JPH01132537A - Production of tetrafluoroethane - Google Patents
Production of tetrafluoroethaneInfo
- Publication number
- JPH01132537A JPH01132537A JP62288451A JP28845187A JPH01132537A JP H01132537 A JPH01132537 A JP H01132537A JP 62288451 A JP62288451 A JP 62288451A JP 28845187 A JP28845187 A JP 28845187A JP H01132537 A JPH01132537 A JP H01132537A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- tetrafluoroethane
- catalyst
- haloethane
- 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
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 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
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 9
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000460 chlorine Chemical group 0.000 claims description 16
- 239000011737 fluorine Substances 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 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
- 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
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 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 18
- 229910052763 palladium Inorganic materials 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000003860 storage 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
- 125000004435 hydrogen atom Chemical group [H]* 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 2
- JNCMHMUGTWEVOZ-UHFFFAOYSA-N F[CH]F Chemical compound F[CH]F JNCMHMUGTWEVOZ-UHFFFAOYSA-N 0.000 description 1
- 108010081348 HRT1 protein Hairy Proteins 0.000 description 1
- 102100021881 Hairy/enhancer-of-split related with YRPW motif protein 1 Human genes 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 239000011148 porous material Substances 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
- 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］
本発明はテトラフルオロエタンを製造する方法に関する
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ＣＦ３ＣＨ２Ｆ（Ｒ−１３４ａ）またはＣＨＦ２ Ｃ
ＨＦ２ （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、弐〇Ｆ２ＸＣＦＹＺ（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。[Prior art and problems] Formula CF3CH2F (R-134a) or CHF2C
One method for producing tetrafluoroethane represented by HF2 (R-134) is 2〇F2XCFYZ (wherein, X is fluorine or chlorine. When X is fluorine, Y and Z are chlorine, Fluorine or hydrogen.
Ｙ、Ｚの一方がフッ素である場合にＬ±、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（ＣＧＩＦ２ＣＧＩＦ２ ）および１．１−
ジクロロ−１，２，２，２−テトラフルオロエタンＣＣ
Ｃ１２ＦＣＦ３ ）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■ａ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られ、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５６−３８１３１号公報を参照）
、シかし、本還元反応においては、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。When one of Y and Z is fluorine, the other of L±, Y and Z is hydrogen or chlorine. When X is chlorine, Y
, 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 feedstocks are 1,2-dichloro-1,1,2,2-tetrafluoroethane (CGIF2CGIF2) and 1.1-dichloro-1,1,2,2-tetrafluoroethane (CGIF2CGIF2)
Dichloro-1,2,2,2-tetrafluoroethane CC
C12FCF3). 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 a catalyst for this purpose, use of known hydrogenation catalysts, i.e. nickel or metals of group IV a of the periodic table, alloys thereof, or oxides and salts thereof, which are particularly resistant to hydrochloric acid. A method using palladium, which is relatively low cost, has already been reported (see Japanese Patent Publication No. 56-38131).
However, in this reduction reaction, hydrogen chloride is produced as a by-product as shown in the following formula, so the catalyst must have acid resistance.
ＣｈＣＣ１２Ｆ＋Ｈｔ→ＣＦ３ＣＨＣＩＦ＋）１０１Ｃ
ＦｓＣＨＣＩＦ＋Ｈｚ→ＣＦ３ＧＨｚＦ＋Ｉ（ＣＩパラ
ジウムは白金族の中では安価であり、水素化能において
も優れている。しかし、水素吸蔵能が高く、最高、原子
比で１：ｌまで水素が吸蔵する。水素の吸蔵量が多くな
ると格子の歪も大きくなり、＃ｌ械的な劣化を受は易く
なる。ChCC12F+Ht→CF3CHCIF+)101C
FsCHCIF+Hz→CF3GHzF+I (CI palladium is inexpensive among the platinum group metals and has excellent hydrogenation ability. However, it has high hydrogen storage ability and can absorb hydrogen up to an atomic ratio of 1:l.Hydrogen storage As the amount increases, the distortion of the lattice also increases, making it more susceptible to mechanical deterioration.
また、パラジウムは同族の他元素とは異なり、濃硝酸や
沸騰硫酸に溶解するほか、酸素が存在する場合には、濃
塩酸にも溶解するなど、化学的変化を受は易いという欠
点を有する。Furthermore, unlike other elements in the same group, palladium has the disadvantage of being easily susceptible to chemical changes, such as being soluble in concentrated nitric acid and boiling sulfuric acid, and in the presence of oxygen, in concentrated hydrochloric acid.
［問題点を解決するための手段］
したがって、より耐食性の優れた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 problem] Therefore, using a catalyst with better corrosion resistance,
It is considered to be effective in extending the life of the catalyst.
白金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。When platinum is used as an electrode for hydrogen generation, the catalyst has high activity, a very low hydrogen overvoltage can be obtained, and is stable.
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。これはパラジウムの水素吸蔵能が
高いため、金属バルク中の水素濃度の増大に伴ない表面
吸着水素原子濃度の増大が著しく、反応活性サイトの減
少が顕著であるためと考えらえる。白金では水素吸蔵量
はパラジウムはど多くはなく、反応活性サイト数に対す
る影響が少ないと推定される。また、耐食性の点におい
ても白金はパラジウムに比較すると優れている。触媒の
調製法、取扱いについてはパラジウムと同様に行ない得
る。したがって、白金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。On the other hand, in the case of palladium electrodes, although the initial activity is high,
As the concentration of surface-adsorbed hydrogen atoms increases, the activity decreases and the hydrogen overpotential increases. This is thought to be because palladium has a high hydrogen storage capacity, so as the hydrogen concentration in the metal bulk increases, the surface adsorbed hydrogen atom concentration increases significantly, and the number of reaction active sites decreases significantly. Platinum does not have as much hydrogen storage capacity as palladium, and it is presumed that it has little effect on the number of reaction active sites. Furthermore, platinum is superior to palladium in terms of corrosion resistance. The catalyst can be prepared and handled in the same manner as palladium. Therefore, it has been found that the platinum 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、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、白金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特ＣＦ３ＣＨ２ＦまたはＣＨＦ２
０ＨＦ２で表わされるテトラフルオロエタンを製造する
方法を新規に提供するものである。Thus, the present invention was completed based on the above findings, and has the formula CF2XCFYZ (wherein, X is fluorine or chlorine. When X is fluorine, Y and Z are chlorine, fluorine or hydrogen. Yes, 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 fluorine. The other is chlorine or hydrogen.
The present invention provides a new method for producing tetrafluoroethane represented by 0HF2.
本発明において、白金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、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 platinum is not limited to a metal, and may be in the form of an oxide or a salt.
As the carrier, for example, alumina, activated carbon, etc. are suitable. 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（ＣＧＩＦ２ＣＧＩＦ２：Ｒ−１１４）、１．１−
ジクロロ−１，２，２，２−テトラフルオロエタｙ （
Ｃ０１２ＦＣＦ３ ：Ｒ−１１４ａ）、ｌ−クロロ−１
，１，２，２，２−ペンタフルオロエタン（ＧＣＩＦ２
ＣＦ３：Ｒ−１１５）、
ｌ−クロロ−１，２，２，２−テトラフルオロエタン（
ＣＨＣＩＦＣＦ３：Ｒ−１２４）、
２−クロロ−１，１，２，２−テトラフルオロエタン（
ＣＨＦ２ＧＯＩＦｚ：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 (CGIF2CGIF2:R-114), 1.1-
Dichloro-1,2,2,2-tetrafluoroethyl (
C012FCF3: R-114a), l-chloro-1
, 1,2,2,2-pentafluoroethane (GCIF2
CF3:R-115), l-chloro-1,2,2,2-tetrafluoroethane (
CHCIFCF3:R-124), 2-chloro-1,1,2,2-tetrafluoroethane (
CHF2GOIFz:R-124a), 1.1,2
, 2.2-pentafluoroethane (CHF2CF3:
R-125) A mixture of the above compounds may also be used as the haloethane raw material. 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、特には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，
１．２−テトラフルオロエタン（ＣＦ３１ＣＩ２Ｆ）が
得られ、１，１，２．２−テトラフルオロエタン（ＣＨ
Ｆ２ 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、ＣＦ３ ＣＨ２
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,
1,2-tetrafluoroethane (CF31CI2F) was obtained, and 1,1,2,2-tetrafluoroethane (CH
F2 CHF2 ) is hardly produced, starting material is 1,2
-dichloro-1,1,2,2-tetrafluoroethane, the reaction product usually consists of a mixture of the two isomers of tetrafluoroethane. 2.2 in the mixture
-As the ratio of dichloro-1,1,1,2-tetrafluoroethane to 1,2-dichloro-1,1,2,2-tetrafluoroethane increases, CF3 CH2
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−テトラブ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 provides that the desired 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane or mixtures thereof can be obtained in various proportions by a simple and convenient method. The present invention provides a manufacturing method with advantages.
［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
。これに塩化白金酸を重量比で８０：ｌＯの割合で、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５５０℃で４時間乾燥した後
、水素を導入し、５時間、３００℃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 chloroplatinic acid was dissolved at a weight ratio of 80:1O by 0.5z of the total weight of the metal components relative to the weight of the activated carbon was gradually added dropwise to the mixture, so that the ionic components were adsorbed onto the activated carbon. After washing with pure water, it was heated at 150℃ for 5 minutes.
After drying for 4 hours at 550° C. in nitrogen, hydrogen was introduced and the mixture was maintained at 300° C. for 5 hours for reduction.
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２．５４ｃＩ＋、長さ１００ｃ■のインコネル６０
０製反応管を塩浴炉中に浸漬した。Example 1 Inconel 60 with an inner diameter of 2.54 cI+ and a length of 100 c■ filled with 300 cc of the catalyst prepared as in the preparation example.
A reaction tube manufactured by 0.0 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４０二
６０）を２：１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 ／分、５０ｃ
ｃ／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 molar ratio of 40 to 60) were introduced into the reaction tube in a molar ratio of 2:1. The flow rates of hydrogen and starting materials were 100cc/min and 50c/min, 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１反応期期に
おいて９８．３％、６ケ月後において６５．４％であっ
た・
実施例２
ハロエタン原料としてＲ−１１４ａ （純度９８．０％
、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 98.3% in one reaction period and 65.4% after 6 months. Example 2 R-114a (purity 98.0%) was used as a haloethane raw material.
, 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９７．８％、６ケ月後では８５．３％であった。The reaction rate of R-114a in Table 2 at 250°C was 97.8% at the initial stage of the reaction and 85.3% 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 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、白金からなる水素
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を製造する方法。 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
記載の方法。 ７、白金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
記載の方法。 ８、白金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. ) is reacted with hydrogen in the presence of a hydrogenation catalyst made of platinum to produce tetrafluoroethane represented by the formula CF_3CH_2F or CHF_2CHF_2. Method. 2. The haloethane raw material is 1,2-dichloro-1,1,2
, 2-tetrafluoroethane.
The method described in section. 3. The haloethane raw material is 1,1-dichloro-1,2,2
, 2-tetrafluoroethane.
The method described in section. 4. The haloethane raw material is 1,2-dichloro-1,1,2
, 2-tetrafluoroethane and 1,1-dichloro-1,
The 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. Method described. 6. A process according to any one of claims 1 to 5, wherein up to 4 moles of hydrogen are used per mole of haloethane feedstock. 7. The method according to any one of claims 1 to 6, which uses a hydrogenation catalyst in which platinum is supported on an activated carbon carrier. 8. The method according to any one of claims 1 to 6, which uses a hydrogenation catalyst in which platinum is supported on an alumina carrier. 9. The 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 |
|---|---|---|---|
| JP62288451A JP2551052B2 (en) | 1987-11-17 | 1987-11-17 | Method for producing 1,1,1,2-tetrafluoroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62288451A JP2551052B2 (en) | 1987-11-17 | 1987-11-17 | Method for producing 1,1,1,2-tetrafluoroethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01132537A true JPH01132537A (en) | 1989-05-25 |
| JP2551052B2 JP2551052B2 (en) | 1996-11-06 |
Family
ID=17730379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62288451A Expired - Lifetime JP2551052B2 (en) | 1987-11-17 | 1987-11-17 | Method for producing 1,1,1,2-tetrafluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2551052B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0347830A2 (en) * | 1988-06-21 | 1989-12-27 | Asahi Glass Company Ltd. | Process for producing 1,1,1,2-tetrafluoroethane |
| WO1995013256A1 (en) * | 1993-11-12 | 1995-05-18 | Daikin Industries, Ltd. | Process for producing 1,1,1,3,3-pentafluoropropane |
-
1987
- 1987-11-17 JP JP62288451A patent/JP2551052B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0347830A2 (en) * | 1988-06-21 | 1989-12-27 | Asahi Glass Company Ltd. | Process for producing 1,1,1,2-tetrafluoroethane |
| WO1995013256A1 (en) * | 1993-11-12 | 1995-05-18 | Daikin Industries, Ltd. | Process for producing 1,1,1,3,3-pentafluoropropane |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2551052B2 (en) | 1996-11-06 |
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