JPH01132538A - Production of tetrafluoroethane - Google Patents
Production of tetrafluoroethaneInfo
- Publication number
- JPH01132538A JPH01132538A JP62288452A JP28845287A JPH01132538A JP H01132538 A JPH01132538 A JP H01132538A JP 62288452 A JP62288452 A JP 62288452A JP 28845287 A JP28845287 A JP 28845287A JP H01132538 A JPH01132538 A JP H01132538A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- tetrafluoroethane
- haloethane
- raw material
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 10
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 10
- 239000010948 rhodium Substances 0.000 claims abstract description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000460 chlorine Chemical group 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 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 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 239000007858 starting material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 4
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JQZFYIGAYWLRCC-UHFFFAOYSA-N 1-chloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)(F)Cl JQZFYIGAYWLRCC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JNCMHMUGTWEVOZ-UHFFFAOYSA-N F[CH]F Chemical compound F[CH]F JNCMHMUGTWEVOZ-UHFFFAOYSA-N 0.000 description 2
- 108010081348 HRT1 protein Hairy Proteins 0.000 description 2
- 102100021881 Hairy/enhancer-of-split related with YRPW motif protein 1 Human genes 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 2
- -1 platinum group metals Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910001055 inconels 600 Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はテトラフルオロエタンの製造方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing tetrafluoroethane.
［従来の技術及び問題点］
式ＣＦ３０Ｈ２Ｆ（Ｒ−１３４ａ）またはＣＨＦ２０Ｈ
Ｆ２（Ｒ−１３４）で表わされるテトラフルオロエタン
の製造方法の一つとして、式ＣＦ２ＸＣＦＹＺ（式中、
Ｘはフッ素または塩素である。Ｘがフッ素である場合に
は、 Ｙ、Ｚは塩素、フッ素または水素であり、Ｙ、Ｚ
の一方がフッ素である場合には、Ｙ、Ｚの他方は水素ま
たは塩素である。Ｘが塩素である場合には、 Ｙ、Ｚの
一方はフッ素であり、Ｙ、Ｚの他方は塩素または水素で
ある。）で表わされる４個または５個のフッ素原子を有
するハロエタン原料を、水素化触媒の存在下で水素と反
応させる製造方法がある。典型的なハロエタン原料は、
１．２−ジクロロ−１，１，２，２−テトラフルオロエ
タン（ＣＨＦ２０ＨＦ２）および１，１−ジクロロ−１
，２，２，２−テトラフルオロエタン（ＣＧ１２ＦＣＦ
３）の混合物である。この方法においては、ハロエタン
原料から２個の塩素原子、または、塩素および（または
）フッ素原子を除去し、これらを水素で置き換える。こ
のための触媒として、既知の水素化触媒、すなわち、ニ
ッケルまたは周期律表の第Ｖｉａ族の金属、それらの合
金、または、それらの酸化物、および塩のうち、特に塩
酸耐性を有するものの適用が考え返れ、既に、比較的低
コストであるパラジウムを用いる方法が報告されている
（特公昭５Ｂ−３８１３１号公報を参照）、シかし１本
選元反応においては、例えば下式に示すように塩化水素
が副生ずるため触媒には耐酸性が必要である。[Prior art and problems] Formula CF30H2F (R-134a) or CHF20H
As one of the methods for producing tetrafluoroethane represented by F2(R-134), the formula CF2XCFYZ (in the formula,
X is fluorine or chlorine. When X is fluorine, Y and Z are chlorine, fluorine or hydrogen;
When one of Y and Z is fluorine, the other of Y and Z is hydrogen or chlorine. When X is chlorine, one of Y and Z is fluorine, and the other of Y and Z is chlorine or hydrogen. There is a production method in which a haloethane raw material having 4 or 5 fluorine atoms represented by the following formula is reacted with hydrogen in the presence of a hydrogenation catalyst. Typical haloethane raw materials are
1,2-dichloro-1,1,2,2-tetrafluoroethane (CHF20HF2) and 1,1-dichloro-1
,2,2,2-tetrafluoroethane (CG12FCF
3). In this method, two chlorine atoms, or chlorine and/or fluorine atoms, are removed from the haloethane raw material and these are replaced with hydrogen. As catalysts for this purpose, known hydrogenation catalysts such as nickel or metals of group Via of the periodic table, alloys thereof, or oxides and salts thereof, which are especially resistant to hydrochloric acid, can be applied. Thinking back, a method using palladium, which is relatively low cost, has already been reported (see Japanese Patent Publication No. 5B-38131). Since hydrogen is produced as a by-product, the catalyst must have acid resistance.
ＣＦ３ＣＧ１２Ｆ＋Ｈ２→ＣＦｘＣＨＣＩＦ＋ＨＣＩＣ
ｈＣＨＣＩＦ＋Ｈｚ→ＣＦ３ＣＨｚＦ＋ＨＣＩパラジウ
ムは白金族の中では水素化能においても優れているもの
の、比較的化学的変化を受は易いという欠点を有する。CF3CG12F+H2→CFxCHCIF+HCIC
hCHCIF+Hz→CF3CHzF+HCIAlthough palladium has excellent hydrogenation ability among the platinum group metals, it has the disadvantage of being relatively susceptible to chemical changes.
［問題点を解決するための手段］
したがって、より耐食性の強い触媒を用いることは、触
媒の長寿命化に有効であると考えられる。[Means for Solving the Problems] Therefore, it is considered that using a catalyst with higher corrosion resistance is effective in extending the life of the catalyst.
ロジウムを水素発生用電極として用いた場合、触媒活性
は高く、非常に低い水素過電圧が得られ、かつ安定であ
る。一方、パラジウム電極の場合、初期活性は高いもの
の、表面吸着水素原子濃度の増大とともに活性が低下し
、水素過電圧は増大する。また、ロジウムは耐食性では
パラジウムよりかなり優れている。触媒の調製法、取扱
いについては他の白金族と同様に行ない得る。したがっ
て、ロジウム触媒は本還元反応系に好適な触媒となり得
ることが見出された。When rhodium is used as an electrode for hydrogen generation, the catalytic activity is high, a very low hydrogen overvoltage can be obtained, and it is stable. On the other hand, in the case of a palladium electrode, although the initial activity is high, the activity decreases as the surface-adsorbed hydrogen atom concentration increases, and the hydrogen overvoltage increases. Rhodium also has significantly better corrosion resistance than palladium. The catalyst can be prepared and handled in the same manner as for other platinum group metals. Therefore, it has been found that the rhodium catalyst can be a suitable catalyst for the present reduction reaction system.
かくして本発明は、上記知見に基づいて完成されたもの
であり、弐〇Ｆ２ＸＧＦＹＺ （式中、Ｘはフッ素また
は塩素である。Ｘがフッ素である場合には、 Ｙ、Ｚは
塩素、フッ素または水素であり、 Ｙ、Ｚの一方がフッ
素である場合には、Ｙ、Ｚの他方は水素または塩素であ
る。Ｘが塩素である場合には、 Ｙ、Ｚの一方はフッ素
であり、Ｙ、Ｚの他方は塩素または水素である。）で表
わされる４１ｉまたは５個のフッ素原子を有するハロエ
タン原料を、ロジウムからなる水素化触媒の存在下で水
素と反応させることを特徴とする式ＣＦ３ ＣＩ２ Ｆ
またはＣＨｈ ＣＨＦ２の製造方法を新規に提供するも
のである。Thus, the present invention has been completed based on the above findings, and is based on the following: 2〇F2XGFYZ (wherein, X is fluorine or chlorine. When When one of Y and Z is fluorine, the other of Y and Z is hydrogen or chlorine. When X is chlorine, one of Y and Z is fluorine; 41i or a haloethane material having 5 fluorine atoms, the other of which is chlorine or hydrogen, is reacted with hydrogen in the presence of a hydrogenation catalyst consisting of rhodium.
Alternatively, the present invention provides a new method for producing CHh CHF2.
本発明において、ロジウムからなる水素化触媒は、金属
に限らず、酸化物あるいは塩の状態であってもよい、ま
た、担体としては１例えば、アルミナ、活性炭等が好適
である。使用に当ってはかかる金属の化合物は少なくと
も一部還元する。In the present invention, the hydrogenation catalyst made of rhodium is not limited to a metal, and may be in the form of an oxide or salt, and suitable carriers include, for example, alumina, activated carbon, and the like. In use, such metal compounds are at least partially reduced.
而して、ハロエタン原料としては次のものが挙げられる
。Examples of haloethane raw materials include the following.
１．２−ジクロロ−１，１，２，２−テトラフルオロエ
タン（ＣＨＦ２０ＨＦ２：Ｒ−１１４）、１．１−ジク
ロロ−１，２，２，２−テトラフルオロエタン（ＣＣ１
ｚＦＣＦ３：Ｒ−１１４ａ）、ｌ−クロロ−１，１，２
，２，２−ペンタフルオロエタン（ＣＨＦ２ＣＦ３：Ｒ
−１１５）、
ｌ−クロロ−１，２，２，２−テトラフルオロエタン（
ＣＣ１ＦＣＦ３：Ｒ−１２４）、
２−クロロ−１，１，２，２−テトラフルオロエタン（
ＣＨＦ２ＣＧＩＦ２：Ｒ−１２４ａ）、１．１，２，２
．２−ペンタフルオロエタン（ＣＨＦ２ＣＦ３ ：Ｒ−
１２５）
ハロエタン原料としては上記化合物の混合物も使用し得
る。特に好ましくはＲ−１１４とＲ−１１４ａの混合物
がよい結果を与える。1,2-dichloro-1,1,2,2-tetrafluoroethane (CHF20HF2:R-114), 1,1-dichloro-1,2,2,2-tetrafluoroethane (CC1
zFCF3:R-114a), l-chloro-1,1,2
,2,2-pentafluoroethane (CHF2CF3:R
-115), l-chloro-1,2,2,2-tetrafluoroethane (
CC1FCF3:R-124), 2-chloro-1,1,2,2-tetrafluoroethane (
CHF2CGIF2:R-124a), 1.1,2,2
．． 2-pentafluoroethane (CHF2CF3 :R-
125) Mixtures of the above compounds can also be used as haloethane raw materials. Particularly preferred is a mixture of R-114 and R-114a which gives good results.
水素とハロエタン原料の割合は大幅に変動させ得る。し
かしながら１通常、化学量論量の水素を使用してハロゲ
ン原子を除去する。出発物質の全モル数に対して、化学
量論量よりかなり多い量、例えば４モルまたはそれ以上
の水素を使用し得る。The proportions of hydrogen and haloethane feedstocks can vary widely. However, one typically uses stoichiometric amounts of hydrogen to remove the halogen atoms. Significantly more than stoichiometric amounts of hydrogen can be used, for example 4 moles or more, based on the total number of moles of starting materials.
反応圧力については大気圧、または大気圧を越える圧力
を使用し得る。As for the reaction pressure, atmospheric pressure or superatmospheric pressure can be used.
反応温度は１２０℃以上が望ましいが、４５０℃を越え
ない温度において気相で行なうことが適当である。The reaction temperature is preferably 120°C or higher, but it is suitable to carry out the reaction in a gas phase at a temperature not exceeding 450°C.
接触時間は、反応を気相で行なう場合には通常０．１〜
３００秒、特に５〜３０秒である。The contact time is usually 0.1 to 0.1 when the reaction is carried out in the gas phase.
300 seconds, especially 5 to 30 seconds.
得られるテトラフルオロエタンは出発物質の選択により
相当変動する。出発物質が２．２−ジクロロ−１，１，
２，２−テトラフルオロエタンである場合には１，１，
１．２−テトラフルオロエタンＣＣＦ３ ＣＩ２ Ｆ）
が得られ、１，１，２．２−テトラフルオロエタン（Ｃ
ＨＦｚ ＣＨＦ２ ）は殆ど生じない、出発物質が１．
２−ジクロロ−１，１，２，２−テトラフルオロエタン
である場合には、反応生成物は通常テトラフルオロエタ
ンの２種の異性体の混合物からなる。混合物中での２．
２−ジクロロ−１，１，１，２−テトラフルオロエタン
の１．２−ジクロロ−１，１，２，２−テトラフルオロ
エタンに対する割合が増大するにつれて、ＣＦ３０Ｈ２
Ｆの生成量が増大する。The tetrafluoroethane obtained varies considerably depending on the choice of starting materials. The starting material is 2,2-dichloro-1,1,
In the case of 2,2-tetrafluoroethane, 1,1,
1.2-Tetrafluoroethane CCF3 CI2 F)
was obtained, and 1,1,2,2-tetrafluoroethane (C
HFz CHF2 ) is hardly produced when the starting material is 1.
In the case of 2-dichloro-1,1,2,2-tetrafluoroethane, the reaction product usually consists of a mixture of the two isomers of tetrafluoroethane. 2. in the mixture.
As the ratio of 2-dichloro-1,1,1,2-tetrafluoroethane to 1,2-dichloro-1,1,2,2-tetrafluoroethane increases, CF30H2
The amount of F produced increases.
本発明は所望の１．１，１．２−テトラフルオロエタン
、１，１，２．２〜テトラフルオロエタンまたはこれら
の混合物を簡単かつ好都合な方法により、種々の割合で
得ることができるという利点を有する製造方法を提供す
るものである。The present invention has the advantage that the desired 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane or mixtures thereof can be obtained in various proportions in a simple and convenient manner. The present invention provides a manufacturing method having the following.
［実施例］ 以下に本発明の実施例を示す。[Example] Examples of the present invention are shown below.
調製例
活性炭を純水中に浸漬し、細孔内部まで水を含浸させた
。これに塩化ロジウムを活性炭の重量に対し金属成分の
全重量で０．５ｚだけ溶解した水溶液を少しずつ滴下し
イオン成分を活性炭に吸着させた。純水を用いて洗浄し
た後、それを１５０℃で５時間乾燥した０次に窒素中５
５０℃で４時間乾燥した後、水素を導入し、５時間、３
００℃に保持して還元した。Preparation Example Activated carbon was immersed in pure water to impregnate the inside of the pores with water. An aqueous solution in which rhodium chloride was dissolved in an amount of 0.5z based on the total weight of the metal components relative to the weight of the activated carbon was added little by little to adsorb the ionic components onto the activated carbon. After washing with pure water, it was dried at 150°C for 5 hours and then washed in nitrogen for 5 hours.
After drying at 50°C for 4 hours, hydrogen was introduced and the mixture was dried for 5 hours for 3 hours.
It was maintained at 00°C and reduced.
実施例１
調製例のようにして調製した触媒を３００ｃｃ充填した
内径２．５４ｃ會、長さ１０００厘のインコネル６００
製反応管を塩浴炉中に浸漬した。Example 1 Inconel 600 with an inner diameter of 2.54 cm and a length of 1000 cm filled with 300 cc of the catalyst prepared as in the preparation example.
The prepared reaction tube was immersed in a salt bath furnace.
水素と出発物質（１，１−ジクロロ−１，２，２，２−
テトラフルオロエタンと１．２−ジクロロ−１，１，２
，２−テトラフルオロエタンよりなる０モル比で４０：
ＢＯ）を２：ｌのモル比で反応管に導入した。水素、出
発物質の流量はそれぞれ、１００ｃｃ ７分、５０ｃｃ
／分とした０反応管出口のガス組成をガスクロを用いて
分析した。その結果を第１表に示す。Hydrogen and starting material (1,1-dichloro-1,2,2,2-
Tetrafluoroethane and 1,2-dichloro-1,1,2
, 2-tetrafluoroethane in a 0 molar ratio of 40:
BO) was introduced into the reaction tube in a molar ratio of 2:1. The flow rates of hydrogen and starting materials were 100cc 7 minutes and 50cc, respectively.
The gas composition at the outlet of the reaction tube was analyzed using gas chromatography. The results are shown in Table 1.
第１表
Ｒ−１１４ａの２５０℃における反応率は、反応初期に
おいて９９．０％、６ケ月後において６００４％であっ
た・
実施例２
へロエタン原料としてＲ−１１４ａ （純度３８．０％
、残部はＲ−１１４）を用いる以外は、実施例１と同様
の条件で還元反応を行なった。結果を第２表に示す。The reaction rate of R-114a in Table 1 at 250°C was 99.0% at the initial stage of the reaction and 6004% after 6 months. Example 2 R-114a (purity 38.0%
, the remainder being R-114), the reduction reaction was carried out under the same conditions as in Example 1. The results are shown in Table 2.
第２表
Ｒ−１１４ａの２５０℃における反応率は、反応初期に
おいて９９．１％、６ケ月後では６０．５％であった。The reaction rate of R-114a in Table 2 at 250°C was 99.1% at the initial stage of the reaction and 60.5% after 6 months.
比較例１
触媒として活性炭に０．５％のパラジウムを調製例と同
様に担持したものを用いる以外は、実施例１と同様にし
て還元反応を行なった。結果を第３表に示す。Comparative Example 1 A reduction reaction was carried out in the same manner as in Example 1, except that activated carbon supported with 0.5% palladium in the same manner as in the Preparation Example was used as a catalyst. The results are shown in Table 3.
第３表
Ｒ−１１４ａの２５０℃における反応率は、反応初期に
おいて９８．０％、６ケ月後では３２．１％であった。The reaction rate of R-114a in Table 3 at 250°C was 98.0% at the initial stage of the reaction and 32.1% after 6 months.
［発明の効果］
本発明における還元触媒は、実施例に示すように、初期
性能を向上させるとともに、耐久性の向上においても優
れた特性を有する。[Effects of the Invention] As shown in Examples, the reduction catalyst of the present invention has excellent properties in improving initial performance and improving durability.
Claims (1)
素である、Ｘがフッ素である場合には、Ｙ、Ｚは塩素、
フッ素または水素であり、Ｙ、Ｚの一方がフッ素である
場合には、Ｙ、Ｚの他方は水素または塩素である、Ｘが
塩素である場合に は、Ｙ、Ｚの一方はフッ素であり、Ｙ、Ｚの他方は塩素
または水素である。）で表わされる４個または５個のフ
ッ素原子を有するハロエタン原料を、ロジウムからなる
水素化触媒の存在下で水素と反応させることを特徴とす
る式ＣＦ＿３ＣＨ＿２ＦまたはＣＨＦ＿２ＣＨＦ＿２で
表わされるテトラフルオロエタンの製造方法。 ２、ハロエタン原料が、１，２−ジクロロ−１，１，２
，２−テトラフルオロエタンである特許請求の範囲第１
項記載の製造方法。 ３、ハロエタン原料が、１，１−ジクロロ−１，２，２
，２−テトラフルオロエタンである特許請求の範囲第１
項記載の製造方法。 ４、ハロエタン原料が、１，２−ジクロロ−１，１，２
，２−テトラフルオロエタンと１，１−ジクロロ−１，
２，２，２テトラフルオロエタンとの混合物である特許
請求の範囲第１項記載の製造方法。 ５、ハロエタン原料に対して少なくとも化学量論量の水
素を使用してハロエタン原料中の１個または複数個のハ
ロゲン原子を除去する特許請求の範囲第１項〜第４項の
いずれか一項に記載の製造方法。 ６、ハロエタン原料１モルあたり４モルまでの水素を使
用する特許請求の範囲第１項〜第５項のいずれか一項に
記載の製造方法。 ７、ロジウムが活性炭担体上に担持されている水素化触
媒を用いる特許請求の範囲第１項〜第６項のいずれか一
項に記載の製造方法。 ８、ロジウムがアルミナ担体上に担持されている水素化
触媒を用いる特許請求の範囲第１項〜第６項のいずれか
一項に記載の製造方法。 ９、反応を気相中において１２０℃から４５０℃の温度
範囲で行なう特許請求の範囲第１項〜第８項のいずれか
一項に記載の製造方法。[Claims] 1. Formula CF_2XCFYZ (wherein, X is fluorine or chlorine; when X is fluorine, Y and Z are chlorine,
is fluorine or hydrogen; when one of Y and Z is fluorine, the other of Y and Z is hydrogen or chlorine; when X is chlorine, one of Y and Z is fluorine; The other of Y and Z is chlorine or hydrogen. ) A method for producing tetrafluoroethane represented by the formula CF_3CH_2F or CHF_2CHF_2, characterized by reacting a haloethane raw material having 4 or 5 fluorine atoms represented by the formula with hydrogen in the presence of a hydrogenation catalyst made of rhodium. . 2. The haloethane raw material is 1,2-dichloro-1,1,2
, 2-tetrafluoroethane.
Manufacturing method described in section. 3. The haloethane raw material is 1,1-dichloro-1,2,2
, 2-tetrafluoroethane.
Manufacturing method described in section. 4. The haloethane raw material is 1,2-dichloro-1,1,2
, 2-tetrafluoroethane and 1,1-dichloro-1,
The manufacturing method according to claim 1, which is a mixture with 2,2,2-tetrafluoroethane. 5. According to any one of claims 1 to 4, in which one or more halogen atoms in the haloethane raw material are removed using at least a stoichiometric amount of hydrogen with respect to the haloethane raw material. Manufacturing method described. 6. The production method according to any one of claims 1 to 5, wherein up to 4 moles of hydrogen are used per mole of haloethane raw material. 7. The manufacturing method according to any one of claims 1 to 6, which uses a hydrogenation catalyst in which rhodium is supported on an activated carbon carrier. 8. The manufacturing method according to any one of claims 1 to 6, which uses a hydrogenation catalyst in which rhodium is supported on an alumina carrier. 9. The manufacturing method according to any one of claims 1 to 8, wherein the reaction is carried out in a gas phase at a temperature range of 120°C to 450°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62288452A JPH01132538A (en) | 1987-11-17 | 1987-11-17 | Production of tetrafluoroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62288452A JPH01132538A (en) | 1987-11-17 | 1987-11-17 | Production of tetrafluoroethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01132538A true JPH01132538A (en) | 1989-05-25 |
Family
ID=17730391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62288452A Pending JPH01132538A (en) | 1987-11-17 | 1987-11-17 | Production of tetrafluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01132538A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995006022A1 (en) * | 1993-08-27 | 1995-03-02 | Daikin Industries, Ltd. | Process for producing hexafluorocyclobutene and process for producing hexafluorocyclobutane |
-
1987
- 1987-11-17 JP JP62288452A patent/JPH01132538A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995006022A1 (en) * | 1993-08-27 | 1995-03-02 | Daikin Industries, Ltd. | Process for producing hexafluorocyclobutene and process for producing hexafluorocyclobutane |
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