TWI680801B - 觸媒及觸媒群 - Google Patents
觸媒及觸媒群 Download PDFInfo
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- TWI680801B TWI680801B TW107110521A TW107110521A TWI680801B TW I680801 B TWI680801 B TW I680801B TW 107110521 A TW107110521 A TW 107110521A TW 107110521 A TW107110521 A TW 107110521A TW I680801 B TWI680801 B TW I680801B
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- catalyst
- cavity
- straight body
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- gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 351
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 56
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 70
- 239000007789 gas Substances 0.000 claims description 41
- 230000003647 oxidation Effects 0.000 claims description 38
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 28
- 150000001299 aldehydes Chemical class 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 23
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 17
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 150000001735 carboxylic acids Chemical class 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 238000000691 measurement method Methods 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000013076 target substance Substances 0.000 abstract description 32
- 239000000126 substance Substances 0.000 abstract description 20
- 238000004939 coking Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 239000012071 phase Substances 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 34
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000011049 filling Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 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 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910021485 fumed silica Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 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 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 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 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 2
- 229940036358 bismuth subcarbonate Drugs 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000005235 decoking Methods 0.000 description 2
- 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 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明之目的在於提供一種觸媒,其於使用觸媒使材料物質進行氣相接觸氧化反應而製造目標物質時抑制壓力損失及結焦,從而能夠以高產率製造目標物質。本發明係關於一種觸媒,其係於使材料物質進行氣相接觸氧化反應而製造目標物質時所使用之具有直體部與空腔部之環形狀之觸媒,並且直體部之長度較空腔部之長度短,且於至少一端部由直體部之端部至空腔部之端部呈凹曲。
Description
本發明係關於一種觸媒及觸媒群。詳細而言,係關於一種於使烯烴或第三丁醇(tertiary butanol)進行氣相接觸氧化反應而製造對應之不飽和醛及/或不飽和羧酸時所使用之觸媒及觸媒群、及於使不飽和醛進行氣相接觸氧化而製造對應之不飽和羧酸時所使用之觸媒及觸媒群。
以往,關於用於使烯烴或第三丁醇進行氣相接觸氧化反應而製造對應之不飽和醛及/或不飽和羧酸之觸媒、或用於使丙烯醛等不飽和醛進行氣相接觸氧化而製造對應之不飽和羧酸之觸媒之形狀,揭示有多種方案。
例如,於專利文獻1中,作為自(甲基)丙烯醛向(甲基)丙烯酸之選擇性氧化所使用之觸媒,記載有一種形成為中空圓筒體狀且該中空圓筒體狀之端面彎曲之非均相系觸媒反應用之成形觸媒。於專利文獻2中,作為用以自丙烯等製造丙烯醛之觸媒,記載有一種至少含有Mo、Bi及Fe之環狀之非擔載觸媒,其具有特定之長度、外徑及壁厚,且端面彎曲。於專利文獻3中,作為於藉由氣相接觸氧化而自丙烯醛合成丙烯酸時所使用之觸媒,記載有一種環形狀之觸媒。又,於專利文獻4中,記載有一種用以製造酞酸酐之擔載觸媒,其環狀載體之兩正面被自內向外斜向地倒角,圓筒外壁 之長度與圓筒內壁之長度相比至少短20%,且含有釩及鈦及/或鋯英石。
專利文獻1:日本專利特開昭61-141933號公報
專利文獻2:日本專利特表2007-505740號公報
專利文獻3:日本專利特開平5-317713號公報
專利文獻4:日本專利特開昭55-139834號公報
然而,該等先前已知之觸媒存在如下問題:藉由填充有該觸媒之反應器使原料物質進行氣相接觸氧化反應而製造目標物質時之壓力損失較高,原料物質之轉化率較低,對應之目標物質之選擇率較低,而產率降低。例如環形狀之觸媒存在未均勻地填充於反應器內之情況,有反應場於反應器內變得不均勻,發生轉化率、選擇率之降低之可能性。又,中空圓筒體狀之端面呈彎曲之觸媒由於相對於觸媒體積之觸媒表面積較小,反應活性點較少,故而存在反應之效率較低,轉化率、選擇率降低的情況。又,於不飽和醛及/或不飽和羧酸之製造中,碳化物附著於觸媒表面。該碳化物向觸媒表面之附著(結焦)係於多管式反應器之壓力損失較高之反應管中因氣體量變少而容易發生。一旦發生結焦,則壓力損失變得更高,故而產生碳化物向觸媒表面之附著進而加速之惡性循環,最終可能導致不得不停止反應之狀況。
本發明係為了解決上述問題點而成者。即,本發明之目的在於提供一種觸媒及觸媒群,其係於使烯烴或第三丁醇進行氣相接觸氧化反應而製造對應之不飽和醛及/或不飽和羧酸時,減少壓力損失而保持高氣體量,藉此能夠抑制結焦而能夠以高產率製造對應之不飽和醛及/或不飽和羧酸。又,本發明之目的在於提供一種觸媒及觸媒群,其係於使丙烯醛等不飽和醛進行氣相接觸氧化而製造對應之不飽和羧酸時,減少壓力損失而保持高氣體量,藉此能夠抑制結焦而能夠以高產率製造對應之不飽和羧酸。
本發明者為了解決上述課題反覆進行了努力研究,結果發現藉由以下觸媒或觸媒群可解決上述課題,從而完成本發明。
即,本發明如下所述。
[1]一種觸媒,其係於使烯烴或第三丁醇進行氣相接觸氧化反應而製造對應之不飽和醛及/或不飽和羧酸時所使用之具有直體部與空腔部之環形狀之觸媒,其直體部之長度較空腔部之長度短,且於至少一端部,由直體部之端部至空腔部之端部呈凹曲。
[2]一種觸媒,其係於使不飽和醛進行氣相接觸氧化而製造對應之不飽和羧酸時所使用之具有直體部與空腔部之環形狀之觸媒,其直體部之長度較空腔部之長度短,且於至少一端部,由直體部之端部至空腔部之端部呈凹曲。
[3]如[1]或[2]所記載之觸媒,其中,直體部位於空腔部之包含一端部之面與包含另一端部之面之間。
[4]如[1]至[3]中任一項所記載之觸媒,其中,於至少一端部,將直體部之端部與空腔部之端部連結之面和凹曲之面間之最大距 離(mm),相對於直體部之端部與空腔部之端部之間之距離(mm)的比為0.01以上且0.2以下。
[5]如[1]至[4]中任一項所記載之觸媒,其中,於兩端部,由直體部之端部至空腔部之端部呈凹曲。
[6]如[1]至[5]中任一項所記載之觸媒,其中,直體部、及將直體部之端部與空腔部之端部連結之線所成之角度為45°~85°。
[7]如[1]至[6]中任一項所記載之觸媒,其中,直體部之外徑a(mm)相對於在軸向上具備空腔部之區域之內徑b(mm)的比(a/b)為2.3以上,直體部長度H(mm)相對於在軸向上具備空腔部之區域之內徑b(mm)的比(H/b)為1.3以上,直體部長度H(mm)為2mm~11mm,且直體部之外徑a(mm)為2mm~11mm。
[8]一種丙烯醛及/或丙烯酸之製造方法,其係於如[1]所記載之觸媒之存在下使包含丙烯與含氧氣體之原料混合氣體進行氣相接觸氧化。
[9]一種丙烯酸之製造方法,其係於如[2]所記載之觸媒之存在下使包含丙烯醛與含氧氣體之原料混合氣體進行氣相接觸氧化。
[10]一種觸媒群,其包含200個以上之環形狀之觸媒,該環形狀之觸媒係於使烯烴或第三丁醇進行氣相接觸氧化反應而製造對應之不飽和醛及/或不飽和羧酸時所使用之具備直體部及空腔部者,並且該觸媒群滿足下述(1)及(2),
(1)包含直體部之長度較空腔部之長度短,直體部位於空腔部之包含一端部之面與包含另一端部之面之間,且於至少一端部由直體部之端部至空腔部之端部為直線狀及/或呈凹曲的觸媒(A)。
(2)觸媒群之藉由振動試驗而得之朝上比率為70%以下。
(觸媒群之藉由振動試驗而得之朝上比率之測定法)
將於觸媒群中隨機地抽選之100個環形狀之觸媒放入至不鏽鋼方型托盤(寬度296mm,長度231mm,高度49mm),將不鏽鋼方型托盤安裝於數位振盪器FLK-L330-D(AS ONE股份有限公司製造),以往返振動寬度10mm且振動速度350次往返/分鐘振動1分鐘後,將100個環形狀之觸媒中空腔部朝上之觸媒之個數設為朝上比率。
[11]一種觸媒群,其包含200個以上之環形狀之觸媒,該環形狀之觸媒係於使不飽和醛進行氣相接觸氧化而製造對應之不飽和羧酸時所使用之具有直體部及空腔部者,並且該觸媒群滿足下述(1)及(2),
(1)包含直體部之長度較空腔部之長度短,直體部位於空腔部之包含一端部之面與包含另一端部之面之間,且於至少一端部由直體部之端部至空腔部之端部為直線狀及/或呈凹曲的觸媒(A)。
(2)觸媒群之藉由振動試驗而得之朝上比率為70%以下。
(觸媒群之藉由振動試驗而得之朝上比率之測定法)
將於觸媒群中隨機地抽選之100個環形狀之觸媒放入至不鏽鋼方型托盤(寬度296mm,長度231mm,高度49mm),將不鏽鋼方型托盤安裝於數位振盪器FLK-L330-D(AS ONE股份有限公司製造),以往返振動寬度10mm且振動速度350次往返/分鐘振動1分鐘後,將100個環形狀之觸媒中空腔部朝上之觸媒之個數設為朝上比率。
[12]如[10]或[11]所記載之觸媒群,其中,觸媒(A)之將直體部之端部與空腔部之端部連結之面和直線狀部或凹曲之面間之最大距離(mm),相對於直體部之端部與空腔部之端部之間之距離(mm) 的比為0以上且0.2以下。
[13]如[9]至[12]中任一項所記載之觸媒群,其中,於觸媒(A)之兩端部,由直體部之端部至空腔部之端部為直線狀及/或呈凹曲。
[14]一種丙烯醛及/或丙烯酸之製造方法,其係於如[10]所記載之觸媒群之存在下,使丙烯進行氣相接觸氧化。
[15]一種丙烯酸之製造方法,其係於如[11]所記載之觸媒群之存在下,使丙烯醛進行氣相接觸氧化。
根據本發明之第1實施形態之觸媒、或本發明之第3實施形態之觸媒群,使用填充有觸媒或觸媒群之反應器並藉由丙烯等烯烴或第三丁醇與含氧氣體之氣相接觸氧化而製造丙烯醛等不飽和醛及/或丙烯酸等不飽和羧酸時之壓力損失減少,可保持高氣體量。藉此可抑制結焦,可自丙烯等烯烴或第三丁醇以高產率製造丙烯醛等不飽和醛及/或丙烯酸等不飽和羧酸。又,即使為已結焦之狀態,亦較習知形狀之觸媒保持減少壓力損失之效果,故而可減少除焦之頻度。根據本發明之第2實施形態之觸媒、或本發明之第4實施形態之觸媒群,使用填充有觸媒或觸媒群之反應器並藉由丙烯醛等不飽和醛與含氧氣體之氣相接觸氧化而製造丙烯酸等不飽和羧酸時之壓力損失減少,可保持高氣體量。藉此可抑制結焦,可自丙烯醛等不飽和醛以高產率製造丙烯酸等不飽和羧酸。又,即使為已結焦之狀態,亦較習知形狀之觸媒保持減少壓力損失之效果,故而可減少除焦之頻度。
1‧‧‧內徑b
2‧‧‧外徑a
3‧‧‧直體部長度H
4‧‧‧直體部及將直體部之端部與空腔部之端部連結之線所成之角度
5‧‧‧直體部之端部與空腔部之端部之間之距離
6‧‧‧將直體部之端部與空腔部之端部連結之面和凹曲面間之最大距離
7‧‧‧空腔部之長度
A‧‧‧直體部
B‧‧‧空腔部
C‧‧‧空腔部之端部
圖1(a)係本發明之第1及第2實施形態之觸媒之一例的橫剖視圖,圖1(b)係本發明之第1及第2實施形態之觸媒之另一例的橫剖視圖。
圖2(a)係本發明之第1及第2實施形態之觸媒之圖1(a)所示之例中之端部的橫剖視圖,圖2(b)係本發明之第1及第2實施形態之觸媒之圖1(b)所示之例中之端部的橫剖視圖。
圖3(a)係本發明之第3及第4實施形態之觸媒群中之觸媒(A)之一例的橫剖視圖,圖3(b)係本發明之第3及第4實施形態之觸媒群中之觸媒(A)之另一例的橫剖視圖。
圖4(a)係本發明之第3及第4實施形態之觸媒群中之觸媒(A)之圖3(a)所示之例中之端部的橫剖視圖,圖4(b)係本發明之第3及第4實施形態之觸媒群中之觸媒(A)之圖3(b)所示之例中之端部的橫剖視圖。
圖5(a)係本發明之第3及第4實施形態之觸媒群中之觸媒(A)之一例的橫剖視圖,圖5(b)係本發明之第3及第4實施形態之觸媒群中之觸媒(A)之另一例的橫剖視圖。
圖6(a)係本發明之第3及第4實施形態之觸媒群中之觸媒(A)之圖5(a)所示之例中之端部的橫剖視圖,圖6(b)係本發明之第3及第4實施形態之觸媒群中之觸媒(A)之圖5(b)所示之例中之端部的橫剖視圖。
圖7係習知觸媒之橫剖視圖。
以下,對用以實施本發明之形態進行詳細說明。再者,本發明並不限於以下所說明之實施形態。再者,於本說明書中, 鉬(Mo)、鉍(Bi)、矽(Si)、鈷(Co)、鎳(Ni)、鐵(Fe)、鈉(Na)、鉀(K)、銣(Rb)、銫(Cs)、鉈(Tl)、硼(B)、磷(P)、砷(As)、鎂(Mg)、鈣(Ca)、鋅(Zn)、鈰(Ce)、釤(Sm)各元素有時分別使用括號內之元素符號表示。於本說明書中,所謂環形狀之觸媒之「端部」,係指環形狀之觸媒之開口方向(軸向)上之末端周邊之區域。環形狀之觸媒具有2個端部(上端及下端)。於本說明書中,所謂環形狀之觸媒之「直體部」,係指於環形狀之觸媒中外徑固定之部分。所謂「直體部之長度」,係指直體部之軸向之長度。所謂「直體部之端部」,係指直體部之軸向之末端上之環形狀觸媒之外緣部。環形狀之觸媒具有2個直體部之端部(上端及下端)。於本說明書中,所謂環形狀之觸媒之「空腔部」,係指環形狀之觸媒之中空部分上之內徑固定之部分。所謂「空腔部之長度」,係指空腔部之軸向之長度。所謂「空腔部之端部」,係指空腔部之軸向之末端上之環形狀觸媒之內緣部,但於如圖1(b)所示,在環形狀之觸媒具有底面部之情形時,係指空腔部之軸向之末端上之環形狀之觸媒之外緣部。環形狀之觸媒具有2個空腔部之端部(上端及下端)。
以下,對本發明之第1實施形態之觸媒(觸媒粒子)、及本發明之第2實施形態之觸媒(觸媒粒子)進行詳細說明。將本發明之第1及第2實施形態之觸媒之形狀之一例示於圖1(a)。本發明之第1實施形態之觸媒係於使烯烴或第三丁醇進行氣相接觸氧化反應而製造對應之不飽和醛及/或不飽和羧酸時所使用之具有直體部與空腔部之環形狀之觸媒,其直體部之長度較空腔部之長度短,且於至少 一端部由直體部之端部至空腔部之端部呈凹曲。本發明之第2實施形態之觸媒係於使不飽和醛進行氣相接觸氧化而製造對應之不飽和羧酸時所使用之具有直體部與空腔部之環形狀之觸媒,其直體部之長度較空腔部之長度短,且於至少一端部由直體部之端部至空腔部之端部呈凹曲。再者,以下有時將本發明之第1實施形態之觸媒及下述第3實施形態之觸媒群之用途中之烯烴或第三丁醇、以及本發明之第2實施形態之觸媒及下述第4實施形態之觸媒群之用途中之不飽和醛合稱為原料物質。又,有時將本發明之第1實施形態之觸媒及下述第3實施形態之觸媒群之用途中之不飽和醛及/或不飽和羧酸、以及本發明之第2實施形態之觸媒及下述第4實施形態之觸媒群之用途中之不飽和羧酸合稱為目標物質。本發明之第1及第2實施形態之觸媒藉由具有上述構成,而減少於填充於反應器內並藉由原料物質與含氧氣體之氣相接觸氧化而製造目標物質時之壓力損失,從而能夠以高產率製造目標物質。
於本實施形態之觸媒中,直體部較佳為位於空腔部之包含一端部之面與包含另一端部之面之間。即,如上所述,空腔部具有上端及下端2個端部,較佳為於空腔部之包含上端之面與包含下端之面之間存在直體部。藉由設為此種結構,而減少於將觸媒填充於反應器內並藉由原料物質與含氧氣體之氣相接觸氧化而製造目標物質時之壓力損失,從而能夠以高產率製造目標物質。
本實施形態之觸媒係直體部之長度較空腔部之長度短,且於至少一端部由直體部之端部至空腔部之端部呈凹曲。於圖1(a)及(b)中表示本實施形態之觸媒之例。再者,圖1(b)為自直體部起之凹曲面未到達空腔部、而停留於環形狀之底面部之例,於如上 所述般環形狀之觸媒具有底面部之情形時,空腔部之軸向之末端上之環形狀之觸媒之外緣部為空腔部之端部,此種例子亦相當於本實施形態之觸媒。本實施形態之觸媒係由相對於體積之表面積較大、反應活性點較多而言,較佳為如圖1(a)般無底面部。
於本實施形態之觸媒之至少一端部,將該直體部之端部與該空腔部之端部連結之面和該凹曲之面(以下,有時稱為「凹曲面」)間之最大距離(mm),相對於直體部之端部與空腔部之端部之間之距離(mm)的比(以下,有時稱為「凹曲程度」)較佳為0.01以上且0.2以下,更佳為0.02以上且0.15以下,再更佳為0.05以上且0.1以下。藉由為此種範圍內,而減少於將觸媒填充於反應器內並藉由原料物質與含氧氣體之氣相接觸氧化而製造目標物質時之壓力損失,從而能夠以高產率製造目標物質。再者,所謂將直體部之端部與空腔部之端部連結之面和凹曲面間之最大距離,係自圖2可知,為將直體部之端部與空腔部之端部連結之面和凹曲面相隔最遠之部分之長度。
本實施形態之觸媒較佳為於兩端部由直體部之端部至空腔部之端部呈凹曲。於該情形時,觸媒之流動性變得良好,於使用漏斗等向反應器內填充觸媒時,於漏斗內抑制觸媒之架橋,於反應管內均勻地填充觸媒,藉此能夠縮短填充時間,進而在填充於反應器內後減少藉由原料物質與含氧氣體之氣相接觸氧化而製造目標物質時之壓力損失,從而能夠以高產率製造目標物質。
直體部、及將直體部之端部與空腔部之端部連結之線所成之角度較佳為45°~85°,更佳為55°~80°,再更佳為65°~75°。於該情形時,可效率良好地減少於將觸媒填充於反應器內並 藉由原料物質與含氧氣體之氣相接觸氧化而製造目標物質時之壓力損失,從而能夠以高產率製造目標物質。
本發明之觸媒較佳為直體部之外徑a(以下,亦簡稱為「外徑a」或「a」,單位為mm)相對於在軸向上具備空腔部之區域之內徑b(以下,亦簡稱為「內徑b」或「b」,單位為mm)的比(a/b)為2.3以上,直體部長度H(mm)相對於內徑b(mm)之比(H/b)為1.3以上,直體部長度H(mm)為2mm~11mm,且外徑a(mm)為2mm~11mm。藉由設為此種結構,可抑制向反應器內進行填充時之觸媒之破裂,減少於藉由原料物質與含氧氣體之氣相接觸氧化而製造目標物質時之壓力損失,從而能夠以高產率製造目標物質。
a/b更佳為2.35以上,再更佳為2.4以上,特佳為2.45以上,尤佳為2.5以上。上限並無特別限定,由觸媒強度之觀點而言,較佳為3.5以下。H/b更佳為1.35以上,再更佳為1.4以上,特佳為1.45以上,尤佳為1.5以上。上限並無特別限定,由向多管式反應器內填充時之架橋抑制效果之觀點而言,較佳為2.5以下。H更佳為2mm~10mm,再更佳為2.3mm~9mm,特佳為2.6mm~7mm,尤佳為3mm~5mm。a更佳為2mm~10mm,再更佳為3mm~9mm,特佳為4mm~7mm,尤佳為4mm~5.6mm。
進而,外徑a(mm)相對於直體部長度H(mm)之比(a/H)較佳為1.47以上,更佳為1.50以上,再更佳為1.53以上,尤佳為1.56以上。上限並無特別限定,較佳為2.5以下。藉由設為此種結構,而減少於將觸媒填充於反應器內並藉由原料物質與含氧氣體之氣相接觸氧化而製造目標物質時之壓力損失,從而能夠以高產率製造目標物質。
本發明之第1實施形態之觸媒較佳為至少包含鉬及鉍之觸媒。若為包含該2種成分之觸媒,則可適應本發明之第1實施形態之觸媒之用途,其中,較佳為下述通式(1)所表示之觸媒。
MoaBibCocNidFeeXfYgZhQiSijOk (1)
(式(1)中,X為選自由Na、K、Rb、Cs及Tl所構成之群中之至少一種元素,Y為選自由B、P、As及W所構成之群中之至少一種元素,Z為選自由Mg、Ca、Zn、Ce及Sm所構成之群中之至少一種元素,Q為氯等鹵素原子;又,a至k表示各元素之原子比,於a=12時,處於0.5≦b≦7、0≦c≦10、0≦d≦10、0≦e≦3、0≦f≦3、0≦g≦3、0≦h≦1、0≦i≦0.5、0≦j≦40之範圍,又,k為滿足其他元素之氧化狀態之數值)
本發明之第2實施形態之觸媒較佳為至少包含鉬及釩之觸媒。若為包含該2種成分之觸媒,則可適應本發明之第2實施形態之觸媒之用途,其中,較佳為下述通式(2)所表示之觸媒。
MoaVbCucSbdSieXfYgZhOi (2)
(式(2)中,X為選自Nb及W所構成之群中之至少一種元素,Y為選自由Mg、Ca、Sr、Ba及Zn所構成之群中之至少一種元素,Z為選自由Fe、Co、Ni及Bi所構成之群中之至少一種元素;又,a至i表示各元素之原子比,於a=12時,處於0<b≦12、0<c≦12、0≦d≦500、0≦e≦500、0≦f≦12、0≦g≦8、0≦h≦500之範圍,又,i為滿足其他元素之氧化狀態之數值)
本發明之第1及第2實施形態之觸媒例如係藉由以下方式而製造。
首先,使含有上述觸媒之各元素成分之原料化合物根據將製造之組成而將所需量適當溶解或分散於水性介質中,藉此製造包含觸媒成分之混合溶液或其水性漿體。關於各觸媒成分之原料,可使用包含各元素之硝酸鹽、銨鹽、氫氧化物、氧化物、硫酸鹽、碳酸鹽、鹵化物、乙酸鹽等。例如,作為鉬,係使用仲鉬酸銨、三氧化鉬、氯化鉬等。作為鉍,係使用氯化鉍、硝酸鉍、氧化鉍、次碳酸鉍等。作為釩,係使用釩酸銨、五氧化釩、草酸釩、硫酸釩等。上述包含觸媒成分之混合溶液或水性漿體較佳係為了防止各成分之不均分佈而充分地進行攪拌、混合。
其次,包含觸媒成分之混合溶液或水性漿體係進行乾燥而製成粉體。乾燥可藉由多種方法實施,可舉例如藉由噴霧乾燥機、漿體乾燥機、轉筒乾燥機等進行之乾燥,尤佳為藉由噴霧乾燥機進行之乾燥。
其後,將藉由乾燥而獲得之粉體成形為環形狀,而獲得本實施形態之觸媒。成形為環形狀之方法並不一定受限,較佳為打錠成形、擠出成形等。尤其由容易控制直體部、及將直體部之端部與空腔部之端部連結之線所成之角度或凹曲程度而言,較佳為打錠成形。於成形時,可使用成形助劑。較佳之成形助劑為:二氧化矽、石墨、晶質纖維素、纖維素、澱粉、聚乙烯醇、硬脂酸。成形助劑係相對於粉體100重量份通常可使用1重量份~50重量份左右。又,亦可視需要使用陶瓷纖維、鬚晶等無機纖維作為觸媒之機械強度提高材料。該等纖維之使用量係相對於粉體100重量份通常為1重量份~30重量份。
以下,對本發明之第3實施形態之觸媒群(觸媒粒子群)、及本發明之第4實施形態之觸媒群(觸媒粒子群)進行詳細說明。本發明之第3實施形態之觸媒群包含200個以上之環形狀之觸媒,該環形狀之觸媒係於使烯烴或第三丁醇進行氣相接觸氧化反應而製造對應之不飽和醛及/或不飽和羧酸時所使用之具有直體部及空腔部者,並且該觸媒群滿足下述(1)及(2)。本發明之第4實施形態之觸媒群包含200個以上之環形狀之觸媒,該環形狀之觸媒係於使不飽和醛進行氣相接觸氧化而製造對應之不飽和羧酸時所使用之具有直體部及空腔部者,並且該觸媒群滿足下述(1)及(2)。(1)包含直體部之長度較空腔部之長度短,直體部位於空腔部之包含一端部之面與包含另一端部之面之間,且於至少一端部由直體部之端部至空腔部之端部為直線狀及/或呈凹曲的觸媒。(2)觸媒群之藉由振動試驗而得之朝上比率為70%以下。(觸媒群之藉由振動試驗而得之朝上比率之測定法)
將於觸媒群中隨機地抽選之100個環形狀之觸媒放入至不鏽鋼方型托盤(寬度296mm,長度231mm,高度49mm),將該不鏽鋼方型托盤安裝於數位振盪器FLK-L330-D(AS ONE股份有限公司製造),以往返振動寬度10mm且振動速度350次往返/分鐘振動1分鐘後,將100個環形狀之觸媒中空腔部朝上之觸媒之個數設為朝上比率。再者,所謂「空腔部朝上」,係指環形狀之觸媒之開口方向(軸向)相對於不鏽鋼方型托盤之底面呈垂直。再者,以下,亦將直體部之長度較空腔部之長度短,直體部位於空腔部之包含一端部之面與包含另一端部之面之間,且於至少一端部由直體部之端部至空腔部之端部為直線狀及/或呈凹曲之觸媒稱為「觸媒(A)」。
本實施形態之觸媒群係包含200個以上之具有直體 部及空腔部之環形狀之觸媒者。本實施形態之觸媒群中所包含之環形狀之觸媒之數量較佳為220以上,更佳為250以上,再更佳為300以上,特佳為1000以上,顯著較佳為2000以上,尤佳為3000以上。藉由為該範圍,而減少於將觸媒群填充於反應管等內並藉由原料物質與含氧氣體之氣相接觸氧化而製造目標物質時之壓力損失,提高原料物質之轉化率,從而能夠以高選擇率製造目標物質。再者,上限係由向反應管等反應器之填充量之觀點而言,較佳為20000以下,更佳為15000以下,再更佳為12000以下。
本實施形態之觸媒群中之觸媒(A)之數量係相對於環形狀之觸媒之總數的比率較佳為10%以上,更佳為50%以上,再更佳為80%以上,尤佳為95%以上。藉由為該範圍,而減少於將觸媒群填充於反應管等反應器內並藉由原料物質與含氧氣體之氣相接觸氧化而製造目標物質時之壓力損失,從而能夠以高產率製造目標物質。
本實施形態之觸媒群之藉由振動試驗而得之朝上比率為70%以下,較佳為50%以下,更佳為40%以下,再更佳為30%以下,特佳為25%以下。朝上比率之下限較佳為1%以上,更佳為3%以上,再更佳為5%以上。藉由為該範圍內,而減少於將觸媒群填充於反應管等反應器內並藉由原料物質與含氧氣體之氣相接觸氧化而製造目標物質時之壓力損失,從而能夠以高產率製造目標物質。
圖3(a)及圖5(a)為由直體部之端部至空腔部之端部為直線狀之觸媒(A)之例,圖3(b)及圖5(b)為由直體部之端部至空腔部之端部呈凹曲之觸媒(A)之例。再者,圖5所示之例為由直體部起 之直線或凹曲之面未到達空腔部而停留於環形狀之底面部之例,於如上所述環形狀之觸媒具有底面部之情形時,空腔部之軸向之末端上之環形狀之觸媒之外緣部為空腔部之端部,此類例子亦相當於觸媒(A)。作為本實施形態之觸媒群中所包含之觸媒(A),係由相對於體積之表面積較大而言,較佳為如圖3所示之例般無底面部之觸媒(A)。
若由直體部之端部至空腔部之端部呈凹曲之端部之數量相對於觸媒(A)之端部之總數的比例(以下,有時稱為「凹曲比例」)為特定範圍,則減少於使用本實施形態之觸媒群並藉由原料物質之氣相接觸氧化而製造目標物質時之壓力損失,從而能夠以高產率製造目標物質。再者,由於相對於1個觸媒(A)而存在2個端部,故而觸媒(A)之端部之總數為觸媒(A)之數量之2倍。於本實施形態之觸媒群中,凹曲比例較佳為40%以上,更佳為50%以上,再更佳為60%以上,特佳為70%以上,顯著較佳為80%以上,尤佳為90%以上,格外較佳為95%以上,最佳為100%。再者,例如於所有之觸媒(A)均於一端部由直體部之端部至空腔部之端部為直線狀,且於另一端部由直體部之端部至空腔部之端部呈凹曲之情形時,凹曲比例為50%。又,於觸媒(A)中之半數為於兩端部由直體部之端部至空腔部之端部為直線狀,且另外半數為於兩端部由直體部之端部至空腔部之端部呈凹曲之情形時,凹曲比例亦成為50%。
於觸媒(A)中,將該直體部之端部與該空腔部之端部連結之面和該凹曲之面(以下,有時稱為「凹曲面」)間之最大距離(mm),相對於直體部之端部與空腔部之端部之間之距離(mm)的比(以下,有時稱為「凹曲程度」)較佳為0以上且0.2以下,更佳為0 以上且0.15以下,再更佳為0以上且0.1以下。藉由為該範圍內,而減少於將觸媒群填充於反應管等反應器內並藉由原料物質之氣相接觸氧化而製造目標物質時之壓力損失,從而能夠以高產率製造目標物質。於觸媒(A)中,所謂將直體部之端部與空腔部之端部連結之面和凹曲面間之最大距離,自圖4(b)、圖6(b)可知,係指將直體部之端部與空腔部之端部連結之面和凹曲面相隔最遠之部分之長度。再者,於如圖4(a)、圖6(a)所示之例般由直體部之端部至空腔部之端部為直線狀之情形時,將直體部之端部與空腔部之端部連結之面和凹曲面間之最大距離為0,故而凹曲程度亦成為0。
觸媒(A)較佳為於兩端部由直體部之端部至空腔部之端部為直線狀及/或呈凹曲。於該情形時,觸媒群之流動性變得良好,於使用漏斗等向反應管等反應器內填充觸媒群時,於漏斗內抑制觸媒之架橋,於反應管內均勻地填充觸媒,藉此能夠縮短填充時間,進而在填充於反應管等反應器內後減少於藉由原料物質之氣相接觸氧化而製造目標物質時之壓力損失,從而能夠以高產率製造目標物質。
於觸媒(A)中,直體部、及將直體部之端部與空腔部之端部連結之線所成之角度、外徑a(mm)相對於內徑b(mm)之比(a/b)、直體部長度H(mm)相對於內徑b(mm)之比(H/b)、直體部長度H(mm)、外徑a(mm)、外徑a(mm)相對於直體部長度H(mm)之比(a/H)之值之較佳範圍、及其理由係與對第1及第2實施形態之觸媒所進行之說明相同。
第3實施形態之觸媒群中之觸媒(A)與第1實施形態之觸媒同樣地較佳為至少包含鉬及鉍之觸媒,且較佳為上述通式(1) 所表示之觸媒。第4實施形態之觸媒群中之觸媒(A)與第2實施形態之觸媒同樣地較佳為至少包含鉬及釩之觸媒,且較佳為上述通式(2)所表示之觸媒。又,關於該等之較佳製造方法,亦與對第1及第2實施形態之觸媒所進行之說明相同。
第3及第4實施形態之觸媒群亦可包含環形狀以外之形狀之觸媒。所謂環形狀以外之形狀,可舉例如球狀、圓柱狀等。第3及第4實施形態之觸媒群即使利用惰性填充物進行稀釋,用於使原料物質進行氣相接觸氧化反應而製造目標物質,亦可表現效果。所謂惰性填充材,只要為不致在氣相接觸氧化反應中引起多餘之副反應之材料即可,例如可使用氧化鋁、氧化鋯、氧化鈦、氧化鎂、二氧化矽等經高溫處理之氧化物或塊滑石、富鋁紅柱石、碳化矽、氮化矽等高溫燒結材料等。
以下,列舉實施例對本發明進行更具體之說明,但本發明只要不超出其主旨,則並不受以下實施例任何限定。
於容器中添加溫水1090ml,進而添加仲鉬酸銨110g加以溶解,而製成溶液。其次,於該溶液中添加發煙二氧化矽水分散液407g,並進行攪拌,而製成懸浮液(以下,稱為「懸浮液A」)。該發煙二氧化矽水分散液係藉由將發煙二氧化矽5kg(比表面積50m2/g)添加至離子交換水22.5L中製成發煙二氧化矽懸浮液後,將該發煙二氧化矽懸浮液利用均質機ULTRA-TURRAX T115KT(IKA公司製 造)進行30分鐘分散處理,而製成發煙二氧化矽水分散液,設為矽之供給源化合物。
於其他容器中添加純水127ml,進而添加硝酸鐵(III)15.1g、硝酸鈷65.7g及硝酸鎳52.5g後,進行加溫加以溶解(以下,稱為「溶液B」)。將溶液B添加至懸浮液A中,攪拌至均勻,並進行加熱乾燥,而獲得固形物。其次,將該固形物於空氣環境下以300℃熱處理1小時。
進而,於其他容器中添加純水110ml、氨水12ml,並添加仲鉬酸銨19.2g後進行溶解,而製成「溶液C」。其次,於溶液C中添加硼砂1.7g及硝酸鉀0.5g後進行溶解,而製成「溶液D」。將上述經熱處理之固形物150g添加至溶液D中,混合至均勻。其次,添加固溶有0.53%之Na之次碳酸鉍17.4g並混合30分鐘後,進行加熱乾燥以去除水分,從而獲得乾燥品。將該乾燥品進行粉碎,將所獲得之粉體打錠成形為各種形狀,而製成密度1.27g/cm3之環形狀之成形品。將該成形品於空氣環境下以515℃焙燒2小時,使用由此所獲得之環形狀之觸媒而獲得以下所示之例1-1~1-6之觸媒群。再者,構成例1-1~1-6之觸媒群之觸媒之組成均相同,如表1所示。
構成例1-1之觸媒群之所有觸媒如圖3所示,無底面部,外徑:5mm、內徑:2mm、直體部長度:3mm、空腔部長度:4mm。又,於兩端部,由直體部之端部至空腔部之端部為直線狀。進而,於兩端部,直體部及將直體部之端部與空腔部之端部連結之線所成之角度、即沿著直體部所拉出之延長線與將直體部之端部與空腔部之端部連結之線所成之角度為72°。
構成例1-2之觸媒群之所有觸媒如圖3所示,無底面部,外徑:5mm、內徑:2mm、直體部長度:3mm、空腔部長度:4mm。又,於一端部由直體部之端部至空腔部之端部為直線狀,於另一端部由直體部之端部至空腔部之端部呈凹曲。即,例1-2之觸媒群之凹曲比例為50%。進而,直體部之端部與空腔部之端部之間之距離為1.59mm,將直體部之端部與空腔部之端部連結之平面和該凹曲面間之最大距離為0.09mm。進而,將直體部之端部與空腔部之端部連結之面和凹曲面間之最大距離相對於直體部之端部與空腔部之端部之間之距離的比為0.06。
構成例1-3之觸媒群之所有觸媒如圖3所示,無底面部,外徑:5mm、內徑:2mm、直體部長度:3mm、空腔部長度:4mm。又,於兩端部,由直體部之端部至空腔部之端部呈凹曲,即例3之觸媒群之凹曲比例為100%。進而,將直體部之端部與空腔部之端部連結之面和凹曲面間之最大距離相對於直體部之端部與空腔部之端部之間之距離的比為0.1。
構成例1-4之觸媒群之所有觸媒如圖3所示,無底面部,外徑:5mm、內徑:2mm、直體部長度:3mm、空腔部長度:4mm。構成例1-4之觸媒群之觸媒係於兩端部混合存在由直體部之端部至空腔部之端部為直線狀者與呈凹曲者,呈凹曲者之將直體部之端部與空腔部之端部連結之面和凹曲面間之最大距離相對於直體部之端部與空腔部之端部之間之距離的比為0.1。例1-4之觸媒群之凹曲比例為75%。
構成例1-5之觸媒群之所有觸媒如圖3所示,無底面部,外徑:5mm、內徑:2mm、直體部長度:3mm、空腔部長度: 4mm。構成例1-5之觸媒群之觸媒係於兩端部混合存在由直體部之端部至空腔部之端部為直線狀者與呈凹曲者,呈凹曲者之將直體部之端部與空腔部之端部連結之面和凹曲面間之最大距離相對於直體部之端部與空腔部之端部之間之距離的比為0.1。例1-5之觸媒群之凹曲比例為80%。
構成例1-6之觸媒群之所有觸媒中,外徑:5mm、內徑:2mm、直體部長度:3mm、空腔部長度:3mm,直體部長度與空腔部長度相同,由直體部之端部至空腔部之端部平坦,除此以外係與例1-1相同之觸媒。
使內徑26mm、長度1000mm之丙烯酸系樹脂製直管直立,分別填充例1-1之觸媒群直至900mm高度,自安裝於該丙烯酸系樹脂製直管之上部的內徑6mm之SUS製配管於室溫下以50NL/分鐘之流量通入乾燥空氣,利用安裝於自SUS製配管分支之配管之數位差壓計testo 506-3測定差壓(差壓A)。其次,自丙烯酸系樹脂製直管抽出環形狀之觸媒而設為空筒,同樣地測定差壓,並設為空白值。壓力損失係作為(差壓A)-空白值而求出。又,對例1-2~1-6之觸媒群亦同樣地進行測定。將測定結果示於表2。再者,構成所填充之觸媒群之觸媒之數量如下所述。
例1-1:4090
例1-2:4014
例1-3:4108
例1-4:4074
例1-5:4091
例1-6:5014
將例1-1之觸媒群40ml與直徑5mm之富鋁紅柱石球52ml進行混合而製成混合物,並填充於內徑15mm之附帶防硝酸浸蝕液套管之不鏽鋼製反應管內。自反應管入口於70kPa下通入丙烯10體積%、蒸氣17體積%、空氣73體積%之原料氣體,以與觸媒群之接觸時間為6.0秒進行通入而實施丙烯之氧化反應。再者,反應管係於硝酸浸蝕液浴中進行加熱,於浴溫為320℃、330℃之條件下實施。反應產物之分析係自反應管出口回收反應產物,使用氣相層析儀並藉由常規方法而實施。又,對例1-2~1-6之觸媒群亦同樣地進行測定。將測定結果示於表2。再者,構成各例之觸媒群40ml之觸媒之數量如下所述。
例1-1:322
例1-2:315
例1-3:322
例1-4:319
例1-5:318
例1-6:359
再者,所謂硝酸浸蝕液,係指包含鹼金屬之硝酸鹽之熱介質,該熱介質於200℃以上下熔融,於400℃之前可使用且除熱效率良好,故而適於放熱量較大之氧化反應。
丙烯轉化率、丙烯醛產率、丙烯酸產率、合計產率之 定義如下所述。
‧丙烯轉化率(莫耳%)=(反應之丙烯之莫耳數/供給之丙烯之莫耳數)×100
‧丙烯醛產率(莫耳%)=(生成之丙烯醛之莫耳數/供給之丙烯之莫耳數)×100
‧丙烯酸產率(莫耳%)=(生成之丙烯酸之莫耳數/供給之丙烯之莫耳數)×100
‧合計產率(莫耳%)=丙烯醛產率(莫耳%)+丙烯酸產率(莫耳%)
於使用填充有滿足本發明之第3實施形態之觸媒群之必要條件的例1-1~1-5之觸媒群之反應器自丙烯製造丙烯醛及/或丙烯酸之情形時,將壓力損失抑制得較低,且丙烯之轉化率較 高,以高選擇率製成丙烯醛及/或丙烯酸,結果能夠以高產率製造丙烯醛及/或丙烯酸。於使用本發明之第1實施形態之觸媒的例1-2~1-5之觸媒群中,尤其將壓力損失抑制得較低。
藉由以下方式製造除氧氣以外之構成成分之實驗式為表3所示之組成的複合金屬氧化物。
使鹼性碳酸鎳分散於純水350ml中,並向其中添加二氧化矽及三氧化二銻後充分地進行攪拌。對該漿狀液體進行加熱而進行濃縮及乾燥。使用馬弗爐將所獲得之乾燥固體以800℃焙燒3小時,對生成固體進行粉碎而獲得通過60目篩之粉體。(Sb-Ni-Si-O粉末)。
另一方面,將純水加熱至80℃,將仲鉬酸銨、偏釩酸銨依序進行攪拌並溶解。向其中添加將硫酸銅溶解於純水100ml中而成之硫酸銅水溶液,進而添加氫氧化鈮後進行攪拌,而獲得漿液。一面攪拌一面緩慢地於該漿液中添加上述Sb-Ni-Si-O粉末,充分地進行攪拌混合。將該漿狀液體以150℃進行噴霧乾燥,而獲得前驅化合物。向其中添加混合1.5重量%之石墨,使用小型打錠成形機成形為密度2.93g/cm3之環形狀。將所獲得之成形體於1%氧氣氣流中以380℃進行焙燒,使用獲得之環形狀之觸媒而獲得以下所示之例2-1~2-4之觸媒群。
構成例2-1之觸媒群之所有觸媒如圖3所示,無底面部,外徑:5mm、內徑:2mm、直體部長度:3mm、空腔部長度: 4mm。又,於兩端部,由直體部之端部至空腔部之端部為直線狀。進而,於兩端部,直體部及將直體部之端部與空腔部之端部連結之線所成之角度、即沿著直體部所拉出之延長線與將直體部之端部與空腔部之端部連結之線所成之角度為72°。
構成例2-2之觸媒群之所有觸媒如圖3所示,無底面部,外徑:5mm、內徑:2mm、直體部長度:3mm、空腔部長度:4mm。又,於兩端部,由直體部之端部至空腔部之端部呈凹曲,即例2-2之觸媒群之凹曲比例為100%。又,直體部之端部與空腔部之端部之間之距離為1.59mm,將直體部之端部與空腔部之端部連結之平面和凹曲面間之最大距離為0.10mm。進而,將直體部之端部與空腔部之端部連結之面和凹曲面間之最大距離相對於直體部之端部與空腔部之端部之間之距離的比為0.06。進而,於兩端部,直體部與將直體部之端部與空腔部之端部連結之線所成之角度、即沿著直體部所拉出之延長線與將直體部之端部與空腔部之端部連結之線所成之角度為72°。
構成例2-3之觸媒群之所有觸媒如圖3所示,無底面部,外徑:5mm、內徑:2mm、直體部長度:3mm、空腔部長度:4mm。又,直體部之端部與空腔部之端部之間之距離為1.59mm。進而,於兩端部,直體部及將直體部之端部與空腔部之端部連結之線所成之角度、即沿著直體部所拉出之延長線與將直體部之端部與空腔部之端部連結之線所成之角度為72°。構成例2-3之觸媒群之觸媒於兩端部混合存在由直體部之端部至空腔部之端部為直線狀者與呈凹曲者,且呈凹曲者之將直體部之端部與空腔部之端部連結之平面與該凹曲面間之最大距離為0.10mm,將直體部之端部與空 腔部之端部連結之面和凹曲面間之最大距離相對於直體部之端部與空腔部之端部之間之距離的比為0.06。例2-3之觸媒群之凹曲比例為75%。
例2-4之觸媒中,外徑:5mm、內徑:2mm、直體部長度:3mm、空腔部長度:3mm,如圖5所示,直體部長度與空腔部長度相同,由直體部之端部至空腔部之端部平坦。
藉由與例1-1~1-6相同之方法測定壓力損失。將測定結果示於表4。再者,構成所填充之觸媒群之觸媒之數量如下所述。
例2-1:3935
例2-2:3847
例2-3:3748
例2-4:5020
於添加有硝酸浸蝕液之附帶套管之反應管(內徑21mm)中填充30ml例2-1之觸媒群,對反應管進行加熱,導入組成氣體(丙烯醛6體積%、氧氣8體積%、蒸氣22體積%、氮氣64體積%),將SV(空間速度:每單位時間之原料氣體之流量/填充之觸媒之表觀容積)設為1550/hr而實施丙烯醛之氣相接觸氧化反應。又,對例2-2~2-4之觸媒群亦同樣地進行測定。將測定結果示於表4。再者,構成各例之觸媒群30ml之觸媒之數量如下所述。
例2-1:266
例2-2:260
例2-3:253
例2-4:298
丙烯醛轉化率、丙烯酸選擇率、丙烯酸產率之定義如下所述。
‧丙烯醛轉化率(莫耳%)=100×(反應之丙烯醛之莫耳數)/(供給之丙烯醛之莫耳數)
‧丙烯酸選擇率(莫耳%)=100×(生成之丙烯酸之莫耳數)/(轉化之丙烯醛之莫耳數)
‧丙烯酸產率(莫耳%)=100×(生成之丙烯酸之莫耳數)/(供給之丙烯醛之莫耳數)
於使用填充有滿足本發明之第4實施形態之觸媒群之必要條件的例2-1~2-3之觸媒群之反應器使作為不飽和醛之丙烯醛進行氣相接觸氧化反應而製造作為對應之不飽和羧酸之丙烯酸之情形時,將壓力損失抑制得較低,且可不使溫度上升而將丙烯醛以高轉化率進行氧化,從而能夠以高產率製造丙烯酸。於使用本 發明之第2實施形態之觸媒的例2-2及2-3之觸媒群中,尤其將壓力損失抑制得較低。
上述例中之壓力損失係藉由將觸媒之填充層長度設為900mm,以50NL/分鐘之氣體流速簡易地通入乾燥空氣的測定而表現出相對於習知技術之優勢。再者,壓力損失一般如下述Ergun式所示,與觸媒之填充層長度及氣體流速之平方成比例。於工業上製造目標物質時,使用固定床管型反應器,通常,固定床管型反應器具有數千~數萬根2000mm~7000mm之反應管(日本專利特開2011-225476號公報、國際公開第2005/005037號公報)。因此,根據實施例中所示之結果,可知於目標物質之製造設備中,本發明之壓力損失相對於習知技術之差異趨於擴大至2.2~7.8倍,工業規模越大,本發明之優勢越大。進而,於目標物質之製造中,壓力損失較高則產生結焦,且隨著時間經過而發生壓力損失之上升與結焦之增大。即,可知隨著時間經過,本發明之壓力損失相對於習知技術之差異趨於變大。
(△P:壓力損失,L:填充層長度,ρ:氣體密度,u:氣體流速,Dp:粒徑,ε:空隙率,Rep:雷諾數)
參照特定態樣對本發明進行了詳細說明,但業者應知曉可於不脫離本發明之精神與範圍內進行各種變更及修正。再者,本申請案係基於在2017年3月27日提出申請之日本專利申請案(日 本專利特願2017-061962)、於2017年4月27日提出申請之日本專利申請案(日本專利特願2017-088648)、於2017年5月16日提出申請之日本專利申請案(日本專利特願2017-097655)、於2017年5月16日提出申請之日本專利申請案(日本專利特願2017-097656)、於2018年1月29日提出申請之日本專利申請案(日本專利特願2018-012547)、於2018年1月29日提出申請之日本專利申請案(日本專利特願2018-012548)、於2018年1月29日提出申請之日本專利申請案(日本專利特願2018-012549)、及於2018年1月29日提出申請之日本專利申請案(日本專利特願2018-012550),並將其全部內容以引用之形式援引。又,引用於本文中之所有參照係整體併入。
1‧‧‧內徑b
2‧‧‧外徑a
3‧‧‧直體部長度H
7‧‧‧空腔部之長度
A‧‧‧直體部
B‧‧‧空腔部
C‧‧‧空腔部之端
Claims (15)
- 一種觸媒,其係於使烯烴或第三丁醇進行氣相接觸氧化反應而製造對應之不飽和醛及/或不飽和羧酸時所使用之具有直體部與空腔部之環形狀之觸媒,該直體部之長度較該空腔部之長度短,且於至少一端部,由該直體部之端部至該空腔部之端部呈凹曲,該觸媒至少包含鉬及鉍。
- 一種觸媒,其係於使不飽和醛進行氣相接觸氧化而製造對應之不飽和羧酸時所使用之具有直體部與空腔部之環形狀之觸媒,該直體部之長度較該空腔部之長度短,且於至少一端部,由該直體部之端部至該空腔部之端部呈凹曲,該觸媒至少包含鉬及釩。
- 如請求項1或2之觸媒,其中,上述直體部位於上述空腔部之包含一端部之面與包含另一端部之面之間。
- 如請求項1或2之觸媒,其中,於至少一端部,將上述直體部之端部與上述空腔部之端部連結之面和該凹曲之面間之最大距離(mm),相對於上述直體部之端部與上述空腔部之端部之間之距離(mm)的比為0.01以上且0.2以下。
- 如請求項1或2之觸媒,其中,於兩端部,由上述直體部之端部至上述空腔部之端部呈凹曲。
- 如請求項1或2之觸媒,其中,上述直體部、及將上述直體部之端部與上述空腔部之端部連結之線所成之角度為45°~85°。
- 如請求項1或2之觸媒,其中,直體部之外徑a(mm)相對於在軸向上具備空腔部之區域之內徑b(mm)的比(a/b)為2.3以上,直體 部長度H(mm)相對於該在軸向上具備空腔部之區域之內徑b(mm)的比(H/b)為1.3以上,該直體部長度H(mm)為2mm~11mm,且該直體部之外徑a(mm)為2mm~11mm。
- 一種丙烯醛及/或丙烯酸之製造方法,其係於請求項1之觸媒之存在下,使包含丙烯與含氧氣體之原料混合氣體進行氣相接觸氧化。
- 一種丙烯酸之製造方法,其係於請求項2之觸媒之存在下,使包含丙烯醛與含氧氣體之原料混合氣體進行氣相接觸氧化。
- 一種觸媒群,其包含200個以上之環形狀之觸媒,該環形狀之觸媒係於使烯烴或第三丁醇進行氣相接觸氧化反應而製造對應之不飽和醛及/或不飽和羧酸時所使用之具有直體部及空腔部者,並且該觸媒群滿足下述(1)及(2),(1)包含該直體部之長度較該空腔部之長度短,該直體部位於該空腔部之包含一端部之面與包含另一端部之面之間,且於至少一端部由該直體部之端部至該空腔部之端部為直線狀及/或呈凹曲的觸媒(A);(2)該觸媒群之藉由振動試驗而得之朝上比率為70%以下;(觸媒群之藉由振動試驗而得之朝上比率之測定法)將於觸媒群中隨機地抽選之100個環形狀之觸媒放入至不鏽鋼方型托盤(寬度296mm,長度231mm,高度49mm),將該不鏽鋼方型托盤安裝於數位振盪器FLK-L330-D(AS ONE股份有限公司製造),以往返振動寬度10mm且振動速度350次往返/分鐘振動1分鐘後,將該100個環形狀之觸媒中空腔部朝上之觸媒之個數設為朝上比率。
- 一種觸媒群,其包含200個以上之環形狀之觸媒,該環形狀之觸媒係於使不飽和醛進行氣相接觸氧化而製造對應之不飽和羧酸時所使用之具有直體部及空腔部者,並且該觸媒群滿足下述(1)及(2),(1)包含該直體部之長度較該空腔部之長度短,該直體部位於該空腔部之包含一端部之面與包含另一端部之面之間,且於至少一端部由該直體部之端部至該空腔部之端部為直線狀及/或呈凹曲的觸媒(A);(2)該觸媒群之藉由振動試驗而得之朝上比率為70%以下;(觸媒群之藉由振動試驗而得之朝上比率之測定法)將於觸媒群中隨機地抽選之100個環形狀之觸媒放入至不鏽鋼方型托盤(寬度296mm,長度231mm,高度49mm),將該不鏽鋼方型托盤安裝於數位振盪器FLK-L330-D(AS ONE股份有限公司製造),以往返振動寬度10mm且振動速度350次往返/分鐘振動1分鐘後,將該100個環形狀之觸媒中空腔部朝上之觸媒之個數設為朝上比率。
- 如請求項10或11之觸媒群,其中,上述觸媒(A)之將上述直體部之端部與上述空腔部之端部連結之面和上述直線狀部或凹曲之面間之最大距離(mm),相對於上述直體部之端部與上述空腔部之端部之間之距離(mm)的比為0以上且0.2以下。
- 如請求項10或11之觸媒群,其中,於上述觸媒(A)之兩端部,由上述直體部之端部至上述空腔部之端部為直線狀及/或呈凹曲。
- 一種丙烯醛及/或丙烯酸之製造方法,其係於請求項10之觸媒群之存在下使丙烯進行氣相接觸氧化。
- 一種丙烯酸之製造方法,其係於請求項11之觸媒群之存在下使丙烯醛進行氣相接觸氧化。
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