JP3582798B2 - Fluorination catalyst and fluorination method - Google Patents
Fluorination catalyst and fluorination method Download PDFInfo
- Publication number
- JP3582798B2 JP3582798B2 JP11174994A JP11174994A JP3582798B2 JP 3582798 B2 JP3582798 B2 JP 3582798B2 JP 11174994 A JP11174994 A JP 11174994A JP 11174994 A JP11174994 A JP 11174994A JP 3582798 B2 JP3582798 B2 JP 3582798B2
- Authority
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- Prior art keywords
- fluorination
- catalyst
- reaction
- halogenated hydrocarbon
- pressure
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- Expired - Lifetime
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- 239000003054 catalyst Substances 0.000 title claims description 97
- 238000003682 fluorination reaction Methods 0.000 title claims description 82
- 238000000034 method Methods 0.000 title claims description 48
- 239000011651 chromium Substances 0.000 claims description 50
- 239000007789 gas Substances 0.000 claims description 33
- 150000008282 halocarbons Chemical class 0.000 claims description 28
- 229910052738 indium Inorganic materials 0.000 claims description 24
- 229910052804 chromium Inorganic materials 0.000 claims description 21
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000975 co-precipitation Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 69
- 238000002360 preparation method Methods 0.000 description 32
- 239000012018 catalyst precursor Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- 238000010304 firing Methods 0.000 description 15
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 14
- 239000000460 chlorine Substances 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 229910001026 inconel Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-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
- 238000010438 heat treatment Methods 0.000 description 5
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 150000001845 chromium compounds Chemical class 0.000 description 3
- QCMJBECJXQJLIL-UHFFFAOYSA-L chromium(6+);oxygen(2-);difluoride Chemical compound [O-2].[O-2].[F-].[F-].[Cr+6] QCMJBECJXQJLIL-UHFFFAOYSA-L 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012025 fluorinating agent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002002 slurry Substances 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
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910018404 Al2 O3 Inorganic materials 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 description 1
- 229910016854 F3 Cl Inorganic materials 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052801 chlorine 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
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- ZJULYDCRWUEPTK-UHFFFAOYSA-N dichloromethyl Chemical compound Cl[CH]Cl ZJULYDCRWUEPTK-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【産業上の利用分野】
本発明はフッ素化触媒およびフッ素化方法に関するものであり、さらに詳しくは分子中に塩素を含まないことからオゾン層を破壊する恐れのないハイドロフルオロカーボン（以下、ＨＦＣと略す）、なかでもジフルオロメタン（以下、ＨＦＣ−３２と略す）、１，１，１，２−テトラフルオロエタン（以下、ＨＦＣ−１３４ａと略す）、ペンタフルオロエタン（以下、ＨＦＣ−１２５と略す）の製造に際し、高い収率でＨＦＣを生産するために改良されたフッ素化触媒および、該触媒を用いて気相でフッ化水素とハロゲン化炭化水素を接触させることにより生産性よくＨＦＣを製造する方法に関するものである。
【０００２】
【従来の技術】
工業的に行われている代表的なＨＦＣの製造方法としては含水素ハロゲン化炭化水素をＨＦと接触させることによりＦ以外のハロゲンをＦに交換する方法（不飽和ハロゲン化炭化水素を原料としてＨＦの付加とＦ以外のハロゲンをＦに交換する反応を同時に実施するケースも多い）、ハロゲン化炭化水素をＨ２ と接触させることによりＦ以外のハロゲン（場合によってはＦの一部）をＨに交換する方法がある。このうち含水素ハロゲン化炭化水素のＨＦによるフッ素化反応は進みにくい場合が多く、ＨＦＣの生産量は用いる触媒に大きく依存する。
【０００３】
最も反応が進みにくい代表として、１−クロロ−２，２，２−トリフルオロエタン（以下、ＨＣＦＣ−１３３ａと略す）のフッ素化によるＨＦＣ−１３４ａの合成反応が挙げられる。本反応は明らかに熱力学的に不利な吸熱反応である。したがって、一般にはＨＣＦＣ−１３３ａに対し化学量論以上のＨＦを共存させて、有意な転化率を与える反応条件（圧力、温度、空間速度）で反応を行う。
【０００４】
一例を挙げると、特開昭５５−２７１３８号公報では、ＣｒＦ３ ・３Ｈ２ Ｏを空気で処理した化合物を触媒として大気圧下、反応温度４００℃、ＨＣＦＣ−１３３ａに対するＨＦのモル比（以下、モル比と略す）８、空間速度（以下、ＳＶと略す）５５０ｈ−１という反応条件でＨＦＣ−１３４ａを収率３２％で得ている。
【０００５】
特開平１−２６８６５１号公報ではＣｏＣｌ２ ／Ａｌ２ Ｏ３ をフッ素化処理して得られる触媒を用いて、大気圧下、反応温度４１０℃、モル比１０、接触時間３０秒（ＳＶ１２０ｈ−１）という反応条件でＨＦＣ−１３４ａ収率は３２％である。このように低いＳＶでの反応は生産性が悪く、また、高温での反応は熱的エネルギーロスばかりでなく、選択率の低下を招き、さらに、本発明者らの知見によれば触媒寿命を短くする。
【０００６】
従って、触媒の高活性化、長寿命化を目指した検討がこれまでにもなされてきた。すなわち、特開平２−１７２９３３号公報では、Ａｌ、Ｍｇ、Ｃａ、Ｂａ、Ｓｒ、Ｆｅ、Ｎｉ、ＣｏおよびＭｎからなる群から選ばれる少なくとも一種の元素およびＣｒを含むハロゲン化物または酸化物からなる触媒が耐久性（寿命）に優れることを開示している。また、ＥＰ第５０２６０５号公報では、Ｚｎを担持したＣｒ系触媒が高い活性を与えることを開示している。さらに、特開平４−３４６９４３号公報では、ＲｕやＰｔを担持した部分的にフッ素化されたＣｒ２ Ｏ３ からなる触媒が寿命が長いことを開示している。
その他、Ｃｒ以外の成分を主成分とする触媒として、特開平２−９５４３８号公報で本出願人が開示したＩｎ化合物をアルミナなどの担体に担持し、ＨＦで処理した触媒等があるが、活性はＣｒを主成分とする触媒に較べて低い。
【０００７】
【発明が解決しようとする課題】
しかしながら、近年、特開平４−３４６９４３号公報の明細書中に記載されている様に、ＨＦによるＨＣＦＣ−１３３ａのフッ素化反応を従来のＣｒ系あるいはＡｌ系触媒を用いて行った場合、反応圧力を高くすると反応速度が小さくなって生産性が低下するという本反応固有の新たな問題があることが明らかになってきた。
【０００８】
すなわち、大気圧下では高い反応収率を示す触媒でも、反応圧力を上げる［例えば１０ｋｇ／ｃｍ２ Ｇ（ゲージ圧）］とＨＦＣ−１３４ａの選択率は若干向上するものの、ＨＣＦＣ−１３３ａ転化率が低下するために収率はかなり低下する［比較の際、他の条件（反応温度、モル比、標準状態に換算したＳＶ）は同一にしている］。程度の差はあるものの本現象は他の含水素ハロゲン化炭化水素のフッ素化反応においても認められる。
【０００９】
実際の製造設備において反応を１ｋｇ／ｃｍ２ Ｇ程度の大気圧付近で行うことは低圧化のための付帯設備を要するため、設備費の増加につながり、好ましくない。さらに、反応の選択率は加圧下の方が優れており、特に、毒性の高い不飽和化合物の副生量を抑えることができる。従って、反応圧力を上げても反応速度が低下しない触媒、さらに好ましくは、反応圧力を上げると反応速度が増加する触媒の開発が求められてる。
【００１０】
もちろん従来の課題である触媒の高活性化、長寿命化も触媒コストや生産性に大きく寄与するため、本発明の重要な課題の一つである。
本発明の目的は、ＨＦＣの製造に際し、高い収率でＨＦＣを生産するために改良されたフッ素化触媒を提供すること、および、該触媒を用いて気相でフッ化水素とハロゲン化炭化水素を接触させることにより生産性よくＨＦＣを製造する方法、具体的には例えば、ＨＦＣ−３２、ＨＦＣ−１３４ａ、ＨＦＣ−１２５を生産性よく製造する方法を提供することである。
【００１１】
【課題を解決するための手段】
本発明者等は上記課題を解決すべく鋭意検討した結果、金属成分としてＩｎとＣｒを組み合わせることにより反応速度に対する圧力のマイナス効果を改善することができることを見いだし本発明を成すに到った。
【００１２】
本発明の請求項１の発明は、インジウム、クロム、酸素、フッ素を必須の構成元素として含み、クロムに対するインジウムの原子比が０．００５〜０．６であるフッ素化触媒であって、該触媒の調製工程に還元性ガス中、３５０〜５００℃で熱処理する工程を含むことを特徴とするフッ素化触媒である。
【００１３】
本発明の請求項２の発明は、共沈法により調製することを特徴とする請求項１記載のフッ素化触媒である。
【００１５】
本発明の請求項３の発明は、長周期型周期表の１１、１２、１３、１４族元素からなる群から選ばれる少なくとも１種の元素を含有することを特徴とする請求項１または２に記載のフッ素化触媒である。
【００１６】
本発明の請求項４の発明は、請求項１から３のいずれかに記載のフッ素化触媒の存在下、気相でフッ化水素とハロゲン化炭化水素を接触させることを特徴とするハロゲン化炭化水素のフッ素化方法である。
【００１７】
本発明の請求項５の発明は、該ハロゲン化炭化水素が含水素ハロゲン化炭化水素であることを特徴とする請求項４記載のフッ素化方法である。
【００１８】
本発明の請求項６の発明は、該含水素ハロゲン化炭化水素がジクロロメタン、クロロフルオロメタン、１−クロロ−２，２，２−トリフルオロエタン、１，１−ジクロロ−２，２，２−トリフルオロエタン、１−クロロ−１，２，２，２−テトラフルオロエタンからなる群から選ばれることを特徴とする請求項５記載のフッ素化方法である。
【００１９】
本発明の請求項７の発明は、該含水素ハロゲン化炭化水素が１−クロロ−２，２，２−トリフルオロエタンであることを特徴とする請求項６記載のフッ素化方法である。
【００２０】
本発明においては、ハロゲン化炭化水素とＨＦとの接触により、ハロゲン化炭化水素をフッ素化する方法において、Ｉｎ、Ｃｒ、Ｏ、Ｆを必須の構成元素として含み、Ｃｒに対するＩｎの原子比が０．００５〜０．６、好ましくは０．０１〜０．５、特に好ましくは０．０１〜０．３である触媒を用いることを解決の手段とした。
【００２１】
Ｉｎ、Ｃｒ、Ｏ、Ｆ以外の触媒の構成元素としてはアルカリ金属が大量に（例えば、重量で％オーダー）含まれることはあまり好ましくないが、その他の元素は重量で％オーダー以上含まれていてもよい。特に、助触媒として触媒の延命効果が期待できる長周期型周期表の１１、１２、１３、１４族の元素（新ＩＵＰＡＣ命名法）からなる群から選ばれる少なくとも１種の元素、なかでも、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ｈｇ、Ａｌ、Ｇａ、Ｓｎ、ＰｂなどはＣｒに対する原子比で０．００１〜０．５、好ましくは０．００３〜０．１の範囲で含まれていてもよい。
【００２２】
本発明の触媒は、ＩｎおよびＣｒを含有する化合物（例えば酸化物や水酸化物）を触媒前駆体として、これをＨＦやＦ２ 、分子中にフッ素を有するハロゲン化炭化水素等によってフッ素化し、ＯやＯＨを部分的にフッ素に置き換えることによって調製することができる。ＩｎおよびＣｒを含有する化合物は担体に担持することも可能であり、適当な担体として活性炭、アルミナ、フッ化アルミニウム、フッ化カルシウム、フッ化マグネシウムなどが挙げられる。
【００２３】
触媒前駆体の調製方法としては従来知られている混練法、含浸法、共沈法等のいかなる方法も用いることができ、また、触媒前駆体を調製するための原料としては工業規模で入手可能ならば、いかなる化合物を用いてもよい。上記の方法のうち、含浸法や共沈法がＩｎとＣｒを均一に分布させ得るため好ましい。
【００２４】
なかでも、共沈法は触媒のバルク組成まで均一に調整することが可能であるためさらに好ましい。従って、好ましい触媒前駆体の調製方法の例としては、ＩｎおよびＣｒの化合物が溶解した液を沈殿剤と反応させて沈殿をつくり、濾別、洗浄、乾燥、焼成する方法（共沈法の例）、酸化クロムや水酸化クロムにＩｎ化合物の溶液を含浸し、乾燥、焼成する方法（含浸法の例）等があげられる。担体を用いる場合には例えばＩｎおよびＣｒの化合物が溶解した液を担体に含浸し、乾燥、焼成することにより調製することができる。
【００２５】
さらに好ましい調製方法の例としては、共沈法においてＩｎおよびＣｒの化合物が溶解した液と沈殿剤とを反応容器の中の反応液のｐＨが６〜１２、特に好ましくは６．５〜１０の範囲内に在るようにコントロールしながら、双方同時に、あるいは交互に滴下して調製したスラリーを濾別、洗浄、乾燥し、焼成する方法があげられる。
【００２６】
ＩｎおよびＣｒの化合物としては硝酸塩、塩化物、硫酸塩が好適に用いられる。なかでも共沈法においては硝酸塩が、含浸法においては塩化物が好ましい。沈殿剤の種類としてはアンモニア、水酸化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、水酸化カリウム、炭酸カリウム、炭酸水素カリウム、炭酸アンモニウム、炭酸水素アンモニウムなどが好ましく、なかでもアンモニアが特に好ましい。
【００２７】
触媒形状として成型物が望ましい場合には焼成前、または焼成後に打錠成型を行ったり、乾燥前に押し出し成型を実施することにより成型物とすることができる。
【００２８】
乾燥方法としては８０〜１３０℃、特には９０〜１２０℃の温度範囲で、空気あるいはＮ２ などの不活性ガス雰囲気中で３０分以上行うことが好ましいが、減圧乾燥などの他の乾燥方法で行うことも可能である。
焼成は３００℃〜６００℃、好ましくは３５０℃〜５００℃の温度範囲で行うことが適当であるが、調製方法によって焼成の雰囲気を選ぶ必要がある。
【００２９】
すなわち、水酸化クロム、酸化クロムなどのクロム化合物は約３５０℃以上の高温でＯ２ に触れると比表面積の大幅な低下を引き起こし、また、活性炭は燃焼して消失する。このため、担体を使用せずにクロム化合物を触媒前駆体の主成分とする場合や、活性炭を担体として用いる場合には３５０℃以上の温度で１０００Ｐａ（絶対圧力）以上のＯ２ を含む雰囲気に曝してはならず、Ｎ２ 、Ａｒなどの不活性ガスもしくは還元性ガス雰囲気で焼成することが望ましい。
ここで言う還元性ガス雰囲気とはＨ２ 、ＣＯ、ＮＯなどの還元力を有するガスを含有する雰囲気のことであり、その他に不活性ガスや水分も含有することができる。Ｏ２ などの酸化性ガスについても安全上問題とならない濃度であれば含まれていてもよいが、含まれていない方が望ましい。
【００３０】
担体としてアルミナや各種金属フッ化物を用いる場合にはＯ２ 雰囲気下でも担体が比表面積の低下を防止する効果をもつため、Ｏ２ を含む雰囲気、代表的には空気中で焼成することも可能である。しかし、特開平５−９２１４１号公報に記載されているように、焼成後に行う前駆体のフッ素化時に、Ｃｒが飛散するという問題が生じる。従って、上記担体を用いる場合にも不活性ガスもしくは還元性ガス雰囲気で焼成する、もしくは、Ｏ２ を含む雰囲気で焼成を行った後にさらに、還元性ガス雰囲気で焼成することが望ましい。
【００３１】
さらに好ましい焼成方法としては、焼成工程の中に還元性ガス雰囲気で熱処理する工程を設ける方法があげられる。すなわち、クロム化合物を触媒前駆体の主成分とする場合や、活性炭を担体として用いる場合には、乾燥工程後に直接、還元性ガス雰囲気で焼成する、もしくは、一旦、不活性ガス中で焼成を行った後にさらに還元性ガス雰囲気で焼成することが好ましい。担体としてアルミナや各種金属フッ化物を用いる場合には、乾燥工程後に直接、還元性ガス雰囲気で焼成する、もしくは、一旦、不活性ガス中やＯ２ を含む雰囲気で焼成を行った後にさらに還元性ガス雰囲気で焼成することが好ましい。
【００３２】
上記の還元性ガス雰囲気で熱処理することにより、反応前に行う前駆体のフッ素化の際に、飛散するＣｒの量を減少させる、触媒の活性を向上させる等の効果が期待できる。熱処理の温度としては３５０〜５００℃が適当であり、好ましくは３７０〜４６０℃、特に３７０〜４５０℃がよい。
【００３３】
用いる還元性ガスの種類としてはＨ２ 、ＣＯ、ＮＯ等があげられるが、取扱いの簡便さからＨ２ を用いるのが適当である。還元性ガスの濃度は０．１〜１００ｖｏｌ％とすることができる。必要に応じてガス中に２０ｖｏｌ％以下の水や９９．９ｖｏｌ％以下の不活性ガスを同伴することも可能であるが、Ｏ２ 濃度は安全上の問題から０．１ｖｏｌ％以下に抑えるべきである。ガス流量はＧＨＳＶ（標準状態換算）で１０〜１００００ｈ−１が適当であり、圧力は大気圧〜１０ｋｇ／ｃｍ２ Ｇが操作上簡便である。処理時間としては少なくも３０分間、好ましくは１〜１０時間熱処理する。
【００３４】
還元性ガス雰囲気で熱処理した触媒前駆体はＯ２ を絶対圧力で１０００Ｐａ以上含む雰囲気で高温に曝すことは好ましくない。従って、還元性ガス雰囲気で焼成した後、さらに空気中などのＯ２ を含有する雰囲気で焼成を行うことは避けるべきである。また、還元性ガス雰囲気での焼成が終了して前駆体を取り出す際に大気解放する場合にも、２００℃以上の温度でＯ２ が系内に導入されるような操作は避けねばならず、好ましくは１５０℃、さらに好ましくは１２０℃以下の温度で空気を系内に少しづつ導入し、徐々に系内のＯ２ 濃度を上げた後に大気解放すべきである。
【００３５】
以上述べた方法およびその他公知のいかなる方法で触媒前駆体の調製を行ってもよいが、Ｃｒに対するＩｎの原子比（以下、Ｉｎ／Ｃｒ比と略す）は０．００５〜０．６、好ましくは０．０１〜０．５、特に好ましくは０．０１〜０．３という範囲にしなければならない。上記の範囲よりＩｎ／Ｃｒ比が小さいと、反応圧力の増加により反応速度が低下する割合が大きく、また、Ｉｎ／Ｃｒ比が大き過ぎても反応速度が低下するため好ましくない。Ｉｎ／Ｃｒ比の調整は、混練法ならば混合する粉の割合、含浸法や共沈法ならばＩｎおよび／またはＣｒ化合物の溶液濃度や溶液組成をコントロールすることにより容易に達成される。
【００３６】
本発明のフッ素化触媒ではさらにＯ、Ｆを必須の構成元素とする。Ｏ、Ｆの含量はＩｎ／Ｃｒ比や触媒前駆体の調製方法によって適切な範囲が変化するが、何れの成分も触媒の全重量に対して０．３重量％以上は必要である。好ましいＯの含量の範囲は１〜２５重量％である。触媒中にＯとＦを含有させるには、上記のようにＩｎおよびＣｒを含有する化合物をＨＦやＦ２ 、分子中にＦを有するハロゲン化炭化水素等によってフッ素化することで達成できる。なかでもＨＦを用いるフッ素化がコスト上優れている。
【００３７】
フッ素化の温度としては３００〜５００℃、特には３００〜４５０℃が好ましい。ＨＦなどのフッ素化剤の濃度としては、０．１〜１００ｖｏｌ％で行い得るが、発熱による温度上昇（以下、△Ｔと略す）が最大でも５０℃以下になるように、必要に応じてＮ２ などの不活性ガスでフッ素化剤を希釈して用いることが望ましい。ガス流量はＧＨＳＶで１０〜１００００ｈ−１が適当であり、圧力は大気圧〜２０ｋｇ／ｃｍ２ Ｇで行うことができる。
【００３８】
好ましい触媒前駆体のフッ素化方法の一例をあげると、大気圧下３００〜４００℃で、ＨＦ濃度５〜３０ｖｏｌ％になるようにＨＦとＮ２ を供給しフッ素化を開始する。ホットスポットが前駆体充填層を通過した後、発熱に注意しながらＨＦ濃度を９０ｖｏｌ％以上に、圧力を２〜１０ｋｇ／ｃｍ２ Ｇになるまで上げていき、最終条件で少なくとも実質的に発熱が観測されなくなるまで処理を継続する。
以上述べた触媒前駆体の焼成およびフッ素化はインコネル、ハステロイ製のものであれば同一の反応器で行うことも可能であり、操作上簡便である。
【００３９】
本発明のＩｎ、Ｃｒ、Ｏ、Ｆを必須の構成元素として含むフッ素化触媒はハロゲン化炭化水素をＨＦによりフッ素化する際に適用できるが、含水素ハロゲン化炭化水素のフッ素化反応を加圧下において行う際には特に効果的である。
つまり、オキシフッ化クロムのような従来のフッ素化触媒を用いた場合に認められる、反応圧力を上げると反応速度が低下し、原料炭化水素の転化率が減少するという反応圧力のマイナス効果が改善できる。
【００４０】
さらに詳細に説明すると、本発明のＩｎ、Ｃｒ、Ｏ、Ｆを必須の構成元素として含む触媒は大気圧付近においてはオキシフッ化クロムのごとき従来のフッ素化触媒と同程度もしくは若干活性が高い程度であるが、反応圧力を高くしても反応速度（原料炭化水素の転化率）の低下はほとんどない。一方、オキシフッ化クロムのごとき従来のフッ素化触媒では、反応圧力を高くすると反応速度が低下していく。従って、反応圧力が高くなるにしたがって、本発明の触媒と従来のフッ素化触媒との転化率の差は大きくなっていく。
【００４１】
すなわち本発明の触媒を用いることにより、従来のフッ素化触媒で認められた反応圧力のマイナス効果を改善することができ、さらに、反応を加圧下で行うことにより副生物の生成量も減少させることができるため、特に、加圧下の含水素ハロゲン化炭化水素のフッ素化反応において高い収率でＨＦＣを得ることができる。
【００４２】
本発明でいう含水素ハロゲン化炭化水素とは、主には炭素数１から４の分子中にＨを含むハロゲン化炭化水素のことであり、一例をあげると、ＣＨＣｌ３ 、ＣＨ２ Ｃｌ２ 、ＣＨ２ ＦＣｌ、ＣＨ３ Ｃｌ、Ｃ２ ＨＣｌ３ 、Ｃ２ Ｈ２ Ｃｌ２ 、Ｃ２ Ｈ３ Ｃｌ、Ｃ２ ＨＣｌ５ 、Ｃ２ ＨＦＣｌ４ 、Ｃ２ ＨＦ２ Ｃｌ３ 、Ｃ２ ＨＦ３ Ｃｌ２ 、Ｃ２ ＨＦ４ Ｃｌ、Ｃ２ Ｈ２ Ｆ３ Ｃｌ、Ｃ２ Ｈ３ Ｃｌ３ 、Ｃ２ Ｈ３ ＦＣｌ２ 、Ｃ２ Ｈ３ Ｆ２ Ｃｌ、Ｃ２ Ｈ４ Ｃｌ２ 、Ｃ２ Ｈ４ ＦＣｌ、Ｃ２ Ｈ５ Ｃｌ、Ｃ３ Ｈ２ Ｆ４ Ｃｌ２ 、Ｃ３ ＨＦ４ Ｃｌ３ などがある。さらに、上記の炭化水素中のＣｌの全部もしくは一部をＢｒやＩに置換した化合物であってもよい。
【００４３】
なかでも、最近オゾン層を破壊する恐れのない代替フロンとして注目されているＨＦＣ−３２やＨＦＣ−１３４ａ、ＨＦＣ−１２５を製造する際の合成ルートとして考えられるＣＨ２ Ｃｌ２ 、ＣＨ２ ＦＣｌ（ＨＣＦＣ−３１）、ＣＨＣｌ＝ＣＣｌ２ （トリクロロエチレン）、ＣＦ３ ＣＨ２ Ｃｌ（ＨＣＦＣ−１３３ａ）、ＣＣｌ２ ＝ＣＣｌ２ （パークロロエチレン）、ＣＦ３ ＣＨＣｌ２ （ＨＣＦＣ−１２３）、ＣＦ３ ＣＨＦＣｌ（ＨＣＦＣ−１２４）のフッ素化反応において有効であり、ＨＣＦＣ−１３３ａのフッ素化によるＨＦＣ−１３４ａの製造には特に効果的である。
【００４４】
フッ素化反応は固定床、流動床、移動床等の反応方法をとり得るが、固定床が一般的である。反応条件は反応によって適切な条件が変化するが、一般的には、ハロゲン化炭化水素に対するＨＦのモル比：０．５〜２０、温度：２００〜４００℃、圧力：大気圧〜２０ｋｇ／ｃｍ２ Ｇ、ＳＶ：５０〜１０００００ｈ−１である。本発明のフッ素化触媒を用いれば加圧下でも生産性が低下しないため反応圧力は大気圧以上に上げてよく、好ましい反応圧力は１〜２０ｋｇ／ｃｍ２ Ｇ、より好ましくは１．５〜２０ｋｇ／ｃｍ２ Ｇである。
【００４５】
【実施例】
以下、実施例および比較例を示して、本発明を具体的に説明するが、かかる説明によって本発明が限定されないことは勿論である。
【００４６】
なお、説明中Ｉｎ／Ｃｒ比は化学分析から求めた触媒に含まれる各元素の原子比を表し、反応例中のモル比とはハロゲン化炭化水素に対するＨＦのモル比を表す。ＳＶは標準状態に換算した値であり、圧力はゲージ圧である。
【００４７】
（触媒調製例１）
純水６００ｍｌを入れた１０ｌの容器に、Ｃｒ（ＮＯ３ ）３ ・９Ｈ２ Ｏ ４５２ｇとＩｎ（ＮＯ３ ）３ ・ｎＨ２ Ｏ（ｎは約５） ４２ｇを純水 １．２ｌに溶かした溶液と２８重量％のアンモニア水 ０．３ｌとを攪拌しながら、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て約１時間かけて滴下した。得られた水酸化物のスラリーを濾別し、純水でよく洗浄した後、１２０℃で１２時間乾燥した。得られた固体を粉砕、黒鉛と混合し、打錠成型機によってペレット化した。このペレットをＮ２ 気流下４００℃で４時間焼成し触媒前駆体とした。触媒前駆体６０ｍｌをインコネル製反応管に充填し、大気圧においてＮ２ 希釈したＨＦ気流下３５０℃で、続いてＮ２ 希釈しない１００％のＨＦ気流下３５０℃で、さらに１００％のＨＦ気流下で昇圧して４ｋｇ／ｃｍ２ Ｇでフッ素化処理を行った。処理後のペレットの組成を以下に示す。
Ｉｎ：１０．８重量％、 Ｃｒ：４９．０重量％Ｏ：１５．１重量％、 Ｆ：２３．９重量％
これらの値からＩｎ／Ｃｒ比は０．１であった。
【００４８】
（比較触媒調製例１）
Ｉｎ（ＮＯ３ ）３ ・ｎＨ２ Ｏを加えないこと以外は触媒調製例１と同様にしてＩｎを含まない触媒前駆体を調製した。この触媒前駆体６０ｍｌをインコネル製反応管に充填し、触媒調製例１と同様にしてフッ素化処理を行った。処理後のペレットの組成を以下に示す。
Ｃｒ：５６．９重量％、 Ｏ：１６．３重量％、 Ｆ：２３．８重量％
【００４９】
（触媒調製例２）
比較触媒調製例１で作った乾燥品２００ｇにＩｎＣｌ３ ・４Ｈ２ Ｏ １７ｇを純水に溶解して含浸し、再度１２０℃で乾燥した。以下の操作は触媒調製例１と同様にしてフッ素化処理まで行った。処理後のペレットの組成を以下に示す。
Ｉｎ： ３．７重量％、 Ｃｒ：５３．６重量％、Ｏ：１６．０重量％、 Ｆ：２３．３重量％
これらの値からＩｎ／Ｃｒ比は０．０３であった。
【００５０】
（触媒調製例３）
触媒調製例１で打錠成型したペレット１００ｍｌをガラス製焼成管に充填し、３ｖｏｌ％の水蒸気を含んだＨ２ 気流下４００℃で４時間焼成して前駆体とした。以下の操作は触媒調製例１と同様にしてフッ素化処理まで行った。
【００５１】
（触媒調製例４）
ＣｒＣｌ３ ・６Ｈ２ Ｏ １１１ｇ、ＩｎＣｌ３ ・４Ｈ２ Ｏ ６ｇを純水７８ｇに溶解し、高純度活性アルミナ１００ｇを浸漬して溶液を全量吸収させた。これを１２０℃で１０時間乾燥した後、ガラス製焼成管に充填し、空気気流下４００℃で３時間、さらに、３ｖｏｌ％の水蒸気を含んだＨ２ 気流下４００℃で４時間焼成して前駆体とした。以下の操作は触媒調製例１と同様にしてフッ素化処理まで行った。処理後の組成を以下に示す。
Ｉｎ：１．１重量％、 Ｃｒ：１０．５重量％、 Ａｌ：４９．０重量％、Ｏ：２．５重量％、 Ｆ：６０．３重量％
【００５２】
（触媒調製例５）
Ｃｒ（ＮＯ３ ）３ ・９Ｈ２ ＯとＩｎ（ＮＯ３ ）３ ・ｎＨ２ Ｏの水溶液にＣｕ（ＮＯ３ ）２ ・３Ｈ２ Ｏ １ｇをさらに追加する以外は触媒調製例１の操作に従ってペレットを作成し、それ以降の操作は触媒調製例３に従ってフッ素化処理まで行った。
【００５３】
（触媒調製例６）
Ｃｒ（ＮＯ３ ）３ ・９Ｈ２ ＯとＩｎ（ＮＯ３ ）３ ・ｎＨ２ Ｏの水溶液にＣｄ（ＮＯ３ ）２ ・４Ｈ２ Ｏ １ｇをさらに追加する以外は触媒調製例１の操作に従ってペレットを作成し、それ以降の操作は触媒調製例３に従ってフッ素化処理まで行った。
【００５４】
（触媒調製例７）
Ｃｒ（ＮＯ３ ）３ ・９Ｈ２ ＯとＩｎ（ＮＯ３ ）３ ・ｎＨ２ Ｏの水溶液にＰｂ（ＮＯ３ ）２ １ｇをさらに追加する以外は触媒調製例１の操作に従ってペレットを作成し、それ以降の操作は触媒調製例３に従ってフッ素化処理まで行った。
【００５５】
（触媒調製例８）
Ｃｒ（ＮＯ３ ）３ ・９Ｈ２ ＯとＩｎ（ＮＯ３ ）３ ・ｎＨ２ Ｏの水溶液にＡｇＮＯ３ １ｇをさらに加えて溶解させる以外は触媒調製例１の操作に従ってペレットを作成し、それ以降の操作は触媒調製例３に従ってフッ素化処理まで行った。
【００５６】
（フッ素化反応例１）
触媒調製例１で調製した触媒５０ｍｌをインコネル製反応管に充填し、以下の反応条件でＨＦによるＨＣＦＣ−１３３ａのフッ素化反応を行った。反応管の出口ガスをアルカリトラップに吹き込んで未反応のＨＦおよび生成したＨＣｌを除去し、ガスクロによりガス組成を分析した。反応開始後６〜８時間目の結果を表１に示す。
温度：３２０℃、圧力：大気圧、モル比：８、ＳＶ：１５００ｈ−１
【００５７】
（フッ素化反応例２）
反応圧力を４ｋｇ／ｃｍ２ Ｇにする以外はフッ素化反応例１と同様にしてＨＣＦＣ−１３３ａのフッ素化反応を行った。結果を表１に示す。
【００５８】
（比較フッ素化反応例１）
比較触媒調製例１で調製した触媒を用いる以外はフッ素化反応例１と同様にしてＨＣＦＣ−１３３ａのフッ素化反応を行った。結果を表１に示す。
【００５９】
（比較フッ素化反応例２）
反応圧力を４ｋｇ／ｃｍ２ Ｇにする以外は比較フッ素化反応例１と同様にしてＨＣＦＣ−１３３ａのフッ素化反応を行った。結果を表１に示す。
【００６０】
（フッ素化反応例３）
触媒調製例２で調製した触媒を用いる以外はフッ素化反応例１と同様にしてＨＣＦＣ−１３３ａのフッ素化反応を行った。結果を表１に示す。
【００６１】
（フッ素化反応例４）
反応圧力を４ｋｇ／ｃｍ２ Ｇにする以外はフッ素化反応例３と同様にしてＨＣＦＣ−１３３ａのフッ素化反応を行った。結果を表１に示す。
【００６２】
【表１】
【００６３】
表１の結果より、大気圧においてはＩｎを添加しても、しなくてもＨＦＣ−１３４ａ収率に大差ないが、反応圧力が高くなる（４ｋｇ／ｃｍ２ Ｇ）とＩｎを添加した触媒の方が高い収率を与えることがわかる。このことはＩｎとＣｒを組み合わせることによりＣｒ単独の触媒でみられる圧力のマイナス効果を改善できることを示している。
【００６４】
（フッ素化反応例５〜１０）
触媒調製例３〜８で調製した触媒を用いる以外はフッ素化反応例２と同様にしてＨＣＦＣ−１３３ａのフッ素化反応を行った。結果を表２に示す。
【００６５】
【表２】
【００６６】
（フッ素化反応例１１）
触媒調製例３で調製した触媒３０ｍｌをインコネル製反応管に充填し、以下の反応条件でＨＦによるジクロロメタンのフッ素化反応を行った。反応管の出口ガスを加温したアルカリトラップに吹き込んで未反応のＨＦおよび生成したＨＣｌを除去し、ガスクロによりガス組成を分析した。
温度：１９０℃、圧力：大気圧、モル比：６、ＳＶ：１５００ｈ−１
未反応ジクロロメタンは３９％であり、主な生成物の収率は以下の通りであった。
ＨＦＣ−３２；５２％、ＨＣＦＣ−３１；８％
【００６７】
（フッ素化反応例１２）
触媒調製例３で調製した触媒３０ｍｌをインコネル製反応管に充填し、以下の反応条件でＨＦによるＨＣＦＣ−１２３のフッ素化反応を行った。反応管の出口ガスをアルカリトラップに吹き込んで未反応のＨＦおよび生成したＨＣｌを除去し、ガスクロによりガス組成を分析した。
温度：３２５℃、圧力：４ｋｇ／ｃｍ２ Ｇ、モル比：６、ＳＶ：１０００ｈ−１
未反応のＨＣＦＣ−１２３は１０％であり、主な生成物の収率は以下の通りであった。
ＨＦＣ−１２５；６０．６％、ＨＣＦＣ−１２４；２４．５％
【００６８】
【発明の効果】
本発明は、インジウム、クロム、酸素、フッ素を必須の構成元素として含み、クロムに対するインジウムの原子比が０．００５〜０．６である、高い収率でＨＦＣを生産するために改良されたフッ素化触媒、および、該触媒を用いて生産性よくＨＦＣを製造する方法を提供するものであり、該触媒を用いて気相でＨＦによるハロゲン化炭化水素のフッ素化反応を行えば、加圧下でも高収率でＨＦＣを得ることができる。[0001]
[Industrial applications]
The present invention relates to a fluorination catalyst and a fluorination method. More specifically, the present invention relates to a hydrofluorocarbon (hereinafter abbreviated as HFC) which does not contain any chlorine in the molecule and thus has no risk of destruction of the ozone layer. Hereinafter, abbreviated as HFC-32), 1,1,1,2-tetrafluoroethane (hereinafter, abbreviated as HFC-134a), and pentafluoroethane (hereinafter, abbreviated as HFC-125) with high yield. The present invention relates to an improved fluorination catalyst for producing HFC, and a method for producing HFC with high productivity by contacting hydrogen fluoride and halogenated hydrocarbon in a gas phase using the catalyst.
[0002]
[Prior art]
A typical HFC production method industrially performed is a method of exchanging halogens other than F with F by contacting a hydrogen-containing halogenated hydrocarbon with HF (HF from an unsaturated halogenated hydrocarbon as a raw material). ) And the reaction of exchanging a halogen other than F for F) at the same time).2 There is a method of exchanging halogen other than F (in some cases, a part of F) with H by contact with H. Of these, the fluorination reaction of hydrogen-containing halogenated hydrocarbons with HF is often difficult to proceed, and the production amount of HFC largely depends on the catalyst used.
[0003]
A representative example of the reaction that is most difficult to proceed is a synthesis reaction of HFC-134a by fluorination of 1-chloro-2,2,2-trifluoroethane (hereinafter abbreviated as HCFC-133a). This reaction is clearly an endothermic reaction that is thermodynamically disadvantageous. Therefore, in general, the reaction is carried out under the reaction conditions (pressure, temperature, space velocity) that give a significant conversion rate in the presence of stoichiometric or more HF in HCFC-133a.
[0004]
As an example, JP-A-55-27138 discloses that CrF3 ・ 3H2 Using a compound obtained by treating O with air as a catalyst, at atmospheric pressure, at a reaction temperature of 400 ° C., a molar ratio of HF to HCFC-133a (hereinafter abbreviated as “molar ratio”) 8, and a space velocity (hereinafter abbreviated as “SV”) 550 h-1Under the reaction conditions described above, HFC-134a was obtained at a yield of 32%.
[0005]
Japanese Patent Application Laid-Open No. 1-268551 discloses CoCl.2 / Al2 O3 Using a catalyst obtained by fluorination treatment at atmospheric pressure, a reaction temperature of 410 ° C., a molar ratio of 10, and a contact time of 30 seconds (SV 120 h-1), The yield of HFC-134a is 32%. The reaction at such a low SV has a low productivity, and the reaction at a high temperature causes not only a thermal energy loss but also a decrease in selectivity. shorten.
[0006]
Therefore, studies have been made so far for the purpose of enhancing the activity and prolonging the life of the catalyst. That is, JP-A-2-172933 discloses a catalyst comprising a halide or oxide containing Cr and at least one element selected from the group consisting of Al, Mg, Ca, Ba, Sr, Fe, Ni, Co and Mn. Has excellent durability (life). Further, EP-502605 discloses that a Cr-based catalyst supporting Zn gives high activity. Further, Japanese Patent Application Laid-Open No. 4-346943 discloses a partially fluorinated Cr carrying Ru or Pt.2 O3 Discloses that the catalyst consisting of
In addition, as a catalyst containing a component other than Cr as a main component, there is a catalyst in which an In compound disclosed by the present applicant in JP-A-2-95438 is supported on a carrier such as alumina and treated with HF. Is lower than that of a catalyst containing Cr as a main component.
[0007]
[Problems to be solved by the invention]
However, in recent years, as described in the specification of JP-A-4-346943, when the fluorination reaction of HCFC-133a by HF is performed using a conventional Cr-based or Al-based catalyst, the reaction pressure is increased. It has been clarified that there is a new problem inherent in the present reaction that the reaction rate decreases and the productivity decreases when the value of is increased.
[0008]
That is, even if the catalyst shows a high reaction yield under atmospheric pressure, the reaction pressure is increased [for example, 10 kg / cm2 G (gauge pressure)] and the selectivity of HFC-134a are slightly improved, but the yield is considerably reduced due to the reduced conversion of HCFC-133a [for comparison, other conditions (reaction temperature, molar ratio, SV converted to the standard state is the same). Although varying in degree, this phenomenon is also observed in the fluorination reaction of other hydrogenated halogenated hydrocarbons.
[0009]
1 kg / cm reaction in actual production equipment2 It is not preferable to perform the process near the atmospheric pressure of about G, because an additional facility for reducing the pressure is required, which leads to an increase in facility cost. Further, the selectivity of the reaction is better under pressure, and in particular, the amount of by-products of highly toxic unsaturated compounds can be suppressed. Accordingly, there is a need for a catalyst that does not decrease the reaction rate even when the reaction pressure is increased, and more preferably a catalyst that increases the reaction rate when the reaction pressure is increased.
[0010]
Of course, high activation and long life of the catalyst, which are conventional problems, greatly contribute to the cost and productivity of the catalyst, and thus are one of the important problems of the present invention.
SUMMARY OF THE INVENTION It is an object of the present invention to provide an improved fluorination catalyst for producing HFC in a high yield in the production of HFC, and to use the catalyst to produce hydrogen fluoride and halogenated hydrocarbon in the gas phase. The method is to provide a method for producing HFC with high productivity by bringing into contact with, for example, a method for producing HFC-32, HFC-134a and HFC-125 with high productivity.
[0011]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the combination of In and Cr as metal components can improve the negative effect of pressure on the reaction rate, and have accomplished the present invention.
[0012]
The invention of claim 1 of the present invention contains indium, chromium, oxygen, and fluorine as essential constituent elements, and the atomic ratio of indium to chromium is 0.005 to 0.6.A fluorination catalyst, wherein the step of preparing the catalyst includes a step of performing a heat treatment at 350 to 500 ° C. in a reducing gas.It is a fluorination catalyst characterized by the above-mentioned.
[0013]
The invention according to claim 2 of the present invention is the fluorination catalyst according to claim 1, which is prepared by a coprecipitation method.
[0015]
Claims of the invention3The invention according to claim 1, characterized in that it contains at least one element selected from the group consisting of elements of groups 11, 12, 13, and 14 of the long period type periodic table.Or 2The fluorination catalyst described in 1. above.
[0016]
Claims of the invention4The invention of claim 1Described in any of 3Wherein the hydrogen fluoride and the halogenated hydrocarbon are brought into contact with each other in the gas phase in the presence of the fluorination catalyst.
[0017]
Claims of the invention5The invention according to claim, wherein the halogenated hydrocarbon is a hydrogen-containing halogenated hydrocarbon.4It is a fluorination method described.
[0018]
Claims of the invention6The invention of the invention is that the hydrogenated halogenated hydrocarbon is dichloromethane, chlorofluoromethane, 1-chloro-2,2,2-trifluoroethane, 1,1-dichloro-2,2,2-trifluoroethane, The chloro-1,2,2,2-tetrafluoroethane is selected from the group consisting of:5It is a fluorination method described.
[0019]
Claims of the invention7The invention according to claim, wherein the hydrogen-containing halogenated hydrocarbon is 1-chloro-2,2,2-trifluoroethane.6It is a fluorination method described.
[0020]
In the present invention, in a method of fluorinating a halogenated hydrocarbon by contacting the halogenated hydrocarbon with HF, In, Cr, O, and F are included as essential constituent elements, and the atomic ratio of In to Cr is 0. The solution is to use a catalyst having a 0.005 to 0.6, preferably 0.01 to 0.5, particularly preferably 0.01 to 0.3.
[0021]
As a constituent element of the catalyst other than In, Cr, O, and F, it is not preferable that a large amount (for example,% order by weight) of an alkali metal is contained, but other elements are contained by% order or more by weight. Is also good. In particular, at least one element selected from the group consisting of elements of Groups 11, 12, 13, and 14 (new IUPAC nomenclature) of the long-periodic periodic table in which the catalyst can be expected to prolong the life of the catalyst, particularly Cu , Ag, Au, Zn, Cd, Hg, Al, Ga, Sn, Pb and the like may be contained in an atomic ratio to Cr of 0.001 to 0.5, preferably 0.003 to 0.1. Good.
[0022]
The catalyst of the present invention uses a compound containing In and Cr (for example, an oxide or a hydroxide) as a catalyst precursor and converts the compound into HF or F.2 It can be prepared by fluorinating with a halogenated hydrocarbon having fluorine in the molecule and partially replacing O and OH with fluorine. The compound containing In and Cr can be supported on a carrier, and suitable carriers include activated carbon, alumina, aluminum fluoride, calcium fluoride, and magnesium fluoride.
[0023]
As a method for preparing the catalyst precursor, any of the conventionally known methods such as a kneading method, an impregnation method, and a coprecipitation method can be used, and a raw material for preparing the catalyst precursor is available on an industrial scale. Then, any compound may be used. Of the above methods, the impregnation method or the coprecipitation method is preferable because In and Cr can be uniformly distributed.
[0024]
Of these, the coprecipitation method is more preferable because it can uniformly adjust the bulk composition of the catalyst. Therefore, as a preferred example of a method for preparing a catalyst precursor, a method in which a solution in which a compound of In and Cr is dissolved is reacted with a precipitant to form a precipitate, which is separated by filtration, washed, dried, and calcined (an example of a coprecipitation method) ), A method of impregnating chromium oxide or chromium hydroxide with a solution of an In compound, drying and firing (an example of the impregnation method). When a carrier is used, it can be prepared, for example, by impregnating the carrier with a liquid in which a compound of In and Cr is dissolved, drying and firing.
[0025]
As a more preferred example of the preparation method, a solution in which the compound of In and Cr is dissolved in the coprecipitation method and a precipitant are mixed so that the pH of the reaction solution in the reaction vessel is 6 to 12, particularly preferably 6.5 to 10. A method of filtering, washing, drying, and calcining a slurry prepared by simultaneously or alternately dripping both while controlling to be within the range, may be mentioned.
[0026]
As compounds of In and Cr, nitrates, chlorides and sulfates are preferably used. Of these, nitrates are preferred in the coprecipitation method and chlorides in the impregnation method. As the kind of the precipitant, ammonia, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, ammonium carbonate, ammonium hydrogen carbonate and the like are preferable, and among them, ammonia is particularly preferable.
[0027]
When a molded product is desired as the catalyst shape, it can be formed into a molded product by performing tablet molding before or after firing, or by performing extrusion molding before drying.
[0028]
As a drying method, air or N is used in a temperature range of 80 to 130 ° C., particularly 90 to 120 ° C.2 Preferably, the drying is performed for 30 minutes or more in an inert gas atmosphere, but the drying can be performed by another drying method such as drying under reduced pressure.
The firing is suitably performed at a temperature in the range of 300 ° C. to 600 ° C., preferably 350 ° C. to 500 ° C., but the firing atmosphere needs to be selected depending on the preparation method.
[0029]
That is, chromium compounds such as chromium hydroxide, chromium oxide, etc.2 Touching causes a significant decrease in the specific surface area, and the activated carbon burns and disappears. For this reason, when a chromium compound is used as a main component of the catalyst precursor without using a carrier, or when activated carbon is used as a carrier, an O pressure of 1000 Pa (absolute pressure) or more at a temperature of 350 ° C. or more is used.2 Must not be exposed to an atmosphere containing2 It is preferable to perform firing in an atmosphere of an inert gas such as Ar, Ar or a reducing gas.
Here, the reducing gas atmosphere is H2 , CO, NO, and the like, and may also contain an inert gas or moisture. O2 Such an oxidizing gas may be contained as long as it does not pose a safety problem, but is preferably not contained.
[0030]
When alumina or various metal fluorides are used as the carrier, O2 Since the carrier has the effect of preventing the specific surface area from decreasing even in an atmosphere,2 It is also possible to bake in an atmosphere containing, typically, air. However, as described in JP-A-5-92141, there is a problem that Cr is scattered during fluorination of the precursor after firing. Therefore, even when the above carrier is used, calcination is performed in an inert gas or reducing gas atmosphere,2 After baking in an atmosphere containing, it is desirable to further bake in a reducing gas atmosphere.
[0031]
A more preferable firing method includes a method of providing a heat treatment in a reducing gas atmosphere during the firing step. In other words, when a chromium compound is used as the main component of the catalyst precursor or when activated carbon is used as a carrier, firing is performed directly in a reducing gas atmosphere after the drying step, or firing is performed once in an inert gas. After that, it is preferable to further bake in a reducing gas atmosphere. When alumina or various metal fluorides are used as the carrier, they are calcined directly in a reducing gas atmosphere after the drying step, or once in an inert gas or O 2.2 After baking in an atmosphere containing, it is preferable to further bake in a reducing gas atmosphere.
[0032]
By performing the heat treatment in the above reducing gas atmosphere, effects such as reducing the amount of scattered Cr and improving the activity of the catalyst at the time of fluorination of the precursor performed before the reaction can be expected. The temperature of the heat treatment is suitably from 350 to 500 ° C, preferably from 370 to 460 ° C, particularly preferably from 370 to 450 ° C.
[0033]
The type of reducing gas used is H2 , CO, NO, etc., but H2 It is appropriate to use The concentration of the reducing gas can be 0.1 to 100 vol%. If necessary, 20 vol% or less of water or 99.9 vol% or less of inert gas can be entrained in the gas.2 The concentration should be kept below 0.1 vol% due to safety concerns. Gas flow rate is 10 to 10000h in GHSV (standard state conversion)-1Is appropriate, and the pressure is atmospheric pressure to 10 kg / cm.2 G is easy to operate. The heat treatment is performed for at least 30 minutes, preferably 1 to 10 hours.
[0034]
The catalyst precursor heat-treated in a reducing gas atmosphere is O2 Exposure to high temperatures in an atmosphere containing 1000 Pa or more in absolute pressure is not preferred. Therefore, after firing in a reducing gas atmosphere, O2 Should be avoided in an atmosphere containing. Also, when the firing in the reducing gas atmosphere is completed and the precursor is released to the atmosphere at the time of taking out the precursor, the O 2 is heated at a temperature of 200 ° C. or more.2 It is necessary to avoid an operation in which air is gradually introduced into the system at a temperature of preferably 150 ° C., more preferably 120 ° C. or lower, and gradually introduce O into the system.2 It should be released to the atmosphere after raising the concentration.
[0035]
The catalyst precursor may be prepared by the method described above or any other known method, but the atomic ratio of In to Cr (hereinafter abbreviated as In / Cr ratio) is 0.005 to 0.6, preferably It must be in the range 0.01 to 0.5, particularly preferably 0.01 to 0.3. If the In / Cr ratio is smaller than the above range, the rate of decrease in the reaction rate due to an increase in the reaction pressure is large, and if the In / Cr ratio is too large, the reaction rate is undesirably decreased. The adjustment of the In / Cr ratio can be easily achieved by controlling the proportion of powder to be mixed in the kneading method, or by controlling the solution concentration or composition of the In and / or Cr compounds in the impregnation method or the coprecipitation method.
[0036]
In the fluorination catalyst of the present invention, O and F are further included as essential constituent elements. The appropriate range of the contents of O and F varies depending on the In / Cr ratio and the method of preparing the catalyst precursor, but each component requires 0.3% by weight or more based on the total weight of the catalyst. The preferred range of O content is 1 to 25% by weight. In order to include O and F in the catalyst, the compound containing In and Cr is converted to HF or F2 Can be achieved by fluorination with a halogenated hydrocarbon having F in the molecule. Among them, fluorination using HF is excellent in cost.
[0037]
The fluorination temperature is preferably 300 to 500C, particularly preferably 300 to 450C. The concentration of the fluorinating agent such as HF can be set at 0.1 to 100 vol%, but if necessary, N may be adjusted so that the temperature rise due to heat generation (hereinafter abbreviated as ΔT) will be 50 ° C or less at the maximum.2 It is desirable to dilute the fluorinating agent with an inert gas such as this. Gas flow rate is 10 to 10000h in GHSV-1Is suitable, and the pressure is from atmospheric pressure to 20 kg / cm.2 G can do it.
[0038]
As an example of a preferred method for fluorinating a catalyst precursor, HF and N are mixed at 300 to 400 ° C. under atmospheric pressure so that the HF concentration becomes 5 to 30 vol%.2 To start fluorination. After the hot spot has passed through the precursor packed layer, the HF concentration was increased to 90 vol% or more and the pressure was increased to 2 to 10 kg / cm while paying attention to heat generation.2 The temperature is increased to G, and the process is continued until at least substantially no heat generation is observed under the final conditions.
The calcination and fluorination of the catalyst precursor described above can be performed in the same reactor as long as they are made of Inconel or Hastelloy, which is convenient in operation.
[0039]
The fluorination catalyst of the present invention containing In, Cr, O, and F as essential constituent elements can be applied when fluorinating a halogenated hydrocarbon with HF. It is particularly effective when performing the above.
In other words, when a conventional fluorination catalyst such as chromium oxyfluoride is used, the negative effect of the reaction pressure that the reaction rate decreases when the reaction pressure is increased and the conversion of the raw material hydrocarbon decreases can be improved. .
[0040]
More specifically, the catalyst of the present invention containing In, Cr, O, and F as essential constituent elements has a similar or slightly higher activity than a conventional fluorination catalyst such as chromium oxyfluoride at about atmospheric pressure. However, even if the reaction pressure is increased, there is almost no decrease in the reaction rate (conversion of the raw material hydrocarbon). On the other hand, in the case of a conventional fluorination catalyst such as chromium oxyfluoride, when the reaction pressure is increased, the reaction rate decreases. Therefore, as the reaction pressure increases, the difference in the conversion between the catalyst of the present invention and the conventional fluorination catalyst increases.
[0041]
That is, by using the catalyst of the present invention, the negative effect of the reaction pressure observed with the conventional fluorination catalyst can be improved, and further, by performing the reaction under pressure, the amount of by-products can be reduced. In particular, HFC can be obtained in a high yield in a fluorination reaction of a hydrogen-containing halogenated hydrocarbon under pressure.
[0042]
The hydrogen-containing halogenated hydrocarbon referred to in the present invention is mainly a halogenated hydrocarbon containing H in a molecule having 1 to 4 carbon atoms.3 , CH2 Cl2 , CH2 FCl, CH3 Cl, C2 HCl3 , C2 H2 Cl2 , C2 H3 Cl, C2 HCl5 , C2 HFCl4 , C2 HF2 Cl3 , C2 HF3 Cl2 , C2 HF4 Cl, C2 H2 F3 Cl, C2 H3 Cl3 , C2 H3 FCl2 , C2 H3 F2 Cl, C2 H4 Cl2 , C2 H4 FCl, C2 H5 Cl, C3 H2 F4 Cl2 , C3 HF4 Cl3 and so on. Further, a compound in which all or part of Cl in the above hydrocarbon is substituted with Br or I may be used.
[0043]
Among them, CH which is considered as a synthetic route for producing HFC-32, HFC-134a, and HFC-125, which have recently attracted attention as alternative chlorofluorocarbons that do not have a risk of depleting the ozone layer.2 Cl2 , CH2 FCl (HCFC-31), CHCl = CCl2 (Trichloroethylene), CF3 CH2 Cl (HCFC-133a), CCl2 = CCl2 (Perchloroethylene), CF3 CHCl2 (HCFC-123), CF3 It is effective in the fluorination reaction of CHFCl (HCFC-124), and is particularly effective in the production of HFC-134a by fluorination of HCFC-133a.
[0044]
The fluorination reaction can take a reaction method such as a fixed bed, a fluidized bed, and a moving bed, but a fixed bed is generally used. Suitable reaction conditions vary depending on the reaction, but generally, the molar ratio of HF to the halogenated hydrocarbon is 0.5 to 20, the temperature is 200 to 400 ° C., and the pressure is atmospheric pressure to 20 kg / cm.2 G, SV: 50-100000h-1It is. If the fluorination catalyst of the present invention is used, the reaction pressure may be raised to atmospheric pressure or higher because the productivity does not decrease even under pressure, and the preferable reaction pressure is 1 to 20 kg / cm.2 G, more preferably 1.5 to 20 kg / cm2 G.
[0045]
【Example】
Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but it is needless to say that the present invention is not limited by such descriptions.
[0046]
In the description, the In / Cr ratio indicates the atomic ratio of each element contained in the catalyst obtained from chemical analysis, and the molar ratio in the reaction examples indicates the molar ratio of HF to halogenated hydrocarbon. SV is a value converted into a standard state, and pressure is a gauge pressure.
[0047]
(Catalyst preparation example 1)
Cr (NO) is placed in a 10-liter container containing 600 ml of pure water.3 )3 ・ 9H2 O 452g and In (NO3 )3 ・ NH2 O (n is about 5) A solution prepared by dissolving 42 g of pure water in 1.2 liters and 0.3 liters of 28% by weight aqueous ammonia were stirred to adjust the pH of the reaction solution within the range of 7.5 to 8.5. The two aqueous solutions were added dropwise over about 1 hour while controlling the flow rates of the two aqueous solutions. The obtained hydroxide slurry was separated by filtration, washed well with pure water, and then dried at 120 ° C. for 12 hours. The obtained solid was pulverized, mixed with graphite, and pelletized by a tableting machine. This pellet is2 It was calcined at 400 ° C. for 4 hours in an air stream to obtain a catalyst precursor. 60 ml of the catalyst precursor was filled in a reaction tube made of Inconel, and N2 350 ° C. in a diluted HF stream followed by N 22 The pressure is increased to 4 kg / cm at 350 ° C. under a 100% HF gas stream which is not diluted, and further under a 100% HF gas stream.2 G was used for fluorination treatment. The composition of the pellet after the treatment is shown below.
In: 10.8% by weight, Cr: 49.0% by weight O: 15.1% by weight, F: 23.9% by weight
From these values, the In / Cr ratio was 0.1.
[0048]
(Comparative catalyst preparation example 1)
In (NO3 )3 ・ NH2 A catalyst precursor containing no In was prepared in the same manner as in Catalyst Preparation Example 1 except that O was not added. 60 ml of this catalyst precursor was filled in a reaction tube made of Inconel, and fluorination treatment was performed in the same manner as in Preparation Example 1 for the catalyst. The composition of the pellet after the treatment is shown below.
Cr: 56.9% by weight, O: 16.3% by weight, F: 23.8% by weight
[0049]
(Catalyst Preparation Example 2)
200 g of the dried product prepared in Comparative Catalyst Preparation Example 13 ・ 4H2 17 g of O was dissolved in pure water for impregnation, and dried at 120 ° C. again. The following operation was performed up to the fluorination treatment in the same manner as in Catalyst Preparation Example 1. The composition of the pellet after the treatment is shown below.
In: 3.7% by weight, Cr: 53.6% by weight, O: 16.0% by weight, F: 23.3% by weight
From these values, the In / Cr ratio was 0.03.
[0050]
(Catalyst Preparation Example 3)
100 ml of the pellets formed by tableting in Catalyst Preparation Example 1 were filled in a glass firing tube, and H containing 3 vol% of steam was added.2 The precursor was fired at 400 ° C. for 4 hours in an air stream to obtain a precursor. The following operation was performed up to the fluorination treatment in the same manner as in Catalyst Preparation Example 1.
[0051]
(Catalyst preparation example 4)
CrCl3 ・ 6H2 O 111g, InCl3 ・ 4H2 6 g of O was dissolved in 78 g of pure water, and 100 g of high-purity activated alumina was immersed to absorb the entire amount of the solution. This was dried at 120 ° C. for 10 hours, filled in a glass firing tube, and heated at 400 ° C. for 3 hours under an air stream, and further containing H at 3 vol%.2 The precursor was fired at 400 ° C. for 4 hours in an air stream to obtain a precursor. The following operation was performed up to the fluorination treatment in the same manner as in Catalyst Preparation Example 1. The composition after the treatment is shown below.
In: 1.1% by weight, Cr: 10.5% by weight, Al: 49.0% by weight, O: 2.5% by weight, F: 60.3% by weight
[0052]
(Catalyst Preparation Example 5)
Cr (NO3 )3 ・ 9H2 O and In (NO3 )3 ・ NH2 Cu (NO3 )2 ・ 3H2 Pellets were prepared according to the procedure of Catalyst Preparation Example 1 except that 1 g of O was further added, and subsequent operations were performed up to fluorination treatment according to Catalyst Preparation Example 3.
[0053]
(Catalyst Preparation Example 6)
Cr (NO3 )3 ・ 9H2 O and In (NO3 )3 ・ NH2 Cd (NO3 )2 ・ 4H2 Pellets were prepared according to the procedure of Catalyst Preparation Example 1 except that 1 g of O was further added, and subsequent operations were performed up to fluorination treatment according to Catalyst Preparation Example 3.
[0054]
(Catalyst Preparation Example 7)
Cr (NO3 )3 ・ 9H2 O and In (NO3 )3 ・ NH2 Pb (NO3 )2 Pellets were prepared according to the procedure of Catalyst Preparation Example 1 except that 1 g was further added, and the subsequent operations were performed up to the fluorination treatment according to Catalyst Preparation Example 3.
[0055]
(Catalyst Preparation Example 8)
Cr (NO3 )3 ・ 9H2 O and In (NO3 )3 ・ NH2 AgNO in aqueous solution of O3 Pellets were prepared according to the procedure of Catalyst Preparation Example 1 except that 1 g was further added and dissolved, and subsequent operations were performed up to fluorination treatment according to Catalyst Preparation Example 3.
[0056]
(Example 1 of fluorination reaction)
50 ml of the catalyst prepared in Catalyst Preparation Example 1 was filled in a reaction tube made of Inconel, and a fluorination reaction of HCFC-133a with HF was performed under the following reaction conditions. The outlet gas of the reaction tube was blown into an alkali trap to remove unreacted HF and generated HCl, and the gas composition was analyzed by gas chromatography. Table 1 shows the results 6 to 8 hours after the start of the reaction.
Temperature: 320 ° C, pressure: atmospheric pressure, molar ratio: 8, SV: 1500h-1
[0057]
(Example 2 of fluorination reaction)
Reaction pressure of 4 kg / cm2 A fluorination reaction of HCFC-133a was carried out in the same manner as in fluorination reaction example 1 except that G was used. Table 1 shows the results.
[0058]
(Comparative fluorination reaction example 1)
A fluorination reaction of HCFC-133a was carried out in the same manner as in fluorination reaction example 1 except that the catalyst prepared in comparative catalyst preparation example 1 was used. Table 1 shows the results.
[0059]
(Comparative fluorination reaction example 2)
Reaction pressure of 4 kg / cm2 A fluorination reaction of HCFC-133a was performed in the same manner as in Comparative Fluorination Reaction Example 1 except that G was used. Table 1 shows the results.
[0060]
(Example 3 of fluorination reaction)
A fluorination reaction of HCFC-133a was performed in the same manner as in fluorination reaction example 1 except that the catalyst prepared in catalyst preparation example 2 was used. Table 1 shows the results.
[0061]
(Example 4 of fluorination reaction)
Reaction pressure of 4 kg / cm2 A fluorination reaction of HCFC-133a was carried out in the same manner as in fluorination reaction example 3 except that G was used. Table 1 shows the results.
[0062]
[Table 1]
[0063]
From the results shown in Table 1, at atmospheric pressure, the HFC-134a yield does not greatly differ with or without the addition of In, but the reaction pressure increases (4 kg / cm).2 It can be seen that the catalyst added with G) and In gives a higher yield. This indicates that the combination of In and Cr can improve the negative pressure effect seen with the Cr-only catalyst.
[0064]
(Fluorination reaction examples 5 to 10)
A fluorination reaction of HCFC-133a was carried out in the same manner as in fluorination reaction example 2 except that the catalysts prepared in catalyst preparation examples 3 to 8 were used. Table 2 shows the results.
[0065]
[Table 2]
[0066]
(Example 11 of fluorination reaction)
30 ml of the catalyst prepared in Catalyst Preparation Example 3 was charged into a reaction tube made of Inconel, and a fluorination reaction of dichloromethane with HF was performed under the following reaction conditions. The outlet gas of the reaction tube was blown into a heated alkali trap to remove unreacted HF and generated HCl, and the gas composition was analyzed by gas chromatography.
Temperature: 190 ° C, pressure: atmospheric pressure, molar ratio: 6, SV: 1500h-1
The unreacted dichloromethane was 39%, and the yields of the main products were as follows.
HFC-32; 52%, HCFC-31; 8%
[0067]
(Example 12 of fluorination reaction)
30 ml of the catalyst prepared in Catalyst Preparation Example 3 was charged into a reaction tube made of Inconel, and a fluorination reaction of HCFC-123 with HF was performed under the following reaction conditions. The outlet gas of the reaction tube was blown into an alkali trap to remove unreacted HF and generated HCl, and the gas composition was analyzed by gas chromatography.
Temperature: 325 ° C, pressure: 4kg / cm2 G, molar ratio: 6, SV: 1000h-1
Unreacted HCFC-123 was 10%, and the yields of main products were as follows.
HFC-125: 60.6%, HCFC-124: 24.5%
[0068]
【The invention's effect】
The present invention comprises indium, chromium, oxygen, and fluorine as essential constituent elements, and has an atomic ratio of indium to chromium of 0.005 to 0.6. Catalyst, and a method for producing HFC with high productivity using the catalyst, and if the fluorination reaction of halogenated hydrocarbons with HF in the gas phase using the catalyst, even under pressure HFC can be obtained in high yield.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP11174994A JP3582798B2 (en) | 1993-06-18 | 1994-04-28 | Fluorination catalyst and fluorination method |
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| JP5-147897 | 1993-06-18 | ||
| JP14789793 | 1993-06-18 | ||
| JP11174994A JP3582798B2 (en) | 1993-06-18 | 1994-04-28 | Fluorination catalyst and fluorination method |
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| JP3582798B2 true JP3582798B2 (en) | 2004-10-27 |
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| JP5013692B2 (en) * | 2004-09-16 | 2012-08-29 | 昭和電工株式会社 | Fluoromethane production method and product |
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