JP2020125272A - Method for producing 1-chloro-2,2-difluoroethylene - Google Patents
Method for producing 1-chloro-2,2-difluoroethylene Download PDFInfo
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- JP2020125272A JP2020125272A JP2019019400A JP2019019400A JP2020125272A JP 2020125272 A JP2020125272 A JP 2020125272A JP 2019019400 A JP2019019400 A JP 2019019400A JP 2019019400 A JP2019019400 A JP 2019019400A JP 2020125272 A JP2020125272 A JP 2020125272A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- chloro
- difluoroethylene
- chloride
- difluoroethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- HTHNTJCVPNKCPZ-UHFFFAOYSA-N 2-chloro-1,1-difluoroethene Chemical group FC(F)=CCl HTHNTJCVPNKCPZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- SKDFWEPBABSFMG-UHFFFAOYSA-N 1,2-dichloro-1,1-difluoroethane Chemical compound FC(F)(Cl)CCl SKDFWEPBABSFMG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011949 solid catalyst Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910001510 metal chloride Inorganic materials 0.000 claims description 4
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 1
- 208000012839 conversion disease Diseases 0.000 abstract description 11
- 239000007789 gas Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000002994 raw material Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- ATEBGNALLCMSGS-UHFFFAOYSA-N 2-chloro-1,1-difluoroethane Chemical compound FC(F)CCl ATEBGNALLCMSGS-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 2
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 2
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 229910021381 transition metal chloride Inorganic materials 0.000 description 2
- 229910021561 transition metal fluoride Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 description 1
- 229910021582 Cobalt(II) fluoride Inorganic materials 0.000 description 1
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910021571 Manganese(III) fluoride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910021587 Nickel(II) fluoride Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 229910001627 beryllium chloride Inorganic materials 0.000 description 1
- JZKFIPKXQBZXMW-UHFFFAOYSA-L beryllium difluoride Chemical compound F[Be]F JZKFIPKXQBZXMW-UHFFFAOYSA-L 0.000 description 1
- 229910001633 beryllium fluoride Inorganic materials 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 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
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 1
- WZJQNLGQTOCWDS-UHFFFAOYSA-K cobalt(iii) fluoride Chemical compound F[Co](F)F WZJQNLGQTOCWDS-UHFFFAOYSA-K 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- SRVINXWCFNHIQZ-UHFFFAOYSA-K manganese(iii) fluoride Chemical compound [F-].[F-].[F-].[Mn+3] SRVINXWCFNHIQZ-UHFFFAOYSA-K 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- LNDHQUDDOUZKQV-UHFFFAOYSA-J molybdenum tetrafluoride Chemical compound F[Mo](F)(F)F LNDHQUDDOUZKQV-UHFFFAOYSA-J 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- XFBLPIPEFDRLTH-UHFFFAOYSA-N oxoruthenium(1+) Chemical compound [Ru+]=O XFBLPIPEFDRLTH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 1
- NFVUDQKTAWONMJ-UHFFFAOYSA-I pentafluorovanadium Chemical compound [F-].[F-].[F-].[F-].[F-].[V+5] NFVUDQKTAWONMJ-UHFFFAOYSA-I 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- 229910001952 rubidium oxide Inorganic materials 0.000 description 1
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- UDBAOKKMUMKEGZ-UHFFFAOYSA-K trichloromanganese Chemical compound [Cl-].[Cl-].[Cl-].[Mn+3] UDBAOKKMUMKEGZ-UHFFFAOYSA-K 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- YRQNNUGOBNRKKW-UHFFFAOYSA-K trifluororuthenium Chemical compound F[Ru](F)F YRQNNUGOBNRKKW-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
【課題】比較的低い温度条件で製造が可能であり、且つ長時間製造を実施した場合においても反応転化率の低下が極めて少ない、より工業的に実施可能な、１，２−ジクロロ−１，１−ジフルオロエタンを原料とし、１−クロロ−２，２−ジフルオロエチレンを製造する方法の提供。【解決手段】１，２−ジクロロ−１，１−ジフルオロエタンを、固体触媒としての活性炭存在下、気相で反応させる１−クロロ−２，２−ジフルオロエチレンの製造方法。【選択図】なしKind Code: A1 A 1,2-dichloro-1, which can be produced under relatively low temperature conditions, exhibits an extremely small reduction in reaction conversion rate even when the production is carried out for a long time, and is more industrially feasible. Provided is a method for producing 1-chloro-2,2-difluoroethylene from 1-difluoroethane. Kind Code: A1 A method for producing 1-chloro-2,2-difluoroethylene by reacting 1,2-dichloro-1,1-difluoroethane in a gas phase in the presence of activated carbon as a solid catalyst. [Selection figure] None
Description
本発明は１，２−ジクロロ−１，１−ジフルオロエタンを原料とし、１−クロロ−２，２−ジフルオロエチレンを製造する方法に関する。１−クロロ−２，２−ジフルオロエチレンは、電子材料や医・農薬の製造中間体として有用な化合物である。 The present invention relates to a method for producing 1-chloro-2,2-difluoroethylene from 1,2-dichloro-1,1-difluoroethane as a raw material. 1-Chloro-2,2-difluoroethylene is a compound useful as an intermediate for the production of electronic materials and medical and agricultural chemicals.
従来より、１，２−ジクロロ−１，１−ジフルオロエタンを原料とし、１−クロロ−２，２−ジフルオロエチレンを製造する方法としては、化学量論量以上の水酸化ナトリウムを用い、液相で１，２−ジクロロ−１，１−ジフルオロエタンを反応させる方法（例えば、特許文献１、特許文献２参照）、ニッケル製反応管を用い、５００〜６００℃で１，２−ジクロロ−１，１−ジフルオロエタンをガスとして流通させる方法（例えば特許文献３参照）、並びに８００〜１，０００℃で熱分解により製造する方法が知られている（例えば特許文献４参照）。 Conventionally, as a method for producing 1-chloro-2,2-difluoroethylene from 1,2-dichloro-1,1-difluoroethane as a raw material, a stoichiometric amount or more of sodium hydroxide is used, and a liquid phase is used. A method of reacting 1,2-dichloro-1,1-difluoroethane (see, for example, Patent Document 1 and Patent Document 2) and a reaction tube made of nickel, and 1,2-dichloro-1,1-at 500 to 600° C. A method of circulating difluoroethane as a gas (see, for example, Patent Document 3) and a method of producing by thermal decomposition at 800 to 1,000° C. are known (see, for example, Patent Document 4).
従来の特許文献１または２に記載の方法では、液相での水酸化ナトリウムとの反応のため、多量の廃液が発生するという課題がある。一方、特許文献３及び４に記載の方法は、６００℃以上の高温での反応が必要という課題がある。 The conventional method described in Patent Document 1 or 2 has a problem that a large amount of waste liquid is generated due to the reaction with sodium hydroxide in the liquid phase. On the other hand, the methods described in Patent Documents 3 and 4 have a problem that a reaction at a high temperature of 600° C. or higher is required.
これに対して特許文献５には固体触媒を用いて２５０〜５５０℃という比較的低い温度条件下、気相で１，２−ジクロロ−１，１−ジフルオロエタンを反応させる方法が提案されているが、この方法も反応を長時間実施した際の、触媒の寿命（反応転化率の低下）については検討がなされておらず、比較的低い温度条件で、且つ長時間製造しても反応が安定している工業的に実施可能な方法が望まれていた。 On the other hand, Patent Document 5 proposes a method of reacting 1,2-dichloro-1,1-difluoroethane in a gas phase under a relatively low temperature condition of 250 to 550° C. using a solid catalyst. In this method, the life of the catalyst (reduction of reaction conversion rate) when the reaction is carried out for a long time has not been examined, and the reaction is stable even under a relatively low temperature condition and for a long time. An industrially viable method was desired.
本発明の目的は、これら従来技術を鑑み、１，２−ジクロロ−１，１−ジフルオロエタンを原料とし、１−クロロ−２，２−ジフルオロエチレンを製造する方法について、比較的低い温度条件で製造が可能であり、且つ長時間製造を実施した場合においても反応転化率の低下が極めて少ない、より工業的に実施可能な方法を提供することにある。 In view of these conventional techniques, an object of the present invention is to produce 1-chloro-2,2-difluoroethylene from 1,2-dichloro-1,1-difluoroethane as a raw material under relatively low temperature conditions. It is an object of the present invention to provide a more industrially feasible method that is capable of achieving the above-mentioned effects and that the reaction conversion rate is extremely low even when the production is carried out for a long time.
そこで本発明者らは、１，２−ジクロロ−１，１−ジフルオロエタンを、固体触媒存在下、気相で反応させる１−クロロ−２，２−ジフルオロエチレンの製造方法について鋭意検討した結果、固体触媒としての活性炭を用いて反応させることにより、比較的低い温度で、１−クロロ−２，２−ジフルオロエチレンの製造が可能であり、且つ長時間製造を実施した場合においても反応転化率の低下が極めて少ない、より工業的に実施可能な１−クロロ−２，２−ジフルオロエチレンの製造方法を見出し、本発明を完成させるに至った。即ち、本発明は下記の要旨に係わるものである。 Therefore, the inventors of the present invention have diligently studied a method for producing 1-chloro-2,2-difluoroethylene by reacting 1,2-dichloro-1,1-difluoroethane in a gas phase in the presence of a solid catalyst, and as a result, a solid By reacting using activated carbon as a catalyst, 1-chloro-2,2-difluoroethylene can be produced at a relatively low temperature, and the reaction conversion rate decreases even when the production is carried out for a long time. The present invention has been accomplished by finding a more industrially feasible method for producing 1-chloro-2,2-difluoroethylene, which is extremely small. That is, the present invention relates to the following points.
（１）１，２−ジクロロ−１，１−ジフルオロエタンを、固体触媒としての活性炭存在下、気相で反応させる、１−クロロ−２，２−ジフルオロエチレンの製造方法。 (1) A method for producing 1-chloro-2,2-difluoroethylene, which comprises reacting 1,2-dichloro-1,1-difluoroethane in the gas phase in the presence of activated carbon as a solid catalyst.
（２）１，２−ジクロロ−１，１−ジフルオロエタンを、金属の酸化物、塩化物又はフッ化物を活性炭に担持してなる固体触媒の存在下、気相で反応させる、１−クロロ−２，２−ジフルオロエチレンの製造方法。 (2) 1,2-Dichloro-1,1-difluoroethane is reacted in a gas phase in the presence of a solid catalyst in which a metal oxide, chloride or fluoride is supported on activated carbon, 1-chloro-2 , 2-Difluoroethylene production method.
（３）前記金属が、アルカリ金属、アルカリ土類金属及び遷移金属からなる群から選ばれる１種以上の金属である、上記（２）に記載の１−クロロ−２，２−ジフルオロエチレンの製造方法。 (3) Production of 1-chloro-2,2-difluoroethylene according to (2) above, wherein the metal is at least one metal selected from the group consisting of alkali metals, alkaline earth metals and transition metals. Method.
（４）反応温度が、２５０〜５５０℃であることを特徴とする上記（１）〜（３）のいずれか１項に記載の１−クロロ−２，２−ジフルオロエチレンの製造方法。 (4) The method for producing 1-chloro-2,2-difluoroethylene according to any one of (1) to (3) above, wherein the reaction temperature is 250 to 550°C.
本発明の方法により、比較的低い温度条件にて反応が可能で、且つ長時間製造を継続実施した場合においても反応転化率及び選択率の低下が極めて少ない、１−クロロ−２，２−ジフルオロエチレンのより工業的に実施可能な製造方法を提供できる。 By the method of the present invention, 1-chloro-2,2-difluoro, which is capable of reacting under relatively low temperature conditions and has very little reduction in reaction conversion rate and selectivity even when production is continuously carried out for a long time. It is possible to provide a more industrially viable manufacturing method of ethylene.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明に用いられる原料の１，２−ジクロロ−１，１−ジフルオロエタンは、１，１，２−トリクロロエチレンとフッ化水素の反応により容易に調製される。 The raw material 1,2-dichloro-1,1-difluoroethane used in the present invention is easily prepared by the reaction of 1,1,2-trichloroethylene and hydrogen fluoride.
本発明に適用可能な活性炭の種類としては、木炭、石炭、ヤシ殻等から調製された活性炭等が挙げられる。 Examples of the activated carbon applicable to the present invention include activated carbon prepared from charcoal, coal, coconut shell and the like.
活性炭の比表面積は、１０〜３０００ｍ２／ｇであることが好ましく、２０〜２５００ｍ２／ｇがより好ましく、５０〜２０００ｍ２／ｇがさらに好ましい。活性炭の比表面積が１０ｍ２／ｇより小さいと十分な反応転化率及び選択率が得られない場合がある。逆に３０００ｍ２／ｇを超えた場合でも比表面積に応じた十分な反応転化率及び選択率の増大は得られにくく、また副反応が起こりやすくなるおそれがある。活性炭の比表面積は、ＢＥＴ法に準拠した方法で測定される。 The specific surface area of the activated carbon is preferably 10~3000m 2 / g, more preferably 20~2500m 2 / g, more preferably 50~2000m 2 / g. If the specific surface area of activated carbon is less than 10 m 2 /g, sufficient reaction conversion and selectivity may not be obtained. On the other hand, even when it exceeds 3000 m 2 /g, it is difficult to obtain a sufficient increase in the reaction conversion rate and the selectivity depending on the specific surface area, and side reactions may easily occur. The specific surface area of activated carbon is measured by a method based on the BET method.
本発明の１−クロロ−２，２−ジフルオロエチレンの製造方法において、固体触媒として活性炭に担持する金属化合物としては、アルカリ金属、アルカリ土類金属及び遷移金属からなる群から選ばれる１種以上の金属の酸化物、塩化物又はフッ化物が好ましく用いられる。 In the method for producing 1-chloro-2,2-difluoroethylene of the present invention, the metal compound supported on the activated carbon as a solid catalyst is at least one selected from the group consisting of alkali metals, alkaline earth metals and transition metals. Metal oxides, chlorides or fluorides are preferably used.
さらに本発明に適用可能な固体触媒としてのアルカリ金属酸化物としては、具体的には例えば、酸化リチウム、酸化ナトリウム、酸化カリウム、酸化ルビジウム、酸化セシウム等が挙げられる。 Specific examples of the alkali metal oxide as a solid catalyst applicable to the present invention include lithium oxide, sodium oxide, potassium oxide, rubidium oxide, and cesium oxide.
本発明に適用可能な固体触媒としてのアルカリ金属塩化物としては、具体的には例えば、塩化リチウム、塩化ナトリウム、塩化カリウム、塩化ルビジウム、塩化セシウム等が挙げられる。 Specific examples of the alkali metal chloride as the solid catalyst applicable to the present invention include lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride and the like.
本発明に適用可能な固体触媒としてのアルカリ金属フッ化物としては、具体的には例えば、フッ化リチウム、フッ化ナトリウム、フッ化ルビジウム、フッ化セシウム等が挙げられる。 Specific examples of the alkali metal fluoride as a solid catalyst applicable to the present invention include lithium fluoride, sodium fluoride, rubidium fluoride, cesium fluoride and the like.
本発明に適用可能な固体触媒としてのアルカリ土類金属酸化物としては、具体的には例えば、酸化ベリリウム、酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム等が挙げられる。 Specific examples of the alkaline earth metal oxide as the solid catalyst applicable to the present invention include beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide and the like.
本発明に適用可能な固体触媒としてのアルカリ土類金属塩化物としては、塩化ベリリウム、塩化マグネシウム、塩化カルシウム、塩化ストロンチウム、塩化バリウム等が挙げられる。 Examples of the alkaline earth metal chloride as a solid catalyst applicable to the present invention include beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride and the like.
本発明に適用可能な固体触媒としてのアルカリ土類金属フッ化物としては、フッ化ベリリウム、フッ化マグネシウム、フッ化カルシウム、フッ化ストロンチウム、フッ化バリウム等が挙げられる。 Examples of the alkaline earth metal fluoride as a solid catalyst applicable to the present invention include beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride and the like.
本発明に適用可能な固体触媒としての遷移金属酸化物としては、具体的には例えば、酸化チタニウム（ＩＶ）、酸化バナジウム（Ｖ）、酸化クロム（ＩＩＩ）、酸化マンガン（ＩＩＩ）、酸化鉄（ＩＩ）、酸化鉄（ＩＩＩ）、酸化コバルト（ＩＩ）、酸化コバルト（ＩＩＩ）、酸化ニッケル（ＩＩ）、酸化銅（ＩＩ）、酸化亜鉛（ＩＩ）、酸化ジルコニウム（ＩＶ）、酸化ニオブ（Ｖ）、酸化モリブデン（ＶＩ）、酸化ルテニウム（ＩＩＩ）等が挙げられる。 Specific examples of the transition metal oxide as the solid catalyst applicable to the present invention include titanium (IV) oxide, vanadium (V) oxide, chromium (III) oxide, manganese (III) oxide, and iron oxide ( II), iron oxide (III), cobalt oxide (II), cobalt oxide (III), nickel oxide (II), copper oxide (II), zinc oxide (II), zirconium oxide (IV), niobium oxide (V) , Molybdenum oxide (VI), ruthenium (III) oxide, and the like.
本発明に適用可能な固体触媒としての遷移金属塩化物としては、具体的には例えば、塩化チタニウム（ＩＶ）、塩化バナジウム（Ｖ）、塩化クロム（ＩＩＩ）、塩化マンガン（ＩＩＩ）、塩化鉄（ＩＩ）、塩化鉄（ＩＩＩ）、塩化コバルト（ＩＩ）、塩化コバルト（ＩＩＩ）、塩化ニッケル（ＩＩ）、塩化銅（ＩＩ）、塩化亜鉛（ＩＩ）、塩化ジルコニウム（ＩＶ）、塩化ニオブ（Ｖ）、塩化モリブデン（ＶＩ）、塩化ルテニウム（ＩＩＩ）等が挙げられる。 Specific examples of the transition metal chloride as a solid catalyst applicable to the present invention include titanium (IV) chloride, vanadium chloride (V), chromium (III) chloride, manganese (III) chloride, iron chloride ( II), iron chloride (III), cobalt chloride (II), cobalt chloride (III), nickel chloride (II), copper chloride (II), zinc chloride (II), zirconium chloride (IV), niobium chloride (V) , Molybdenum chloride (VI), ruthenium (III) chloride and the like.
本発明に適用可能な固体触媒としての遷移金属フッ化物としては、具体的には例えば、フッ化チタニウム（ＩＶ）、フッ化バナジウム（Ｖ）、フッ化クロム（ＩＩＩ）、フッ化マンガン（ＩＩＩ）、フッ化鉄（ＩＩ）、フッ化鉄（ＩＩＩ）、フッ化コバルト（ＩＩ）、フッ化コバルト（ＩＩＩ）、フッ化ニッケル（ＩＩ）、フッ化銅（ＩＩ）、フッ化亜鉛（ＩＩ）、フッ化ジルコニウム（ＩＶ）、フッ化ニオブ（Ｖ）、フッ化モリブデン（ＶＩ）、フッ化ルテニウム（ＩＩＩ）等が挙げられる。 Specific examples of the transition metal fluoride as a solid catalyst applicable to the present invention include titanium (IV) fluoride, vanadium fluoride (V), chromium (III) fluoride, and manganese (III) fluoride. , Iron (II) fluoride, iron (III) fluoride, cobalt (II) fluoride, cobalt (III) fluoride, nickel (II) fluoride, copper (II) fluoride, zinc (II) fluoride, Examples thereof include zirconium fluoride (IV), niobium fluoride (V), molybdenum fluoride (VI), ruthenium (III) fluoride and the like.
活性炭に対して前記したアルカリ金属酸化物、アルカリ土類金属酸化物、遷移金属酸化物、アルカリ金属塩化物、アルカリ土類金属塩化物、遷移金属塩化物、アルカリ金属フッ化物、アルカリ土類金属フッ化物、遷移金属フッ化物を物理的混合または化学的処理により担持させる。 Alkali metal oxides, alkaline earth metal oxides, transition metal oxides, alkali metal chlorides, alkaline earth metal chlorides, transition metal chlorides, alkali metal fluorides, alkaline earth metal fluorides described above for activated carbon. And a transition metal fluoride are supported by physical mixing or chemical treatment.
金属の酸化物、塩化物又はフッ化物の活性炭への担持方法は、本発明の属する技術分野における当業者の間で公知の方法を用いることができるが、本発明を制限するものではない。 As a method for supporting a metal oxide, chloride or fluoride on activated carbon, a method known to those skilled in the art to which the present invention belongs can be used, but the present invention is not limited thereto.
触媒の担持量としては、担体に対して、０．０１重量比〜５０重量比が好ましく、０．１重量比〜３０重量比がより好ましく、０．５重量比〜２０重量比がさらに好ましい。触媒担持量が０．０１重量比より少ないと十分な反応効率が得られない場合があり、逆に５０重量比を超えて担持しても、反応効率の増大は得られにくく、また副反応が起こりやすくなるおそれがある。 The supported amount of the catalyst is preferably 0.01 to 50 weight ratio, more preferably 0.1 to 30 weight ratio, and further preferably 0.5 to 20 weight ratio, with respect to the carrier. If the amount of the catalyst supported is less than 0.01 weight ratio, sufficient reaction efficiency may not be obtained, and conversely, even if the catalyst is supported in an amount of more than 50 weight ratio, it is difficult to increase the reaction efficiency and the side reaction may occur. May occur easily.
本発明に用いる固体触媒は、反応装置の大きさにもよるが、通常、粉末または１ｍｍ〜３０ｍｍの成形体として用い、担体に担持した触媒を用いる場合は、粉末または１ｍｍ〜３０ｍｍの成形された担体に担持し用いても良いし、粉末の担体に触媒を担持の後、成形したものを用いても良い。 Although the solid catalyst used in the present invention depends on the size of the reaction apparatus, it is usually used as a powder or a molded body of 1 mm to 30 mm, and when a catalyst supported on a carrier is used, it is powdered or molded of 1 mm to 30 mm. The carrier may be supported and used, or the powder carrier may be used after being molded after supporting the catalyst.
本発明の反応方法は、通常、石英、パイレックス（登録商標）ガラス、鉄、ニッケル製の反応管を用い、反応管内に固体触媒を充填し、所定の温度に加熱の後、窒素、ヘリウム、またはアルゴンで希釈した１，２−ジクロロ−１，１−ジフルオロエタンをガス状態で供給し、反応を行う。 The reaction method of the present invention is usually a reaction tube made of quartz, Pyrex (registered trademark) glass, iron, nickel, filled with a solid catalyst in the reaction tube, heated to a predetermined temperature, then nitrogen, helium, or 1,2-Dichloro-1,1-difluoroethane diluted with argon is supplied in a gas state to carry out the reaction.
本発明に適用可能な希釈された１，２−ジクロロ−１，１−ジフルオロエタンの濃度としては、５．０容量％〜５０．０容量％の濃度範囲である。 The concentration of diluted 1,2-dichloro-1,1-difluoroethane applicable to the present invention is in the concentration range of 5.0% by volume to 50.0% by volume.
本発明の反応温度としては、固体触媒の種類にもよるが、２５０℃〜５５０℃が好ましく、３００℃〜５００℃がより好ましく、３２０℃〜４５０℃がさらに好ましい。反応温度が２５０℃より低い場合、十分な反応転化率が得られない場合がある。 The reaction temperature of the present invention depends on the type of solid catalyst, but is preferably 250°C to 550°C, more preferably 300°C to 500°C, and further preferably 320°C to 450°C. When the reaction temperature is lower than 250°C, a sufficient reaction conversion rate may not be obtained.
本発明の反応時間（触媒との接触時間）は、原料の転化率と選択率を制御するために、反応温度が高ければ反応時間を短く、反応温度が低ければ反応時間を長くすることができるが、０．０５秒〜２０秒が好ましく、０．１秒〜１０秒がより好ましく、０．３秒〜５秒がさらに好ましい。反応時間が０．０５秒より短いと十分な反応転化率及び選択率が得られない場合があり、逆に２０秒を超えても、反応転化率及び選択率の増大は得られにくく、また副反応が起こりやすくなるおそれがある。 Regarding the reaction time (contact time with the catalyst) of the present invention, the reaction time can be shortened if the reaction temperature is high, and the reaction time can be lengthened if the reaction temperature is low, in order to control the conversion and selectivity of the raw materials. However, 0.05 second to 20 seconds is preferable, 0.1 second to 10 seconds is more preferable, and 0.3 second to 5 seconds is further preferable. If the reaction time is shorter than 0.05 seconds, sufficient reaction conversion rate and selectivity may not be obtained, and conversely, if it exceeds 20 seconds, it is difficult to obtain an increase in reaction conversion rate and selectivity. Reaction may occur easily.
本発明の反応後の後処理としては、特に制約はないが、一般的には、生成物を冷却し液化の後、常圧または加圧条件下で蒸留精製することにより、精製１−クロロ−２，２−ジフルオロエチレンを得る。 The post-treatment after the reaction of the present invention is not particularly limited, but in general, the product is cooled, liquefied, and then purified by distillation under normal pressure or pressure conditions to give purified 1-chloro- 2,2-difluoroethylene is obtained.
以下実施例により本発明を具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
実施例１ 活性炭を用い、原料中酸素０．０容量％条件下での１−クロロ−２，２−ジフルオロエチレンの製造
内径６．０ｍｍ石英製反応管に、活性炭を充填（充填長さ８．０ｍｍ）し、窒素を３０ｍＬ／ｍｉｎ流通下、２００℃で１時間乾燥の後、触媒層の温度を３５０℃とし、窒素で１，２−ジクロロ−１，１−ジフルオロエタン濃度１３．７容量％に希釈したガスを反応管に１３．９ｍＬ／ｍｉｎの速度で供給し、反応を行った。
Example 1 Production of 1-chloro-2,2-difluoroethylene using activated carbon under the condition of 0.0% by volume of oxygen in the raw material A reaction tube made of quartz with an inner diameter of 6.0 mm was filled with activated carbon (filling length 8. 0 mm), and after drying at 200° C. for 1 hour under a nitrogen flow of 30 mL/min, the temperature of the catalyst layer is set to 350° C. and nitrogen is used to bring the 1,2-dichloro-1,1-difluoroethane concentration to 13.7 vol %. The diluted gas was supplied to the reaction tube at a rate of 13.9 mL/min to carry out the reaction.
反応実施直後に反応管から流出するガスをガスクロマトグラフィーで分析した結果、１，２−ジクロロ−１，１−ジフルオロエタンの転化率は２７％で、目的物の１−クロロ−２，２−ジフルオロエチレンの選択率は９６％であった。 The gas flowing out from the reaction tube immediately after the reaction was analyzed by gas chromatography. As a result, the conversion rate of 1,2-dichloro-1,1-difluoroethane was 27%, and the target product, 1-chloro-2,2-difluoroethane. The selectivity of ethylene was 96%.
さらに反応を継続実施６０分後に反応管から流出するガスをガスクロマトグラフィーで分析した結果、１，２−ジクロロ−１，１−ジフルオロエタンの転化率は２７％で、目的物の１−クロロ−２，２−ジフルオロエチレンの選択率は９６％であった。 Furthermore, as a result of gas chromatography analysis of the gas flowing out from the reaction tube 60 minutes after the reaction was continuously carried out, the conversion rate of 1,2-dichloro-1,1-difluoroethane was 27%, and the target 1-chloro-2 The selectivity of 2,2-difluoroethylene was 96%.
比較例１ １．３重量％塩化セシウム／１．０重量％酸化ルテニウム担持シリカゲルを用い、原料中酸素０．０容量％条件下での１−クロロ−２，２−ジフルオロエチレンの製造
固体触媒を１．３重量％塩化セシウム／１．０重量％酸化ルテニウム担持シリカゲルとした以外は、実施例１と同様の方法にて反応を行った。
Comparative Example 1 1.3 wt% cesium chloride/1.0 wt% ruthenium oxide-supported silica gel was used to produce 1-chloro-2,2-difluoroethylene under the condition of 0.0 vol% oxygen in the raw material. The reaction was performed in the same manner as in Example 1 except that the silica gel supported was 1.3 wt% cesium chloride/1.0 wt% ruthenium oxide.
反応実施直後に反応管から流出するガスをガスクロマトグラフィーで分析した結果、１，２−ジクロロ−１，１−ジフルオロエタンの転化率は１０％で、目的物の１−クロロ−２，２−ジフルオロエチレンの選択率は１００％であった。 The gas flowing out from the reaction tube immediately after the reaction was analyzed by gas chromatography. As a result, the conversion rate of 1,2-dichloro-1,1-difluoroethane was 10%, and the target product 1-chloro-2,2-difluoroethane was obtained. The selectivity of ethylene was 100%.
さらに反応を継続実施６０分後に反応管から流出するガスをガスクロマトグラフィーで分析した結果、１，２−ジクロロ−１，１−ジフルオロエタンの転化率は１．０％であった（目的物の１−クロロ−２，２−ジフルオロエチレンの選択率は測定困難）。
比較例２ ５．０重量％塩化セシウム担持シリカゲルを用い、原料中酸素０．０容量％条件下での１−クロロ−２，２−ジフルオロエチレンの製造
固体触媒を５．０重量％塩化セシウム担持シリカゲルとし、触媒層の温度を５００℃とした以外は、実施例１と同様の方法にて反応を行った。
Furthermore, as a result of gas chromatography analysis of the gas flowing out from the reaction tube 60 minutes after the reaction was continued, the conversion of 1,2-dichloro-1,1-difluoroethane was 1.0% ( -Selectivity of chloro-2,2-difluoroethylene is difficult to measure).
Comparative Example 2 Using 1 wt% cesium chloride-supported silica gel, production of 1-chloro-2,2-difluoroethylene under conditions of 0.0 vol% oxygen in the raw material Solid catalyst loaded with 5.0 wt% cesium chloride The reaction was performed in the same manner as in Example 1 except that silica gel was used and the temperature of the catalyst layer was 500°C.
反応実施直後に反応管から流出するガスをガスクロマトグラフィーで分析した結果、１，２−ジクロロ−１，１−ジフルオロエタンの転化率は２８％で、目的物の１−クロロ−２，２−ジフルオロエチレンの選択率は８３．８％であった。 The gas flowing out from the reaction tube immediately after the reaction was analyzed by gas chromatography, and as a result, the conversion rate of 1,2-dichloro-1,1-difluoroethane was 28%, and 1-chloro-2,2-difluoro of the target product was obtained. The selectivity of ethylene was 83.8%.
さらに反応を継続実施６０分後に反応管から流出するガスをガスクロマトグラフィーで分析した結果、１，２−ジクロロ−１，１−ジフルオロエタンの転化率は１６．６％で、目的物の１−クロロ−２，２−ジフルオロエチレンの選択率は８５％であった。 Furthermore, as a result of gas chromatography analysis of the gas flowing out from the reaction tube 60 minutes after the reaction was continuously carried out, the conversion rate of 1,2-dichloro-1,1-difluoroethane was 16.6%, and 1-chloro of the desired product was obtained. The selectivity for -2,2-difluoroethylene was 85%.
比較例３ １．０重量％塩化セシウム担持シリカゲルを用い、原料中酸素１７．３容量％条件下での１−クロロ−２，２−ジフルオロエチレンの製造 Comparative Example 3 Production of 1-chloro-2,2-difluoroethylene under the condition of oxygen of 17.3% by volume in raw material, using 1.0 wt% cesium chloride-supported silica gel.
固体触媒を１．０重量％塩化セシウム担持シリカゲルとし、原料中酸素１７．３容量％条件下で反応させた以外は、実施例１と同様の方法にて反応を行った。 The reaction was carried out in the same manner as in Example 1 except that the solid catalyst was 1.0 wt% cesium chloride-supported silica gel and the reaction was carried out under the conditions of 17.3 vol% oxygen in the raw material.
反応実施直後に反応管から流出するガスをガスクロマトグラフィーで分析した結果、１，２−ジクロロ−１，１−ジフルオロエタンの転化率は２．０％で、目的物の１−クロロ−２，２−ジフルオロエチレンの選択率は４０．０％であった。 The gas flowing out from the reaction tube immediately after the reaction was analyzed by gas chromatography. As a result, the conversion rate of 1,2-dichloro-1,1-difluoroethane was 2.0%, and 1-chloro-2,2 of the target product was obtained. The selectivity for difluoroethylene was 40.0%.
さらに反応を継続実施６０分後に反応管から流出するガスをガスクロマトグラフィーで分析した結果、１，２−ジクロロ−１，１−ジフルオロエタンの転化率は２．０％で、目的物の１−クロロ−２，２−ジフルオロエチレンの選択率は５６．０％であった。 Furthermore, as a result of gas chromatography analysis of the gas flowing out from the reaction tube 60 minutes after the reaction was continuously carried out, the conversion rate of 1,2-dichloro-1,1-difluoroethane was 2.0%, and 1-chloro of the target product was obtained. The selectivity for -2,2-difluoroethylene was 56.0%.
実施例２、３ 金属化合物を担持させた活性炭を用い、原料中酸素０．０容量％条件下での１−クロロ−２，２−ジフルオロエチレンの製造 Examples 2 and 3 Production of 1-chloro-2,2-difluoroethylene under the condition of 0.0% by volume of oxygen in the raw material, using activated carbon carrying a metal compound.
反応装置に充填する固体触媒を、表１に示す金属化合物を担持させた活性炭に替えた以外は実施例１と同様の方法で反応を行った。結果を表１に示す。 The reaction was carried out in the same manner as in Example 1 except that the solid catalyst charged in the reactor was replaced with activated carbon carrying the metal compound shown in Table 1. The results are shown in Table 1.
表１に示す実施例１および比較例１，２，３から、活性炭は反応を進行させ、さらに反応継続６０分後においても反応を進行させる作用が維持されていることが認められる。 From Example 1 and Comparative Examples 1, 2, and 3 shown in Table 1, it is recognized that the activated carbon maintains the action of causing the reaction to proceed, and further after 60 minutes of continuing the reaction.
表１に示す実施例２，３および比較例１，２，３から、塩化セシウム、塩化カリウム等の金属化合物を活性炭へ担持させることで、反応開始時の転化率、選択率に優れており、さらに反応継続６０分後においても反応を進行させる作用が維持されていることが認められる。 From Examples 2 and 3 and Comparative Examples 1, 2, and 3 shown in Table 1, by loading a metal compound such as cesium chloride and potassium chloride on activated carbon, the conversion rate at the start of the reaction and the selectivity are excellent, Furthermore, it is recognized that the action of promoting the reaction is maintained even after 60 minutes of continuing the reaction.
本発明により、比較的低い温度条件において反応が進行し、且つ、長時間反応を継続実施した場合においても反応転化率及び選択率の低下が極めて少ない１−クロロ−２，２−ジフルオロエチレンの工業的な製造が可能となった。本発明の方法で得られる１−クロロ−２，２−ジフルオロエチレンは各種、医農薬、電子材料の合成原料として利用可能である。 INDUSTRIAL APPLICABILITY According to the present invention, 1-chloro-2,2-difluoroethylene industry in which the reaction proceeds under relatively low temperature conditions and the reaction conversion rate and the selectivity are not significantly reduced even when the reaction is continued for a long time Manufacturing became possible. The 1-chloro-2,2-difluoroethylene obtained by the method of the present invention can be used as a raw material for synthesizing various kinds of pharmaceuticals, agricultural chemicals and electronic materials.
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