WO2023112433A1 - Method for producing hydrogen substitution product of 1,2-dichloro-1,2-difluoroethylene - Google Patents

Abstract

A method for producing a hydrogen substitution product of 1,2-dichloro-1,2-difluoroethylene, the method comprising causing 1,2-dichloro-1,2-difluoroethylene to react with hydrogen in the presence of a metal catalyst mixture containing a first catalyst including at least one platinum group metal selected from the group consisting of palladium, platinum, nickel, iridium, rhodium, and ruthenium, and a second catalyst containing at least one second metal selected from the group consisting of copper, silver, gold, zinc, chromium, and cobalt.

Description

Method for producing hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene

The present disclosure relates to a method for producing a hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene.

Conventionally, refrigerants for refrigerators, refrigerants for air conditioners, working media for power generation systems (waste heat recovery power generation, etc.), working media for latent heat transport devices (heat pipes, etc.), and working media for heat cycle systems such as secondary cooling media As such, chlorofluorocarbons such as chlorotrifluoromethane and dichlorodifluoromethane (hereinafter also referred to as "CFC") and hydrochlorofluorocarbons such as chlorodifluoromethane (hereinafter also referred to as "HCFC") have been used. However, CFCs and HCFCs have been pointed out to affect the ozone layer in the stratosphere, and are currently subject to regulation.

From this background, hydrofluorocarbons such as difluoromethane, tetrafluoroethane, pentafluoroethane (hereinafter also referred to as "HFC"), which have less impact on the ozone layer, have been replaced with CFCs and HCFCs as working fluids for thermal cycles. ) came to be used. However, it has been pointed out that HFCs may cause global warming.

In recent years, the use of hydrofluoroolefins (HFOs) such as 1,2-difluoroethylene (hereinafter also referred to as "HFO-1132"), etc., has been studied in place of HFCs because of their low global warming potential (GWP). ing.
HFO-1132 is prepared by reacting 1,2-dichloro-1,2-difluoroethylene (hereinafter also referred to as “CFO-1112”) with hydrogen in the presence of a hydrogenation catalyst such as a Pd catalyst to obtain a hydrogen-substituted product. (See Japanese Patent Laid-Open No. 2013-237624, etc.).

The present inventors have found that when CFO-1112 is reacted with hydrogen using a Pd catalyst or the like, a hydrogenated product in which hydrogen is added to the double bond, a superreduced product in which the fluorine atom is replaced by a hydrogen atom By-products such as HFO-1132 and its precursors 1,2-difluoroethylene and 1-chloro-1,2-difluoroethylene (hereinafter “HCFO-1122a”) may be produced. Also described.) was found to have room for improvement in selectivity.
The problem to be solved by one embodiment of the present disclosure is that the generation of by-products can be suppressed, and HFO-1132 and HCFO-1122a (hereinafter, HFO-1132 and HCFO-1122a are collectively referred to as “CFO-1112 An object of the present invention is to provide a method for producing a hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene which can selectively produce a hydrogen-substituted product.

Means for solving the above problems include the following aspects.
<1> A first catalyst containing one or more platinum group metals selected from the group consisting of palladium, platinum, nickel, iridium, rhodium and ruthenium, and selected from the group consisting of copper, silver, gold, zinc, chromium and cobalt reacting 1,2-dichloro-1,2-difluoroethylene with hydrogen in the presence of a mixed metal catalyst containing a second catalyst comprising one or more second metals of 1,2-dichloro-1,2- A method for producing a hydrogen-substituted difluoroethylene.
<2> The 1,2-dichloro-1,2-difluoro according to <1> above, wherein in the mixed metal catalyst, the ratio of the mass of the platinum group metal to the mass of the second metal is 1/1 or less. A method for producing a hydrogen-substituted ethylene.
<3> The mixed metal catalyst is supported by a carrier, and the total supported amount of the platinum group metal and the second metal supported on the carrier is 1 to 20 parts by mass with respect to 100 parts by mass of the carrier. A method for producing a hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene according to <1> or <2> above.
<4> The method for producing a hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene according to <3>, wherein the carrier contains activated carbon.
<5> 1, according to any one of <1> to <4> above, wherein the temperature at which the 1,2-dichloro-1,2-difluoroethylene and the hydrogen are reacted is 150 to 400°C. A method for producing a hydrogen-substituted 2-dichloro-1,2-difluoroethylene.
<6> any one of <1> to <5> above, wherein the molar ratio of the amount of hydrogen used to the amount of 1,2-dichloro-1,2-difluoroethylene used is 1 to 50; A method for producing a hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene described above.
<7> The 1,2-dichloro-1, according to any one of <1> to <6>, wherein the platinum group metal is one or more metals selected from the group consisting of platinum and nickel. A method for producing a hydrogen-substituted 2-difluoroethylene.
<8> The 1,2-dichloro-1, according to any one of <1> to <7>, wherein the second metal is one or more metals selected from the group consisting of copper and silver. A method for producing a hydrogen-substituted 2-difluoroethylene.
<9> The above <1> to <, wherein the hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene contains at least one of 1,2-difluoroethylene and 1-chloro-1,2-difluoroethylene. 8>.
<10> The hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene includes 1,2-difluoroethylene and 1-chloro-1,2-difluoroethylene, and the 1-chloro-1,2 - 1, according to any one of <1> to <9>, wherein difluoroethylene is recovered and the 1-chloro-1,2-difluoroethylene is reacted with hydrogen in the presence of the mixed metal catalyst. A method for producing a hydrogen-substituted 2-dichloro-1,2-difluoroethylene.

According to the present disclosure, there is provided a method for producing a hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene that can suppress the production of by-products and selectively produce a hydrogen-substituted CFO-1112. can.

FIG. 1 is a schematic diagram showing an embodiment of a reactor that can be used in the method for producing a hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene of the present disclosure.

Hereinafter, the form for implementing the embodiment of the present disclosure will be described in detail. However, embodiments of the present disclosure are not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the embodiments of the present disclosure.

In the present disclosure, the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
In the present disclosure, each component may contain multiple types of applicable substances. When there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. means quantity.

CFO-1112, HFO-1132, and HCFO-1122a exist as geometric isomers, Z-isomer and E-isomer, depending on the position of the substituent on the double bond.
In the present disclosure, when a compound name or a compound abbreviation is used without particular mention, it indicates at least one selected from the group consisting of Z isomer and E isomer, more specifically, Z isomer or E isomer, Alternatively, it represents a mixture of Z isomer and E isomer in an arbitrary ratio.
When (E) or (Z) is attached to the end of a compound name or a compound abbreviation, the (E)-form or (Z)-form of the respective compound is indicated. For example, CFO-1112(Z) indicates the Z form and CFO-1112(E) indicates the E form.

The method for producing a hydrogen-substituted CFO-1112 of the present disclosure (hereinafter also simply referred to as the “production method of the present disclosure”) is one selected from the group consisting of palladium, platinum, nickel, iridium, rhodium and ruthenium. In the presence of a metal mixed catalyst containing a first catalyst containing the above platinum group metals and a second catalyst containing at least one second metal selected from the group consisting of copper, silver, gold, zinc, chromium and cobalt , CFO-1112 with hydrogen.
According to the production method of the present disclosure, production of by-products can be suppressed, and hydrogen-substituted CFO-1112 can be selectively produced. Although the mechanism of action is not clear, it is roughly estimated as follows.
When CFO-1112 is reacted with hydrogen in the presence of one kind of metal catalyst such as a Pd catalyst, hydrogen molecules are taken in between the bonds of Pd atoms, and the taken-in hydrogen molecules become chlorine atoms possessed by CFO-1112. In addition, it may also react with the double bond of CFO-1112 to produce by-products such as hydrogenated products and overreduced products.
In the production method of the present disclosure, a first catalyst containing one or more platinum group metals selected from the group consisting of palladium, platinum, nickel, iridium, rhodium and ruthenium, and copper, silver, gold, zinc, chromium and a second catalyst containing at least one second metal selected from the group consisting of cobalt. That is, the metal mixed catalyst contains, in addition to the first catalyst containing a platinum group metal having a high affinity with hydrogen, a second catalyst containing a second metal having a low affinity with hydrogen, and CFO-1112 The reaction of hydrogen to the double bond of is suppressed,
It is speculated that the production of by-products can be suppressed and the hydrogen-substituted CFO-1112 is selectively produced.

CFO-1112 produced by the production method of the present disclosure may contain at least one of HFO-1132 and HCFO-1122a.

When the hydrogen-substituted product of CFO-1112 contains HCFO-1122a, the production method of the present disclosure recovers it by a conventionally known method such as distillation, and 1-chloro-1,2- in the presence of a mixed metal catalyst. Difluoroethylene may be reacted with hydrogen.
As a result, HFO-1132, which is a hydrogen-substituted product of HCFO-1122a, is obtained.

The mixed metal catalyst used in the production method of the present disclosure contains the first catalyst containing the platinum group metal and the second catalyst containing the second metal.
From the viewpoint of suppressing the production of by-products, in the mixed metal catalyst, the ratio of the mass of the platinum group metal to the mass of the second metal is preferably 1/1 or less, more preferably 1/20 or less, and 1/60. The following is more preferable, 1/80 or less is particularly preferable, and 1/100 or less is most preferable.
From the viewpoint of improving the reactivity between CFO-1112 and hydrogen, the ratio is preferably 1/600 or more, more preferably 1/500 or more, and even more preferably 1/300 or more.

The first catalyst contains one or more platinum group metals selected from the group consisting of palladium, platinum, nickel, iridium, rhodium and ruthenium.
Examples of the first catalyst include palladium, platinum, nickel, iridium, rhodium, ruthenium, oxides thereof, and halides thereof. From the viewpoint of improving the reactivity between CFO-1112 and hydrogen, platinum and nickel It preferably contains one or more metals selected from the group consisting of
The valence of the platinum group metal is not particularly limited, but from the viewpoint of improving the reactivity between CFO-1112 and hydrogen, it is preferably divalent or tetravalent, more preferably divalent.

The second catalyst contains one or more second metals selected from the group consisting of copper, silver, gold, zinc, chromium and cobalt.
The second catalyst includes copper, silver, gold, zinc, chromium, cobalt, oxides thereof, and halides thereof. From the viewpoint of suppressing the production of by-products, It preferably contains one or more selected metals.
Examples of the halides include fluorides and chlorides, and chlorides are preferred from the viewpoint of suppressing the production of by-products.

In a particularly preferred embodiment, the mixed metal catalyst contains a first catalyst selected from the group consisting of platinum and platinum halides and a second catalyst selected from the group consisting of copper and copper halides.

The mixed metal catalyst may be supported by a carrier.
When the metal mixed catalyst is supported on a support, from the viewpoint of improving the specific surface area of the metal mixed catalyst and improving the reactivity between CFO-1112 and hydrogen, the platinum group metal supported on the support with respect to 100 parts by mass of the support and The total amount of the second metal supported is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and even more preferably 3 to 10 parts by mass.

The carrier includes at least one selected from the group consisting of activated carbon, alumina, chromia, silica, zirconia, alkali metal oxides and alkaline earth metal oxides, and has a large surface area for supporting metals. For this reason, activated carbon is preferred.
The carrier may be subjected to a treatment such as acid washing in order to enhance the function of supporting the catalyst.
A conventionally known method can be adopted as a method for preparing a mixed metal catalyst supported on a carrier.
industrial Practice", 2nd. (McGraw-Hill, N.
York, 1991), pp. 87-112, by either precipitation or impregnation methods.

The reaction of CFO-1112 and hydrogen may be carried out in a reactor. The shape and structure of the reactor are not particularly limited. For example, when performing a reaction between CFO-1112 and hydrogen by a gas phase reaction, a cylindrical vertical reactor that can be filled with a catalyst inside the reactor. is mentioned. Materials for the reactor include glass, iron, nickel, stainless steel, iron, nickel, and alloys thereof.
The reactor may be internally equipped with a heating unit such as an electric heater. The reactor may have a sheath tube into which a thermometer is inserted to measure the temperature inside.

From the viewpoint of improving the reactivity between CFO-1112 and hydrogen, the temperature at which CFO-1112 and hydrogen are reacted (hereinafter also referred to as "reaction temperature") is preferably 150 to 400°C, and 200 to 380°C. More preferably, 270 to 370°C is even more preferable.
In the present disclosure, the reaction temperature refers to the temperature of the environment where CFO-1112 and hydrogen react, and when the reaction is carried out in a reactor, the temperature inside the reactor corresponds to the reaction temperature.

From the viewpoint of improving the reactivity between CFO-1112 and hydrogen, the molar ratio of the amount of hydrogen used to the amount of CFO-1112 used (amount of hydrogen used/amount of CFO-1112 used) is preferably 1 to 50. , more preferably 2 to 30, more preferably 2 to 20, and particularly preferably 2 to 10.

The reaction between CFO-1112 and hydrogen may be either a liquid phase reaction or a gas phase reaction, and the gas phase reaction is preferred from the viewpoint of improving the reactivity between CFO-1112 and hydrogen.
A liquid phase reaction means a reaction between CFO-1112 in a liquid state and hydrogen, and a gas phase reaction means a reaction between CFO-1112 in a gaseous state and hydrogen.
The above reaction may be carried out in any of a batch system, a semi-continuous system and a continuous flow system.

A gas phase reaction will be described in detail.
In the gas phase reaction of CFO-1112 and hydrogen, gaseous CFO-1112 and hydrogen are separately and continuously supplied into a reactor, and gaseous state is generated in the presence of a metal mixed catalyst packed in the reactor. of CFO-1112 and hydrogen.
A gas inert to the reaction (diluent gas) may be supplied to the reactor from the viewpoint of being effective in adjusting the flow rate, suppressing by-products, suppressing deactivation of the catalyst, and the like. Diluent gases include nitrogen, carbon dioxide, helium, argon, and the like.

From the viewpoint of improving the reactivity between CFO-1112 and hydrogen, the time for gas phase reaction between CFO-1112 and hydrogen (hereinafter also referred to as "gas phase reaction time") is preferably 1 second to 1000 seconds, 5 seconds to 800 seconds is more preferable, and 10 seconds to 500 seconds is even more preferable.
When the reaction of CFO-1112 and hydrogen is carried out in a reactor, the reaction time means the residence time of CFO-1112 and hydrogen in the reactor.

The pressure of the reaction system (pressure inside the reactor) in the gas phase reaction is preferably 0 to 2.0 MPa, more preferably 0 to 0.5 MPa. The pressure inside the reactor may be negative pressure. The pressure inside the reactor is particularly preferably normal pressure (atmospheric pressure) from the viewpoint of ease of handling. In the present disclosure, pressure indicates gauge pressure unless otherwise specified.

The liquid phase reaction will be explained in detail.
The liquid phase reaction between CFO-1112 and hydrogen can be carried out by continuously or discontinuously supplying hydrogen into a reactor in which a mixture of CFO-1112 and a mixed metal catalyst exists in a liquid state. Further, the hydrogen-substituted CFO-1112 produced by the reaction can be continuously or discontinuously withdrawn from the reactor.
From the viewpoint of improving the reactivity between CFO-1112 and hydrogen, the liquid phase reaction time between CFO-1112 and hydrogen (hereinafter also referred to as “liquid phase reaction time”) is 0.1 to 100 hours. Preferably, 0.5 hours to 50 hours, and even more preferably 1 hour to 20 hours.
A liquid phase reaction may be carried out in the presence of a solvent, if desired. Examples of the solvent include straight-chain perfluoroalkyl compounds having 5 to 8 carbon atoms represented by CF ₃ (CF ₂ )nCF ₃ (wherein n represents an integer of 3 to 6). .

Next, one aspect of the gas phase reaction between CFO-1112 and hydrogen will be described in more detail with reference to FIG.
In FIG. 1, reference numeral 20 designates a reactor used for gas phase reactions. Note that the reaction apparatus indicated by reference numeral 20 is one embodiment, and the present invention is not limited to this.
Reactor 20 comprises reactor 1 . The reactor 1 is connected to a CFO-1112 supply line 2, a hydrogen supply line 3, and a diluent gas supply line 4. The reactor 1 includes a heating section such as an electric heater (not shown).
In FIG. 1, the supply line 2 and the supply line 3 are connected before the reactor 1 and connected to the reactor 1. However, it is not limited to this, and each reactor is separately connected. 1 may be connected.
In FIG. 1, feed line 2, feed line 3 and feed line 4 are connected before the reactor, and the mixture of CFO-1112, hydrogen and diluent gas is fed to reactor 1 via mixture feed line 5. supplied to

In the reactor 20 shown in FIG. 1, the supply line 2, the supply line 3 and the supply line 4 are provided with preheaters (preheaters) 2a, 3a and 4a provided with electric heaters and the like, respectively.
The CFO-1112, hydrogen and nitrogen supplied to the reactor 1 are preferably preheated to predetermined temperatures by preheaters 2a, 3a and 4a, respectively, before being supplied to the reactor 1. Thereby, CFO-1112, hydrogen and nitrogen can be efficiently heated to a predetermined reaction temperature inside the reactor 1 . Preheaters 2a, 3a and 4a are preferably, but not essential, installed.

In the reactor 20 shown in FIG. 1, an outlet line 7 is connected to the outlet of the reactor 1 via a cooling section 6 such as a heat exchanger.
The outlet line 7 is further connected with a recovery tank 8 for water vapor and acid liquid, an alkali washing device 9, and a dehydration tower 10 in this order.
The reaction mixture taken out from the reactor 1 is treated after the exit line 7 to remove acidic substances such as hydrogen chloride and hydrogen fluoride, water vapor and water. The gas thus obtained is hereinafter referred to as "outlet gas". Each component in the outlet gas is analyzed and quantified by an analyzer 11 such as gas chromatography (GC).

The outlet gas contains at least one of HFO-1132 and HCFO-1122a. Compounds other than HFO-1132 and HCFO-1122a contained in the outlet gas include CFO-1112, water, hydrogen, hydrogen chloride, and hydrogen fluoride.

Compounds other than HFO-1132 contained in the outlet gas can be removed and recovered by a conventionally known method such as distillation. For example, HCFO-1122a has a boiling point of −15 to 15° C., whereas HFO-1132 has a boiling point of −44 to −28° C. Since there is a large difference in boiling points, recovery by distillation is possible.
The recovered HCFO-1122a may be returned to the reactor as part of the feedstock, thereby improving the production efficiency of HFO-1132.

The mixed metal catalyst for the production of hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene of the present disclosure includes at least one platinum group selected from the group consisting of palladium, platinum, nickel, iridium, rhodium and ruthenium. It contains a first catalyst containing a metal and a second catalyst containing at least one second metal selected from the group consisting of copper, silver, gold, zinc, chromium and cobalt.
Preferred aspects such as the ratio of the mass of the platinum group metal to the mass of the second metal are as described above, and are omitted here.

Hereinafter, embodiments of the present disclosure will be described in detail by examples, but the embodiments of the present disclosure are not limited to these.
In the present disclosure, Examples 1 to 10 are examples, and Example 11 is a comparative example.

(Preparation of activated carbon supporting mixed metal catalyst A)
Copper (I) chloride (15 g, manufactured by Nacalai Tesque Co., Ltd.), platinum (II) chloride (0.14 g, manufactured by Junsei Chemical Co., Ltd.), 35% by mass hydrochloric acid (320 g, manufactured by Nacalai Tesque Co., Ltd.) and activated carbon (150 g, Osaka Gas Chemical Co., Ltd. Coconut shell raw material, 4 to 6 mesh granular compact (pellet), BET specific surface area 1336 m ² /g, no pretreatment for activated carbon) were mixed in a flask and left static for 12 hours. After placing, hydrogen chloride and water were distilled off under reduced pressure at 60° C. using an evaporator.
When the ratio of water (water content) to the weight of the supported catalyst becomes 30% by mass or less, the supported catalyst in the flask is transferred to the reaction tube, and then the reaction tube is kept at 200° C. and 16.7 mL of nitrogen gas is supplied. /sec for 16 hours and dried. As a result, activated carbon carrying a mixed metal catalyst A containing copper (I) chloride and platinum (II) chloride (referred to as CuCl—PtCl ₂ catalyst in Table 1) was obtained.
In the mixed metal catalyst A, the mass ratio of Pt to the mass of Cu supported on the activated carbon (Pt/Cu) was 1/100.
The total amount of Cu and Pt carried on the activated carbon per 100 parts by mass of the activated carbon was 6 parts by mass.

(Preparation of activated carbon supporting mixed metal catalyst B)
The above copper (I) chloride (15 g), palladium (II) chloride (0.16 g, manufactured by Junsei Chemical Co., Ltd.), deionized water (300 g), the above 35% by mass hydrochloric acid (41 g) and the above activated carbon (150 g) were placed in a flask. After the mixture was mixed inside and allowed to stand for 18 hours, hydrogen chloride and water were distilled off under reduced pressure at 60°C using an evaporator.
When the ratio of water (water content) to the weight of the supported catalyst becomes 30% by mass or less, the supported catalyst in the flask is transferred to the reaction tube, and then the reaction tube is kept at 200° C. and 16.7 mL of nitrogen gas is supplied. /sec for 16 hours and dried. As a result, activated carbon carrying a mixed metal catalyst B containing copper (I) chloride and palladium chloride (referred to as CuCl—PdCl ₂ in Table 1) was obtained.
In the mixed metal catalyst B, the mass ratio of Pd to the mass of Cu supported on the activated carbon (Pd/Cu) was 1/100.
The total amount of Cu and Pd carried on the activated carbon per 100 parts by mass of the activated carbon was 6 parts by mass.

(Preparation of activated carbon supporting mixed metal catalyst C)
The above copper (I) chloride (15 g), nickel (II) chloride (0.21 g, manufactured by Junsei Chemical Co., Ltd.), deionized water (75 g), the above 35% by mass hydrochloric acid (188 g) and the above activated carbon (150 g) were placed in a flask. After the mixture was mixed inside and allowed to stand for 18 hours, hydrogen chloride and water were distilled off under reduced pressure at 60°C using an evaporator.
When the ratio of water (water content) to the weight of the supported catalyst becomes 30% by mass or less, the supported catalyst in the flask is transferred to the reaction tube, and then the reaction tube is kept at 200° C. and 16.7 mL of nitrogen gas is supplied. /sec for 16 hours and dried. As a result, activated carbon carrying a mixed metal catalyst C containing copper (I) chloride and nickel (II) chloride (referred to as CuCl—NiCl ₂ in Table 1) was obtained.
In the mixed metal catalyst C, the ratio of the mass of Ni to the mass of Cu supported on the activated carbon (N
i/Cu) was 1/100.
The total amount of Cu and Ni carried on the activated carbon per 100 parts by mass of the activated carbon was 6 parts by mass.

(Preparation of activated carbon supporting catalyst X)
Palladium (II) chloride (1.25 g, manufactured by Junsei Chemical Co., Ltd.), the 35% by mass hydrochloric acid (320 g) and the activated carbon (37.5 g) were mixed in a flask, allowed to stand for 12 hours, and then evaporated using an evaporator. Hydrogen chloride and water were distilled off under reduced pressure at 60°C.
When the ratio of water (water content) to the weight of the supported catalyst becomes 30% by mass or less, the supported catalyst in the flask is transferred to the reaction tube, and then the reaction tube is kept at 200° C. and 16.7 mL of nitrogen gas is supplied. /sec for 16 hours and dried. As a result, activated carbon supporting catalyst X containing palladium(II) chloride (referred to as Pd/C catalyst in Table 1) was obtained.
The amount of Pd carried on the activated carbon was 0.5 parts by mass with respect to 100 parts by mass of the activated carbon.

[Example 1]
A reaction apparatus 20 shown in FIG. 1 described above was prepared. As the reactor 1, a reaction tube (made of SUS304, inner diameter 35.3 mm) installed in an electric furnace was used. In addition, a thermometer was inserted into the sheath tube of the reaction tube to measure the internal temperature.
The reaction tube was filled with activated carbon carrying mixed metal catalyst A with a length of 50 cm. The temperature inside the reaction tube was controlled at 249°C.
Reactor 1 was continuously fed with CFO-1112, hydrogen and nitrogen through feed lines 2-4, which were stainless steel tubes, respectively. The molar ratio of CFO-1112, hydrogen and nitrogen supplied to the reactor 1 was controlled to be 1:2:0.1.
In addition, the mixed gas flow rate (supply amount per unit time) was controlled so that the residence time of the mixed gas (CFO-1112, hydrogen and nitrogen) inside the reactor 1 was 23 seconds. The pressure inside the reactor 1 was the same as the atmospheric pressure.
As the preheaters 2a to 4a, electric furnaces set to a furnace temperature of 200° C. were used.

The composition analysis of the resulting outlet gas was performed using gas chromatography (GC). In the GC, DB-1301 (length 60 m×inner diameter 250 μm×thickness 1 μm, manufactured by Agilent Technologies) was used as a column.
HFO-1132, HCFO-1122a, dichlorodifluoroethane (hereinafter also referred to as “HCFC-132”), difluoroethane (hereinafter also referred to as “HFC-152”) in the outlet gas relative to the molar amount of CFO-1112 supplied to the reactor ) and fluoroethane (hereinafter also referred to as “HFC-161”) were determined (unit: %).
Then, the ratio of the molar amount of HFO-1132 and the ratio of the molar amount of HCFO-1122a to the conversion amount of CFO-1112 are shown in Table 1 as "HFO-1132 selectivity" and "HCFO-1122a selectivity", respectively. Summarized.
Similarly, "HCFC-132 selectivity", "HFC-152 selectivity" and "HFC-161 selectivity" are summarized in Table 1.
In addition, the conversion rate and the ratio of the mass of E isomer to the mass of Z isomer contained in HFO-1132 (mass of E isomer/mass of Z isomer) were determined and summarized in Table 1 (in Table 1, "E/ Z”). E/Z was obtained in the same manner in the following examples and summarized in Table 1.

[Example 2]
After obtaining the outlet gas in the same manner as in Example 1, except that the temperature inside the reaction tube was changed to 269° C. and the residence time was changed to 22.1 seconds, HFO-1132 selectivity, HCFO-1122a selectivity , HCFC-132 selectivity, HFC-152 selectivity, HFC-161 selectivity, conversion and E/Z were determined and summarized in Table 1.

[Example 3]
In the same manner as in Example 1, except that the molar ratio of CFO-1112, hydrogen and nitrogen supplied to reactor 1 was changed to 1:3:0.1 and the residence time was changed to 16.7 seconds. After obtaining the outlet gas, HFO-1132 selectivity, HCFO-1122a selectivity, HCFC-132 selectivity, HFC-152 selectivity, HFC-161 selectivity, conversion and E/Z were determined and summarized in Table 1. rice field.

[Example 4]
Change the temperature in the reaction tube to 301° C., change the residence time to 33.9 seconds, and change the molar ratio of CFO-1112, hydrogen and nitrogen supplied to the reactor 1 to 1:1:0.1. After obtaining the outlet gas, HFO-1132 selectivity, HCFO-1122a selectivity, HCFC-132 selectivity, HFC-152 selectivity, HFC-161 selectivity, conversion and E/Z was determined and summarized in Table 1.

[Example 5]
After obtaining the outlet gas, the HFO-1132 selectivity, HCFO-1122a selectivity, HCFC-132 selectivity, HFC-152 selectivity, HFC-161 selectivity, conversion and E/Z were determined and summarized in Table 1.

[Example 6]
Change the temperature in the reaction tube to 301° C., change the residence time to 17.4 seconds, and change the molar ratio of CFO-1112, hydrogen and nitrogen supplied to the reactor 1 to 1:3:0.1. After obtaining the outlet gas, HFO-1132 selectivity, HCFO-1122a selectivity, HCFC-132 selectivity, HFC-152 selectivity, HFC-161 selectivity, conversion and E/Z was determined and summarized in Table 1.

[Example 7]
Using activated carbon in which the mass ratio of Pt and Cu of the activated carbon supporting the mixed metal catalyst A was changed to 1/20, the temperature in the reaction tube was changed to 303 ° C., the residence time was changed to 16.1 seconds, and After obtaining the outlet gas in the same manner as in Example 1, except that the molar ratio of CFO-1112, hydrogen and nitrogen supplied to reactor 1 was changed to 1:2:0.1, HFO-1132 selectivity, HCFO-1122a selectivity, HCFC-132 selectivity, HFC-152 selectivity, HFC-161 selectivity, conversion and E/Z were determined and summarized in Table 1.

[Example 8]
Using activated carbon with a length of 30 cm supporting metal mixed catalyst B instead of the activated carbon supporting metal mixed catalyst A, changing the temperature in the reaction tube to 200 ° C., changing the residence time to 28.9 seconds, and After obtaining the outlet gas in the same manner as in Example 1, except that the molar ratio of CFO-1112, hydrogen and nitrogen supplied to reactor 1 was changed to 1:1:0.1, HFO-1132 selectivity, HCFO-1122a selectivity, HCFC-132 selectivity, HFC-152 selectivity, HFC-161 selectivity, conversion and E/Z were determined and summarized in Table 1.

[Example 9]
After obtaining the outlet gas in the same manner as in Example 7, except that the temperature inside the reaction tube was changed to 281° C. and the residence time was changed to 24.7 seconds, HFO-1132 selectivity, HCFO-1122a selectivity, HCFC-132 selectivity, HFC-152 selectivity, HFC-161 selectivity, conversion and E/Z were determined and summarized in Table 1.

[Example 10]
Using activated carbon with a length of 30 cm supporting mixed metal catalyst C instead of activated carbon supporting mixed metal catalyst A, changing the temperature in the reaction tube to 352° C., changing the residence time to 14.8 seconds, and After obtaining the outlet gas in the same manner as in Example 1, except that the molar ratio of CFO-1112, hydrogen and nitrogen supplied to reactor 1 was changed to 1:2:0.1, HFO-1132 selectivity, HCFO-1122a selectivity, HCFC-132 selectivity, HFC-152 selectivity, HFC-161 selectivity, conversion and E/Z were determined and summarized in Table 1.

[Example 11]
Catalyst X was used instead of activated carbon supporting mixed metal catalyst A, the temperature in the reaction tube was changed to 80°C, the residence time was changed to 35.5 seconds, nitrogen was not supplied to reactor 1, and After obtaining the outlet gas in the same manner as in Example 1, except that the molar ratio of CFO-1112 and hydrogen supplied to the reactor 1 was changed to 1:2, HFO-1132 selectivity, HCFO-1122a selectivity , HCFC-132 selectivity, HFC-152 selectivity, HFC-161 selectivity and conversion were determined and summarized in Table 1.

From Table 1, the first catalyst containing one or more platinum group metals selected from the group consisting of palladium, platinum, nickel, iridium, rhodium and ruthenium and the group consisting of copper, silver, gold, zinc, chromium and cobalt By reacting CFO-1112 with hydrogen in the presence of a mixed metal catalyst containing a second catalyst containing one or more selected second metals, the formation of by-products can be suppressed and HFO-1132 and HCFO-1122a was synthesized with high selectivity, and it can be seen that hydrogen-substituted CFO-1112 can be selectively produced.

The disclosure of Japanese Patent Application No. 2021-202874 filed on December 14, 2021 is incorporated herein by reference in its entirety. All publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application and technical standard were specifically and individually indicated to be incorporated by reference. incorporated herein by reference.

Claims (10)

1. A first catalyst containing one or more platinum group metals selected from the group consisting of palladium, platinum, nickel, iridium, rhodium and ruthenium and one selected from the group consisting of copper, silver, gold, zinc, chromium and cobalt reacting 1,2-dichloro-1,2-difluoroethylene with hydrogen in the presence of a mixed metal catalyst containing a second catalyst comprising at least one second metal; A method for producing a hydrogen-substituted product.
2. 2. Hydrogenation of 1,2-dichloro-1,2-difluoroethylene according to claim 1, wherein in the mixed metal catalyst, the ratio of the mass of the platinum group metal to the mass of the second metal is 1/1 or less. body manufacturing method.
3. The mixed metal catalyst is supported by a carrier, and the total supported amount of the platinum group metal and the second metal supported on the carrier with respect to 100 parts by mass of the carrier is 1 to 20 parts by mass. 3. The method for producing the hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene according to claim 1 or 2.
4. The method for producing a hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene according to claim 3, wherein the carrier contains activated carbon.
5. The 1,2-dichloro-1 according to any one of claims 1 to 4, wherein the temperature at which the 1,2-dichloro-1,2-difluoroethylene and the hydrogen are reacted is 150 to 400°C. A method for producing a hydrogen-substituted product of ,2-difluoroethylene.
6. 1, according to any one of claims 1 to 5, wherein the molar ratio of the amount of hydrogen used to the amount of 1,2-dichloro-1,2-difluoroethylene used is 1 to 50. A method for producing a hydrogen-substituted 2-dichloro-1,2-difluoroethylene.
7. The 1,2-dichloro-1,2-difluoroethylene according to any one of claims 1 to 6, wherein the platinum group metal is one or more metals selected from the group consisting of platinum and nickel. A method for producing a hydrogen-substituted product of
8. The 1,2-dichloro-1,2-difluoroethylene according to any one of claims 1 to 7, wherein the second metal is one or more metals selected from the group consisting of copper and silver. A method for producing a hydrogen-substituted product of
9. Any one of claims 1 to 8, wherein the hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene includes at least one of 1,2-difluoroethylene and 1-chloro-1,2-difluoroethylene. A method for producing a hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene according to any one of items.
10. The hydrogen-substituted 1,2-dichloro-1,2-difluoroethylene includes 1,2-difluoroethylene and 1-chloro-1,2-difluoroethylene, and the 1-chloro-1,2-difluoroethylene 1,2-dichloro-1 according to any one of claims 1 to 9, wherein the 1-chloro-1,2-difluoroethylene is reacted with hydrogen in the presence of the mixed metal catalyst. A method for producing a hydrogen-substituted product of ,2-difluoroethylene.

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