WO2022014488A1 - Method for producing 1-chloro-2, 3, 3-trifluoropropene - Google Patents
Method for producing 1-chloro-2, 3, 3-trifluoropropene Download PDFInfo
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Abstract
The present invention provides a method for producing 1233yd in a vapor phase, said method having a high conversion rate of a starting material and enabling the achievement of 1233yd with high selectivity, while suppressing the production amount of impurities. A method for producing 1-chloro-2, 3, 3-trifluoropropene by subjecting 3-chloro-1, 1, 2, 2-tetrafluoropropane to a hydrogen fluoride elimination reaction in a vapor phase in the presence of a catalyst, said method being characterized in that a metal compound catalyst, which is activated in a vapor phase by a fluorine compound that does not contain a chlorine atom, is used as the catalyst.
Description
本発明は、１－クロロ－２，３，３－トリフルオロプロペンを製造する方法に関する。
The present invention relates to a method for producing 1-chloro-2,3,3-trifluoropropene.
１－クロロ－２，３，３－トリフルオロプロペン（以下、１２３３ｙｄともいう。）は、３，３－ジクロロ－１，１，１，２，２－ペンタフルオロプロパン（以下、２２５ｃａともいう。）や１，３－ジクロロ－１，１，２，２，３－ペンタフルオロプロパン（以下、２２５ｃｂともいう。）に代わる地球温化係数（ＧＷＰ）の小さい新しい洗浄剤、冷媒、発泡剤、溶剤、およびエアゾール用途に用いられる化合物である。
本明細書において、ハロゲン化炭化水素については、化合物名の後の括弧内にその化合物の略称を記すが、本明細書では必要に応じて化合物名に代えてその略称を用いる。 1-Chloro-2,3,3-trifluoropropene (hereinafter, also referred to as 1233yd) is 3,3-dichloro-1,1,1,2,2-pentafluoropropane (hereinafter, also referred to as 225ca). , 1,3-Dichloro-1,1,2,2,3-pentafluoropropane (hereinafter also referred to as 225cc), new cleaning agents with a smaller global warming coefficient (GWP), refrigerants, foaming agents, solvents, And a compound used in aerosol applications.
In the present specification, for halogenated hydrocarbons, the abbreviation of the compound is described in parentheses after the compound name, but in the present specification, the abbreviation is used instead of the compound name as necessary.
本明細書において、ハロゲン化炭化水素については、化合物名の後の括弧内にその化合物の略称を記すが、本明細書では必要に応じて化合物名に代えてその略称を用いる。 1-Chloro-2,3,3-trifluoropropene (hereinafter, also referred to as 1233yd) is 3,3-dichloro-1,1,1,2,2-pentafluoropropane (hereinafter, also referred to as 225ca). , 1,3-Dichloro-1,1,2,2,3-pentafluoropropane (hereinafter also referred to as 225cc), new cleaning agents with a smaller global warming coefficient (GWP), refrigerants, foaming agents, solvents, And a compound used in aerosol applications.
In the present specification, for halogenated hydrocarbons, the abbreviation of the compound is described in parentheses after the compound name, but in the present specification, the abbreviation is used instead of the compound name as necessary.
１２３３ｙｄは二重結合上の置換基の位置により、幾何異性体であるＺ異性体とＥ異性体が存在する。本明細書中では特に断らずに化合物名や化合物の略称を用いた場合には、Ｚ異性体およびＥ異性体から選ばれる少なくとも１種を示し、化合物名や化合物の略称の後ろに（Ｚ）または（Ｅ）を付した場合には、其々の化合物のＺ異性体またはＥ異性体であることを示す。例えば、１２３３ｙｄ（Ｚ）はＺ異性体を示し、１２３３ｙｄ（Ｅ）はＥ異性体を示す。
1233yd has Z isomers and E isomers, which are geometric isomers, depending on the position of the substituent on the double bond. When the compound name or the abbreviation of the compound is used in the present specification, at least one selected from the Z isomer and the E isomer is indicated, and (Z) is added after the compound name or the abbreviation of the compound. Or, when (E) is attached, it indicates that it is a Z isomer or an E isomer of each compound. For example, 1233yd (Z) represents the Z isomer and 1233yd (E) represents the E isomer.
１２３３ｙｄの製造例としては、特許文献１の実施例に、活性炭やクロロジフルオロメタンで活性化処理をしたアルミナを触媒として充填した垂直固定床反応器に窒素気流下で３－クロロ－１，１，２，２－テトラフルオロプロパン（以下、２４４ｃａともいう。）を気体状態で導入すると、微量の１２３３ｙｄが生成することが記載されている。
As an example of production of 1233yd, in the example of Patent Document 1, 3-chloro-1,1,1 in a vertical fixed bed reactor filled with alumina activated by activated carbon or chlorodifluoromethane as a catalyst under a nitrogen stream. It is described that when 2,2-tetrafluoropropane (hereinafter, also referred to as 244ca) is introduced in a gaseous state, a trace amount of 1233yd is produced.
しかし、特許文献１に記載される気相での脱フッ化水素反応による１２３３ｙｄの製造方法は、原料の転化率が低く、かつ、１－クロロ－３，３－ジフルオロプロピン等の不純物の生成量が多いという問題があり、工業的規模の大量生産に適さない。
本発明は、原料の転化率が高く、高選択率で１２３３ｙｄを得ることができ、かつ不純物の生成量が少ない、気相での１２３３ｙｄの製造方法の提供を課題とする。 However, the method for producing 1233yd by the defluorinated hydrogen reaction in the gas phase described in Patent Document 1 has a low conversion rate of raw materials and produces impurities such as 1-chloro-3,3-difluoropropine. It has the problem of large quantity and is not suitable for mass production on an industrial scale.
An object of the present invention is to provide a method for producing 1233 yd in a gas phase, which has a high conversion rate of raw materials, can obtain 1233 yd with a high selectivity, and produces a small amount of impurities.
本発明は、原料の転化率が高く、高選択率で１２３３ｙｄを得ることができ、かつ不純物の生成量が少ない、気相での１２３３ｙｄの製造方法の提供を課題とする。 However, the method for producing 1233yd by the defluorinated hydrogen reaction in the gas phase described in Patent Document 1 has a low conversion rate of raw materials and produces impurities such as 1-chloro-3,3-difluoropropine. It has the problem of large quantity and is not suitable for mass production on an industrial scale.
An object of the present invention is to provide a method for producing 1233 yd in a gas phase, which has a high conversion rate of raw materials, can obtain 1233 yd with a high selectivity, and produces a small amount of impurities.
本発明者らは、上記課題を解決すべく鋭意検討した結果、以下の構成により上記課題を解決できることを見出した。
［１］ ３－クロロ－１，１，２，２－テトラフルオロプロパンを、触媒の存在下、気相で脱フッ化水素反応させて、１－クロロ－２，３，３－トリフルオロプロペンを製造する方法であって、
前記触媒として、気相において塩素原子を含まないフッ素化合物で活性化した金属化合物触媒を用いることを特徴とする１－クロロ－２，３，３－トリフルオロプロペンの製造方法。
［２］ 前記金属化合物触媒が、Ｃｒ、Ａｌ、Ｚｎ、ＴｉおよびＮｉからなる群より選ばれる少なくとも１種の金属元素を含む金属化合物触媒である、［１］に記載の製造方法。
［３］ 前記金属化合物触媒が、金属の酸化物、金属のフッ化物、または金属の酸化フッ素化物である、［１］～［２］のいずれか一項に記載の製造方法。
［４］ 前記金属化合物触媒が、酸化アルミニウム、または酸化クロムである、［１］～［３］のいずれか一項に記載の製造方法。
［５］ 前記金属化合物触媒の活性化が、前記塩素原子を含まないフッ素化合物と前記金属化合物触媒とを気相で接触させることによりなされる、［１］～［４］のいずれか一項に記載の製造方法。
［６］ 前記塩素原子を含まないフッ素化合物が、フッ化水素および炭素数１～３の塩素原子を含まないフッ素化合物である、［１］～［５］のいずれか一項に記載の製造方法。
［７］ 前記塩素原子を含まないフッ素化合物が、フッ化水素、トリフルオロメタンまたはジフルオロメタンである、［１］～［６］のいずれか一項に記載の製造方法。
［８］ 前記金属化合物触媒の活性化における活性化処理温度が１００～４００℃である、［１］～［７］のいずれか一項に記載の製造方法。
［９］ 前記金属化合物触媒の活性化における塩素原子を含まないフッ素化合物と触媒の接触時間が０．１～１００秒間である、［１］～［８］のいずれか一項に記載の製造方法。
［１０］ 前記脱フッ化水素反応における反応温度が２００～４００℃である、［１］～［９］のいずれか一項に記載の製造方法。
［１１］ 前記脱フッ化水素反応における３－クロロ－１，１，２，２－テトラフルオロプロパンと触媒の接触時間が０．１～１００秒間である、［１］～［１０］のいずれか一項に記載の製造方法。
［１２］ 前記脱フッ化水素反応後の反応粗液における１－クロロ－３，３－ジフルオロプロピンの含有量が、反応粗液全量に対して１０質量％以下である、［１］～［１１］のいずれか一項に記載の製造方法。
［１３］ 前記脱フッ化水素反応において、３－クロロ－１，１，２，２－テトラフルオロプロパンを、希釈ガスと混合して、反応器に供給する、［１］～［１２］のいずれか一項に記載の製造方法。
［１４］ 前記脱フッ化水素反応後の反応粗液から、精製された１－クロロ－２，３，３－トリフルオロプロペンを回収する、［１］～［１３］のいずれか一項に記載の製造方法。
［１５］ 前記精製された１－クロロ－２，３，３－トリフルオロプロペンにおける、塩素イオンおよびフッ素イオンの含有量は、それぞれ、前記精製された１－クロロ－２，３，３－トリフルオロプロペンの全量に対して、１０質量ｐｐｍ未満であり、
水分濃度は、前記精製された１－クロロ－２，３，３－トリフルオロプロペンの全量に対して、２０００質量ｐｐｍ未満であり、
酸素濃度は、前記精製された１－クロロ－２，３，３－トリフルオロプロペンの全量に対して、１０００質量ｐｐｍ以下である、［１４］に記載の製造方法。 As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by the following configurations.
[1] 3-Chloro-1,1,2,2-tetrafluoropropane is reacted with defluorinated hydrogen in the gas phase in the presence of a catalyst to obtain 1-chloro-2,3,3-trifluoropropene. It ’s a manufacturing method,
A method for producing 1-chloro-2,3,3-trifluoropropene, which comprises using a metal compound catalyst activated with a fluorine compound containing no chlorine atom in the gas phase as the catalyst.
[2] The production method according to [1], wherein the metal compound catalyst is a metal compound catalyst containing at least one metal element selected from the group consisting of Cr, Al, Zn, Ti and Ni.
[3] The production method according to any one of [1] to [2], wherein the metal compound catalyst is a metal oxide, a metal fluoride, or a metal oxide fluoride.
[4] The production method according to any one of [1] to [3], wherein the metal compound catalyst is aluminum oxide or chromium oxide.
[5] The item according to any one of [1] to [4], wherein the activation of the metal compound catalyst is performed by bringing the chlorine atom-free fluorine compound and the metal compound catalyst into contact with each other in a gas phase. The manufacturing method described.
[6] The production method according to any one of [1] to [5], wherein the chlorine atom-free fluorine compound is a fluorine compound containing hydrogen fluoride and a chlorine atom having 1 to 3 carbon atoms. ..
[7] The production method according to any one of [1] to [6], wherein the fluorine compound containing no chlorine atom is hydrogen fluoride, trifluoromethane or difluoromethane.
[8] The production method according to any one of [1] to [7], wherein the activation treatment temperature in the activation of the metal compound catalyst is 100 to 400 ° C.
[9] The production method according to any one of [1] to [8], wherein the contact time between the chlorine atom-free fluorine compound and the catalyst in the activation of the metal compound catalyst is 0.1 to 100 seconds. ..
[10] The production method according to any one of [1] to [9], wherein the reaction temperature in the defluorinated hydrogen reaction is 200 to 400 ° C.
[11] Any of [1] to [10], wherein the contact time between 3-chloro-1,1,2,2-tetrafluoropropane and the catalyst in the defluorinated hydrogen reaction is 0.1 to 100 seconds. The manufacturing method according to paragraph 1.
[12] The content of 1-chloro-3,3-difluoropropine in the reaction crude solution after the defluorinated hydrogen reaction is 10% by mass or less based on the total amount of the reaction crude solution [1] to [ 11] The manufacturing method according to any one of the following items.
[13] In any of [1] to [12], in the defluorinated hydrogen reaction, 3-chloro-1,1,2,2-tetrafluoropropane is mixed with a diluting gas and supplied to the reactor. The manufacturing method according to item 1.
[14] The item according to any one of [1] to [13], wherein the purified 1-chloro-2,3,3-trifluoropropene is recovered from the reaction crude liquid after the defluorinated hydrogen reaction. Manufacturing method.
[15] The contents of chloride ion and fluorine ion in the purified 1-chloro-2,3,3-trifluoropropene are the same as the purified 1-chloro-2,3,3-trifluoro, respectively. Less than 10 mass ppm with respect to the total amount of propene,
The water concentration was less than 2000 mass ppm with respect to the total amount of the purified 1-chloro-2,3,3-trifluoropropene.
The production method according to [14], wherein the oxygen concentration is 1000 mass ppm or less with respect to the total amount of the purified 1-chloro-2,3,3-trifluoropropene.
［１］ ３－クロロ－１，１，２，２－テトラフルオロプロパンを、触媒の存在下、気相で脱フッ化水素反応させて、１－クロロ－２，３，３－トリフルオロプロペンを製造する方法であって、
前記触媒として、気相において塩素原子を含まないフッ素化合物で活性化した金属化合物触媒を用いることを特徴とする１－クロロ－２，３，３－トリフルオロプロペンの製造方法。
［２］ 前記金属化合物触媒が、Ｃｒ、Ａｌ、Ｚｎ、ＴｉおよびＮｉからなる群より選ばれる少なくとも１種の金属元素を含む金属化合物触媒である、［１］に記載の製造方法。
［３］ 前記金属化合物触媒が、金属の酸化物、金属のフッ化物、または金属の酸化フッ素化物である、［１］～［２］のいずれか一項に記載の製造方法。
［４］ 前記金属化合物触媒が、酸化アルミニウム、または酸化クロムである、［１］～［３］のいずれか一項に記載の製造方法。
［５］ 前記金属化合物触媒の活性化が、前記塩素原子を含まないフッ素化合物と前記金属化合物触媒とを気相で接触させることによりなされる、［１］～［４］のいずれか一項に記載の製造方法。
［６］ 前記塩素原子を含まないフッ素化合物が、フッ化水素および炭素数１～３の塩素原子を含まないフッ素化合物である、［１］～［５］のいずれか一項に記載の製造方法。
［７］ 前記塩素原子を含まないフッ素化合物が、フッ化水素、トリフルオロメタンまたはジフルオロメタンである、［１］～［６］のいずれか一項に記載の製造方法。
［８］ 前記金属化合物触媒の活性化における活性化処理温度が１００～４００℃である、［１］～［７］のいずれか一項に記載の製造方法。
［９］ 前記金属化合物触媒の活性化における塩素原子を含まないフッ素化合物と触媒の接触時間が０．１～１００秒間である、［１］～［８］のいずれか一項に記載の製造方法。
［１０］ 前記脱フッ化水素反応における反応温度が２００～４００℃である、［１］～［９］のいずれか一項に記載の製造方法。
［１１］ 前記脱フッ化水素反応における３－クロロ－１，１，２，２－テトラフルオロプロパンと触媒の接触時間が０．１～１００秒間である、［１］～［１０］のいずれか一項に記載の製造方法。
［１２］ 前記脱フッ化水素反応後の反応粗液における１－クロロ－３，３－ジフルオロプロピンの含有量が、反応粗液全量に対して１０質量％以下である、［１］～［１１］のいずれか一項に記載の製造方法。
［１３］ 前記脱フッ化水素反応において、３－クロロ－１，１，２，２－テトラフルオロプロパンを、希釈ガスと混合して、反応器に供給する、［１］～［１２］のいずれか一項に記載の製造方法。
［１４］ 前記脱フッ化水素反応後の反応粗液から、精製された１－クロロ－２，３，３－トリフルオロプロペンを回収する、［１］～［１３］のいずれか一項に記載の製造方法。
［１５］ 前記精製された１－クロロ－２，３，３－トリフルオロプロペンにおける、塩素イオンおよびフッ素イオンの含有量は、それぞれ、前記精製された１－クロロ－２，３，３－トリフルオロプロペンの全量に対して、１０質量ｐｐｍ未満であり、
水分濃度は、前記精製された１－クロロ－２，３，３－トリフルオロプロペンの全量に対して、２０００質量ｐｐｍ未満であり、
酸素濃度は、前記精製された１－クロロ－２，３，３－トリフルオロプロペンの全量に対して、１０００質量ｐｐｍ以下である、［１４］に記載の製造方法。 As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by the following configurations.
[1] 3-Chloro-1,1,2,2-tetrafluoropropane is reacted with defluorinated hydrogen in the gas phase in the presence of a catalyst to obtain 1-chloro-2,3,3-trifluoropropene. It ’s a manufacturing method,
A method for producing 1-chloro-2,3,3-trifluoropropene, which comprises using a metal compound catalyst activated with a fluorine compound containing no chlorine atom in the gas phase as the catalyst.
[2] The production method according to [1], wherein the metal compound catalyst is a metal compound catalyst containing at least one metal element selected from the group consisting of Cr, Al, Zn, Ti and Ni.
[3] The production method according to any one of [1] to [2], wherein the metal compound catalyst is a metal oxide, a metal fluoride, or a metal oxide fluoride.
[4] The production method according to any one of [1] to [3], wherein the metal compound catalyst is aluminum oxide or chromium oxide.
[5] The item according to any one of [1] to [4], wherein the activation of the metal compound catalyst is performed by bringing the chlorine atom-free fluorine compound and the metal compound catalyst into contact with each other in a gas phase. The manufacturing method described.
[6] The production method according to any one of [1] to [5], wherein the chlorine atom-free fluorine compound is a fluorine compound containing hydrogen fluoride and a chlorine atom having 1 to 3 carbon atoms. ..
[7] The production method according to any one of [1] to [6], wherein the fluorine compound containing no chlorine atom is hydrogen fluoride, trifluoromethane or difluoromethane.
[8] The production method according to any one of [1] to [7], wherein the activation treatment temperature in the activation of the metal compound catalyst is 100 to 400 ° C.
[9] The production method according to any one of [1] to [8], wherein the contact time between the chlorine atom-free fluorine compound and the catalyst in the activation of the metal compound catalyst is 0.1 to 100 seconds. ..
[10] The production method according to any one of [1] to [9], wherein the reaction temperature in the defluorinated hydrogen reaction is 200 to 400 ° C.
[11] Any of [1] to [10], wherein the contact time between 3-chloro-1,1,2,2-tetrafluoropropane and the catalyst in the defluorinated hydrogen reaction is 0.1 to 100 seconds. The manufacturing method according to paragraph 1.
[12] The content of 1-chloro-3,3-difluoropropine in the reaction crude solution after the defluorinated hydrogen reaction is 10% by mass or less based on the total amount of the reaction crude solution [1] to [ 11] The manufacturing method according to any one of the following items.
[13] In any of [1] to [12], in the defluorinated hydrogen reaction, 3-chloro-1,1,2,2-tetrafluoropropane is mixed with a diluting gas and supplied to the reactor. The manufacturing method according to item 1.
[14] The item according to any one of [1] to [13], wherein the purified 1-chloro-2,3,3-trifluoropropene is recovered from the reaction crude liquid after the defluorinated hydrogen reaction. Manufacturing method.
[15] The contents of chloride ion and fluorine ion in the purified 1-chloro-2,3,3-trifluoropropene are the same as the purified 1-chloro-2,3,3-trifluoro, respectively. Less than 10 mass ppm with respect to the total amount of propene,
The water concentration was less than 2000 mass ppm with respect to the total amount of the purified 1-chloro-2,3,3-trifluoropropene.
The production method according to [14], wherein the oxygen concentration is 1000 mass ppm or less with respect to the total amount of the purified 1-chloro-2,3,3-trifluoropropene.
本発明によれば、原料の転化率が高く、高選択率で１２３３ｙｄを得ることができ、かつ不純物の生成量の少ない、気相での１２３３ｙｄの製造方法を提供できる。
According to the present invention, it is possible to provide a method for producing 1233 yd in a gas phase, which has a high conversion rate of raw materials, can obtain 1233 yd with a high selectivity, and produces a small amount of impurities.
本発明の１２３３ｙｄの製造方法は、２４４ｃａを原料として１２３３ｙｄを得る方法である。
本発明に製造方法に係る２４４ｃａの脱フッ化水素反応（以下、単に「脱フッ化水素反応」ともいう。）は、以下の式（１）で示される反応である。 The method for producing 1233 yd of the present invention is a method for obtaining 1233 yd using 244ca as a raw material.
The 244ca defluorinated hydrogen reaction (hereinafter, also simply referred to as “defluorinated hydrogen reaction”) according to the production method of the present invention is a reaction represented by the following formula (1).
本発明に製造方法に係る２４４ｃａの脱フッ化水素反応（以下、単に「脱フッ化水素反応」ともいう。）は、以下の式（１）で示される反応である。 The method for producing 1233 yd of the present invention is a method for obtaining 1233 yd using 244ca as a raw material.
The 244ca defluorinated hydrogen reaction (hereinafter, also simply referred to as “defluorinated hydrogen reaction”) according to the production method of the present invention is a reaction represented by the following formula (1).
本発明の製造方法においては、原料である２４４ｃａの転化率が高く、かつ、不純物である１－クロロ－３，３－ジフルオロプロピンの生成量が少ない。
本発明の製造方法における、脱フッ化水素反応は、製造後の廃棄物が少なく、生産性が高くなる観点から、気相で脱フッ化水素反応させる。気相で脱フッ化水素反応させるとは、気体状態の２４４ｃａを脱フッ化水素反応させることをいう。 In the production method of the present invention, the conversion rate of 244ca, which is a raw material, is high, and the amount of 1-chloro-3,3-difluoropropine, which is an impurity, is small.
In the hydrogen fluoride reaction in the production method of the present invention, the hydrogen fluoride reaction is carried out in the gas phase from the viewpoint of reducing the amount of waste after production and increasing the productivity. The hydrogen fluoride reaction in the gas phase means that 244ca in a gaseous state is subjected to a hydrogen fluoride reaction.
本発明の製造方法における、脱フッ化水素反応は、製造後の廃棄物が少なく、生産性が高くなる観点から、気相で脱フッ化水素反応させる。気相で脱フッ化水素反応させるとは、気体状態の２４４ｃａを脱フッ化水素反応させることをいう。 In the production method of the present invention, the conversion rate of 244ca, which is a raw material, is high, and the amount of 1-chloro-3,3-difluoropropine, which is an impurity, is small.
In the hydrogen fluoride reaction in the production method of the present invention, the hydrogen fluoride reaction is carried out in the gas phase from the viewpoint of reducing the amount of waste after production and increasing the productivity. The hydrogen fluoride reaction in the gas phase means that 244ca in a gaseous state is subjected to a hydrogen fluoride reaction.
本発明の製造方法は、気相において塩素原子を含まないフッ素化合物で活性化した金属化合物触媒を用いて、その存在下に、気相で２４４ｃａを脱フッ化水素反応させることを特徴とする。
The production method of the present invention is characterized in that a metal compound catalyst activated with a fluorine atom containing no chlorine atom in the gas phase is used, and 244ca is subjected to a hydrogen fluoride reaction in the gas phase in the presence thereof.
（２４４ｃａ）
本発明の１２３３ｙｄの製造方法は２４４ｃａを原料とする。２４４ｃａは、含フッ素化合物の製造原料または中間体として知られる化合物であり、容易に入手できる。 (244ca)
The method for producing 1233yd of the present invention uses 244ca as a raw material. 244ca is a compound known as a raw material or an intermediate for producing a fluorine-containing compound, and is easily available.
本発明の１２３３ｙｄの製造方法は２４４ｃａを原料とする。２４４ｃａは、含フッ素化合物の製造原料または中間体として知られる化合物であり、容易に入手できる。 (244ca)
The method for producing 1233yd of the present invention uses 244ca as a raw material. 244ca is a compound known as a raw material or an intermediate for producing a fluorine-containing compound, and is easily available.
２４４ｃａの入手方法は特に限定されず、例えば、式（２）に示されるとおり、２，２，３，３－テトラフルオロプロパノール（ＴＦＰＯ）をＮ，Ｎ－ジメチルホルムアミド（ＤＭＦ）の存在下、塩化チオニル（ＳＯＣｌ２）によって塩素化する方法により製造可能である。この方法は、液相中または気相中で行うことができる。
The method for obtaining 244ca is not particularly limited, and for example, as shown in the formula (2), 2,2,3,3-tetrafluoropropanol (TFPO) is chloride in the presence of N, N-dimethylformamide (DMF). It can be produced by a method of chlorination with thionyl (SOCl 2). This method can be carried out in the liquid phase or the gas phase.
式（２）の反応において、反応器は、ガラスフラスコ、ＳＵＳ製オートクレーブ、およびガラスライニング反応器等の、一般的な反応器を使用できる。ガラスフラスコを用いる場合、ラシヒリングを充填したガラス蒸留塔を設置し、２４４ｃａの生成と分離を同時に行うことが好ましい。
In the reaction of the formula (2), a general reactor such as a glass flask, a SUS autoclave, and a glass lining reactor can be used as the reactor. When using a glass flask, it is preferable to install a glass distillation column filled with Raschig ring and simultaneously generate and separate 244ca.
ＴＦＰＯの１モルに対するＤＭＦの投入量は、０．００１～０．２モル、塩化チオニルの投入量は０．５～１．５モル程度が好ましい。ＤＭＦは触媒的に作用して反応を進行させる作用を有する。式（２）の反応は等モルで定量的に反応が進行するので、どちらかが過剰である必要はない。
The amount of DMF added to 1 mol of TFPO is preferably 0.001 to 0.2 mol, and the amount of thionyl chloride added is preferably about 0.5 to 1.5 mol. DMF acts catalytically to promote the reaction. Since the reaction of the formula (2) proceeds quantitatively in equimolar amounts, it is not necessary that either of them is excessive.
ＴＦＰＯの１モルに対する塩化チオニルの添加速度が速すぎると、塩化水素の生成速度が上がり、ＴＦＰＯや生成物が塩化水素に同伴して系外へ排出されロスとなる可能性がある。したがって、反応進行による温度変動が３０℃以内となるような速度で塩化チオニルを滴下することが好ましい。なお、水が存在する場合、塩化チオニルは水と反応して加水分解され、ＳＯ２とＨＣｌに分解する。さらに２，２，３，３－テトラフルオロプロパンスルホン酸クロライドも加水分解し、ＴＦＰＯとＳＯ２とＨＣｌに分解する。これらを防ぐために、反応器内の雰囲気は乾燥窒素ガスにて置換することが好ましい。
If the rate of addition of thionyl chloride to 1 mol of TFPO is too fast, the rate of hydrogen chloride production increases, and TFPO and products may be discharged to the outside of the system along with hydrogen chloride, resulting in loss. Therefore, it is preferable to add thionyl chloride at a rate such that the temperature fluctuation due to the reaction progress is within 30 ° C. In the presence of water, thionyl chloride reacts with water and is hydrolyzed to SO 2 and HCl. Further, 2,2,3,3-tetrafluoropropanesulfonic acid chloride is also hydrolyzed to decompose into TFPO, SO 2 and HCl. In order to prevent these, it is preferable to replace the atmosphere in the reactor with dry nitrogen gas.
式（２）の反応においては、塩化チオニルの添加により、ＴＦＰＯと塩化チオニルが反応し、２，２，３，３－テトラフルオロプロパンスルホン酸クロライドが生成する。２，２，３，３－テトラフルオロプロパンスルホン酸クロライドは加熱されると、脱二酸化硫黄反応を起こし、２４４ｃａが生成する。加熱時の温度は７０℃～１５０℃であり、好ましくは９０℃～１３０℃である。昇温速度は任意であるが、生成した二酸化硫黄の処理が不十分となることや、生成した２４４ｃａの回収が不十分となることを避けるために、１～２℃／分程度のゆっくりとした速度で昇温して、生成速度を調整することが望ましい。
２，２，３，３－テトラフルオロプロパンスルホン酸クロライドの加熱において、昇温速度の調整が難しい場合には、例えば、２，２，３，３－テトラフルオロプロパンスルホン酸クロライドを溶媒中で加熱する方法（液相反応）を採用するのが好ましい。溶媒は２，２，３，３－テトラフルオロプロパンスルホン酸クロライド分解反応の反応温度より沸点が高く、式（２）で示される反応に関与する化合物と反応しにくい溶媒であって、非プロトン性溶媒を用いることが好ましい。具体例的には、ジメチルスルホキシド、ＤＭＦ等が挙げられる。溶媒の使用量は２，２，３，３－テトラフルオロプロパンスルホン酸クロライドの１モルに対して、０．５～３モル程度が好ましい。
２，２，３，３－テトラフルオロプロパンスルホン酸クロライドの脱二酸化硫黄反応には、上記と同様の反応器を準備し、液相反応で実施するのが好ましい。すなわち、反応器中に溶媒を添加して脱二酸化硫黄反応する温度まで加熱したところに、２，２，３，３－テトラフルオロプロパンスルホン酸クロライドを滴下することによって２４４ｃａを製造する。脱二酸化硫黄反応の反応温度は７０℃～１５０℃であり、好ましくは９０℃～１３０℃である。反応容器内の雰囲気は乾燥窒素ガスにて置換することが好ましい。 In the reaction of formula (2), the addition of thionyl chloride causes TFPO to react with thionyl chloride to produce 2,2,3,3-tetrafluoropropanesulfonic acid chloride. When 2,2,3,3-tetrafluoropropanesulfonic acid chloride is heated, it undergoes a sulfur dioxide desulfurization reaction to produce 244ca. The temperature at the time of heating is 70 ° C. to 150 ° C., preferably 90 ° C. to 130 ° C. The rate of temperature rise is arbitrary, but it is slowed down to about 1 to 2 ° C./min in order to avoid insufficient treatment of the produced sulfur dioxide and insufficient recovery of the produced 244ca. It is desirable to raise the temperature at a rate to adjust the production rate.
When it is difficult to adjust the temperature rise rate in heating 2,2,3,3-tetrafluoropropanesulfonic acid chloride, for example, 2,2,3,3-tetrafluoropropanesulfonic acid chloride is heated in a solvent. It is preferable to adopt the method (liquid phase reaction). The solvent has a boiling point higher than the reaction temperature of the 2,2,3,3-tetrafluoropropanesulfonic acid chloride decomposition reaction, and is a solvent that does not easily react with the compound involved in the reaction represented by the formula (2) and is aprotic. It is preferable to use a solvent. Specific examples include dimethyl sulfoxide, DMF and the like. The amount of the solvent used is preferably about 0.5 to 3 mol with respect to 1 mol of 2,2,3,3-tetrafluoropropanesulfonic acid chloride.
For the sulfur dioxide desulfurization reaction of 2,2,3,3-tetrafluoropropanesulfonic acid chloride, it is preferable to prepare a reactor similar to the above and carry out the liquid phase reaction. That is, 244ca is produced by dropping 2,2,3,3-tetrafluoropropanesulfonic acid chloride in a reactor where a solvent is added and the mixture is heated to a temperature at which a sulfur dioxide reaction occurs. The reaction temperature of the sulfur dioxide removal reaction is 70 ° C. to 150 ° C., preferably 90 ° C. to 130 ° C. The atmosphere in the reaction vessel is preferably replaced with dry nitrogen gas.
２，２，３，３－テトラフルオロプロパンスルホン酸クロライドの加熱において、昇温速度の調整が難しい場合には、例えば、２，２，３，３－テトラフルオロプロパンスルホン酸クロライドを溶媒中で加熱する方法（液相反応）を採用するのが好ましい。溶媒は２，２，３，３－テトラフルオロプロパンスルホン酸クロライド分解反応の反応温度より沸点が高く、式（２）で示される反応に関与する化合物と反応しにくい溶媒であって、非プロトン性溶媒を用いることが好ましい。具体例的には、ジメチルスルホキシド、ＤＭＦ等が挙げられる。溶媒の使用量は２，２，３，３－テトラフルオロプロパンスルホン酸クロライドの１モルに対して、０．５～３モル程度が好ましい。
２，２，３，３－テトラフルオロプロパンスルホン酸クロライドの脱二酸化硫黄反応には、上記と同様の反応器を準備し、液相反応で実施するのが好ましい。すなわち、反応器中に溶媒を添加して脱二酸化硫黄反応する温度まで加熱したところに、２，２，３，３－テトラフルオロプロパンスルホン酸クロライドを滴下することによって２４４ｃａを製造する。脱二酸化硫黄反応の反応温度は７０℃～１５０℃であり、好ましくは９０℃～１３０℃である。反応容器内の雰囲気は乾燥窒素ガスにて置換することが好ましい。 In the reaction of formula (2), the addition of thionyl chloride causes TFPO to react with thionyl chloride to produce 2,2,3,3-tetrafluoropropanesulfonic acid chloride. When 2,2,3,3-tetrafluoropropanesulfonic acid chloride is heated, it undergoes a sulfur dioxide desulfurization reaction to produce 244ca. The temperature at the time of heating is 70 ° C. to 150 ° C., preferably 90 ° C. to 130 ° C. The rate of temperature rise is arbitrary, but it is slowed down to about 1 to 2 ° C./min in order to avoid insufficient treatment of the produced sulfur dioxide and insufficient recovery of the produced 244ca. It is desirable to raise the temperature at a rate to adjust the production rate.
When it is difficult to adjust the temperature rise rate in heating 2,2,3,3-tetrafluoropropanesulfonic acid chloride, for example, 2,2,3,3-tetrafluoropropanesulfonic acid chloride is heated in a solvent. It is preferable to adopt the method (liquid phase reaction). The solvent has a boiling point higher than the reaction temperature of the 2,2,3,3-tetrafluoropropanesulfonic acid chloride decomposition reaction, and is a solvent that does not easily react with the compound involved in the reaction represented by the formula (2) and is aprotic. It is preferable to use a solvent. Specific examples include dimethyl sulfoxide, DMF and the like. The amount of the solvent used is preferably about 0.5 to 3 mol with respect to 1 mol of 2,2,3,3-tetrafluoropropanesulfonic acid chloride.
For the sulfur dioxide desulfurization reaction of 2,2,3,3-tetrafluoropropanesulfonic acid chloride, it is preferable to prepare a reactor similar to the above and carry out the liquid phase reaction. That is, 244ca is produced by dropping 2,2,3,3-tetrafluoropropanesulfonic acid chloride in a reactor where a solvent is added and the mixture is heated to a temperature at which a sulfur dioxide reaction occurs. The reaction temperature of the sulfur dioxide removal reaction is 70 ° C. to 150 ° C., preferably 90 ° C. to 130 ° C. The atmosphere in the reaction vessel is preferably replaced with dry nitrogen gas.
式（２）の反応を経て生成する２４４ｃａの粗生成物は、通常はガス状の粗い生成物であり、水洗などの方法で、塩酸および二酸化硫黄を除去する処理を行い、塩化カルシウムやモレキュラーシーブなどの乾燥剤により乾燥してコールドトラップなどの方法に供することで不純物を除き、２４４ｃａを含む組成物を回収することができる。得られた２４４ｃａを含む組成物は、そのまま、または、これをさらに精製して、例えば、純度が９９．５質量％以上の２４４ｃａの組成物として、本発明の製造方法に用いることができる。
本発明の製造方法に用いる２４４ｃａとしては、純度１００％の２４４ｃａ以外に、精製工程を経た高純度の２４４ｃａの組成物を用いてよく、２４４ｃａと２４４ｃａ以外の成分（例えば、不純物等）を含む、２４４ｃａを含む組成物、を用いてもよい。ただし、後者の２４４ｃａを含む組成物を用いる場合においては、不純物が本発明における脱フッ化水素反応に活性な不純物である場合には、予め除去しておくのが好ましい。例えば、式（２）の方法で２４４ｃａを製造する場合、生成する２４４ｃａとともにＴＦＰＯが残留すると、本発明の製造目的物である１２３３ｙｄと反応する場合があるため、生成物中からＴＦＰＯをできるだけ除くのが好ましい。 The crude product of 244ca produced through the reaction of the formula (2) is usually a gaseous crude product, and is treated to remove hydrochloric acid and sulfur dioxide by a method such as washing with water to remove calcium chloride or molecular sieve. By drying with a desiccant such as the above and subjecting it to a method such as cold trap, impurities can be removed and the composition containing 244ca can be recovered. The obtained composition containing 244ca can be used as it is or by further purifying it, for example, as a composition having a purity of 99.5% by mass or more and used in the production method of the present invention.
As the 244ca used in the production method of the present invention, a composition having a high purity of 244ca that has undergone a purification step may be used in addition to the 244ca having a purity of 100%, and contains components other than 244ca and 244ca (for example, impurities). A composition containing 244ca may be used. However, when the latter composition containing 244ca is used, if the impurity is an impurity active in the defluorinated hydrogen reaction in the present invention, it is preferable to remove it in advance. For example, in the case of producing 244ca by the method of the formula (2), if TFPO remains together with the produced 244ca, it may react with 1233yd, which is the production object of the present invention. Therefore, TFPO should be removed from the product as much as possible. Is preferable.
本発明の製造方法に用いる２４４ｃａとしては、純度１００％の２４４ｃａ以外に、精製工程を経た高純度の２４４ｃａの組成物を用いてよく、２４４ｃａと２４４ｃａ以外の成分（例えば、不純物等）を含む、２４４ｃａを含む組成物、を用いてもよい。ただし、後者の２４４ｃａを含む組成物を用いる場合においては、不純物が本発明における脱フッ化水素反応に活性な不純物である場合には、予め除去しておくのが好ましい。例えば、式（２）の方法で２４４ｃａを製造する場合、生成する２４４ｃａとともにＴＦＰＯが残留すると、本発明の製造目的物である１２３３ｙｄと反応する場合があるため、生成物中からＴＦＰＯをできるだけ除くのが好ましい。 The crude product of 244ca produced through the reaction of the formula (2) is usually a gaseous crude product, and is treated to remove hydrochloric acid and sulfur dioxide by a method such as washing with water to remove calcium chloride or molecular sieve. By drying with a desiccant such as the above and subjecting it to a method such as cold trap, impurities can be removed and the composition containing 244ca can be recovered. The obtained composition containing 244ca can be used as it is or by further purifying it, for example, as a composition having a purity of 99.5% by mass or more and used in the production method of the present invention.
As the 244ca used in the production method of the present invention, a composition having a high purity of 244ca that has undergone a purification step may be used in addition to the 244ca having a purity of 100%, and contains components other than 244ca and 244ca (for example, impurities). A composition containing 244ca may be used. However, when the latter composition containing 244ca is used, if the impurity is an impurity active in the defluorinated hydrogen reaction in the present invention, it is preferable to remove it in advance. For example, in the case of producing 244ca by the method of the formula (2), if TFPO remains together with the produced 244ca, it may react with 1233yd, which is the production object of the present invention. Therefore, TFPO should be removed from the product as much as possible. Is preferable.
本発明の製造方法においては、塩素原子を含まないフッ素化合物で活性化した金属化合物触媒の存在下に２４４ｃａを脱フッ化水素反応させる。この脱フッ化水素反応は、原料である２４４ｃａを、気相において、活性化した金属化合物触媒と接触させる方法で行う。
In the production method of the present invention, 244ca is subjected to a hydrogen fluoride reaction in the presence of a metal compound catalyst activated by a fluorine compound containing no chlorine atom. This defluorinated hydrogen reaction is carried out by a method in which the raw material 244ca is brought into contact with the activated metal compound catalyst in the gas phase.
（金属化合物触媒）
本発明における活性化前の金属化合物触媒としては、金属の酸化物、金属のフッ化物、金属の酸化フッ素化物等が挙げられる。金属化合物触媒としては、１種単独で使用してもよいし、２種以上を併用してもよい。
金属化合物触媒に含まれる金属元素は、１種であってもよく、２種以上でもよい。金属化合物触媒が２種以上の金属元素を含む場合、金属化合物は、金属元素が異なる２種以上の金属化合物の混合物であってもよく、２種以上の金属元素を含む金属化合物であってもよい。
活性化前の金属化合物触媒としては、Ｃｏ、Ｆｅ、Ｐｄ、Ｓｎ、Ｍｇ、Ｌａ、Ｃｒ、Ａｌ、Ｚｎ、ＴｉおよびＮｉからなる群より選ばれる少なくとも１種の金属元素を含む金属化合物であることが好ましく、Ｃｒ、Ａｌ、Ｚｎ、ＴｉおよびＮｉからなる群より選ばれる少なくとも１種の金属元素を含む金属化合物であることがより好ましい。
金属の酸化物としては、酸化クロム、酸化アルミニウム、酸化亜鉛、酸化チタン、酸化ニッケル等が挙げられる。
金属のフッ化物としては、水和物であってもよく、フッ化クロム、フッ化アルミニウム、フッ化チタン、フッ化亜鉛、フッ化チタン、フッ化ニッケル等が挙げられる。
金属の酸化フッ素化物としては、酸化クロム、酸化アルミニウム、酸化亜鉛、酸化チタン、酸化ニッケル等が部分的にフッ素化されたものが挙げられる。
金属化合物触媒としては、転化率と選択率の観点から、金属の酸化物が好ましく、酸化アルミニウム、酸化クロムがより好ましい。 (Metal compound catalyst)
Examples of the metal compound catalyst before activation in the present invention include metal oxides, metal fluorides, and metal oxide fluorides. As the metal compound catalyst, one type may be used alone, or two or more types may be used in combination.
The metal element contained in the metal compound catalyst may be one kind or two or more kinds. When the metal compound catalyst contains two or more kinds of metal elements, the metal compound may be a mixture of two or more kinds of metal compounds having different metal elements, or may be a metal compound containing two or more kinds of metal elements. good.
The metal compound catalyst before activation is a metal compound containing at least one metal element selected from the group consisting of Co, Fe, Pd, Sn, Mg, La, Cr, Al, Zn, Ti and Ni. Is preferable, and it is more preferable that the metal compound contains at least one metal element selected from the group consisting of Cr, Al, Zn, Ti and Ni.
Examples of metal oxides include chromium oxide, aluminum oxide, zinc oxide, titanium oxide, nickel oxide and the like.
The fluoride of the metal may be a hydrate, and examples thereof include chromium fluoride, aluminum fluoride, titanium fluoride, zinc fluoride, titanium fluoride, and nickel fluoride.
Examples of the fluorinated metal oxide include those in which chromium oxide, aluminum oxide, zinc oxide, titanium oxide, nickel oxide and the like are partially fluorinated.
As the metal compound catalyst, metal oxides are preferable, and aluminum oxide and chromium oxide are more preferable, from the viewpoint of conversion and selectivity.
本発明における活性化前の金属化合物触媒としては、金属の酸化物、金属のフッ化物、金属の酸化フッ素化物等が挙げられる。金属化合物触媒としては、１種単独で使用してもよいし、２種以上を併用してもよい。
金属化合物触媒に含まれる金属元素は、１種であってもよく、２種以上でもよい。金属化合物触媒が２種以上の金属元素を含む場合、金属化合物は、金属元素が異なる２種以上の金属化合物の混合物であってもよく、２種以上の金属元素を含む金属化合物であってもよい。
活性化前の金属化合物触媒としては、Ｃｏ、Ｆｅ、Ｐｄ、Ｓｎ、Ｍｇ、Ｌａ、Ｃｒ、Ａｌ、Ｚｎ、ＴｉおよびＮｉからなる群より選ばれる少なくとも１種の金属元素を含む金属化合物であることが好ましく、Ｃｒ、Ａｌ、Ｚｎ、ＴｉおよびＮｉからなる群より選ばれる少なくとも１種の金属元素を含む金属化合物であることがより好ましい。
金属の酸化物としては、酸化クロム、酸化アルミニウム、酸化亜鉛、酸化チタン、酸化ニッケル等が挙げられる。
金属のフッ化物としては、水和物であってもよく、フッ化クロム、フッ化アルミニウム、フッ化チタン、フッ化亜鉛、フッ化チタン、フッ化ニッケル等が挙げられる。
金属の酸化フッ素化物としては、酸化クロム、酸化アルミニウム、酸化亜鉛、酸化チタン、酸化ニッケル等が部分的にフッ素化されたものが挙げられる。
金属化合物触媒としては、転化率と選択率の観点から、金属の酸化物が好ましく、酸化アルミニウム、酸化クロムがより好ましい。 (Metal compound catalyst)
Examples of the metal compound catalyst before activation in the present invention include metal oxides, metal fluorides, and metal oxide fluorides. As the metal compound catalyst, one type may be used alone, or two or more types may be used in combination.
The metal element contained in the metal compound catalyst may be one kind or two or more kinds. When the metal compound catalyst contains two or more kinds of metal elements, the metal compound may be a mixture of two or more kinds of metal compounds having different metal elements, or may be a metal compound containing two or more kinds of metal elements. good.
The metal compound catalyst before activation is a metal compound containing at least one metal element selected from the group consisting of Co, Fe, Pd, Sn, Mg, La, Cr, Al, Zn, Ti and Ni. Is preferable, and it is more preferable that the metal compound contains at least one metal element selected from the group consisting of Cr, Al, Zn, Ti and Ni.
Examples of metal oxides include chromium oxide, aluminum oxide, zinc oxide, titanium oxide, nickel oxide and the like.
The fluoride of the metal may be a hydrate, and examples thereof include chromium fluoride, aluminum fluoride, titanium fluoride, zinc fluoride, titanium fluoride, and nickel fluoride.
Examples of the fluorinated metal oxide include those in which chromium oxide, aluminum oxide, zinc oxide, titanium oxide, nickel oxide and the like are partially fluorinated.
As the metal compound catalyst, metal oxides are preferable, and aluminum oxide and chromium oxide are more preferable, from the viewpoint of conversion and selectivity.
金属化合物触媒は、担体に担持されていてもよい。担体としては、アルミナ担体、シリカ担体、シリカアルミナ担体等が挙げられる。担体は、脱フッ化水素反応を促進する触媒活性を有していてもよい。担体としては、前述の金属化合物触媒と同様の、Ｃｒ、Ａｌ、Ｚｎ、ＴｉおよびＮｉからなる群より選ばれる少なくとも１種の金属元素を含む金属化合物である、担体が好ましい。
The metal compound catalyst may be supported on a carrier. Examples of the carrier include an alumina carrier, a silica carrier, and a silica alumina carrier. The carrier may have a catalytic activity that promotes the defluorinated hydrogen reaction. As the carrier, a carrier which is a metal compound containing at least one metal element selected from the group consisting of Cr, Al, Zn, Ti and Ni, which is the same as the above-mentioned metal compound catalyst, is preferable.
（触媒の活性化）
本発明の製造方法においては、活性化した金属化合物触媒を用いる。ここでの活性化とは、塩素原子を含まないフッ素化合物と金属化合物触媒とを気相で接触させることをいう。活性化された金属化合物触媒は、部分的にフッ素化されていることが好ましい。塩素原子を含まないフッ素化合物としては、１種単独で使用してもよいし、２種以上を併用してもよい。
塩素原子を含まないフッ素化合物としては、フッ化水素、フッ素化アルカン、フッ素化アルケンが好ましく、フッ化水素、フッ素化アルカンがより好ましい。
塩素原子を含まないフッ素化合物としては、フッ化水素および炭素数１～３の塩素原子を含まないフッ素化合物が好ましく、フッ化水素および炭素数１～２の塩素原子を含まないフッ素化合物がより好ましく、フッ化水素および炭素数１の塩素原子を含まないフッ素化合物が最も好ましい。
炭素数１の塩素原子を含まないフッ素化合物としては、トリフルオロメタン、ジフルオロメタン等が挙げられる。
炭素数２の塩素原子を含まないフッ素化合物としては、ペンタフルオロエタン、１，１，２，２－テトラフルオロエタン、１，１，1－トリフルオロエタン等が挙げられる。
炭素数３の塩素原子を含まないフッ素化合物としては、ヘキサフルオロプロパン、１，２，３，３－テトラフルオロプロペン等が挙げられる。
塩素原子を含まないフッ素化合物としては、フッ化水素、トリフルオロメタン、ジフルオロメタンが好ましく、原料の転化率と不純物の抑制の観点から、フッ化水素およびトリフルオロメタンがより好ましい。 (Activation of catalyst)
In the production method of the present invention, an activated metal compound catalyst is used. The activation here means that the fluorine compound containing no chlorine atom and the metal compound catalyst are brought into contact with each other in the gas phase. The activated metal compound catalyst is preferably partially fluorinated. As the fluorine compound containing no chlorine atom, one type may be used alone, or two or more types may be used in combination.
As the fluorine compound containing no chlorine atom, hydrogen fluoride, fluorinated alkane, and fluorinated alkene are preferable, and hydrogen fluoride and fluorinated alkane are more preferable.
As the fluorine compound containing no chlorine atom, a fluorine compound containing hydrogen fluoride and a chlorine atom having 1 to 3 carbon atoms is preferable, and a fluorine compound containing hydrogen fluoride and a chlorine atom having 1 to 2 carbon atoms is more preferable. , Fluorine compounds free of hydrogen fluoride and chlorine atom having 1 carbon atom are most preferable.
Examples of the fluorine compound containing no chlorine atom having 1 carbon atom include trifluoromethane and difluoromethane.
Examples of the fluorine compound containing no chlorine atom having 2 carbon atoms include pentafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1-trifluoroethane and the like.
Examples of the fluorine compound containing no chlorine atom having 3 carbon atoms include hexafluoropropane, 1,2,3,3-tetrafluoropropene and the like.
As the fluorine compound containing no chlorine atom, hydrogen fluoride, trifluoromethane and difluoromethane are preferable, and hydrogen fluoride and trifluoromethane are more preferable from the viewpoint of conversion rate of raw materials and suppression of impurities.
本発明の製造方法においては、活性化した金属化合物触媒を用いる。ここでの活性化とは、塩素原子を含まないフッ素化合物と金属化合物触媒とを気相で接触させることをいう。活性化された金属化合物触媒は、部分的にフッ素化されていることが好ましい。塩素原子を含まないフッ素化合物としては、１種単独で使用してもよいし、２種以上を併用してもよい。
塩素原子を含まないフッ素化合物としては、フッ化水素、フッ素化アルカン、フッ素化アルケンが好ましく、フッ化水素、フッ素化アルカンがより好ましい。
塩素原子を含まないフッ素化合物としては、フッ化水素および炭素数１～３の塩素原子を含まないフッ素化合物が好ましく、フッ化水素および炭素数１～２の塩素原子を含まないフッ素化合物がより好ましく、フッ化水素および炭素数１の塩素原子を含まないフッ素化合物が最も好ましい。
炭素数１の塩素原子を含まないフッ素化合物としては、トリフルオロメタン、ジフルオロメタン等が挙げられる。
炭素数２の塩素原子を含まないフッ素化合物としては、ペンタフルオロエタン、１，１，２，２－テトラフルオロエタン、１，１，1－トリフルオロエタン等が挙げられる。
炭素数３の塩素原子を含まないフッ素化合物としては、ヘキサフルオロプロパン、１，２，３，３－テトラフルオロプロペン等が挙げられる。
塩素原子を含まないフッ素化合物としては、フッ化水素、トリフルオロメタン、ジフルオロメタンが好ましく、原料の転化率と不純物の抑制の観点から、フッ化水素およびトリフルオロメタンがより好ましい。 (Activation of catalyst)
In the production method of the present invention, an activated metal compound catalyst is used. The activation here means that the fluorine compound containing no chlorine atom and the metal compound catalyst are brought into contact with each other in the gas phase. The activated metal compound catalyst is preferably partially fluorinated. As the fluorine compound containing no chlorine atom, one type may be used alone, or two or more types may be used in combination.
As the fluorine compound containing no chlorine atom, hydrogen fluoride, fluorinated alkane, and fluorinated alkene are preferable, and hydrogen fluoride and fluorinated alkane are more preferable.
As the fluorine compound containing no chlorine atom, a fluorine compound containing hydrogen fluoride and a chlorine atom having 1 to 3 carbon atoms is preferable, and a fluorine compound containing hydrogen fluoride and a chlorine atom having 1 to 2 carbon atoms is more preferable. , Fluorine compounds free of hydrogen fluoride and chlorine atom having 1 carbon atom are most preferable.
Examples of the fluorine compound containing no chlorine atom having 1 carbon atom include trifluoromethane and difluoromethane.
Examples of the fluorine compound containing no chlorine atom having 2 carbon atoms include pentafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1-trifluoroethane and the like.
Examples of the fluorine compound containing no chlorine atom having 3 carbon atoms include hexafluoropropane, 1,2,3,3-tetrafluoropropene and the like.
As the fluorine compound containing no chlorine atom, hydrogen fluoride, trifluoromethane and difluoromethane are preferable, and hydrogen fluoride and trifluoromethane are more preferable from the viewpoint of conversion rate of raw materials and suppression of impurities.
気相において塩素原子を含まないフッ素化合物と金属化合物触媒を接触させる方法としては、反応器内に充填した固体状態の金属化合物触媒に気体状態の塩素原子を含まないフッ素化合物を導入し、接触させる方法が挙げられる。この触媒活性化方法では、金属化合物触媒を活性化したのち、反応器に原料２４４ｃａを導入して脱フッ化水素反応させる。
また、固体状態の金属化合物触媒を充填した反応器内に、原料２４４ｃａと塩素原子を含まないフッ素化合物との混合気体を導入し、金属化合物触媒の活性化と脱フッ化水素反応を同時に行う方法でもよい。
触媒活性化方法としては、金属化合物触媒を充分に活性化させる観点から、前者の方法が好ましい。また、場合によっては、反応器外で金属化合物触媒を塩素原子を含まないフッ素化合物の気体で活性化したのち、活性化した金属触媒を反応器に充填し、原料２４４ｃａを導入して脱フッ化水素反応させることもできる。 As a method of bringing a chlorine atom-free fluorine compound into contact with a metal compound catalyst in a gas phase, a gaseous chlorine atom-free fluorine compound is introduced into a solid metal compound catalyst filled in a reactor and brought into contact with the catalyst. The method can be mentioned. In this catalyst activation method, after activating the metal compound catalyst, the raw material 244ca is introduced into the reactor to cause a defluorinated hydrogen reaction.
Further, a method in which a mixed gas of a raw material 244ca and a fluorine compound containing no chlorine atom is introduced into a reactor filled with a metal compound catalyst in a solid state to activate the metal compound catalyst and perform a defluorinated hydrogen reaction at the same time. But it may be.
As the catalyst activation method, the former method is preferable from the viewpoint of sufficiently activating the metal compound catalyst. In some cases, the metal compound catalyst is activated outside the reactor with a fluorine compound gas containing no chlorine atom, the activated metal catalyst is filled in the reactor, and the raw material 244ca is introduced to defluoride. It can also be reacted with hydrogen.
また、固体状態の金属化合物触媒を充填した反応器内に、原料２４４ｃａと塩素原子を含まないフッ素化合物との混合気体を導入し、金属化合物触媒の活性化と脱フッ化水素反応を同時に行う方法でもよい。
触媒活性化方法としては、金属化合物触媒を充分に活性化させる観点から、前者の方法が好ましい。また、場合によっては、反応器外で金属化合物触媒を塩素原子を含まないフッ素化合物の気体で活性化したのち、活性化した金属触媒を反応器に充填し、原料２４４ｃａを導入して脱フッ化水素反応させることもできる。 As a method of bringing a chlorine atom-free fluorine compound into contact with a metal compound catalyst in a gas phase, a gaseous chlorine atom-free fluorine compound is introduced into a solid metal compound catalyst filled in a reactor and brought into contact with the catalyst. The method can be mentioned. In this catalyst activation method, after activating the metal compound catalyst, the raw material 244ca is introduced into the reactor to cause a defluorinated hydrogen reaction.
Further, a method in which a mixed gas of a raw material 244ca and a fluorine compound containing no chlorine atom is introduced into a reactor filled with a metal compound catalyst in a solid state to activate the metal compound catalyst and perform a defluorinated hydrogen reaction at the same time. But it may be.
As the catalyst activation method, the former method is preferable from the viewpoint of sufficiently activating the metal compound catalyst. In some cases, the metal compound catalyst is activated outside the reactor with a fluorine compound gas containing no chlorine atom, the activated metal catalyst is filled in the reactor, and the raw material 244ca is introduced to defluoride. It can also be reacted with hydrogen.
本発明における触媒の活性化処理の温度（以下、活性化処理温度ともいう。）は、１００～４００℃が好ましく、１５０～４００℃がより好ましく、２００～４００℃がさらに好ましく、２５０～４００℃が特に好ましく、２５０～３５０℃が最も好ましい。上記範囲とすることで、金属化合物触媒を十分に活性化させることができる。活性化処理温度が上記範囲に達しない場合、金属化合物触媒の活性が不十分となり、原料の転化率が低下する可能性がある。活性化処理温度が上記範囲を超える場合、金属化合物触媒の活性および寿命が低下する可能性がある。
The temperature of the catalyst activation treatment in the present invention (hereinafter, also referred to as activation treatment temperature) is preferably 100 to 400 ° C, more preferably 150 to 400 ° C, still more preferably 200 to 400 ° C, and 250 to 400 ° C. Is particularly preferable, and 250 to 350 ° C. is most preferable. Within the above range, the metal compound catalyst can be sufficiently activated. If the activation treatment temperature does not reach the above range, the activity of the metal compound catalyst may be insufficient and the conversion rate of the raw material may decrease. If the activation treatment temperature exceeds the above range, the activity and lifetime of the metal compound catalyst may decrease.
活性化処理では、反応時間（該時間は、塩素原子を含まないフッ素化合物と金属化合物触媒との接触時間をいう。）は、０．１～１００秒間が好ましく、１～８０秒間がより好ましく、５～６０秒間が最も好ましい。上記範囲とすることで、金属化合物触媒を十分に活性化させることができる。反応温度が高ければ、反応時間を短く、反応温度が低ければを長く調節することが好ましい。また、脱フッ化水素反応する反応器内の圧力は、０～２ＭＰａが好ましい。
In the activation treatment, the reaction time (the time refers to the contact time between the fluorine compound containing no chlorine atom and the metal compound catalyst) is preferably 0.1 to 100 seconds, more preferably 1 to 80 seconds. Most preferably 5 to 60 seconds. Within the above range, the metal compound catalyst can be sufficiently activated. If the reaction temperature is high, the reaction time is short, and if the reaction temperature is low, the reaction time is preferably long. The pressure inside the reactor that undergoes the hydrogen defluorination reaction is preferably 0 to 2 MPa.
（脱フッ化水素反応）
本発明の製造方法においては、反応器内に充填されている活性化された金属化合物触媒に気体状態の原料２４４ｃａを導入し、両者を接触させることで、脱フッ化水素反応させる。 (Hydrogen fluoride reaction)
In the production method of the present invention, a gaseous raw material 244ca is introduced into an activated metal compound catalyst packed in a reactor, and the two are brought into contact with each other to cause a defluorinated hydrogen reaction.
本発明の製造方法においては、反応器内に充填されている活性化された金属化合物触媒に気体状態の原料２４４ｃａを導入し、両者を接触させることで、脱フッ化水素反応させる。 (Hydrogen fluoride reaction)
In the production method of the present invention, a gaseous raw material 244ca is introduced into an activated metal compound catalyst packed in a reactor, and the two are brought into contact with each other to cause a defluorinated hydrogen reaction.
脱フッ化水素反応は、バッチ式で行ってもよく、連続式（半連続式または連続流通式等を含む）で行ってもよく、生産効率の点から連続式で行うことが好ましい。連続式の場合、２４４ｃａの反応器への供給、反応器内での２４４ｃａと活性化された金属化合物触媒の接触、反応、および生成した１２３３ｙｄの反応器からの取り出しは、いずれも連続的に行うのが好ましい。
反応器の材質としては、原料、溶媒、および反応生成物等に不活性で、耐蝕性の材質であれば特に制限されない。反応器の材質として例えば、ガラス、鉄、ニッケル、および鉄等を主成分とするステンレス鋼等の合金などが挙げられる。 The defluorinated hydrogen reaction may be carried out by a batch method or a continuous method (including a semi-continuous type or a continuous flow type), and is preferably performed by a continuous method from the viewpoint of production efficiency. In the case of the continuous system, the supply of 244ca to the reactor, the contact between 244ca and the activated metal compound catalyst in the reactor, the reaction, and the removal from the generated 1233yd reactor are all performed continuously. Is preferable.
The material of the reactor is not particularly limited as long as it is a material that is inert to the raw material, solvent, reaction product and the like and has corrosion resistance. Examples of the material of the reactor include alloys such as glass, iron, nickel, and stainless steel containing iron as a main component.
反応器の材質としては、原料、溶媒、および反応生成物等に不活性で、耐蝕性の材質であれば特に制限されない。反応器の材質として例えば、ガラス、鉄、ニッケル、および鉄等を主成分とするステンレス鋼等の合金などが挙げられる。 The defluorinated hydrogen reaction may be carried out by a batch method or a continuous method (including a semi-continuous type or a continuous flow type), and is preferably performed by a continuous method from the viewpoint of production efficiency. In the case of the continuous system, the supply of 244ca to the reactor, the contact between 244ca and the activated metal compound catalyst in the reactor, the reaction, and the removal from the generated 1233yd reactor are all performed continuously. Is preferable.
The material of the reactor is not particularly limited as long as it is a material that is inert to the raw material, solvent, reaction product and the like and has corrosion resistance. Examples of the material of the reactor include alloys such as glass, iron, nickel, and stainless steel containing iron as a main component.
気相での脱フッ化水素反応では、脱フッ化水素反応の温度（以下、反応温度ともいう。）は、２００～４００℃が好ましく、２５０～４００℃がより好ましく、２７５～４００℃が最も好ましい。上記範囲とすることで、不純物の生成を抑制し、高選択率で１２３３ｙｄを得ることができる。反応温度が上記範囲に達しない場合、反応速度、反応収率が低下する可能性があり、未反応の２４４ｃａが過剰に残っている場合、１２３３ｙｄとの分離が困難になりうる。また、反応温度が上記範囲を超える場合、１２３３ｙｄがさらに脱フッ化水素して生成する１－クロロ－３，３－ジフルオロプロピンの生成量が増える可能性や、１２３３ｙｄの選択率が低下する可能性がある。
In the defluorinated hydrogen reaction in the gas phase, the temperature of the defluorinated hydrogen reaction (hereinafter, also referred to as reaction temperature) is preferably 200 to 400 ° C, more preferably 250 to 400 ° C, and most preferably 275 to 400 ° C. preferable. Within the above range, the generation of impurities can be suppressed and 1233 yd can be obtained with a high selectivity. If the reaction temperature does not reach the above range, the reaction rate and the reaction yield may decrease, and if unreacted 244ca remains in excess, it may be difficult to separate from 1233yd. Further, when the reaction temperature exceeds the above range, the amount of 1-chloro-3,3-difluoropropine produced by further defluorinating hydrogen of 1233yd may increase, and the selectivity of 1233yd may decrease. There is sex.
気相での脱フッ化水素反応では、反応時間（該時間は、原料と活性化された金属化合物触媒との接触時間をいう。）は、原料の転化率と不純物の生成を抑制する観点から、０．１～１００秒間が好ましく、１～８０秒間がより好ましく、５～６０秒間が最も好ましい。反応温度が高ければ、反応時間を短く、反応温度が低ければを長く調節することが好ましい。また、脱フッ化水素反応する反応器内の圧力は、０～２ＭＰａが好ましい。
In the defluorinated hydrogen reaction in the gas phase, the reaction time (the time refers to the contact time between the raw material and the activated metal compound catalyst) is from the viewpoint of suppressing the conversion rate of the raw material and the formation of impurities. , 0.1 to 100 seconds, more preferably 1 to 80 seconds, and most preferably 5 to 60 seconds. If the reaction temperature is high, the reaction time is short, and if the reaction temperature is low, the reaction time is preferably long. The pressure inside the reactor that undergoes the hydrogen defluorination reaction is preferably 0 to 2 MPa.
本発明の気相の脱フッ化水素反応においては、１２３３ｙｄの選択率の観点から、反応粗液全量に対する、１－クロロ－３，３－ジフルオロプロピンの含有量が１０質量％以下であることが好ましく、５質量％以下であることがより好ましく、１質量％以下であることが最も好ましい。本発明における反応粗液は、未反応の原料と反応生成物を含む粗液である。
未反応の２４４ｃａが残っている場合、蒸留によって２４４ｃａを濃縮し、本発明の原料としてリサイクルすることも可能である。 In the defluorinated hydrogen reaction of the gas phase of the present invention, the content of 1-chloro-3,3-difluoropropine is 10% by mass or less with respect to the total amount of the reaction crude liquid from the viewpoint of the selectivity of 1233 yd. Is preferable, and it is more preferably 5% by mass or less, and most preferably 1% by mass or less. The crude reaction solution in the present invention is a crude solution containing unreacted raw materials and reaction products.
If unreacted 244ca remains, it is also possible to concentrate 244ca by distillation and recycle it as a raw material of the present invention.
未反応の２４４ｃａが残っている場合、蒸留によって２４４ｃａを濃縮し、本発明の原料としてリサイクルすることも可能である。 In the defluorinated hydrogen reaction of the gas phase of the present invention, the content of 1-chloro-3,3-difluoropropine is 10% by mass or less with respect to the total amount of the reaction crude liquid from the viewpoint of the selectivity of 1233 yd. Is preferable, and it is more preferably 5% by mass or less, and most preferably 1% by mass or less. The crude reaction solution in the present invention is a crude solution containing unreacted raw materials and reaction products.
If unreacted 244ca remains, it is also possible to concentrate 244ca by distillation and recycle it as a raw material of the present invention.
本発明の製造方法においては、目的物の１２３３ｙｄ以外に、未反応の２４４ｃａ、および１２３３ｙｄがさらに脱フッ化水素反応して生成する１－クロロ－３，３－ジフルオロプロピン等が含まれうる。これら含む反応粗液から、１２３３ｙｄを回収する際には、一般的な蒸留などによる分離精製方法を採用することが好ましい。ここで、生成物中に１２３３ｙｄ（Ｚ）を含む場合は、２４４ｃａと１２３３ｙｄ（Ｚ）の沸点が近いことから、精度の高い蒸留を行うことが好ましい。
また、１２３３ｙｄ（Ｚ）の収率を高くするために１２３３ｙｄ（Ｅ）と１２３３ｙｄ（Ｚ）の分離を蒸留などの分離精製方法で実施してもよい。 In the production method of the present invention, in addition to the target substance 1233yd, unreacted 244ca, 1-chloro-3,3-difluoropropine and the like produced by further defluorination hydrogen reaction of 1233yd may be included. When recovering 1233 yd from the reaction crude liquid containing these, it is preferable to adopt a separation and purification method by general distillation or the like. Here, when the product contains 1233 yd (Z), it is preferable to carry out highly accurate distillation because the boiling points of 244 ca and 1233 yd (Z) are close to each other.
Further, in order to increase the yield of 1233 yd (Z), the separation of 1233 yd (E) and 1233 yd (Z) may be carried out by a separation and purification method such as distillation.
また、１２３３ｙｄ（Ｚ）の収率を高くするために１２３３ｙｄ（Ｅ）と１２３３ｙｄ（Ｚ）の分離を蒸留などの分離精製方法で実施してもよい。 In the production method of the present invention, in addition to the target substance 1233yd, unreacted 244ca, 1-chloro-3,3-difluoropropine and the like produced by further defluorination hydrogen reaction of 1233yd may be included. When recovering 1233 yd from the reaction crude liquid containing these, it is preferable to adopt a separation and purification method by general distillation or the like. Here, when the product contains 1233 yd (Z), it is preferable to carry out highly accurate distillation because the boiling points of 244 ca and 1233 yd (Z) are close to each other.
Further, in order to increase the yield of 1233 yd (Z), the separation of 1233 yd (E) and 1233 yd (Z) may be carried out by a separation and purification method such as distillation.
本発明の製造方法により得られる１２３３ｙｄを上記のように分離精製して回収することで、１２３３ｙｄを高純度に含有する精製１２３３ｙｄが得られる。このようにして得られる精製１２３３ｙｄに、ＨＣｌ等の酸分や水、酸素が含まれると、その使用に際して設備が腐食したり、１２３３ｙｄの安定性が低下する等の可能性がある。したがって、酸分、つまり塩素イオンおよびフッ素イオンの含有量は、それぞれ、精製１２３３ｙｄの全量に対して、好ましくは１０質量ｐｐｍ未満、より好ましくは１質量ｐｐｍ未満、最も好ましくは０．１質量ｐｐｍ未満である。また、精製１２３３ｙｄにおける水分濃度は２０００質量ｐｐｍ未満が好ましく、１５００質量ｐｐｍ未満がより好ましく、１０００質量ｐｐｍ未満がさらに好ましく、最も好ましくは１００質量ｐｐｍ未満である。精製１２３３ｙｄにおける酸素濃度は１０００質量ｐｐｍ以下が好ましく、５００質量ｐｐｍ以下がより好ましい。上記範囲外では、１２３３ｙｄの分解が起きたり、脱脂洗浄性能が阻害されたりする可能性がある。
By separating, purifying and recovering 1233 yd obtained by the production method of the present invention as described above, purified 1233 yd containing 1233 yd with high purity can be obtained. If the purified 1233yd thus obtained contains an acid such as HCl, water, or oxygen, there is a possibility that the equipment may be corroded or the stability of the 1233yd may be lowered during its use. Therefore, the acid content, that is, the content of chloride ion and fluorine ion, is preferably less than 10 mass ppm, more preferably less than 1 mass ppm, and most preferably less than 0.1 mass ppm, respectively, with respect to the total amount of purified 1233 yd. Is. The water concentration in the purified 1233 yd is preferably less than 2000 mass ppm, more preferably less than 1500 mass ppm, still more preferably less than 1000 mass ppm, and most preferably less than 100 mass ppm. The oxygen concentration in the purified 1233 yd is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less. Outside the above range, decomposition of 1233 yd may occur and degreasing cleaning performance may be impaired.
１２３３ｙｄを高純度に含有する精製１２３３ｙｄは、１２３３ｙｄ（Ｚ）または１２３３ｙｄ（Ｅ）の一方のみであってもよいが、生産性を考慮すると１２３３ｙｄ（Ｚ）の割合が高いことが好ましい。精製１２３３ｙｄにおいて、１２３３ｙｄ（Ｚ）の含有量は５０質量％以上であることが好ましく、７５～９８質量％であることがより好ましく、９０～９８質量％であることが特に好ましい。
The purified 1233 yd containing 1233 yd with high purity may be only one of 1233 yd (Z) or 1233 yd (E), but the ratio of 1233 yd (Z) is preferably high in consideration of productivity. In the purified 1233 yd, the content of 1233 yd (Z) is preferably 50% by mass or more, more preferably 75 to 98% by mass, and particularly preferably 90 to 98% by mass.
気相での脱フッ化水素反応では、２４４ｃａを予熱し、気化させた後に、反応器に供給することが好ましい。この際の、予熱温度は、２４４ｃａの沸点以上、２００℃以下であることが好ましい。本明細書において、化合物の沸点は、圧力１．０１３×１０５Ｐａ（絶対圧）における値である。
In the defluorinated hydrogen reaction in the gas phase, it is preferable to preheat 244ca, vaporize it, and then supply it to the reactor. At this time, the preheating temperature is preferably 244 ca or more and 200 ° C. or less. In the present specification, the boiling point of the compound is the value of the pressure 1.013 × 10 5 Pa (absolute pressure).
気相での脱フッ化水素反応では、副生物の生成を抑えるためには、２４４ｃａを、希釈ガスと混合して、反応器に供給することが好ましい。希釈ガスとしては、窒素ガス、ヘリウムガス、アルゴンガスなどの不活性ガスを用いることができる。希釈ガスの量は、反応器へ供給される２４４ｃａの１ｍｏｌに対して０．１～１０ｍｏｌであることが好ましい。
希釈ガスを用いる場合、２４４ｃａを予熱する際には、２４４ｃａを希釈ガスと混合する前に予熱してもよく、混合した後に予熱してもよい。 In the defluorinated hydrogen reaction in the gas phase, it is preferable to mix 244ca with a diluting gas and supply it to the reactor in order to suppress the formation of by-products. As the diluting gas, an inert gas such as nitrogen gas, helium gas, or argon gas can be used. The amount of the diluted gas is preferably 0.1 to 10 mol with respect to 1 mol of 244ca supplied to the reactor.
When a diluted gas is used, when preheating 244ca, 244ca may be preheated before being mixed with the diluted gas, or may be preheated after mixing.
希釈ガスを用いる場合、２４４ｃａを予熱する際には、２４４ｃａを希釈ガスと混合する前に予熱してもよく、混合した後に予熱してもよい。 In the defluorinated hydrogen reaction in the gas phase, it is preferable to mix 244ca with a diluting gas and supply it to the reactor in order to suppress the formation of by-products. As the diluting gas, an inert gas such as nitrogen gas, helium gas, or argon gas can be used. The amount of the diluted gas is preferably 0.1 to 10 mol with respect to 1 mol of 244ca supplied to the reactor.
When a diluted gas is used, when preheating 244ca, 244ca may be preheated before being mixed with the diluted gas, or may be preheated after mixing.
以下に、本発明の実施例によって具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。例１、５および６が本発明の実施例、例２～４が比較例である。
Hereinafter, the present invention will be specifically described with reference to examples of the present invention, but the present invention is not limited to these examples. Examples 1, 5 and 6 are examples of the present invention, and Examples 2 to 4 are comparative examples.
（ガスクロマトグラフィーの条件）
以下の各種化合物の製造において、得られた反応生成物の組成分析はガスクロマトグラフィー（ＧＣ）を用いて行った。カラムはＤＢ－１３０１（長さ６０ｍ×内径２５０μｍ×厚さ１μｍ、アジレント・テクノロジー株式会社製）を用いた。 (Conditions for gas chromatography)
In the production of the following various compounds, the composition analysis of the obtained reaction product was performed using gas chromatography (GC). As the column, DB-1301 (length 60 m × inner diameter 250 μm × thickness 1 μm, manufactured by Agilent Technologies, Inc.) was used.
以下の各種化合物の製造において、得られた反応生成物の組成分析はガスクロマトグラフィー（ＧＣ）を用いて行った。カラムはＤＢ－１３０１（長さ６０ｍ×内径２５０μｍ×厚さ１μｍ、アジレント・テクノロジー株式会社製）を用いた。 (Conditions for gas chromatography)
In the production of the following various compounds, the composition analysis of the obtained reaction product was performed using gas chromatography (GC). As the column, DB-1301 (length 60 m × inner diameter 250 μm × thickness 1 μm, manufactured by Agilent Technologies, Inc.) was used.
（２４４ｃａの製造例）
２４４ｃａを以下の方法によって製造した。以下の方法は、上記式（２）に示すようにＴＦＰＯを塩化チオニルによって塩素化して２４４ｃａを得る方法である。
撹拌機、ジムロート、冷却器、ラシヒリングを充填したガラス蒸留塔（段数測定値５段）を設置した２リットル四つ口フラスコにＴＦＰＯの１２０４ｇ（９．１２モル）およびＮ，Ｎ－ジメチルホルムアミド（ＤＭＦ）の１２ｇ（０．１７ｇ）を加えた。塩化チオニルの１０７８ｇ（０．１２モル）を滴下し、室温で１２時間撹拌した。その後、反応器を１００℃に加熱し、還流タイマーにより還流時間／留出時間の比を５／１で反応蒸留を行った。留出した２４４ｃａは２０質量％水酸化カリウム水溶液で中和した。回収した２４４ｃａ（純度１００％）は、９７９ｇ（６．５０モル）であった。 (Manufacturing example of 244ca)
244ca was produced by the following method. The following method is a method for obtaining 244ca by chlorinating TFPO with thionyl chloride as shown in the above formula (2).
1204 g (9.12 mol) of TFPO and N, N-dimethylformamide (DMF) in a 2-liter four-necked flask equipped with a glass distillation column (measured number of stages: 5 stages) filled with a stirrer, Dimroth condenser, condenser, and Raschig ring. ) 12 g (0.17 g) was added. 1078 g (0.12 mol) of thionyl chloride was added dropwise, and the mixture was stirred at room temperature for 12 hours. Then, the reactor was heated to 100 ° C., and the reaction distillation was performed with a reflux time / distillation time ratio of 5/1 by a reflux timer. The distilled 244ca was neutralized with a 20 mass% potassium hydroxide aqueous solution. The recovered 244ca (100% pure) was 979 g (6.50 mol).
２４４ｃａを以下の方法によって製造した。以下の方法は、上記式（２）に示すようにＴＦＰＯを塩化チオニルによって塩素化して２４４ｃａを得る方法である。
撹拌機、ジムロート、冷却器、ラシヒリングを充填したガラス蒸留塔（段数測定値５段）を設置した２リットル四つ口フラスコにＴＦＰＯの１２０４ｇ（９．１２モル）およびＮ，Ｎ－ジメチルホルムアミド（ＤＭＦ）の１２ｇ（０．１７ｇ）を加えた。塩化チオニルの１０７８ｇ（０．１２モル）を滴下し、室温で１２時間撹拌した。その後、反応器を１００℃に加熱し、還流タイマーにより還流時間／留出時間の比を５／１で反応蒸留を行った。留出した２４４ｃａは２０質量％水酸化カリウム水溶液で中和した。回収した２４４ｃａ（純度１００％）は、９７９ｇ（６．５０モル）であった。 (Manufacturing example of 244ca)
244ca was produced by the following method. The following method is a method for obtaining 244ca by chlorinating TFPO with thionyl chloride as shown in the above formula (2).
1204 g (9.12 mol) of TFPO and N, N-dimethylformamide (DMF) in a 2-liter four-necked flask equipped with a glass distillation column (measured number of stages: 5 stages) filled with a stirrer, Dimroth condenser, condenser, and Raschig ring. ) 12 g (0.17 g) was added. 1078 g (0.12 mol) of thionyl chloride was added dropwise, and the mixture was stirred at room temperature for 12 hours. Then, the reactor was heated to 100 ° C., and the reaction distillation was performed with a reflux time / distillation time ratio of 5/1 by a reflux timer. The distilled 244ca was neutralized with a 20 mass% potassium hydroxide aqueous solution. The recovered 244ca (100% pure) was 979 g (6.50 mol).
（例１）
垂直固定床反応器（材質：ＳＵＳ３１６、内径２２．６ｍｍ×高さ２００ｍｍ）の中心に差込管（材質：ＳＵＳ３１６、直径：３ｍｍ）を導入し、その中にＫ型熱電対を挿入し、内温を測定した。反応器の中央部にアルミナ（日揮触媒化成株式会社製、Ｎ６１２Ｎ）を充填し、ここを触媒層とした。該触媒層を、窒素ガスを３００ｍＬ／ｍｉｎで供給しながら電気炉によって３００℃に加熱し、乾燥させた。その後トリフルオロメタン（Ｒ－２３）を３００ｍＬ／ｍｉｎで供給し、出口ガスの組成が安定化するまで約１０時間触媒を活性化した。ガスフィードラインおよび原料供給ラインを接続した７０℃に加熱された原料予熱混合ラインを反応器の上部に接続した。
窒素は、マスフローコントローラを用いてガス流量を調整し、ガスフィードラインから原料予熱混合ラインに供給した。原料である２４４ｃａは、プランジャーポンプを用いて液流量を調整し、原料供給ラインを通して７０℃に加熱された原料予熱混合ラインに供給した。生成物は、反応器の下部から連続的に取り出した。反応器の下部から取り出された生成物の一部を採取し、ガスクロマトグラフィ（ＧＣ）による組成分析を行った。以下、反応器の下部から取り出された生成物を出口ガスという。
表１に示す条件にて窒素および原料を反応器に導入し、連続で１０時間反応させた。反応終了直前に出口ガスの一部を採取し、ガスクロマトグラフィ（ＧＣ）による組成分析を行った。結果を表１に示す。 (Example 1)
An insertion tube (material: SUS316, diameter: 3 mm) is introduced in the center of a vertical fixed floor reactor (material: SUS316, inner diameter 22.6 mm x height 200 mm), and a K-type thermocouple is inserted into it. The temperature was measured. Alumina (manufactured by JGC Catalysts and Chemicals Co., Ltd., N612N) was filled in the central part of the reactor, and this was used as a catalyst layer. The catalyst layer was heated to 300 ° C. by an electric furnace while supplying nitrogen gas at 300 mL / min and dried. After that, trifluoromethane (R-23) was supplied at 300 mL / min, and the catalyst was activated for about 10 hours until the composition of the outlet gas was stabilized. A raw material preheating mixing line heated to 70 ° C. connecting a gas feed line and a raw material supply line was connected to the upper part of the reactor.
Nitrogen was supplied from the gas feed line to the raw material preheating mixing line by adjusting the gas flow rate using a mass flow controller. The raw material 244ca was supplied to a raw material preheating mixing line heated to 70 ° C. through a raw material supply line by adjusting the liquid flow rate using a plunger pump. The product was continuously removed from the bottom of the reactor. A part of the product taken out from the lower part of the reactor was collected and subjected to composition analysis by gas chromatography (GC). Hereinafter, the product taken out from the lower part of the reactor is referred to as an outlet gas.
Nitrogen and raw materials were introduced into the reactor under the conditions shown in Table 1 and reacted continuously for 10 hours. Immediately before the end of the reaction, a part of the outlet gas was sampled and the composition was analyzed by gas chromatography (GC). The results are shown in Table 1.
垂直固定床反応器（材質：ＳＵＳ３１６、内径２２．６ｍｍ×高さ２００ｍｍ）の中心に差込管（材質：ＳＵＳ３１６、直径：３ｍｍ）を導入し、その中にＫ型熱電対を挿入し、内温を測定した。反応器の中央部にアルミナ（日揮触媒化成株式会社製、Ｎ６１２Ｎ）を充填し、ここを触媒層とした。該触媒層を、窒素ガスを３００ｍＬ／ｍｉｎで供給しながら電気炉によって３００℃に加熱し、乾燥させた。その後トリフルオロメタン（Ｒ－２３）を３００ｍＬ／ｍｉｎで供給し、出口ガスの組成が安定化するまで約１０時間触媒を活性化した。ガスフィードラインおよび原料供給ラインを接続した７０℃に加熱された原料予熱混合ラインを反応器の上部に接続した。
窒素は、マスフローコントローラを用いてガス流量を調整し、ガスフィードラインから原料予熱混合ラインに供給した。原料である２４４ｃａは、プランジャーポンプを用いて液流量を調整し、原料供給ラインを通して７０℃に加熱された原料予熱混合ラインに供給した。生成物は、反応器の下部から連続的に取り出した。反応器の下部から取り出された生成物の一部を採取し、ガスクロマトグラフィ（ＧＣ）による組成分析を行った。以下、反応器の下部から取り出された生成物を出口ガスという。
表１に示す条件にて窒素および原料を反応器に導入し、連続で１０時間反応させた。反応終了直前に出口ガスの一部を採取し、ガスクロマトグラフィ（ＧＣ）による組成分析を行った。結果を表１に示す。 (Example 1)
An insertion tube (material: SUS316, diameter: 3 mm) is introduced in the center of a vertical fixed floor reactor (material: SUS316, inner diameter 22.6 mm x height 200 mm), and a K-type thermocouple is inserted into it. The temperature was measured. Alumina (manufactured by JGC Catalysts and Chemicals Co., Ltd., N612N) was filled in the central part of the reactor, and this was used as a catalyst layer. The catalyst layer was heated to 300 ° C. by an electric furnace while supplying nitrogen gas at 300 mL / min and dried. After that, trifluoromethane (R-23) was supplied at 300 mL / min, and the catalyst was activated for about 10 hours until the composition of the outlet gas was stabilized. A raw material preheating mixing line heated to 70 ° C. connecting a gas feed line and a raw material supply line was connected to the upper part of the reactor.
Nitrogen was supplied from the gas feed line to the raw material preheating mixing line by adjusting the gas flow rate using a mass flow controller. The raw material 244ca was supplied to a raw material preheating mixing line heated to 70 ° C. through a raw material supply line by adjusting the liquid flow rate using a plunger pump. The product was continuously removed from the bottom of the reactor. A part of the product taken out from the lower part of the reactor was collected and subjected to composition analysis by gas chromatography (GC). Hereinafter, the product taken out from the lower part of the reactor is referred to as an outlet gas.
Nitrogen and raw materials were introduced into the reactor under the conditions shown in Table 1 and reacted continuously for 10 hours. Immediately before the end of the reaction, a part of the outlet gas was sampled and the composition was analyzed by gas chromatography (GC). The results are shown in Table 1.
（例２～４）
反応器として垂直固定床反応器（材質：ＳＵＳ３１６、内径２２．６ｍｍ×高さ２００ｍｍ）、触媒にアルミナ（日揮触媒化成株式会社製、Ｎ６１２Ｎ）を使用し、実施例１と同様の手順で、３００℃で触媒を乾燥させた。その後クロロジフルオロメタン（Ｒ－２２）を３００ｍＬ／ｍｉｎで供給し、出口ガスの組成が安定化するまで約１０時間触媒を活性化した。反応温度、その他反応条件を表１に示す条件に変更した以外は実施例１と同様の手順で反応を行わせた。反応条件および結果を表１に示す。 (Examples 2 to 4)
A vertical fixed-bed reactor (material: SUS316, inner diameter 22.6 mm x height 200 mm) was used as the reactor, and alumina (manufactured by JGC Catalysts and Chemicals Co., Ltd., N612N) was used as the catalyst. The catalyst was dried at ° C. After that, chlorodifluoromethane (R-22) was supplied at 300 mL / min, and the catalyst was activated for about 10 hours until the composition of the outlet gas was stabilized. The reaction was carried out in the same procedure as in Example 1 except that the reaction temperature and other reaction conditions were changed to the conditions shown in Table 1. The reaction conditions and results are shown in Table 1.
反応器として垂直固定床反応器（材質：ＳＵＳ３１６、内径２２．６ｍｍ×高さ２００ｍｍ）、触媒にアルミナ（日揮触媒化成株式会社製、Ｎ６１２Ｎ）を使用し、実施例１と同様の手順で、３００℃で触媒を乾燥させた。その後クロロジフルオロメタン（Ｒ－２２）を３００ｍＬ／ｍｉｎで供給し、出口ガスの組成が安定化するまで約１０時間触媒を活性化した。反応温度、その他反応条件を表１に示す条件に変更した以外は実施例１と同様の手順で反応を行わせた。反応条件および結果を表１に示す。 (Examples 2 to 4)
A vertical fixed-bed reactor (material: SUS316, inner diameter 22.6 mm x height 200 mm) was used as the reactor, and alumina (manufactured by JGC Catalysts and Chemicals Co., Ltd., N612N) was used as the catalyst. The catalyst was dried at ° C. After that, chlorodifluoromethane (R-22) was supplied at 300 mL / min, and the catalyst was activated for about 10 hours until the composition of the outlet gas was stabilized. The reaction was carried out in the same procedure as in Example 1 except that the reaction temperature and other reaction conditions were changed to the conditions shown in Table 1. The reaction conditions and results are shown in Table 1.
触媒の活性化をトリフルオロメタンの代わりにフッ化水素またはジフルオロメタンで行う以外は例１と同様の手順で反応を行うと、例１と同様の結果となる。そのような例として、以下に（例５）および（例６）を示す。
If the reaction is carried out in the same procedure as in Example 1 except that the catalyst is activated with hydrogen fluoride or difluoromethane instead of trifluoromethane, the same result as in Example 1 is obtained. As such examples, (Example 5) and (Example 6) are shown below.
（例５）
反応器として垂直固定床反応器（材質：ＳＵＳ３１６、内径２２．６ｍｍ×高さ２００ｍｍ）、触媒にアルミナ（日揮触媒化成株式会社製、Ｎ６１２Ｎ）を使用し、実施例１と同様の手順で、３００℃で触媒を乾燥させた。その後フッ化水素を１００ｍＬ／ｍｉｎで供給し、約１０時間触媒を活性化した。反応温度、その他反応条件を表２に示す条件に変更した以外は実施例１と同様の手順で反応を行わせた。反応条件および結果を表２に示す。 (Example 5)
A vertical fixed-bed reactor (material: SUS316, inner diameter 22.6 mm x height 200 mm) was used as the reactor, and alumina (manufactured by JGC Catalysts and Chemicals Co., Ltd., N612N) was used as the catalyst. The catalyst was dried at ° C. After that, hydrogen fluoride was supplied at 100 mL / min to activate the catalyst for about 10 hours. The reaction was carried out in the same procedure as in Example 1 except that the reaction temperature and other reaction conditions were changed to the conditions shown in Table 2. The reaction conditions and results are shown in Table 2.
反応器として垂直固定床反応器（材質：ＳＵＳ３１６、内径２２．６ｍｍ×高さ２００ｍｍ）、触媒にアルミナ（日揮触媒化成株式会社製、Ｎ６１２Ｎ）を使用し、実施例１と同様の手順で、３００℃で触媒を乾燥させた。その後フッ化水素を１００ｍＬ／ｍｉｎで供給し、約１０時間触媒を活性化した。反応温度、その他反応条件を表２に示す条件に変更した以外は実施例１と同様の手順で反応を行わせた。反応条件および結果を表２に示す。 (Example 5)
A vertical fixed-bed reactor (material: SUS316, inner diameter 22.6 mm x height 200 mm) was used as the reactor, and alumina (manufactured by JGC Catalysts and Chemicals Co., Ltd., N612N) was used as the catalyst. The catalyst was dried at ° C. After that, hydrogen fluoride was supplied at 100 mL / min to activate the catalyst for about 10 hours. The reaction was carried out in the same procedure as in Example 1 except that the reaction temperature and other reaction conditions were changed to the conditions shown in Table 2. The reaction conditions and results are shown in Table 2.
（例６）
反応器として垂直固定床反応器（材質：ＳＵＳ３１６、内径２２．６ｍｍ×高さ２００ｍｍ）、触媒にアルミナ（日揮触媒化成株式会社製、Ｎ６１２Ｎ）を使用し、実施例１と同様の手順で、３００℃で触媒を乾燥させた。その後ジフルオロメタン（Ｒ－３２）を３００ｍＬ／ｍｉｎで供給し、約１０時間触媒を活性化した。反応温度、その他反応条件を表２に示す条件に変更した以外は実施例１と同様の手順で反応を行わせた。反応条件および結果を表２に示す。 (Example 6)
A vertical fixed-bed reactor (material: SUS316, inner diameter 22.6 mm x height 200 mm) was used as the reactor, and alumina (manufactured by JGC Catalysts and Chemicals Co., Ltd., N612N) was used as the catalyst. The catalyst was dried at ° C. Then, difluoromethane (R-32) was supplied at 300 mL / min to activate the catalyst for about 10 hours. The reaction was carried out in the same procedure as in Example 1 except that the reaction temperature and other reaction conditions were changed to the conditions shown in Table 2. The reaction conditions and results are shown in Table 2.
反応器として垂直固定床反応器（材質：ＳＵＳ３１６、内径２２．６ｍｍ×高さ２００ｍｍ）、触媒にアルミナ（日揮触媒化成株式会社製、Ｎ６１２Ｎ）を使用し、実施例１と同様の手順で、３００℃で触媒を乾燥させた。その後ジフルオロメタン（Ｒ－３２）を３００ｍＬ／ｍｉｎで供給し、約１０時間触媒を活性化した。反応温度、その他反応条件を表２に示す条件に変更した以外は実施例１と同様の手順で反応を行わせた。反応条件および結果を表２に示す。 (Example 6)
A vertical fixed-bed reactor (material: SUS316, inner diameter 22.6 mm x height 200 mm) was used as the reactor, and alumina (manufactured by JGC Catalysts and Chemicals Co., Ltd., N612N) was used as the catalyst. The catalyst was dried at ° C. Then, difluoromethane (R-32) was supplied at 300 mL / min to activate the catalyst for about 10 hours. The reaction was carried out in the same procedure as in Example 1 except that the reaction temperature and other reaction conditions were changed to the conditions shown in Table 2. The reaction conditions and results are shown in Table 2.
本発明の製造方法によれば、入手が容易で安定的に供給されうる２４４ｃａを用いて、特別な操作や反応装置を用いることなく反応を実施することで、高反応率および高選択率で１２３３ｙｄを製造でき、工業規模の大量生産の適用が可能となった。
According to the production method of the present invention, the reaction is carried out using 244ca, which is easily available and can be stably supplied, without using a special operation or a reaction device, thereby having a high reaction rate and a high selectivity of 1233yd. It has become possible to apply industrial-scale mass production.
なお、２０２０年７月１５日に出願された日本特許出願２０１９－１２１３８０号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2019-121380 filed on July 15, 2020 are cited here as the disclosure of the specification of the present invention. It is something to incorporate.
Claims (15)
- ３－クロロ－１，１，２，２－テトラフルオロプロパンを、触媒の存在下、気相で脱フッ化水素反応させて、１－クロロ－２，３，３－トリフルオロプロペンを製造する方法であって、
前記触媒として、気相において塩素原子を含まないフッ素化合物で活性化した金属化合物触媒を用いることを特徴とする１－クロロ－２，３，３－トリフルオロプロペンの製造方法。 A method for producing 1-chloro-2,3,3-trifluoropropene by subjecting 3-chloro-1,1,2,2-tetrafluoropropane to a hydrogen fluoride reaction in the gas phase in the presence of a catalyst. And
A method for producing 1-chloro-2,3,3-trifluoropropene, which comprises using a metal compound catalyst activated with a fluorine compound containing no chlorine atom in the gas phase as the catalyst. - 前記金属化合物触媒が、Ｃｒ、Ａｌ、Ｚｎ、ＴｉおよびＮｉからなる群より選ばれる少なくとも１種の金属元素を含む金属化合物触媒である、請求項１に記載の製造方法。 The production method according to claim 1, wherein the metal compound catalyst is a metal compound catalyst containing at least one metal element selected from the group consisting of Cr, Al, Zn, Ti and Ni.
- 前記金属化合物触媒が、金属の酸化物、金属のフッ化物、または金属の酸化フッ素化物である、請求項１～２のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 and 2, wherein the metal compound catalyst is a metal oxide, a metal fluoride, or a metal oxide fluoride.
- 前記金属化合物触媒が、酸化アルミニウム、または酸化クロムである、請求項１～３のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 3, wherein the metal compound catalyst is aluminum oxide or chromium oxide.
- 前記金属化合物触媒の活性化が、前記塩素原子を含まないフッ素化合物と前記金属化合物触媒とを気相で接触させることによりなされる、請求項１～４のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 4, wherein the activation of the metal compound catalyst is performed by bringing the chlorine atom-free fluorine compound and the metal compound catalyst into contact with each other in a gas phase.
- 前記塩素原子を含まないフッ素化合物が、フッ化水素および炭素数１～３の塩素原子を含まないフッ素化合物である、請求項１～５のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 5, wherein the fluorine compound containing no chlorine atom is a fluorine compound containing hydrogen fluoride and a chlorine atom having 1 to 3 carbon atoms.
- 前記塩素原子を含まないフッ素化合物が、フッ化水素、トリフルオロメタンまたはジフルオロメタンである、請求項１～６のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 6, wherein the fluorine compound containing no chlorine atom is hydrogen fluoride, trifluoromethane or difluoromethane.
- 前記金属化合物触媒の活性化における活性化処理温度が１００～４００℃である、請求項１～７のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 7, wherein the activation treatment temperature in the activation of the metal compound catalyst is 100 to 400 ° C.
- 前記金属化合物触媒の活性化における塩素原子を含まないフッ素化合物と触媒の接触時間が０．１～１００秒間である、請求項１～８のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 8, wherein the contact time between the fluorine atom-free fluorine compound and the catalyst in the activation of the metal compound catalyst is 0.1 to 100 seconds.
- 前記脱フッ化水素反応における反応温度が２００～４００℃である、請求項１～９のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 9, wherein the reaction temperature in the defluorinated hydrogen reaction is 200 to 400 ° C.
- 前記脱フッ化水素反応における３－クロロ－１，１，２，２－テトラフルオロプロパンと触媒の接触時間が０．１～１００秒間である、請求項１～１０のいずれか一項に記載の製造方法。 The invention according to any one of claims 1 to 10, wherein the contact time between 3-chloro-1,1,2,2-tetrafluoropropane and the catalyst in the defluorinated hydrogen reaction is 0.1 to 100 seconds. Production method.
- 前記脱フッ化水素反応後の反応粗液における１－クロロ－３，３－ジフルオロプロピンの含有量が、反応粗液全量に対して１０質量％以下である、請求項１～１１のいずれか一項に記載の製造方法。 Any of claims 1 to 11, wherein the content of 1-chloro-3,3-difluoropropine in the reaction crude solution after the hydrogen fluoride reaction is 10% by mass or less based on the total amount of the reaction crude solution. The manufacturing method according to paragraph 1.
- 前記脱フッ化水素反応において、３－クロロ－１，１，２，２－テトラフルオロプロパンを、希釈ガスと混合して、反応器に供給する、請求項１～１２のいずれか一項に記載の製造方法。 The invention according to any one of claims 1 to 12, wherein in the defluorinated hydrogen reaction, 3-chloro-1,1,2,2-tetrafluoropropane is mixed with a diluting gas and supplied to the reactor. Manufacturing method.
- 前記脱フッ化水素反応後の反応粗液から、精製された１－クロロ－２，３，３－トリフルオロプロペンを回収する、請求項１～１３のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 13, wherein the purified 1-chloro-2,3,3-trifluoropropene is recovered from the reaction crude liquid after the defluorinated hydrogen reaction.
- 前記精製された１－クロロ－２，３，３－トリフルオロプロペンにおける、塩素イオンおよびフッ素イオンの含有量は、それぞれ、前記精製された１－クロロ－２，３，３－トリフルオロプロペンの全量に対して、１０質量ｐｐｍ未満であり、
水分濃度は、前記精製された１－クロロ－２，３，３－トリフルオロプロペンの全量に対して、２０００質量ｐｐｍ未満であり、
酸素濃度は、前記精製された１－クロロ－２，３，３－トリフルオロプロペンの全量に対して、１０００質量ｐｐｍ以下である、請求項１４に記載の製造方法。 The content of chloride ion and fluorine ion in the purified 1-chloro-2,3,3-trifluoropropene is the total amount of the purified 1-chloro-2,3,3-trifluoropropene, respectively. On the other hand, it is less than 10 mass ppm,
The water concentration was less than 2000 mass ppm with respect to the total amount of the purified 1-chloro-2,3,3-trifluoropropene.
The production method according to claim 14, wherein the oxygen concentration is 1000 mass ppm or less with respect to the total amount of the purified 1-chloro-2,3,3-trifluoropropene.
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