JP4738035B2 - Process for producing 1,1,1,2-tetrafluoroethane and / or pentafluoroethane and use thereof - Google Patents
Process for producing 1,1,1,2-tetrafluoroethane and / or pentafluoroethane and use thereof Download PDFInfo
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- JP4738035B2 JP4738035B2 JP2005086660A JP2005086660A JP4738035B2 JP 4738035 B2 JP4738035 B2 JP 4738035B2 JP 2005086660 A JP2005086660 A JP 2005086660A JP 2005086660 A JP2005086660 A JP 2005086660A JP 4738035 B2 JP4738035 B2 JP 4738035B2
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- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 title claims description 42
- 238000000034 method Methods 0.000 title claims description 34
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 title description 36
- 239000003054 catalyst Substances 0.000 claims description 75
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 64
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 64
- 239000007789 gas Substances 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 45
- 238000004519 manufacturing process Methods 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 39
- 239000012043 crude product Substances 0.000 claims description 33
- 238000003682 fluorination reaction Methods 0.000 claims description 28
- 239000012535 impurity Substances 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 claims description 4
- -1 1,1-difluoro-2-chloroethylene, 1,2-difluoro-1-chloroethylene, 1-chloro-2-fluoroethylene, 1,1,2-trifluoroethylene Chemical group 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 241000282376 Panthera tigris Species 0.000 claims 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims 1
- 230000003796 beauty Effects 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000460 chlorine Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052731 fluorine Inorganic materials 0.000 description 13
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 229950011008 tetrachloroethylene Drugs 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 229910001055 inconels 600 Inorganic materials 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 2
- HTHNTJCVPNKCPZ-UHFFFAOYSA-N 2-chloro-1,1-difluoroethene Chemical group FC(F)=CCl HTHNTJCVPNKCPZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、１，１，１，２−テトラフルオロエタンおよび／またはペンタフルオロエタンの製造方法およびその用途に関する。 The present invention relates to a method for producing 1,1,1,2-tetrafluoroethane and / or pentafluoroethane and use thereof.
１，１，１，２−テトラフルオロエタン（ＨＦＣ−１３４ａまたはＣＦ3 ＣＨ2 Ｆ）およびペンタフルオロエタン（ＨＦＣ−１２５またはＣＦ3 ＣＨＦ2 ）の製造方法として、従来から以下の方法が知られている。 Conventionally, the following methods are known as production methods of 1,1,1,2-tetrafluoroethane (HFC-134a or CF 3 CH 2 F) and pentafluoroethane (HFC-125 or CF 3 CHF 2 ). Yes.
１，１，１，２−テトラフルオロエタンの製造方法としては、例えば、トリクロロエチレンとフッ化水素とをフッ素化触媒の存在下に反応させて製造する方法が知られている。また、ペンタフルオロエタンの製造方法としては、テトラクロロエチレンとフッ化水素とをフッ素化触媒の存在下に反応させて製造する方法が知られている。これらの方法によって１，１，１，２−テトラフルオロエタンやペンタフルオロエタンを製造する場合、用いる反応条件によって様々な不純物が副生物として生成する。これらの不純物は、例えば、ＣＦ2 ＝ＣＣｌＦ、ＣＦ2 ＝ＣＨＣｌ、ＣＨＦ＝ＣＣｌＦ、ＣＣｌＦ＝ＣＨＣｌ、ＣＨＣｌ＝ＣＨＦ、ＣＦ2 ＝ＣＨＦ、ＣＦ2 ＝ＣＣｌＦ等の不飽和化合物を含み、またＣＣｌ2 Ｆ2 、ＣＨ2 ＣｌＦ、ＣＨ2 ＣｌＣＣｌＦ2 、ＣＦ3 ＣＨＣｌ2 、ＣＦ3 ＣＣｌＦ2 等のクロロフルオロカーボン類、ＣＨ2 Ｆ2 、ＣＦ3 ＣＨ3 、ＣＨＦ2 ＣＨＦ2 等のハイドロフルオロカ−ボン類を含む。 As a method for producing 1,1,1,2-tetrafluoroethane, for example, a method is known in which trichlorethylene and hydrogen fluoride are reacted in the presence of a fluorination catalyst. As a method for producing pentafluoroethane, a method is known in which tetrachloroethylene and hydrogen fluoride are reacted in the presence of a fluorination catalyst. When 1,1,1,2-tetrafluoroethane or pentafluoroethane is produced by these methods, various impurities are generated as by-products depending on the reaction conditions used. These impurities include, for example, unsaturated compounds such as CF 2 = CClF, CF 2 = CHCl, CHF = CClF, CClF = CHCl, CHCl = CHF, CF 2 = CHF, CF 2 = CClF, and CCl 2 F 2, CH 2 ClF, CH 2 ClCClF 2, CF 3 CHCl 2, CF 3 CClF chlorofluorocarbons such as 2, CH 2 F 2, CF 3 CH 3, CHF 2 CHF 2 , etc. hydrofluoroether mosquito - including carbon such .
これらの不純物のうち、ハイドロフルオロカーボン類は少量であれば問題はないが、不飽和化合物およびクロロフルオロカ−ボン類の含有量はできるだけ減少させることが必要であり、分別蒸留等によってある程度除去することができる。しかしながら、１，１，１，２−テトラフルオロエタンおよびペンタフルオロエタンと沸点が近似している不純物を分別蒸留によって実質的に存在しない低レベルまで除去することは極めて困難であり、また共沸組成物や共沸様組成物を形成する不純物を除去することも同様に困難である。このため、この問題を解決する方法として種々のプロセスが提案されている。 Of these impurities, hydrofluorocarbons are fine as long as they are small, but the content of unsaturated compounds and chlorofluorocarbons needs to be reduced as much as possible and should be removed to some extent by fractional distillation and the like. Can do. However, it is extremely difficult to remove impurities whose boiling points are close to those of 1,1,1,2-tetrafluoroethane and pentafluoroethane to a low level that does not substantially exist by fractional distillation, and azeotropic composition It is also difficult to remove impurities that form products and azeotrope-like compositions. For this reason, various processes have been proposed as methods for solving this problem.
例えば、塩化水素をある程度除去した粗ＣＦ3 ＣＨ2 Ｆ中に不純物として含まれる不飽和化合物（主としてＣＦ2 ＝ＣＨＣｌ）をフッ素化触媒の存在下に、ＣＦ3 ＣＨ2 Ｆと共沸組成分のフッ化水素と反応させて精製する方法（特開平６−１８４０１５号公報）が知られている。しかしながら、この方法は、目的物であるＣＦ3 ＣＨ2 Ｆ中に含まれる中間体の２−クロロ−１，１，１−トリフルオロエタン（ＣＦ3 ＣＨ2 Ｃｌ）の脱ハロゲン化反応によって不飽和化合物が生成し、またフッ素化触媒の寿命が短くなる等の技術的課題を残している。
本発明が解決しようとする課題は、前記のような従来技術の課題を解決するための新規な１，１，１，２−テトラフルオロエタンおよび／またはペンタフルオロエタンの製造方法およびその用途を提供しようとするものである。 The problem to be solved by the present invention is to provide a novel method for producing 1,1,1,2-tetrafluoroethane and / or pentafluoroethane and use thereof for solving the problems of the prior art as described above. It is something to try.
本発明者らは、前記の事情に鑑み、工業的に実施可能でかつ経済的な１，１，１，２−テトラフルオロエタンおよび／またはペンタフルオロエタンの製造方法を開発すべく鋭意検討した結果、トリクロロエチレンおよび／またはテトラクロロエチレンとフッ化水素とを反応させて得られる粗生成物が、１，１，１，２−テトラフルオロエタンおよび／またはペンタフルオロエタンを含む主生成物、該主生成物との共沸組成分のフッ化水素、および少なくとも不飽和化合物を含む不純物成分からなり、該粗生成物を精製する工程を行うことによって高純度の１，１，１，２−テトラフルオロエタンおよび／またはペンタフルオロエタンを製造する方法において、前記精製工程が、前記粗生成物に新たにフッ化水素を添加した混合物をフッ素化触媒と気相で接触させて、前記粗生成物に含まれる不飽和化合物の含有量を低減させる工程と、蒸留工程とを含む方法を用いることにより前記の課題を解決できることを見出し、本発明を完成するに至った。 In light of the above circumstances, the present inventors have conducted extensive studies to develop an industrially feasible and economical production method of 1,1,1,2-tetrafluoroethane and / or pentafluoroethane. A main product containing 1,1,1,2-tetrafluoroethane and / or pentafluoroethane, a crude product obtained by reacting trichlorethylene and / or tetrachloroethylene with hydrogen fluoride, Of high purity 1,1,1,2-tetrafluoroethane and / or an impurity component containing at least an unsaturated compound, and by purifying the crude product Alternatively, in the method for producing pentafluoroethane, the purification step may be carried out by fluorinating a mixture in which hydrogen fluoride is newly added to the crude product. The present invention has been found by using a method comprising a step of reducing the content of unsaturated compounds contained in the crude product by contacting with a gas phase and a distillation step, and completed the present invention. It came to do.
すなわち、本発明は、例えば、以下の（１）〜（１３）の手段を含む。 That is, the present invention includes, for example, the following means (1) to (13).
（１）トリクロロエチレンおよび／またはテトラクロロエチレンとフッ化水素とを反応させて得られる粗生成物が、１，１，１，２−テトラフルオロエタンおよび／またはペンタフルオロエタンを含む主生成物、該主生成物との共沸組成分のフッ化水素、および少なくとも不飽和化合物を含む不純物成分からなり、該粗生成物を精製する工程を行うことによって高純度の１，１，１，２−テトラフルオロエタンおよび／またはペンタフルオロエタンを製造する方法において、前記精製工程が、前記粗生成物に新たにフッ化水素を添加した混合物をフッ素化触媒と気相で接触させて、前記粗生成物に含まれる不飽和化合物の含有量を低減させる工程と、蒸留工程とを含むことを特徴とする１，１，１，２−テトラフルオロエタンおよび／またはペンタフルオロエタンの製造方法。 (1) A main product in which a crude product obtained by reacting trichlorethylene and / or tetrachloroethylene with hydrogen fluoride contains 1,1,1,2-tetrafluoroethane and / or pentafluoroethane, the main product High-purity 1,1,1,2-tetrafluoroethane comprising the step of purifying the crude product, comprising hydrogen fluoride having an azeotropic composition with the product and an impurity component containing at least an unsaturated compound In the method for producing pentafluoroethane, the purification step is included in the crude product by bringing a mixture obtained by newly adding hydrogen fluoride into the crude product into contact with a fluorination catalyst in a gas phase. 1,1,1,2-tetrafluoroethane and / or characterized by comprising a step of reducing the content of unsaturated compounds and a distillation step Method of manufacturing a printer fluoroethane.
（２）前記粗生成物に不純物として含まれる塩化水素の含有量が２モル％以下である前記（１）に記載の製造方法。 (2) The production method according to (1), wherein the content of hydrogen chloride contained as an impurity in the crude product is 2 mol% or less.
（３）前記粗生成物に含まれる１，１，１，２−テトラフルオロエタンおよび／またはペンタフルオロエタンの濃度が７０モル％以上である前記（１）または（２）に記載の製造方法。 (3) The production method according to (1) or (2), wherein the concentration of 1,1,1,2-tetrafluoroethane and / or pentafluoroethane contained in the crude product is 70 mol% or more.
（４）前記不飽和化合物が、１，１−ジフルオロ−２−クロロエチレン、１，２−ジフルオロ−１−クロロエチレン、１−クロロ−２−フルオロエチレン、１，１，２−トリフルオロエチレンおよび１−クロロ−１，２，２−トリフルオロエチレンからなる群より選ばれる少なくとも１種の化合物である前記（１）〜（３）のいずれかに記載の製造方法。 (4) the unsaturated compound is 1,1-difluoro-2-chloroethylene, 1,2-difluoro-1-chloroethylene, 1-chloro-2-fluoroethylene, 1,1,2-trifluoroethylene and The production method according to any one of (1) to (3), wherein the production method is at least one compound selected from the group consisting of 1-chloro-1,2,2-trifluoroethylene.
（５）前記フッ素化触媒が、Ｃｕ、Ｍｇ、Ｚｎ、Ｐｂ、Ｖ、Ｂｉ、Ｃｒ、Ｉｎ、Ｍｎ、Ｆｅ、Ｃｏ、ＮｉおよびＡｌ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前記（１）〜（４）のいずれかに記載の製造方法。 (5) The fluorination catalyst contains at least one metal element selected from the group consisting of Cu, Mg, Zn, Pb, V, Bi, Cr, In, Mn, Fe, Co, Ni, and Al ( The manufacturing method in any one of 1)-(4).
（６）前記混合物と前記フッ素化触媒との接触温度が１３０〜２８０℃の範囲である前記（１）〜（５）のいずれかに記載の製造方法。 (6) The manufacturing method in any one of said (1)-(5) whose contact temperature of the said mixture and the said fluorination catalyst is the range of 130-280 degreeC.
（７）前記粗生成物が、１，１，１，２−テトラフルオロエタンを含む主生成物、該主生成物との共沸組成分のフッ化水素、および少なくとも不飽和化合物を含む不純物成分からなり、前記粗生成物に新たにフッ化水素を添加した混合物をフッ素化触媒と気相で接触させて、前記粗生成物に含まれる不飽和化合物の含有量を低減させる前記（１）〜（６）のいずれかに記載の製造方法。 (7) Impurity component in which the crude product contains a main product containing 1,1,1,2-tetrafluoroethane, hydrogen fluoride in an azeotropic composition with the main product, and at least an unsaturated compound (1) to reducing the content of unsaturated compounds contained in the crude product by bringing a mixture in which hydrogen fluoride is newly added to the crude product into contact with the fluorination catalyst in a gas phase. (6) The manufacturing method in any one of.
（８）前記混合物と前記フッ素化触媒との接触温度が１３０〜２００℃の範囲である前記（７）に記載の製造方法。 (8) The manufacturing method as described in said (7) whose contact temperature of the said mixture and the said fluorination catalyst is the range of 130-200 degreeC.
（９）前記蒸留工程においてフッ化水素を分離し、分離されたフッ化水素を前記粗生成物を得る工程に再循環する前記（１）〜（８）のいずれかに記載の製造方法。 (9) The production method according to any one of (1) to (8), wherein hydrogen fluoride is separated in the distillation step, and the separated hydrogen fluoride is recycled to the step of obtaining the crude product.
（１０）前記（１）〜（９）のいずれかに記載の製造方法によって得られる１、１，１，２−テトラフルオロエタンであって、塩素含有化合物の総含有量が２ｖｏｌｐｐｍ以下であることを特徴とする１，１，１，２−テトラフルオロエタン。 (10) 1,1,1,2-tetrafluoroethane obtained by the production method according to any one of (1) to (9), wherein the total content of chlorine-containing compounds is 2 volppm or less 1,1,1,2-tetrafluoroethane characterized by
（１１）前記（１０）に記載の１，１，１，２−テトラフルオロエタンとフッ素ガスとを、希釈ガスの存在下に反応させることを特徴とするペンタフルオロエタンおよび／またはヘキサフルオロエタンの製造方法。 (11) The 1,1,1,2-tetrafluoroethane described in the above (10) is reacted with fluorine gas in the presence of a diluent gas, and pentafluoroethane and / or hexafluoroethane Production method.
（１２）前記（１１）に記載の製造方法によって得られるペンタフルオロエタンおよび／またはヘキサフルオロエタンを含むことを特徴とするエッチングガス。 (12) An etching gas comprising pentafluoroethane and / or hexafluoroethane obtained by the production method according to (11).
（１３）前記（１１）に記載の製造方法によって得られるペンタフルオロエタンおよび／またはヘキサフルオロエタンを含むことを特徴とするクリーニングガス。 (13) A cleaning gas comprising pentafluoroethane and / or hexafluoroethane obtained by the production method according to (11).
本発明によれば、１，１，１，２−テトラフルオロエタンおよび／またはペンタフルオロエタン中に含まれる不飽和不純物の含有量を低減させて、低温用冷媒、エッチングガスやクリーニングガスとして有利に利用できる１，１，１，２−テトラフルオロエタンおよび／またはペンタフルオロエタンを得るための工業的に有利な製造方法およびその用途を提供することができる。 According to the present invention, the content of unsaturated impurities contained in 1,1,1,2-tetrafluoroethane and / or pentafluoroethane is reduced, which is advantageous as a low-temperature refrigerant, etching gas or cleaning gas. It is possible to provide an industrially advantageous production method and use thereof for obtaining available 1,1,1,2-tetrafluoroethane and / or pentafluoroethane.
以下、本発明について詳しく説明する。 The present invention will be described in detail below.
ＣＦ3 ＣＨ2 Ｆの製造方法としては、例えば、トリクロロエチレンとフッ化水素とをフッ素化触媒の存在下に、２段階で反応させて製造する方法が知られている。また、ＣＦ3 ＣＨＦ2 の製造方法としては、例えば、テトラクロロエチレンとフッ化水素とをフッ素化触媒の存在下に、２段階で反応させて製造する方法が知られている。これらの方法を用いてＣＦ3 ＣＨ2 ＦやＣＦ3 ＣＨＦ2 を製造すると、一般に行なわれている蒸留操作等の精製を行った場合であっても、目的物であるＣＦ3 ＣＨ2 ＦやＣＦ3 ＣＨＦ2 と分離することが困難な不純物が含まれる。これらの不純物としては、例えば、前述の不飽和化合物類、クロロフルオロカーボン類、ハイドロフルオロカーボン類等が挙げられ、これらの不純物はできる限り除去して高純度化する必要がある。 As a method for producing CF 3 CH 2 F, for example, a method is known in which trichlorethylene and hydrogen fluoride are reacted in two stages in the presence of a fluorination catalyst. As a method for producing CF 3 CHF 2 , for example, a method is known in which tetrachloroethylene and hydrogen fluoride are reacted in two stages in the presence of a fluorination catalyst. When CF 3 CH 2 F or CF 3 CHF 2 is produced by using these methods, the target product CF 3 CH 2 F or CF 3 can be obtained even when purification such as a general distillation operation is performed. 3 Impurities that are difficult to separate from CHF 2 are included. Examples of these impurities include the aforementioned unsaturated compounds, chlorofluorocarbons, hydrofluorocarbons and the like, and it is necessary to remove these impurities as much as possible to achieve high purity.
本発明の１，１，１，２−テトラフルオロエタンおよび／またはペンタフルオロエタンの製造方法は、トリクロロエチレンおよび／またはテトラクロロエチレンとフッ化水素とを反応させて得られる粗生成物が、１，１，１，２−テトラフルオロエタンおよび／またはペンタフルオロエタンを含む主生成物、該主生成物との共沸組成分のフッ化水素、および少なくとも不飽和化合物を含む不純物成分からなり、該粗生成物を精製する工程を行うことによって高純度の１，１，１，２−テトラフルオロエタンおよび／またはペンタフルオロエタンを製造する方法において、前記精製工程が、前記粗生成物に新たにフッ化水素を添加した混合物をフッ素化触媒と気相で接触させて、前記粗生成物に含まれる不飽和化合物の含有量を低減させる工程と、蒸留工程とを含むことを特徴とする。 In the method for producing 1,1,1,2-tetrafluoroethane and / or pentafluoroethane of the present invention, a crude product obtained by reacting trichloroethylene and / or tetrachloroethylene with hydrogen fluoride is obtained by reacting 1,1,1,2-tetrafluoroethane and / or pentafluoroethane. The crude product comprising a main product containing 1,2-tetrafluoroethane and / or pentafluoroethane, hydrogen fluoride having an azeotropic composition with the main product, and an impurity component containing at least an unsaturated compound. In the method for producing high-purity 1,1,1,2-tetrafluoroethane and / or pentafluoroethane by performing a step of purifying the crude product, the purification step newly adds hydrogen fluoride to the crude product. The step of bringing the added mixture into contact with the fluorination catalyst in a gas phase to reduce the content of unsaturated compounds contained in the crude product , Characterized in that it comprises a distillation step.
ハイドロフルオロカーボン類の多くの化合物は、フッ化水素と共沸混合物を形成することが知られている。ＣＦ3 ＣＨ2 ＦやＣＦ3 ＣＨＦ2 もフッ化水素と共沸混合物を形成し、例えば、ＣＦ3 ＣＨ2 Ｆとフッ化水素の共沸混合物のモル比は、ＨＦ／ＣＦ3 ＣＨ2 Ｆ＝約０．１２である。例えば、前述した特開平６−１８４０１５号公報には、この共沸混合物と、例えば、１，１−ジフルオロ−２−クロロエチレン（ＣＦ2 ＝ＣＨＣｌ）のような不飽和化合物を含む混合物を、２００〜３８０℃の温度でクロム系触媒と接触させて不飽和化合物を低減させる方法が記載されている。しかしながら、接触温度が高くなると前記の混合物中に含まれる２−クロロ−１，１，１−トリフルオロエタン（ＣＦ3 ＣＨ2 Ｃｌ）の脱ハロゲン化反応によって１，１−ジフルオロ−２−クロロエチレンが副生物として生成し、それに伴って触媒表面のコーキングが進行して触媒寿命が短くなる等の課題を有していた。本発明では、ＣＦ3 ＣＨ2 Ｆおよび／またはＣＦ3 ＣＨＦ2 を含む主生成物と主生成物との共沸組成分のフッ化水素、および１種以上の不飽和化合物を含む不純物成分を含む混合物中に、新たにフッ化水素を添加し、気相状態でフッ素化触媒と接触させることにより、目的物をロスすることなく、不飽和化合物の含有量を低減し、さらに触媒寿命を長くすることができるという利点が得られる。 Many compounds of hydrofluorocarbons are known to form azeotropes with hydrogen fluoride. CF 3 CH 2 F and CF 3 CHF 2 also form an azeotrope with hydrogen fluoride. For example, the molar ratio of the azeotrope of CF 3 CH 2 F and hydrogen fluoride is HF / CF 3 CH 2 F = About 0.12. For example, in the above-mentioned JP-A-6-184015, a mixture containing this azeotrope and an unsaturated compound such as 1,1-difluoro-2-chloroethylene (CF 2 = CHCl) is disclosed in 200 A method for reducing unsaturated compounds by contacting with a chromium-based catalyst at a temperature of ˜380 ° C. is described. However, when the contact temperature is increased, 1,1-difluoro-2-chloroethylene is obtained by dehalogenation reaction of 2-chloro-1,1,1-trifluoroethane (CF 3 CH 2 Cl) contained in the mixture. Is produced as a by-product, and coking of the catalyst surface proceeds accordingly, resulting in a problem that the catalyst life is shortened. In the present invention, hydrogen fluoride corresponding to the azeotropic composition of the main product containing CF 3 CH 2 F and / or CF 3 CHF 2 and an impurity component containing one or more unsaturated compounds is included. By adding new hydrogen fluoride to the mixture and bringing it into contact with the fluorination catalyst in the gas phase, the content of unsaturated compounds is reduced and the catalyst life is extended without losing the target product. The advantage that it can be obtained.
トリクロロエチレンとフッ化水素とを反応させた後に粗精製工程を行って得られるＣＦ3 ＣＨ2 Ｆ粗生成物には、共沸組成分のフッ化水素、１種以上の不飽和化合物、ＣＦ3 ＣＨ2 Ｆの製造中間体のＣＦ3 ＣＨ2 Ｃｌが含まれる。通常、ＣＦ3 ＣＨ2 Ｃｌの濃度は約１０モル％以下であり、目的物であるＣＦ3 ＣＨ2 Ｆの濃度は約７０モル％以上である。中間体のＣＦ3 ＣＨ2 Ｃｌもまたフッ化水素と共沸混合物を形成し、その共沸混合物のモル比はＨＦ／ＣＦ3 ＣＨ2 Ｃｌ＝約１．０である。 A crude product of CF 3 CH 2 F obtained by reacting trichlorethylene with hydrogen fluoride and then performing a crude purification step includes hydrogen fluoride having an azeotropic composition, one or more unsaturated compounds, CF 3 CH The production intermediate of 2 F, CF 3 CH 2 Cl, is included. Usually, the concentration of CF 3 CH 2 Cl is about 10 mol% or less, and the concentration of the target CF 3 CH 2 F is about 70 mol% or more. The intermediate CF 3 CH 2 Cl also forms an azeotrope with hydrogen fluoride, the molar ratio of the azeotrope being HF / CF 3 CH 2 Cl = about 1.0.
また、不飽和化合物の総含有量は、使用する触媒や反応条件によって異なるが、一般には０．４〜０．９モル％程度であり、不飽和化合物としては１，１−ジフルオロ−２−クロロエチレン、１，２−ジフルオロ−１−クロロエチレン、１−クロロ−２−フルオロエチレン、１，１，２−トリフルオロエチレンおよび１−クロロ−１，２，２−トリフルオロエチレンが挙げられる。新たに添加するフッ化水素の量は、ＣＦ3 ＣＨ2 Ｆとフッ化水素の共沸混合物のモル比がＨＦ／ＣＦ3 ＣＨ2 Ｆ＝約０．１２であるので、それ以上となるように添加することが好ましく、例えば、ＣＦ3 ＣＨ2 Ｆとのモル比でＨＦ／ＣＦ3 ＣＨ2 Ｆ＝０．３以上となるように添加することが好ましい。フッ化水素の添加量を多くすれば不飽和化合物へのフッ化水素の付加反応が進行しやすく、また反応温度を下げることができる。これは、副生物の生成を抑制し、目的物のロスを低減することや触媒の寿命を長くすることができる等の大きな利点となる。また、粗生成物がＣＦ3 ＣＨＦ2 である場合は、ＣＦ3 ＣＨＦ2 とフッ化水素の共沸混合物のモル比がＨＦ／ＣＦ3 ＣＨＦ2 ＝約０．１であり、新たに添加するフッ化水素の量はＣＦ3 ＣＨＦ2 とのモル比がＨＦ／ＣＦ3 ＣＨＦ2 ＝０．２以上となるように添加することが好ましい。本発明の方法において、粗生成物に新たにフッ化水素を添加した混合物をフッ素化触媒と気相で接触させる工程は、ＣＦ3 ＣＨ2 ＦおよびＣＦ3 ＣＨＦ2 を、それぞれ単独でフッ化水素と混合してフッ素化触媒と接触させてもよいし、２つの化合物が混合された状態でフッ化水素との混合物を形成してフッ素化触媒と接触させてもよいが、２つの化合物を混合した状態でフッ素化触媒と接触させ、その後蒸留して分離する方法が好ましい。また、新たに添加するフッ化水素の供給方法としては、一括供給方式と分割供給方式のどちらも選択可能である。 The total content of unsaturated compounds varies depending on the catalyst used and reaction conditions, but is generally about 0.4 to 0.9 mol%. As an unsaturated compound, 1,1-difluoro-2-chloro Mention may be made of ethylene, 1,2-difluoro-1-chloroethylene, 1-chloro-2-fluoroethylene, 1,1,2-trifluoroethylene and 1-chloro-1,2,2-trifluoroethylene. The amount of hydrogen fluoride to be newly added should be more than that because the molar ratio of the azeotropic mixture of CF 3 CH 2 F and hydrogen fluoride is HF / CF 3 CH 2 F = about 0.12. it is preferable to add, for example, is preferably added such that the HF / CF 3 CH 2 F = 0.3 or more in the molar ratio of CF 3 CH 2 F. If the addition amount of hydrogen fluoride is increased, the addition reaction of hydrogen fluoride to the unsaturated compound can easily proceed, and the reaction temperature can be lowered. This is a great advantage, such as suppressing the production of by-products, reducing the loss of the target product, and extending the life of the catalyst. When the crude product is CF 3 CHF 2 , the molar ratio of the azeotropic mixture of CF 3 CHF 2 and hydrogen fluoride is HF / CF 3 CHF 2 = about 0.1, and the newly added fluorine is added. of the amount of hydrogen it is preferably added such that the molar ratio of the CF 3 CHF 2 is HF / CF 3 CHF 2 = 0.2 or more. In the method of the present invention, the step of bringing the mixture obtained by newly adding hydrogen fluoride into the crude product into contact with the fluorination catalyst in the gas phase comprises CF 3 CH 2 F and CF 3 CHF 2 each independently of hydrogen fluoride. May be mixed with the fluorination catalyst, or may be contacted with the fluorination catalyst by forming a mixture with hydrogen fluoride in a state where the two compounds are mixed. In this state, a method of contacting with a fluorination catalyst and then separating by distillation is preferable. In addition, as a supply method of hydrogen fluoride to be newly added, either a batch supply method or a divided supply method can be selected.
本発明の方法において用いられるフッ素化触媒は、フッ素化反応に対して触媒作用を有するものであればよく、触媒としては、周期表の１Ｂ族、２Ａ族、２Ｂ族、４Ｂ族、５Ａ族、５Ｂ族、６Ａ族、７Ａ族および８族の金属化合物で、Ｃｕ、Ｍｇ、Ｚｎ、Ｐｂ、Ｖ、Ｂｉ、Ｃｒ、Ｉｎ、Ｍｎ、Ｆｅ、Ｃｏ、ＮｉおよびＡｌからなる群より選ばれる少なくとも１種の元素を含むフッ素化触媒であって、例えば、３価の酸化クロムを主成分とする塊状型触媒、あるいはアルミナ、フッ化アルミニウムまたは活性炭を担体として用いる担時型触媒のどちらをも選択することができる。フッ素化触媒の調製法としては、通常の方法が適用できるが、例えば、塩化コバルト水溶液にアルミナを含浸した後、乾燥し、空気流通下で焼成を行って製造することができる。このように調製した触媒は反応に使用する前段で、窒素および／またはフッ化水素を用いて活性化することが好ましい。 The fluorination catalyst used in the method of the present invention may be any catalyst that has a catalytic action on the fluorination reaction. Examples of the catalyst include 1B group, 2A group, 2B group, 4B group, 5A group, 5B group, 6A group, 7A group and 8 group metal compound, at least one selected from the group consisting of Cu, Mg, Zn, Pb, V, Bi, Cr, In, Mn, Fe, Co, Ni and Al A fluorination catalyst containing any of these elements, for example, a bulk catalyst mainly composed of trivalent chromium oxide, or a supported catalyst using alumina, aluminum fluoride or activated carbon as a carrier. Can do. As a method for preparing the fluorination catalyst, a normal method can be applied. For example, it can be produced by impregnating a cobalt chloride aqueous solution with alumina, then drying and firing in an air stream. The catalyst thus prepared is preferably activated using nitrogen and / or hydrogen fluoride before the reaction.
粗生成物とフッ素化触媒を接触させる温度は１３０〜２８０℃の範囲が好ましく、１３０〜２００℃の範囲がより好ましい。１３０℃より低い温度では不飽和化合物の反応速度が遅くなる傾向があり、２８０℃より高い温度では前記のような副反応の割合が増加する傾向が見られる。 The temperature for bringing the crude product into contact with the fluorination catalyst is preferably in the range of 130 to 280 ° C, more preferably in the range of 130 to 200 ° C. When the temperature is lower than 130 ° C., the reaction rate of the unsaturated compound tends to be slow, and when the temperature is higher than 280 ° C., the side reaction rate tends to increase.
粗生成物に不純物として含まれる塩化水素の含有量は２モル％以下であることが好ましい。塩化水素の含有量が２モル％より多いと不純物が増加する傾向が見られる。 The content of hydrogen chloride contained as an impurity in the crude product is preferably 2 mol% or less. When the content of hydrogen chloride is more than 2 mol%, there is a tendency for impurities to increase.
粗生成物とフッ素化触媒を接触させた後、共沸成分のフッ化水素と新たに添加したフッ化水素の少なくとも一部は蒸留工程で分離され、分離されたフッ化水素は粗生成物を得る工程に再循環されることが好ましい。ＣＦ3 ＣＨ2 Ｆは蒸留によって分離精製することができるので、不飽和化合物や含塩素化合物をほとんど含まない高純度なＣＦ3 ＣＨ2 Ｆを収率よく得ることができ、塩素含有化合物の総含有量を２ｖｏｌｐｐｍ以下とすることができる。 After bringing the crude product into contact with the fluorination catalyst, at least a part of the azeotropic component hydrogen fluoride and the newly added hydrogen fluoride are separated in the distillation step, and the separated hydrogen fluoride is separated from the crude product. Preferably it is recycled to the obtaining step. Since CF 3 CH 2 F can be separated and purified by distillation, high-purity CF 3 CH 2 F containing almost no unsaturated compounds or chlorine-containing compounds can be obtained with good yield, and the total content of chlorine-containing compounds can be obtained. The amount can be 2 volppm or less.
ＣＦ3 ＣＨ2 Ｆ中に含まれる不純物の含有量の測定は、ガスクロマトグラフ（ＧＣ）法のＴＣＤ法、ＦＩＤ法あるいはガスクロマトグラフ−質量分析計（ＧＣ−ＭＳ）法等により行うことができる。 The content of impurities contained in CF 3 CH 2 F can be measured by a gas chromatography (GC) TCD method, an FID method, a gas chromatograph-mass spectrometer (GC-MS) method, or the like.
また、このような高純度の１，１，１，２−テトラフルオロエタンとフッ素ガスとを、希釈ガスの存在下に反応させることにより、ペンタフルオロエタンおよび／またはヘキサフルオロエタンを製造することができる。本発明の製造方法によれば、ペンタフルオロエタンおよびヘキサフルオロエタンの製造原料となる１，１，１，２−テトラフルオロエタンは不純物として含まれる塩素含有化合物の総含有量が極めて少ないので高純度のペンタフルオロエタンおよびヘキサフルオロエタンを製造することができる。例えば、ペンタフルオロエタンは９９．９９９８ｖｏｌ％以上の純度とすることができる。 Also, pentafluoroethane and / or hexafluoroethane can be produced by reacting such high-purity 1,1,1,2-tetrafluoroethane with fluorine gas in the presence of a diluent gas. it can. According to the production method of the present invention, 1,1,1,2-tetrafluoroethane, which is a raw material for producing pentafluoroethane and hexafluoroethane, has a high purity because the total content of chlorine-containing compounds contained as impurities is extremely small. Of pentafluoroethane and hexafluoroethane can be produced. For example, pentafluoroethane can have a purity of 99.99998 vol% or more.
次に、上記の製造方法を用いて得られる高純度のペンタフルオロエタンおよびヘキサフルオロエタンの用途について説明する。高純度のペンタフルオロエタンは、例えば、Ｈｅ、Ｎ2 、Ａｒ等の不活性ガス、およびＯ2 あるいはＮＦ3 等のガスとの混合ガス（以下においては「ペンタフルオロエタン製品」ということがある）は、半導体デバイス製造工程の中のエッチング工程におけるエッチングガスとして使用することができる。また、高純度のヘキサフルオロエタンは半導体デバイス製造工程におけるクリーニングガスとして使用することができる。 Next, uses of high-purity pentafluoroethane and hexafluoroethane obtained by using the above production method will be described. High-purity pentafluoroethane is, for example, a mixed gas with an inert gas such as He, N 2 , or Ar, and a gas such as O 2 or NF 3 (hereinafter sometimes referred to as “pentafluoroethane product”). Can be used as an etching gas in an etching process in a semiconductor device manufacturing process. Moreover, high purity hexafluoroethane can be used as a cleaning gas in the semiconductor device manufacturing process.
以下、実施例および比較例により本発明をさらに説明するが、本発明はこれらの実施例により何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further, this invention is not limited at all by these Examples.
粗１，１，１，２−テトラフルオロエタンの調製例（原料例１）
トリクロロエチレン（ＣＣｌ2 ＝ＣＨＣｌ）を出発原料とし、クロム系フッ素化触媒の存在下に、気相でフッ化水素と反応させて主として中間体であるＣＦ3 ＣＨ2 Ｃｌを得、これをクロム系フッ素化触媒が充填されている別の反応器に導入してさらにフッ化水素と反応させる２段階の反応を行った。粗精製工程を経て得られた粗１，１，１，２−テトラフルオロエタンを分析したところ、次のような組成を有していた。
Preparation example of crude 1,1,1,2-tetrafluoroethane (raw material example 1)
Using trichlorethylene (CCl 2 = CHCl) as a starting material, it is reacted with hydrogen fluoride in the gas phase in the presence of a chromium-based fluorination catalyst to obtain CF 3 CH 2 Cl, which is mainly an intermediate, and this is converted to chromium-based fluorine. A two-stage reaction was carried out by introducing it into another reactor filled with a fluorination catalyst and further reacting with hydrogen fluoride. When crude 1,1,1,2-tetrafluoroethane obtained through the crude purification step was analyzed, it had the following composition.
ＣＦ3 ＣＨ2 Ｆ ８１．２０８０ ＣＨＣｌ＝ＣＨＦ ０．００２０
ＣＦ3 ＣＨ2 Ｃｌ ６．２４００ ＣＦ3 ＣＨ3 ０．５６３０
ＣＦ3 ＣＨＦ2 ０．５３２０ ＣＦ3 ＣＨＣｌＦ ０．５３１０
ＣＨＦ2 ＣＨＦ2 ０．１６００ ＣＦ3 ＣＣｌＦ2 ０．０５４０
ＣＦ2 ＝ＣＨＣｌ ０．６４２０ ＨＦ（フッ化水素） ９．５０６０
ＨＣｌ（塩化水素） ０．５６２０
単位：ｖｏｌ％
粗ペンタフルオロエタンの調製例（原料例２）
テトラクロロエチレン（ＣＣｌ2 ＝ＣＣｌ2 ）を原料としてクロム系触媒の存在下、気相でフッ化水素と反応させて主として中間体であるＣＦ3 ＣＨＣｌ2 およびＣＦ3 ＣＨＣｌＦを得、これをクロム系フッ素化触媒が充填されている別の反応器に導入してフッ化水素と反応させる２段階の反応を行った。粗精製工程を経て得られた粗ペンタフルオロエタンを分析したところ、次のような組成を有していた。
CF 3 CH 2 F 81.2080 CHCl═CHF 0.0020
CF 3 CH 2 Cl 6.2400 CF 3 CH 3 0.5630
CF 3 CHF 2 0.5320 CF 3 CHClF 0.5310
CHF 2 CHF 2 0.1600 CF 3 CClF 2 0.0540
CF 2 = CHCl 0.6420 HF (hydrogen fluoride) 9.5060
HCl (hydrogen chloride) 0.5620
Unit: vol%
Example of preparation of crude pentafluoroethane (raw material example 2)
Tetrachloroethylene (CCl 2 = CCl 2 ) as a raw material is reacted with hydrogen fluoride in the gas phase in the presence of a chromium-based catalyst to obtain mainly intermediates CF 3 CHCl 2 and CF 3 CHClF, which are then fluorinated with chromium A two-stage reaction was carried out by introducing it into another reactor filled with a catalyst and reacting with hydrogen fluoride. When the crude pentafluoroethane obtained through the crude purification step was analyzed, it had the following composition.
ＣＦ3 ＣＨＦ2 ８６．９７１２ ＣＦ3 ＣＨＣｌＦ ３．８２０４
ＣＦ3 ＣＨＣｌ2 ０．００５１ ＣＦ3 ＣＣｌＦ2 ０．３１２１
ＣＦ3 ＣＨ3 ０．０１６１ ＣＨ2 Ｆ2 ０．０１２１
ＣＦ2 ＝ＣＣｌＦ ０．０２４１ ＣＦ2 ＝ＣＨＦ ０．００１２
ＨＦ ８．３２７６ ＨＣｌ ０．４８２０
その他 ０．０２８１
単位：ｖｏｌ％
触媒の調製例１（触媒例１）
１０Ｌの容器に純水０．６Ｌを入れて撹拌し、この中に純水１．２Ｌに４５２ｇのＣｒ（ＮＯ3 ）3 ・９Ｈ2 Ｏと４２ｇのＩｎ（ＮＯ3 ）3 ・ｎＨ2 Ｏ（ｎは約５）を溶かした溶液と、０．３１Ｌの２８％アンモニア水とを、反応液のｐＨが７．５〜８．５の範囲内になるように、２種の水溶液の流量をコントロールしながら約１時間かけて滴下した。得られたスラリーを濾別し、濾別した固形物を純水でよく洗浄した後、１２０℃で１２時間乾燥した。乾燥した固形物を粉砕後、黒鉛と混合し、打錠成型器によってペレットを作成した。このペレットを窒素気流下に、４００℃で４時間焼成して触媒前駆体とした。次に、触媒前駆体をインコネル製反応器に充填し、フッ化水素を用いて３５０℃でフッ素化処理（触媒の活性化）を行ない、触媒を調製した。
CF 3 CHF 2 86.9712 CF 3 CHClF 3.8204
CF 3 CHCl 2 0.0051 CF 3 CClF 2 0.3121
CF 3 CH 3 0.0161 CH 2 F 2 0.0121
CF 2 = CClF 0.0241 CF 2 = CHF 0.0012
HF 8.3276 HCl 0.4820
Other 0.0281
Unit: vol%
Catalyst Preparation Example 1 (Catalyst Example 1)
Into a 10 L container, 0.6 L of pure water was added and stirred. Into this, 1.2 L of pure water, 452 g of Cr (NO 3 ) 3 .9H 2 O and 42 g of In (NO 3 ) 3 .nH 2 O ( Control the flow rates of the two aqueous solutions so that the pH of the reaction solution is in the range of 7.5 to 8.5 with a solution in which n is about 5) and 0.31 L of 28% aqueous ammonia. The solution was added dropwise over about 1 hour. The obtained slurry was filtered off, and the solid matter separated by filtration was thoroughly washed with pure water and then dried at 120 ° C. for 12 hours. The dried solid was pulverized and then mixed with graphite, and pellets were prepared with a tableting machine. The pellet was calcined at 400 ° C. for 4 hours under a nitrogen stream to obtain a catalyst precursor. Next, the catalyst precursor was filled in an Inconel reactor, and fluorination treatment (activation of the catalyst) was performed at 350 ° C. using hydrogen fluoride to prepare a catalyst.
触媒の調製例２（触媒例２）
塩化クロム（ＣｒＣｌ3 ・６Ｈ2 Ｏ）１９１．５ｇを純水１３２ｍｌに投入し、湯浴上で７０〜８０℃に加熱して溶解した。溶液を室温まで冷却後、活性アルミナ（日揮ユニバ−サル（株）ＮＳＴ−７）４００ｇを浸漬して、アルミナに触媒液を全量吸収させた。次いで、触媒液で濡れた状態のアルミナを９０℃の湯浴上で乾燥し、乾固した。乾固した触媒を空気循環型の熱風乾燥器で１１０℃で３時間乾燥し、乾燥触媒をＳＵＳ製容器に充填し、空気流通下に４００℃まで昇温して、触媒前駆体を作成した。触媒のフッ素化処理（触媒の活性化）を触媒の調製例１と同様な手順、条件で実施し、触媒を調製した。
Catalyst Preparation Example 2 (Catalyst Example 2)
191.5 g of chromium chloride (CrCl 3 .6H 2 O) was put into 132 ml of pure water and dissolved by heating to 70 to 80 ° C. on a hot water bath. After cooling the solution to room temperature, 400 g of activated alumina (JGC Universal Co., Ltd. NST-7) was immersed to absorb the entire amount of the catalyst solution in the alumina. Next, the alumina wet with the catalyst solution was dried on a hot water bath at 90 ° C. and solidified. The dried catalyst was dried at 110 ° C. for 3 hours with an air circulation type hot air drier, filled with a dry catalyst in a SUS container, and heated to 400 ° C. under air flow to prepare a catalyst precursor. The catalyst was prepared by subjecting the catalyst to fluorination treatment (activation of the catalyst) in the same procedure and conditions as in Preparation Example 1 of the catalyst.
触媒の調製例３（触媒例３）
触媒例２に第２成分として塩化亜鉛（ＺｎＣｌ2 ）１６．６ｇを添加した以外は、触媒の調製例２と同様な手順、操作で実施し、触媒を調製した。
Catalyst Preparation Example 3 (Catalyst Example 3)
A catalyst was prepared by performing the same procedure and operation as in Catalyst Preparation Example 2, except that 16.6 g of zinc chloride (ZnCl 2 ) was added as a second component to Catalyst Example 2.
比較例
内径１インチ、長さ１ｍのインコネル６００型反応器に触媒の調製例１で得られた触媒（触媒例１）８０ｍｌを充填し、窒素ガスを流しながら反応器温度を１８０℃に保持し、粗１，１，１，２−テトラフルオロエタン（原料例１）を反応器に導入し、その後窒素ガスの供給を停止し、粗１，１，１，２−テトラフルオロエタンのみを触媒に７２ＮＬ／ｈｒで供給し、約４時間後、排出ガスをアルカリ水溶液で酸分除去後、ガス組成をガスクロマトグラフを用いて分析したところ、次のような組成を有していた。
Comparative Example An Inconel 600 type reactor having an inner diameter of 1 inch and a length of 1 m was filled with 80 ml of the catalyst obtained in Catalyst Preparation Example 1 (Catalyst Example 1), and the reactor temperature was maintained at 180 ° C. while flowing nitrogen gas. Then, crude 1,1,1,2-tetrafluoroethane (raw material example 1) was introduced into the reactor, and then the supply of nitrogen gas was stopped, and only crude 1,1,1,2-tetrafluoroethane was used as a catalyst. The gas was supplied at 72 NL / hr, and after about 4 hours, the exhaust gas was acid-removed with an aqueous alkaline solution, and the gas composition was analyzed using a gas chromatograph. The gas composition had the following composition.
ＣＦ3 ＣＨ2 Ｆ ９０．２９９３ ＣＨＣｌ＝ＣＨＦ ０．０００３
ＣＦ3 ＣＨ2 Ｃｌ ７．６２４７ ＣＦ3 ＣＨ3 ０．６２６０
ＣＦ3 ＣＨＦ2 ０．５９１６ ＣＦ3 ＣＨＣｌＦ ０．５９０４
ＣＨＦ2 ＣＨＦ2 ０．１７７９ ＣＦ3 ＣＣｌＦ2 ０．０６０１
ＣＦ2 ＝ＣＨＣｌ ０．０２７８ ＣＨ2 ＣｌＣＨＦ2 ０．００１９
単位：ｖｏｌ％
上記の分析結果から明らかなように粗１，１，１、２−テトラフルオロエタン中の不飽和化合物の転化率は約９５．８％であり、完全に除去できていないことが分かる。
CF 3 CH 2 F 90.993 CHCl═CHF 0.0003
CF 3 CH 2 Cl 7.6247 CF 3 CH 3 0.6260
CF 3 CHF 2 0.5916 CF 3 CHClF 0.5904
CHF 2 CHF 2 0.1779 CF 3 CClF 2 0.0601
CF 2 = CHCl 0.0278 CH 2 ClCHF 2 0.0019
Unit: vol%
As apparent from the above analysis results, the conversion of the unsaturated compound in the crude 1,1,1,2-tetrafluoroethane is about 95.8%, and it can be seen that it has not been completely removed.
次に、上記の条件で反応を継続し、２４００時間後、排出ガスの組成を分析したところ、ＣＦ2 ＝ＣＨＣｌの含有量が増加したことが認められ、不飽和化合物の転化率は約９３％に低下した。この時点で反応を停止し、触媒を取り出して表面観察をおこなったところ、カーボン（黒色）の触媒表面への付着が認められた。 Next, the reaction was continued under the above conditions, and after 2400 hours, the composition of the exhaust gas was analyzed. As a result, it was found that the content of CF 2 ═CHCl was increased, and the conversion rate of the unsaturated compound was about 93%. Declined. At this point, the reaction was stopped, the catalyst was taken out and the surface was observed, and adhesion of carbon (black) to the catalyst surface was observed.
実施例１
内径１インチ、長さ１ｍのインコネル６００型反応器に比較例と同様に、触媒の調製例１で得られた触媒（触媒例１）８０ｍｌを充填し、窒素ガスを流しながら反応器温度を１８０℃に保持し、反応器入り口よりフッ化水素を１０ＮＬ／ｈｒ供給し、次いで粗１，１，１，２−テトラフルオロエタン（原料例１）を反応器に７２ＮＬ／ｈｒで供給し、その後窒素ガスの供給を停止し、約４時間後、排出ガスをアルカリ水溶液で酸分除去後、ガス組成をガスクロマトグラフを用いて分析したところ、次のような組成を有していた。
Example 1
As in the comparative example, an Inconel 600 type reactor having an inner diameter of 1 inch and a length of 1 m was filled with 80 ml of the catalyst obtained in Catalyst Preparation Example 1 (Catalyst Example 1), and the reactor temperature was increased to 180 while flowing nitrogen gas. Then, hydrogen fluoride is supplied at 10 NL / hr from the reactor inlet, and then crude 1,1,1,2-tetrafluoroethane (raw material example 1) is supplied to the reactor at 72 NL / hr, and then nitrogen is supplied. The gas supply was stopped, and after about 4 hours, the exhaust gas was acid-removed with an alkaline aqueous solution, and the gas composition was analyzed using a gas chromatograph. The gas composition had the following composition.
ＣＦ3 ＣＨ2 Ｆ ９０．２９９８ ＣＨＣｌ＝ＣＨＦ ＜０．０００１
ＣＦ3 ＣＨ2 Ｃｌ ７．６５２４ ＣＦ3 ＣＨ3 ０．６２５９
ＣＦ3 ＣＨＦ2 ０．５９１８ ＣＦ3 ＣＨＣｌＦ ０．５９０２
ＣＨＦ2 ＣＨＦ2 ０．１７７７ ＣＦ3 ＣＣｌＦ2 ０．０６００
ＣＦ2 ＝ＣＨＣｌ ＜０．０００１ ＣＨ2 ＣｌＣＨＦ2 ０．００２０
単位：ｖｏｌ％
分析結果から明らかなように、新たにフッ化水素を粗１，１，１，２−テトラフルオロエタンに添加することにより不飽和化合物の転化率は約９９．９％となった。
CF 3 CH 2 F 90.2998 CHCl═CHF <0.0001
CF 3 CH 2 Cl 7.6524 CF 3 CH 3 0.6259
CF 3 CHF 2 0.5918 CF 3 CHClF 0.5902
CHF 2 CHF 2 0.1777 CF 3 CClF 2 0.0600
CF 2 ═CHCl <0.0001 CH 2 ClCHF 2 0.0020
Unit: vol%
As is apparent from the analysis results, the conversion of the unsaturated compound was about 99.9% by newly adding hydrogen fluoride to the crude 1,1,1,2-tetrafluoroethane.
次に、上記のアルカリ水溶液で酸分除去後のガスをシリンダーを冷却しながら回収し、蒸留することによって低沸カットおよび高沸カットを行い、高純度の１，１，１，２−テトラフルオロエタンを得て、純度分析をガスクロマトグラフ（ＴＣＤ法、ＦＩＤ法）およびガスクロマトグラフ−質量分析計（ＧＣ−ＭＳ法）を用いて分析したところ、次のような組成を有していた。 Next, the gas after acid removal with the above alkaline aqueous solution is recovered while cooling the cylinder, and is distilled to perform low boiling cut and high boiling cut to obtain high purity 1,1,1,2-tetrafluoro. Ethane was obtained, and purity analysis was performed using a gas chromatograph (TCD method, FID method) and a gas chromatograph-mass spectrometer (GC-MS method). The resulting composition had the following composition.
ＣＦ3 ＣＨ2 Ｆ ９９．９９５６ ＣＨＦ2 ＣＨＦ2 ０．００４２
含塩素化合物 ＜０．０００２
単位：ｖｏｌ％
上記の結果から明らかなように、１，１，１、２−テトラフルオロエタン中には含塩素化合物は２ｖｏｌｐｐｍ以下であり、異性体である１，１，２，２−テトラフルオロエタンを併せれば純度は約９９．９９９ｖｏｌ％以上となる。
CF 3 CH 2 F 99.9956 CHF 2 CHF 2 0.0042
Chlorine-containing compound <0.0002
Unit: vol%
As is clear from the above results, the chlorine-containing compound is 2 volppm or less in 1,1,1,2-tetrafluoroethane, and the isomer 1,1,2,2-tetrafluoroethane is combined. The purity is about 99.999 vol% or more.
また、上記の粗１，１，１，２−テトラフルオロエタンの精製反応を同様な条件で継続し、２４００時間後排出ガスの組成を分析したところ、比較例で見られたようなＣＦ2 ＝ＣＨＣｌの増加は認められず、不飽和化合物の転化率も約９９％以上を維持していた。 Further, the purification reaction of the crude 1,1,1,2-tetrafluoroethane was continued under the same conditions, and the composition of the exhaust gas was analyzed after 2400 hours. As a result, CF 2 = No increase in CHCl was observed, and the conversion rate of unsaturated compounds was maintained at about 99% or more.
この時点で比較例と同様に反応を停止し、触媒を取り出して表面観察を行なったところ、カ−ボンの付着は認められなかった。その後、触媒を反応器に再充填し、さらに２０００時間、同様な条件で反応を継続したが、不飽和化合物の転化率は約９９％以上を維持していた。 At this time, the reaction was stopped as in the comparative example, and the catalyst was taken out and the surface was observed. As a result, no adhesion of carbon was observed. Thereafter, the catalyst was recharged in the reactor, and the reaction was continued under the same conditions for 2000 hours. However, the conversion rate of the unsaturated compound was maintained at about 99% or more.
実施例２
内径２０．６ｍｍφ、長さ５００ｍｍのインコネル６００製反応器（電気ヒーター加熱方式：フッ素ガスで温度５００℃で不動態化処理を実施済）に窒素ガスを３０ＮＬ／ｈｒ流し、２８０℃に昇温した。次いで、希釈ガスとしてフッ化水素を５０ＮＬ／ｈｒ流し、さらに分岐した希釈ガスのガス流の一方へ実施例１で得られた１，１，１，２−テトラフルオロエタンを１．８ＮＬ／ｈｒ流した。その後、同様に分岐した希釈ガスのガス流のもう一方へフッ素ガスを２．７ＮＬ／ｈｒ流し、反応を行なった。３時間後、反応ガスを水酸化カリウム水溶液およびヨウ化カリウム水溶液でフッ化水素およびフッ素ガスを除去し、次いでガスクロマトグラフにて組成分析を行なったところ、ガス組成は次の通りであった。
Example 2
Nitrogen gas was supplied at a flow rate of 30 NL / hr to an Inconel 600 reactor having an inner diameter of 20.6 mmφ and a length of 500 mm (electric heater heating system: passivated with fluorine gas at a temperature of 500 ° C.) and heated to 280 ° C. . Next, hydrogen fluoride was flowed as a dilution gas at 50 NL / hr, and 1,1,1,2-tetrafluoroethane obtained in Example 1 was flowed at 1.8 NL / hr into one of the branched dilution gas flows. did. Thereafter, fluorine gas was allowed to flow at 2.7 NL / hr to the other of the branched diluting gas flows to carry out the reaction. Three hours later, hydrogen fluoride and fluorine gas were removed from the reaction gas with an aqueous potassium hydroxide solution and an aqueous potassium iodide solution, and then composition analysis was performed by gas chromatography. The gas composition was as follows.
ＣＦ4 ０．４８７０ ＣＦ3 ＣＦ3 ４９．６００１
ＣＦ3 ＣＨＦ2 ４９．９１２６ ＣＦ3 ＣＨ2 Ｆ ＜０．０００１
含塩素化合物 ＜０．０００２
単位：ｖｏｌ％
次に、上記のフッ化水素およびフッ素ガスを除去した後のガスをシリンダーを冷却しながら回収し、蒸留することによってＣＦ3 ＣＦ3 およびＣＦ3 ＣＨＦ2 を分離し、それぞれを低沸カットおよび高沸カットし、製品をガスクロマトグラフおよびＧＣ−ＭＳで分析したところ、ＣＦ3 ＣＦ3 の純度は９９．９９９９ｖｏｌ％以上であり、またＣＦ3 ＣＨＦ2 の純度は９９．９９９８ｖｏｌ％であり、高純度製品を取得することができた。
CF 4 0.4870 CF 3 CF 3 49.6001
CF 3 CHF 2 49.9126 CF 3 CH 2 F <0.0001
Chlorine-containing compound <0.0002
Unit: vol%
Next, the gas after removing the above hydrogen fluoride and fluorine gas was recovered while cooling the cylinder, and distilled to separate CF 3 CF 3 and CF 3 CHF 2 , respectively. When boiling cut and the product was analyzed by gas chromatograph and GC-MS, the purity of CF 3 CF 3 was 99.9999 vol% or more, and the purity of CF 3 CHF 2 was 99.998 vol%, which is a high purity product Was able to get.
実施例３
内径１インチ、長さ１ｍのインコネル６００型反応器に触媒の調製例２で得られた触媒（触媒例２）８０ｍｌを充填し、窒素ガスを流しながら反応器温度を１８０℃に保持し、反応器入り口よりフッ化水素を１０ＮＬ／ｈｒ供給し、次いで粗ペンタフルオロエタン（原料例２）を反応器に７２ＮＬ／ｈｒ供給し、その後窒素ガスの供給を停止し、約４時間後、排出ガスをアルカリ水溶液で酸分除去後、ガスクロマトグラフを用いて分析したところ、次のような組成を有していた。
Example 3
An Inconel 600 type reactor having an inner diameter of 1 inch and a length of 1 m is filled with 80 ml of the catalyst obtained in Catalyst Preparation Example 2 (Catalyst Example 2), and the reactor temperature is maintained at 180 ° C. while flowing nitrogen gas. Hydrogen fluoride is supplied from the inlet of the reactor at 10 NL / hr, then crude pentafluoroethane (raw material example 2) is supplied to the reactor at 72 NL / hr, and then the supply of nitrogen gas is stopped. After about 4 hours, the exhaust gas is discharged. When the acid content was removed with an alkaline aqueous solution and analyzed using a gas chromatograph, it had the following composition.
ＣＦ3 ＣＨＦ2 ９５．３７３４ ＣＦ3 ＣＨＣｌＦ ４．２１５６
ＣＦ3 ＣＨＣｌ2 ０．００５６ ＣＦ3 ＣＣｌＦ2 ０．３４２２
ＣＦ3 ＣＨ3 ０．０１７６ ＣＨ2 Ｆ2 ０．０１３３
ＣＦ2 ＝ＣＣｌＦ ＜０．０００２ ＣＦ2 ＝ＣＨＦ ＜０．０００１
ＣＦ3 ＣＨ2 Ｆ ０．００１２ その他 ０．０３０８
単位：ｖｏｌ％
上記の結果から明らかなように、粗ペンタフルオロエタン中の不飽和化合物は約９９％を除去（転化）することができた。
CF 3 CHF 2 95.3734 CF 3 CHClF 4.2156
CF 3 CHCl 2 0.0056 CF 3 CClF 2 0.3422
CF 3 CH 3 0.0176 CH 2 F 2 0.0133
CF 2 = CClF <0.0002 CF 2 = CHF <0.0001
CF 3 CH 2 F 0.0012 Other 0.0308
Unit: vol%
As is apparent from the above results, about 99% of the unsaturated compound in the crude pentafluoroethane could be removed (converted).
実施例４
内径１インチ、長さ１ｍのインコネル６００型反応器に触媒の調製例３で得られた触媒（触媒例３）８０ｍｌを充填し、窒素ガスを流しながら反応器温度を１８０℃に保持し、反応器入り口よりフッ化水素を１０ＮＬ／ｈｒ供給し、次いで粗１，１，１，２−テトラフルオロエタン（原料例１）３６ＮＬ／ｈｒと粗ペンタフルオロエタン（原料例２）３６ＮＬ／ｈｒを反応器入り口で混合して反応器に供給し、その後窒素ガスの供給を停止し、約４時間後、排出ガスをアルカリ水溶液で酸分除去後、ガス組成をガスクロマトグラフで分析したところ、含有されていた不飽和化合物は約９９％が除去（転化）できた。
Example 4
An Inconel 600 type reactor having an inner diameter of 1 inch and a length of 1 m was filled with 80 ml of the catalyst obtained in Catalyst Preparation Example 3 (Catalyst Example 3), and the reactor temperature was maintained at 180 ° C. while flowing nitrogen gas. Hydrogen fluoride is supplied at 10 NL / hr from the inlet of the vessel, and then crude 1,1,1,2-tetrafluoroethane (raw material example 1) 36 NL / hr and crude pentafluoroethane (raw material example 2) 36 NL / hr are reacted in the reactor. After mixing at the inlet and supplying to the reactor, the supply of nitrogen gas was stopped, and after about 4 hours, the exhaust gas was acid-removed with an alkaline aqueous solution, and the gas composition was analyzed by gas chromatography. About 99% of unsaturated compounds could be removed (converted).
本発明は、低温用冷媒、エッチングガスやクリーニングガスとして有利に利用することのできる１，１，１，２−テトラフルオロエタンおよびペンタフルオロエタンの製造に有用である。 The present invention is useful for the production of 1,1,1,2-tetrafluoroethane and pentafluoroethane that can be advantageously used as a low-temperature refrigerant, etching gas or cleaning gas.
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| JPH06184015A (en) * | 1992-08-05 | 1994-07-05 | Elf Atochem Sa | Method for purifying 1,1,1,2-tetrafluoroethane |
| JPH1112200A (en) * | 1997-06-18 | 1999-01-19 | Showa Denko Kk | Production of perfluorocarbon |
| JP2002003415A (en) * | 2000-06-21 | 2002-01-09 | Showa Denko Kk | Method for producing hexafluoroethane and its use |
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| JPH06184015A (en) * | 1992-08-05 | 1994-07-05 | Elf Atochem Sa | Method for purifying 1,1,1,2-tetrafluoroethane |
| JPH1112200A (en) * | 1997-06-18 | 1999-01-19 | Showa Denko Kk | Production of perfluorocarbon |
| JP2002003415A (en) * | 2000-06-21 | 2002-01-09 | Showa Denko Kk | Method for producing hexafluoroethane and its use |
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