JP2005255514A - Method of manufacturing iodide - Google Patents
Method of manufacturing iodide Download PDFInfo
- Publication number
- JP2005255514A JP2005255514A JP2005021631A JP2005021631A JP2005255514A JP 2005255514 A JP2005255514 A JP 2005255514A JP 2005021631 A JP2005021631 A JP 2005021631A JP 2005021631 A JP2005021631 A JP 2005021631A JP 2005255514 A JP2005255514 A JP 2005255514A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- iodide
- gas
- reaction
- iodine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 102
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims abstract description 89
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 88
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 78
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims description 87
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 75
- 239000011630 iodine Substances 0.000 claims description 75
- 229910052740 iodine Inorganic materials 0.000 claims description 75
- 238000000034 method Methods 0.000 claims description 41
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 229910052697 platinum Inorganic materials 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 229910052703 rhodium Inorganic materials 0.000 claims description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052878 cordierite Inorganic materials 0.000 claims description 8
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000002407 reforming Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 238000000629 steam reforming Methods 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 47
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract description 8
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 33
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 23
- 229910002091 carbon monoxide Inorganic materials 0.000 description 22
- 239000002994 raw material Substances 0.000 description 20
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000035484 reaction time Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- -1 iodo compound Chemical class 0.000 description 11
- 239000010948 rhodium Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 150000004694 iodide salts Chemical class 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000012494 Quartz wool Substances 0.000 description 4
- 229940071870 hydroiodic acid Drugs 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001351 alkyl iodides Chemical class 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 1
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 229910017771 LaFeO Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- KBUATVUEKKJORO-UHFFFAOYSA-N [N+](=O)([O-])N([Rh]N)[N+](=O)[O-] Chemical compound [N+](=O)([O-])N([Rh]N)[N+](=O)[O-] KBUATVUEKKJORO-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
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- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012022 methylating agents Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 150000002826 nitrites Chemical class 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
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- BALRIWPTGHDDFF-UHFFFAOYSA-N rhodium Chemical compound [Rh].[Rh] BALRIWPTGHDDFF-UHFFFAOYSA-N 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
本発明は、酸化物や活性炭に白金族元素を担持した触媒を用いて、気相法によってヨウ化水素やヨウ化メチルなどのヨウ化物を製造する方法に関する。 The present invention relates to a method for producing an iodide such as hydrogen iodide or methyl iodide by a gas phase method using a catalyst in which a platinum group element is supported on an oxide or activated carbon.
ヨウ化水素は、医薬中間体やメチル化剤であるヨウ化メチルなどの原料として重要な商品である。現在、ヨウ素と水とを懸濁冷却させながら赤リンを加え、これを蒸留および精製して製造している。また、水に懸濁させたヨウ素を硫化水素で還元させる方法によっても製造することができる。また、ヨウ化メチルは、メチルアルコールにヨウ素と赤リンを作用させることで製造することもでき、ガス状水素とヨウ素からヨウ化水素を製造する方法が種々提案されている。例えば、ヨウ素を飽和した水素気流を１００℃に加熱した白金上を通す方法がある（非特許文献１）。 Hydrogen iodide is an important product as a raw material for pharmaceutical intermediates and methyl iodide, which is a methylating agent. Currently, red phosphorus is added while suspending and cooling iodine and water, and this is distilled and purified. It can also be produced by a method in which iodine suspended in water is reduced with hydrogen sulfide. Methyl iodide can also be produced by allowing iodine and red phosphorus to act on methyl alcohol, and various methods for producing hydrogen iodide from gaseous hydrogen and iodine have been proposed. For example, there is a method of passing a hydrogen stream saturated with iodine over platinum heated to 100 ° C. (Non-patent Document 1).
このようなヨウ化水素やヨウ化メチルなどのヨウ化物の製造方法として、天然ガスの主成分であるメタンとヨウ素とから、ヨウ化水素酸もしくはその誘導体を製造する方法が開示されている（特許文献１）。しかしながら、該方法は触媒を使用しないため反応温度が９５０℃以上と極めて高く、反応域の空間速度が３８５ｈｒ−１以下であって低く、生産性が低い。 As a method for producing such iodides such as hydrogen iodide and methyl iodide, a method for producing hydroiodic acid or a derivative thereof from methane and iodine, which are main components of natural gas, is disclosed (patent) Reference 1). However, since this method does not use a catalyst, the reaction temperature is extremely high at 950 ° C. or higher, the space velocity in the reaction zone is 385 hr −1 or less, and the productivity is low.
一方、飽和炭化水素またはそのハロゲン化合物を溶媒として、ロジウム、ルテニウム、パラジウム、白金黒等の白金族元素触媒の存在下に、ヨウ素と水素を５０〜２００℃で直接反応させてヨウ化水素を製造する方法が開示されている（特許文献２）。該方法は溶媒を使用しており、液相法によるヨウ化水素の製造方法である。 On the other hand, iodine is produced by reacting iodine and hydrogen directly at 50 to 200 ° C. in the presence of a platinum group element catalyst such as rhodium, ruthenium, palladium, or platinum black using a saturated hydrocarbon or a halogen compound thereof as a solvent. Is disclosed (Patent Document 2). This method uses a solvent and is a method for producing hydrogen iodide by a liquid phase method.
このような液相法による合成として、金属成分がロジウムあるいはイリジウムである金属性触媒との接触状態で約７５〜２００℃の反応温度、約２５〜５００ｐｓｉｇの反応圧力、約５〜３００ｐｓｉｇの一酸化炭素分圧で強酸含有反応媒体中でヨウ素を水ならびに一酸化炭素と反応させてヨウ化水素を製造する方法も開示されている（特許文献３）。上記の温度と圧力に保たれた固定床反応器中でアランダム、活性炭、粘土、アルミナ、シリカ−アルミナその他の不活性支持担体物質上に沈着させたロジウムあるいはイリジウム触媒を用いている。なお、全反応物を気相で行うには、ＨＩ、ＨＢｒ、ＨＣｌ、Ｈ２ＳＯ４、ＨＮＯ３などの強酸の強酸反応媒体が必要である。 As a synthesis by such a liquid phase method, the reaction temperature is about 75 to 200 ° C., the reaction pressure is about 25 to 500 psig, and the monoxide is about 5 to 300 psig in contact with a metallic catalyst whose metal component is rhodium or iridium. A method for producing hydrogen iodide by reacting iodine with water and carbon monoxide in a strong acid-containing reaction medium at a carbon partial pressure is also disclosed (Patent Document 3). A rhodium or iridium catalyst deposited on an inert support carrier material such as alundum, activated carbon, clay, alumina, silica-alumina or the like in a fixed bed reactor maintained at the above temperature and pressure is used. In order to carry out all the reactants in the gas phase, a strong acid reaction medium of strong acid such as HI, HBr, HCl, H 2 SO 4 , HNO 3 is required.
更に液相法によるヨウ化アルキルの製造方法として、触媒として不活性物質に坦持させた金属ロジウム、ルテニウム、イリジウムから選ばれた元素またはこれらの元素のヨード化合物の存在下、炭素数１〜６のアルカノールと水素とヨウ素とから、反応温度７０〜１２５℃でヨウ化アルキルを製造させる方法も開示されている（特許文献４）。また、液相法によるヨウ化水素の製造方法として、触媒として不活性物に坦持させた金属ロジウムとルテニウムまたはこれらの元素のヨード化合物の存在下、水を反応媒体とし水素とヨウ素とから、反応温度７０〜１２５℃でヨウ化水素を製造させる方法も開示されている（特許文献５）。なお、水素源には、窒素、一酸化炭素、二酸化炭素、低級炭化水素などの水素以外の成分を含むことが可能であると記載されている。
ヨウ化水素やヨウ化メチルは、医療用原料などとして多用される化合物であり、簡単な工程、安価な原料で収率高く製造されることが望まれる。しかしながら、非特許文献１記載の方法では生産性が低い。また、特許文献２記載の方法では、飽和炭化水素またはそのハロゲン化合物を溶媒を使うため、工程が複雑である。また、特許文献３、４は液相法によるヨウ化水素やヨウ化アルキル製造方法であるが、気相法で合成できればその後の目的物の処理が容易である。しかしながら、気相法による効率的なヨウ化物の製造方法は存在しない。 Hydrogen iodide and methyl iodide are compounds that are frequently used as medical raw materials and the like, and it is desired that they be produced with a simple process and inexpensive raw materials with a high yield. However, the method described in Non-Patent Document 1 has low productivity. Further, in the method described in Patent Document 2, a saturated hydrocarbon or its halogen compound is used as a solvent, so that the process is complicated. Patent Documents 3 and 4 are methods for producing hydrogen iodide or alkyl iodide by a liquid phase method, but if they can be synthesized by a gas phase method, the subsequent treatment of the target product is easy. However, there is no efficient method for producing iodide by the vapor phase method.
そこで、本発明は、効率よくヨウ化水素やヨウ化メチルなどのヨウ化物を製造する方法を提供することを目的とする。 Then, an object of this invention is to provide the method of manufacturing iodides, such as hydrogen iodide and methyl iodide, efficiently.
また、水素源として他の成分が含まれる場合であっても、長期に亘り安定してヨウ化物を製造し得る、ヨウ化物の製造方法を提供することを目的とする。 Moreover, even if it is a case where another component is contained as a hydrogen source, it aims at providing the manufacturing method of the iodide which can manufacture an iodide stably over a long period of time.
本願発明者等は、ヨウ化物の製造方法について詳細に検討した結果、酸化物および／または活性炭に白金族元素を坦持してなる触媒の存在下に、気相法でヨウ素と、水素および／またはメタンを反応させると、ヨウ素転化率を向上させ、その結果効率よくヨウ化水素やヨウ化メチルなどのヨウ化物を製造できることを見出し、本発明を完成させた。 The inventors of the present invention have studied in detail the method for producing iodide, and as a result, in the presence of a catalyst in which a platinum group element is supported on oxide and / or activated carbon, iodine, hydrogen and / or Alternatively, when methane was reacted, the iodine conversion was improved, and as a result, it was found that iodides such as hydrogen iodide and methyl iodide could be produced efficiently, and the present invention was completed.
しかも、原料の水素として、メタンやメタノールからの改質ガスを使用することができる。これらはガス状で入手できるため特に気相反応に好適に使用することができる。このため、ヨウ化水素やヨウ化メチルの需要拡大に伴い、安価に入手できる原料を用いて簡便に大量のヨウ化水素やヨウ化メチルを生産することができる。 Moreover, reformed gas from methane or methanol can be used as the raw material hydrogen. Since these can be obtained in a gaseous state, they can be suitably used particularly for a gas phase reaction. For this reason, with the expansion of demand for hydrogen iodide and methyl iodide, a large amount of hydrogen iodide and methyl iodide can be easily produced using raw materials that can be obtained at low cost.
本願発明によれば、気相法で反応させるため、低温かつ高空間速度で生産性高くヨウ化物を製造することができる。 According to the present invention, since the reaction is carried out by the gas phase method, iodide can be produced with high productivity at low temperature and high space velocity.
本発明では、炭化水素などの改質反応によって得られる改質ガスに含まれる水素を利用することができ、安価な水素源を利用することでヨウ化水素および／またはヨウ化メチルを安価に製造することができる。 In the present invention, hydrogen contained in a reformed gas obtained by a reforming reaction such as hydrocarbon can be used, and hydrogen iodide and / or methyl iodide can be produced at low cost by using an inexpensive hydrogen source. can do.
本発明のヨウ化物の製造方法によれば、不純物を含む水素源を使用しても、長期に亘り安定してヨウ化物を製造することができる。 According to the method for producing iodide of the present invention, iodide can be produced stably over a long period of time even when a hydrogen source containing impurities is used.
本発明は、ヨウ素と、分子状水素含有ガスおよび／またはメタンとを、白金族元素の一種以上の元素を酸化物および／または活性炭に分散担持させた触媒の存在下に気相反応させることを特徴とするヨウ化物の製造方法である。 In the present invention, iodine, a molecular hydrogen-containing gas and / or methane are subjected to a gas phase reaction in the presence of a catalyst in which one or more elements of a platinum group element are dispersed and supported on an oxide and / or activated carbon. This is a method for producing iodide.
従来から、水素とヨウ素とを触媒存在下に気相法で効率的にヨウ化物を製造する例は存在しない。触媒を使用した場合であっても触媒活性が低下く、このため生産性が向上しないと考えられる。しかしながら、本発明では特定の触媒を使用することで気相法によってヨウ化物を製造することができ、転化率の向上に加えてヨウ化水素やヨウ化メチルなどのヨウ化物の回収が容易となり、極めて収率および操作性高くヨウ化物を製造することができる。 Conventionally, there is no example of efficiently producing iodide by a gas phase method in the presence of a catalyst of hydrogen and iodine. Even when a catalyst is used, the catalytic activity is lowered, and it is considered that productivity is not improved. However, in the present invention, iodide can be produced by a vapor phase method using a specific catalyst, and in addition to improving the conversion rate, it is easy to recover iodides such as hydrogen iodide and methyl iodide. Iodide can be produced with extremely high yield and operability.
すなわち、本願発明では白金族元素を酸化物および／または活性炭に分散坦持させることを要件とするが、白金族元素を酸化物および／または活性炭などの担体に坦持させずに単体で使用すると、ヨウ素の転化率が向上せずその結果ヨウ化水素などのヨウ化物の収率が低くなる。また、酸化物や活性炭に代えて金属担体に白金族元素を坦持させると、担体基材がヨウ化水素などのヨウ化物で腐食されるため、長期にわたる製造に適しない。本発明では、白金族元素を酸化物および／または活性炭の表面に分散坦持させることでヨウ素と水素とを活性化させることができ、この結果、比較的低い反応温度でもヨウ化水素の生成速度を向上させることができる。また、本願発明はガス状水素および／またはメタンまたは水素含有ガスとガス状ヨウ素とから、触媒を固定床とした気相法で反応を行うことにより、生産性よく、触媒寿命が長く、ヨウ化水素および／またはヨウ化メチルの回収が容易なヨウ化水素および／またはヨウ化メチルを製造する方法を提供するものである。 That is, in the present invention, the platinum group element is required to be dispersed and supported on the oxide and / or activated carbon, but when the platinum group element is used alone without being supported on a support such as oxide and / or activated carbon. Therefore, the conversion rate of iodine is not improved, and as a result, the yield of iodide such as hydrogen iodide is lowered. In addition, when a platinum group element is supported on a metal support instead of oxide or activated carbon, the support base material is corroded with an iodide such as hydrogen iodide, which is not suitable for long-term production. In the present invention, iodine and hydrogen can be activated by dispersing and supporting platinum group elements on the surface of oxide and / or activated carbon. As a result, the production rate of hydrogen iodide can be achieved even at a relatively low reaction temperature. Can be improved. In addition, the invention of the present application is carried out by reacting gaseous hydrogen and / or methane or hydrogen-containing gas and gaseous iodine by a gas phase method using a catalyst as a fixed bed. The present invention provides a method for producing hydrogen iodide and / or methyl iodide, in which hydrogen and / or methyl iodide can be easily recovered.
本発明における白金族元素とは、白金、パラジウム、ロジウム、オスミウム、ルテニウム及びイリジウムからなる群より選ばれる少なくとも一種の元素である。これらの中でも、白金、パラジウム、ロジウムまたはルテニウムを使用することが好ましい。転化率に優れるからである。これらの元素を含有する化合物としては、上記白金族元素の硝酸塩、硫酸塩、アンモニウム塩、アミン、炭酸塩、重炭酸塩、ハロゲン塩、亜硝酸塩、蓚酸などの無機塩類、ギ酸塩などのカルボン酸塩および水酸化物、アルコキサイド、酸化物などが例示でき、これらを溶解する溶媒の種類やｐＨなどによって適宜選択することができる。これらの中でも、工業的に使用するにあっては硝酸塩、炭酸塩、酸化物、水酸化物などが好ましい。 The platinum group element in the present invention is at least one element selected from the group consisting of platinum, palladium, rhodium, osmium, ruthenium and iridium. Among these, it is preferable to use platinum, palladium, rhodium or ruthenium. This is because the conversion rate is excellent. Compounds containing these elements include nitrates, sulfates, ammonium salts, amines, carbonates, bicarbonates, halogen salts, nitrites, oxalic acid, and other inorganic salts, and carboxylic acids such as formate. Examples thereof include salts and hydroxides, alkoxides, oxides, and the like, which can be appropriately selected depending on the type of solvent in which these are dissolved, pH, and the like. Among these, nitrates, carbonates, oxides, hydroxides and the like are preferable for industrial use.
より具体的には、白金の場合は塩化白金、塩化白金酸、ヘキサクロロ白金酸、ジクロロアンミン白金、トリクロロアンミン白金塩、ヘキサアンミン白金塩、白金黒などが使用される。また、パラジウムの場合には塩化パラジウム、酢酸パラジウム、硝酸パラジウム、バラジウムアセチルアセトナート、バラジウム黒などが使用される。ロジウムの場合には酢酸ロジウム、硝酸ロジウム、塩化ロジウム、ジニトロジアミノロジウム、ロジウムアセチルアセトナートなどが使用される。また、ルテニウムの場合は、塩化ルテニウム水和物、ルテニウムアセチルアセトナート、ルテニウムブロマイド等が使用される。 More specifically, in the case of platinum, platinum chloride, chloroplatinic acid, hexachloroplatinic acid, dichloroammineplatinum, trichloroammineplatinum salt, hexaammineplatinum salt, platinum black and the like are used. In the case of palladium, palladium chloride, palladium acetate, palladium nitrate, baradium acetylacetonate, baradium black and the like are used. In the case of rhodium, rhodium acetate, rhodium nitrate, rhodium chloride, dinitrodiamino rhodium, rhodium acetylacetonate and the like are used. In the case of ruthenium, ruthenium chloride hydrate, ruthenium acetylacetonate, ruthenium bromide and the like are used.
酸化物としては、酸化チタン、ジルコニア、酸化亜鉛、酸化クロム、酸化セリウムなどの遷移金属酸化物、酸化マグネシウムなどのアルカリ土類金属の酸化物、シリカ、アルミナ、その他コージライト、ゼオライト、シリカアルミナ、コランダム、ムライト、リチウムアルミニウムシリケート、アルミニウムシリケート、ヘキサアルミネート、チタニヤシリカ、メソポーラスマテリアル、酸化物層状化合物、ペロブスカイト型酸化物、スピネル型酸化物、逆スピネル型酸化物等の複合酸化物が好ましい。 Examples of oxides include transition metal oxides such as titanium oxide, zirconia, zinc oxide, chromium oxide and cerium oxide, oxides of alkaline earth metals such as magnesium oxide, silica, alumina, other cordierite, zeolite, silica alumina, Complex oxides such as corundum, mullite, lithium aluminum silicate, aluminum silicate, hexaaluminate, titania silica, mesoporous material, oxide layered compound, perovskite oxide, spinel oxide, and reverse spinel oxide are preferred.
ゼオライトには、ＺＳＭ−５、Ａ型、Ｙ型、Ｘ型、モルデナイト、β型、シリカライトなどのマイクロポーラスマテリアル、アルミノシリケート型の結晶性マイクロポーラスマテリアルがあり、メソポーラスマテリアルにはＭＣＭ−４１、ＦＳＭ−１６等がある。また、酸化物層状化合物としてはモンモリロナイト、ハイドロタルサイト、アパタイト、セピオライト、雲母などがある。ペロブスカイト型酸化物としては、ＬａＦｅＯ３，ＢａＴｉＯ３、Ｌａ１−ｘＳｒｘＣｏＯ３等があり、スピネル型酸化物としては、ＭｇＡｌ２Ｏ４、ＺｎＡｌ２Ｏ４等がある。また、逆スピネル型酸化物には、Ｆｅ（ＭｇＦｅ）Ｏ４などがある。本発明では、上記酸化物その中でも特に酸化マグネシウム、酸化チタン、シリカ、アルミナ、コージライト、ジルコニヤ、シリカアルミナ、またはゼオライトであることが好ましい。 Zeolite includes ZSM-5, A type, Y type, X type, mordenite, β type, silicalite and other microporous materials, aluminosilicate type crystalline microporous materials, and mesoporous materials include MCM-41, FSM-16 etc. Examples of the oxide layered compound include montmorillonite, hydrotalcite, apatite, sepiolite, and mica. Examples of perovskite oxides include LaFeO 3 , BaTiO 3 , and La 1 -xSrxCoO 3. Examples of spinel oxides include MgAl 2 O 4 and ZnAl 2 O 4 . In addition, examples of the reverse spinel oxide include Fe (MgFe) O 4 . In the present invention, among these oxides, magnesium oxide, titanium oxide, silica, alumina, cordierite, zirconia, silica alumina, or zeolite is particularly preferable.
また、活性炭としては、木片、木粉、ヤシ殻、クルミ殻などを原料として活性化した植物系活性炭、泥炭、石炭コークス、タール等を原料として活性化した鉱物系活性炭、その他再生繊維、レーヨンなどの天然素材やフェノール樹脂、アクリル樹脂などの合成素材を原料として活性化した活性炭がある。一般には、ＢＥＴ比表面積が３００〜１０，０００ｍ２／ｇ、好ましくは５００〜３，０００ｍ２／ｇである。ＢＥＴ比表面積が３００ｍ２／ｇを下回ると活性炭上の白金族元素の分散性が悪くなり、粒子径が大きくなり活性が低くなり好ましくない。一方、ＢＥＴ比表面積が１０，０００ｍ２／ｇを上回るとサブミクロンの細孔が多くなり、白金族元素の分散性が高くなりすぎ超高分散となり、反応初期は活性が高いが反応時間とともに元素の凝集が起こり活性の低下を招き好ましくない。 In addition, as activated carbon, plant activated carbon activated using wood chips, wood flour, coconut husk, walnut shell, etc., mineral activated carbon activated using peat, coal coke, tar, etc. as raw materials, other regenerated fibers, rayon, etc. Activated carbon made from synthetic materials such as natural materials, phenolic resins and acrylic resins. Generally, the BET specific surface area is 300 to 10,000 m 2 / g, preferably 500 to 3,000 m 2 / g. When the BET specific surface area is less than 300 m 2 / g, the dispersibility of the platinum group element on the activated carbon is deteriorated, the particle size is increased, and the activity is lowered, which is not preferable. On the other hand, when the BET specific surface area exceeds 10,000 m 2 / g, the number of submicron pores increases, the dispersibility of the platinum group element becomes too high, and the dispersion becomes extremely high. Aggregation occurs and the activity is lowered, which is not preferable.
上記酸化物や活性炭は白金族元素の担体として使用され、担体として酸化物や活性炭を単独で使用しても両者を併用してもよい。これら担体は、粉体状態であってもよく、あらかじめリング状、球状、ハニカム状、円柱状、サドル状等に成型しておき、かかる成型体に白金族元素を坦持させてもよい。また、粉末状の担体に白金族元素を坦持させ、その後にリング状、球状、ハニカム状、円柱状、サドル状等に成型してもよい。また、上記酸化物の粉体に白金族元素を坦持させたものを、予めリング状、球状、ハニカム状、円柱状、サドル状等の形状に成型したコージライトを含む酸化物、ＳｉＣや窒化物等に坦持させて使用してもよい。ＳｉＣや窒化物等を使用すると熱伝導性、耐熱性に優れるからである。 The oxides and activated carbons are used as platinum group element carriers, and the oxides and activated carbons may be used alone or in combination. These carriers may be in a powder state, or may be previously formed into a ring shape, a spherical shape, a honeycomb shape, a cylindrical shape, a saddle shape, and the like, and a platinum group element may be supported on the formed body. Alternatively, a platinum group element may be supported on a powdery carrier, and then molded into a ring shape, a spherical shape, a honeycomb shape, a cylindrical shape, a saddle shape, or the like. In addition, oxides containing cordierite formed by supporting platinum group elements on the above oxide powder in a ring shape, spherical shape, honeycomb shape, cylindrical shape, saddle shape, SiC or nitriding It may be used by being carried on an object. This is because using SiC, nitride, or the like is excellent in thermal conductivity and heat resistance.
白金族元素は、酸化物および／または活性炭に分散担持されるが、この際の白金族元素の平均粒子径は、０．５〜２０，０００ｎｍ、より好ましくは１〜１０，０００ｎｍである。平均粒子径がこの範囲であれば転化率に優れ、白金族元素の単位質量当たりの触媒活性量を増大させることができる。なお、本発明において触媒金属の平均粒子径とは、ガス吸着法、粉末Ｘ線回折法、走査型電子顕微鏡、透過型電子顕微鏡等によって測定することができる。 The platinum group element is dispersed and supported on the oxide and / or activated carbon, and the average particle size of the platinum group element at this time is 0.5 to 20,000 nm, more preferably 1 to 10,000 nm. If the average particle diameter is within this range, the conversion rate is excellent, and the amount of catalytic activity per unit mass of the platinum group element can be increased. In the present invention, the average particle diameter of the catalyst metal can be measured by a gas adsorption method, a powder X-ray diffraction method, a scanning electron microscope, a transmission electron microscope, or the like.
本願発明における白金族元素の好ましい坦持量は酸化物および／または活性炭１リットル当たり、白金族元素の量は０．０５〜２０ｇ、より好ましくは０．５〜１０ｇである。この範囲で転化率が高く、かつ活性が安定する。 In the present invention, a preferable carrying amount of the platinum group element is 0.05 to 20 g, more preferably 0.5 to 10 g, per liter of oxide and / or activated carbon. Within this range, the conversion is high and the activity is stable.
本発明においては、白金族元素と共にＣｒ、Ｎｉ、Ｆｅ、Ｃｏ、Ｖ、Ｍｎ、Ｓｎ、Ｗ、Ｍｏを担体上に担持させてもよい。これによって触媒活性を更に向上させることができる。 In the present invention, Cr, Ni, Fe, Co, V, Mn, Sn, W, and Mo may be supported on the carrier together with the platinum group element. As a result, the catalytic activity can be further improved.
また、ヨウ素とメタンとを反応させる場合には、白金族元素と共に、アルカリ金属、アルカリ土類金属、稀土類元素の酸化物や塩化物を担体１Ｌ当たり０．０１〜１０ｇより好ましくは０．０２〜５ｇ加えることが好ましい。メタンを原料とする場合には炭素が析出しやすいが、上記元素を併用することで炭素の析出を防ぐことができる。特にこれらは酸化物や塩化物として使用すると、その効果が高い。 In the case of reacting iodine and methane, 0.01 to 10 g, more preferably 0.02 g of oxide or chloride of alkali metal, alkaline earth metal, or rare earth element together with platinum group element per 1 L of carrier. It is preferable to add ~ 5g. When methane is used as a raw material, carbon is likely to be precipitated, but carbon can be prevented from being precipitated by using the above elements in combination. These are particularly effective when used as oxides or chlorides.
ここで白金族元素を担体としての酸化物および／または活性炭へ坦持する方法としては、特別の調製方法を必要とせず従来公知の浸漬法や含侵法、イオン交換法、カルボニルなどの揮発性錯体の蒸着法などで坦持させることができる。白金族元素含有化合物としてヘキサクロロ白金（ＩＶ）酸（Ｈ２［ＰｔＣｌ６］・６Ｈ２Ｏ）を、担体としてアルミナを使用する場合で例示すると、ヘキサクロロ白金（ＩＶ）酸を塩酸酸性のイオン交換水に溶解させ、熱処理後の白金坦持量がアルミナ担体１Ｌ当たり例えば１ｇとなるように該溶液を量りとりアルミナに添加する。攪拌下にアルミナ担体に白金元素を担持させた後に、熱風空気気流中で水分を蒸発させ、充分に乾燥させる。次いで、空気、水素、あるいは窒素等のガス雰囲気下２００〜８００℃で１〜２４時間熱処理を行うと触媒を得ることができる。このような方法で白金族元素を酸化物および／または活性炭に高分散させるとヨウ素の転化率が向上し、従ってヨウ化水素および／またはヨウ化メチルなどのヨウ化物の収率が高くなる。 Here, as a method for supporting platinum group elements on oxides and / or activated carbons as a carrier, no special preparation method is required, and a conventionally known immersion method, impregnation method, ion exchange method, volatility such as carbonyl, etc. It can be supported by the vapor deposition method of the complex. For example, hexachloroplatinum (IV) acid (H 2 [PtCl 6 ] · 6H 2 O) is used as the platinum group element-containing compound and alumina is used as the carrier. The solution is weighed and added to alumina so that the amount of platinum supported after heat treatment is, for example, 1 g per liter of alumina support. After the platinum element is supported on the alumina carrier under stirring, moisture is evaporated in a hot air stream and dried sufficiently. Next, a catalyst can be obtained by performing heat treatment at 200 to 800 ° C. for 1 to 24 hours in a gas atmosphere such as air, hydrogen, or nitrogen. When the platinum group element is highly dispersed in the oxide and / or activated carbon by such a method, the conversion rate of iodine is improved, and thus the yield of iodide such as hydrogen iodide and / or methyl iodide is increased.
本発明のヨウ化物の製造方法によれば、ヨウ素と分子状水素含有ガスとを気相法で反応させることでヨウ化水素を製造することができる。または、ヨウ素とメタンとを気相法で反応させることでヨウ化メチルおよび／またはヨウ化水素を製造することができる。ヨウ素１モルとメタン２モルとを反応させると２モルのヨウ化メチルと１モルの水素とが生成するが、過剰のヨウ素が含まれる場合には副生する水素がヨウ素と反応し、生成したヨウ化メチルが分解するためヨウ化水素のみが製造される場合がある。したがって、本発明のヨウ化物の製造方法としては、上記原料を使用して、ヨウ化物としてヨウ化水素および／またはヨウ化メチルを製造することができる。 According to the method for producing iodide of the present invention, hydrogen iodide can be produced by reacting iodine with a molecular hydrogen-containing gas by a gas phase method. Alternatively, methyl iodide and / or hydrogen iodide can be produced by reacting iodine and methane by a gas phase method. When 1 mol of iodine and 2 mol of methane are reacted, 2 mol of methyl iodide and 1 mol of hydrogen are produced, but when excess iodine is contained, hydrogen produced as a by-product reacts with iodine and produced. Since methyl iodide decomposes, only hydrogen iodide may be produced. Therefore, as a method for producing iodide according to the present invention, hydrogen iodide and / or methyl iodide can be produced as iodide using the above raw materials.
本発明において、ヨウ素と分子状水素含有ガスとを反応させてヨウ化水素を製造する場合には、両者の混合比はヨウ素１モルに対して水素２０〜０．５モルであることが好ましく、より好ましくは１０〜１モルである。また、ヨウ素とメタンとを反応させてヨード化合物を製造する場合には、両者の混合比はヨウ素１モルに対してメタン２０〜１モルであることが好ましく、より好ましくは１０〜１モルである。なお、原料ガスには、ヨウ素、分子状水素含有ガス、メタンのほかに、窒素ガス、アルゴンガス、ヘリウムガスなどの不活性ガスが含まれていてもよい。 In the present invention, when hydrogen iodide is produced by reacting iodine with a molecular hydrogen-containing gas, the mixing ratio of the two is preferably 20 to 0.5 mol of hydrogen with respect to 1 mol of iodine. More preferably, it is 10-1 mol. Moreover, when iodine and methane are made to react and an iodo compound is manufactured, it is preferable that both mixing ratio is 20-1 mol of methane with respect to 1 mol of iodine, More preferably, it is 10-1 mol. . The source gas may contain an inert gas such as nitrogen gas, argon gas, helium gas, in addition to iodine, molecular hydrogen-containing gas, and methane.
本発明において上記触媒を使用し、ヨウ素と、分子状水素含有ガスおよび／またはメタンとを気相法で反応させる場合の反応温度は原料化合物の種類によって相違するが、１５０〜１，０００℃、より好ましくは２００〜９００℃、特に好ましくは２５０〜８５０℃である。１５０℃を下回ると水素やヨウ素の活性化が不十分となり、また生成物の触媒表面からの脱離が不十分となる場合がある。特に一酸化炭素が共存する場合には、一酸化炭素が優先的に白金族元素上に吸着されるためその影響が大きくなる。一方、温度が１，０００℃を超えると、ヨウ素の転化率が著しく低下してヨウ化水素やヨウ化メチルなどのヨウ化物の収率が低くなる場合がある。更に、白金族元素が担体上で凝集しやすくなり、または担体内部への移動が生じるため反応時間と共に触媒活性が低下する場合がある。更に熱力学平衡の観点からも反応温度は低い方が有利である。 In the present invention, the above catalyst is used, and the reaction temperature in the case of reacting iodine with a molecular hydrogen-containing gas and / or methane by a gas phase method varies depending on the kind of the raw material compound. More preferably, it is 200-900 degreeC, Most preferably, it is 250-850 degreeC. When the temperature is lower than 150 ° C., activation of hydrogen and iodine is insufficient, and the product may be insufficiently detached from the catalyst surface. In particular, when carbon monoxide coexists, carbon monoxide is preferentially adsorbed on the platinum group element, so that the influence is increased. On the other hand, when the temperature exceeds 1,000 ° C., the conversion rate of iodine is significantly lowered, and the yield of iodides such as hydrogen iodide and methyl iodide may be lowered. Furthermore, the platinum group element tends to aggregate on the support, or the catalyst activity may decrease with the reaction time because of movement into the support. Further, from the viewpoint of thermodynamic equilibrium, a lower reaction temperature is advantageous.
なお、水素を原料とする場合に比べて、メタンを使用する場合にはガスの活性化に高温度を必要とする。より具体的には、水素とヨウ素からヨウ化水素を得るには比較的低温の反応でよいが、メタンとヨウ素とからヨウ化水素及び／またはヨウ化メチルをはじめとするヨード化合物を得る場合にはより高い温度が必要となる。しかしこの場合であっても、１，０００℃を越えるような場合にはメタンが更に活性化されてＣＨ３−ｘ基が生成し、メチル基やＣＨ３−ｘ基のカップリング反応を起したり、さらには炭化物や炭素にまで進み目的とするヨード化合物の選択率及び収率を下げる結果となり好ましくない。したがって本願発明の実施に当たり、メタンとヨウ素の反応、または反応原料ガス中にメタンを含みこのメタンも有効に利用する場合においては、反応温度は２５０〜１，０００℃、より好ましくは３００〜１，０００℃、特に好ましくは４００〜１，０００℃の範囲であることが好適である。 Note that, when methane is used, a higher temperature is required for gas activation than when hydrogen is used as a raw material. More specifically, in order to obtain hydrogen iodide from hydrogen and iodine, a reaction at a relatively low temperature may be used. However, when obtaining an iodine compound such as hydrogen iodide and / or methyl iodide from methane and iodine. Requires a higher temperature. However, even in this case, when the temperature exceeds 1,000 ° C., methane is further activated to form a CH 3-x group, which causes a coupling reaction of a methyl group or a CH 3-x group. Further, the process proceeds to carbides and carbon, which is not preferable because the selectivity and yield of the target iodo compound are lowered. Therefore, in carrying out the present invention, when the reaction between methane and iodine, or when methane is contained in the reaction raw material gas and effectively used, the reaction temperature is 250 to 1,000 ° C., more preferably 300 to 1, It is suitable that it is 000 degreeC, Most preferably, it is the range of 400-1,000 degreeC.
なお、反応原料ガス中のメタンを活性化させて有効に使うには、反応温度ほどには重要な要件とはならないが反応系内の圧力が、常圧より高い方が好ましい。 In order to activate and use methane in the reaction raw material gas effectively, it is not as important as the reaction temperature, but the pressure in the reaction system is preferably higher than normal pressure.
本発明においては、ガス空間速度（標準状態で、単位時間当たりの反応ガス容積と触媒容積の比率）は重要な要件であり、３００〜１０，０００Ｈｒ−１の範囲が好ましく、より好ましくは５００〜４，０００Ｈｒ−１の範囲である。３００Ｈｒ−１を下回ると、ヨウ素や生成物の触媒表面からの脱離が不十分となり、特にメタンを水素源に使用した場合は炭素の析出を引き起こしやすくなる。特に、一酸化炭素が共存すると一酸化炭素の脱離が不十分となる場合がある。一方、１０，０００Ｈｒ−１を超えると、原料水素やメタン、ヨウ素の触媒上での滞留時間が短か過ぎて反応性が低下して、ヨウ化水素および／またはヨウ化メチルの収率が大幅に低下する場合がある。 In the present invention, the gas space velocity (reaction gas volume / catalyst volume ratio per unit time in the standard state) is an important requirement, and is preferably in the range of 300 to 10,000 Hr −1 , more preferably 500 to It is in the range of 4,000 Hr- 1 . When it is below 300 Hr −1 , iodine and products are not sufficiently desorbed from the catalyst surface, and particularly when methane is used as a hydrogen source, carbon is likely to be precipitated. In particular, when carbon monoxide coexists, desorption of carbon monoxide may be insufficient. On the other hand, if it exceeds 10,000 Hr −1 , the residence time of the raw material hydrogen, methane, and iodine on the catalyst is too short and the reactivity is lowered, resulting in a large yield of hydrogen iodide and / or methyl iodide. May fall.
なお、反応圧力は特に制限はないが、通常は常圧から１０Ｍｐａまでの範囲で実施される。 The reaction pressure is not particularly limited, but it is usually carried out in the range from normal pressure to 10 MPa.
本発明は、気相法でヨウ素と分子状水素含有ガスおよび／またはメタンとを反応させ、ヨウ化水素やヨウ化メチルなどのヨウ化物を製造するものである。生成したヨウ化水素を捕集するには、例えば、冷却して液状ヨウ化水素として回収してもよく、水で回収してヨウ化水素酸として回収することもでき、または水酸化カリウム溶液でヨウ化カリウムとして捕集してもよい。ヨウ化水素と同様にしてヨウ化メチルを捕集することができる。 The present invention produces iodine such as hydrogen iodide and methyl iodide by reacting iodine with a molecular hydrogen-containing gas and / or methane by a gas phase method. In order to collect the produced hydrogen iodide, for example, it may be cooled and recovered as liquid hydrogen iodide, recovered with water and recovered as hydroiodic acid, or with potassium hydroxide solution. It may be collected as potassium iodide. Methyl iodide can be collected in the same manner as hydrogen iodide.
なお、生成したヨウ化水素、ヨウ化メチル、未反応ヨウ素の水での回収に当たり、反応生成ガスを耐食性の材質からなる例えば、セラミック製、磁器製、ガラス製、ハステロイ製などの充填材を充填した充填塔に導入し、そこに回収液水を反応生成ガスに対して向流または並流に供給させて生成物などを回収することが好ましい。ここで回収液は一回使用でも、循環使用でも可能である。 In the recovery of the generated hydrogen iodide, methyl iodide, and unreacted iodine with water, the reaction product gas is made of a corrosion-resistant material, for example, filled with a filler such as ceramic, porcelain, glass, or Hastelloy. It is preferable to introduce the recovered liquid water into the packed tower and supply the recovered liquid water countercurrently or in parallel with the reaction product gas to recover the product and the like. Here, the recovered liquid can be used once or circulated.
なお、ヨウ化物製造装置の出口ガスに未反応水素やヨウ素が含まれる場合には、ヨウ化物回収後、水素ガスやヨウ素を回収し原料の一部として再利用したり、ヨウ化物回収後の排ガスの一部を水素源の一部として再使用することもできる。 In addition, when unreacted hydrogen and iodine are contained in the exit gas of the iodide manufacturing apparatus, after recovering iodide, hydrogen gas and iodine are recovered and reused as part of the raw material, or exhaust gas after iodide recovery Can be reused as part of the hydrogen source.
また、本発明で使用する上記触媒の活性が低下した場合には、触媒を反応器に充填したまま、または一旦反応器から抜き出して空気、酸素、窒素、ヘリウムなどの不活性ガス、またはメタンなどの低級炭化水素ガスと共に熱処理すると、容易に触媒活性を回復させることができる。 Further, when the activity of the catalyst used in the present invention is reduced, the catalyst is filled in the reactor, or once extracted from the reactor, an inert gas such as air, oxygen, nitrogen, helium, or methane, etc. When the heat treatment is performed together with the lower hydrocarbon gas, the catalytic activity can be easily recovered.
本発明では、分子状水素含有ガスとして、純水素のほか、（１）メタンの水蒸気改質および／または二酸化炭素改質により得られる改質ガス、（２）メタンの部分酸化反応により得られる改質ガス、（３）メタノールの水蒸気改質または分解反応により得られる改質ガスを使用することができる。本発明における反応ガス組成は（ヨウ素ガス量を除いて）、水素ガス１０〜９９体積％、一酸化炭素０〜７０体積％、二酸化炭素０〜７０体積％、水蒸気０〜７０体積％、メタン０〜９９体積％であることが好ましい。 In the present invention, as the molecular hydrogen-containing gas, in addition to pure hydrogen, (1) a reformed gas obtained by steam reforming and / or carbon dioxide reforming of methane, and (2) a modified gas obtained by partial oxidation reaction of methane. A reformed gas obtained by a gas reforming or (3) steam reforming or decomposition reaction of methanol can be used. The reaction gas composition in the present invention (excluding the amount of iodine gas) is 10 to 99% by volume of hydrogen gas, 0 to 70% by volume of carbon monoxide, 0 to 70% by volume of carbon dioxide, 0 to 70% by volume of water vapor, 0% of methane. It is preferable that it is -99 volume%.
分子状水素含有ガスなどの水素源としては、昨今燃料電池や電気自動車などの燃料用としての需要の高まりに加えて水素の製造技術の向上によって安価に水素が入手できるようになっている。現在実施されたり開発中の水素製造技術として、メタンをはじめとする低級飽和炭化水素を原料とする改質方法、メタノールを原料とする改質方法などが知られている。本発明では、メタン、メタノールなどを原料とする改質ガスを分子状水素含有ガスとして使用することができ、安価にヨウ化物を製造することができる。一方、このような改質ガスには、改質反応に由来する一酸化炭素が含まれており、一酸化炭素は白金触媒に対する触媒毒として作用することが知られている。しかしながら本発明によれば、触媒としてアルミナやコージライト等の酸化物や活性炭を担体に白金族元素を分散担持させた触媒を使用することで一酸化炭素による活性低下を防止することができる。この効果は反応ガス中に酸化作用のあるヨウ素ガスが含まれるためと考えられる。特に、反応温度１５０〜１，０００℃、ガス空間速度３００〜１０，０００ｈｒ−１でガス状ヨウ素と分子状水素含有ガスおよび／またはメタンとを反応させる場合には、初期から触媒活性が高く、触媒活性を長期に亘り安定させることができ、原料ガス中の水素ガスのヨウ素ガスに対する比率を理論比率にまで下げても高い生産性を確保でき、かつ一酸化炭素による触媒毒を抑制して長期にわたる安定したヨウ化水素および／またはヨウ化メチルの製造を行うことができる。 As a hydrogen source such as a molecular hydrogen-containing gas, hydrogen has recently become available at low cost due to an increase in demand for fuels such as fuel cells and electric vehicles, as well as improvement of hydrogen production technology. As a hydrogen production technology currently being implemented or under development, a reforming method using lower saturated hydrocarbons such as methane as a raw material, a reforming method using methanol as a raw material, and the like are known. In the present invention, a reformed gas using methane, methanol or the like as a raw material can be used as a molecular hydrogen-containing gas, and iodide can be produced at low cost. On the other hand, such reformed gas contains carbon monoxide derived from the reforming reaction, and carbon monoxide is known to act as a catalyst poison for the platinum catalyst. However, according to the present invention, it is possible to prevent a decrease in activity due to carbon monoxide by using a catalyst in which a platinum group element is dispersed and supported on an oxide or activated carbon such as alumina or cordierite as a catalyst. This effect is considered to be because iodine gas having an oxidizing action is contained in the reaction gas. In particular, when reacting gaseous iodine with molecular hydrogen-containing gas and / or methane at a reaction temperature of 150 to 1,000 ° C. and a gas space velocity of 300 to 10,000 hr −1 , the catalytic activity is high from the beginning, The catalyst activity can be stabilized over a long period of time, high productivity can be secured even if the ratio of hydrogen gas to iodine gas in the raw material gas is lowered to the theoretical ratio, and the catalyst poison caused by carbon monoxide is suppressed for a long time. A wide range of stable hydrogen iodide and / or methyl iodide can be produced.
このような改質ガスを使用する場合には、予め他所で製造した改質ガスをボンベに収納し、該ボンベから必要量を供給してもよいし、本発明のヨウ化物の製造方法の一部として改質工程を含ませてもよい。改質反応で得た水素ガスを直接ヨウ化物の製造工程で使用する場合には、改質装置をヨウ化物製造装置に配設し、改質装置の出口ガスを分子状水素含有ガスとしてヨウ化物製造装置に供給すればよい。さらに、上記改質ガスに含まれる水素濃度を高め、一酸化炭素を下げるために更にシフト工程をはさみ、これらの工程によって得られた分子状水素含有ガスを使用してもよい。 When such a reformed gas is used, a reformed gas produced in advance elsewhere may be stored in a cylinder, and a necessary amount may be supplied from the cylinder, or one of the methods for producing an iodide of the present invention. A reforming step may be included as a part. When the hydrogen gas obtained by the reforming reaction is used directly in the production process of iodide, the reformer is disposed in the iodide production apparatus, and the outlet gas of the reformer is used as the molecular hydrogen-containing gas. What is necessary is just to supply to a manufacturing apparatus. Furthermore, in order to increase the concentration of hydrogen contained in the reformed gas and lower carbon monoxide, a shift step may be further interposed, and the molecular hydrogen-containing gas obtained by these steps may be used.
以下、実施例を用いて本発明をより詳細に説明する。各実施例の結果を表１に、比較例の結果を表２に示す。 Hereinafter, the present invention will be described in more detail with reference to examples. The results of each Example are shown in Table 1, and the results of Comparative Examples are shown in Table 2.
（実施例１−１）
３ｍｍφの球状アルミナに白金坦持量が１ｇ／Ｌ（担体１リットル当たりの白金の坦持量が１ｇであることを示す。）である触媒５．０ｍｌを内径３０ｍｍ、加熱部分５００ｍｍの反応石英管に充填し、外部加熱器で触媒層の温度を３００℃に保った。標準状態で１００％水素ガス７２ｍｌ／分とヨウ素ガス１２ｍｌ／分（ヨウ素８．１６ｇ／時相当）とをよく混合させて前記触媒層に通した。この際のガス空間速度は１０００Ｈｒ−１とした。反応を１時間行った。
(Example 1-1)
A reaction quartz tube having an inner diameter of 30 mm and a heated portion of 500 mm with a 3 mmφ spherical alumina and a platinum support amount of 1 g / L (indicating that the support amount of platinum per liter of support is 1 g). The temperature of the catalyst layer was kept at 300 ° C. with an external heater. Under standard conditions, 100% hydrogen gas 72 ml / min and iodine gas 12 ml / min (equivalent to iodine 8.16 g / hr) were mixed well and passed through the catalyst layer. The gas space velocity at this time was set to 1000 Hr −1 . The reaction was carried out for 1 hour.
反応中、反応石英管出口のガスを直径５ｍｍのガラス玉を充填したガラス管に導入し、そこにガスと並列にイオン交換水１００ｇ／分の速度で導入してヨウ化水素ガスを吸収させ、ヨウ化水素をヨウ化水素酸として回収した。なお、未反応のヨウ素はヨウ化水素酸に溶解し同時に回収した。 During the reaction, the gas at the outlet of the reaction quartz tube is introduced into a glass tube filled with a glass ball having a diameter of 5 mm, and is introduced into the gas tube at a rate of 100 g / min in parallel with the gas to absorb hydrogen iodide gas. Hydrogen iodide was recovered as hydriodic acid. Unreacted iodine was dissolved in hydroiodic acid and recovered at the same time.
回収液中のヨウ化水素は水酸化ナトリウム溶液で、未反応ヨウ素はチオ硫酸ナトリウム溶液でいずれも滴定法で測定し、反応ヨウ素モル数×１００／供給ヨウ素モル数を算出して転化率（％）とし、生成ヨウ化水素モル数×１００／供給ヨウ素モル数を算出して収率（％）とした。 Hydrogen iodide in the recovered solution is a sodium hydroxide solution, and unreacted iodine is a sodium thiosulfate solution, both of which are measured by titration method, and the conversion rate (%) is calculated by calculating the reaction iodine mole number × 100 / feed iodine mole number. ) And the number of moles of hydrogen iodide produced × 100 / number of moles of supplied iodine was calculated as the yield (%).
その結果、ヨウ素の転化率は９９．５％であり、ヨウ化水素の収率は９９．５％であった。（実施例１−２）
反応時間を１００時間連続して行う以外は、実施例１−１と同様に操作した。その結果、ヨウ素転化率９９．２％、ヨウ化水素収率９９．２％であった。１００時間の連続使用でも触媒活性の安定性が保たれた。
As a result, the conversion rate of iodine was 99.5%, and the yield of hydrogen iodide was 99.5%. (Example 1-2)
The same operation as in Example 1-1 was performed except that the reaction time was continuously 100 hours. As a result, the iodine conversion was 99.2%, and the hydrogen iodide yield was 99.2%. The stability of the catalytic activity was maintained even after 100 hours of continuous use.
（実施例２）
実施例１−１において触媒量を７．４ｍｌとし、１００％水素に代えて水素７２ｍｌ／分に一酸化炭素４０ｍｌ／分を加えた混合ガスを１２４ｍｌ／分量で触媒層に供給した以外は実施例１−１と同様に操作した。その結果、ヨウ化水素の収率は９９．５％であった。
(Example 2)
In Example 1-1, the catalyst amount was 7.4 ml, and a mixed gas obtained by adding carbon monoxide 40 ml / min to hydrogen 72 ml / min instead of 100% hydrogen was supplied to the catalyst layer at 124 ml / min. The same operation as in 1-1 was performed. As a result, the yield of hydrogen iodide was 99.5%.
（実施例３−１）
実施例１−１において水素ガスとしてメタンを水蒸気と二酸化炭素による改質で得られた改質ガス（組成：水素５９．５体積％、二酸化炭素４．６体積％、一酸化炭素３３．２体積％、メタン２．７体積％）を使用し、ヨウ素ガス１２ｍｌ／分（ヨウ素８．１６ｇ／時相当）との混合ガスを１２１ｍｌ／分の量で供給し、触媒量を５ｍｌから７．９ｍｌに増やした。反応中、反応石英管出口のガスを直径５ｍｍのガラス玉を充填したガラス管に導入し、そこにガスと並列に最初の吸収用イオン交換水５０ｇを用いて毎分２ｇ／分の割合で循環させながら反応ガス中のヨウ化水素ガスをヨウ化水素酸として回収し、同時に未反応のヨウ素を回収した。それ以外は実施例１−１と同様に操作した。
(Example 3-1)
Reformed gas obtained by reforming methane with steam and carbon dioxide as hydrogen gas in Example 1-1 (composition: hydrogen 59.5% by volume, carbon dioxide 4.6% by volume, carbon monoxide 33.2% by volume) %, 2.7% by volume of methane), and a mixed gas with iodine gas 12 ml / min (equivalent to iodine 8.16 g / hr) is supplied in an amount of 121 ml / min, and the catalyst amount is changed from 5 ml to 7.9 ml. Increased. During the reaction, the gas at the outlet of the reaction quartz tube is introduced into a glass tube filled with a glass ball having a diameter of 5 mm and circulated at a rate of 2 g / min per minute using 50 g of the first ion-exchange water for absorption in parallel with the gas. Then, hydrogen iodide gas in the reaction gas was recovered as hydroiodic acid, and at the same time, unreacted iodine was recovered. Otherwise, the same operation as in Example 1-1 was performed.
反応時間１時間後のヨウ化水素の収率は９９．４％であり、回収溶液のヨウ化水素濃度は１４．１質量％であった。 The yield of hydrogen iodide after 1 hour of reaction time was 99.4%, and the concentration of hydrogen iodide in the recovered solution was 14.1% by mass.
（実施例３−２）
反応を１００時間連続反応させた以外は実施例３−１と同様に操作した。その結果、ヨウ化水素の収率は９９．２％であった。原料ガスが一酸化炭素を含む場合であっても、１００時間の連続反応による収率の低下はほとんどなかった。
(Example 3-2)
The same operation as in Example 3-1 was performed except that the reaction was allowed to react continuously for 100 hours. As a result, the yield of hydrogen iodide was 99.2%. Even when the raw material gas contained carbon monoxide, there was almost no decrease in yield due to 100 hours of continuous reaction.
（実施例４）
実施例１−１において水素ガスとしてメタンを部分酸化反応で得た改質ガス（組成：水素２８体積％、一酸化炭素１４体積％、メタン５体積％、二酸化炭素４体積％、窒素４９体積％を使用し、ヨウ素ガス１２ｍｌ／分（ヨウ素８．１６ｇ／時相当）との混合ガスを２６９ｍｌ／分で供給し、触媒量を５ｍｌから１６ｍｌに増やした以外は実施例１−１と同様に操作した。反応時間１時間後のヨウ化水素の収率は９９．４％であった。
Example 4
Reformed gas obtained by partial oxidation reaction of methane as hydrogen gas in Example 1-1 (composition: 28 vol% hydrogen, 14 vol% carbon monoxide, 5 vol% methane, 4 vol% carbon dioxide, 49 vol% nitrogen) Was used in the same manner as in Example 1-1, except that a mixed gas of iodine gas 12 ml / min (equivalent to iodine 8.16 g / hr) was supplied at 269 ml / min and the catalyst amount was increased from 5 ml to 16 ml. The yield of hydrogen iodide after 1 hour of reaction time was 99.4%.
（実施例５）
実施例１−１において水素ガスとしてメタンの部分酸化反応で得た改質ガス（組成：水素６１体積％、二酸化炭素３体積％、一酸化炭素３５体積％、窒素１体積％）を使用し、ヨウ素ガス１２ｍｌ／分（ヨウ素８．１６ｇ／時相当）との混合ガスを１３０ｍｌ／分で供給し、触媒量を５ｍｌから７．７ｍｌに増やした以外は実施例１−１と同様に操作した。反応時間１時間後のヨウ化水素の収率は９９．４％であった。原料ガスが一酸化炭素を含む場合であっても、１００時間の連続反応による収率の低下はほとんどなかった。
(Example 5)
In Example 1-1, a reformed gas (composition: 61 vol% hydrogen, 3 vol% carbon dioxide, 35 vol% carbon monoxide, 1 vol% nitrogen) obtained by partial oxidation reaction of methane was used as hydrogen gas, The same operation as in Example 1-1 was performed except that a mixed gas of iodine gas 12 ml / min (equivalent to iodine 8.16 g / hr) was supplied at 130 ml / min and the catalyst amount was increased from 5 ml to 7.7 ml. The yield of hydrogen iodide after 1 hour of reaction time was 99.4%. Even when the raw material gas contained carbon monoxide, there was almost no decrease in yield due to 100 hours of continuous reaction.
（実施例６−１）
実施例１−１において１００％水素ガスの代わりにメタンガスを用い、反応温度を５００℃とした以外は実施例１−１に従って反応を行った。
(Example 6-1)
In Example 1-1, the reaction was performed according to Example 1-1 except that methane gas was used instead of 100% hydrogen gas and the reaction temperature was 500 ° C.
その結果、反応時間１時間後の分析の結果、ヨウ素の転化率は６５％、ヨウ化水素の収率は５３．５％、ヨウ化メチルの収率は１１．２％であった。 As a result, as a result of analysis after 1 hour of reaction time, the conversion rate of iodine was 65%, the yield of hydrogen iodide was 53.5%, and the yield of methyl iodide was 11.2%.
（実施例６−２）
実施例６−１において反応温度を８００℃とした以外は実施例６−１と同様に操作した。その結果、ヨウ素の転化率８６％、ヨウ化水素の収率８０．５％であった。
(Example 6-2)
The same operation as in Example 6-1 was performed, except that the reaction temperature in Example 6-1 was 800 ° C. As a result, the conversion rate of iodine was 86%, and the yield of hydrogen iodide was 80.5%.
（実施例６−３）
実施例６−１において反応系内の圧力を５気圧とした以外は実施例６−１と同様に操作した。その結果、ヨウ素の転化率は６５．３％、ヨウ化水素の収率は５０．４％、ヨウ化メチルの収率は１４．５％であった。反応系内の圧力を上げると活性はあまり変化はなかったが、ヨウ化メチルの生成比率が向上した。
(Example 6-3)
The same operation as in Example 6-1 was performed except that the pressure in the reaction system was changed to 5 atm in Example 6-1. As a result, the conversion rate of iodine was 65.3%, the yield of hydrogen iodide was 50.4%, and the yield of methyl iodide was 14.5%. When the pressure in the reaction system was increased, the activity did not change much, but the production ratio of methyl iodide was improved.
（実施例６−４）
実施例６−１において触媒を０．５ｇＰｔ；０．２５ｇＰｄ；０．２５ｇＲｕ／Ｌアルミナ触媒に代えて反応系内圧力を５気圧に代えた以外は実施例６−１と同様に操作した。その結果ヨウ素の転化率７５．０％であり、ヨウ化水素の収率は３８．０％、ヨウ化メチルの収率は３６．３％であった。
(Example 6-4)
The same operation as in Example 6-1 was conducted, except that in Example 6-1, the catalyst was replaced with 0.5 g Pt; 0.25 g Pd; 0.25 g Ru / L alumina catalyst, and the internal pressure of the reaction system was changed to 5 atm. As a result, the conversion rate of iodine was 75.0%, the yield of hydrogen iodide was 38.0%, and the yield of methyl iodide was 36.3%.
（実施例７）
実施例１−１において水素ガスとしてメタノールの水蒸気改質で得た改質ガス（組成：水素６３体積％、二酸化炭素２２体積％、窒素４体積％、水蒸気１１体積％）を使用し、ヨウ素ガス１２ｍｌ／分（ヨウ素８．１６ｇ／時相当）との混合ガスを１２６．３ｍｌ／分で供給し、触媒量を５ｍｌから７．５ｍｌに増やした以外は実施例１−１と同様に操作した。反応時間１時間後のヨウ化水素の収率は９９．４％であった。
(Example 7)
In Example 1-1, reformed gas obtained by steam reforming of methanol (composition: 63% by volume of hydrogen, 22% by volume of carbon dioxide, 4% by volume of nitrogen, 11% by volume of steam) was used as hydrogen gas, and iodine gas was used. The same operation as in Example 1-1 was performed except that a mixed gas of 12 ml / min (equivalent to iodine 8.16 g / hr) was supplied at 126.3 ml / min and the catalyst amount was increased from 5 ml to 7.5 ml. The yield of hydrogen iodide after 1 hour of reaction time was 99.4%.
（実施例８）
実施例１−１において１．０ｇ白金／Ｌアルミナを１．０ｇＰｄ／Ｌアルミナとした以外は実施例１−１に従って反応を行った。その結果ヨウ化水素の収率は９８．８％であった。
(Example 8)
The reaction was conducted according to Example 1-1 except that 1.0 g platinum / L alumina was changed to 1.0 g Pd / L alumina in Example 1-1. As a result, the yield of hydrogen iodide was 98.8%.
（実施例９）
実施例３−１において１．０ｇ白金／Ｌアルミナを１．０ｇＰｄ／Ｌアルミナとした以外は実施例３−１に従って反応を行った。その結果ヨウ化水素の収率は９８．７％であった。
Example 9
The reaction was conducted according to Example 3-1, except that 1.0 g platinum / L alumina was changed to 1.0 g Pd / L alumina in Example 3-1. As a result, the yield of hydrogen iodide was 98.7%.
（実施例１０）
実施例１−１において１．０ｇ白金／Ｌアルミナを１．０ｇＲｕ／Ｌアルミナとした以外は実施例１−１に従って反応を行った。その結果ヨウ化水素の収率は９９．５％であった。
(Example 10)
The reaction was conducted according to Example 1-1 except that 1.0 g platinum / L alumina was changed to 1.0 g Ru / L alumina in Example 1-1. As a result, the yield of hydrogen iodide was 99.5%.
（実施例１１）
実施例１−１において１．０ｇ白金／Ｌアルミナを１．０ｇＲｈ／Ｌアルミナとした以外は実施例１−１に従って反応を行った。その結果ヨウ化水素の収率は９９．１％であった。
(Example 11)
The reaction was conducted according to Example 1-1 except that 1.0 g platinum / L alumina was changed to 1.0 g Rh / L alumina in Example 1-1. As a result, the yield of hydrogen iodide was 99.1%.
（実施例１２）
実施例１−１において触媒量を１．４ｍｌに変え、水素の流量を１２ｍｌ／分に変え水素とヨウ素の比率を下げて、更に反応温度を４００℃とした以外は実施例１−１に従って反応を行った。その結果ヨウ化水素の収率は９７．０％であった。
(Example 12)
In Example 1-1, the reaction was performed according to Example 1-1, except that the catalyst amount was changed to 1.4 ml, the hydrogen flow rate was changed to 12 ml / min, and the hydrogen / iodine ratio was lowered to 400 ° C. Went. As a result, the yield of hydrogen iodide was 97.0%.
（実施例１３）
実施例１−１において１．０ｇ白金／Ｌアルミナを０．５ｇＰｔ＋０．５ｇＰｄ／Ｌアルミナとした以外は実施例１−１に従って反応を行った。その結果ヨウ化水素の収率は９９．４％であった。
(Example 13)
The reaction was conducted according to Example 1-1 except that 1.0 g platinum / L alumina was changed to 0.5 g Pt + 0.5 g Pd / L alumina in Example 1-1. As a result, the yield of hydrogen iodide was 99.4%.
（実施例１４）
実施例１−１においてアルミナに変えてハニカム状のコージライトを使用した以外は実施例１−１に従って反応を行った。その結果ヨウ化水素の収率は９９．４％であった。
(Example 14)
The reaction was conducted according to Example 1-1 except that honeycomb cordierite was used instead of alumina in Example 1-1. As a result, the yield of hydrogen iodide was 99.4%.
（実施例１５）
実施例１４において反応を１００時間継続して行った。その時点でのヨウ化水素の収率は９９．３％であった。１００時間の連続反応による収率の低下はほとんどなかった。
(Example 15)
In Example 14, the reaction was continued for 100 hours. The yield of hydrogen iodide at that time was 99.3%. There was almost no decrease in yield due to the continuous reaction for 100 hours.
（実施例１６）
実施例１４において触媒量を５ｍｌから１６ｍｌに増やし、１００％水素ガスを水素含有ガス（組成：水素ガス２８体積％、一酸化炭素１４体積％、二酸化炭素４体積％、メタン５体積％、窒素４９体積％）とし、ヨウ素ガス１２ｍｌ／分（ヨウ素８．１６ｇ／時相当）との混合ガスを２６９ｍｌ／分の量に変更した以外は、実施例１４と同様に操作した。反応時間１時間後のヨウ化水素の収率は９９．４％であった。
(Example 16)
In Example 14, the catalyst amount was increased from 5 ml to 16 ml, and 100% hydrogen gas was replaced with hydrogen-containing gas (composition: hydrogen gas 28% by volume, carbon monoxide 14% by volume, carbon dioxide 4% by volume, methane 5% by volume, nitrogen 49 Volume%), and the mixed gas with iodine gas 12 ml / min (equivalent to iodine 8.16 g / hr) was changed to an amount of 269 ml / min. The yield of hydrogen iodide after 1 hour of reaction time was 99.4%.
（実施例１７）
実施例１４において１００％水素ガスに代えてメタンの水蒸気改質ガス（組成：水素ガス５９．５体積％、一酸化炭素３３．２体積％、二酸化炭素４．６体積％、メタン２．７体積％）とし、ヨウ素ガス１２ｍｌ／分（ヨウ素８．１６ｇ／時相当）との混合ガスを１２１ｍｌ／分の量に変更した以外は、実施例１４と同様に操作した。反応時間１時間後のヨウ化水素の収率は９９．５％であった。
(Example 17)
In Example 14, instead of 100% hydrogen gas, steam reformed gas of methane (composition: hydrogen gas 59.5% by volume, carbon monoxide 33.2% by volume, carbon dioxide 4.6% by volume, methane 2.7% by volume) %), And the mixed gas with iodine gas 12 ml / min (equivalent to iodine 8.16 g / hr) was changed to 121 ml / min, and the same operation as in Example 14 was performed. The yield of hydrogen iodide after 1 hour of reaction time was 99.5%.
（実施例１８〜２１）
実施例３−１におけるアルミナ酸化物担体に代えてジルコニアを使用し（実施例１８）、アルミナ酸化物担体に代えてＳｉＯ２を使用し（実施例１９）、アルミナ酸化物担体に代えて酸化マグネシウムを使用し（実施例２０）、アルミナ酸化物担体に代えて酸化チタニウムとした（実施例２１）以外は実施例３−１に従って反応を行った。
(Examples 18 to 21)
Zirconia is used instead of the alumina oxide support in Example 3-1 (Example 18), SiO 2 is used instead of the alumina oxide support (Example 19), and magnesium oxide is used instead of the alumina oxide support. (Example 20), and the reaction was performed according to Example 3-1 except that titanium oxide was used instead of the alumina oxide support (Example 21).
その結果、ヨウ化水素の収率はそれぞれ実施例１８では９５％、実施例１９では９４．６％、実施例２０では９３．２％であった。なお、実施例２０の反応を１００時間継続した後のヨウ化水素の収率は９３．０％と安定していた。そして実施例２１ではヨウ化水素の収率は９６．１％であった。 As a result, the yield of hydrogen iodide was 95% in Example 18, 94.6% in Example 19, and 93.2% in Example 20, respectively. The yield of hydrogen iodide after the reaction of Example 20 was continued for 100 hours was stable at 93.0%. In Example 21, the yield of hydrogen iodide was 96.1%.
（実施例２２）
実施例３−１において水素ガスに代えて水素含有ガス（組成：水素ガス５９．５体積％、一酸化炭素３３．２体積％、二酸化炭素４．６体積％、メタン２．７体積％）とし、ヨウ素ガス１２ｍｌ／分（ヨウ素８．１６ｇ／時相当）との混合ガスを４８４ｍｌ／分の量に変更し、ガス空間速度を４，０００Ｈｒ−１に更に反応温度を４００℃とした以外は実施例３−１と同様に操作した。反応時間１時間後のヨウ化水素の収率は９４．６％であった。
(Example 22)
Instead of hydrogen gas in Example 3-1, a hydrogen-containing gas (composition: hydrogen gas 59.5% by volume, carbon monoxide 33.2% by volume, carbon dioxide 4.6% by volume, methane 2.7% by volume) was used. , Except that the mixed gas with iodine gas 12ml / min (equivalent to iodine 8.16g / hr) was changed to 484ml / min, the gas space velocity was 4,000Hr- 1 and the reaction temperature was 400 ° C. The same operation as in Example 3-1 was performed. The yield of hydrogen iodide after 1 hour of reaction time was 94.6%.
（実施例２３）
粒径２００メッシュの粉末状の活性炭に白金５質量％を坦持した白金触媒０．１ｇを０．７ｇの石英ウールにまぶせ全体を５ｍｌとした触媒を用いた以外は実施例３−１に従って反応を行った。その結果ヨウ化水素の収率は９９．４％であった。
(Example 23)
According to Example 3-1, except that 0.1 g of a platinum catalyst carrying 5% by mass of platinum on powdery activated carbon having a particle size of 200 mesh was coated with 0.7 g of quartz wool to make a total of 5 ml. Reaction was performed. As a result, the yield of hydrogen iodide was 99.4%.
（実施例２４）
粒径２００メッシュの粉末状の活性炭にルテニウム５質量％を担持したルテニウム触媒０．１ｇを０．７ｇの石英ウールにまぶせ、全体が５ｍｌとした触媒を用いた以外は実施例２３に従って反応を行った。その結果ヨウ化水素の収率は９８．１％であった。
(Example 24)
The reaction was carried out in accordance with Example 23 except that 0.1 g of ruthenium catalyst carrying 5 mass% of ruthenium on powdery activated carbon having a particle size of 200 mesh was coated on 0.7 g of quartz wool and the total catalyst was 5 ml. went. As a result, the yield of hydrogen iodide was 98.1%.
（実施例２５）
粒径２００メッシュの粉末状の活性炭にロジウム５質量％を担持したロジウム触媒０．１ｇを０．７ｇの石英ウールにまぶせ、全体が５ｍｌとした触媒を用いた以外は実施例１に従って反応を行った。その結果ヨウ化水素の収率は９７．５％であった。
(Example 25)
The reaction was carried out according to Example 1 except that 0.1 g of rhodium catalyst supporting 5% by mass of rhodium on powdery activated carbon having a particle size of 200 mesh was coated on 0.7 g of quartz wool and the total amount of the catalyst was 5 ml. went. As a result, the yield of hydrogen iodide was 97.5%.
（実施例２６）
粉末状の活性炭に代えて粉末状のモレキュラシーブ４Ａを使用した以外は実施例２３に従って反応を行った。その結果ヨウ化水素の収率は９９．０％であった。
(Example 26)
The reaction was carried out according to Example 23 except that powdered molecular sieve 4A was used instead of powdered activated carbon. As a result, the yield of hydrogen iodide was 99.0%.
（実施例２７−１）
アルミナ粉末をイオン交換水に分散させ、ハニカム状コージライト１００質量部にアルミナ粉末を１０質量部担持させた。次いで、乾燥後５００℃で３時間熱処理を行ない、コージライトに担持させたアルミナ粉末（以下、コージライト担持アルミナ粉体とも称する。）を得た。別に白金源としてヘキサクロロ白金（ＩＶ）酸を塩酸酸性のイオン交換水に溶解させ、前記コージライト担持アルミナ粉体に含浸法により、コージライト担持アルミナ粉体１リットルに白金が１ｇ含まれるよう担持させ、次いで５００℃で３時間熱処理し、これを触媒とした。この触媒を用いて実施例１−１と同様に操作した。その結果、ヨウ化水素の収率は９９．４％であった。
(Example 27-1)
The alumina powder was dispersed in ion-exchanged water, and 10 parts by mass of the alumina powder was supported on 100 parts by mass of honeycomb cordierite. Then, after drying, heat treatment was performed at 500 ° C. for 3 hours to obtain alumina powder supported on cordierite (hereinafter also referred to as cordierite-supported alumina powder). Separately, hexachloroplatinum (IV) acid as a platinum source is dissolved in hydrochloric acid acidic ion-exchanged water, and the cordierite-carrying alumina powder is supported by impregnation so that 1 liter of cordierite-carrying alumina powder contains 1 g of platinum. Then, heat treatment was performed at 500 ° C. for 3 hours, and this was used as a catalyst. The same operation as in Example 1-1 was performed using this catalyst. As a result, the yield of hydrogen iodide was 99.4%.
（実施例２７−２）
反応時間を５０００時間連続して行う以外は、実施例２７−１と同様に操作した。その結果ヨウ素転化率９９．２％、ヨウ化水素の収率９９．２％であった。５０００時間の連続反応でも触媒活性が極めて安定であることが確認された。
(Example 27-2)
The same operation as in Example 27-1 was performed except that the reaction time was continuously performed for 5000 hours. As a result, the iodine conversion was 99.2% and the yield of hydrogen iodide was 99.2%. It was confirmed that the catalytic activity was very stable even after 5000 hours of continuous reaction.
（実施例２８）
ヘキサクロロ白金（ＩＶ）酸を塩酸酸性のイオン交換水に溶解させ、アルミナ粉体１００質量部に白金１質量部となるように含浸した。次いで、乾燥後５００℃で３時間熱処理を行い、白金担持アルミナ担体を得た。この担体をイオン交換水に分散させ、これにハニカム状に形成されたアルミナシリカ支持体を含浸させ、白金が該支持体１リットル当たり１ｇとなるように担持させて、次いで乾燥後５００℃で３時間熱処理し、これを触媒とした。この触媒を用いて実施例１−１と同様に操作した。その結果、ヨウ化水素の収率は９９．４％であった。
(Example 28)
Hexachloroplatinum (IV) acid was dissolved in hydrochloric acid acidic ion-exchanged water, and 100 parts by mass of alumina powder was impregnated to 1 part by mass of platinum. Next, after drying, heat treatment was performed at 500 ° C. for 3 hours to obtain a platinum-supported alumina carrier. This carrier is dispersed in ion-exchanged water, impregnated with an alumina silica support formed in a honeycomb shape, and supported so that platinum becomes 1 g per liter of the support. This was heat treated for a time and used as a catalyst. The same operation as in Example 1-1 was performed using this catalyst. As a result, the yield of hydrogen iodide was 99.4%.
（比較例１）
粒径１μｍの白金粉末５ｍｇ（実施例１−１で使用した触媒に担持された白金量に相当）を０．７ｇの石英ウールにまぶし、触媒とし全体が５ｍｌとなるように反応管に充填した。それ以外は実施例１−１に従って反応を行った。
(Comparative Example 1)
5 mg of platinum powder having a particle size of 1 μm (corresponding to the amount of platinum supported on the catalyst used in Example 1-1) was applied to 0.7 g of quartz wool, and the reaction tube was filled so that the total amount was 5 ml as a catalyst. . Otherwise, the reaction was carried out according to Example 1-1.
その結果ヨウ化水素の収率は６１％であった。なお、反応を２時間継続すると出口配管に未反応ヨウ素が析出し反応の継続は不可能となった。 As a result, the yield of hydrogen iodide was 61%. When the reaction was continued for 2 hours, unreacted iodine was deposited on the outlet pipe, making it impossible to continue the reaction.
（比較例２−１）
実施例１−１において触媒量を２０ｍｌとし、ガス空間速度を２５０Ｈｒ−１にした以外は実施例１−１に従って反応を行った。その結果、ヨウ素転化率９７．５％、ヨウ化水素収率９７．５％であった。
(Comparative Example 2-1)
The reaction was carried out according to Example 1-1 except that the catalyst amount was 20 ml and the gas space velocity was 250 Hr −1 in Example 1-1. As a result, the iodine conversion was 97.5%, and the hydrogen iodide yield was 97.5%.
（比較例２−２）
比較例２−１における反応時間を１００時間とした。その結果、ヨウ素転化率９０．１％、ヨウ化水素の収率９０．１％となった。ガス空間速度が本願発明要件からはずれためにヨウ素転化率は低下した。
(Comparative Example 2-2)
The reaction time in Comparative Example 2-1 was 100 hours. As a result, the iodine conversion was 90.1%, and the yield of hydrogen iodide was 90.1%. Since the gas space velocity deviated from the requirements of the present invention, the iodine conversion rate decreased.
（比較例２−３）
実施例１−１において反応温度１４５℃とした以外は実施例１−１に従って反応を行った。その結果ヨウ化水素の収率は８７．３であった。
(Comparative Example 2-3)
The reaction was conducted according to Example 1-1 except that the reaction temperature was 145 ° C. in Example 1-1. As a result, the yield of hydrogen iodide was 87.3.
（比較例２−４）
比較例２−３における反応時間を１００時間とした。その結果、１００時間時点でのヨウ化水素の収率は８２．３％にまで低下した。
(Comparative Example 2-4)
The reaction time in Comparative Example 2-3 was 100 hours. As a result, the yield of hydrogen iodide at 100 hours decreased to 82.3%.
（比較例３−１）
実施例２−１において触媒量７．４ｍｌから２９．６ｍｌに増やしガス空間速度２５０Ｈｒ−１とした以外は実施例２−１に従って反応を行った。その結果、ヨウ化水素の収率は９６．３％であった。
(Comparative Example 3-1)
The reaction was carried out according to Example 2-1 except that the catalyst amount was increased from 7.4 ml to 29.6 ml in Example 2-1, and the gas space velocity was 250 Hr- 1 . As a result, the yield of hydrogen iodide was 96.3%.
（比較例３−２）
実施例２−１において反応温度を１４５℃に代えた以外は実施例２−１に従って反応を行った。その結果ヨウ化水素の収率は８５．０％であった。
(Comparative Example 3-2)
The reaction was conducted according to Example 2-1 except that the reaction temperature was changed to 145 ° C. in Example 2-1. As a result, the yield of hydrogen iodide was 85.0%.
（比較例４−１）
実施例３−１において触媒量を３１．６ｍｌに増やし、ガス空間速度を２５０Ｈｒ−１にした以外は実施例３−１に従って反応を行った。その結果、ヨウ化水素の収率は９６．２％であった。実施例３−１に比べて収率が低下したことは明らかである。
(Comparative Example 4-1)
The reaction was carried out according to Example 3-1, except that the catalyst amount was increased to 31.6 ml and the gas space velocity was 250 Hr −1 in Example 3-1. As a result, the yield of hydrogen iodide was 96.2%. It is clear that the yield decreased compared to Example 3-1.
（比較例４−２）
実施例３−１において反応温度を１４５℃にした以外は実施例３−１に従って反応を行った。その結果ヨウ化水素の収率は８４．８％であった。実施例３−１に比べて更に収率が低下したのは、反応温度が下がったことと共存する一酸化炭素の影響であったと考えられる。
(Comparative Example 4-2)
The reaction was conducted according to Example 3-1 except that the reaction temperature was 145 ° C. in Example 3-1. As a result, the yield of hydrogen iodide was 84.8%. It is considered that the yield was further reduced compared to Example 3-1 due to the influence of carbon monoxide coexisting with the decrease in the reaction temperature.
本発明によれば、収率高くかつヨウ化水素やヨウ化メチルなどのヨウ化物を製造することができ、有用である。 According to the present invention, iodide such as hydrogen iodide and methyl iodide can be produced with high yield, which is useful.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008523092A (en) * | 2004-12-09 | 2008-07-03 | ハネウェル・インターナショナル・インコーポレーテッド | Direct one-step synthesis of CF3-I |
| WO2009096446A1 (en) * | 2008-01-31 | 2009-08-06 | Nippoh Chemicals Co., Ltd. | Iodine compound production system and production process |
| WO2009096447A1 (en) * | 2008-01-31 | 2009-08-06 | Nippoh Chemicals Co., Ltd. | Inorganic iodide, production method thereof, and production system thereof |
| CN109824015A (en) * | 2019-01-10 | 2019-05-31 | 南昌大学 | A method of catalysis reduction elemental iodine prepares hydroiodic acid |
| JP2020091166A (en) * | 2018-12-05 | 2020-06-11 | 株式会社東芝 | Oxygen concentration measuring device and nuclear reactor facility |
| WO2020214766A1 (en) * | 2019-04-16 | 2020-10-22 | Honeywell International Inc. | An integrated process and catalysts for manufacturing hydrogen iodide from hydrogen and iodine |
| US11459284B2 (en) | 2018-08-24 | 2022-10-04 | Honeywell International Inc. | Processes for producing trifluoroiodomethane and trifluoroacetyl iodide |
| WO2023288200A1 (en) * | 2021-07-16 | 2023-01-19 | Honeywell International Inc. | Systems and methods for removal of iodine from hydrogen iodide streams |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3848065A (en) * | 1972-09-29 | 1974-11-12 | Monsanto Co | Method for producing hydrogen iodide |
| JPS57501781A (en) * | 1980-11-21 | 1982-10-07 | ||
| JPS58501376A (en) * | 1981-09-01 | 1983-08-18 | オラ−，ジヨ−ジ アンドル− | Methane to methyl halides and methyl alcohol |
-
2005
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3848065A (en) * | 1972-09-29 | 1974-11-12 | Monsanto Co | Method for producing hydrogen iodide |
| JPS57501781A (en) * | 1980-11-21 | 1982-10-07 | ||
| JPS58501376A (en) * | 1981-09-01 | 1983-08-18 | オラ−，ジヨ−ジ アンドル− | Methane to methyl halides and methyl alcohol |
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| JP2008523092A (en) * | 2004-12-09 | 2008-07-03 | ハネウェル・インターナショナル・インコーポレーテッド | Direct one-step synthesis of CF3-I |
| WO2009096446A1 (en) * | 2008-01-31 | 2009-08-06 | Nippoh Chemicals Co., Ltd. | Iodine compound production system and production process |
| WO2009096447A1 (en) * | 2008-01-31 | 2009-08-06 | Nippoh Chemicals Co., Ltd. | Inorganic iodide, production method thereof, and production system thereof |
| US8268284B2 (en) | 2008-01-31 | 2012-09-18 | Nippoh Chemicals Co., Ltd. | System and method for producing iodine compound |
| JP5437082B2 (en) * | 2008-01-31 | 2014-03-12 | 日宝化学株式会社 | Iodine compound production system and production method |
| JP5520610B2 (en) * | 2008-01-31 | 2014-06-11 | 日宝化学株式会社 | Inorganic iodide, its production method and its production system |
| KR101526030B1 (en) * | 2008-01-31 | 2015-06-04 | 닛포가가쿠 가부시키가이샤 | Inorganic iodide, production method thereof, and production system thereof |
| KR101531734B1 (en) * | 2008-01-31 | 2015-06-25 | 닛포가가쿠 가부시키가이샤 | Iodine compound production system and production process |
| US9272922B2 (en) | 2008-01-31 | 2016-03-01 | Nippoh Chemicals Co., Ltd. | Inorganic iodide, production method thereof, and production system thereof |
| US11459284B2 (en) | 2018-08-24 | 2022-10-04 | Honeywell International Inc. | Processes for producing trifluoroiodomethane and trifluoroacetyl iodide |
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| CN109824015B (en) * | 2019-01-10 | 2022-03-22 | 南昌大学 | Method for preparing hydroiodic acid by catalytic reduction of iodine elementary substance |
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| WO2020214766A1 (en) * | 2019-04-16 | 2020-10-22 | Honeywell International Inc. | An integrated process and catalysts for manufacturing hydrogen iodide from hydrogen and iodine |
| CN113767064A (en) * | 2019-04-16 | 2021-12-07 | 霍尼韦尔国际公司 | Integrated process and catalyst for the production of hydrogen iodide from hydrogen and iodine |
| US11554956B2 (en) | 2019-04-16 | 2023-01-17 | Honeywell International Inc. | Integrated process and catalysts for manufacturing hydrogen iodide from hydrogen and iodine |
| CN113767064B (en) * | 2019-04-16 | 2024-03-22 | 霍尼韦尔国际公司 | Integrated process and catalyst for the production of hydrogen iodide from hydrogen and iodine |
| WO2023288200A1 (en) * | 2021-07-16 | 2023-01-19 | Honeywell International Inc. | Systems and methods for removal of iodine from hydrogen iodide streams |
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