WO2014178352A1 - トリフルオロエチレンを含む組成物 - Google Patents
トリフルオロエチレンを含む組成物 Download PDFInfo
- Publication number
- WO2014178352A1 WO2014178352A1 PCT/JP2014/061764 JP2014061764W WO2014178352A1 WO 2014178352 A1 WO2014178352 A1 WO 2014178352A1 JP 2014061764 W JP2014061764 W JP 2014061764W WO 2014178352 A1 WO2014178352 A1 WO 2014178352A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- difluoroethylene
- composition
- compound
- trifluoroethylene
- total amount
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 112
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 title claims description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 101
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 16
- WGZYQOSEVSXDNI-UHFFFAOYSA-N 1,1,2-trifluoroethane Chemical compound FCC(F)F WGZYQOSEVSXDNI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 66
- 239000003054 catalyst Substances 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 57
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 46
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims description 42
- 238000004519 manufacturing process Methods 0.000 claims description 30
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 28
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- -1 1,1-difluoroethylene, chlorotrifluoroethylene, 1-chloro-2,2-difluoroethylene Chemical group 0.000 claims description 22
- 229910052763 palladium Inorganic materials 0.000 claims description 21
- WFLOTYSKFUPZQB-OWOJBTEDSA-N (e)-1,2-difluoroethene Chemical group F\C=C\F WFLOTYSKFUPZQB-OWOJBTEDSA-N 0.000 claims description 16
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 12
- WFLOTYSKFUPZQB-UPHRSURJSA-N (z)-1,2-difluoroethene Chemical group F\C=C/F WFLOTYSKFUPZQB-UPHRSURJSA-N 0.000 claims description 10
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 claims description 9
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 8
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 8
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 8
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 claims description 7
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 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 4
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 4
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 4
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 claims description 4
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims description 4
- YMRMDGSNYHCUCL-UHFFFAOYSA-N 1,2-dichloro-1,1,2-trifluoroethane Chemical compound FC(Cl)C(F)(F)Cl YMRMDGSNYHCUCL-UHFFFAOYSA-N 0.000 claims description 4
- JQZFYIGAYWLRCC-UHFFFAOYSA-N 1-chloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)(F)Cl JQZFYIGAYWLRCC-UHFFFAOYSA-N 0.000 claims description 4
- HILNUELUDBMBJQ-UHFFFAOYSA-N 1-chloro-1,1,2-trifluoroethane Chemical compound FCC(F)(F)Cl HILNUELUDBMBJQ-UHFFFAOYSA-N 0.000 claims description 4
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 claims description 4
- FWAQVJAOVDYHAF-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethane Chemical compound FC(F)C(F)Cl FWAQVJAOVDYHAF-UHFFFAOYSA-N 0.000 claims description 4
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims description 4
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 4
- 235000019404 dichlorodifluoromethane Nutrition 0.000 claims description 4
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 claims description 4
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 claims description 3
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 claims description 3
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 claims description 3
- UPVJEODAZWTJKZ-UPHRSURJSA-N (z)-1,2-dichloro-1,2-difluoroethene Chemical group F\C(Cl)=C(/F)Cl UPVJEODAZWTJKZ-UPHRSURJSA-N 0.000 claims description 2
- CDOOAUSHHFGWSA-UPHRSURJSA-N (z)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C/C(F)(F)F CDOOAUSHHFGWSA-UPHRSURJSA-N 0.000 claims description 2
- CJENPNUXCMYXPT-OWOJBTEDSA-N (z)-1-chloro-1,2-difluoroethene Chemical group F\C=C(\F)Cl CJENPNUXCMYXPT-OWOJBTEDSA-N 0.000 claims description 2
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 claims description 2
- ATEBGNALLCMSGS-UHFFFAOYSA-N 2-chloro-1,1-difluoroethane Chemical compound FC(F)CCl ATEBGNALLCMSGS-UHFFFAOYSA-N 0.000 claims description 2
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004338 Dichlorodifluoromethane Substances 0.000 claims description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019407 octafluorocyclobutane Nutrition 0.000 claims description 2
- MTKHTBWXSHYCGS-OWOJBTEDSA-N (e)-1-chloro-2-fluoroethene Chemical group F\C=C\Cl MTKHTBWXSHYCGS-OWOJBTEDSA-N 0.000 claims 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 239000004604 Blowing Agent Substances 0.000 abstract description 5
- 239000000443 aerosol Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000007921 spray Substances 0.000 abstract description 4
- 239000004088 foaming agent Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 description 65
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 238000004821 distillation Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000003507 refrigerant Substances 0.000 description 9
- 238000004378 air conditioning Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229910001252 Pd alloy Inorganic materials 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000005057 refrigeration Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CJENPNUXCMYXPT-UPHRSURJSA-N (e)-1-chloro-1,2-difluoroethene Chemical group F\C=C(/F)Cl CJENPNUXCMYXPT-UPHRSURJSA-N 0.000 description 1
- MTKHTBWXSHYCGS-UHFFFAOYSA-N 1-chloro-2-fluoroethene Chemical group FC=CCl MTKHTBWXSHYCGS-UHFFFAOYSA-N 0.000 description 1
- HTHNTJCVPNKCPZ-UHFFFAOYSA-N 2-chloro-1,1-difluoroethene Chemical group FC(F)=CCl HTHNTJCVPNKCPZ-UHFFFAOYSA-N 0.000 description 1
- BUMFHKJRHRUGNU-UHFFFAOYSA-N 3,3-difluoroprop-1-ene Chemical compound FC(F)C=C BUMFHKJRHRUGNU-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/30—Materials not provided for elsewhere for aerosols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only 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
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/11—Ethers
- C09K2205/112—Halogenated ethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
Definitions
- the present invention relates to a composition containing trifluoroethylene, and particularly to a composition useful as a heat transfer composition.
- HFO-1123 trifluoroethylene
- HFO-1123 has attracted attention as a compound having a low GWP.
- the abbreviation of the compound is described in parentheses after the compound name, but in this specification, the abbreviation is used instead of the compound name as necessary.
- HFO-1123 has been used for applications such as refrigeration and heat transfer fluids, aerosol propellants, and foam expansion agents, but has recently been promising as a substitute for saturated HFC (hydrofluorocarbon) refrigerants with high GWP. It is believed that.
- Patent Document 1 proposes a composition containing HFO-1123 as a working medium used in a thermal cycle system.
- compositions that include HFO-1123 that can be used in a variety of applications.
- the object of the present invention is to provide a composition containing HFO-1123 having a low GWP and useful as a heat transfer composition, an aerosol spray, a blowing agent, a blowing agent, a solvent and the like.
- the present invention relates to trifluoroethylene (HFO-1123), E-1,2-difluoroethylene (HFO-1132), Z-1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO).
- the present invention also relates to a method for producing trifluoroethylene by gas phase hydrogen reduction reaction of chlorotrifluoroethylene, wherein chlorotrifluoroethylene and hydrogen are reacted at 80 ° C.
- a method for producing a composition containing trifluoroethylene which comprises obtaining trifluoroethylene containing at least one compound selected from: Furthermore, the present invention was obtained by reacting at a temperature of 400 to 1200 ° C. in a method for producing trifluoroethylene from a mixture of chlorodifluoromethane and chlorofluoromethane by a synthetic reaction involving thermal decomposition in the presence of a heat medium.
- the reaction product is distilled to obtain E-1,2-difluoroethylene, Z-1,2-difluoroethylene, 1,1-difluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, fluoroethylene, 1,1,1
- composition of the present invention 1,1,1,2-tetrafluoroethane (HFC-134a) and R410A (difluoromethane (HFC-32) and pentafluoroethane (HFC-125), which are greenhouse gases, are used.
- a composition containing HFO-1123, which is expected to be used as a new refrigerant having a low GWP instead of a mixed medium having a mass ratio of 1: 1, can be used for various applications.
- the composition of the first embodiment of the present invention includes HFO-1123 and the first compound.
- the first compound is at least one compound selected from the group consisting of HFO-1132, VdF, CTFE, HCFO-1122, HCFO-1122a, HFC-143, and methane.
- the content ratio of each of the first compounds contained is preferably less than 0.5% by mass with respect to the total amount of HFO-1123 and the compound. Further, the content ratio of the total amount of the first compound contained in the composition is preferably less than 0.5% by mass with respect to the total amount of HFO-1123 and the total amount of the first compound. Furthermore, it is preferable that the minimum of content of the 1st compound whole quantity is 0.0001 mass%.
- HFO-1123 can be produced, for example, by a method in which (I) chlorotrifluoroethylene (CTFE) (CFO-1113) is hydrogen reduced in a gas phase. Accordingly, in certain embodiments, compounds other than HFO-1123 obtained by the method of hydrogenating CTFE in the gas phase are present in the product composition obtained with HFO-1123. In some embodiments, impurities present in CTFE, which is a raw material for producing HFO-1123, are present as they are in the reaction for producing HFO-1123, and are present in the product composition obtained together with HFO-1123.
- CTFE chlorotrifluoroethylene
- the composition of the second embodiment of the present invention contains HFO-1123 and the first compound, and further comprises 1,1-difluoroethane (HFC-152a), 2-chloro-1,1-difluoroethane.
- HFC-152a 1,1-difluoroethane
- HCFC-142 1-chloro-1,1-difluoroethane
- HCFC-142b 1-chloro-1,2,2-trifluoroethane
- HCFC-133 1-chloro-1,1,2- Trifluoroethane
- HCFC-133b 1,2-dichloro-1,1,2-trifluoroethane
- CFC- 113 1,1,2-trichloro-1,2,2-trifluoroethane
- One of the can comprises a second compound.
- the content ratio of each of the second compounds contained is preferably less than 0.5% by mass with respect to the total amount of HFO-1123, the first compound, and the compound. .
- the content ratio of the total amount of the second compound contained in the composition is less than 0.5% by mass with respect to the total amount of HFO-1123, the first compound, and the total amount of the second compound. Is preferred.
- the lower limit of the total content of the second compound is preferably 0.0001% by mass.
- HFO-1123 is composed of (II) chlorodifluoromethane (HCFC-22 (hereinafter referred to as R22)) and chlorofluoromethane (HCFC-31 (referred to as R31)) in the presence of a heat medium. It can be produced by a synthesis reaction involving thermal decomposition of a mixture of
- compounds other than HFO-1123 obtained by synthesis involving pyrolysis of a mixture of R22 and R31 are present in the resulting composition obtained with HFO-1123.
- impurities present in R22 or R31, which are the raw materials for producing HFO-1123 are present as they are in the reaction for producing HFO-1123, and are present in the product composition obtained together with HFO-1123. .
- the composition of the third embodiment of the present invention includes HFO-1123 and the first compound, and further includes tetrafluoroethylene (FO-1114, TFE), E- and / or Z-1-.
- the content of each of the third compounds contained is preferably less than 0.5% by mass with respect to the total amount of HFO-1123, the first compound, and the compound. .
- the content ratio of the total amount of the third compound contained in the composition is less than 0.5% by mass with respect to the total amount of HFO-1123, the first compound, and the total amount of the third compound. Is preferred.
- the minimum of content of the 3rd compound whole quantity is 0.0001 mass%.
- halogenated hydrocarbons are abbreviated, but the chemical formulas and names of these compounds represented by the abbreviations are shown in Table 1. And as shown in Table 2.
- compositions of embodiments of the present invention include heat transfer compositions, aerosol sprays, foaming agents, blowing agents, solvents, cleaning agents, carrier fluids, displacement drying agents, buffing abrasives, polymerization media, polyolefins and polyurethanes. It is useful as a swelling agent, a gaseous dielectric, a fire extinguishing agent, and a liquid or gaseous fire extinguishing agent.
- a composition having a total content of the first compounds of less than 0.5% by mass has a low GWP and is useful as a new refrigerant that replaces greenhouse gases.
- the total content of the first compounds is less than 0.5% by mass, and the total content of the second compounds is less than 0.5% by mass. It has a low GWP and is useful as a new refrigerant to replace greenhouse gases.
- the total amount of the first compound and the second compound is more preferably less than 0.5% by mass.
- the composition in which the total content of the first compounds is less than 0.5% by mass and the total content of the third compounds is less than 0.5% by mass.
- GWP is low and useful.
- the total amount of the first compound and the third compound is more preferably less than 0.5% by mass.
- these content rates are the rates with respect to the total amount with a trifluoroethylene like the above.
- the composition of the embodiment of the present invention can act as a working fluid that transfers heat from a heat source to a heat sink.
- the heat transfer composition is useful as a refrigerant in a cycle in which a fluid changes phase from gas to liquid to liquid.
- the heat transfer system include an air conditioner, a freezer, a refrigerator, a heat pump, a water cooler, a full liquid evaporative cooler, a direct expansion cooler, a walk nomer, a movable refrigerator, a movable air conditioning unit, and combinations thereof. .
- movable refrigeration device refers to any refrigerant, air conditioning or heating device incorporated in a road, rail, sea or air transportation unit.
- Mobile refrigeration or air conditioning units also include devices known as “intermodal” systems that are independent of any mobile carrier. Such “intermodal systems” include “containers (combined sea / land transport)” and “swap bodies (combined road / rail transport)”.
- a fixed heat transfer system is a system that is related or installed in various buildings. These fixed applications include fixed air conditioning and heat pumps (including but not limited to coolers, high temperature heat pumps, residential, commercial or industrial air conditioning systems, windows, ductless, ducts, package terminals, coolers and rooftop systems, etc. There is an exterior connected to the building.
- the compositions of the present invention can be used in commercial, industrial or residential refrigerators and freezers, ice machines, built-in coolers and freezers, full-fledged evaporative coolers, direct expansion coolers, walk-in and reach incubators and freezers and It is useful for equipment including combination systems.
- the composition of the embodiment of the present invention can be used, for example, in a refrigeration system in a supermarket.
- HFO-1123 As embodiments for producing HFO-1123, there can be mentioned two embodiments: (I) hydrogen reduction of CTFE and (II) synthesis involving thermal decomposition of R22 and R31. Hereinafter, these aspects and compounds obtained together with the production of HFO-1123 will be described.
- the raw material composition used for the production of HFO-1123 by hydrogen reduction of CTFE contains CTFE and hydrogen.
- the ratio of CTFE and hydrogen in the raw material composition is in the range of 0.01 to 4.0 moles of hydrogen per mole of CTFE. That is, the molar ratio of the supply amount of hydrogen to the supply amount of CTFE supplied to the reactor (CTFE supply mole amount, hydrogen supply mole amount in terms of CTFE and hydrogen, respectively, hydrogen / CTFE) is 0.01. ⁇ 4.0.
- the conversion rate of the raw material components can be increased. Further, the ratio of components other than HFO-1123, that is, by-products, in the obtained reaction product can be suppressed.
- the hydrogen / CTFE is more preferably in the range of 0.1 to 4.0, and particularly preferably in the range of 0.1 to 2.
- the conversion rate is also referred to as a reaction rate, and means a ratio (mol%) in which raw material components are reacted. For example, when the ratio (yield) of the raw material components in the outlet gas is X%, (100 ⁇ X)% is referred to as the conversion rate.
- Examples of the reactor include known reactors that can be filled with a catalyst-supporting carrier to form a catalyst layer.
- Examples of the material of the reactor include glass, iron, nickel, iron or an alloy containing nickel as a main component.
- the pressure in the reactor is preferably normal pressure from the viewpoint of handleability.
- the catalyst is preferably a palladium catalyst.
- the palladium catalyst is preferably used by being supported on a carrier.
- the palladium catalyst may be not only palladium alone but also a palladium alloy.
- carrier may be sufficient.
- the palladium alloy catalyst include a palladium / platinum alloy catalyst and a palladium / rhodium alloy catalyst.
- a catalyst in which only palladium or a palladium alloy is supported on a carrier, or a catalyst in which palladium and a metal other than palladium are supported on a carrier is preferable.
- a catalyst in which palladium and a metal other than palladium are supported on a carrier tends to have higher catalyst durability than a catalyst in which only palladium is supported on a carrier.
- Other metals than palladium include group 8 elements (iron, ruthenium, osmium, etc.), group 9 elements (cobalt, rhodium, iridium, etc.), group 10 elements (nickel, platinum, etc.), and gold. Can be mentioned.
- Another metal may be used individually by 1 type and may be used in combination of 2 or more type. The proportion of other metals is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of palladium.
- Examples of the carrier include activated carbon and metal oxides (alumina, zirconia, silica, etc.), and activated carbon is preferable from the viewpoint of activity, durability, and reaction selectivity.
- Examples of the activated carbon include those obtained from plant raw materials (wood, charcoal, fruit shells, coconut shells, etc.), mineral materials (peat, lignite, coal, etc.), etc. From the viewpoint of catalyst durability, What was obtained is preferred, and coconut shell activated carbon is particularly preferred.
- Examples of the shape of the activated carbon include formed coal having a length of about 2 to 10 m, crushed coal having a size of about 4 to 50 mesh, granular coal, etc. From the viewpoint of activity, 4 to 20 mesh crushed coal, or a length of 2 to 5 mm of charcoal is preferred.
- the supported amount of palladium is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 1 part by mass with respect to 100 parts by mass of the activated carbon.
- the supported amount of palladium is 0.1 parts by mass or more, the reaction rate between CTFE, which is a raw material compound, and hydrogen is improved. If the supported amount of palladium is 10 parts by mass or less, it is easy to suppress an excessive temperature rise of the catalyst layer due to reaction heat, and it is easy to reduce the production of by-products.
- the amount of palladium supported is preferably the same as that of the activated carbon.
- a catalyst layer is formed in the reactor by filling the reactor with a catalyst-supporting carrier.
- Packing density of the catalyst-supporting carrier in the catalyst layer is preferably 0.5 ⁇ 1g / cm 3, more preferably 0.6 ⁇ 0.8g / cm 3. If the packing density of the catalyst-carrying carrier is 0.5 g / cm 3 or more, the filling amount of the catalyst-carrying carrier per unit volume is large and the amount of gas to be reacted can be increased, so that productivity is improved.
- the packing density of the catalyst-supporting carrier is 1 g / cm 3 or less, it is easy to suppress an excessive temperature rise of the catalyst layer due to reaction heat, and it is easy to reduce the production of by-products. There may be one packed portion of the catalyst-supporting support in the reactor, or two or more.
- the temperature of the catalyst layer is set to a temperature equal to or higher than the dew point of the raw material composition (mixed gas) containing CTFE and hydrogen.
- a more preferable temperature of the catalyst layer is preferably 80 ° C. or higher from the viewpoint of reactivity, and preferably 180 ° C. or higher from the viewpoint of improving the reaction rate.
- a range of 220 ° C to 240 ° C is more preferable.
- the temperature of the catalyst layer gradually decreases as the deterioration of the catalyst progresses, there is a problem that the reaction rate decreases. Therefore, it is preferable to perform an operation of keeping the temperature of the catalyst layer at a sufficient temperature so that a high reaction rate can be maintained. For example, when the temperature is maintained by heating the catalyst layer from the outside with a heat medium or the like, the temperature of the heat medium can be gradually increased to increase the temperature of the catalyst layer.
- the temperature of the catalyst layer refers to the temperature of the catalyst layer that is maintained by heating from the outside.
- the raw material mixed gas reacts in a partial region of the catalyst layer, and the reaction zone (region in which the raw material mixed gas reacts) becomes hotter than the other catalyst layer regions due to generation of reaction heat. Since the catalytic activity of the reaction zone decreases with time, the reaction zone usually moves gradually from the inlet of the raw material mixed gas to the downstream side in the gas flow direction. Further, a product gas having a high temperature generated in the reaction zone flows downstream from the reaction zone, and usually becomes higher than the temperature of the catalyst layer, and gradually decreases as the distance from the reaction zone increases. Therefore, the temperature of the catalyst layer refers to the temperature on the upstream side of the reaction zone, that is, the temperature of the catalyst layer that is heated from the outside with a heat medium or the like and maintained at that temperature.
- the temperature in the reaction zone where the raw material mixed gas is reacting and the downstream region thereof becomes higher than the temperature of the catalyst layer in the other region due to the reaction heat.
- the catalyst near the gas inlet side contributes to the reaction
- the catalyst on the gas outlet side contributes to the reaction.
- the reaction zone in the catalyst layer gradually moves from the gas inlet side toward the gas outlet side.
- the measurement part of the insertion type thermometer is positioned on the gas inlet side of the catalyst layer in the initial stage of operation, and the reaction is performed. It is preferable to measure the maximum temperature of the catalyst layer by moving the measuring unit to the gas outlet side as the gas advances.
- the contact time with the catalyst of the raw material CTFE is preferably 4 to 60 seconds, and more preferably 8 to 40 seconds. This contact time is calculated from the amount of gas introduced into the reactor and the volume of the catalyst layer.
- the linear velocity u of the raw material compound (gas) represented by the following formula in the catalyst layer is preferably 0.1 to 100 cm / second, and more preferably 1 to 30 cm / second.
- This linear velocity u is the linear velocity of the raw material compound calculated from the amount of gas introduced into the reactor and the catalyst layer volume.
- productivity is improved.
- the linear velocity u of the raw material compound is 100 cm / second or less, the reaction rate between the raw material compound and hydrogen is improved.
- W is the concentration (mol%) of the raw material compound gas in the total gas flowing through the catalyst layer
- V is the flow rate (cm 3 / sec) of the total gas flowing through the catalyst layer
- S is The cross-sectional area (cm 2 ) of the catalyst layer with respect to the gas flow direction.
- a composition containing HFO-1123 can be obtained as the outlet gas of the reactor.
- compounds other than HFO-1123 contained in the outlet gas in addition to CTFE (CFO-1113) which is an unreacted raw material, HFO-1132, HFO-1132a, HCFO-1122, HCFO-1122a, HFC-143, Examples include methane, HFC-152a, HCFC-142, HCFC-142b, HCFC-133, HCFC-133b, HCFC-123a, CFC-113, and CFO-1112.
- the above components other than HFO-1123 contained in the outlet gas can be removed to a desired extent by known means such as distillation. In particular, it is preferable to purify by distillation.
- the separated CTFE can be recycled as a part of the raw material.
- the composition containing HFO-1123 obtained by purification includes, in addition to HFO-1123, E-1,2-difluoroethylene, Z-1,2-difluoroethylene, chlorotrifluoroethylene, 1-chloro-2, A composition containing at least one compound selected from the group consisting of 2-difluoroethylene and 1,1-difluoroethylene is preferred.
- the content ratio of each of the above compounds other than HFO-1123 is preferably less than 0.5% by mass with respect to the total amount of HFO-1123 and the compound. Further, the content ratio of the total amount of the compounds other than HFO-1123 contained in the composition is preferably less than 0.5% by mass with respect to the total amount of HFO-1123 and the total amount of these compounds. Furthermore, the lower limit of the total content of these compounds is preferably 0.0001% by mass.
- composition containing HFO-1123 of the present invention can be obtained by hydrogen reduction of CTFE.
- HFO-1123 having a low GWP and useful as a new refrigerant can be efficiently produced in a single reaction using R22 and R31 as raw materials.
- the heat medium since the heat medium is used, it is easy to control the manufacturing (reaction) conditions, particularly the temperature conditions, so that quantitative HFO-1123 can be manufactured.
- This method may be a continuous production method or a batch production method.
- the continuous production method both the supply of the raw material composition containing R22 and R31 in the above ratio to the reactor and the supply of the heat medium to the reactor are continuously performed, and the step (a) and ( The step b) is performed at the same time.
- the batch type production either the supply of the raw material composition in the step (a) or the supply of the heat medium in the step (b) may be performed first or simultaneously. That is, when one of the raw material composition and the heat medium is supplied, even if the other is not supplied into the reactor, it is supplied later while the previously supplied raw material composition or the heat medium is retained.
- the raw material composition and the heat medium may be in contact with each other for a predetermined time in the reactor.
- This production method is preferably a continuous method in terms of production efficiency.
- an embodiment in which the production of HFO-1123 is applied to continuous production will be described.
- the main reaction in the reactor in this embodiment is shown in the following formula (2).
- the raw material composition containing R22 and R31 generates a reaction mixture containing difluorocarbene (F 2 C :) and R31 by pyrolysis and dehydrochlorination reaction in the reactor, and these reaction mixtures are directly added to the reaction. Alternatively, it is considered that it is converted into HFO-1123 via one or more intermediates.
- the raw material composition used for manufacturing HFO-1123 by the reaction includes R22 and R31.
- the ratio of R22 and R31 in the raw material composition is such that R31 is in the range of 0.01 to 4.0 moles per mole of R22. That is, the molar ratio of the supply amount of R31 to the supply amount of R22 supplied to the reactor (the supply molar amount of R22, the R31 / R22 when the supply molar amount of R31 is represented by R31 and R22, respectively) is 0.01 ⁇ 4.0.
- the supply amounts of the raw material components and the heat medium indicate supply amounts per unit time. .
- R31 / R22 By setting R31 / R22 within the above range, the conversion rate (reaction rate) of the raw material components, particularly the conversion rate of R31, can be increased. Further, the ratio of components other than HFO-1123, that is, by-products, in the obtained reaction product can be suppressed.
- R31 / R22 is more preferably in the range of 0.1 to 4.0, and particularly preferably in the range of 0.1 to 1.5.
- the raw material composition is a fluorine-containing compound that can be thermally decomposed in a reactor to generate F 2 C :, for example, TFE (FO-1114), FO-1216, RC318, VdF (HFO— 1132a), HFO-1113, HFO-1123, and the like.
- a fluorine-containing compound that can be thermally decomposed in such a reactor to generate F 2 C: is used for the raw material composition
- a newly prepared fluorine-containing compound may be used. From the viewpoint of recycling, it is preferable to use a fluorine-containing compound by-produced by the thermal decomposition reaction of R31.
- the raw material composition containing R22 and R31 may be introduced into the reactor at room temperature, but in order to improve the reactivity in the reactor, the temperature at the time of introduction into the reactor is adjusted by heating or the like. May be. However, since the temperature range suitable for improving the reactivity of the fluorine-containing compound capable of generating F 2 C: containing R22 and R31 is different, it is preferable to perform temperature adjustment separately.
- the temperature of R31 supplied to the reactor and the temperature of the fluorine-containing compound capable of generating F 2 C: containing R22 supplied to the reactor are high in reactivity but are not easily carbonized. Therefore, the temperature is preferably 0 to 600 ° C. From the viewpoint of further increasing the reactivity, the fluorine-containing compound capable of generating R 22 or F 2 C: containing R 22 may be heated to normal temperature (25 ° C.) or higher and 600 ° C. or lower before being introduced into the reactor. Preferably, heating to 100 to 500 ° C. is more preferable.
- the temperature of R31 supplied to the reactor is preferably 0 to 1200 ° C. from the viewpoint of reactivity. From the viewpoint of increasing the reactivity, it is preferable to heat R31 to normal temperature or higher and 1200 ° C. or lower, and more preferably 100 to 800 ° C. before introducing R31 into the reactor.
- the supply of the fluorine-containing compound capable of generating R22 and R31, and F 2 C: used as necessary, to the reactor may be separate, or may be supplied after mixing each component. .
- each component after mixing divide the raw material composition into groups, for example, fluorinated compounds that can generate F 2 C: and other components, and mix each component in each group It may be supplied separately to the reactor, or may be supplied after mixing all the components.
- a fluorine-containing compound capable of generating F 2 C: containing R22 is mixed, adjusted to the preferred temperature condition and supplied to the reactor, and separately from this, R31 is preferred. It is preferable to adjust to temperature conditions and to supply to a reactor.
- the heat medium in this embodiment is supplied to the reactor so as to come into contact with the raw material composition in the reactor for a certain period of time.
- the heat medium is a medium that does not undergo thermal decomposition at the temperature in the reactor, and specifically, a medium that does not undergo thermal decomposition at a temperature of 100 to 1200 ° C. is preferable.
- Examples of the heat medium include one or more gases selected from water vapor, nitrogen, and carbon dioxide. It is preferable to use a gas containing 50% by volume or more of water vapor and the balance being nitrogen and / or carbon dioxide.
- the content ratio of water vapor in the heat medium is preferably 50% by volume or more, and the use of a gas substantially consisting of only water vapor (100% by volume) is particularly preferable. preferable.
- the supply amount of the heat medium is preferably 20 to 98% by volume, more preferably 50 to 95% by volume with respect to the total supply amount of the heat medium and the raw material composition.
- the contact time in the reactor between the heat medium supplied in this way and the raw material composition is preferably 0.01 to 10 seconds, more preferably 0.2 to 3.0 seconds. . By setting the contact time to 0.01 to 10 seconds, the formation reaction of HFO-1123 can sufficiently proceed and the production of by-products can be suppressed.
- the contact time between the heat medium and the raw material composition corresponds to the residence time of the raw material composition in the reactor, and can be controlled by adjusting the supply amount (flow rate) of the raw material composition to the reactor.
- the shape of the reactor is not particularly limited as long as it can withstand the temperature and pressure in the reactor described later, and examples thereof include a cylindrical vertical reactor.
- Examples of the material of the reactor include glass, iron, nickel, or an alloy mainly composed of iron and nickel.
- the temperature in the reactor in the step (b) is preferably 400 to 1200 ° C, more preferably 600 to 900 ° C, and particularly preferably 710 to 900 ° C.
- the reaction rate of the synthesis reaction involving thermal decomposition represented by the above formula (2) can be increased, and HFO-1123 can be obtained efficiently.
- the temperature in the reactor can be controlled by adjusting the temperature and pressure of the heat medium supplied to the reactor. Further, the inside of the reactor can be supplementarily heated with an electric heater or the like so that the temperature in the reactor falls within a particularly preferable temperature range (710 to 900 ° C.).
- the pressure in the reactor is preferably 0 to 2.0 MPa as gauge pressure, and more preferably in the range of 0 to 0.5 MPa.
- a composition containing HFO-1123 can be obtained as the outlet gas of the reactor.
- the compounds other than HF-1123 contained in the outlet gas include HFO-1132, HFO-1132a, HFO-1141, CFO-1113, HCFO-1122, HCFO-1122a, HFC-143, FO-1114, HCFO-1131, HFO-1252zf, HFO-1243zf, HFO-1234yf, HFO-1234ze, FO-1216, HFC-125, HFC-134, HFC-134a, HFC-143a, HCFC- 124, HCFC-124a, HFC-227ca, HFC-227ea, HFC-236fa, HFC-236ea, CFC-12, HFC-23, HFC-32, HFC-41, chloromethane, RC-318, methane, etc.
- the above components other than HFO-1123 contained in the outlet gas can be removed to a desired extent by known means such as distillation. In particular, it is preferable to purify by distillation.
- the separated FO-1114 (TFE), FO-1216 (HFP), CFO-1113 (CTFE), and RC318 are compounds that can generate F 2 C: and are recycled as a part of the raw material composition. Is possible.
- the composition containing HFO-1123 obtained by purification includes E-1,2-difluoroethylene, Z-1,2-difluoroethylene, 1,1-difluoroethylene, chlorotrifluoroethylene, in addition to HFO-1123.
- a composition comprising at least one compound selected from the group consisting of tetrafluoroethylene, fluoroethylene, 1,1,1-trifluoroethane, difluoromethane, trifluoromethane, and pentafluoroethane.
- the content ratio of each of the above compounds other than HFO-1123 is preferably less than 0.5% by mass with respect to the total amount of HFO-1123 and the compound.
- the content ratio of the total amount of the compounds other than HFO-1123 contained in the composition is preferably less than 0.5% by mass with respect to the total amount of HFO-1123 and the total amount of these compounds. Furthermore, the lower limit of the total content of these compounds is preferably 0.0001% by mass.
- composition containing HFO-1123 of the present invention can be obtained by synthesis involving thermal decomposition of R22 and R31.
- Example 1 A stainless steel reaction tube having an inner diameter of 2.3 cm and a length of 50 cm is filled with palladium-supported activated carbon in which 0.5 parts by weight of palladium is loaded with respect to 100 parts by weight of coconut shell activated carbon. A layer was formed. The packing density of the palladium-supported activated carbon in the catalyst layer was 0.74 g / cm 3 .
- the catalyst layer in the reaction tube thus formed is controlled at 80 ° C. by an electric heater, and a raw material composition (hereinafter also referred to as a raw material gas) composed of CTFE and hydrogen at an internal pressure (gauge pressure) of 0.04 MPa is used as the reaction tube. Supplied. Hereinafter, all the pressures are assumed to be gauge pressures.
- the source gas was circulated in the reaction tube so that the molar ratio of hydrogen to CTFE (hydrogen / CTFE) in the source gas was 1.0.
- the contact time of the raw material gas with respect to the catalyst layer was 30 seconds, and the linear velocity u of the raw material gas component (CTFE) was 1.3 cm / second.
- CTFE raw material gas component
- the maximum temperature of the catalyst layer during the reaction was measured with an insertion-type thermometer inserted into the catalyst layer while moving the position.
- the maximum temperature of the catalyst layer was 236 ° C.
- the outlet gas taken out from the outlet of the reactor includes unreacted raw material gas in addition to the gas generated or by-produced by the reaction. In the following description, the outlet gas may be referred to as generated gas. .
- the product gas discharged from the outlet of the reaction tube was subjected to alkali washing and dehydration, and then analyzed by gas chromatography to calculate the molar composition of the gas component contained in the outlet gas.
- the reaction rate (conversion rate) of CTFE was calculated
- the results are shown in Table 3 together with the production conditions.
- the conversion rate of CTFE means the ratio (mol%) of the reacted CTFE, and when the ratio (yield) of CTFE in the outlet gas is X%, (100-X) % Is referred to as the conversion rate of CTFE.
- the crude HFO-1123 composition obtained by the above production method was recovered and supplied to the 21st stage from the top of the 30-stage distillation column so as to obtain a speed of 8826.8 g / h.
- Distillation is continuously performed at a pressure of 0.0 MPa (gauge pressure), a column top temperature of 4.9 ° C., and a column bottom temperature of 36.9 ° C.
- the reflux liquid is supplied to the uppermost stage of the distillation column.
- the column was operated at a reflux ratio of 21.0, and a fraction in which low-boiling components were concentrated from the top of the column was distilled at a rate of 916.8 g / h (distillate 1).
- the high-purity HFO-1123 is distilled at a rate of 3705.1 g / h from the 14th stage from the top of the column (distillate 2), and further at a rate of 4214.9 g / h from the bottom of the column. Distill (drain).
- Table 4 shows the composition of each distillate and bottoms, the column top temperature, the 14th stage temperature, and the column bottom temperature.
- HFO-1123 (distillate 2 in Table 4) obtained by this production method, methane, VdF, (E) -HFO-1132, CTFE, (Z) -HFO-1132, HFC It can be seen that -152a, HCFO-1122a, HCFO-1122, HCFC-142b, and HFC-143 are contained in a total of less than 0.5% by weight.
- a raw material gas having a molar ratio of R31 and R22 (R31 / R22) of 1.0 was continuously introduced into a stainless steel tube in an electric furnace set at a furnace temperature of 300 ° C. and heated to 300 ° C.
- the flow rate of the raw material gas (amount supplied per unit time) was controlled so that the residence time of the raw material gas in the reactor was 0.5 seconds, and the product gas was taken out from the outlet of the reactor.
- the actually measured value of the reactor internal temperature was 750 ° C.
- the actually measured value of the reactor internal pressure was 0.042 MPa.
- the product gas taken out from the outlet of the reactor is cooled to 100 ° C. or less, and after performing steam and acidic liquid recovery and alkali washing in order, dehydration treatment is performed, and analysis by gas chromatography is performed.
- the molar composition of the gas component was calculated. Table 5 shows the production conditions, and Table 6 shows the composition of the obtained crude HFO-1123.
- the temperature of the raw material gases (R31 and R22) is the set temperature in the preheating electric furnace described above, and the water vapor temperature is the set temperature in the electric furnace for steam heating described above.
- the crude HFO-1123 is supplied to the 15th stage from the top of the distillation tower (distillation tower 1) having 30 stages so that the speed is 7533 g / h, and the operating pressure is 1.5 MPa (gauge pressure), the top temperature is Distillation is continuously carried out at -54 ° C and a column bottom temperature of 40.3 ° C. At this time, the reflux liquid is supplied to the uppermost stage of the distillation column.
- the reflux ratio was operated at 10.0, and a fraction enriched in low-boiling components was distilled from the top of the distillation column 1 at a rate of 2987 g / h (distillate 1), and further HFO- The component containing 1123 is distilled (bottom liquid 1) so as to have a speed of 4546 g / h.
- the bottoms recovered from the bottom of the distillation column 1 is fed to the 48th stage from the top of the 50-stage distillation tower (distillation tower 2) at a speed of 4546 g / h. Distillation is continuously performed at 0 MPa (gauge pressure), a column top temperature of 9.2 ° C, and a column bottom temperature of 45.7 ° C.
- the reflux liquid is supplied to the uppermost stage of the distillation column. Further, the reflux ratio was operated at 50.0, and the purified HFO-1123 was distilled from the top of the distillation column 2 at a rate of 186 g / h (distillate 2). The fraction is distilled from the stage at a rate of 854.4 g / h (distillate 3), and the bottoms (bottom liquor 2) is recovered from the bottom of the column at 3505.3 g / h.
- Tables 7 and 8 show the composition of each distillate and bottoms, the column top temperature, the 46th stage temperature, and the column bottom temperature.
- HFO-1123 (distillate 2 in Table 8) obtained by this production method, VdF, trifluoromethane (HFC-23), difluoromethane (HFC-32), fluoromethane (HFC- 41), pentafluoroethane (HFC-125), 1,1,1-trifluoroethane (HFC-143a), tetrafluoroethylene (TFE), vinyl fluoride (HFO-1141), (E) -HFO-1132 It is understood that the total amount is less than 0.5% by weight.
- the composition comprising HFO-1123 of the present invention comprises a heat transfer composition, an aerosol spray, a foaming agent, a blowing agent, a solvent, a cleaning agent, a carrier fluid, a displacement drying agent, a buffing abrasive, a polymerization medium, a polyolefin and a polyurethane.
- a heat transfer composition e.g., a heat transfer composition, a foaming agent, a blowing agent, a solvent, a cleaning agent, a carrier fluid, a displacement drying agent, a buffing abrasive, a polymerization medium, a polyolefin and a polyurethane.
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Abstract
Description
HFO-1123は、従来から、冷蔵および熱伝達流体、エアロゾル噴霧剤、発泡膨張剤等の用途に用いられてきたが、近年、GWPが高い飽和HFC(ハイドロフルオロカーボン)系の冷媒の代替物質として有望と考えられている。
しかし、HFO-1123を含み、種々の用途に使用可能な組成物がさらに求められている。
本発明は、トリフルオロエチレン(HFO-1123)と、E-1,2-ジフルオロエチレン(HFO-1132)、Z-1,2-ジフルオロエチレン(HFO-1132)、1,1-ジフルオロエチレン(HFO-1132a、VdF)、クロロトリフルオロエチレン(CFO-1113、CTFE)、1-クロロ-2,2-ジフルオロエチレン(HCFO-1122)、E-1-クロロ-1,2-ジフルオロエチレン(HCFO-1122a)、Z-1-クロロ-1,2-ジフルオロエチレン(HCFO-1122a)、1,1,2-トリフルオロエタン(HFC-143)、およびメタンからなる群から選択される少なくとも1つの第1の化合物とを含むことを特徴とする組成物を提供する。
また、本発明は、クロロトリフルオロエチレンの気相水素還元反応によりトリフルオロエチレンを製造する方法において、パラジウム触媒存在下にクロロトリフルオロエチレンと水素とを80℃以上で反応させ、得られた反応生成物を蒸留して、E-1,2-ジフルオロエチレン、Z-1,2-ジフルオロエチレン、クロロトリフルオロエチレン、1-クロロ-2,2-ジフルオロエチレンおよび1,1-ジフルオロエチレンからなる群から選択される少なくとも1つの化合物を含むトリフルオロエチレンを得ることを特徴とするトリフルオロエチレンを含む組成物の製造方法を提供する。
さらに、本発明は、クロロジフルオロメタンとクロロフルオロメタンの混合物から、熱媒体の存在下における熱分解を伴う合成反応によりトリフルオロエチレンを製造する方法において、400~1200℃で反応させ、得られた反応生成物を蒸留して、E-1,2-ジフルオロエチレン、Z-1,2-ジフルオロエチレン、1,1-ジフルオロエチレン、クロロトリフルオロエチレン、テトラフルオロエチレン、フルオロエチレン、1,1,1-トリフルオロエタン、ジフルオロメタン、トリフルオロメタンおよびペンタフルオロエタンからなる群から選択される少なくとも1つの化合物を含むトリフルオロエチレンを得ることを特徴とするトリフルオロエチレンを含む組成物の製造方法を提供する。
また、第2の実施形態において、第1の化合物の含有割合の合計が0.5質量%未満であり、かつ第2の化合物の含有割合の合計が0.5質量%未満である組成物は、GWPが低く、温室効果ガスに代わる新しい冷媒として有用である。第2の実施形態において、第1の化合物と第2の化合物の合計量は0.5質量%未満であることがより好ましい。
さらに、第3の実施形態において、第1の化合物の含有割合の合計が0.5質量%未満であり、かつ第3の化合物の含有割合の合計が0.5質量%未満である組成物は、GWPが低く有用である。第3の実施形態において、第1の化合物と第3の化合物の合計量は0.5質量%未満であることがより好ましい。
なお、これらの含有割合は、前記と同様、トリフルオロエチレンとの合計量に対する割合である。
HFO-1123を製造する態様としては、(I)CTFEの水素還元と(II)R22とR31との熱分解を伴う合成の2つの態様を挙げることができる。
以下、これらの態様と、HFO-1123の生成とともに得られる化合物について説明する。
CTFE(CFO-1113)からなる原料化合物と水素とを、触媒担持担体が充填された触媒層を有する反応器内で気相で反応させ、HFO-1123を含むガスを生成する。
この態様における反応器内の主な反応を、下記式(1)に示す。
CTFEの水素還元によるHFO-1123の生成に用いられる原料組成物は、CTFEと水素を含む。
原料組成物におけるCTFEと水素の割合は、CTFEの1モルに対して水素が0.01~4.0モルの範囲である。すなわち、反応器に供給するCTFEの供給量に対する水素の供給量のモル比(CTFEの供給モル量、水素の供給モル量をそれぞれCTFE、水素で表した場合の水素/CTFE)は、0.01~4.0である。
なお、転化率とは反応率ともいい、原料成分の反応した割合(モル%)を意味する。例えば、出口ガス中でその原料成分が占める割合(収率)がX%であるとき、(100-X)%を転化率という。
反応器としては、触媒担持担体を充填して触媒層を形成できる、公知の反応器が挙げられる。反応器の材質としては、ガラス、鉄、ニッケル、鉄もしくはニッケルを主成分とする合金等が挙げられる。反応器内の圧力は、取り扱い性の点から、常圧が好ましい。
触媒としてはパラジウム触媒が好ましい。パラジウム触媒は、担体に担持して用いることが好ましい。パラジウム触媒は、パラジウム単体のみならず、パラジウム合金であってもよい。また、パラジウムと他の金属との混合物を担持させた触媒や、パラジウムと他の金属とを担体に別々に担持させた複合触媒であってもよい。パラジウム合金触媒としては、パラジウム/白金合金触媒やパラジウム/ロジウム合金触媒等が挙げられる。
パラジウム以外の他の金属としては、第8族元素(鉄、ルテニウム、オスミウム等)、第9族元素(コバルト、ロジウム、イリジウム等)、第10族元素(ニッケル、白金等)、および金等が挙げられる。他の金属は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。他の金属の割合は、パラジウム100質量部に対して、0.01~50質量部が好ましい。
反応器に触媒担持担体を充填することにより、反応器内に触媒層が形成される。触媒層における触媒担持担体の充填密度は、0.5~1g/cm3が好ましく、0.6~0.8g/cm3がより好ましい。触媒担持担体の充填密度が0.5g/cm3以上であれば、単位容積当たりの触媒担持担体の充填量が多く、反応させるガス量を多くすることができるため、生産性が向上する。触媒担持担体の充填密度が1g/cm3以下であれば、反応熱による触媒層の過剰な温度上昇を抑制しやすく、副生物の生成を低減しやすい。触媒担持担体の充填部分は、反応器内に1つあってもよく、2つ以上あってもよい。
u=(W/100)×V/S
式中、Wは、触媒層を流通する全ガス中の原料化合物ガスの濃度(モル%)であり、Vは、触媒層を流通する全ガスの流量(cm3/秒)であり、Sは、ガスの流通方向に対する触媒層の断面積(cm2)である。
このようなCTFEの水素還元においては、HFO-1123を含む組成物を上記反応器の出口ガスとして得ることができる。出口ガスに含有されるHFO-1123以外の化合物としては、未反応原料であるCTFE(CFO-1113)に加えて、HFO-1132、HFO-1132a、HCFO-1122、HCFO-1122a、HFC-143、メタン、HFC-152a、HCFC-142、HCFC-142b、HCFC-133、HCFC-133b、HCFC-123a、CFC-113、およびCFO-1112等が挙げられる。
含有されているHFO-1123以外の上記化合物のそれぞれの含有割合は、HFO-1123と当該化合物との合計量に対して0.5質量%未満であることが好ましい。また、この組成物に含有されるHFO-1123以外の上記化合物全量の含有割合は、HFO-1123とこれら化合物全量との合計量に対して0.5質量%未満であることが好ましい。さらに、これら化合物全量の含有量の下限は、0.0001質量%であることが好ましい。
R22とR31を含む原料組成物を用い、熱媒体の存在下で熱分解を伴う合成反応により、HFO-1123を製造する。
この製造方法は、
(a)R22の1モルに対してR31を0.01~4.0モルの割合で予め混合し、または別々に反応器に供給し、該反応器内に所定の時間滞留させる工程と、
(b)熱媒体を反応器に供給し、この反応器内で、前記(a)工程で反応器に供給されて所定の時間滞留する原料組成物と前記熱媒体とを接触させる工程とを有する。
この製造方法は、製造効率の点で連続式の方法であるのが好ましい。以下、このようなHFO-1123の製造を、連続式の製造に適用する態様について説明する。
前記反応によるHFO-1123の製造に用いられる原料組成物は、R22とR31を含む。
原料組成物におけるR22とR31の割合は、R22の1モルに対してR31が0.01~4.0モルの範囲である。すなわち、反応器に供給するR22の供給量に対するR31の供給量のモル比(R22の供給モル量、R31の供給モル量をそれぞれR31、R22で表した場合のR31/R22)は、0.01~4.0である。なお、原料組成物および熱媒体を、反応器内を連続的に流通させて反応を行わせる本態様において、原料各成分および熱媒体の供給量は、単位時間当たりの供給量を示すものとする。
より反応性を高めるという観点からは、R22、またはR22を含むF2C:を発生しうる含フッ素化合物を、反応器に導入する前に常温(25℃)以上600℃以下に加熱することが好ましく、100~500℃に加熱することがより好ましい。
また、反応器に供給するR31の温度は、反応性の観点から0~1200℃とするのが好ましい。より反応性を高めるという観点からは、R31を反応器に導入する前に常温以上1200℃以下に加熱することが好ましく、100~800℃に加熱することがより好ましい。
本態様における熱媒体は、前記原料組成物と反応器内で一定の時間接触するように、反応器に供給される。熱媒体は、反応器内の温度で熱分解が生じない媒体であり、具体的には、100~1200℃の温度で熱分解しない媒体であるのが好ましい。熱媒体としては、水蒸気、窒素、二酸化炭素から選ばれる1種または2種以上の気体が挙げられる。水蒸気を50体積%以上含み、残部が窒素および/または二酸化炭素である気体の使用が好ましい。上記式(2)の反応で生成するHClを塩酸にして除くため、熱媒体における水蒸気の含有割合は50体積%以上が好ましく、実質的に水蒸気のみ(100体積%)からなる気体の使用が特に好ましい。
反応器としては、後述する反応器内温度および圧力に耐えるものであれば、特に形状は限定されず、例えば円筒状の縦型反応器が挙げられる。反応器の材質としては、ガラス、鉄、ニッケル、または鉄、ニッケルを主成分とする合金等が挙げられる。
このようなR22とR31との熱分解を伴う合成においては、HFO-1123を含む組成物を上記反応器の出口ガスとして得ることができる。出口ガスが含有するHFO-1123以外の化合物としては、未反応原料であるR22およびR31に加えて、HFO-1132、HFO-1132a、HFO-1141、CFO-1113、HCFO-1122、HCFO-1122a、HFC-143、FO-1114、HCFO-1131、HFO-1252zf、HFO-1243zf、HFO-1234yf、HFO-1234ze、FO-1216、HFC-125、HFC-134、HFC-134a、HFC-143a、HCFC-124、HCFC-124a、HFC-227ca、HFC-227ea、HFC-236fa、HFC-236ea、CFC-12、HFC-23、HFC-32、HFC-41、クロロメタン、RC-318およびメタン等が挙げられる。
含有されているHFO-1123以外の上記化合物のそれぞれの含有割合は、HFO-1123と当該化合物との合計量に対して0.5質量%未満であることが好ましい。また、この組成物に含有されるHFO-1123以外の上記化合物全量の含有割合は、HFO-1123とこれら化合物全量との合計量に対して0.5質量%未満であることが好ましい。さらに、これら化合物全量の含有量の下限は、0.0001質量%であることが好ましい。
内径2.3cm、長さ50cmのステンレス製の反応管に、ヤシ殻活性炭の100質量部に対して0.5質量部のパラジウムを担持させたパラジウム担持活性炭を充填して、高さ40cmの触媒層を形成した。触媒層におけるパラジウム担持活性炭の充填密度は、0.74g/cm3であった。
反応中の触媒層の最高温度は、位置を移動させながら触媒層に挿入した挿し込み型の温度計により測定した。触媒層の最高温度は、236℃であった。
なお、反応器の出口より取り出された出口ガスには、反応により生成または副生したガスの他に、未反応の原料ガスも含まれるが、以下の記載では出口ガスを生成ガスということもある。
なお、前記したように、CTFEの転化率は、反応したCTFEの割合(モル%)を意味し、出口ガス中のCTFEの占める割合(収率)がX%であるとき、(100-X)%をCTFEの転化率という。
また、還流比を21.0で運転し、塔頂から低沸点成分が濃縮した留分を916.8g/hの速度で留出(留出液1)し、塔内温度が9.0℃の部分、すなわち塔頂から14段目から純度の高いHFO-1123を3705.1g/hの速度で留出させ(留出液2)、さらに塔底から4214.9g/hの速度となるよう留出(缶出液)させる。各留出液および缶出液の組成、塔頂温度、14段目の温度、塔底温度を表4に示す。
R22とR31とからなる原料ガスから、以下に示すようにして粗HFO-1123を得た。
また、還流比を10.0で運転し、蒸留塔1の塔頂から低沸点成分が濃縮した留分を2987g/hの速度で留出(留出液1)し、さらに塔底からHFO-1123を含む成分を4546g/hの速度となるよう留出(缶出液1)させる。
次に、蒸留塔1の塔底から回収した缶出液を段数50段の蒸留塔(蒸留塔2)の塔頂から48段目に4546g/hの速度となるよう供給し、運転圧力1.0MPa(ゲージ圧)、塔頂温度9.2℃、塔底温度45.7℃で連続的に蒸留を行う。このとき、還流液は蒸留塔の最上段に供給する。
また、還流比を50.0で運転し、蒸留塔2の塔頂から高純度化されたHFO-1123を186g/hの速度で留出させ、(留出液2)、さらに塔頂から46段目から留分を854.4g/hの速度で留出させ(留出液3)、塔底から3505.3g/hで缶出液(缶出液2)を回収する。
各留出液および缶出液の組成、塔頂温度、46段目の温度、塔底温度を表7と表8に示す。
なお、2013年4月30日に出願された日本特許出願2013-095491号の明細書、特許請求の範囲、図面および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (15)
- トリフルオロエチレンと、
E-1,2-ジフルオロエチレン、Z-1,2-ジフルオロエチレン、1,1-ジフルオロエチレン、クロロトリフルオロエチレン、1-クロロ-2,2-ジフルオロエチレン、E-1-クロロ-1,2-ジフルオロエチレン、Z-1-クロロ-1,2-ジフルオロエチレン、1,1,2-トリフルオロエタンおよびメタンからなる群から選択される少なくとも1つの第1の化合物と
を含むことを特徴とする組成物。 - 前記組成物に含有される個々の第1の化合物の含有割合が、トリフルオロエチレンと当該第1の化合物との合計量に対して0.5質量%未満である、請求項1に記載の組成物。
- 前記組成物に含有される第1の化合物の全量の含有割合が、トリフルオロエチレンと前記第1の化合物の合計量に対して0.5質量%未満である、請求項1または2に記載の組成物。
- さらに、1,1-ジフルオロエタン、2-クロロ-1,1-ジフルオロエタン、1-クロロ-1,1-ジフルオロエタン、1-クロロ-1,2,2-トリフルオロエタン、1-クロロ-1,1,2-トリフルオロエタン、1,2-ジクロロ-1,1,2-トリフルオロエタン、1,1,2-トリクロロ-1,2,2-トリフルオロエタン、E-1,2-ジクロロ-1,2-ジフルオロエチレンおよびZ-1,2-ジクロロ-1,2-ジフルオロエチレンからなる群から選択される少なくとも1つの第2の化合物を含む、請求項1に記載の組成物。
- 前記組成物に含有される個々の第2の化合物の含有割合が、トリフルオロエチレンと当該第2の化合物との合計量に対して0.5質量%未満である、請求項4に記載の組成物。
- 前記組成物に含有される第2の化合物の全量の含有割合が、トリフルオロエチレンと前記第2の化合物の合計量に対して0.5質量%未満である、請求項4または5に記載の組成物。
- さらに、テトラフルオロエチレン、E-1-クロロ-2-フルオロエチレン、Z-1-クロロ-2-フルオロエチレン、フルオロエチレン、3,3-ジフルオロプロペン、3,3,3-トリフルオロプロペン、2,3,3,3-テトラフルオロプロペン、E-1,3,3,3-テトラフルオロプロペン、Z-1,3,3,3-テトラフルオロプロペン、ヘキサフルオロプロペン、ペンタフルオロエタン、1,1,2,2-テトラフルオロエタン、1,1,1,2-テトラフルオロエタン、1,1,1-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、1-クロロ-1,1,2,2-テトラフルオロエタン、1,1,1,2,2,3,3-ヘプタフルオロプロパン、1,1,1,2,3,3,3-ヘプタフルオロプロパン、1,1,1,3,3,3-ヘキサフルオロプロパン、1,1,1,2,3,3-ヘキサフルオロプロパン、ジクロロジフルオロメタン、クロロジフルオロメタン、クロロフルオロメタンン、ジフルオロメタン、トリフルオロメタン、フルオロメタン、クロロメタンおよびパーフルオロシクロブタンからなる群から選択される少なくとも1つの第3の化合物を含む、請求項1に記載の組成物。
- 前記組成物に含有される個々の第3の化合物の含有割合が、トリフルオロエチレンと当該第3の化合物との合計量に対して0.5質量%未満である、請求項7に記載の組成物。
- 前記組成物に含有される第3の化合物の全量の含有割合が、トリフルオロエチレンと前記第3の化合物の合計量に対して0.5質量%未満である、請求項7または8に記載の組成物。
- クロロトリフルオロエチレンの気相水素還元反応によりトリフルオロエチレンを製造する方法において、パラジウム触媒存在下にクロロトリフルオロエチレンと水素とを80℃以上で反応させ、得られた反応生成物を蒸留して、E-1,2-ジフルオロエチレン、Z-1,2-ジフルオロエチレン、クロロトリフルオロエチレン、1-クロロ-2,2-ジフルオロエチレンおよび1,1-ジフルオロエチレンからなる群から選択される少なくとも1つの化合物を含むトリフルオロエチレンを得ることを特徴とするトリフルオロエチレンを含む組成物の製造方法。
- トリフルオロエチレン、E-1,2-ジフルオロエチレン、Z-1,2-ジフルオロエチレンおよび1,1-ジフルオロエチレンの合計量に対する、前記組成物に含有される、E-1,2-ジフルオロエチレン、Z-1,2-ジフルオロエチレン、クロロトリフルオロエチレン、1-クロロ-2,2-ジフルオロエチレンおよび1,1-ジフルオロエチレンのいずれの化合物の割合も0.5質量%未満である、請求項10に記載の製造方法。
- トリフルオロエチレン、E-1,2-ジフルオロエチレン、Z-1,2-ジフルオロエチレンおよび1,1-ジフルオロエチレンの合計量に対する、E-1,2-ジフルオロエチレン、Z-1,2-ジフルオロエチレン、クロロトリフルオロエチレン、1-クロロ-2,2-ジフルオロエチレンおよび1,1-ジフルオロエチレンの合計量の割合が0.5質量%未満である、請求項10または11に記載の製造方法。
- クロロジフルオロメタンとクロロフルオロメタンの混合物から、熱媒体の存在下における熱分解を伴う合成反応によりトリフルオロエチレンを製造する方法において、400~1200℃で反応させ、得られた反応生成物を蒸留して、E-1,2-ジフルオロエチレン、Z-1,2-ジフルオロエチレン、1,1-ジフルオロエチレン、クロロトリフルオロエチレン、テトラフルオロエチレン、フルオロエチレン、1,1,1-トリフルオロエタン、ジフルオロメタン、トリフルオロメタンおよびペンタフルオロエタンからなる群から選択される少なくとも1つの化合物を含むトリフルオロエチレンを得ることを特徴とするトリフルオロエチレンを含む組成物の製造方法。
- トリフルオロエチレン、E-1,2-ジフルオロエチレン、1,1-ジフルオロエチレン、テトラフルオロエチレン、フルオロエチレン、1,1,1-トリフルオロエタン、ジフルオロメタン、トリフルオロメタンおよびペンタフルオロエタンの合計量に対する、前記組成物に含有される、E-1,2-ジフルオロエチレン、Z-1,2-ジフルオロエチレン、1,1-ジフルオロエチレン、クロロトリフルオロエチレン、テトラフルオロエチレン、フルオロエチレン、1,1,1-トリフルオロエタン、ジフルオロメタン、トリフルオロメタンおよびペンタフルオロエタンのいずれの化合物の割合も0.5質量%未満である、請求項13に記載の製造方法。
- トリフルオロエチレン、E-1,2-ジフルオロエチレン、1,1-ジフルオロエチレン、テトラフルオロエチレン、フルオロエチレン、1,1,1-トリフルオロエタン、ジフルオロメタン、トリフルオロメタンおよびペンタフルオロエタンの合計量に対する、E-1,2-ジフルオロエチレン、1,1-ジフルオロエチレン、テトラフルオロエチレン、フルオロエチレン、1,1,1-トリフルオロエタン、ジフルオロメタン、トリフルオロメタンおよびペンタフルオロエタンの合計量の割合が0.5質量%未満である、請求項13または14に記載の製造方法。
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Also Published As
Publication number | Publication date |
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EP2993213B1 (en) | 2020-07-15 |
RU2015151178A3 (ja) | 2018-03-30 |
JPWO2014178352A1 (ja) | 2017-02-23 |
US20160002518A1 (en) | 2016-01-07 |
BR112015025238A2 (pt) | 2017-07-18 |
JP6379391B2 (ja) | 2018-08-29 |
CN105164227A (zh) | 2015-12-16 |
RU2669280C2 (ru) | 2018-10-09 |
RU2015151178A (ru) | 2017-06-05 |
CN115160988A (zh) | 2022-10-11 |
EP2993213A1 (en) | 2016-03-09 |
US10081749B2 (en) | 2018-09-25 |
CN115160988B (zh) | 2024-05-14 |
EP2993213A4 (en) | 2016-12-28 |
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