JPH09255596A - Production of lower perfluoroalkane - Google Patents
Production of lower perfluoroalkaneInfo
- Publication number
- JPH09255596A JPH09255596A JP8065985A JP6598596A JPH09255596A JP H09255596 A JPH09255596 A JP H09255596A JP 8065985 A JP8065985 A JP 8065985A JP 6598596 A JP6598596 A JP 6598596A JP H09255596 A JPH09255596 A JP H09255596A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- oxygen
- molar ratio
- trifluoromethane
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 15
- 229910052738 indium Inorganic materials 0.000 abstract description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- MLGFOYVBHZGRBK-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]-2-hydroxy-n-methyl-2-phenyl-2-thiophen-2-ylacetamide;hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(O)(C(=O)N(C)CCN(C)C)C1=CC=CS1 MLGFOYVBHZGRBK-UHFFFAOYSA-N 0.000 description 21
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000007423 decrease Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001512 metal fluoride Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004341 Octafluorocyclobutane Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical class F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 1
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 1
- -1 perfluoro compound Chemical class 0.000 description 1
- 229960004065 perflutren Drugs 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、低級パーフルオロ
アルカンの製造方法に関するものであり、更に詳しく
は、近年半導体用ドライエッチングガス及びチャンバー
内クリーニングガス等に用いられるようになり、その有
用性が著しく増大しているので安定供給が求められてい
るガスであるテトラフルオロメタン（ＣＦ4 ）（以下、
ＦＣ−１４と称す）およびヘキサフルオロエタン（ＣＦ
3 ＣＦ3 ）（以下、ＦＣ−１１６と称す）などの低級パ
ーフルオロアルカンの製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a lower perfluoroalkane, and more specifically, it has been recently used as a dry etching gas for semiconductors, a cleaning gas in a chamber, etc. Since it has increased remarkably, tetrafluoromethane (CF 4 ) (hereinafter, referred to as a gas that requires stable supply)
FC-14) and hexafluoroethane (CF
3 CF 3 ) (hereinafter referred to as FC-116) and the like.
【０００２】[0002]
【従来の技術】従来からのＦＣ−１４及びＦＣ−１１６
の製造方法としては下記の（１）〜（５）の方法などが
知られている。 （１）テトラフルオロエチレンと二酸化炭素とを熱分解
反応させる方法（特開昭５７−１２６４３０号公報）。 （２）トリフルオロメタン（ＣＨＦ3 ）（以下、ＨＦＣ
−２３と称す）を活性炭触媒、１８族型元素周期表の１
族または２族の金属フッ化物触媒、フッ化アルミニウム
触媒の存在下で熱分解反応させる方法（特公昭３９−２
１２２５号公報）。 （３）トリフルオロモノブロモメタン（ＣＦ3 Ｂｒ）を
白金触媒の存在下で熱分解する方法（特開平５−２８６
８７４号公報）。 （４）炭化水素又はハイドロフルオロカーボン（以下、
ＨＦＣと称す）又はパーハロカーボン（例えば、ＣＦ3
Ｃｌ、Ｃ2 Ｆ5 Ｃｌ等）とフッ素ガス（以下、Ｆ2 と称
す）とを反応させる方法（Ｊ．Ａｍｅｒ．Ｃｈｅｍ．Ｓ
ｏｃ．，７７，３００７（１９５５）、英国特許第１１
１６９２０号、ヨーロッパ特許第３２２１０号、米国特
許第５４０６００８号、特開昭６１−１３４３３０号公
報、特開昭６１−１４８１３１号公報）。 （５）パークロロカーボンあるいは部分的にフッ素化さ
れたクロロフルオロカーボンとフッ化水素（ＨＦ）を触
媒の存在下反応させる方法。2. Description of the Related Art Conventional FC-14 and FC-116
The following methods (1) to (5) are known as methods for producing (1) A method of thermally decomposing tetrafluoroethylene and carbon dioxide (JP-A-57-126430). (2) Trifluoromethane (CHF 3 ) (hereinafter HFC
-23) is an activated carbon catalyst, 1 of the periodic table of 18 group elements.
Method of thermal decomposition reaction in the presence of Group 3 or Group 2 metal fluoride catalyst and aluminum fluoride catalyst (Japanese Patent Publication No. 39-2
1225). (3) thermally decomposing in the presence of trifluoroacetic monobromo methane (CF 3 Br) a platinum catalyst (JP-A-5-286
874). (4) Hydrocarbon or hydrofluorocarbon (hereinafter,
HFC) or perhalocarbons (eg CF 3
Cl, C 2 F 5 Cl, etc.) and a fluorine gas (hereinafter referred to as F 2 ) are reacted (J. Amer. Chem. S.
oc. , 77, 3007 (1955), British Patent No. 11
16920, European Patent 32210, US Pat. No. 5,406,008, JP-A-61-134330, JP-A-61-148131). (5) A method of reacting perchlorocarbon or partially fluorinated chlorofluorocarbon with hydrogen fluoride (HF) in the presence of a catalyst.
【０００３】しかし、上記の（１）〜（５）の従来の方
法は下記のような問題点があり、商業生産の観点から有
効な製造方法とはいえない。上記（１）の方法は、１０
００℃を越える温度が必要であり、また、滞留時間も約
１分間と長いため反応器が大きくなる。上記（２）の方
法は、反応の進行に伴い発生する炭素が触媒上に蓄積す
るため触媒の活性を維持することが困難である。上記
（３）の方法は、高価な白金系の触媒を使用し、経済性
に問題が有る。上記（４）の方法は、高価なＦ2 を用い
るため経済的に不利となる。上記（５）の方法は、塩素
とフッ素の置換によりパーフルオロ体に至るが、最後の
１つの塩素の置換段階が極めて困難である上、反応にか
なりの高温を要し触媒の寿命が短い。However, the conventional methods (1) to (5) described above have the following problems and cannot be said to be effective production methods from the viewpoint of commercial production. The method of (1) above is 10
A temperature of more than 00 ° C is required, and the residence time is as long as about 1 minute, so that the reactor becomes large. In the above method (2), it is difficult to maintain the activity of the catalyst because the carbon generated as the reaction proceeds accumulates on the catalyst. The method (3) uses an expensive platinum-based catalyst and has a problem in economic efficiency. The above method (4) is economically disadvantageous because expensive F 2 is used. In the above method (5), a perfluoro compound is obtained by substituting chlorine with fluorine, but the last step of substituting one chlorine is extremely difficult, the reaction requires a considerably high temperature, and the life of the catalyst is short.
【０００４】[0004]
【発明が解決しようとする課題】ＨＦＣ−２３を触媒の
存在下、加熱して、低級パーフルオロアルカンを製造す
る従来の方法は、反応の進行に伴い発生する炭素が触媒
上に炭素が析出して、触媒の活性が低下し、連続して低
級パーフルオロアルカンを製造できない問題が有る。本
発明の目的は、触媒の活性低下を起こすことなく、連続
して、ＦＣ−１４、ＦＣ−１１６などの低級パーフルオ
ロアルカンを高収率、低価格で製造方法を提供すること
である。In the conventional method for producing a lower perfluoroalkane by heating HFC-23 in the presence of a catalyst, carbon generated as the reaction progresses and carbon is deposited on the catalyst. Therefore, there is a problem that the activity of the catalyst is lowered and the lower perfluoroalkane cannot be continuously produced. An object of the present invention is to provide a method for continuously producing a lower perfluoroalkane such as FC-14 and FC-116 in a high yield and at a low price without causing a decrease in the activity of the catalyst.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、上記の課
題を解決すべく鋭意研究を重ねた結果、ＨＦＣ−２３を
触媒存在下で５００〜９００℃に加熱してＦＣ−１４、
ＦＣ−１１６などの低級パーフルオロアルカンを製造す
る際に、酸素をモル比（Ｏ2 ／ＨＦＣ−２３）０．１〜
１．０の範囲でＨＦＣ−２３と同時に供給し、その触媒
に接触させて反応させることで、連続して高収率で低級
パーフルオロアルカンを製造できることを明らかにし、
本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have heated HFC-23 to 500 to 900 ° C. in the presence of a catalyst to produce FC-14,
When producing a lower perfluoroalkane such as FC-116, oxygen is added in a molar ratio (O 2 / HFC-23) of 0.1 to 0.1.
It was clarified that a lower perfluoroalkane can be continuously produced at a high yield by supplying HFC-23 at the same time in the range of 1.0 and contacting the catalyst to cause a reaction,
The present invention has been completed.
【０００６】すなわち、本発明の請求項１の発明は、Ｈ
ＦＣ−２３と酸素の混合比（モル比：酸素／ＨＦＣ−２
３）が０．１〜１．０の混合ガスを５００〜９００℃の
温度範囲で触媒存在下、この触媒に接触させて反応させ
ることを特徴とする低級パーフルオロアルカンの製造方
法である。That is, the invention of claim 1 of the present invention is H
Mixing ratio of FC-23 and oxygen (molar ratio: oxygen / HFC-2
3) is a process for producing a lower perfluoroalkane, which comprises reacting a mixed gas of 0.1 to 1.0 in the temperature range of 500 to 900 ° C. in the presence of the catalyst to bring it into contact with the catalyst.
【０００７】本発明の請求項２の発明は、請求項１に記
載の製造方法において、触媒が、１８族型元素周期表の
８族、１０族、１１族、１２族および１３族から選ばれ
る少なくとも１つの金属の塩又は酸化物を無水フッ酸又
はフッ素ガスで処理をしたものを使用することを特徴と
する。According to a second aspect of the present invention, in the production method according to the first aspect, the catalyst is selected from Group 8, Group 10, Group 11, Group 12 and Group 13 of the Group 18 type periodic table. It is characterized in that at least one metal salt or oxide treated with hydrofluoric acid anhydride or fluorine gas is used.
【０００８】本発明の請求項３の発明は、請求項１ある
いは請求項２に記載の製造方法において、低級パーフル
オロアルカンがＦＣ−１１６であることを特徴とする。The invention according to claim 3 of the present invention is characterized in that, in the manufacturing method according to claim 1 or 2, the lower perfluoroalkane is FC-116.
【０００９】本発明の請求項４の発明は、請求項２ある
いは請求項３に記載の製造方法において、前記金属が亜
鉛および／またはニッケルであることを特徴とする。The invention according to claim 4 of the present invention is characterized in that, in the manufacturing method according to claim 2 or 3, the metal is zinc and / or nickel.
【００１０】本発明の請求項５の発明は、請求項１ない
し請求項４に記載の製造方法において、ＨＦＣ−２３と
酸素の混合比を０．２〜０．５の範囲で変えることによ
り、生成物中のＦＣ−１１６の比率を変えることを特徴
とする請求項１ないし請求項４に記載の製造方法。According to a fifth aspect of the present invention, in the manufacturing method according to the first to fourth aspects, the mixing ratio of HFC-23 and oxygen is changed within the range of 0.2 to 0.5. The method according to claim 1, wherein the ratio of FC-116 in the product is changed.
【００１１】[0011]
【発明の実施の形態】本発明における反応生成ガスは、
以下に示した反応式［３］〜反応式［７］により発生し
ているものと推察される。従来のＨＦＣ−２３の熱分解
反応では、以下に示した反応式［１］及び反応式［２］
に示されるように、反応の進行に伴い発生する炭素が触
媒上に蓄積し活性の維持継続が困難であったのに対し
て、本発明の第１の利点は酸素を反応ガスと共に供給す
ることで触媒活性の低下を防ぐ効果がある点である。BEST MODE FOR CARRYING OUT THE INVENTION The reaction product gas in the present invention is
It is presumed that this occurs due to the reaction formulas [3] to [7] shown below. In the conventional thermal decomposition reaction of HFC-23, the following reaction formula [1] and reaction formula [2]
As shown in Fig. 3, carbon generated with the progress of the reaction accumulated on the catalyst and it was difficult to maintain the activity, whereas the first advantage of the present invention is that oxygen is supplied together with the reaction gas. That is, it has an effect of preventing a decrease in catalytic activity.
【００１２】[0012]
【化１】 ２ＣＨＦ3 → ＣＦ4 ＋Ｃ ＋２ＨＦ ［１］ ３ＣＨＦ3 → Ｃ2 Ｆ6 ＋Ｃ ＋３ＨＦ ［２］ ２ＣＨＦ3 ＋Ｏ2 → ＣＦ4 ＋ＣＯ2 ＋２ＨＦ ［３］ ３ＣＨＦ3 ＋Ｏ2 → Ｃ2 Ｆ6 ＋ＣＯ2 ＋３ＨＦ ［４］ ２ＣＨＦ3 ＋ＣＯ2 → ＣＦ4 ＋２ＣＯ＋２ＨＦ ［５］ ３ＣＨＦ3 ＋ＣＯ2 → Ｃ2 Ｆ6 ＋３ＣＯ＋３ＨＦ ［６］ ２ＣＨＦ3 ＋Ｏ2 →２ＣＯＦ2 ＋２ＨＦ ［７］Embedded image 2CHF 3 → CF 4 + C + 2HF [1] 3CHF 3 → C 2 F 6 + C + 3HF [2] 2CHF 3 + O 2 → CF 4 + CO 2 + 2HF [3] 3CHF 3 + O 2 → C 2 F 6 + CO 2 + 3HF [4] 2CHF 3 + CO 2 → CF 4 + 2CO + 2HF [5] 3CHF 3 + CO 2 → C 2 F 6 + 3CO + 3HF [6] 2CHF 3 + O 2 → 2COF 2 + 2HF [7]
【００１３】本発明の第２の利点は、酸素を供給しない
場合に比べ、酸素を供給しながら熱分解反応を行うと触
媒表面が一部酸化されてオキシフッ化物となると考えら
れ、それにより低級パーフルオロアルカンの空間時間収
率が増加するため、使用する触媒量が少なくてすみ、反
応器のコンパクト化が可能となり、経済的である点であ
る。更に本発明の第３の利点は、触媒に使用する金属種
を選択することで、ＦＣ−１４とＦＣ−１１６の生成す
る比率を変化させることができる点である。The second advantage of the present invention is considered to be that when the thermal decomposition reaction is carried out while oxygen is supplied, the catalyst surface is partially oxidized to form an oxyfluoride, as compared with the case where oxygen is not supplied. Since the space-time yield of fluoroalkane increases, the amount of catalyst used can be small and the reactor can be made compact, which is economical. A third advantage of the present invention is that the ratio of FC-14 and FC-116 produced can be changed by selecting the metal species used for the catalyst.
【００１４】上記のように、副生成物として、ＣＯ2 、
ＣＯ、ＣＯＦ2 が発生するが、ＣＯＦ2 は水と容易に反
応してＣＯ2 とＨＦになるため反応ガスを洗浄すること
で容易に除去することができる。また、反応式［５］及
び反応式［６］に示されるように、ＣＯ2 も触媒上に炭
素が析出することの防止に寄与している。熱分解反応中
に酸素を供給するのと同様に、ＣＯ2 を供給しても良い
が、酸素ほどの効果は得られない。As described above, as a by-product, CO 2 ,
CO and COF 2 are generated, but since COF 2 easily reacts with water to form CO 2 and HF, it can be easily removed by washing the reaction gas. Further, as shown in the reaction formulas [5] and [6], CO 2 also contributes to the prevention of carbon deposition on the catalyst. Although CO 2 may be supplied in the same manner as oxygen is supplied during the thermal decomposition reaction, it is not as effective as oxygen.
【００１５】酸素／ＨＦＣ−２３のモル比は０．１〜
１．０の範囲が好ましく、より好ましくは０．２〜０．
５の範囲である。モル比が０．１未満であると酸素によ
る触媒上の炭素析出防止効果が小さく触媒上に炭素が蓄
積して行くため活性の維持ができなくなる。モル比が
１．０を超えると上記反応式［７］の副反応が顕著とな
り低級パーフルオロアルカンの生成量が減少する。更に
注目すべき点は、酸素／ＨＦＣ−２３のモル比を変える
ことで、ＦＣ−１１６の生成比率を変えられることであ
る。酸素／ＨＦＣ−２３のモル比を０．２〜０．５の範
囲内で低くすることで、ＦＣ−１１６の生成比率を高く
することができる。The molar ratio of oxygen / HFC-23 is 0.1.
The range of 1.0 is preferable, and more preferably 0.2-0.
The range is 5. If the molar ratio is less than 0.1, the effect of preventing carbon deposition on the catalyst by oxygen is small, and the carbon cannot be maintained because the carbon is accumulated on the catalyst. When the molar ratio exceeds 1.0, the side reaction of the above reaction formula [7] becomes remarkable and the amount of lower perfluoroalkane produced decreases. More noteworthy is that the production ratio of FC-116 can be changed by changing the molar ratio of oxygen / HFC-23. By lowering the oxygen / HFC-23 molar ratio within the range of 0.2 to 0.5, the production ratio of FC-116 can be increased.
【００１６】反応温度は５００〜９００℃の範囲が望ま
しく、より望ましくは６５０〜８００℃の範囲であり、
触媒に使用する金属のフッ化物の融点を越えない温度を
選択する。５００℃未満の温度ではＨＦＣ−２３の反応
率が低くなり、９００℃を超える温度では反応器の材質
の腐食量が著しく増加し、また、触媒の構造変化が発生
し活性低下を生ずるため好ましくない。The reaction temperature is preferably in the range of 500 to 900 ° C, more preferably in the range of 650 to 800 ° C.
Select a temperature that does not exceed the melting point of the fluoride of the metal used in the catalyst. If the temperature is lower than 500 ° C, the reaction rate of HFC-23 is low, and if the temperature is higher than 900 ° C, the amount of corrosion of the material of the reactor is remarkably increased, and the structural change of the catalyst occurs, which is not preferable because the activity is lowered. .
【００１７】本発明の反応形式は、流動床でも固定床で
も可能であり、触媒の製造方法及び形状については特に
制限されない。固定床での触媒は、金属フッ化物を成形
したものを使用しても良いし、金属酸化物の焼結体をフ
ッ化水素またはフッ素でフッ素化したものを使用しても
良いし、各触媒金属の塩化物もしくは硝酸塩もしくは硫
酸塩等の水溶液を例えばアルミナのような、そのフッ化
物が担体となり得るようなポーラスな金属酸化物に含浸
させ、乾燥、焼成したものをフッ化水素またはフッ素で
フッ素化したものを使用しても良い。金属フッ化物を触
媒として充填した場合、反応中にオキシフッ化物となる
と考えられる。The reaction system of the present invention may be either a fluidized bed or a fixed bed, and the method and shape of the catalyst are not particularly limited. As the catalyst in the fixed bed, a molded product of metal fluoride may be used, or a sintered product of metal oxide may be fluorinated with hydrogen fluoride or fluorine. An aqueous solution of a metal chloride, nitrate, or sulfate is impregnated with a porous metal oxide such as alumina whose fluoride can serve as a carrier, dried, and calcined to give hydrogen fluoride or fluorine. You may use what was converted. When a metal fluoride is filled as a catalyst, it is considered to become an oxyfluoride during the reaction.
【００１８】各金属の内で特に、亜鉛、ニッケル、イン
ジウムはＦＣ−１１６を選択的に生成し、銅及び鉄はＨ
ＦＣ−２３の酸化反応（上記反応式［７］）を抑制する
作用に優れ、マンガン、鉛、アルミは副生物のオクタフ
ルオロプロパン、オクタフルオロシクロブタン、ペンタ
フルオロエタン等の生成を抑制する作用がある。本発明
の触媒に用いる金属は、単独で用いても良いし、１種類
以上を混合して用いても良い。Among the metals, zinc, nickel and indium selectively produce FC-116, and copper and iron produce H.
It has an excellent effect of suppressing the oxidation reaction of FC-23 (the above reaction formula [7]), and manganese, lead and aluminum have an effect of suppressing the formation of by-products such as octafluoropropane, octafluorocyclobutane and pentafluoroethane. . The metals used in the catalyst of the present invention may be used alone or in combination of one or more.
【００１９】本発明に用いる反応器の構造及び材質に
は、特に制限を受けない。本発明による反応温度が確保
できる反応器で、反応ガス雰囲気での腐食に耐える材質
であれば良い。また、反応圧力については厳密な制限は
なく、常圧で反応は進行し、減圧、加圧でもなんら支障
はない。The structure and material of the reactor used in the present invention are not particularly limited. Any material can be used as long as it is a reactor capable of ensuring the reaction temperature according to the present invention and can withstand corrosion in a reaction gas atmosphere. Further, the reaction pressure is not strictly limited, the reaction proceeds at normal pressure, and there is no problem even if the pressure is reduced or increased.
【００２０】[0020]
【実施例】以下本発明を実施例、比較例により、具体的
に説明するが、本発明はこれら実施例によって限定され
るものではない。 （実施例１）比表面積が１５０ｍ2 ／ｇ、嵩密度が０．
３７ｇ／ｃｃ、吸水率が１．３のアルミナ（日揮ユニバ
ーサル社製ＮＳＴ−３）に塩化ニッケル水溶液をＮｉ／
Ａｌモル比が０．３になるように含浸させ、常圧下、１
２０℃で２４時間乾燥し、４５０℃で窒素気流中５時間
焼成し、フッ化水素を用いて４００℃で触媒の８５％を
フッ素化し、更に７５０℃でフッ素ガスにてフッ素化処
理を行い触媒を調製した。調製した触媒を反応器に１０
０ｃｃ充填し、反応温度７５０℃、接触時間２．４秒、
モル比（Ｏ2 ／ＨＦＣ−２３）０．３５で反応を行っ
た。１時間後の反応結果を表１に示した。EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Example 1 A specific surface area of 150 m 2 / g and a bulk density of 0.
Alumina (NST-3 manufactured by JGC Universal Co., Ltd.) having a water absorption rate of 37 g / cc and a water absorption rate of 1.3 was mixed with nickel chloride aqueous solution Ni /
It is impregnated so that the Al molar ratio becomes 0.3, and under normal pressure, 1
The catalyst is dried at 20 ° C for 24 hours, calcined at 450 ° C in a nitrogen stream for 5 hours, 85% of the catalyst is fluorinated with hydrogen fluoride at 400 ° C, and further fluorinated at 750 ° C with fluorine gas. Was prepared. The prepared catalyst was placed in the reactor.
0 cc filled, reaction temperature 750 ° C., contact time 2.4 seconds,
The reaction was carried out in a molar ratio (O 2 /HFC-23)0.35. The reaction results after 1 hour are shown in Table 1.
【００２１】（実施例２）塩化亜鉛水溶液を用いＺｎ／
Ａｌモル比を０．３としたこと以外は実施例１と同様に
して触媒を調製し、実施例１と同じ反応条件で反応を行
った。１時間後の反応結果を表１に示した。(Example 2) Using a zinc chloride aqueous solution, Zn /
A catalyst was prepared in the same manner as in Example 1 except that the Al molar ratio was 0.3, and the reaction was performed under the same reaction conditions as in Example 1. The reaction results after 1 hour are shown in Table 1.
【００２２】（実施例３）塩化鉄水溶液を用いＦｅ／Ａ
ｌモル比を０．３としたこと以外は実施例１と同様にし
て触媒を調製し、実施例１と同じ反応条件で反応を行っ
た。１時間後の反応結果を表１に示した。(Example 3) Fe / A using an aqueous solution of iron chloride
A catalyst was prepared in the same manner as in Example 1 except that the 1 mol ratio was 0.3, and the reaction was carried out under the same reaction conditions as in Example 1. The reaction results after 1 hour are shown in Table 1.
【００２３】（実施例４）硝酸銅水溶液を用いＣｕ／Ａ
ｌモル比を０．１としたこと以外は実施例１と同様にし
て触媒を調製し、実施例１と同じ反応条件で反応を行っ
た。１時間後の反応結果を表１に示した。(Example 4) Cu / A using an aqueous solution of copper nitrate
A catalyst was prepared in the same manner as in Example 1 except that the molar ratio was 0.1, and the reaction was carried out under the same reaction conditions as in Example 1. The reaction results after 1 hour are shown in Table 1.
【００２４】（実施例５）実施例１に用いたアルミナを
フッ化水素を用いて４００℃で触媒の８５％をフッ素化
し、更に７５０℃でフッ素ガスにてフッ素化処理を行い
触媒を調製した。調製した触媒を反応器１００ｃｃ充填
し、反応温度７５０℃、接触時間２．４秒、モル比０．
３５で反応を行った。１時間後の反応結果を表１に示し
た。(Example 5) The alumina used in Example 1 was fluorinated with hydrogen fluoride at 400 ° C to 85% of the catalyst, and further fluorinated at 750 ° C with fluorine gas to prepare a catalyst. . The prepared catalyst was charged in a reactor of 100 cc, the reaction temperature was 750 ° C., the contact time was 2.4 seconds, and the molar ratio was 0.1.
The reaction was carried out at 35. The reaction results after 1 hour are shown in Table 1.
【００２５】実施例１〜５より、アルミのみの触媒の場
合（実施例５）より、ニッケル及び亜鉛を担持した触媒
を用いると（実施例１、実施例２）、ＦＣ−１４より、
選択的にＦＣ−１１６の生成量が増加し、鉄及び銅を担
持した触媒を用いると（実施例３、実施例４）、ＦＣ−
１４及びＦＣ−１１６共に生成量が増加した。From Examples 1 to 5, from the case of a catalyst containing only aluminum (Example 5), using a catalyst supporting nickel and zinc (Examples 1 and 2), from FC-14,
When the amount of FC-116 produced increased selectively and a catalyst supporting iron and copper was used (Examples 3 and 4), FC-
Both 14 and FC-116 increased the production amount.
【００２６】（実施例６）モル比（Ｏ2 ／ＨＦＣ−２
３）を０．５とした以外は実施例１と同じ条件で反応を
行った。１時間後の反応結果を表１に示した。Example 6 Molar ratio (O 2 / HFC-2
The reaction was carried out under the same conditions as in Example 1 except that 3) was changed to 0.5. The reaction results after 1 hour are shown in Table 1.
【００２７】（実施例７）反応温度を６５０℃とした以
外は実施例１と同じ条件で反応を行った。１時間後の反
応結果を表１に示した。Example 7 The reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was 650 ° C. The reaction results after 1 hour are shown in Table 1.
【００２８】実施例１と実施例６との比較より、モル比
（Ｏ2 ／ＨＦＣ−２３）を変えることにより、ＦＣ−１
４とＦＣ−１１６の生成比率を変えることができること
がわかる。モル比（Ｏ2 ／ＨＦＣ−２３）を０．５（実
施例６）から０．３５（実施例１）と低くすることで、
ＦＣ−１１６の生成比率を高くすることができることが
わかる。また、実施例１と実施例７との比較より、反応
温度を７５０℃から６５０℃に下げることにより、パー
フルオロアルカンの生成速度が低下することがわかる。From the comparison between Example 1 and Example 6, FC-1 was changed by changing the molar ratio (O 2 / HFC-23).
It can be seen that the production ratio of 4 and FC-116 can be changed. Molar ratio (O 2 / HFC-23) by lowering 0.5 (Example 6) 0.35 (Example 1),
It can be seen that the production ratio of FC-116 can be increased. In addition, comparison between Example 1 and Example 7 reveals that the production rate of perfluoroalkane is reduced by lowering the reaction temperature from 750 ° C to 650 ° C.
【００２９】（実施例８）実施例２の触媒を反応器に１
００ｃｃ充填し、反応温度７５０℃、触媒時間２．４
秒、モル比０．３５で連続して反応を行った。５００時
間経過しても触媒活性の低下はなかった。Example 8 The catalyst of Example 2 was added to the reactor 1 times.
00cc filled, reaction temperature 750 ° C, catalyst time 2.4
The reaction was continuously performed at a molar ratio of 0.35 sec. The catalyst activity did not decrease even after 500 hours.
【００３０】（比較例１）実施例２の触媒を反応器に１
００ｃｃ充填し、反応温度７５０℃、触媒時間２．４秒
で酸素を供給せずに反応を行った。反応を開始してから
１時間後のＦＣ−１４の空間時間収率は１ｇ／ｈｒ／ｃ
ａｔ−ｌであり、ＦＣ−１１６の空間時間収率は９４ｇ
／ｈｒ／ｃａｔ−ｌであった。反応を継続するとＦＣ−
１４とＦＣ−１１６の空間時間収率は、徐々に低下し、
５０時間後のＦＣ−１４及びＦＣ−１１６の空間時間収
率は０ｇ／ｈｒ／ｃａｔ−ｌであった。(Comparative Example 1) The catalyst of Example 2 was placed in a reactor.
The reaction was performed at a reaction temperature of 750 ° C. and a catalyst time of 2.4 seconds without supplying oxygen. The space-time yield of FC-14 one hour after the reaction was started was 1 g / hr / c.
and the space-time yield of FC-116 is 94 g.
It was / hr / cat-1. If the reaction is continued, FC-
14 and FC-116 space-time yields gradually decreased
The space-time yield of FC-14 and FC-116 after 50 hours was 0 g / hr / cat-1.
【００３１】比較例１と実施例８との比較より、ＨＦＣ
−２３のみの反応では、炭素の析出により触媒活性が低
下し、ＨＦＣ−２３と共に酸素を供給すると触媒活性の
低下がなく、触媒の活性の維持ができることが明らかで
ある。From the comparison between Comparative Example 1 and Example 8, the HFC
It is clear that in the reaction of only -23, the catalytic activity decreases due to the deposition of carbon, and when oxygen is supplied together with HFC-23, the catalytic activity does not decrease and the activity of the catalyst can be maintained.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【発明の効果】本発明の低級パーフルオロアルカンの製
造方法により、ＦＣ−１４もしくはＦＣ−１１６などの
低級パーフルオロアルカンの収率が増加し、触媒の活性
低下を起こすことなく、連続して、ＦＣ−１４、ＦＣ−
１１６などの低級パーフルオロアルカンを高収率、低価
格で製造することができる。本発明の低級パーフルオロ
アルカンの製造方法により、低級パーフルオロアルカン
の空間時間収率が増加するため、使用する触媒量が少な
くてすみ、反応器のコンパクト化が可能となり、経済的
である。更に、触媒に使用する金属種を選択すること
で、ＦＣ−１４とＦＣ−１１６の生成する比率を変化さ
せることができる。更に、酸素／ＨＦＣ−２３のモル比
を変えることで、ＦＣ−１１６の生成比率を変えること
ができ、酸素／ＨＦＣ−２３のモル比を０．２〜０．５
の範囲内で低くすることで、ＦＣ−１１６の生成比率を
高くすることができる。INDUSTRIAL APPLICABILITY By the method for producing lower perfluoroalkane according to the present invention, the yield of lower perfluoroalkane such as FC-14 or FC-116 is increased, and the activity of the catalyst is not lowered, and continuously, FC-14, FC-
Lower perfluoroalkanes such as 116 can be produced with high yield and low cost. By the method for producing lower perfluoroalkane according to the present invention, the space-time yield of lower perfluoroalkane is increased, so that the amount of catalyst used can be small and the reactor can be made compact, which is economical. Furthermore, by selecting the metal species used for the catalyst, the ratio of FC-14 and FC-116 produced can be changed. Furthermore, by changing the molar ratio of oxygen / HFC-23, the production ratio of FC-116 can be changed, and the molar ratio of oxygen / HFC-23 is 0.2 to 0.5.
The production ratio of FC-116 can be increased by lowering the ratio within the range.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ ──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 6 Identification number Agency reference number FI Technical display location // C07B 61/00 300 C07B 61/00 300
Claims (5)
の混合比（モル比：酸素／トリフルオロメタン）が０．
１〜１．０の混合ガスを５００〜９００℃の温度範囲で
触媒存在下、この触媒に接触させて反応させることを特
徴とする低級パーフルオロアルカンの製造方法。1. A mixing ratio (molar ratio: oxygen / trifluoromethane) of trifluoromethane (CHF 3 ) and oxygen is 0.
A method for producing a lower perfluoroalkane, which comprises contacting a mixed gas of 1 to 1.0 in the temperature range of 500 to 900 ° C. in the presence of a catalyst to the catalyst to cause reaction.
０族、１１族、１２族および１３族から選ばれる少なく
とも１つの金属の塩又は酸化物を無水フッ酸又はフッ素
ガスで処理をしたものを使用することを特徴とする請求
項１に記載の製造方法。2. The catalyst is a group 18 element of the periodic table, group 1 of 8
The process according to claim 1, wherein a salt or oxide of at least one metal selected from Group 0, Group 11, Group 12 and Group 13 is treated with hydrofluoric acid anhydride or fluorine gas. Method.
オロエタン（ＣＦ3ＣＦ3 ）であることを特徴とする請
求項１あるいは請求項２に記載の製造方法。3. The production method according to claim 1, wherein the lower perfluoroalkane is hexafluoroethane (CF 3 CF 3 ).
であることを特徴とする請求項２あるいは請求項３に記
載の製造方法。4. The method according to claim 2 or 3, wherein the metal is zinc and / or nickel.
の混合比を０．２〜０．５の範囲で変えることにより、
生成物中のヘキサフルオロエタン（ＣＦ3 ＣＦ3 ）の比
率を変えることを特徴とする請求項１ないし請求項４に
記載の製造方法。5. By changing the mixing ratio of trifluoromethane (CHF 3 ) and oxygen in the range of 0.2 to 0.5,
The production method according to claim 1, wherein the ratio of hexafluoroethane (CF 3 CF 3 ) in the product is changed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8065985A JPH09255596A (en) | 1996-03-22 | 1996-03-22 | Production of lower perfluoroalkane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8065985A JPH09255596A (en) | 1996-03-22 | 1996-03-22 | Production of lower perfluoroalkane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09255596A true JPH09255596A (en) | 1997-09-30 |
Family
ID=13302824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8065985A Pending JPH09255596A (en) | 1996-03-22 | 1996-03-22 | Production of lower perfluoroalkane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09255596A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100353491B1 (en) * | 2000-02-22 | 2002-09-19 | 울산화학주식회사 | Manufacturing method for perfluoroethane |
| WO2003014047A1 (en) * | 2001-08-06 | 2003-02-20 | Showa Denko K. K. | Production and use of hexafluoroethane |
| JP2003055278A (en) * | 2001-08-06 | 2003-02-26 | Showa Denko Kk | Method for producing hexafluoroethane and use thereof |
| JP2003055277A (en) * | 2001-08-16 | 2003-02-26 | Showa Denko Kk | Method for producing hexafluoroethane and use thereof |
| WO2005105668A1 (en) * | 2004-04-28 | 2005-11-10 | Daikin Industries, Ltd. | Method for producing carbonyl difluoride |
| JP2014534899A (en) * | 2011-10-12 | 2014-12-25 | バイエル・インテレクチユアル・プロパテイー・ゲー・エム・ベー・ハー | Catalytic gas phase fluorination of 1,1,2-trichloroethane and / or 1,2-dichloroethene to produce 1-chloro-2,2-difluoroethane |
| CN113620841A (en) * | 2021-08-03 | 2021-11-09 | 南京硕达生物科技有限公司 | Method for preparing 2, 6-difluorobenzonitrile |
-
1996
- 1996-03-22 JP JP8065985A patent/JPH09255596A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100353491B1 (en) * | 2000-02-22 | 2002-09-19 | 울산화학주식회사 | Manufacturing method for perfluoroethane |
| WO2003014047A1 (en) * | 2001-08-06 | 2003-02-20 | Showa Denko K. K. | Production and use of hexafluoroethane |
| JP2003055278A (en) * | 2001-08-06 | 2003-02-26 | Showa Denko Kk | Method for producing hexafluoroethane and use thereof |
| US7045668B2 (en) | 2001-08-06 | 2006-05-16 | Showa Denko K.K. | Production and use of hexafluoroethane |
| US7208644B2 (en) | 2001-08-06 | 2007-04-24 | Showa Denko K.K. | Production and use of hexafluoroethane |
| JP2003055277A (en) * | 2001-08-16 | 2003-02-26 | Showa Denko Kk | Method for producing hexafluoroethane and use thereof |
| WO2005105668A1 (en) * | 2004-04-28 | 2005-11-10 | Daikin Industries, Ltd. | Method for producing carbonyl difluoride |
| JPWO2005105668A1 (en) * | 2004-04-28 | 2008-03-13 | ダイキン工業株式会社 | Method for producing carbonyl difluoride |
| US7592484B2 (en) | 2004-04-28 | 2009-09-22 | Daikin Industries, Ltd. | Method for producing carbonyl difluoride |
| JP5315610B2 (en) * | 2004-04-28 | 2013-10-16 | ダイキン工業株式会社 | Method for producing carbonyl difluoride |
| JP2014534899A (en) * | 2011-10-12 | 2014-12-25 | バイエル・インテレクチユアル・プロパテイー・ゲー・エム・ベー・ハー | Catalytic gas phase fluorination of 1,1,2-trichloroethane and / or 1,2-dichloroethene to produce 1-chloro-2,2-difluoroethane |
| CN113620841A (en) * | 2021-08-03 | 2021-11-09 | 南京硕达生物科技有限公司 | Method for preparing 2, 6-difluorobenzonitrile |
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