JP5081225B2 - ハイドロフルオロオレフィンの併産 - Google Patents
ハイドロフルオロオレフィンの併産 Download PDFInfo
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- JP5081225B2 JP5081225B2 JP2009503070A JP2009503070A JP5081225B2 JP 5081225 B2 JP5081225 B2 JP 5081225B2 JP 2009503070 A JP2009503070 A JP 2009503070A JP 2009503070 A JP2009503070 A JP 2009503070A JP 5081225 B2 JP5081225 B2 JP 5081225B2
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- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 32
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- FYIRUPZTYPILDH-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoropropane Chemical compound FC(F)C(F)C(F)(F)F FYIRUPZTYPILDH-UHFFFAOYSA-N 0.000 claims description 13
- ZDCWZRQSHBQRGN-UHFFFAOYSA-N 1,1,1,2,3-pentafluoropropane Chemical compound FCC(F)C(F)(F)F ZDCWZRQSHBQRGN-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 8
- DMUPYMORYHFFCT-UPHRSURJSA-N (z)-1,2,3,3,3-pentafluoroprop-1-ene Chemical compound F\C=C(/F)C(F)(F)F DMUPYMORYHFFCT-UPHRSURJSA-N 0.000 claims description 6
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 25
- 238000005796 dehydrofluorination reaction Methods 0.000 description 23
- 229910052799 carbon Inorganic materials 0.000 description 22
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- 239000011737 fluorine Substances 0.000 description 13
- 229910052731 fluorine Inorganic materials 0.000 description 13
- 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 12
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 12
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 12
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910000856 hastalloy Inorganic materials 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229910000990 Ni alloy Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 4
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 229910001512 metal fluoride Inorganic materials 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229910052701 rubidium Inorganic materials 0.000 description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- SUAMPXQALWYDBK-UHFFFAOYSA-N 1,1,1,2,2,3-hexafluoropropane Chemical compound FCC(F)(F)C(F)(F)F SUAMPXQALWYDBK-UHFFFAOYSA-N 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012025 fluorinating agent Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 229910017768 LaF 3 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- VFZCPZOOBHMUBZ-UHFFFAOYSA-N [Mg].FOF Chemical compound [Mg].FOF VFZCPZOOBHMUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- -1 bone Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000001354 calcination Methods 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
- 239000006229 carbon black Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 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
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
1.1,2,3,3,3−ペンタフルオロプロペンと2,3,3,3−テトラフルオロプロペンを併産する方法であって:
触媒を有する反応ゾーンで1,1,1,2,3,3−ヘキサフルオロプロパンと1,1,1,2,3−ペンタフルオロプロパンとのブレンドを脱フッ化水素させ、それによって、上記1,2,3,3,3−ペンタフルオロプロペンと2,3,3,3−テトラフルオロプロペン、未反応のハイドロフルオロカーボン、およびフッ化水素を含む生成混合物を形成させること、およびフッ化水素と上記未反応のハイドロフルオロカーボンから上記1,2,3,3,3−ペンタフルオロプロペンと2,3,3,3−テトラフルオロプロペンとのブレンドを分離して、1,2,3,3,3−ペンタフルオロプロペンと2,3,3,3−テトラフルオロプロペンを生成させること
を含む、上記方法。
2.未反応のハイドロフルオロカーボンを反応ゾーンに戻して再循環させることを更に含む、上記1に記載の方法。
3.方法が、約200℃から約500℃の温度で実施される、上記1に記載の方法。
4.触媒が、フッ化アルミニウム、フッ化物化アルミナ、およびフッ化物化アルミナ上金属からなる群から選択される、上記1に記載の方法。
5.触媒がフッ化アルミニウムである、上記4に記載の方法。
6.方法が、不活性ガスの存在下で実施される、上記1に記載の方法。
7.不活性ガスが窒素である、上記6に記載の方法。
8.反応ゾーンに供給される1,1,1,2,3,3−ヘキサフルオロプロパンと1,1,1,2,3−ペンタフルオロプロパンとのモル比が約10:1〜約80:1である、上記1に記載の方法。
9.反応ゾーンに供給される1,1,1,2,3,3−ヘキサフルオロプロパンと1,1,1,2,3−ペンタフルオロプロパンとのモル比が約35:1〜約80:1である、上記8に記載の方法。
10.ハイドロフルオロオレフィンを、フッ化水素とハイドロフルオロカーボンから蒸留により分離する、上記1に記載の方法。
以下の実施例は本発明を説明するものであり、限定するものではない。
炭質触媒でのCF3CHFCHF2とCF3CHFCH2Fの、CF3CF=CHF(EおよびZ異性体)とCF3CF=CH2への脱フッ化水素
CF3CHFCHF2、CF3CHFCH2F(モル比30:1)と窒素との混合物を以下のように反応器に流通させる。ハステロイ(Hastelloy)(商標)ニッケル合金反応器(外径2.54cm×内径2.17cm×長さ24.1cm)に、実質的に米国特許第4,978,649号明細書(参照により本明細書に援用される)に記載されているように調製された球状(8メッシュ)の三次元マトリックス多孔質炭質材料14.32g(25mL)を装填する。反応器の充填された部分を反応器の外側に固定された5インチ×1インチのセラミックバンドヒータで加熱する。反応器壁とヒータとの間に位置決めされた熱電対は反応器の温度を測定する。反応器に炭質材料を装填した後、窒素(10ml/分、1.7×10−7m3/秒)を反応器に流通させ、1時間、200℃まで温度を上昇させ、更に4時間この温度に維持する。350℃の温度で、窒素10sccm(1.7×10−7m3/秒)およびCF3CHFCHF2/CF3CHFCH2Fのブレンド15sccm(2.5×10−7m3/秒)を混合し、反応器に流通させる。次いで、温度を400℃まで上昇させ、流量を一定に保つ。両方の温度での流出液をサンプリングし、19F NMRで分析する。全反応器流出液の一部をオンラインでサンプリングし、質量選択検出器を装備したガスクロマトグラフィー(GC−MS)を使用して有機生成物を分析する;結果を表1に要約する。有機生成物およびHFなどの無機酸も含有する反応器流出液を中和のため苛性アルカリ水溶液で処理する。
フッ化物化アルミナを用いたCF3CF=CH2とCF3CF=CHFの合成
15インチ(38.1cm)×3/8インチ(0.95cm)のハステロイ(Hastelloy)管に、12〜20メッシュ(0.84〜1.68mm)に粉砕されたγ−アルミナ7.96グラム(13cc)を装填する。200℃で15分間、窒素パージ(50sccm、8.3×10−7m3/秒))下で加熱することにより触媒を活性化させる。温度を325℃に10分間、400℃に20分間上昇させた後、300℃に60分間下降させる。窒素流量を35sccm(5.8×10−7m3/秒)に減少させ、無水HF蒸気を12sccm(2.0×10−7m3/秒)で35分間供給する。次いで、温度を325℃に60分間、350℃に60分間、375℃に90分間、400℃に30分間、425℃に40分間上昇させる。次いで、窒素流量を25sccm(4.2×10−7m3/秒)に減少させ、HFを20sccm(3.3×10−7m3/秒)に20分間増加させる。次いで、窒素流量を15sccm(2.5×10−7m3/秒)に減少させ、HF流量を28sccm(4.7×10−7m3/秒)に20分間増加させる。次いで、窒素流量を5sccm(8.3×10−8m3/秒)に減少させ、HFを36sccm(6.0×10−7m3/秒)に20分間増加させる。次いで、窒素流を停止し、HF流量を40sccm(6.7×10−7m3/秒)に121分間増加させる。
フッ化物化アルミナを用いたCF3CF=CH2とCF3CF=CHFの合成
15インチ(38.1cm)×3/8インチ(0.95cm)のハステロイ(Hastelloy)管に、12〜20メッシュ(0.84〜1.68mm)に粉砕されたγ−アルミナ7.87グラム(13cc)を装填した。200℃で15分間、窒素パージ(50sccm、8.3×10−7m3/秒))下で加熱することにより触媒を活性化させた。温度を325℃に10分間、400℃に20分間上昇させた後、300℃に60分間下降させた。窒素流量を35sccm(5.8×10−7m3/秒)に減少させ、無水HF蒸気を12sccm(2.0×10−7m3/秒)で35分間供給した。次いで、温度を325℃に60分間、350℃に60分間、375℃に90分間、400℃に30分間、425℃に40分間上昇させた。次いで、窒素流量を25sccm(4.2×10−7m3/秒)に減少させ、HFを20sccm(3.3×10−7m3/秒)に20分間増加させた。次いで、窒素流量を15sccm(2.5×10−7m3/秒)に減少させ、HF流量を28sccm(4.7×10−7m3/秒)に20分間増加させた。次いで、窒素流量を5sccm(8.3×10−8m3/秒)に減少させ、HFを36sccm(6.0×10−7m3/秒)に20分間増加させた。次いで、窒素流を停止し、HF流量を40sccm(6.7×10−7m3/秒)に121分間増加させた。
Claims (1)
- 1,2,3,3,3−ペンタフルオロプロペンと2,3,3,3−テトラフルオロプロペンを併産する方法であって:
触媒を有する反応ゾーンで1,1,1,2,3,3−ヘキサフルオロプロパンと1,1,1,2,3−ペンタフルオロプロパンとのブレンドを脱フッ化水素させ、それによって、上記1,2,3,3,3−ペンタフルオロプロペンと2,3,3,3−テトラフルオロプロペン、未反応のハイドロフルオロカーボン、およびフッ化水素を含む生成混合物を形成させること、およびフッ化水素と上記未反応のハイドロフルオロカーボンから上記1,2,3,3,3−ペンタフルオロプロペンと2,3,3,3−テトラフルオロプロペンとのブレンドを分離して、1,2,3,3,3−ペンタフルオロプロペンと2,3,3,3−テトラフルオロプロペンを生成させること
を含む、上記方法。
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