fraction is the largest, and the content of 1223yd is preferably 90 mass% or more, more preferably 95 mass% relative to the total mass of the fraction.

As described above, the difference in boiling point between the target 1223yd and the raw material 224ca is as large as 40 to 50 ℃, so that 1223yd and 224ca can be easily separated by distillation.

Distillation devices such as packed columns and tray columns may be used in the distillation operation. In addition, in order to efficiently purify and recover the target compound 1223yd from various impurities, for example, multistage distillation is preferable. In the case of using a multistage distillation, the theoretical plate number is preferably 20 stages or more.

The temperature at the time of distillation (for example, the temperature of the distillation still) is preferably 80℃or less, more preferably 70℃or less, from the viewpoint of energy costs. The temperature during the distillation operation is preferably 58℃or higher, which is the boiling point of 1223yd (Z).

Examples

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. Examples 1 and 2 described later correspond to examples.

(conditions of gas chromatography)

In the production of the following various compounds, the composition analysis of the obtained products was performed by Gas Chromatography (GC). The column was DB-1301 (length 60 m. Times. Inner diameter 250. Mu.m. Times. Thickness 1. Mu.m, manufactured by Agilent technologies Co., ltd.).

< production example of 1223yd >

(production of 224 ca)

224ca was produced in the following procedure according to the following reaction scheme.

CHCl ₃ +trifluoroethylene (TFE) →224ca

First, anhydrous aluminum chloride (25 g,0.19 mol), CHCl were charged into a 500mL stainless steel autoclave ₃ (500 g,4.19 mol) and 224ca (100 g,0.45 mol), the reaction mixture was degassed under reduced pressure while stirring, TFE was supplied until the pressure in the autoclave became 0.05MPa, and the temperature in the autoclave was raised to 80 ℃. Then, TFE was further supplied while maintaining the pressure in the autoclave at 0.8 MPa. The total amount of TFE fed to the autoclave was 0.17 kg (1.65 mol).

After the reaction solution was further stirred for 1 hour, it was cooled to room temperature, and the reaction solution was analyzed by gas chromatography to obtain CHCl ₃ The conversion of 33%, and the selectivity of 224ca was 84%. To the crude liquid obtained by filtering the reaction solution after the reaction, 102g of molecular sieve 4A was added and stirred overnight for dehydration. The crude product obtained by filtering the stirred crude liquid was purified by distillation to obtain 224ca (230 g,1.05 mol).

(production of 1223 yd)

9.44g of DMF (manufactured by Kanto chemical Co., ltd.), 1.57g of zinc powder (D50: 6 to 9 μm, manufactured by Fuji photo-pure chemical Co., ltd.), 1.36g of zinc chloride (manufactured by pure chemical Co., ltd.), 4.39g of 224ca and a magnetic rotor were charged into a 30cc glass flask, the upper portion of which was connected with a reflux tube cooled to 10 ℃.

The flask was then placed in an oil bath and warmed to a reaction temperature of 130 ℃. The temperature increase was performed within about 30 minutes, and the magnetic rotor was rotated at 300rpm using a magnetic stirrer during the temperature increase and during the reaction. After holding at 130 ℃ for 5.5 hours, the temperature of the oil bath was reduced and cooled to room temperature. After cooling to room temperature, the reaction solution was analyzed by GC. The composition of the reaction solution was analyzed by GC analysis, and the conversion and selectivity were calculated.

The reaction solution contained 1223yd.

224ca was 65.4%, the selectivity to 1223yd was 94.4% (the selectivity to 1223yd (Z) was 83.5%, and the selectivity to 1223yd (E) was 10.9%). In addition, the selectivity for conversion to 234cc was 1.5%.

After repeating the above reaction until the total amount of the products reached about 150g, the products were distilled and purified, and a distillate containing 93.2 mass% of 1223yd (Z), 6.0 mass% of 1223yd (E), and 0.2 mass% of 234cc was obtained from the top of the distillation column.

The following 1233yd production was performed using the above distillate.

< example 1>

To a 10ml glass vessel, 0.165g of zinc powder (D50: 6 to 9 μm, manufactured by Fuji photo-pure chemical Co., ltd.), 0.021g of CuCl (manufactured by Kato chemical Co., ltd.), 1.9g of DMF (manufactured by Kato chemical Co., ltd.), and 0.349g of the distillate were charged, and the mixture obtained at room temperature was stirred.

After mixing for 4.5 hours, 0.05g of ion-exchanged water and 0.03g of a pH4 buffer solution (acetic acid/sodium acetate) were added to the mixture. Stirring was then continued and, 28 hours after the start of mixing, 1ml of 1M aqueous HCl was added to the mixture, and the reaction was stopped. The supernatant fraction of the resulting mixture was collected and analyzed by GC.

The resulting mixture contained 1233yd.

The conversion of 1223yd was 82.2%, the selectivity of 1233yd was 78.0% (the selectivity of conversion to 1233yd (Z) was 76.2%, and the selectivity of conversion to 1233yd (E) was 1.8%).

< example 2>

Into a 10ml glass vessel were charged 0.161g of zinc powder (D50: 6 to 9 μm, manufactured by Fuji photo-pure chemical Co., ltd.), 0.024g of CuCl (manufactured by Kato chemical Co., ltd.), 1.89g of DMF (manufactured by Kato chemical Co., ltd.), and 0.361g of the distillate, and the mixture was stirred while being heated (temperature: 60 ℃ C.).

After 2 hours of mixing, 0.05g of pH4 buffer (acetic acid/sodium acetate) was added to the mixture. Stirring was then continued, heating was stopped 4 hours after the start of mixing, and after cooling to room temperature, 1ml of 1M aqueous HCl was added to the mixture to stop the reaction. The supernatant fraction of the resulting mixture was collected and analyzed by GC.

The resulting mixture contained 1233yd.

The conversion of 1223yd was 62.8% and the selectivity of 1233yd was 76.8%. (the selectivity for conversion to 1233yd (Z) was 75.4% and the selectivity for conversion to 1233yd (E) was 1.4%)

< example 3>

Into a 10ml glass vessel were charged 0.060g of magnesium (cut glass, manufactured by Grignard reaction: fuji photo-pure chemical Co., ltd.), 0.022g of CuCl (manufactured by Kadong chemical Co., ltd.), 1.90g of DMF (manufactured by Kadong chemical Co., ltd.), and 0.360g of the distillate, and the mixture was stirred while being heated (temperature: 60 ℃ C.).

The resulting mixture contained 1233yd.

The conversion of 1223yd was 45.6% and the selectivity of 1233yd was 73.1%. (the selectivity for conversion to 1233yd (Z) was 71.9% and the selectivity for conversion to 1233yd (E) was 1.2%)

< example 4>

Into a 10ml glass container, 0.160g of zinc powder (D50: 6 to 9 μm, manufactured by Fuji film and Wako pure chemical industries, ltd.) and 0.034g of NiCl were charged ₂ (anhydrous substance, fuji photo-alignment film and Wako pure chemical industries, ltd.), 1.89g of DMF (manufactured by Kanto chemical Co., ltd.), and 0.355g of the above distillate were mixed and heated (temperature:60 ℃ C.) while stirring.

The resulting mixture contained 1233yd.

The conversion of 1223yd was 29.8% and the selectivity of 1233yd was 65.0%. (the selectivity for conversion to 1233yd (Z) was 63.4% and the selectivity for conversion to 1233yd (E) was 1.6%)

Further, the entire contents of the specification, claims and abstract of japanese patent application No. 2021-094497, which was filed on even date 04 of 2021, are incorporated herein by reference as if fully set forth in the present specification.

Claims

1. A process for producing 1-chloro-2, 3-trifluoropropene, wherein 1, 3-dichloro-2, 3-trifluoropropene is contacted with a metal salt and a 0-valent metal and then contacted with an acid to produce 1-chloro-2, 3-trifluoropropene.

2. The production method according to claim 1, wherein the metal atom contained in the metal salt is a copper atom, an iron atom, a cobalt atom or a nickel atom.

3. The production method according to claim 1 or 2, wherein the metal salt is copper chloride.

4. The production method according to any one of claims 1 to 3, wherein the 0-valent metal is zinc, magnesium, iron, cobalt, or nickel.

5. The method according to claim 4, wherein the 0-valent metal is zinc.

6. The production process according to any one of claims 1 to 5, wherein the acid is hydrogen chloride, sulfuric acid, nitric acid, acetic acid or phosphoric acid.

7. The production process according to any one of claims 1 to 6, wherein the temperature at which the 1, 3-dichloro-2, 3-trifluoropropene is brought into contact with the metal salt and the 0-valent metal is from 0 to 200 ℃.

8. The production process according to any one of claims 1 to 7, wherein the production of 1-chloro-2, 3-trifluoropropene is carried out in a liquid phase.

9. The process according to claim 8, wherein the 1-chloro-2, 3-trifluoropropene is produced in the presence of a solvent.

10. The production process according to any one of claims 1 to 9, wherein 1, 3-dichloro-2, 3-trifluoropropene obtained by subjecting 1, 3-trichloro-1, 2-tetrafluoropropane to a defluorination reaction and a dechlorination reaction in an aprotic solvent is used as the 1, 3-dichloro-2, 3-trifluoropropene.