JPH02172934A - Production of 2,2-dichloro-1,1,1,2-tetrafluoroethane - Google Patents
Production of 2,2-dichloro-1,1,1,2-tetrafluoroethaneInfo
- Publication number
- JPH02172934A JPH02172934A JP63324998A JP32499888A JPH02172934A JP H02172934 A JPH02172934 A JP H02172934A JP 63324998 A JP63324998 A JP 63324998A JP 32499888 A JP32499888 A JP 32499888A JP H02172934 A JPH02172934 A JP H02172934A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen fluoride
- alumina
- catalyst
- gamma
- raw material
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- BAMUEXIPKSRTBS-UHFFFAOYSA-N 1,1-dichloro-1,2,2,2-tetrafluoroethane Chemical compound FC(F)(F)C(F)(Cl)Cl BAMUEXIPKSRTBS-UHFFFAOYSA-N 0.000 title claims description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000010574 gas phase reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 4
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000003507 refrigerant Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000003682 fluorination reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
【産業上の利用分野］
本発明は、適度な安定性を有する冷媒である１４．１．
２−テトラフルオロエタンの原料として有用な２．２−
ジクロロ−１，１，１，２−テトラフルオロエタン（以
後、Ｒ−１１４ａと略す、）の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides a refrigerant with moderate stability, 14.1.
2.2- useful as a raw material for 2-tetrafluoroethane
The present invention relates to a method for producing dichloro-1,1,1,2-tetrafluoroethane (hereinafter abbreviated as R-114a).
［従来技術とその解決しようとする１ｌｆｌｌ従来、Ｒ
−１１４ａを製造するには１，１．１−トリクロ０−２
．２．２− ）リフルオロエタン（以後、Ｒ−１１３ａ
と略す、）を触媒の存在下、フッ化水素でフッ素化する
方法が知られている。[Prior art and its solution 1lfll Conventional technology, R
-1,1.1-Trichlor0-2 to produce 114a
．． 2.2-) Rifluoroethane (hereinafter referred to as R-113a
A method of fluorinating (abbreviated as ) with hydrogen fluoride in the presence of a catalyst is known.
この反応に使われる触媒としては、■五塩化アンチモン
［Ｈｅｎｎｅ、Ｒｕｈ、Ｊ、Ａｍ、Ｃｈｅｍ、Ｓｏｃ、
、Ｔｏ、１０２５（１９４８）］ 、■塩化アルミニウ
ムをフッ素化したフッ化アルミニウム（米国特許筒２，
７４８．１７７号）■工業的製造法による市販のフッ化
アルミニウム粉末［ＭＪｅｃｃｈｉｏ、Ｇ、Ｇｒｏｐｐ
ｅｌ目、Ｊ、Ｃ，τａｔｊｏｗ、Ｊ。Catalysts used in this reaction include: ■ Antimony pentachloride [Henne, Ruh, J, Am, Chem, Soc,
, To, 1025 (1948)], ■ Aluminum fluoride obtained by fluorinating aluminum chloride (U.S. Patent No. 2,
No. 748.177) ■ Commercially available aluminum fluoride powder by industrial production method [MJecchio, G., Gropp
el order, J., C., τatjow, J.;
Ｆｌｕｏｒｉｎｅ Ｃｈｅｍ、４．１１７（１９７４）
］■酸化クロム［Ｌ。Fluorine Chem, 4.117 (1974)
]■Chromium oxide [L.
Ｍａｒａｎｇｏｎｉ ｅｔ ａｌ、、Ｃｈｉｍ、Ｉ
ｎｄ、（Ｍｉｌａｎ）、、６４，１３５（１９８２）］
等が提案されている。しかしながら、■の方法は腐食性
の五塩化アンチモンを使用するため製造装置の材料等の
選定が難しく、実験室での製造に限られているため実用
的でない。Marangoni et al., Chim, I.
(Milan), 64, 135 (1982)]
etc. have been proposed. However, method (2) uses corrosive antimony pentachloride, making it difficult to select materials for the manufacturing equipment, and is not practical because it is limited to manufacturing in a laboratory.
■〜■の反応は気相反応であるので製造装置としては比
較的簡単な構造となり基本的には工業化に適した方法で
あるといえるが、■の原料である塩化アルミニウムは吸
湿性が大きいため触媒調整が難しく、■は触媒自体は容
易に入手でき好ましいが、十分な活性を示さないという
問題点がある。さらに■は触媒活性には優れるが毒性等
の問題から使用済み触媒の廃棄や生産現場での環境に問
題がある。Since the reactions of ■ to ■ are gas phase reactions, the manufacturing equipment has a relatively simple structure and is basically a method suitable for industrialization.However, aluminum chloride, the raw material for (■), is highly hygroscopic. Catalyst preparation is difficult, and although the catalyst itself is easily available and is preferred, it does not exhibit sufficient activity. Furthermore, although ① has excellent catalytic activity, there are problems with the disposal of used catalysts and the environment at production sites due to issues such as toxicity.
［課題を解決するための手段］
本発明者らはこのような現状に鑑み、経済的かつ工業的
に有利なＲ−１１４ａの製造方法につき種々の検討を行
った。普通、ハロゲン化炭化水素とフッ化水素との反応
による気相フッ素化の触媒には、多くの金属酸化物、金
属ハロゲン化物がそれ自身単独の成型体、またはそれを
活性炭、アルミナ等の担体に担持させた系が知られてい
るが、その中で量も一般的なものはクロムを活性金属と
するものである。[Means for Solving the Problems] In view of the current situation, the present inventors conducted various studies on an economically and industrially advantageous method for producing R-114a. Usually, catalysts for gas-phase fluorination through the reaction of halogenated hydrocarbons and hydrogen fluoride contain many metal oxides and metal halides either in the form of individual molds or in a carrier such as activated carbon or alumina. Supported systems are known, among which the most common one is one in which chromium is the active metal.
しかし、ハロゲン化炭化水素をフッ化水素でフッ素化す
る場合、クロムやニッケル等をアルミナ等に担持させた
触媒を用いると塩素原子のフッ素原子による置換反応活
性は著しく高く、Ｒ−１１３ａの場合Ｒ−１１４ａが生
成するだけでなく、さらにフン素化の進んだクロロベン
クンフルオロエタンの副生を伴いＲ１１４ａの選択率を
低下させる。フッ化アルミ自体がフッ素化活性をもっこ
と自体は公知であるが、通常同時に異性化、不均化が起
こり所望のｔＩＩＦＩ質のみ得る目的には適さない、し
かしながら、本発明者らは上記問題点を解決すべく鋭意
検討を行った結果、Ｒ−１１３ａを原料とし、フッ化水
素で適度にフッ素化したγ−アルミナを触媒としてフッ
素水素と反応を行うことにより極めて選択率よく目的物
のＲ−１１４ａが得られることを見出し、本発明に到達
したものである。However, when fluorinating halogenated hydrocarbons with hydrogen fluoride, if a catalyst in which chromium, nickel, etc. are supported on alumina or the like is used, the substitution reaction activity of chlorine atoms with fluorine atoms is extremely high, and in the case of R-113a, R -114a is not only produced, but also chlorobencune fluoroethane, which is highly fluorinated, is produced as a by-product, thereby reducing the selectivity of R114a. Although it is known that aluminum fluoride itself has fluorination activity, it usually undergoes isomerization and disproportionation at the same time, making it unsuitable for obtaining only the desired tIIFI quality.However, the present inventors have solved the above problems. As a result of intensive studies to solve the problem, we found that the target R- The present invention was achieved based on the discovery that 114a can be obtained.
すなわち本発明は、Ｒ−１１３ａとフン化水素の気相反
応を行う際、γ−アルミナをフッ化水素で処理した触媒
を使用することを特徴とするＲ１１−１ａの製造法であ
る。That is, the present invention is a method for producing R11-1a characterized by using a catalyst obtained by treating γ-alumina with hydrogen fluoride when performing a gas phase reaction between R-113a and hydrogen fluoride.
触媒の調整法としては、直径的５■の球状γ−アルミナ
を、水分等がふくまれている場合最初２５０”Ｃ以上で
乾燥し、その後フッ化水素・窒素混合ガスにより２５０
℃でフッ素水素処理し、さらに４００℃に昇温してフッ
素処理を続行する。To prepare the catalyst, spherical γ-alumina with a diameter of 5 cm is first dried at 250"C or higher if it contains moisture, and then heated to 250"C with a hydrogen fluoride/nitrogen mixed gas.
The fluorine and hydrogen treatment is carried out at 400°C, and the temperature is further raised to 400°C to continue the fluorine treatment.
このような処理により、Ｔ−アルミナの６０〜８０％が
フッ素化され、且つこのフッ化アルミニウムがγ−アル
ミナ中にうまく分散しているため、本発明のフッ素化反
応に適応した触媒活性を示すと考えられる。Through such treatment, 60 to 80% of T-alumina is fluorinated, and this aluminum fluoride is well dispersed in γ-alumina, so it exhibits catalytic activity suitable for the fluorination reaction of the present invention. it is conceivable that.
上述のようにして調整された触媒を用い、通常ニッケル
あるいはステンレス製の反応管に上記触媒を充填した後
、原料とフッ化水素の混合物を原料の沸点以上に予熱し
、反応管に導入する。After filling a reaction tube, usually made of nickel or stainless steel, with the catalyst prepared as described above, a mixture of raw materials and hydrogen fluoride is preheated to a temperature higher than the boiling point of the raw materials and introduced into the reaction tube.
反応の際の反応器の温度は、３００〜３８０°Ｃが好ま
しい１反応器の温度が３００″Ｃより低い場合は、反応
率が低下し、一方３８０℃より高い場合は、副生物であ
るクロロペンタフルオロエタン（以後、Ｒ−１１５と略
す、）の生成率が増加して、目的物であるＲ１１４ａの
選択率が低下するため、好ましくない、接触時間は、反
応が十分に進行しかつ経済的な反応時間を考えると、２
〜１００秒が好ましい０次に、フッ化水素とＲ−１１３
ａのモル比（フッ化水素／Ｒ−１１３ａ）は０．８〜１
．８が好ましい、前記モル比が０．８より小さい場合、
反応率が低下し、一方モル比が１．８より大きい場合、
副生物のＲ−１１５の生成率が増加するためＲ１１４ａ
の選択率が低下し、好ましくない。 反応の際の圧力は
、特に限定する必要はないが、普通常圧から１０ｋｇ／
−の範囲で行う。The temperature of the reactor during the reaction is preferably 300-380°C.If the temperature of the reactor is lower than 300"C, the reaction rate will decrease, while if it is higher than 380"C, the by-product chloro The contact time is unfavorable because the production rate of pentafluoroethane (hereinafter abbreviated as R-115) increases and the selectivity of the target product R114a decreases. Considering the reaction time, 2
~100 seconds is preferable 0th order, hydrogen fluoride and R-113
The molar ratio of a (hydrogen fluoride/R-113a) is 0.8 to 1
．． 8 is preferred, when the molar ratio is less than 0.8,
If the reaction rate decreases while the molar ratio is greater than 1.8,
R114a increases the production rate of by-product R-115.
selectivity decreases, which is not preferable. The pressure during the reaction does not need to be particularly limited, but it is usually between normal pressure and 10 kg/
Perform within the range of –.
上述のような条件で反応を行うことにより、十分に高い
収率で目的のＲ−１！４ａを得ることができ、また反応
器より取り出される組成物を蒸留により分離して原料を
再使用できるため、その収率を上げることができる。ま
た、使用する触媒は工業的な“条件での使用において十
分耐久性のあるものであるが、ある程度の時間使用した
後、加熱等の処理により付着した有機物を取り除き、さ
らにフッ化水素処理することにより再使用できる。この
際、触媒は一旦フン化水素処理されているため、より簡
単にその処理を行うことができる。By carrying out the reaction under the conditions described above, the target R-1!4a can be obtained with a sufficiently high yield, and the raw material can be reused by separating the composition taken out from the reactor by distillation. Therefore, the yield can be increased. In addition, the catalyst used is sufficiently durable for use under industrial conditions, but after being used for a certain period of time, it is necessary to remove the attached organic matter by treatment such as heating, and then to treat it with hydrogen fluoride. In this case, since the catalyst has already been treated with hydrogen fluoride, the treatment can be carried out more easily.
本発明によって得られるＲ−１１４ａは公知の反応すな
わちＲ−１１４ａと水素との反応により、適当な安定性
を有し、冷媒として有用な１．１．１．２−テトラフル
オロエタン（以後、Ｒ−１３４ａと略す、）に変換する
ことができる。上記方法で使用される触媒としては、種
々の担体にパラジウムを担持させた触媒等があり、本出
願人のさきの提案にかかる特願昭６３−１３２３９５の
方法、すなわちＲ−１１４ａ等を活性アルミナ担持パラ
ジウム触媒の存在下、１２０〜２００°Ｃ未満の温度範
囲で水素と反応させることにより、目的のＲ−１３４ａ
を有利に製造することができる。The R-114a obtained by the present invention has appropriate stability through a known reaction, that is, the reaction between R-114a and hydrogen, and 1.1.1.2-tetrafluoroethane (hereinafter referred to as R -134a). Catalysts used in the above method include catalysts in which palladium is supported on various carriers. The desired R-134a can be obtained by reacting with hydrogen in the presence of a supported palladium catalyst in the temperature range from 120 to less than 200 °C.
can be advantageously manufactured.
［実施例］
以下、実施例により本発明を具体的に説明するが、本発
明は係る実施例に限定されるものではない。[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
実施例１ 直径５１のＴ−アルミナ２００ｃ ｃを直径５ ｃｍ。Example 1 T-alumina 200c with a diameter of 51 cm.
長さ５０ｃｍの円筒形ＳＵＳ反応管に充填した。A cylindrical SUS reaction tube with a length of 50 cm was filled.
窒素ガスを流しながら３００℃まで昇温し、１時間保っ
た後、その温度で窒素ガスに同伴したフッ化水素ガスを
供給した。充填された触媒のフッ素化によるホットスポ
ットが出口側に達したところで、反応器を４００℃に上
げ、その状態を１時間保ち、触媒副整を行った。The temperature was raised to 300° C. while flowing nitrogen gas, and after keeping it for 1 hour, hydrogen fluoride gas entrained in the nitrogen gas was supplied at that temperature. When the hot spot due to fluorination of the packed catalyst reached the outlet side, the temperature of the reactor was raised to 400°C, and this state was maintained for 1 hour to perform catalyst sub-conditioning.
上記方法で調整した触媒および反応管を用い、反応管内
の温度を３００°Ｃに保ち、原料のＲ−１１３ａとフン
化水素をそれぞれ０．５ ｓｏｌ／ｈｒ、 ０．５ｍｕ
ｌ／ｈｒで導入した０反応品出ロガスをガスクロマトグ
ラフで分析してその組成を調べた。原料の導入条件、反
応温度、生成物組成、反応率、選択率を第１表に示す。Using the catalyst and reaction tube prepared by the above method, the temperature inside the reaction tube was maintained at 300°C, and the raw materials R-113a and hydrogen fluoride were added at 0.5 sol/hr and 0.5 mu, respectively.
The zero reaction product log gas introduced at a rate of 1/hr was analyzed by gas chromatography to determine its composition. Table 1 shows the raw material introduction conditions, reaction temperature, product composition, reaction rate, and selectivity.
この触媒は、１００時間を経過後も活性の低下はなかっ
た。This catalyst showed no decrease in activity even after 100 hours had passed.
実施例２〜７
実施例１の触媒を用い、フッ化水素とＲ−１１３ａの流
量すなわちフン化水素／Ｒ−１１３ａ（モル比）を変え
て、実施例１と同様の操作で反応を行った。実施条件お
よびその結果を実施例１と同様に第１表に表わす。Examples 2 to 7 Using the catalyst of Example 1, a reaction was carried out in the same manner as in Example 1 by changing the flow rate of hydrogen fluoride and R-113a, that is, the hydrogen fluoride/R-113a (molar ratio). . The implementation conditions and results are shown in Table 1 as in Example 1.
［発明の効果］
本発明の方法によれば、原料のＲ−１１３ａをｒ −ア
ルミナをフン化水素により処理するという比較的容易な
方法により調整された耐久性の優れた触媒を用い、高い
反応率および選択率で目的とするＲ−１１４ａを製造す
ることができるという工業的に極めて優れたＲ−１１４
ａの製造法である。[Effects of the Invention] According to the method of the present invention, a highly durable catalyst prepared by treating R-113a as a raw material with a relatively easy method of treating r-alumina with hydrogen fluoride is used to achieve a high reaction rate. R-114 is industrially excellent and can produce the target R-114a with high efficiency and selectivity.
This is the manufacturing method of a.
特許出願人 セントラル硝子株式会社代理人 弁
理士 坂 本 栄Patent applicant Central Glass Co., Ltd. Agent Patent attorney Sakae Sakamoto
Claims (1)
オロエタンとフッ化水素の気相反応を行う際、γ−アル
ミナをフッ化水素で処理した触媒を使用することを特徴
とする２，２−ジクロロ−１，１，１，２−テトラフル
オロエタンの製造法(1) When performing a gas phase reaction between 1,1,1-trichloro-2,2,2-trifluoroethane and hydrogen fluoride, a catalyst in which γ-alumina is treated with hydrogen fluoride is used. Method for producing 2,2-dichloro-1,1,1,2-tetrafluoroethane
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63324998A JPH0692326B2 (en) | 1988-12-23 | 1988-12-23 | Method for producing 2,2-dichloro-1,1,1,2-tetrafluoroethane |
| US07/357,291 US4996379A (en) | 1988-05-30 | 1989-05-26 | Method of preparing 1,1,1,2-tetrafluoroethane from 1,1-dichloro-1,2,2,2-tetrafluoroethane |
| FR8907005A FR2631959A1 (en) | 1988-05-30 | 1989-05-29 | PROCESS FOR THE PREPARATION OF 1,1,1,2-TETRAFLUOROETHANE FROM 1,1-DICHLORO-1,2,2,2-TETRAFLUOROETHANE |
| GB8912325A GB2219796B (en) | 1988-05-30 | 1989-05-30 | Method of preparing 1,1,1,2-tetrafluoroethane from 1,1-dichloro-1,2,2,2-tetrafluoroethane |
| IT8920692A IT1230795B (en) | 1988-05-30 | 1989-05-30 | PROCEDURE FOR PREPARING 1,1,1,2 TETRAFLUOROETHANE FROM 1,1 DICHLOR 1,2,2,2 TETRAFLUOROETHANE. |
| DE3917573A DE3917573A1 (en) | 1988-05-30 | 1989-05-30 | METHOD FOR PRODUCING 1,1,1,2-TETRAFLUORETHANE FROM 1,1-DICHLOR-1,2,2,2-TETRAFLUORETHANE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63324998A JPH0692326B2 (en) | 1988-12-23 | 1988-12-23 | Method for producing 2,2-dichloro-1,1,1,2-tetrafluoroethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02172934A true JPH02172934A (en) | 1990-07-04 |
| JPH0692326B2 JPH0692326B2 (en) | 1994-11-16 |
Family
ID=18171993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63324998A Expired - Lifetime JPH0692326B2 (en) | 1988-05-30 | 1988-12-23 | Method for producing 2,2-dichloro-1,1,1,2-tetrafluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0692326B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1007822A5 (en) * | 1993-12-10 | 1995-10-31 | Solvay | SUPPORT FOR CATALYST hydrogenate ION SYSTEM INCLUDING THE CATALYST SUPPORT AND METHOD OF hydrodechlorination chlorofluorocarbons. |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01139541A (en) * | 1987-11-26 | 1989-06-01 | Asahi Glass Co Ltd | Production of 1,1-dichloro-1,2,2,2-tetrafluoroethane |
-
1988
- 1988-12-23 JP JP63324998A patent/JPH0692326B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01139541A (en) * | 1987-11-26 | 1989-06-01 | Asahi Glass Co Ltd | Production of 1,1-dichloro-1,2,2,2-tetrafluoroethane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0692326B2 (en) | 1994-11-16 |
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