[go: up one dir, main page]

WO2025169840A1 - Method for producing chlorotrifluoroethylene and trifluoroethylene - Google Patents

Method for producing chlorotrifluoroethylene and trifluoroethylene

Info

Publication number
WO2025169840A1
WO2025169840A1 PCT/JP2025/003051 JP2025003051W WO2025169840A1 WO 2025169840 A1 WO2025169840 A1 WO 2025169840A1 JP 2025003051 W JP2025003051 W JP 2025003051W WO 2025169840 A1 WO2025169840 A1 WO 2025169840A1
Authority
WO
WIPO (PCT)
Prior art keywords
raw material
water
composition
hydrogen
material composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/003051
Other languages
French (fr)
Japanese (ja)
Inventor
耀 岩崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of WO2025169840A1 publication Critical patent/WO2025169840A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • This disclosure relates to a method for producing chlorotrifluoroethylene and trifluoroethylene.
  • Chlorotrifluoroethylene is being considered for use as a monomer for various polymers, a precursor for trifluoroethylene, etc.
  • Trifluoroethylene has a low global warming potential and a low boiling point, and is expected to be used as a type of high-pressure refrigerant.
  • chlorotrifluoroethylene will also be referred to as "CTFE”
  • trifluoroethylene will also be referred to as "HFO-1123.
  • Known methods for producing CTFE include a zinc dechlorination method of 1,1,2-trichloro-1,2,2-trifluoroethane, as well as a hydrogen reduction method of 1,1,2-trichloro-1,2,2-trifluoroethane using a catalyst (for example, Patent Document 1).
  • HFO-1123 can be produced, for example, by reacting CTFE obtained by reacting CFC-113 with hydrogen, and then reacting the CTFE with hydrogen. Alternatively, HFO-1123 can be obtained directly as a by-product in the reaction of CFC-113 with hydrogen.
  • a method for producing chlorotrifluoroethylene and trifluoroethylene comprising contacting a raw material composition containing 1,1,2-trichloro-1,2,2-trifluoroethane, hydrogen, and water, wherein the raw material composition has a water content of 200 mass ppm or less relative to the total raw material composition, with a catalyst, and producing chlorotrifluoroethylene and trifluoroethylene by reacting 1,1,2-trichloro-1,2,2-trifluoroethane with hydrogen.
  • the catalyst includes a catalyst containing a first metal element that is at least one selected from the group consisting of Pd, Pt, Ni, Ir, Ru, Rh, and Os, and a second metal element that is at least one selected from the group consisting of Cu, Fe, Au, Ag, Zn, Sn, and Co.
  • ⁇ 3> The manufacturing method according to ⁇ 1>, wherein the catalyst includes a catalyst containing a first metal element that is Pd or Pt and a second metal element that is Cu.
  • ⁇ 4> ⁇ 4> The method according to any one of ⁇ 1> to ⁇ 3>, wherein the raw material composition has a water content of 50 ppm by mass or less relative to the entire raw material composition.
  • the target compounds, CTFE and HFO-1123 both have unsaturated bonds. Therefore, if the raw material composition contains more than 200 ppm by mass of water, it is thought that water vapor heated to the reaction temperature will cause a hydrolysis reaction of the generated target compound, converting it into a by-product. In addition, if the raw material composition contains water, it is thought that side reactions will be more likely to occur due to water adsorption on the active sites of the catalyst, and side reactions will also be more likely to occur due to modification and detachment of the catalyst surface caused by water vapor heated to the reaction temperature.
  • the water content of the raw material composition is likely to be high. If a raw material composition with a high water content is used to react CFC-113 with hydrogen, hydrolysis reactions of the target compound, side reactions, etc. are likely to occur, and the total selectivity of CTFE and HFO-1123 is thought to be low. In contrast, in the present embodiment, the water content of the raw material composition is 200 ppm by mass or less, and therefore it is presumed that the hydrolysis reaction and side reactions of the target compound are less likely to occur, and a high total selectivity for CTFE and HFO-1123 can be obtained.
  • the first composition contains hydrogen chloride. That is, the first composition contains, for example, CFC-113 that remains unreacted in the pre-reaction step, and CTFE, HFO-1123, and hydrogen chloride produced in the pre-reaction step. Therefore, in order to remove hydrogen chloride from the first composition, a water contact step is carried out in which the first composition is brought into contact with water.
  • the water removal step at least a portion of the water is removed from the second composition by, for example, contacting the second composition with a desiccant such as a molecular sieve.
  • a desiccant such as a molecular sieve.
  • the product separation step at least a portion of the CTFE and HFO-1123 is separated from the second composition by, for example, distillation, etc.
  • the catalyst may be a metal catalyst containing at least one metal element, such as Pd, Pt, Ni, Ir, Ru, Rh, Os, Cu, Fe, Au, Ag, Zn, Sn, or Co.
  • the catalyst may contain only one metal element or two or more metal elements. The amount of catalyst used is determined depending on the amounts of CFC-113 and hydrogen that are the raw materials to be fed to the reactor.
  • the specific catalyst preferably contains a first metal element which is Pd or Pt and a second metal element which is Cu. That is, the catalyst preferably contains at least one of a Pd—Cu catalyst and a Pt—Cu catalyst as the specific catalyst.
  • the specific catalyst contains a first metal element with a relatively high affinity for hydrogen gas and a second metal element with a relatively low affinity for hydrogen gas. It is believed that in catalytic reactions using the specific catalyst, the difference in affinity for hydrogen gas is utilized to control the reactivity between CFC-113 and hydrogen. Therefore, when water is adsorbed onto the surface of the specific catalyst, the reactivity on the catalyst surface changes, resulting in the production of by-products. In contrast, in this embodiment, because the water content of the raw material composition is within the above-mentioned range, it is believed that the adsorption of water onto the surface of the specific catalyst is suppressed, thereby suppressing the production of by-products, resulting in a high combined selectivity for CTFE and HFO-1123.
  • the specific catalyst may contain other metal components in addition to the first metal element and the second metal element, as necessary.
  • the other metal components include Bi and Al.
  • the content of the other metal components is preferably less than 0.05 mass% each, and more preferably less than 0.5 mass% in total, relative to the entire specific catalyst.
  • the content of the first metal element contained in the specific catalyst is preferably 0.10 to 1.6 mass%, more preferably 0.16 to 1.4 mass%, and even more preferably 0.33 to 1.1 mass%, relative to the total of the first metal element and the second metal element.
  • the content of the second metal element contained in the specific catalyst is preferably 98.4 to 99.9 mass%, more preferably 98.6 to 99.8 mass%, and even more preferably 98.9 to 99.7 mass%, based on the total of the first metal element and the second metal element.
  • the form of the catalyst is not particularly limited, and may be in the form of a powder, pellets, or spheres.
  • the catalyst may be supported on a carrier.
  • the carrier preferably contains activated carbon, and more preferably consists of activated carbon.
  • Activated carbon prepared from raw materials such as wood, charcoal, fruit shells, coconut shells, peat, lignite, and coal can be used, but activated carbon obtained from plant materials is preferable to mineral materials, and coconut shell activated carbon is particularly optimal.
  • the carrier shape may be formed charcoal with a length of about 2 to 5 mm, crushed charcoal with a size of about 4 to 50 mesh, or granular charcoal with a size of 2 to 50 mesh. From the viewpoint of improving the total selectivity of CTFE and HFO-1123, the carrier shape is preferably crushed charcoal with a size of 4 to 20 mesh or granular charcoal with a size of 4 to 20 mesh.
  • the amount of the catalyst supported is preferably 0.5 to 50 parts by mass, more preferably 1 to 50 parts by mass, even more preferably 1 to 30 parts by mass, particularly preferably 3 to 30 parts by mass, and extremely preferably 5 to 30 parts by mass, per 100 parts by mass of the carrier, from the viewpoints of being able to sufficiently increase the specific surface area of the catalyst and achieving excellent catalytic activity.
  • the specific catalyst is supported on a carrier, the first metal element and the second metal element may be supported individually on a carrier and used as a mixture, or a mixture of the first metal element and the second metal element may be supported on a carrier.
  • the catalyst may contain a metal salt compound.
  • the metal salt compound include oxides, halides, hydroxides, nitrate compounds, etc. containing a first metal element or a second metal element.
  • examples of the metal salt compound include CuO, CuCl, CuCl2 , CuF, CuF2 , Cu2Cl (OH) 3 , Cu2 ( NO3 (OH) 3 ), etc.
  • examples of the metal salt compound include PdO, PdCl2, etc.
  • the specific surface area of the entire supported catalyst in which the catalyst is supported on the carrier is, for example, 0.1 to 1500 m 2 /g, and from the viewpoint of improving the total selectivity of CTFE and HFO-1123, it is preferably 1 to 1500 m 2 /g, and more preferably 100 to 1500 m 2 /g.
  • the specific surface area is a value measured by the BET method (BET specific surface area).
  • the temperature of the raw material composition when it is brought into contact with the catalyst i.e., the reaction temperature
  • the reaction temperature is preferably 150 to 350° C., more preferably 180 to 300° C., and even more preferably 190 to 300° C., from the viewpoint of improving the total selectivity of CTFE and HFO-1123.
  • the reaction temperature means the temperature inside the reactor, and is measured using a thermocouple or the like.
  • the pressure when the raw material composition is brought into contact with the catalyst is preferably 0 to 1 MPa, more preferably 0 to 0.9 MPa, and even more preferably 0 to 0.5 MPa, in terms of gauge pressure, from the viewpoint of improving the total selectivity of CTFE and HFO-1123.
  • the above pressure means the pressure inside the reactor.
  • a product composition containing the target compounds CTFE and HFO-1123 is obtained.
  • Compounds contained in the product composition other than CTFE and HFO-1123 include unreacted raw materials CFC-113 and hydrogen, water, and, if the raw material composition contains a diluent, 1,1-difluoroethylene (HFO-1132a), 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane, 1,3-dichloro-1,2,2,3,4,4-hexafluorocyclobutane, 1,2-dichloro-1,1,2-trifluoroethane ...
  • Examples of by-products include oroethane (HCFC-123a), 1,1-dichloro-1,2,2-trifluoroethane (HCFC-123b), 1,1-dichloro-2,2-difluoroethylene (CFO-1112), 1-chloro-2,2-difluoroethylene (HFO-1122), 1-chloro-2,2-difluoroethylene (HFO-1122a(E)), and 1-chloro-2,2-difluoroethylene (HFO-1122a(Z)).
  • the total selectivity of CTFE and HFO-1123 in the reaction of CFC-113 with hydrogen is preferably 94.0% or more, more preferably 94.3% or more, and even more preferably 94.5% or more, from the viewpoint of efficiently obtaining HFO-1123.
  • the selectivity is determined by analyzing the resulting product composition by gas chromatography. Specifically, the measurement is performed using a gas chromatograph (GC-7890A, manufactured by Agilent Technologies Inc.) as a measuring device, a DB-1 column (manufactured by Agilent Technologies Inc., length 60 m, inner diameter 250 ⁇ m, filter thickness 1 ⁇ m), and a flame ionization detector (FID) as a detector under the following measurement conditions.
  • GC-7890A gas chromatograph
  • DB-1 column manufactured by Agilent Technologies Inc., length 60 m, inner diameter 250 ⁇ m, filter thickness 1 ⁇ m
  • FID flame ionization detector
  • Injection temperature 240°C Sample injection volume: 0.5 mL Split ratio: 60/1 Linear velocity: 35.8 cm/sec. Start of measurement: -30°C, holding time: 10 minutes. Heating rate: 10°C/min. End of measurement: 240°C, holding time: 20 minutes. Detection temperature: 250°C.
  • the resulting product composition may be subjected to a separation process in which components other than CTFE and HFO-1123 are separated.
  • separation processes include a raw material separation process in which the raw materials CFC-113 and hydrogen are separated from the product composition, and a hydrogen chloride separation process in which hydrogen chloride is separated from the product composition.
  • the CTFE contained in the resulting product composition is useful as a raw material for HFO-1123, as well as a raw material for polymers. Furthermore, the HFO-1123 contained in the resulting product composition is useful as a refrigerant that replaces the greenhouse gases difluoromethane and pentafluoroethane.
  • a Pd—Cu catalyst was used.
  • the Pd—Cu catalyst used was a catalyst composed of 1.0 mass% palladium and 99.0 mass% copper.
  • the Pd—Cu catalyst was supported on activated carbon (4-6 mesh granular carbon), and the amount of catalyst supported was 6.41 mass parts per 100 mass parts of the support.
  • the above-mentioned Pd—Cu catalyst supported on activated carbon was packed into a 20A SUS tubular reactor so that the catalyst length was 30 cm.
  • the mass of the supported catalyst used was 57 g, and the specific surface area of the entire supported catalyst was 1100 m 2 /g.
  • a hydrogen reduction reaction of CFC-113 was carried out by passing a raw material composition, which was a mixed gas of CFC-113 and hydrogen, through the catalyst in the reactor.
  • the molar ratio of hydrogen/CFC-113 in the raw material composition was 4/1. That is, in each raw material composition, the volume ratio of the hydrogen content to the CFC-113 content (H 2 /CFC-113) was 4. No diluent was used.
  • the water content of the raw material composition in each example was measured using Karl Fischer (coulometric method) by the method described above, and the values were shown in Table 1.
  • the water content of the raw material composition was adjusted, as necessary, for each of CFC-113 and hydrogen, by removing water by passing it through a molecular sieve or by adding water by passing it through pure water.
  • reaction conditions for the hydrogen reduction reaction were a reaction temperature of 200° C., a residence time (i.e., reaction time) of 13.9 seconds, a linear velocity of 2.2 cm/second, and atmospheric pressure (i.e., gauge pressure: 0 MPa) in the reactor.
  • the crude product gas which is the product composition obtained by the reaction, was sampled and the components contained therein were analyzed using a gas chromatograph.
  • the CFC-113 conversion rate, CTFE selectivity, HFO-1123 selectivity, and the combined selectivity for CTFE and HFO-1123 were calculated.
  • the measuring equipment and conditions for the gas chromatographic analysis were as described above. The results are shown in Table 1.
  • Examples 1 to 3 are working examples, and Example 4 is a comparative example. As shown in Table 1, in Examples 1 to 3 in which the water content of the raw material composition was 200 ppm by mass or less, the total selectivity for CTFE and HFO-1123 was higher than in Example 4.

Landscapes

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

Abstract

Provided is a method for producing chlorotrifluoroethylene and trifluoroethylene by bringing a raw material composition containing 1,1,2-trichloro-1,2,2-trifluoroethane, hydrogen, and water into contact with a catalyst, the composition having a water content of 200 ppm by mass or less with respect to the entire raw material composition, to produce chlorotrifluoroethylene and trifluoroethylene through a reaction between the 1,1,2-trichloro-1,2,2-trifluoroethane and hydrogen.

Description

クロロトリフルオロエチレン及びトリフルオロエチレンの製造方法Method for producing chlorotrifluoroethylene and trifluoroethylene

　本開示は、クロロトリフルオロエチレン及びトリフルオロエチレンの製造方法に関する。 This disclosure relates to a method for producing chlorotrifluoroethylene and trifluoroethylene.

　クロロトリフルオロエチレンは、各種ポリマーのモノマー、トリフルオロエチレンの前駆体等としての利用が考えられている。トリフルオロエチレンは、地球温暖化係数が低く、かつ、低沸点であり、高圧冷媒の一種として期待されている。以下、クロロトリフルオロエチレンを「ＣＴＦＥ」ともいい、トリフルオロエチレンを「ＨＦＯ－１１２３」ともいう。
　ＣＴＦＥの製造方法としては、１，１，２－トリクロロ－１，２，２－トリフルオロエタンの亜鉛脱塩素法のほか、触媒を用いた１，１，２－トリクロロ－１，２，２－トリフルオロエタンの水素還元法（例えば特許文献１）等が知られている。以下、１，１，２－トリクロロ－１，２，２－トリフルオロエタンを「ＣＦＣ－１１３」ともいう。
　ＨＦＯ－１１２３は、例えば、ＣＦＣ－１１３と水素との反応により得られるＣＴＦＥを、さらに水素と反応させることで製造できるほか、ＣＦＣ－１１３と水素との反応における副生成物として直接得られることもある。 Chlorotrifluoroethylene is being considered for use as a monomer for various polymers, a precursor for trifluoroethylene, etc. Trifluoroethylene has a low global warming potential and a low boiling point, and is expected to be used as a type of high-pressure refrigerant. Hereinafter, chlorotrifluoroethylene will also be referred to as "CTFE," and trifluoroethylene will also be referred to as "HFO-1123."
Known methods for producing CTFE include a zinc dechlorination method of 1,1,2-trichloro-1,2,2-trifluoroethane, as well as a hydrogen reduction method of 1,1,2-trichloro-1,2,2-trifluoroethane using a catalyst (for example, Patent Document 1). Hereinafter, 1,1,2-trichloro-1,2,2-trifluoroethane will also be referred to as "CFC-113."
HFO-1123 can be produced, for example, by reacting CTFE obtained by reacting CFC-113 with hydrogen, and then reacting the CTFE with hydrogen. Alternatively, HFO-1123 can be obtained directly as a by-product in the reaction of CFC-113 with hydrogen.

中国特許出願公開第１０５４５７６５１号明細書Chinese Patent Application Publication No. 105457651

　ＨＦＯ－１１２３を効率的に得ることを目的とした場合、ＣＦＣ－１１３と水素との反応において、ＣＴＦＥ単体の選択率ではなく、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率が高いことが望ましい。
　本開示は、ＣＦＣ－１１３と水素との反応において、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率の高い製造方法を提供することを目的とする。 For the purpose of efficiently obtaining HFO-1123, it is desirable that the total selectivity of CTFE and HFO-1123 is high in the reaction of CFC-113 with hydrogen, rather than the selectivity of CTFE alone.
An object of the present disclosure is to provide a process for producing CTFE and HFO-1123 with a high total selectivity in the reaction of CFC-113 with hydrogen.

　本開示には、以下の態様が含まれる。
＜１＞
　１，１，２－トリクロロ－１，２，２－トリフルオロエタン、水素、及び水を含有する原料組成物であって、前記原料組成物全体に対する水の含有率が２００質量ｐｐｍ以下である原料組成物を、触媒に接触させ、１，１，２－トリクロロ－１，２，２－トリフルオロエタンと水素との反応によりクロロトリフルオロエチレン及びトリフルオロエチレンを製造する、クロロトリフルオロエチレン及びトリフルオロエチレンの製造方法。
＜２＞
　前記触媒は、Ｐｄ、Ｐｔ、Ｎｉ、Ｉｒ、Ｒｕ、Ｒｈ、及びＯｓからなる群より選択される少なくとも１種である第一の金属元素と、Ｃｕ、Ｆｅ、Ａｕ、Ａｇ、Ｚｎ、Ｓｎ、及びＣｏからなる群より選択される少なくとも１種である第二の金属元素と、を含有する触媒を含む、＜１＞に記載の製造方法。
＜３＞
　前記触媒は、Ｐｄ又はＰｔである第一の金属元素と、Ｃｕである第二の金属元素と、を含有する触媒を含む、＜１＞に記載の製造方法。
＜４＞
　前記原料組成物は、前記原料組成物全体に対する水の含有率が５０質量ｐｐｍ以下である、＜１＞～＜３＞のいずれか１つに記載の製造方法。
＜５＞
　前記原料組成物は、
　１，１，２－トリクロロ－１，２，２－トリフルオロエタンと水素とを反応させてクロロトリフルオロエチレン及びトリフルオロエチレンを生成させ、１，１，２－トリクロロ－１，２，２－トリフルオロエタンとクロロトリフルオロエチレンとトリフルオロエチレンと塩化水素とを含有する第１の組成物を得る前反応工程と、
　前記第１の組成物に水を接触させて前記塩化水素の少なくとも一部を除去することで、水を含有する第２の組成物を得る水接触工程と、
　前記第２の組成物から前記水の少なくとも一部を除去する水除去工程と、
　前記第２の組成物からクロロトリフルオロエチレン及びトリフルオロエチレンの少なくとも一部を分離する生成物分離工程と、
　を少なくとも経て得られた、１，１，２－トリクロロ－１，２，２－トリフルオロエタンを含有する組成物を含む、＜１＞～＜４＞のいずれか１つに記載の製造方法。
＜６＞
　前記反応におけるクロロトリフルオロエチレン及びトリフルオロエチレンの合計選択率は、９４％以上である、＜１＞～＜５＞のいずれか１つに記載の製造方法。
＜７＞
　前記原料組成物は、希釈剤を含有しないか、又は、希釈剤をさらに含有し前記原料組成物全体に対する希釈剤の含有率が５．０体積％以下である、＜１＞～＜６＞のいずれか１つに記載の製造方法。
＜８＞
　前記原料組成物における水素の含有量は、１，１，２－トリクロロ－１，２，２－トリフルオロエタンの含有量に対し、体積基準で５．０倍以下である、＜１＞～＜７＞のいずれか１つに記載の製造方法。 The present disclosure includes the following aspects.
<1>
A method for producing chlorotrifluoroethylene and trifluoroethylene, comprising contacting a raw material composition containing 1,1,2-trichloro-1,2,2-trifluoroethane, hydrogen, and water, wherein the raw material composition has a water content of 200 mass ppm or less relative to the total raw material composition, with a catalyst, and producing chlorotrifluoroethylene and trifluoroethylene by reacting 1,1,2-trichloro-1,2,2-trifluoroethane with hydrogen.
<2>
The catalyst includes a catalyst containing a first metal element that is at least one selected from the group consisting of Pd, Pt, Ni, Ir, Ru, Rh, and Os, and a second metal element that is at least one selected from the group consisting of Cu, Fe, Au, Ag, Zn, Sn, and Co. The manufacturing method according to <1>.
<3>
The manufacturing method according to <1>, wherein the catalyst includes a catalyst containing a first metal element that is Pd or Pt and a second metal element that is Cu.
＜4＞
<4> The method according to any one of <1> to <3>, wherein the raw material composition has a water content of 50 ppm by mass or less relative to the entire raw material composition.
<5>
The raw material composition is
a pre-reaction step of reacting 1,1,2-trichloro-1,2,2-trifluoroethane with hydrogen to produce chlorotrifluoroethylene and trifluoroethylene, thereby obtaining a first composition containing 1,1,2-trichloro-1,2,2-trifluoroethane, chlorotrifluoroethylene, trifluoroethylene, and hydrogen chloride;
a water contacting step of contacting the first composition with water to remove at least a portion of the hydrogen chloride, thereby obtaining a second composition containing water;
a water removal step of removing at least a portion of the water from the second composition;
a product separation step of separating at least a portion of the chlorotrifluoroethylene and trifluoroethylene from the second composition;
<4> The method according to any one of <1> to <4>, wherein the composition contains 1,1,2-trichloro-1,2,2-trifluoroethane, and is obtained through at least the steps of:
<6>
<5> The production method according to any one of <1> to <5>, wherein the total selectivity of chlorotrifluoroethylene and trifluoroethylene in the reaction is 94% or more.
＜７＞
<6> The production method according to any one of <1> to <6>, wherein the raw material composition does not contain a diluent, or further contains a diluent and the content of the diluent relative to the entire raw material composition is 5.0 vol% or less.
＜8＞
<8> The production method according to any one of <1> to <7>, wherein the content of hydrogen in the raw material composition is 5.0 times or less, by volume, the content of 1,1,2-trichloro-1,2,2-trifluoroethane.

　本開示によれば、ＣＦＣ－１１３と水素との反応において、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率の高い製造方法が提供される。 This disclosure provides a method for producing CTFE and HFO-1123 with a high total selectivity in the reaction of CFC-113 with hydrogen.

　以下に、本開示の実施形態について説明する。これらの説明及び実施例は実施形態を例示するものであり、実施形態の範囲を制限するものではない。 The following describes embodiments of the present disclosure. These descriptions and examples are intended to illustrate the embodiments and do not limit the scope of the embodiments.

　本開示において「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を意味する。
　本開示に段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　本開示において、２以上の好ましい態様の組み合わせは、より好ましい態様である。
　本開示において、各成分の量は、各成分に該当する物質が複数種存在する場合には、特に断らない限り、複数種の物質の合計量を意味する。 In the present disclosure, a numerical range indicated using "to" means a range that includes the numerical values before and after "to" as the minimum and maximum values, respectively.
In the numerical ranges described in stages in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.
In the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.
In the present disclosure, when there are multiple substances corresponding to each component, the amount of each component means the total amount of the multiple substances unless otherwise specified.

［ＣＴＦＥ及びＨＦＯ－１１２３の製造方法］
　本開示の一実施形態に係る製造方法は、１，１，２－トリクロロ－１，２，２－トリフルオロエタン（ＣＦＣ－１１３）、水素、及び水を含有する原料組成物であって、前記原料組成物全体に対する水の含有率が２００質量ｐｐｍ以下である原料組成物を、触媒に接触させ、ＣＦＣ－１１３と水素との反応によりクロロトリフルオロエチレン（ＣＴＦＥ）及びトリフルオロエチレン（ＨＦＯ－１１２３）を製造する、ＣＴＦＥ及びＨＦＯ－１１２３の製造方法である。
　以下、組成物全体に対する水の含有率を「組成物の水含有率」ともいう。 [Method for producing CTFE and HFO-1123]
A production method according to one embodiment of the present disclosure is a method for producing CTFE and HFO-1123, which comprises contacting a raw material composition containing 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), hydrogen, and water, wherein the water content relative to the total amount of the raw material composition is 200 ppm by mass or less, with a catalyst, and producing chlorotrifluoroethylene (CTFE) and trifluoroethylene (HFO-1123) by reacting CFC-113 with hydrogen.
Hereinafter, the water content relative to the total composition will also be referred to as the "water content of the composition."

　前記の通り、ＨＦＯ－１１２３を効率的に得るためには、ＣＦＣ－１１３と水素との反応においてＣＴＦＥ及びＨＦＯ－１１２３の合計選択率が高いことが求められる。
　本実施形態では、原料組成物の水含有率が２００質量ｐｐｍ以下であることにより、ＣＴＦＥ及びＨＦＯ－１１２３の高い合計選択率が得られる。その理由は定かではないが、以下のように推測される。 As mentioned above, in order to efficiently obtain HFO-1123, a high total selectivity for CTFE and HFO-1123 is required in the reaction of CFC-113 with hydrogen.
In this embodiment, by keeping the water content of the raw material composition at 200 ppm by mass or less, a high total selectivity for CTFE and HFO-1123 can be obtained. The reason for this is not clear, but is presumed to be as follows.

　ＣＦＣ－１１３と水素との反応によりＣＴＦＥ及びＨＦＯ－１１２３を製造する場合において、目的化合物であるＣＴＦＥ及びＨＦＯ－１１２３は、いずれも不飽和結合を有する。そのため、原料組成物が２００質量ｐｐｍより多く水を含有すると、反応温度に加熱された水蒸気が、生成した目的化合物の加水分解反応を引き起こし、副生成物に変換されることが考えられる。加えて、原料組成物が水を含有すると、触媒の活性サイトに水が吸着することにより副反応が起こりやすくなるとともに、反応温度に加熱された水蒸気に起因する触媒表面の改質、脱落等によっても副反応が起こりやすくなると考えられる。
　特に、原料組成物が後述する前反応組成物を含む場合、原料組成物の水含有率が高くなりやすい。そして、水含有率の高い原料組成物を用いてＣＦＣ－１１３と水素とを反応させると、上記目的化合物の加水分解反応、副反応等が起こりやすく、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率が低くなることが考えられる。
　これに対して、本実施形態では、原料組成物の水含有率が２００質量ｐｐｍ以下であるため、上記目的化合物の加水分解反応及び副反応が起こりにくく、ＣＴＦＥ及びＨＦＯ－１１２３の高い合計選択率が得られると推測される。 When CTFE and HFO-1123 are produced by the reaction of CFC-113 with hydrogen, the target compounds, CTFE and HFO-1123, both have unsaturated bonds. Therefore, if the raw material composition contains more than 200 ppm by mass of water, it is thought that water vapor heated to the reaction temperature will cause a hydrolysis reaction of the generated target compound, converting it into a by-product. In addition, if the raw material composition contains water, it is thought that side reactions will be more likely to occur due to water adsorption on the active sites of the catalyst, and side reactions will also be more likely to occur due to modification and detachment of the catalyst surface caused by water vapor heated to the reaction temperature.
In particular, when the raw material composition contains a pre-reaction composition described below, the water content of the raw material composition is likely to be high. If a raw material composition with a high water content is used to react CFC-113 with hydrogen, hydrolysis reactions of the target compound, side reactions, etc. are likely to occur, and the total selectivity of CTFE and HFO-1123 is thought to be low.
In contrast, in the present embodiment, the water content of the raw material composition is 200 ppm by mass or less, and therefore it is presumed that the hydrolysis reaction and side reactions of the target compound are less likely to occur, and a high total selectivity for CTFE and HFO-1123 can be obtained.

　以下、本開示の製造方法の一実施形態について詳細に説明する。
　本開示の一実施形態に係る製造方法では、例えば、触媒が収容された反応器へ、原料であるＣＦＣ－１１３と水素とを供給し、反応器内において、ＣＦＣ－１１３、水素、及び水を含有する原料組成物を触媒に接触させる。
　ＣＦＣ－１１３及び水素の反応器への供給は、ＣＦＣ－１１３と水素とを別々に反応器へ供給することで行ってもよく、あらかじめＣＦＣ－１１３及び水素を混合させた原料組成物を反応器へ供給することで行ってもよい。ＣＦＣ－１１３と水素とを別々に反応器へ供給する場合、原料組成物に含有される水としては、例えば、反応器へ供給する前のＣＦＣ－１１３及び水素の少なくとも一方に混入した水が挙げられる。
　なお、触媒に接触させる際のＣＦＣ－１１３は、気相であってもよく、液相であってもよく、気相であることが好ましい。 Hereinafter, one embodiment of the manufacturing method of the present disclosure will be described in detail.
In a production method according to an embodiment of the present disclosure, for example, raw materials CFC-113 and hydrogen are supplied to a reactor containing a catalyst, and a raw material composition containing CFC-113, hydrogen, and water is brought into contact with the catalyst in the reactor.
The supply of CFC-113 and hydrogen to the reactor may be carried out by separately supplying CFC-113 and hydrogen to the reactor, or by supplying a raw material composition in which CFC-113 and hydrogen are mixed in advance to the reactor. When CFC-113 and hydrogen are separately supplied to the reactor, examples of water contained in the raw material composition include water mixed in at least one of CFC-113 and hydrogen before being supplied to the reactor.
When brought into contact with the catalyst, CFC-113 may be in the gas phase or liquid phase, preferably in the gas phase.

　本実施形態の製造方法は、連続式であってもよく、バッチ式であってもよい。連続式の製造方法においては、例えば、反応器へＣＦＣ－１１３と水素とを供給すること、反応器内でＣＦＣ－１１３、水素、及び水を含有する原料組成物を触媒に接触させること、及びＣＦＣ－１１３と水素との反応により生成したＣＴＦＥ及びＨＦＯ－１１２３を含有する生成組成物を反応器から取り出すことは、いずれも連続的に行われる。 The production method of this embodiment may be continuous or batch-wise. In a continuous production method, for example, the steps of supplying CFC-113 and hydrogen to a reactor, contacting a raw material composition containing CFC-113, hydrogen, and water with a catalyst in the reactor, and removing the product composition containing CTFE and HFO-1123 produced by the reaction of CFC-113 and hydrogen from the reactor are all carried out continuously.

　反応器としては、後述する反応温度及び圧力に耐えるものであれば、形状及び構造は特に限定されず、例えば円筒状の縦型反応器が挙げられる。本実施形態の製造方法が連続式である場合、上記円筒状の縦型反応器を反応経路として用いてもよい。
　反応器の材質としては、鉄、ニッケルを主成分とする合金等が挙げられる。また、反応器は、電気ヒータ等の加熱手段を備えていてもよい。 The reactor is not particularly limited in shape or structure as long as it can withstand the reaction temperature and pressure described below, and examples thereof include a cylindrical vertical reactor. When the production method of the present embodiment is a continuous process, the cylindrical vertical reactor may be used as a reaction path.
Examples of materials for the reactor include alloys containing iron and nickel as main components, etc. The reactor may also be equipped with a heating means such as an electric heater.

＜原料組成物＞
　原料組成物とは、反応器に供給される全成分を表す。原料組成物は、少なくとも原料であるＣＦＣ－１１３及び水素、並びに水を含有する。必要に応じて希釈剤等の他の成分が反応器に供給される場合は、前記他の成分も原料組成物に含有される。
　原料組成物全体に対するＣＦＣ－１１３及び水素の合計含有率は、例えば５０体積％以上が挙げられ、生産量の観点から、６０体積％以上が好ましく、７０体積％以上がより好ましく、８０体積％以上がさらに好ましく、９０体積％以上が特に好ましく、９５体積％以上が極めて好ましい。
　以下、原料組成物に含有される各成分について説明する。 <Raw material composition>
The raw material composition refers to all components supplied to a reactor. The raw material composition contains at least the raw materials CFC-113 and hydrogen, as well as water. When other components such as a diluent are supplied to a reactor as needed, the other components are also contained in the raw material composition.
The total content of CFC-113 and hydrogen in the entire raw material composition is, for example, 50% by volume or more, and from the viewpoint of production amount, is preferably 60% by volume or more, more preferably 70% by volume or more, even more preferably 80% by volume or more, particularly preferably 90% by volume or more, and extremely preferably 95% by volume or more.
Each component contained in the raw material composition will be described below.

（水）
　本実施形態では、原料組成物の水含有率が２００質量ｐｐｍ以下である。反応器内において気相の原料組成物を触媒に接触させる場合、原料組成物の水含有率は、反応器内に供給されるガスの全成分の合計量に対する水の含有率を意味する。 (water)
In this embodiment, the water content of the raw material composition is 200 ppm by mass or less. When the gaseous raw material composition is brought into contact with the catalyst in a reactor, the water content of the raw material composition means the content of water relative to the total amount of all components of the gas supplied into the reactor.

　水含有率は、カールフィッシャー水分測定器を使用し、ＪＩＳ　Ｋ　００６８：２００１に準拠してカールフィッシャー法により測定する。
　反応器内において原料組成物を触媒に接触させる場合、水含有率の測定は、反応器内に供給され触媒に接触する前の原料組成物の一部を取り出した試料に対して行ってもよく、反応器内に供給する前の試料に対して行ってもよい。ＣＦＣ－１１３と水素とを別々に反応器へ供給する場合は、供給前のＣＦＣ－１１３の水含有率と、供給前の水素ガスの水含有率と、をそれぞれ測定し、供給比を考慮して、反応器内における原料組成物の水含有率を算出してもよい。 The water content is measured by the Karl Fischer method in accordance with JIS K 0068:2001 using a Karl Fischer moisture meter.
When the raw material composition is brought into contact with the catalyst in the reactor, the water content may be measured on a sample obtained by taking a part of the raw material composition before it is supplied to the reactor and brought into contact with the catalyst, or on a sample before it is supplied to the reactor. When CFC-113 and hydrogen are supplied separately to the reactor, the water content of the CFC-113 before supply and the water content of the hydrogen gas before supply may be measured separately, and the water content of the raw material composition in the reactor may be calculated taking into account the supply ratio.

　原料組成物の水含有率は、２００質量ｐｐｍ以下であり、１００質量ｐｐｍ以下が好ましく、５０質量ｐｐｍ以下がより好ましく、１５質量ｐｐｍ以下がさらに好ましく、１０質量ｐｐｍ以下が特に好ましく、５質量ｐｐｍ以下が極めて好ましい。原料組成物の水含有率の下限値は特に限定されるものではない。原料組成物の水含有率は、０．１質量ｐｐｍ以上であってもよく、０．５質量ｐｐｍ以上であってもよく、１質量ｐｐｍ以上であってもよい。
　原料組成物の水含有率を前記範囲に制御する方法は特に制限されず、モレキュラーシーブ、活性アルミナ等の乾燥剤を用いる方法などが挙げられる。乾燥剤を用いる方法では、乾燥剤を接触させたＣＦＣ－１１３及び乾燥剤を接触させた水素の少なくとも一方を用いて原料組成物を調製してもよく、調製した後の原料組成物に乾燥剤を接触させてもよい。 The water content of the raw material composition is 200 ppm by mass or less, preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less, even more preferably 15 ppm by mass or less, particularly preferably 10 ppm by mass or less, and extremely preferably 5 ppm by mass or less. The lower limit of the water content of the raw material composition is not particularly limited. The water content of the raw material composition may be 0.1 ppm by mass or more, 0.5 ppm by mass or more, or 1 ppm by mass or more.
The method for controlling the water content of the raw material composition within the above range is not particularly limited, and examples thereof include a method using a desiccant such as a molecular sieve, activated alumina, etc. In the method using a desiccant, the raw material composition may be prepared using at least one of CFC-113 contacted with a desiccant and hydrogen contacted with a desiccant, or the prepared raw material composition may be contacted with the desiccant.

（ＣＦＣ－１１３及び水素）
　ＣＦＣ－１１３は、例えば、触媒の存在下でテトラクロロエチレンをフッ化水素によりフッ素化することで得られる。
　原料組成物全体に対するＣＦＣ－１１３の含有率としては、例えば、９～９１体積％が挙げられ、ＣＴＦＥ及びＨＦＯ－１１２３の生産性の点から、１６～６７体積％が好ましく、２０～５０体積％がより好ましい。
　原料組成物全体に対する水素の含有率としては、例えば、９～９１体積％が挙げられ、ＣＴＦＥ及びＨＦＯ－１１２３の生産性の点から、３３～８４体積％が好ましく、５０～８０体積％がより好ましい。 (CFC-113 and hydrogen)
CFC-113 can be obtained, for example, by fluorinating tetrachloroethylene with hydrogen fluoride in the presence of a catalyst.
The content of CFC-113 in the entire raw material composition is, for example, 9 to 91% by volume, and from the viewpoint of productivity of CTFE and HFO-1123, it is preferably 16 to 67% by volume, and more preferably 20 to 50% by volume.
The hydrogen content relative to the entire raw material composition is, for example, 9 to 91% by volume, and from the viewpoint of productivity of CTFE and HFO-1123, is preferably 33 to 84% by volume, and more preferably 50 to 80% by volume.

　原料組成物における水素の含有量は、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率を向上させる観点から、ＣＦＣ－１１３の含有量に対し、体積基準で、１０倍以下が好ましく、５．０倍以下がより好ましく、４．０倍以下がさらに好ましい。つまり、ＣＦＣ－１１３の含有量に対する水素の含有量の体積比（Ｈ２／ＣＦＣ－１１３）は、１０以下が好ましく、５．０以下がより好ましく、４．０以下がさらに好ましい。体積比（Ｈ２／ＣＦＣ－１１３）が上記上限値以下であることにより、ＣＴＦＥと共沸する１，１，２－トリフルオロエタンの生成が抑制され、目的化合物と副生成物との分離性が向上し、純度の高い目的化合物が得られやすくなると推測される。
　体積比（Ｈ２／ＣＦＣ－１１３）は、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率を向上させる観点から、０．１以上が好ましく、０．５以上がより好ましく、１．０以上がさらに好ましい。体積比（Ｈ２／ＣＦＣ－１１３）は、０．１～１０が好ましく、０．５～５．０がより好ましく、１．０～４．０がさらに好ましい。 From the viewpoint of improving the total selectivity for CTFE and HFO-1123, the hydrogen content in the raw material composition is preferably not more than 10 times, more preferably not more than 5.0 times, and even more preferably not more than 4.0 times, the CFC-113 content on a volume basis. In other words, the volume ratio of the hydrogen content to the CFC-113 content (H 2 /CFC-113) is preferably not more than 10, more preferably not more than 5.0, and even more preferably not more than 4.0. It is presumed that by having the volume ratio (H 2 /CFC-113) be equal to or less than the above upper limit, the production of 1,1,2-trifluoroethane, which forms an azeotrope with CTFE, is suppressed, the separability of the target compound and by-products is improved, and the target compound with a high purity is more easily obtained.
From the viewpoint of improving the total selectivity of CTFE and HFO-1123, the volume ratio (H 2 /CFC-113) is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. The volume ratio (H 2 /CFC-113) is preferably 0.1 to 10, more preferably 0.5 to 5.0, and even more preferably 1.0 to 4.0.

（希釈剤）
　原料組成物は、必要に応じて希釈剤を含有してもよく、含有しなくてもよい。
　原料組成物が希釈剤を含有する場合、原料組成物の水含有率は、希釈剤も含めた原料組成物全体に対する水の含有率を意味する。
　希釈剤として、具体的には、窒素、アルゴン、ヘリウム、二酸化炭素等が挙げられる。希釈剤は、これらのうち１種を単独で用いてもよく、２種以上を併用してもよい。低反応性の観点から、希釈剤は、これらの中でも、窒素、アルゴン、及びヘリウムが好ましい。 (Diluent)
The raw material composition may or may not contain a diluent, as required.
When the raw material composition contains a diluent, the water content of the raw material composition means the water content relative to the entire raw material composition including the diluent.
Specific examples of the diluent include nitrogen, argon, helium, and carbon dioxide. The diluent may be used alone or in combination of two or more. From the viewpoint of low reactivity, nitrogen, argon, and helium are preferred.

　希釈剤は、例えば、原料の濃度を低く調整することで反応熱による影響を低減する等の目的で用いられる。本実施形態では、発生する反応熱が少ないため、希釈剤を用いなくてもＣＴＦＥ及びＨＦＯ－１１２３の高い合計選択率が得られる。また、希釈剤を用いない場合は、生成したＣＴＦＥ及びＨＦＯ－１１２３から希釈剤を分離する工程が不要になるという利点もある。
　原料組成物全体に対する希釈剤の含有率は、５．０体積％以下が好ましく、４．０体積％以下がより好ましく、３．０体積％以下がさらに好ましい。 The diluent is used for the purpose of, for example, reducing the influence of reaction heat by adjusting the concentration of the raw material to a low level. In this embodiment, since the amount of reaction heat generated is small, a high total selectivity for CTFE and HFO-1123 can be obtained even without using a diluent. In addition, when a diluent is not used, there is also the advantage that a step of separating the diluent from the produced CTFE and HFO-1123 is not required.
The content of the diluent in the entire raw material composition is preferably 5.0% by volume or less, more preferably 4.0% by volume or less, and even more preferably 3.0% by volume or less.

（前反応組成物）
　原料組成物は、ＣＦＣ－１１３と水素とを反応させてＣＴＦＥ及びＨＦＯ－１１２３を生成させ、ＣＦＣ－１１３とＣＴＦＥとＨＦＯ－１１２３と塩化水素とを含有する第１の組成物を得る前反応工程と、第１の組成物に水を接触させて塩化水素の少なくとも一部を除去することで水を含有する第２の組成物を得る水接触工程と、第２の組成物から水の少なくとも一部を除去する水除去工程と、第２の組成物からＣＴＦＥ及びＨＦＯ－１１２３の少なくとも一部を分離する生成物分離工程と、を少なくとも経て得られた、ＣＦＣ－１１３を含有する前反応組成物を含んでもよい。つまり、原料組成物は、前反応工程において反応せずに残ったＣＦＣ－１１３を含んでもよい。 Pre-reaction Composition
The feedstock composition may comprise a pre-reacted composition containing CFC-113 obtained through at least the following steps: a pre-reacted step of reacting CFC-113 with hydrogen to produce CTFE and HFO-1123 and obtain a first composition containing CFC-113, CTFE, HFO-1123, and hydrogen chloride, a water-contacting step of contacting the first composition with water to remove at least a portion of the hydrogen chloride to obtain a second composition containing water, a water-removing step of removing at least a portion of the water from the second composition, and a product-separating step of separating at least a portion of the CTFE and HFO-1123 from the second composition. In other words, the feedstock composition may comprise CFC-113 that remains unreacted in the pre-reacted step.

　前反応工程では、ＣＦＣ－１１３と水素との反応により塩化水素が脱離する。そのため、第１の組成物が塩化水素を含有する。つまり、第１の組成物は、例えば、前反応工程において反応せずに残ったＣＦＣ－１１３と、前反応工程によって生成したＣＴＦＥ、ＨＦＯ－１１２３、及び塩化水素と、を含有する。
　そこで、第１の組成物から塩化水素を除去する目的で、第１の組成物に水を接触させる水接触工程を施す。 In the pre-reaction step, hydrogen chloride is released by the reaction between CFC-113 and hydrogen. Therefore, the first composition contains hydrogen chloride. That is, the first composition contains, for example, CFC-113 that remains unreacted in the pre-reaction step, and CTFE, HFO-1123, and hydrogen chloride produced in the pre-reaction step.
Therefore, in order to remove hydrogen chloride from the first composition, a water contact step is carried out in which the first composition is brought into contact with water.

　水接触工程では、例えば、水酸化ナトリウム、水酸化カリウム、炭酸水素カリウム、炭酸カリウム、アンモニア等の塩基性化合物の水溶液に第１の組成物を通過させるアルカリ洗浄；イオン交換水等の水に第１の組成物を通過させる水洗浄；などを行うことで、第１の組成物に水を接触させる。水接触工程では、アルカリ洗浄及び水洗浄の少なくとも一方を行うことが好ましく、アルカリ洗浄及び水洗浄の両方を行うことがより好ましい。水接触工程においてアルカリ洗浄及び水洗浄の両方を行う場合、いずれを先に行ってもよく、アルカリ洗浄の後に水洗浄を行うことがさらに好ましい。
　第１の組成物が水接触工程を経ることで、第１の組成物よりも塩化水素の含有率が低く、かつ、水含有率が高い、第２の組成物が得られる。 In the water contact step, the first composition is brought into contact with water by, for example, alkaline washing in which the first composition is passed through an aqueous solution of a basic compound such as sodium hydroxide, potassium hydroxide, potassium bicarbonate, potassium carbonate, or ammonia; or water washing in which the first composition is passed through water such as ion-exchanged water. In the water contact step, it is preferable to perform at least one of alkaline washing and water washing, and it is more preferable to perform both alkaline washing and water washing. When both alkaline washing and water washing are performed in the water contact step, either one may be performed first, and it is more preferable to perform water washing after alkaline washing.
By subjecting the first composition to the water contact step, a second composition is obtained which has a lower hydrogen chloride content and a higher water content than the first composition.

　第２の組成物は、例えば、前反応工程において反応せずに残ったＣＦＣ－１１３と、前反応工程によって生成したＣＴＦＥ及びＨＦＯ－１１２３と、水接触工程において混入した水と、を含有する。
　そこで、第２の組成物に対し、水の少なくとも一部を除去する水除去工程と、ＣＴＦＥ及びＨＦＯ－１１２３の少なくとも一部を分離する生成物分離工程と、を施す。水除去工程及び生成物分離工程は、同時に行ってもよく、別々に行ってもよい。水除去工程及び生成物分離工程を別々に行う場合、水除去工程の後に生成物分離工程を行ってもよく、生成物分離工程の後に水除去工程を行ってもよい。 The second composition contains, for example, CFC-113 that remains unreacted in the pre-reaction step, CTFE and HFO-1123 produced in the pre-reaction step, and water that is mixed in in the water-contacting step.
Therefore, the second composition is subjected to a water removal step of removing at least a portion of the water, and a product separation step of separating at least a portion of the CTFE and HFO-1123. The water removal step and the product separation step may be carried out simultaneously or separately. When the water removal step and the product separation step are carried out separately, the product separation step may be carried out after the water removal step, or the water removal step may be carried out after the product separation step.

　水除去工程では、例えば、モレキュラーシーブ等の乾燥剤に第２の組成物を接触させることで、第２の組成物から水の少なくとも一部を除去する。水除去工程では、第２の組成物に含まれる水の少なくとも一部を除去すればよいが、原料化合物の水含有率を前記範囲とする観点から、できるだけ多くの水を第２の組成物から除去することが好ましい。
　生成物分離工程では、例えば蒸留等により、第２の組成物からＣＴＦＥ及びＨＦＯ－１１２３の少なくとも一部を分離する。生成物分離工程では、第２の組成物に含まれるＣＴＦＥ及びＨＦＯ－１１２３の少なくとも一部を分離すればよいが、目的化合物を効率的に得る観点から、できるだけ多くのＣＴＦＥ及びＨＦＯ－１１２３を第２の組成物から分離することが好ましい。 In the water removal step, at least a portion of the water is removed from the second composition by, for example, contacting the second composition with a desiccant such as a molecular sieve. In the water removal step, it is sufficient to remove at least a portion of the water contained in the second composition, but from the viewpoint of keeping the water content of the raw material compound within the above range, it is preferable to remove as much water as possible from the second composition.
In the product separation step, at least a portion of the CTFE and HFO-1123 is separated from the second composition by, for example, distillation, etc. In the product separation step, it is sufficient to separate at least a portion of the CTFE and HFO-1123 contained in the second composition, but from the viewpoint of efficiently obtaining the target compound, it is preferable to separate as much of the CTFE and HFO-1123 as possible from the second composition.

　第２の組成物が水除去工程及び生成物分離工程を経ることで、少なくともＣＦＣ－１１３を含有し、第２の組成物よりも水、ＣＴＦＥ、及びＨＦＯ－１１２３の含有率が低い、前反応組成物が得られる。
　前反応組成物は、ＣＦＣ－１１３からなる組成物であってもよく、生成物分離工程において分離しきれなかったＣＴＦＥ及びＨＦＯ－１１２３の少なくとも一方を含有してもよい。また、前反応組成物は、原料化合物の水含有率が前記範囲内となる程度であれば、水除去工程において除去しきれなかった微量の水を含有してもよい。
　第１の組成物が前反応工程において反応せずに残った水素を含有する場合、前反応組成物は、水素を含有するものであってもよく、水素の少なくとも一部が除去されたものであってもよい。また、第１の組成物が希釈剤を含有する場合、前反応組成物は、希釈剤を含有するものであってもよく、希釈剤の少なくとも一部が除去されたものであってもよい。
　以上のようにして得られた前反応組成物は、例えば、水素と混合され、原料組成物として用いられる。 The second composition is subjected to a water removal step and a product separation step to obtain a pre-reacted composition containing at least CFC-113 and having lower contents of water, CTFE, and HFO-1123 than the second composition.
The pre-reaction composition may be a composition consisting of CFC-113, or may contain at least one of CTFE and HFO-1123 that was not completely separated in the product separation step. Furthermore, the pre-reaction composition may contain a trace amount of water that was not completely removed in the water removal step, so long as the water content of the raw material compounds is within the above range.
When the first composition contains hydrogen that remains unreacted in the pre-reaction step, the pre-reaction composition may contain hydrogen or may be one from which at least a portion of the hydrogen has been removed. When the first composition contains a diluent, the pre-reaction composition may contain the diluent or may be one from which at least a portion of the diluent has been removed.
The pre-reaction composition obtained as described above is mixed with, for example, hydrogen and used as a raw material composition.

＜触媒＞
　触媒としては、少なくとも１種以上の金属元素を含有する金属触媒が挙げられる。金属元素としては、Ｐｄ、Ｐｔ、Ｎｉ、Ｉｒ、Ｒｕ、Ｒｈ、Ｏｓ、Ｃｕ、Ｆｅ、Ａｕ、Ａｇ、Ｚｎ、Ｓｎ、Ｃｏ等が挙げられる。触媒は、金属元素を１種のみ含有してもよく、２種以上含有してもよい。
　用いる触媒の量は、原料であるＣＦＣ－１１３及び水素の反応器への供給量等に応じて設定される。 <Catalyst>
The catalyst may be a metal catalyst containing at least one metal element, such as Pd, Pt, Ni, Ir, Ru, Rh, Os, Cu, Fe, Au, Ag, Zn, Sn, or Co. The catalyst may contain only one metal element or two or more metal elements.
The amount of catalyst used is determined depending on the amounts of CFC-113 and hydrogen that are the raw materials to be fed to the reactor.

　触媒は、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率を向上させる観点から、Ｐｄ、Ｐｔ、Ｎｉ、Ｉｒ、Ｒｕ、Ｒｈ、及びＯｓからなる群より選択される少なくとも１種である第一の金属元素と、Ｃｕ、Ｆｅ、Ａｕ、Ａｇ、Ｚｎ、Ｓｎ、及びＣｏからなる群より選択される少なくとも１種である第二の金属元素と、を含有する触媒を含むことが好ましい。以下、上記第一の金属元素と上記第二の金属元素とを含有する触媒を「特定触媒」ともいう。
　第一の金属元素と第二の金属元素とは、それぞれ個別に存在していてもよく、合金として存在していてもよい。
　特定触媒は、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率を向上させる観点から、Ｐｄ又はＰｔである第一の金属元素と、Ｃｕである第二の金属元素と、を含有することが好ましい。つまり、触媒は、特定触媒として、Ｐｄ－Ｃｕ触媒及びＰｔ－Ｃｕ触媒の少なくとも一方を含むことが好ましい。 From the viewpoint of improving the total selectivity of CTFE and HFO-1123, the catalyst preferably contains a catalyst containing a first metal element which is at least one selected from the group consisting of Pd, Pt, Ni, Ir, Ru, Rh, and Os, and a second metal element which is at least one selected from the group consisting of Cu, Fe, Au, Ag, Zn, Sn, and Co. Hereinafter, a catalyst containing the first metal element and the second metal element will also be referred to as a "specific catalyst."
The first metal element and the second metal element may exist individually or as an alloy.
From the viewpoint of improving the total selectivity of CTFE and HFO-1123, the specific catalyst preferably contains a first metal element which is Pd or Pt and a second metal element which is Cu. That is, the catalyst preferably contains at least one of a Pd—Cu catalyst and a Pt—Cu catalyst as the specific catalyst.

　特定触媒は、水素ガスに対する親和性が相対的に高い第一の金属元素と、水素ガスに対する親和性が相対的に低い第二の金属元素と、を含有する。特定触媒を用いた触媒反応では、上記水素ガスに対する親和性の違いを利用してＣＦＣ－１１３と水素との反応性が制御されると推測される。そのため、特定触媒の表面に水が吸着すると、触媒表面上の反応性が変化し、副生成物が生成することが考えられる。一方、本実施形態では、原料組成物の水含有率が前記範囲であるため、特定触媒の表面への水の吸着が抑制されることで副生成物の生成も抑制され、ＣＴＦＥ及びＨＦＯ－１１２３の高い合計選択率が得られると推測される。 The specific catalyst contains a first metal element with a relatively high affinity for hydrogen gas and a second metal element with a relatively low affinity for hydrogen gas. It is believed that in catalytic reactions using the specific catalyst, the difference in affinity for hydrogen gas is utilized to control the reactivity between CFC-113 and hydrogen. Therefore, when water is adsorbed onto the surface of the specific catalyst, the reactivity on the catalyst surface changes, resulting in the production of by-products. In contrast, in this embodiment, because the water content of the raw material composition is within the above-mentioned range, it is believed that the adsorption of water onto the surface of the specific catalyst is suppressed, thereby suppressing the production of by-products, resulting in a high combined selectivity for CTFE and HFO-1123.

　特定触媒は、必要に応じて、第一の金属元素及び第二の金属元素以外のその他の金属成分を含有してもよい。その他の金属成分としては、Ｂｉ、Ａｌ等が挙げられる。その他の金属成分の含有率は、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率を向上させる観点から、特定触媒全体に対し、それぞれ０．０５質量％未満であることが好ましく、合計で０．５質量％未満であることがより好ましい。
　特定触媒に含まれる第一の金属元素の含有率は、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率を向上させる観点から、第一の金属元素と第二の金属元素との合計に対し、０．１０～１．６質量％が好ましく、０．１６～１．４質量％がより好ましく、０．３３～１．１質量％がさらに好ましい。
　特定触媒に含まれる第二の金属元素の含有率は、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率を向上させる観点から、第一の金属元素と第二の金属元素との合計に対し、９８．４～９９．９質量％が好ましく、９８．６～９９．８質量％がより好ましく、９８．９～９９．７質量％がさらに好ましい。 The specific catalyst may contain other metal components in addition to the first metal element and the second metal element, as necessary. Examples of the other metal components include Bi and Al. From the viewpoint of improving the total selectivity of CTFE and HFO-1123, the content of the other metal components is preferably less than 0.05 mass% each, and more preferably less than 0.5 mass% in total, relative to the entire specific catalyst.
From the viewpoint of improving the total selectivity of CTFE and HFO-1123, the content of the first metal element contained in the specific catalyst is preferably 0.10 to 1.6 mass%, more preferably 0.16 to 1.4 mass%, and even more preferably 0.33 to 1.1 mass%, relative to the total of the first metal element and the second metal element.
From the viewpoint of improving the total selectivity of CTFE and HFO-1123, the content of the second metal element contained in the specific catalyst is preferably 98.4 to 99.9 mass%, more preferably 98.6 to 99.8 mass%, and even more preferably 98.9 to 99.7 mass%, based on the total of the first metal element and the second metal element.

　触媒の形態は特に限定されず、粉末であってもよく、ペレット状、球状であってもよい。
　触媒は、担体に担持されていてもよい。担体は、活性炭を含むことが好ましく、活性炭からなることがより好ましい。活性炭としては、木材、木炭、果実ガラ、ヤシガラ、泥炭、亜炭、石炭等の原料から調製したものを使用しうるが、鉱物質原料よりも植物原料から得られたものが好ましく、特にヤシガラ活性炭が最適である。担体形状としては、長さ２～５ｍｍ程度の成形炭、４～５０メッシュ程度の破砕炭、２～５０メッシュの粒状炭等を用いることができる。ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率を向上させる観点から、担体形状は、４～２０メッシュの破砕炭又は４～２０メッシュの粒状炭が好ましい。 The form of the catalyst is not particularly limited, and may be in the form of a powder, pellets, or spheres.
The catalyst may be supported on a carrier. The carrier preferably contains activated carbon, and more preferably consists of activated carbon. Activated carbon prepared from raw materials such as wood, charcoal, fruit shells, coconut shells, peat, lignite, and coal can be used, but activated carbon obtained from plant materials is preferable to mineral materials, and coconut shell activated carbon is particularly optimal. The carrier shape may be formed charcoal with a length of about 2 to 5 mm, crushed charcoal with a size of about 4 to 50 mesh, or granular charcoal with a size of 2 to 50 mesh. From the viewpoint of improving the total selectivity of CTFE and HFO-1123, the carrier shape is preferably crushed charcoal with a size of 4 to 20 mesh or granular charcoal with a size of 4 to 20 mesh.

　触媒が担体に担持されている場合、触媒の比表面積を十分に大きくでき、かつ、触媒活性に優れる点から、触媒の担持量は担体の質量の１００質量部に対して、０．５～５０質量部が好ましく、１～５０質量部がより好ましく、１～３０質量部がさらに好ましく、３～３０質量部が特に好ましく、５～３０質量部が極めて好ましい。
　特定触媒を担体に担持する場合、第一の金属元素と第二の金属元素とをそれぞれ個別に担体に担持させたものを混合物として用いてもよく、第一の金属元素と第二の金属元素との混合物を担体に担持させてもよい。 When the catalyst is supported on a carrier, the amount of the catalyst supported is preferably 0.5 to 50 parts by mass, more preferably 1 to 50 parts by mass, even more preferably 1 to 30 parts by mass, particularly preferably 3 to 30 parts by mass, and extremely preferably 5 to 30 parts by mass, per 100 parts by mass of the carrier, from the viewpoints of being able to sufficiently increase the specific surface area of the catalyst and achieving excellent catalytic activity.
When the specific catalyst is supported on a carrier, the first metal element and the second metal element may be supported individually on a carrier and used as a mixture, or a mixture of the first metal element and the second metal element may be supported on a carrier.

　触媒は、金属塩化合物を含有してもよい。
　触媒が特定触媒である場合、金属塩化合物としては、第一の金属元素又は第二の金属元素を含む酸化物、ハロゲン化物、水酸化物、硝酸化合物等が挙げられる。例えば特定触媒が第二の金属元素としてＣｕを含有する場合、金属塩化合物としては、ＣｕＯ、ＣｕＣｌ、ＣｕＣｌ２、ＣｕＦ、ＣｕＦ２、Ｃｕ２Ｃｌ（ＯＨ）３、Ｃｕ２（ＮＯ３（ＯＨ）３）等が挙げられる。また、特定触媒が第一の金属元素としてＰｄを含有する場合、金属塩化合物としては、ＰｄＯ、ＰｄＣｌ２等が挙げられる。 The catalyst may contain a metal salt compound.
When the catalyst is a specific catalyst, examples of the metal salt compound include oxides, halides, hydroxides, nitrate compounds, etc. containing a first metal element or a second metal element. For example, when the specific catalyst contains Cu as the second metal element, examples of the metal salt compound include CuO, CuCl, CuCl2 , CuF, CuF2 , Cu2Cl (OH) 3 , Cu2 ( NO3 (OH) 3 ), etc. When the specific catalyst contains Pd as the first metal element, examples of the metal salt compound include PdO, PdCl2, etc.

　触媒が担体に担持されている場合、担体に触媒が担持された担持触媒全体の比表面積は、例えば０．１～１５００ｍ２／ｇが挙げられ、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率を向上させる観点から、１～１５００ｍ２／ｇが好ましく、１００～１５００ｍ２／ｇがより好ましい。上記比表面積はＢＥＴ法により測定した値（ＢＥＴ比表面積）である。 When the catalyst is supported on a carrier, the specific surface area of the entire supported catalyst in which the catalyst is supported on the carrier is, for example, 0.1 to 1500 m 2 /g, and from the viewpoint of improving the total selectivity of CTFE and HFO-1123, it is preferably 1 to 1500 m 2 /g, and more preferably 100 to 1500 m 2 /g. The specific surface area is a value measured by the BET method (BET specific surface area).

＜反応工程＞
　原料組成物を触媒に接触させる際における原料組成物の温度、つまり反応温度は、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率を向上させる観点から、１５０～３５０℃が好ましく、１８０～３００℃がより好ましく、１９０～３００℃がさらに好ましい。上記反応温度は、反応器内の温度を意味し、熱電対等により測定される。
　原料組成物を触媒に接触させる際における圧力は、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率を向上させる観点から、ゲージ圧で、０～１ＭＰａが好ましく、０～０．９ＭＰａがより好ましく、０～０．５ＭＰａがさらに好ましい。上記圧力は、反応器内の圧力を意味する。 <Reaction step>
The temperature of the raw material composition when it is brought into contact with the catalyst, i.e., the reaction temperature, is preferably 150 to 350° C., more preferably 180 to 300° C., and even more preferably 190 to 300° C., from the viewpoint of improving the total selectivity of CTFE and HFO-1123. The reaction temperature means the temperature inside the reactor, and is measured using a thermocouple or the like.
The pressure when the raw material composition is brought into contact with the catalyst is preferably 0 to 1 MPa, more preferably 0 to 0.9 MPa, and even more preferably 0 to 0.5 MPa, in terms of gauge pressure, from the viewpoint of improving the total selectivity of CTFE and HFO-1123. The above pressure means the pressure inside the reactor.

　原料組成物を触媒に接触させる時間、つまり反応時間は、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率を向上させる観点から、１～５００秒が好ましく、１～７５秒がより好ましく、２～５０秒がさらに好ましい。
　上記反応時間（秒）は、製造方法が連続式である場合、例えば、以下の式を用いて算出される。
　反応時間（秒）＝［反応器における触媒が充填されている長さ（ｃｍ）］／［線速度（ｃｍ／秒）］
　線速度は、単位時間当たりに、原料組成物が触媒を通過する長さを意味する。
　線速度としては、０．１～１００ｃｍ／秒が挙げられ、０．１～２０ｃｍ／秒が好ましく、０．５～２０ｃｍ秒がより好ましい。 The time for which the raw material composition is brought into contact with the catalyst, i.e., the reaction time, is preferably from 1 to 500 seconds, more preferably from 1 to 75 seconds, and even more preferably from 2 to 50 seconds, from the viewpoint of improving the total selectivity of CTFE and HFO-1123.
When the production method is a continuous method, the reaction time (seconds) is calculated, for example, using the following formula.
Reaction time (seconds) = [length of catalyst packed in reactor (cm)] / [linear velocity (cm/second)]
The linear velocity refers to the length that the feed composition passes through the catalyst per unit time.
The linear velocity is 0.1 to 100 cm/sec, preferably 0.1 to 20 cm/sec, and more preferably 0.5 to 20 cm/sec.

　上記ＣＦＣ－１１３と水素との反応工程における水素化熱分解反応では、目的化合物であるＣＴＦＥ及びＨＦＯ－１１２３を含む生成組成物が得られる。
　生成組成物に含有されるＣＴＦＥ及びＨＦＯ－１１２３以外の化合物としては、未反応原料であるＣＦＣ－１１３及び水素、水、原料組成物が希釈剤を含む場合は希釈剤に加えて、１，１－ジフルオロエチレン（ＨＦＯ－１１３２ａ）、１，２－ジクロロ－１，２，３，３，４，４－ヘキサフルオロシクロブタン、１，３－ジクロロ－１，２，２，３，４，４－ヘキサフルオロシクロブタン、１，２－ジクロロ－１，１，２－トリフルオロエタン（ＨＣＦＣ－１２３ａ）、１，１－ジクロロ－１，２，２－トリフルオロエタン（ＨＣＦＣ－１２３ｂ）、１，１－ジクロロ－２，２－ジフルオロエチレン（ＣＦＯ－１１１２）、１－クロロ－２，２－ジフルオロエチレン（ＨＦＯ－１１２２）、１－クロロ－２，２－ジフルオロエチレン（ＨＦＯ－１１２２ａ（Ｅ））、１－クロロ－２，２－ジフルオロエチレン（ＨＦＯ－１１２２ａ（Ｚ））等の副生成物が挙げられる。 In the hydrothermal cracking reaction in the reaction step of CFC-113 and hydrogen, a product composition containing the target compounds CTFE and HFO-1123 is obtained.
Compounds contained in the product composition other than CTFE and HFO-1123 include unreacted raw materials CFC-113 and hydrogen, water, and, if the raw material composition contains a diluent, 1,1-difluoroethylene (HFO-1132a), 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane, 1,3-dichloro-1,2,2,3,4,4-hexafluorocyclobutane, 1,2-dichloro-1,1,2-trifluoroethane ... Examples of by-products include oroethane (HCFC-123a), 1,1-dichloro-1,2,2-trifluoroethane (HCFC-123b), 1,1-dichloro-2,2-difluoroethylene (CFO-1112), 1-chloro-2,2-difluoroethylene (HFO-1122), 1-chloro-2,2-difluoroethylene (HFO-1122a(E)), and 1-chloro-2,2-difluoroethylene (HFO-1122a(Z)).

　上記ＣＦＣ－１１３と水素との反応におけるＣＴＦＥ及びＨＦＯ－１１２３の合計選択率は、ＨＦＯ－１１２３を効率的に得る観点から、９４．０％以上が好ましく、９４．３％以上がより好ましく、９４．５％以上がさらに好ましい。
　上記選択率は、得られた生成組成物をガスクロマトグラフィーにより分析することにより求める。具体的には、測定装置としてガスクロマトグラフィー（ＧＣ－７８９０Ａ、アジレント・テクノロジー株式会社製）を用い、カラムとしてＤＢ－１（アジレント・テクノロジー株式会社製、長さ６０ｍ、内径２５０μｍ、フィルターの厚さ１μｍ）を用い、検出器として水素炎イオン化検出器（ＦＩＤ）を用いて、下記測定条件により測定を行う。
・インジェクション温度：２４０℃
・試料注入量：０．５ｍＬ
・スプリット比：６０／１
・線速度：３５．８ｃｍ／秒
・測定開始：温度－３０℃、保持時間１０分
・昇温速度：１０℃／分
・測定終了：温度２４０℃、保持時間２０分
・検出温度：２５０℃ The total selectivity of CTFE and HFO-1123 in the reaction of CFC-113 with hydrogen is preferably 94.0% or more, more preferably 94.3% or more, and even more preferably 94.5% or more, from the viewpoint of efficiently obtaining HFO-1123.
The selectivity is determined by analyzing the resulting product composition by gas chromatography. Specifically, the measurement is performed using a gas chromatograph (GC-7890A, manufactured by Agilent Technologies Inc.) as a measuring device, a DB-1 column (manufactured by Agilent Technologies Inc., length 60 m, inner diameter 250 μm, filter thickness 1 μm), and a flame ionization detector (FID) as a detector under the following measurement conditions.
Injection temperature: 240°C
Sample injection volume: 0.5 mL
Split ratio: 60/1
Linear velocity: 35.8 cm/sec. Start of measurement: -30°C, holding time: 10 minutes. Heating rate: 10°C/min. End of measurement: 240°C, holding time: 20 minutes. Detection temperature: 250°C.

　得られた生成組成物は、必要に応じて、ＣＴＦＥ及びＨＦＯ－１１２３以外の成分を分離する分離工程を含んでもよい。分離工程としては、生成組成物から原料であるＣＦＣ－１１３及び水素を分離する原料分離工程、生成組成物から塩化水素を分離する塩化水素分離工程等が挙げられる。 If necessary, the resulting product composition may be subjected to a separation process in which components other than CTFE and HFO-1123 are separated. Examples of separation processes include a raw material separation process in which the raw materials CFC-113 and hydrogen are separated from the product composition, and a hydrogen chloride separation process in which hydrogen chloride is separated from the product composition.

　得られた生成組成物に含有されるＣＴＦＥは、ＨＦＯ－１１２３の原料として有用であるほか、ポリマーの原料としても有用である。また、得られた生成組成物に含有されるＨＦＯ－１１２３は、温室効果ガスであるジフルオロメタン及びペンタフルオロエタンに代わる冷媒として有用である。 The CTFE contained in the resulting product composition is useful as a raw material for HFO-1123, as well as a raw material for polymers. Furthermore, the HFO-1123 contained in the resulting product composition is useful as a refrigerant that replaces the greenhouse gases difluoromethane and pentafluoroethane.

　以下、本開示を実施例によりさらに具体的に説明するが、本開示はその主旨を超えない限り、以下の実施例に限定されるものではない。 The present disclosure will be explained in more detail below using examples, but the present disclosure is not limited to the following examples as long as they do not deviate from the gist of the disclosure.

［例１～４］
　触媒として、Ｐｄ－Ｃｕ触媒を用いた。用いたＰｄ－Ｃｕ触媒は、パラジウム１．０質量％と銅９９．０質量％とで構成された触媒であった。Ｐｄ－Ｃｕ触媒は、活性炭（４～６メッシュの粒状炭）に担持されており、触媒の担持量は担体の質量１００質量部に対して６．４１質量部であった。
　上記Ｐｄ－Ｃｕ触媒が活性炭に担持された担持触媒を、２０ＡのＳＵＳ管型反応器に、触媒長が３０ｃｍとなるように充填した。用いた担持触媒の質量は５７ｇであり、担持触媒全体の比表面積は１１００ｍ２／ｇであった。 [Examples 1 to 4]
A Pd—Cu catalyst was used. The Pd—Cu catalyst used was a catalyst composed of 1.0 mass% palladium and 99.0 mass% copper. The Pd—Cu catalyst was supported on activated carbon (4-6 mesh granular carbon), and the amount of catalyst supported was 6.41 mass parts per 100 mass parts of the support.
The above-mentioned Pd—Cu catalyst supported on activated carbon was packed into a 20A SUS tubular reactor so that the catalyst length was 30 cm. The mass of the supported catalyst used was 57 g, and the specific surface area of the entire supported catalyst was 1100 m 2 /g.

　ＣＦＣ－１１３及び水素の混合ガスである原料組成物を、上記反応器の触媒へ流通させることで、ＣＦＣ－１１３の水素還元反応を行った。原料組成物における水素／ＣＦＣ－１１３のモル比を４／１とした。つまり、各例の原料組成物における、ＣＦＣ－１１３の含有量に対する水素の含有量の体積比（Ｈ２／ＣＦＣ－１１３）を４とした。なお、希釈剤は用いなかった。
　各例における原料組成物の水含有率は、前述の方法によりカールフィッシャー（電量法）を用いて測定した結果、それぞれ表１に示す値であった。原料組成物の水含有率は、ＣＦＣ－１１３及び水素それぞれについて、必要に応じて、モレキュラーシーブに通すことによる水分の除去、又は、純水に通すことによる水分の添加を行うことで、調整した。
　水素還元反応の反応条件は、反応温度を２００℃、滞留時間（つまり、反応時間）を１３．９秒、線速度を２．２ｃｍ／秒、反応器内の圧力を常圧（つまり、ゲージ圧：０ＭＰａ）とした。 A hydrogen reduction reaction of CFC-113 was carried out by passing a raw material composition, which was a mixed gas of CFC-113 and hydrogen, through the catalyst in the reactor. The molar ratio of hydrogen/CFC-113 in the raw material composition was 4/1. That is, in each raw material composition, the volume ratio of the hydrogen content to the CFC-113 content (H 2 /CFC-113) was 4. No diluent was used.
The water content of the raw material composition in each example was measured using Karl Fischer (coulometric method) by the method described above, and the values were shown in Table 1. The water content of the raw material composition was adjusted, as necessary, for each of CFC-113 and hydrogen, by removing water by passing it through a molecular sieve or by adding water by passing it through pure water.
The reaction conditions for the hydrogen reduction reaction were a reaction temperature of 200° C., a residence time (i.e., reaction time) of 13.9 seconds, a linear velocity of 2.2 cm/second, and atmospheric pressure (i.e., gauge pressure: 0 MPa) in the reactor.

　反応により得られた生成組成物である粗生成ガスをサンプリングし、含有される成分の分析をガスクロマトグラフによって実施し、ＣＦＣ－１１３の転化率、ＣＴＦＥの選択率、ＨＦＯ－１１２３の選択率、並びにＣＴＦＥ及びＨＦＯ－１１２３の合計選択率を算出した。なお、ガスクロマトグラフによる分析における測定装置及び測定条件は、前述の通りとした。結果を表１に示す。 The crude product gas, which is the product composition obtained by the reaction, was sampled and the components contained therein were analyzed using a gas chromatograph. The CFC-113 conversion rate, CTFE selectivity, HFO-1123 selectivity, and the combined selectivity for CTFE and HFO-1123 were calculated. The measuring equipment and conditions for the gas chromatographic analysis were as described above. The results are shown in Table 1.

　例１～例３は実施例であり、例４は比較例である。
　表１に示すように、原料組成物の水含有率が２００質量ｐｐｍ以下である例１～３では、例４に比べて、ＣＴＦＥ及びＨＦＯ－１１２３の合計選択率が高かった。 Examples 1 to 3 are working examples, and Example 4 is a comparative example.
As shown in Table 1, in Examples 1 to 3 in which the water content of the raw material composition was 200 ppm by mass or less, the total selectivity for CTFE and HFO-1123 was higher than in Example 4.

　２０２４年２月８日に出願された日本国特許出願第２０２４－０１８０６１号の開示は、その全体が参照により本明細書に取り込まれる。また、本明細書に記載された全ての文献、特許出願及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The disclosure of Japanese Patent Application No. 2024-018061, filed February 8, 2024, is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims (8)

　１，１，２－トリクロロ－１，２，２－トリフルオロエタン、水素、及び水を含有する原料組成物であって、前記原料組成物全体に対する水の含有率が２００質量ｐｐｍ以下である原料組成物を、触媒に接触させ、１，１，２－トリクロロ－１，２，２－トリフルオロエタンと水素との反応によりクロロトリフルオロエチレン及びトリフルオロエチレンを製造する、クロロトリフルオロエチレン及びトリフルオロエチレンの製造方法。 A method for producing chlorotrifluoroethylene and trifluoroethylene, comprising contacting a raw material composition containing 1,1,2-trichloro-1,2,2-trifluoroethane, hydrogen, and water, wherein the water content of the entire raw material composition is 200 mass ppm or less, with a catalyst, and producing chlorotrifluoroethylene and trifluoroethylene by reacting 1,1,2-trichloro-1,2,2-trifluoroethane with hydrogen. 　前記触媒は、Ｐｄ、Ｐｔ、Ｎｉ、Ｉｒ、Ｒｕ、Ｒｈ、及びＯｓからなる群より選択される少なくとも１種である第一の金属元素と、Ｃｕ、Ｆｅ、Ａｕ、Ａｇ、Ｚｎ、Ｓｎ、及びＣｏからなる群より選択される少なくとも１種である第二の金属元素と、を含有する触媒を含む、請求項１に記載の製造方法。 The manufacturing method described in claim 1, wherein the catalyst contains a first metal element that is at least one selected from the group consisting of Pd, Pt, Ni, Ir, Ru, Rh, and Os, and a second metal element that is at least one selected from the group consisting of Cu, Fe, Au, Ag, Zn, Sn, and Co. 　前記触媒は、Ｐｄ又はＰｔである第一の金属元素と、Ｃｕである第二の金属元素と、を含有する触媒を含む、請求項１に記載の製造方法。 The manufacturing method described in claim 1, wherein the catalyst includes a catalyst containing a first metal element that is Pd or Pt and a second metal element that is Cu. 　前記原料組成物は、前記原料組成物全体に対する水の含有率が５０質量ｐｐｍ以下である、請求項１～３のいずれか１項に記載の製造方法。 The manufacturing method described in any one of claims 1 to 3, wherein the raw material composition has a water content of 50 mass ppm or less relative to the entire raw material composition. 　前記原料組成物は、
　１，１，２－トリクロロ－１，２，２－トリフルオロエタンと水素とを反応させてクロロトリフルオロエチレン及びトリフルオロエチレンを生成させ、１，１，２－トリクロロ－１，２，２－トリフルオロエタンとクロロトリフルオロエチレンとトリフルオロエチレンと塩化水素とを含有する第１の組成物を得る前反応工程と、
　前記第１の組成物に水を接触させて前記塩化水素の少なくとも一部を除去することで、水を含有する第２の組成物を得る水接触工程と、
　前記第２の組成物から前記水の少なくとも一部を除去する水除去工程と、
　前記第２の組成物からクロロトリフルオロエチレン及びトリフルオロエチレンの少なくとも一部を分離する生成物分離工程と、
　を少なくとも経て得られた、１，１，２－トリクロロ－１，２，２－トリフルオロエタンを含有する組成物を含む、請求項１～３のいずれか１項に記載の製造方法。 The raw material composition is
a pre-reaction step of reacting 1,1,2-trichloro-1,2,2-trifluoroethane with hydrogen to produce chlorotrifluoroethylene and trifluoroethylene, thereby obtaining a first composition containing 1,1,2-trichloro-1,2,2-trifluoroethane, chlorotrifluoroethylene, trifluoroethylene, and hydrogen chloride;
a water contacting step of contacting the first composition with water to remove at least a portion of the hydrogen chloride, thereby obtaining a second composition containing water;
a water removal step of removing at least a portion of the water from the second composition;
a product separation step of separating at least a portion of the chlorotrifluoroethylene and trifluoroethylene from the second composition;
The method according to any one of claims 1 to 3, comprising a composition containing 1,1,2-trichloro-1,2,2-trifluoroethane obtained through at least the steps of: 　前記反応におけるクロロトリフルオロエチレン及びトリフルオロエチレンの合計選択率は、９４％以上である、請求項１～３のいずれか１項に記載の製造方法。 The production method described in any one of claims 1 to 3, wherein the total selectivity of chlorotrifluoroethylene and trifluoroethylene in the reaction is 94% or more. 　前記原料組成物は、希釈剤を含有しないか、又は、希釈剤をさらに含有し前記原料組成物全体に対する希釈剤の含有率が５．０体積％以下である、請求項１～３のいずれか１項に記載の製造方法。 The manufacturing method described in any one of claims 1 to 3, wherein the raw material composition does not contain a diluent, or further contains a diluent, and the diluent content relative to the entire raw material composition is 5.0% by volume or less. 　前記原料組成物における水素の含有量は、１，１，２－トリクロロ－１，２，２－トリフルオロエタンの含有量に対し、体積基準で５．０倍以下である、請求項１～３のいずれか１項に記載の製造方法。 The manufacturing method described in any one of claims 1 to 3, wherein the hydrogen content in the raw material composition is 5.0 times or less, by volume, the 1,1,2-trichloro-1,2,2-trifluoroethane content.
PCT/JP2025/003051 2024-02-08 2025-01-30 Method for producing chlorotrifluoroethylene and trifluoroethylene Pending WO2025169840A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024-018061 2024-02-08
JP2024018061 2024-02-08

Publications (1)

Publication Number Publication Date
WO2025169840A1 true WO2025169840A1 (en) 2025-08-14

Family

ID=96699943

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2025/003051 Pending WO2025169840A1 (en) 2024-02-08 2025-01-30 Method for producing chlorotrifluoroethylene and trifluoroethylene

Country Status (1)

Country Link
WO (1) WO2025169840A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09104647A (en) * 1995-06-06 1997-04-22 Solvay & Cie Production of chlorotrifluoroethylene and trifluoroethylene from 1,1,2-trichloro-1,2,2-trifluoroethane and catalyst composition used therefor
WO2016159205A1 (en) * 2015-03-31 2016-10-06 ダイキン工業株式会社 Composition containing hydrofluoroolefin compound
WO2019216175A1 (en) * 2018-05-08 2019-11-14 ダイキン工業株式会社 Method for producing fluoroolefin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09104647A (en) * 1995-06-06 1997-04-22 Solvay & Cie Production of chlorotrifluoroethylene and trifluoroethylene from 1,1,2-trichloro-1,2,2-trifluoroethane and catalyst composition used therefor
WO2016159205A1 (en) * 2015-03-31 2016-10-06 ダイキン工業株式会社 Composition containing hydrofluoroolefin compound
WO2019216175A1 (en) * 2018-05-08 2019-11-14 ダイキン工業株式会社 Method for producing fluoroolefin

Similar Documents

Publication Publication Date Title
JP5964823B2 (en) Process for the synthesis of trifluoroethylene
CN120698844A (en) Method for producing fluorinated olefins
EP0775100B1 (en) Process for the production of trifluoroethylene
EP2457889B1 (en) Process for production of 2-chloro-3,3,3-trifluoropropene
EP3187478B1 (en) Method for producing hydrofluoroolefin
EP2380866A1 (en) Process for preparation of 1,1-dichloro-2,2,3,3,3 penta- fluoropropane
JP2010083818A (en) Method of dehydrating 1,3,3,3-tetrafluoropropene
JPH05279275A (en) Production of difluoromethane
WO2002055457A2 (en) Process for purifying octafluoropropane, process for preparing the same, and use thereof
WO2018123911A1 (en) Production method for chlorine-containing propene
WO2011102167A1 (en) Method for producing 3,3,3-trifluoro propene
WO2025169840A1 (en) Method for producing chlorotrifluoroethylene and trifluoroethylene
JP4356149B2 (en) Method for treating 1,1,1,3,3-pentafluoropropane
US3468964A (en) Hydrogenation process
JP4057103B2 (en) Method for selectively removing perfluoroisobutylene from a halogenated hydrocarbon stream
US11453631B2 (en) Methods for removal HI/I2/HI3 from trifluoroacetyl iodide (TFAI) feedstock and pyrolysis reactor effluent
KR100854983B1 (en) Purification method of 1,1-dichloroethane and preparation method of 1,1-difluoroethane using the method
JP7719333B2 (en) Method for producing 1-chloro-2,3,3,3-tetrafluoropropene
JPH06279328A (en) Production of hexafluoropropane
US11192842B2 (en) Compositions and methods for the purification of CFC-113 by adsorption
US11987553B2 (en) Methods for removal of sulfur dioxide (SO2) from trifluoroacetyl chloride (TFAC)
US20240300884A1 (en) Methods for removal of sulfur dioxide (so2) from trifluoroacetyl chloride (tfac)
WO2020213600A1 (en) Method for producing 1-chloro-2,3,3,3-tetrafluoropropene
WO2003080549A1 (en) Process for the production of fluoroethane and use of the produced fluoroethane
EP0640577A1 (en) Processes for converting chlorinated alkenes to useful, less chlorinated alkenes

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 25751910

Country of ref document: EP

Kind code of ref document: A1