JPH0776535A - Production of monohydrohalogenoethanes - Google Patents
Production of monohydrohalogenoethanesInfo
- Publication number
- JPH0776535A JPH0776535A JP5223183A JP22318393A JPH0776535A JP H0776535 A JPH0776535 A JP H0776535A JP 5223183 A JP5223183 A JP 5223183A JP 22318393 A JP22318393 A JP 22318393A JP H0776535 A JPH0776535 A JP H0776535A
- Authority
- JP
- Japan
- Prior art keywords
- monohydrohalogenoethanes
- hydrogen fluoride
- mol
- pretreatment
- activated alumina
- 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 description 12
- 239000011148 porous material Substances 0.000 claims abstract description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 22
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 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 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 5
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- QDGONURINHVBEW-UHFFFAOYSA-N dichlorodifluoroethylene Chemical group FC(F)=C(Cl)Cl QDGONURINHVBEW-UHFFFAOYSA-N 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 2
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 2
- JDAWHMRSFSKYTB-UHFFFAOYSA-N 1,1,1,2-tetrafluoro-2-iodoethane Chemical compound FC(I)C(F)(F)F JDAWHMRSFSKYTB-UHFFFAOYSA-N 0.000 description 1
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 description 1
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- -1 bromotrifluoroethylene, trifluoroiodoethylene Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- QCMJBECJXQJLIL-UHFFFAOYSA-L chromium(6+);oxygen(2-);difluoride Chemical compound [O-2].[O-2].[F-].[F-].[Cr+6] QCMJBECJXQJLIL-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910001055 inconels 600 Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RZXZIZDRFQFCTA-UHFFFAOYSA-N teflurane Chemical compound FC(Br)C(F)(F)F RZXZIZDRFQFCTA-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、１，１−ジフルオロパ
ーハロゲノオレフィンのＨＦ付加によるモノヒドロハロ
ゲノエタン類の製造方法に関するものである。FIELD OF THE INVENTION The present invention relates to a method for producing monohydrohalogenoethanes by HF addition of 1,1-difluoroperhalogenoolefin.
【０００２】[0002]
【従来の技術】フッ素含有エチレンのＨＦ付加による部
分フッ素化エタンの製造方法については、従来よりいく
つかの方法が知られている。ドイツ特許第２１０５７４
８号公報によれば、酸化アルミニウムまたは水酸化アル
ミニウムもしくはその混合物および三酸化ホウ素との混
合物を混錬後成型し、フッ化水素で前処理した触媒を用
いて二重および三重結合へのフッ化水素付加、有機結合
した塩素または臭素のフッ素置換反応を行っている。こ
の触媒は種々のハロゲン化オレフィンへのＨＦ付加で、
反応温度が６０℃前後と低く、また反応後の組成物中の
原料オレフィン０％、フッ化水素付加物１００％と高活
性を示している。2. Description of the Related Art As a method for producing a partially fluorinated ethane by adding HF to fluorine-containing ethylene, several methods have been known. German Patent No. 210574
According to the publication No. 8, aluminum oxide or aluminum hydroxide or a mixture thereof and a mixture with boron trioxide are kneaded, molded, and then fluorinated into double and triple bonds using a catalyst pretreated with hydrogen fluoride. Hydrogenation and fluorine substitution reaction of organically bonded chlorine or bromine are carried out. This catalyst is a HF addition to various halogenated olefins,
The reaction temperature is as low as about 60 ° C., and the composition after the reaction shows high activity with 0% of the raw material olefin and 100% of hydrogen fluoride adduct.
【０００３】しかしこのホウ素含有アルミナ触媒は、三
酸化ホウ素の融点が４５０℃であり、またフッ化水素に
よる前処理で生成する三フッ化ホウ素は沸点が−１０１
℃のため１２０〜２００℃での乾燥時、および２００〜
５００℃での前処理時に分離、揮散するため、その取り
扱いは困難である。However, in this boron-containing alumina catalyst, the melting point of boron trioxide is 450 ° C., and the boiling point of boron trifluoride produced by pretreatment with hydrogen fluoride is -101.
For drying at 120-200 ° C, and 200-
It is difficult to handle because it separates and volatilizes during pretreatment at 500 ° C.
【０００４】また、クロム系触媒を用いたドイツ特許３
００９７６０号公報によれば、フッ化水素で処理したオ
キシフッ化クロム触媒がフッ素含有エチレンのＨＦ付加
に有効であり、９０％以上のフッ化水素付加物を与えて
いる。しかしクロム系触媒は毒性の高い６価のクロムを
含有する可能性があり、触媒製造時、反応使用時、また
使用後の取り扱いには注意を要する。誤って廃棄される
と環境上重大な問題を引き起こすなど、工業化を進める
上でも困難が多い。German Patent 3 using a chromium-based catalyst
According to Japanese Patent Laid-Open No. 1997760, a chromium oxyfluoride catalyst treated with hydrogen fluoride is effective for HF addition of fluorine-containing ethylene, and gives 90% or more of hydrogen fluoride adduct. However, chromium-based catalysts may contain hexavalent chromium, which is highly toxic, and care must be taken during catalyst production, reaction use, and handling after use. There are many difficulties in industrialization, such as accidental disposal causing serious environmental problems.
【０００５】[0005]
【発明が解決しようとする課題】そこで本発明では、高
収率で長寿命な触媒を用いて、活性化時の成分揮散等を
起こすことなく、また取り扱い上注意を要するクロム化
合物を取り扱わずに、１，１−ジフルオロパーハロゲノ
オレフィンをフッ化水素化する、新規なモノヒドロハロ
ゲノエタン類の製造方法を提供することを目的とするも
のである。Therefore, in the present invention, a catalyst having a high yield and a long life is used, without causing volatilization of components during activation, and without handling a chromium compound requiring careful handling. An object of the present invention is to provide a novel method for producing monohydrohalogenoethanes by hydrofluorinating 1,1-difluoroperhalogenoolefin.
【０００６】[0006]
【課題を解決するための手段】そこで本発明者らは、前
述の目的を達成すべく研究・探索を行った結果、平均細
孔径４０〜５００Åを有する孔が７０〜９０％を占める
活性アルミナをフッ素原子を導入する前処理により調製
されるオキシハロゲン化アルミニウム触媒を使用するこ
とにより、三酸化ホウ素、クロム化合物を用いることな
く１，１−ジフルオロパーハロゲノオレフィンへのフッ
化水素付加により高収率、長寿命でモノヒドロハロゲノ
エタン類が生成することを見出した。Therefore, as a result of conducting research and search for achieving the above-mentioned object, the present inventors have found that activated alumina containing 70 to 90% of pores having an average pore diameter of 40 to 500Å is selected. By using an aluminum oxyhalide catalyst prepared by a pretreatment of introducing a fluorine atom, a high yield can be obtained by hydrogen fluoride addition to 1,1-difluoroperhalogenoolefin without using boron trioxide or a chromium compound. It was found that monohydrohalogenoethanes are formed with a long life.
【０００７】本発明は一般式ＣＦ2 ＝ＣＸＹ（ここで、
ＸはＦまたはＣｌ、ＹはＦ、Ｃｌ、ＢｒまたはＩ）で表
される１、１−ジフルオロパーハロゲノオレフィンを気
相中少なくとも等モル以上のフッ化水素でフッ素化し、
一般式ＣＦ3 −ＣＨＸＹ（ここで、ＸはＦまたはＣｌ、
ＹはＦ、Ｃｌ、ＢｒまたはＩ）で表されるモノヒドロハ
ロゲノエタン類を製造する方法において、フッ化水素ま
たは元素フッ素またはハロゲン化炭化水素あるいはそれ
らの混合物を用いて平均細孔径４０〜５００Åを有する
孔が７０〜９０％を占める活性アルミナを前処理するこ
とにより調製されるオキシハロゲン化アルミニウム触媒
存在下、温度２０〜４００℃で反応することを特徴とす
る上記モノヒドロハロゲノエタン類の製造方法である。The present invention has the general formula CF 2 = CXY (where
X is F or Cl, Y is F, Cl, Br or I) and the 1,1-difluoroperhalogenoolefin represented by the formula (1) is fluorinated with at least an equimolar amount or more of hydrogen fluoride in a gas phase,
Formula CF 3 -CHXY (where, X is F or Cl,
Y is F, Cl, Br or I) in the method for producing monohydrohalogenoethanes, hydrogen fluoride or elemental fluorine or halogenated hydrocarbon or a mixture thereof is used to obtain an average pore diameter of 40 to 500Å. A method for producing the above monohydrohalogenoethanes, which comprises reacting at a temperature of 20 to 400 ° C. in the presence of an aluminum oxyhalide catalyst prepared by pretreatment of activated alumina having 70 to 90% of pores. Is.
【０００８】本発明で用いられるオキシハロゲン化アル
ミニウム触媒は、平均細孔径４０〜５００Åを有する孔
が７０〜９０％を占める活性アルミナを充填した１５０
〜２５０℃の反応管中にフッ化水素、フッ素ガスまたは
フッ素原子を含むハロゲン化炭化水素、あるいはそれら
の混合物を必要に応じて窒素、アルゴン等の不活性ガス
で希釈したものを数〜数十時間導入することで得られ
る。これらの不活性ガスは混合するだけでなく、単独で
順次導入することもできる。The aluminum oxyhalide catalyst used in the present invention is filled with activated alumina containing 150 to 90% of pores having an average pore diameter of 40 to 500Å.
Hydrogen fluoride, a fluorine gas or a halogenated hydrocarbon containing a fluorine atom, or a mixture thereof is diluted with an inert gas such as nitrogen or argon into a reaction tube at a temperature of up to 250 ° C for several to several tens. Obtained by introducing time. These inert gases can be introduced not only in a mixed manner but individually in sequence.
【０００９】ここで用いる活性アルミナは、平均細孔径
４０〜５００Åを有する孔が７０〜９０％を占めるもの
が適当である。比表面積および細孔径分布によって決ま
る細孔容積は、０．５５ｍｌ／ｇ以下では適切な比表面
積および細孔構造が得られず、触媒活性が低く、収率が
悪くなることがある。このため、０．５５ｍｌ／ｇ以
上、特に０．５５〜１．６ｍｌ／ｇであるのが好まし
い。これらの性質をもつ活性アルミナは工業的に入手可
能であり、一般にγ−アルミナやγ、ηの両相が存在す
るγ／η−アルミナであることが多い。As the activated alumina used here, it is suitable that the pores having an average pore diameter of 40 to 500Å account for 70 to 90%. If the pore volume determined by the specific surface area and the pore size distribution is 0.55 ml / g or less, an appropriate specific surface area and pore structure cannot be obtained, the catalytic activity is low, and the yield may be poor. Therefore, it is preferably 0.55 ml / g or more, particularly 0.55 to 1.6 ml / g. Activated alumina having these properties is industrially available, and is generally γ-alumina or γ / η-alumina in which both γ and η phases exist.
【００１０】本発明による方法は一般に、反応されるべ
き１，１−ジフルオロパーハロゲノオレフィンおよびフ
ッ化水素からなるガス混合物を、上記オキシハロゲン化
アルミニウム触媒を充填した加熱装置付き反応管に連続
的に導入することにより、通常の触媒によるガス−固体
反応の方法に従って実施される。The process according to the invention generally comprises continuously feeding a gas mixture of the 1,1-difluoroperhalogeno-olefin to be reacted and hydrogen fluoride into a heated reaction tube filled with the above-mentioned aluminum oxyhalide catalyst. When introduced, the reaction is carried out according to a conventional method of gas-solid reaction with a catalyst.
【００１１】一般式ＣＦ2 ＝ＣＸＹで表わされる本発明
の１，１−ジフルオロパーハロゲノオレフィンには、テ
トラフルオロエチレン、クロロトリフルオロエチレン、
ブロモトリフルオロエチレン、トリフルオロヨードエチ
レン、または１，１−ジクロロ−２，２−ジフルオロエ
チレン等があげられる。この場合、それぞれ対応する一
般式ＣＦ3 −ＣＨＸＹで表わされるモノヒドロハロゲノ
エタン類、つまり、ペンタフルオロエタン、２−クロロ
−１，１，１，２−テトラフルオロエタン、２−ブロモ
−１，１，１，２−テトラフルオロエタン、１，１，
１，２−テトラフルオロ−２−ヨードエタンまたは２，
２−ジクロロ−１，１，１−トリフルオロエタンがほと
んど定量的に得られる。The 1,1-difluoroperhalogenoolefin of the present invention represented by the general formula CF 2 ═CXY includes tetrafluoroethylene, chlorotrifluoroethylene,
Examples thereof include bromotrifluoroethylene, trifluoroiodoethylene, and 1,1-dichloro-2,2-difluoroethylene. In this case, monohydrohalogenoethanes represented by the corresponding general formula CF 3 —CHXY, that is, pentafluoroethane, 2-chloro-1,1,1,2-tetrafluoroethane, 2-bromo-1,1 , 1,2-Tetrafluoroethane, 1,1,
1,2-tetrafluoro-2-iodoethane or 2,
2-dichloro-1,1,1-trifluoroethane is obtained almost quantitatively.
【００１２】フッ化水素化反応に使用するフッ化水素の
量は、１，１−ジフルオロパーハロゲノオレフィンに対
して過剰量使用する限り問題にならない。しかし、大過
剰は操作の複雑化、経費の増大を引き起こすため、一般
に１，１−ジフルオロパーハロゲノオレフィンに対して
１〜３倍モルである。反応の温度は、２０〜４００℃、
特に５０〜３５０℃で実施される。The amount of hydrogen fluoride used in the hydrofluorination reaction does not matter as long as it is used in excess with respect to the 1,1-difluoroperhalogenoolefin. However, since a large excess causes complicated operation and an increase in cost, it is generally 1 to 3 times the mol of 1,1-difluoroperhalogenoolefin. The reaction temperature is 20 to 400 ° C,
In particular, it is carried out at 50 to 350 ° C.
【００１３】[0013]
【実施例】以下に本発明の実施例を示す。EXAMPLES Examples of the present invention will be shown below.
【００１４】実施例１ 内径２．４ｃｍのインコネル６００製のＵ字型反応器
に、平均細孔径４０〜５００Åを有する孔が全体の細孔
容積中７５％を占める活性アルミナを６００ｍｌ充填
し、窒素雰囲気下２５０℃で乾燥させた後、同一温度に
て窒素４００ｍｌ／ｍｉｎとジクロロジフルオロメタン
５０ｍｌ／ｍｉｎとを１２時間流通させ、触媒活性化を
行った。２００℃まで降温してテトラフルオロエチレン
２００ｍｌ／ｍｉｎとフッ化水素４００ｍｌ／ｍｉｎを
供給した。脱酸後、ＦＩＤガスクロマトグラフィーにて
有機物分析をした結果、ＣＦ3 −ＣＨＦ2 （８９．８モ
ル％）、ＣＦ2 ＝ＣＦ2 （８．４モル％）、ＣＦ3 −Ｃ
Ｆ3 （０．５モル％）およびパーフルオロシクロブタン
（１．３モル％）であった。Example 1 A U-shaped reactor made of Inconel 600 having an inner diameter of 2.4 cm was filled with 600 ml of activated alumina whose pores having an average pore diameter of 40 to 500Å accounted for 75% of the total pore volume, and nitrogen was charged. After drying in an atmosphere at 250 ° C., 400 ml / min of nitrogen and 50 ml / min of dichlorodifluoromethane were circulated for 12 hours at the same temperature to activate the catalyst. The temperature was lowered to 200 ° C., and 200 ml / min of tetrafluoroethylene and 400 ml / min of hydrogen fluoride were supplied. After deoxidation, organic matter analysis by FID gas chromatography revealed that CF 3 —CHF 2 (89.8 mol%), CF 2 ═CF 2 (8.4 mol%), CF 3 —C.
It was F 3 (0.5 mol%) and perfluorocyclobutane (1.3 mol%).
【００１５】実施例２ 実施例１の反応を継続して行ない、４０００時間後の生
成ガスを採取し、脱酸後、ＦＩＤガスクロマトグラフィ
ーにて有機物分析をした結果、ＣＦ3 −ＣＨＦ2 （８
９．２モル％）、ＣＦ2 ＝ＣＦ2 （９．０モル％）、Ｃ
Ｆ3 −ＣＦ3 （０．６モル％）、およびパーフルオロシ
クロブタン（１．２モル％）であった。実施例１と比べ
て、長期間運転の後もほとんど反応率の低下がなく、触
媒の劣化傾向は見られなかった。Example 2 The reaction of Example 1 was carried out continuously, and the produced gas after 4000 hours was collected, deoxidized and subjected to organic substance analysis by FID gas chromatography. As a result, CF 3 --CHF 2 (8
9.2 mol%), CF 2 = CF 2 (9.0 mol%), C
F 3 -CF 3 (0.6 mol%), and was perfluorocyclobutane (1.2 mol%). Compared with Example 1, even after a long period of operation, there was almost no decrease in the reaction rate, and no catalyst deterioration tendency was observed.
【００１６】実施例３ 実施例１で示した触媒を用いて、２５０℃でクロロトリ
フルオロエチレン２００ｍｌ／ｍｉｎとフッ化水素４０
０ｍｌ／ｍｉｎを供給した。脱酸後、ＦＩＤガスクロマ
トグラフィーにて有機物分析をした結果、ＣＦ3 −ＣＨ
ＣｌＦ（７８．０モル％）、ＣＦ2 ＝ＣＦＣｌ（２１．
３モル％）、ＣＦ3 −ＣＨＣｌ2 （０．２モル％）およ
びＣＦ3 −ＣＨＦ2 （０．５モル％）であった。Example 3 Using the catalyst shown in Example 1, 200 ml / min of chlorotrifluoroethylene and 40% of hydrogen fluoride at 250 ° C.
0 ml / min was supplied. After deoxidation, organic matter analysis by FID gas chromatography showed that CF 3 --CH
ClF (78.0 mol%), CF 2 = CFCl (21.
3 mol%), it was CF 3 -CHCl 2 (0.2 mol%) and CF 3 -CHF 2 (0.5 mol%).
【００１７】実施例４ 実施例１で示した装置を用い、ジクロロジフルオロメタ
ンのかわりに窒素２５０ ｍｌ／ｍｉｎ、フッ素８ｍｌ
／ｍｉｎおよびフッ化水素６ｍｌ／ｍｉｎで触媒活性化
を行った。２００℃まで降温してテトラフルオロエチレ
ン２００ｍｌ／ｍｉｎとフッ化水素４００ｍｌ／ｍｉｎ
を供給した。脱酸後、ＦＩＤガスクロマトグラフィーに
て有機物分析をした結果、ＣＦ3 −ＣＨＦ2 （８１．０
モル％）、ＣＦ2 ＝ＣＦ2 （１８．５モル％）、ＣＨＦ
3 （０．２モル％）およびＣＦ3-CF3 （０．３モル％）
であった。Example 4 Using the apparatus shown in Example 1, 250 ml / min of nitrogen and 8 ml of fluorine were used instead of dichlorodifluoromethane.
/ Min and hydrogen fluoride 6 ml / min for catalyst activation. After cooling to 200 ° C, tetrafluoroethylene 200 ml / min and hydrogen fluoride 400 ml / min
Was supplied. After deoxidation, organic matter analysis by FID gas chromatography showed that CF 3 —CHF 2 (81.0
Mol%), CF 2 = CF 2 (18.5 mol%), CHF
3 (0.2 mol%) and CF 3 -CF 3 (0.3 mol%)
Met.
【００１８】実施例５ 実施例１で示した触媒を用いて、２５０℃で１，１−ジ
クロロ−２，２−ジフルオロエチレン２００ｍｌ／ｍｉ
ｎとフッ化水素４００ｍｌ／ｍｉｎを供給した。脱酸
後、ＦＩＤガスクロマトグラフィーにて有機物分析をし
た結果、ＣＦ3 −ＣＨＣｌ2 （８２．３モル％）、ＣＦ
2 ＝ＣＣｌ2 （１７．１モル％）、ＣＦ3−ＣＨＣｌＦ
（０．５モル％）およびＣＦ3 −ＣＨＦ2 （０．１モル
％）であった。Example 5 1,1-dichloro-2,2-difluoroethylene 200 ml / mi at 250 ° C. using the catalyst shown in Example 1.
n and hydrogen fluoride 400 ml / min were supplied. After deacidification, as a result of the organics analyzed by FID gas chromatography, CF 3 -CHCl 2 (82.3 mol%), CF
2 = CCl 2 (17.1 mol%), CF 3 -CHClF
It was (0.5 mol%) and CF 3 -CHF 2 (0.1 mol%).
【００１９】実施例６ 実施例１で示した触媒を用いて、２５０℃で１−クロロ
−１，２，２−トリフルオロエチレン２００ｍｌ／ｍｉ
ｎとフッ化水素４００ｍｌ／ｍｉｎを供給した。脱酸
後、ガスクロマトグラフィーにて分析した結果、ＣＦ3
−ＣＨＣｌＦ（６７．９モル％）、ＣＦ2 ＝ＣＣｌ2
（３１．４モル％）、ＣＦ3 −ＣＨＣｌ2 （０．５モル
％）およびＣＦ3 −ＣＨＦ2 （０．１モル％）であっ
た。Example 6 Using the catalyst shown in Example 1, 200 ml / mi of 1-chloro-1,2,2-trifluoroethylene at 250 ° C.
n and hydrogen fluoride 400 ml / min were supplied. After deoxidation, gas chromatography analysis revealed that CF 3
-CHClF (67.9 mol%), CF 2 = CCl 2
(31.4 mol%) was CF 3 -CHCl 2 (0.5 mol%) and CF 3 -CHF 2 (0.1 mol%).
【００２０】比較例１ 実施例１で示した反応器に、平均細孔径４０〜５００Å
を有する孔が全体の細孔容積中６０％を占める活性アル
ミナを６００ｍｌ充填し、実施例１と同様に活性化、反
応を行った。脱酸後、ガスクロマトグラフィーにて分析
した結果、ＣＦ3 −ＣＨＦ2 （１１．１モル％）および
ＣＦ2 ＝ＣＦ2 （８８．９モル％）であった。Comparative Example 1 The reactor shown in Example 1 was charged with an average pore diameter of 40 to 500Å.
600 ml of activated alumina in which the pores having occupy 60% of the total pore volume were filled, and activation and reaction were carried out in the same manner as in Example 1. After deoxidation, gas chromatographic analysis revealed that CF 3 —CHF 2 (11.1 mol%) and CF 2 ═CF 2 (88.9 mol%).
【００２１】[0021]
【発明の効果】環境上問題なく、工業的に有利な高収率
でモノヒドロハロゲノエタン類を製造することができ
る。INDUSTRIAL APPLICABILITY The monohydrohalogenoethanes can be produced in high yield, which is industrially advantageous without causing environmental problems.
───────────────────────────────────────────────────── 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 (72)発明者 宇佐見 陽子 神奈川県横浜市神奈川区羽沢町松原1160番 地 エイ・ジー・テクノロジー株式会社内 (72)発明者 立松 伸 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内 (72)発明者 横山 孝彰 千葉県市原市五井海岸10番地 旭硝子株式 会社千葉工場内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number within the agency FI Technical indication location // C07B 61/00 300 (72) Inventor Yoko Usami 1160 Matsubara, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Address AGC Technology Co., Ltd. (72) Inventor Shin Tatematsu 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Asahi Glass Co., Ltd. Central Research Institute (72) Inventor Takaaki Yokoyama 10 Goi Kaigan, Ichihara, Chiba Asahi Glass Co., Ltd. Company Chiba factory
Claims (4)
たはＣｌ、ＹはＦ、Ｃｌ、ＢｒまたはＩ）で表される
１，１−ジフルオロパーハロゲノオレフィンを気相中少
なくとも等モル以上のフッ化水素を用いてフッ化水素付
加し、一般式ＣＦ3 −ＣＨＸＹ（ここで、ＸはＦまたは
Ｃｌ、ＹはＦ、Ｃｌ、ＢｒまたはＩ）で表されるモノヒ
ドロハロゲノエタン類を製造する方法において、平均細
孔径４０〜５００Åを有する孔が全体の細孔容積中７０
〜９０％を占める活性アルミナを前処理することにより
調製されるオキシハロゲン化アルミニウム触媒存在下、
温度２０〜４００℃で反応することを特徴とする上記モ
ノヒドロハロゲノエタン類の製造方法。1. A 1,1-difluoroperhalogeno olefin represented by the general formula CF 2 ═CXY (where X is F or Cl, Y is F, Cl, Br or I) in a gas phase at least equimolar. Hydrogen fluoride is added using the above hydrogen fluoride to give monohydrohalogenoethanes represented by the general formula CF 3 —CHXY (where X is F or Cl and Y is F, Cl, Br or I). In the manufacturing method, the pores having an average pore diameter of 40 to 500Å are contained in the total pore volume of 70
In the presence of an aluminum oxyhalide catalyst prepared by pretreatment of activated alumina, which accounts for ˜90%,
A method for producing the above monohydrohalogenoethanes, which comprises reacting at a temperature of 20 to 400 ° C.
る請求項１のモノヒドロハロゲノエタン類の製造方法。2. The method for producing monohydrohalogenoethanes according to claim 1, wherein fluorine gas is used for pretreatment of activated alumina.
る請求項１のモノヒドロハロゲノエタン類の製造方法。3. The method for producing monohydrohalogenoethanes according to claim 1, wherein hydrogen fluoride is used for pretreatment of activated alumina.
ハロゲン化炭化水素を用いる請求項１のモノヒドロハロ
ゲノエタン類の製造方法。4. The method for producing monohydrohalogenoethanes according to claim 1, wherein a halogenated hydrocarbon containing a fluorine atom is used for pretreatment of activated alumina.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5223183A JPH0776535A (en) | 1993-09-08 | 1993-09-08 | Production of monohydrohalogenoethanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5223183A JPH0776535A (en) | 1993-09-08 | 1993-09-08 | Production of monohydrohalogenoethanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0776535A true JPH0776535A (en) | 1995-03-20 |
Family
ID=16794111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5223183A Pending JPH0776535A (en) | 1993-09-08 | 1993-09-08 | Production of monohydrohalogenoethanes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0776535A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020130036A1 (en) * | 2018-12-19 | 2020-06-25 | ダイキン工業株式会社 | Production method for fluoro-ethane and production method for fluoro-olefin |
| WO2020130042A1 (en) * | 2018-12-19 | 2020-06-25 | ダイキン工業株式会社 | Fluoroethane production method and fluoroolefin production method |
| KR20210070322A (en) * | 2018-10-09 | 2021-06-14 | 다이킨 고교 가부시키가이샤 | Method for preparing perfluoroalkyne compounds |
-
1993
- 1993-09-08 JP JP5223183A patent/JPH0776535A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210070322A (en) * | 2018-10-09 | 2021-06-14 | 다이킨 고교 가부시키가이샤 | Method for preparing perfluoroalkyne compounds |
| WO2020130036A1 (en) * | 2018-12-19 | 2020-06-25 | ダイキン工業株式会社 | Production method for fluoro-ethane and production method for fluoro-olefin |
| WO2020130042A1 (en) * | 2018-12-19 | 2020-06-25 | ダイキン工業株式会社 | Fluoroethane production method and fluoroolefin production method |
| JP2020100620A (en) * | 2018-12-19 | 2020-07-02 | ダイキン工業株式会社 | Fluoroethane production method and fluoroolefin production method |
| JP2020100619A (en) * | 2018-12-19 | 2020-07-02 | ダイキン工業株式会社 | Fluoroethane production method and fluoroolefin production method |
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