SE457506B - Catalyst for ammoxidation of olefin(s) and alkyl-substd. aromatic(s) - Google Patents
Catalyst for ammoxidation of olefin(s) and alkyl-substd. aromatic(s)Info
- Publication number
- SE457506B SE457506B SE8800769A SE8800769A SE457506B SE 457506 B SE457506 B SE 457506B SE 8800769 A SE8800769 A SE 8800769A SE 8800769 A SE8800769 A SE 8800769A SE 457506 B SE457506 B SE 457506B
- Authority
- SE
- Sweden
- Prior art keywords
- catalyst
- oxygen
- ammonia
- mixtures
- olefins
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 title description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000001301 oxygen Substances 0.000 claims abstract description 41
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 23
- 238000002485 combustion reaction Methods 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005977 Ethylene Substances 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract 4
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 150000002825 nitriles Chemical class 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 150000002924 oxiranes Chemical class 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 150000002118 epoxides Chemical class 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 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 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 235000019854 cupric carbonate Nutrition 0.000 description 2
- 239000011646 cupric carbonate Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101100298295 Drosophila melanogaster flfl gene Proteins 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 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
- -1 NO and NO 1 Chemical class 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- OVFCVRIJCCDFNQ-UHFFFAOYSA-N carbonic acid;copper Chemical compound [Cu].OC(O)=O OVFCVRIJCCDFNQ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
457 506 10 15 20 25 30 35 2 de kända katalysatorerna är ofta komplex, men i regel ingår en eller flera oxider av vanadin, vismut, volfram, molybden, antimon och tenn. De kända kataly- satorerna kan även innehålla promotorer, och fosfor, såsom kalium och den aktiva fasen kan vara fixerad på en bärare. 457 506 10 15 20 25 30 35 2 the known catalysts are often complex, but usually one or more oxides of vanadium, bismuth, tungsten, molybdenum, antimony and tin are included. The known catalysts may also contain promoters, and phosphorus, such as potassium and the active phase, may be fixed on a support.
Icke selektiv katalytisk oxidation av kolväten till koloxider och vatten är av intresse ur miljövårds- synpunkt. Rökgaser från stationära källor liksom ut- släpp från motorfordon kan renas genom denna typ av oxidation.Non-selective catalytic oxidation of hydrocarbons to carbon oxides and water is of interest from an environmental point of view. Flue gases from stationary sources as well as emissions from motor vehicles can be purified by this type of oxidation.
Som katalysatorer har man ädelmetaller på bärare. här ofta använt Metalloxider har lägre aktivi- tet, men vid rening av rökgaser kan dock CuO och Cr2O3 användas.As catalysts, precious metals are supported. Metal oxides often used here have lower activity, but CuO and Cr2O3 can be used when purifying flue gases.
Beträffande rening av utsläpp innehållande kväve- oxider har man i motorfordon särskilt använt ädelmetall- katalysatorer, medan man vid rökgasrening företrädesvis använt katalysatorer baserade på vanadinoxider. Ändamålet med föreliggande uppfinning är att åstadkomma en katalysator för - ammonoxidation av olefiner och alkylsubstituerade aromater, som även kan vara halidsubstituerade, motsvarande nitriler i närvaro av atmosfär inneh syrgas och ammoniak, - totalförbränning av kolväten i nä haltig atmosfär, till ållande rvaro av'syrgas- - oxidation av koloxid till koldioxid i närvaro av syrgashaltig atmosfär, ~ oxidation av olefiner, företrädesvis eten och propen, till epoxider, företrädesvis etenoxider och propen- oxider, - reduktion av kväveoxider till kvävgas i närvaro av atmosfär innehållande ammoniak och syrgas.With regard to the purification of emissions containing nitrogen oxides, precious metal catalysts have been used in motor vehicles in particular, while in the case of flue gas purification, catalysts based on vanadium oxides have preferably been used. The object of the present invention is to provide a catalyst for - ammonoxidation of olefins and alkyl-substituted aromatics, which may also be halide-substituted, corresponding to nitriles in the presence of atmosphere containing oxygen and ammonia, - total combustion of hydrocarbons in a nitrogen atmosphere, - oxidation of carbon monoxide to carbon dioxide in the presence of an oxygen-containing atmosphere, - oxidation of olefins, preferably ethylene and propylene, to epoxides, preferably ethylene oxides and propylene oxides, - reduction of nitrogen oxides to nitrogen gas in the presence of an atmosphere containing ammonia and oxygen.
Katalysatorn enligt uppfinningen kännetecknas av att den har sammansättningen AE2C306+¿ varvid o5a<1, 10 15 20 25 30 35 457^506 3 A är yttrium, någon av de sällsynta jordartsmetallerna <57La till 71 B är barium,-kalcium eller strontium eller blandningar Lu) eller vismut, eller blandningar därav, därav, C är koppar, nickel eller kobolt eller blandningar därav, O är syre, och av att den har någon av följande kristallstruk- turtyper: eller övergángsformer mellan dessa.The catalyst according to the invention is characterized in that it has the composition AE2C306 + ¿wherein o5a <1, 10 15 is 457 ^ 506 3 A is yttrium, any of the rare earth metals <57La to 71B is barium, -calcium or strontium or mixtures Lu ) or bismuth, or mixtures thereof, thereof, C is copper, nickel or cobalt or mixtures thereof, O is oxygen, and in that it has any of the following crystal structure types: or transition forms between them.
Katalysatorn enligt uppfinningen kan även föreligga såsom Al203, Si02, TiO2 eller ZrO2.The catalyst according to the invention may also be present as Al 2 O 3, SiO 2, TiO 2 or ZrO 2.
Ett känt material med denna atomstruktur, YBa2Cu3O6+¿, ingår i de på senare tid utvecklade högtemperatursupra- ledande oxidsystemen. Att material av denna typ även uppburen av en bärare, kan användas som katalysatorer är emellertid helt överraskande och inte tidigare beskrivet.A known material with this atomic structure, YBa2Cu3O6 + ¿, is part of the recently developed high-temperature superconducting oxide systems. However, it is quite surprising and not previously described that materials of this type, even supported by a support, can be used as catalysts.
En katalysators egenskaper är relaterade till dess atomstruktur. Olika faser har således mer eller mindre skilda katalytiska egenskaper. Även en och samma fas kan, beroende pá tillverkningsmetod, uppvisa olika katalytiska egenskaper. Detta kan bero på att olika framställningsmetoder ger produkter som exponerar 457 506 10 15 20 25 30 35 4 olika kristallografiska plan av samma fas. Man kan inte direkt av ett materials kristallstruktur se om detta går att använda som en katalysator eller inte.The properties of a catalyst are related to its atomic structure. Different phases thus have more or less different catalytic properties. Even one and the same phase can, depending on the manufacturing method, exhibit different catalytic properties. This may be because different production methods give products that expose 457 506 10 15 20 25 30 35 4 different crystallographic planes of the same phase. It is not possible to see directly from the crystal structure of a material whether this can be used as a catalyst or not.
Att en eller flera av de i strukturen ingående grund- ämnena återfinnes i andra katalysatorer som kan använ- das på liknande områden som föreliggande katalysator är inget som helst bevis för att materialet använda som katalysator för dessa ändamål. gàr att Katalysatorn enligt föreliggande uppfinning skiljer sig fràn tidigare kända katalysatorer med samma använd- ning både beträffande sin atomstruktur ning. och sammansätt- Katalysatorn enligt föreliggande uppfinning har ovan angivna sammansättning. Det typiska för denna katalysator är att den kan variera sitt innehåll av syreatomer. Syreinnehâllet kan således variera från 6 syreatomer per enhetscell till 7 syreatomer. Upp till ett syretal av ungefär 6,5 atomer har katalysatorn ovanstående atomstrukturtyp I. Det finns en A-atom per enhetscell och två B-atomer, såsom framgår av figuren. De tre C-atomerna är koordinerade till syret så att den ena typen har två syregrannar medan den andra typen har fem syregrannar. är tetragonal.The fact that one or more of the elements included in the structure are found in other catalysts which can be used in similar fields as the present catalyst is no proof whatsoever that the material is used as a catalyst for these purposes. The catalyst according to the present invention differs from previously known catalysts with the same use both in terms of its atomic structure. and composition The catalyst of the present invention has the above composition. The typical thing about this catalyst is that it can vary its content of oxygen atoms. The oxygen content can thus vary from 6 oxygen atoms per unit cell to 7 oxygen atoms. Up to an oxygen number of about 6.5 atoms, the catalyst has the above atomic structure type I. There is one A atom per unit cell and two B atoms, as shown in the figure. The three C atoms are coordinated to oxygen so that one type has two oxygen neighbors while the other type has five oxygen neighbors. is tetragonal.
Denna atomstruktur Som exempel på material med denna struk- turtyp kan nämnas YBa2Cu3O6, och karaktäristiska enhets- celldata för denna förening är angivna i tabell l.This atomic structure Examples of materials with this type of structure include YBa2Cu3O6, and characteristic unit cell data for this compound are given in Table 1.
Syrehalten i katalysatorns kristaller bestäms bland annat av omgivande temperatur och omgivningens redoxegenskaper. När det tvâ-koordinerade kopparläget i den exemplifierade strukturtypen har uppnått en viss syrekoordination (nära 4) slår atomstrukturen om till en ny fas med nästan samma atomstruktur, gen strukturtypen II ovan. Denna struktur har nu delvis fyr-koordinerade C-atomer i ett plan och är ortorombisk.The oxygen content of the catalyst crystals is determined, among other things, by the ambient temperature and the redox properties of the environment. When the two-coordinated copper position in the exemplified structure type has reached a certain oxygen coordination (close to 4), the atomic structure switches to a new phase with almost the same atomic structure, gene structure type II above. This structure now has partially four-coordinated C atoms in a plane and is orthorombic.
Enhetscelldata for denna strukturtyp, med YBa nämli- exemplifierad 2Cu307, är likaså angivna i tabell 1. 10 15 20 25 30 35 457 50.6 5 Tabell 1 Kristalldata för strukturtyperna exemplifierade av YBa2Cu3O6 och YBa2Cu3O7 (från Swinnea, J.S. & Steinfink, H., J. Mater. Res. 2, 424 (1987)) och Beech, F. et al, Phys. Rev. gåâ, 8778 (1987) Cellinnehàll YBa2Cu3O6 YBa2Cu3O7 Kristallsystem tetragonal ortorombisk Rymdgrupp P4/mmm Pmmm Enhetscelldimensioner a = b = 3,863(2) a = 3,8l98(l) (Å) ) = ll,830(4) b = 3,8849(l) c = ll,6762(3) Denna strukturtyp kan även uttryckas på följande Sätt: Strukturbeskrivning Atm- Brâkdelskoordinater Antal abuner per Antal atrner per slag i enhštsceålen cell i YBa2Cu3O6 cell i YBa2CU3O7 Y l/2 l/2 l/2 1 l Ba 1/2 l/2 i!! 0,19 2 2 Cul 0 0 0 1 1 Cu2 0 0 nå 0,36 2 2 01 O O Q! 0,15 2 2 02 1/2 0 Q! 0,38 2 2 03 0 1/2 Rå 0,38 2 2 04 0 l/2 0 O l I YBa2Cu3O6 slås O2 och O3 ihop till ett läge pga den högre symmetrin. Vid intermediära syresammansätt- ningar uppträder dessutom en viss halt av syreatomer i läget (05: 1/2 O 0).Unit cell data for this structure type, with YBa namely-exemplified 2Cu307, are also given in Table 1. 10 15 20 25 30 35 457 50.6 Table 1 Crystal data for the structure types exemplified by YBa2Cu3O6 and YBa2Cu3O7 (from Swinnea, JS & Jf Steinfink, H. Mater, Res. 2, 424 (1987)) and Beech, F. et al, Phys. Reef. gåâ, 8778 (1987) Cell contents YBa2Cu3O6 YBa2Cu3O7 Crystal system tetragonal orthorhombic Space group P4 / mmm Pmmm Unit cell dimensions a = b = 3.863 (2) a = 3.8l98 (l) (Å)) = ll, 830 (4) b = 3.8849 (l) c = ll, 6762 (3) This structure type can also be expressed in the following ways: Structure description Atm- Fractional coordinates Number of subscribers per Number of atrns per type in the unit cell cell in YBa2Cu3O6 cell in YBa2CU3O7 Y l / 2 l / 2 l / 2 1 l Ba 1/2 l / 2 i !! 0.19 2 2 Cul 0 0 0 1 1 Cu2 0 0 now 0.36 2 2 01 O O Q! 0.15 2 2 02 1/2 0 Q! 0.38 2 2 03 0 1/2 Raw 0.38 2 2 04 0 l / 2 0 O l In YBa2Cu3O6, O2 and O3 are combined to a position due to the higher symmetry. In the case of intermediate oxygen compositions, a certain content of oxygen atoms also occurs in the position (05: 1/2 O 0).
Att den katalytiskt aktiva föreningen enligt uppfinningen har den angivna strukturtypen har veri- fierats med flera metoder: l Atomupplösande transmissionselektronmikroskopi.The fact that the catalytically active compound according to the invention has the specified structure type has been verified by several methods: Atomic resolution transmission electron microscopy.
Denna har verifierat att katalysatorn har den angivna atomstrukturen genom att varje metallatom kan identi- fieras i direkta bilder av kristaller undersökta före och efter katalytiska reaktioner i en reaktor. 2 Kvantitativ kemisk analys medelst energidispersiv 457 506 10 15 6 analys av karaktäristisk röntgenstrálning alstrad i svepelektronmikroskop eller transmissionselektron- mikroskop. Katalysatorn uppvisar både före och efter reaktionen den typiska l:2:3-sammansättningen beträf- fande de tre positiva metalljonslagen. Analysspektra före och efter användning av en katalysator enligt uppfinningen såsom nitrilselektiv katalysator visas i fig l. Dataanalys av dessa spektra gav inom experimen- tella standardavvikelser formeln YBa2Cu3O6+¿. Syrehalten kan inte bestämmas med denna metod. 3 Katalysatorfaserna har även undersökts av pulverröntgendiffraktion. med hjälp Noggranna avstånd mellan atomgitterplan har bestämts och röntgenlinjernas inten- sitet har undersökts. Av nedanstående tabell 2 framgår det att dessa värden visar god överensstämmelse med litteraturdata och man kan därför med fullständig säkerhet sluta sig till att katalysatorerna har den angivna atomstrukturen. 5 10 15 20 25 30 35 457 506 7 Tabe11 2 Pulverröntgendata a) Färsk katalysator b) Referensdata för YBa2Cu3O6,9x aOBS(A) 1/16 <8) h k 1 d0BS(Å) 1/IQ (3) 11,809 1 0 0 2 5,844 2 5,878 2 0 0 3 3,893 11 3,903 10 1 0 0 3,822 3,830 3 0 1 2 3,235 3,240 1 0 2 3,198 3,199 0 1 3 2,750 60 2,924 1 0 3 2,726 100 2,754 53 1 1 0) 2,728 100 1 1 1 2,653 2 2,657 1 1 1 2 2,469 2,471 3 0 0 5 2,336 11 2,338 15 1 0 4 2,321 3 2,234 17 1 1 3 2,232 13 ' 1,994 1 0 2 0 1,946 23 1,946 23 0 0 6J 1,911 13 2 0 0 1,911 10 1,774 4 1 ~1 5 1,775 3 1,741 2 0 1 6 1,741 2 1,735 2 0 2 3} 1,716 2 1 0 6 1,734 2 1,669 2 1 2 o} ' 1,659 1 2 0 3 1,645 1 2 1 0} 1,716 2 1,583 35 1 2 1 1,569 14 1 2 2 1,662 1 1,529 1 1 2 3 1,584 24 1,494 2 1 1 6] 1,478 3 2 1 3 1,569 11 1,423 2 1,375 4 1,363 13 “ 58, 1676 (1987) R. J. Cava et al., Phys. Rev. Lett. 457 506 8 4 Längden på enhetscellens c-axel ändras kontinuer- ligt med halten av syreatomer i kristaller av exempelvis YBa2Cu3O6+¿ (0 3 6 5 1). Skillnaden i c-axelns längd mellan ändkomponenterna är 0,15 Å (se tabell l). Denna längd har använts för att genom extrapolering beräkna resultatet framgår av tabell 3. 457 506 ^mvmmNæ.~H ^Hvwmæ\HH ^HV«wß.HH ^Hvoæw.~H ^<.o m u m H m u ^wvmwæw_m ^<.n ^Nvmwmw.m ^mvowmæ\m ^mVHæmm.m ^vVmmHm.m ñævm umcofimcwäflv |HHmUwuw:cm Hmcommuuwu Hmcommuumu Hmcommuuwu xmflnaououuo flnuwääæw O.@om:u~mm» o_womøu~mmæ «.wom:u~mm> o_>om:u~mmw mcflnuuwwsmeewm mflflumwwmnn Acofluxøfimu umuwwv ^C0flvMøUwH Hwvwwv Acøflvxflwmu W%muv uoßmwæfimwmx uoumwæfimumx uoummæfimwmx noflmmhfimwmx >fluxmfimm| Oo >HuxmHwm|HfluuflZ >fluxwHww| oo xwnmm boum HÜGOH WGÜEHÜHHQUWPUÃCmH m fifiwßmä 457 506 10 15 20 25 30 35 10 Sammantaget ger således dessa analyser en bekräftelse av den angivna strukturen.This has verified that the catalyst has the specified atomic structure in that each metal atom can be identified in direct images of crystals examined before and after catalytic reactions in a reactor. 2 Quantitative chemical analysis by means of energy dispersive 457 506 10 15 6 analysis of characteristic X-rays generated in a scanning electron microscope or transmission electron microscope. Both before and after the reaction, the catalyst exhibits the typical 1: 2: 3 composition with respect to the three positive metal ion layers. Analytical spectra before and after use of a catalyst according to the invention as nitrile-selective catalyst are shown in Fig. 1. Data analysis of these spectra gave, within experimental standard deviations, the formula YBa2Cu3O6 + ¿. The oxygen content cannot be determined with this method. The catalyst phases have also been examined by powder X-ray diffraction. with help Accurate distances between atomic lattice planes have been determined and the intensity of the X-ray lines has been investigated. Table 2 below shows that these values show good agreement with the literature data and it can therefore be concluded with complete certainty that the catalysts have the specified atomic structure. 5 10 15 20 25 30 35 457 506 7 Tabe11 2 Powder X-ray data a) Fresh catalyst b) Reference data for YBa2Cu3O6,9x aOBS (A) 1/16 <8) hp 1 d0BS (Å) 1 / IQ (3) 11,809 1 0 0 2 5,844 2 5,878 2 0 0 3 3,893 11 3,903 10 1 0 0 3,822 3,830 3 0 1 2 3,235 3,240 1 0 2 3,198 3,199 0 1 3 2,750 60 2,924 1 0 3 2,726 100 2,754 53 1 1 0) 2,728 100 1 1 1 2,653 2 2,657 1 1 1 2 2,469 2,471 3 0 0 5 2,336 11 2,338 15 1 0 4 2,321 3 2,234 17 1 1 3 2,232 13 '1,994 1 0 2 0 1,946 23 1,946 23 0 0 6J 1,911 13 2 0 0 1,911 10 1,774 4 1 ~ 1 5 1,775 3 1,741 2 0 1 6 1,741 2 1,735 2 0 2 3} 1,716 2 1 0 6 1,734 2 1,669 2 1 2 o} '1,659 1 2 0 3 1,645 1 2 1 0} 1,716 2 1,583 35 1 2 1 1,569 14 1 2 2 1,662 1 1,529 1 1 2 3 1,584 24 1,494 2 1 1 6] 1,478 3 2 1 3 1,569 11 1,423 2 1,375 4 1,363 13 “58, 1676 (1987) RJ Cava et al., Phys. Reef. Easy. 457 506 8 4 The length of the c-axis of the unit cell changes continuously with the content of oxygen atoms in crystals of, for example, YBa2Cu3O6 + ¿(0 3 6 5 1). The difference in the length of the c-axis between the end components is 0.15 Å (see Table 1). This length has been used to calculate the result by extrapolation is shown in Table 3. 457 506 ^ mvmmNæ. ~ H ^ Hvwmæ \ HH ^ HV «wß.HH ^ Hvoæw. ~ H ^ <. Omum H mu ^ wvmwæw_m ^ <. N ^ Nvmwmw.m ^ mvowmæ \ m ^ mVHæmm.m ^ vVmmHm.m ñævm umco fi mcwä fl v | HHmUwuw: cm Hmcommuuwu Hmcommuumu Hmcommuuwu xm fl naououuo fl nuwääæw O. ~ om: u om ~ u ~ mm: u. u ~ mmw mc fl nuuwwsmeewm m flfl umwwmnn Aco fl uxø fi mu umuwwv ^ C0 fl vMøUwH Hwvwwv Acø fl vx fl wmu W% muv uoßmwæ fi mwmx uoumwæ fi mumx uoummæ fl mwm fl mwm um mwm> Oo> HuxmHwm | H fl uu fl Z> fl uxwHww | oo xwnmm boum HÜGOH WGÜEHÜHHQUWPUÃCmH m fifi wßmä 457 506 10 15 20 25 30 35 10 Taken together, these analyzes thus provide a confirmation of the specified structure.
Katalysatorn enligt föreliggande uppfinning har den unika egenskapen att den fungerar både som en selektiv ammonoxidationskatalysator och som en total- förbränningskatalysator. Som selektiv ammonoxidations- katalysator har den den ovan angivna strukturen I, dvs dess syrehalt ligger i området närmast 6 syreatomer.The catalyst of the present invention has the unique property of functioning both as a selective ammonia oxidation catalyst and as a total combustion catalyst. As a selective ammonia oxidation catalyst, it has the above-mentioned structure I, i.e. its oxygen content is in the range closest to 6 oxygen atoms.
Som totalförbränningskatalysator har katalysatorn en syrehalt i området upp till 7 syreatomer.As a total combustion catalyst, the catalyst has an oxygen content in the range up to 7 oxygen atoms.
Katalysatorn kan således användas för selektiv ammonoxidation av olefiner och alkylsubstituerade aromatiska föreningar, tuerade, som även kan vara halidsubsti- till motsvarande nitriler. Den kan även använ- das vid totalförbränning av kolväten i frånvaro av ammoniak till koldioxid och vatten. Eftersom koloxid utgör en mellanprodukt vid totaloxidationen av kolväten till koldioxid kan katalysatorn således även användas för oxidation av kolmonoxid till koldioxid.The catalyst can thus be used for the selective ammonium oxidation of olefins and alkyl-substituted aromatic compounds, which can also be halide substituents for the corresponding nitriles. It can also be used for the total combustion of hydrocarbons in the absence of ammonia to carbon dioxide and water. Thus, since carbon monoxide is an intermediate in the total oxidation of hydrocarbons to carbon dioxide, the catalyst can also be used to oxidize carbon monoxide to carbon dioxide.
Det första steget vid totaloxidation av aromatiska föreningar och olefiner utgöres av ett angrepp på reaktantmolekylens dubbelbindning(ar) och således kan katalysatorn även användas vid epoxidation av olefiner till epoxider. f Vid selektiv ammonoxidation uppvisar katalysatorn bättre aktivitet och selektivitet än hittills kända katalysatorer. Den har vidare en mycket hög aktivitet under totalförbränningsbetingelser. På grund av kataly- satorns förmåga att aktivera ammoniak kan den med fördel även användas för reduktion av kväveoxider genom reaktion med ammoniak.The first step in the total oxidation of aromatic compounds and olefins is an attack on the double bond (s) of the reactant molecule and thus the catalyst can also be used in the epoxidation of olefins to epoxides. f In selective ammonia oxidation, the catalyst exhibits better activity and selectivity than hitherto known catalysts. It also has a very high activity under total combustion conditions. Due to the catalyst's ability to activate ammonia, it can also be used to advantage for the reduction of nitrogen oxides by reaction with ammonia.
Katalysatorns selektivitet, dvs dess förmåga att omvandla kolväten till nitriler, koldioxid, epoxider respektive styrs huvudsakligen genom noggrann regle- ring av syrgasens partialtryck i reaktionsatmosfären.The selectivity of the catalyst, ie its ability to convert hydrocarbons to nitriles, carbon dioxide, epoxides, respectively, is mainly controlled by careful control of the partial pressure of the oxygen in the reaction atmosphere.
Som exempel på aromatisk oxidation i närvaro av ammoniak, s k ammonoxidation, där katalysatorn 10 15 20 25 30 35 4-57 506 ll enligt föreliggande uppfinning kan användas för fram- ställning av nitriler, kan nämnas ammonoxidation av toluen och xylener (orto-, meta- och para-) till benso- nitril respektive tolu- och dinitriler. Ett annat exempel är ammonoxidation av alkylsubstituerade pyri- dinringar, t ex a-pikolin, B-pikolin och Y-pikolin, till motsvarande nitriler. Även olefiner kan reagera med ammoniak i närvaro av syrgas till nitriler. Ett exempel är ammonoxidation av propen till akrylnitril.As examples of aromatic oxidation in the presence of ammonia, so-called ammonia oxidation, where the catalyst 10 15 20 25 30 35 4-57 506 ll according to the present invention can be used for the production of nitriles, may be mentioned ammonoxidation of toluene and xylenes (ortho, meta and para-) to benzonitrile and toluene and dinitriles, respectively. Another example is ammonium oxidation of alkyl-substituted pyridine rings, eg α-picoline, β-picoline and γ-picoline, to corresponding nitriles. Olefins can also react with ammonia in the presence of oxygen to nitriles. An example is ammonium oxidation of propylene to acrylonitrile.
Oxidation av olefiner kan även genomföras i från- varo av ammoniak som en s k epoxidation. Vid denna reagerar olefinens dubbelbindning med syre, varvid en epoxid bildas. Exempel på sådana reaktioner är epoxidation av eten till etenoxid och propen till propenoxid.Oxidation of olefins can also be carried out in the absence of ammonia as a so-called epoxidation. In this case, the double bond of the olefin reacts with oxygen, whereby an epoxide is formed. Examples of such reactions are epoxidation of ethylene to ethylene oxide and propylene to propylene oxide.
Reduktion av kväveoxider, som t ex NO och NO 1 kan ske i närvaro av syrgas och ammoniak. I dettaz fall omvandlas kväveoxiden till N2, genom reaktion med ammoniak under bildning av vatten.Reduction of nitrogen oxides, such as NO and NO 1, can take place in the presence of oxygen and ammonia. In this case, the nitric oxide is converted to N2, by reaction with ammonia to form water.
I de bifogade ritningarna visar: fig l intensiteten i röntgenspektrum från katalysatorn enligt uppfinningen före och efter användning som nitrilselektiv katalysator, fig 2 hastigheten för bildning av bensonitril och C02 som funktion av partialtrycket för syrgas.In the accompanying drawings: Fig. 1 shows the intensity of X-ray spectrum from the catalyst according to the invention before and after use as a nitrile selective catalyst, Fig. 2 shows the rate of formation of benzonitrile and CO 2 as a function of the partial pressure of oxygen.
Uppfinningen kommer att närmare beskrivas i nedan- stående exempel, som dels är exempel pà framställning av katalysatorer enligt uppfinningen och dels är exempel som visar användningen av katalysatorerna enligt uppfin- ningen. I samtliga nedanstående syntesexempel kan yttrium (Y) bytas ut mot de sällsynta jordartsmetallerna (grundämnena 57La t o m 7lLu) utan att katalysatorns atomstruktur förändras. Yttrium kan även bytas ut mot Bi. Barium kan bytas ut helt eller delvis mot strontium eller kalcium med samma atomstruktur hos katalysatorn som slutresultat. Kopparatomerna i kata- lysatorn kan bytas ut mot kobolt och/eller mot nickel 457 506 10 15 20 25 30 35 12 så att en kopparatom av de tre i strukturen b Exempel l 1/2 mol yttriumoxid (YZO lir utbytt. 3), 2 mol bariumkarbonat (BaCO3) och 3 mol koppar(II)oxid (CuO) blandas under aceton i kulkvarn under 2 h och pressas därefter samman under ett tryck av ca 600 MPa. Det sammanpressade materialet kalcineras under lufttillträde vid 900°C i minst 24 h. Provet pulveriseras sedan åter och blandas väl i mortel eller kulkvarn. Sammanpressning sker sedan åter under ett tryck av ca 600 MPa. Materialet upphettas åter till 900°C och får sedan svalna mycket långsamt under minst 8 h ned till 600°C under ren syrgas eller med snabb genomströmning av luft. Tempe- raturen sänks sedan under 8 h ned till 200°C, under ren syrgas. fortfarande Den bildade katalysatorn har en sammansättning av YBa Cu O . 2 3 7 Exempel_2 Under användning av samma utgángsmaterial och i samma mängder som i exempel l genomföres en blandning, sammanpressning och kalcinering såsom enligt exempel 1.The invention will be described in more detail in the examples below, which are partly examples of the preparation of catalysts according to the invention and partly are examples which show the use of the catalysts according to the invention. In all of the synthetic examples below, yttrium (Y) can be replaced by the rare earth metals (elements 57La to 7lLu) without changing the atomic structure of the catalyst. Yttrium can also be replaced with Bi. Barium can be replaced in whole or in part by strontium or calcium with the same atomic structure of the catalyst as the end result. The copper atoms in the catalyst can be exchanged for cobalt and / or for nickel 457 506 10 15 20 25 30 35 12 12 so that a copper atom of the three in structure b Example 1 1/2 mol of yttrium oxide (YZO lir replaced. 3), 2 moles of barium carbonate (BaCO3) and 3 moles of copper (II) oxide (CuO) are mixed under acetone in a ball mill for 2 hours and then compressed under a pressure of about 600 MPa. The compressed material is calcined during air access at 900 ° C for at least 24 hours. The sample is then pulverized again and mixed well in a mortar or ball mill. Compression then takes place again under a pressure of about 600 MPa. The material is reheated to 900 ° C and then allowed to cool very slowly for at least 8 hours down to 600 ° C under pure oxygen or with rapid flow of air. The temperature is then lowered for 8 hours down to 200 ° C, under pure oxygen. still The catalyst formed has a composition of YBa Cu O. Example 2 Using the same starting material and in the same amounts as in Example 1, a mixing, compression and calcination is carried out as in Example 1.
Därefter mals och blandas katalysatorn och pressas sedan ihop och värms i en strömmande gasatmosfär av argon eller kväve till 900°C och får sedan svalna mycket långsamt under minst 24 h till 200°C. Härvid erhålles en katalysator med sammansättningen YBa2Cu306.The catalyst is then ground and mixed and then compressed and heated in a flowing gas atmosphere of argon or nitrogen to 900 ° C and then allowed to cool very slowly for at least 24 hours to 200 ° C. This gives a catalyst with the composition YBa2Cu3O6.
Exempel_â l mol yttriumnitrat (Y(N03)3.4H2O), 2 mol barium- nitrat (Ba(NO3)2) och 3 mol kopparnitrat (Cu(NO3)2.3H20) löses i lO0 ml vatten. Därefter inblandas långsamt en lösning av oxalsyra (HOZCCOZH) i överskott (mer än 6 mol). Den erhållna samfällningen av yttrium-, barium- och kopparoxalat filtreras av och torkas vid l50°C. Oxalatblandningen sammanpressas under ett tryck av ca 600 MPa och upphettas långsamt under 8 h till 900°C i luft. Därefter fortsätter man i enlighet med exempel l eller 2. Härigenom erhålles en produkt med sammansättningen YBa Cu O 2 3 7 enligt exempel l respektive 10 15 20 25 30 35 457 506 13 YBa Cu 0 enligt exempel 2. 2 3 6 åæmpelil 1/2 mol yttriumkarbonat (Y2(C03)3.3H2O), 2 mol bariumkarbonat (BaCO3) och 1 1/2 mol basiskt koppar(II)- karbonat (CuCO3.Cu(OH)2) blandas med ett molärt över- skott (mer än 4 mol) av fast citronsyra (HOC(CH2CO2H)2CO2H) och l/2 ml vatten per gram blandning tillsätts under omröring. Lösningen värms sedan till 70°C, varvid en klar blåaktig viskös vätska slutligen erhålles.Example 1 - 1 mole of yttrium nitrate (Y (NO 3) 3,4H 2 O), 2 moles of barium nitrate (Ba (NO 3) 2) and 3 moles of copper nitrate (Cu (NO 3) 2,3H 2 O) are dissolved in 10 ml of water. Then slowly add a solution of oxalic acid (HOZCCOZH) in excess (more than 6 mol). The resulting precipitate of yttrium, barium and copper oxalate is filtered off and dried at 150 ° C. The oxalate mixture is compressed under a pressure of about 600 MPa and heated slowly for 8 hours to 900 ° C in air. Then proceed in accordance with Example 1 or 2. This gives a product with the composition YBa Cu O 2 3 7 according to Example 1 and 10 15 20 25 30 35 457 506 13 YBa Cu 0 according to Example 2, respectively. mol of yttrium carbonate (Y2 (CO3) 3.3H2O), 2 mol of barium carbonate (BaCO3) and 1 1/2 mol of basic copper (II) carbonate (CuCO3.Cu (OH) 2) are mixed with a molar excess (more than 4 mol) of solid citric acid (HOC (CH 2 CO 2 H) 2 CO 2 H) and 1/2 ml of water per gram of mixture are added with stirring. The solution is then heated to 70 ° C, whereby a clear bluish viscous liquid is finally obtained.
Denna lösning är homogen och kan förvaras länge.This solution is homogeneous and can be stored for a long time.
Fortsatt syntes av katalysatorn sker genom in- dunstning av lösningen vid l50°C. Kalcinering av pulvret genomföres sedan vid 850-880°C under minst 8 h i luft.Further synthesis of the catalyst takes place by evaporating the solution at 150 ° C. Calcination of the powder is then carried out at 850-880 ° C for at least 8 hours in air.
Pulvret pressas sedan till en tablett under ett tryck av ca 600 MPa och upphettas till 900°C i syrgas i minst 24 h. Avsvalning och temperering i syrgas sker i enlighet med exempel 1.The powder is then compressed into a tablet under a pressure of about 600 MPa and heated to 900 ° C in oxygen for at least 24 hours. Cooling and tempering in oxygen takes place in accordance with Example 1.
Exempel 5 En katalysator med sammansättningen YBa2Cu3O7 framställes genom att blanda stökiometriska mängder 2 3, BaCO3 mortel i närvaro av aceton. Blandningen pressades av Y och CuO. Denna blandning maldes i en till tabletter, vilka därefter upphettades vid 950°C i 17 h. Blandningen ommaldes och tabletterades och de bildade tabletterna behandlades i en syrgasström vid 950°C i ytterligare 17 h. Den framställda kataly- satorn kyldes i en syrgasström under 8 h till l80°C.Example 5 A catalyst with the composition YBa 2 Cu 3 O 7 is prepared by mixing stoichiometric amounts of 2 3, BaCO 3 mortar in the presence of acetone. The mixture was pressed by Y and CuO. This mixture was ground in another tablet, which was then heated at 950 ° C for 17 hours. The mixture was ground and tableted and the resulting tablets were treated in a stream of oxygen at 950 ° C for a further 17 hours. The prepared catalyst was cooled in a stream of oxygen for 8 hours to 180 ° C.
Tabletterna krossades därefter till mindre partiklar, vilka satsades i tubreaktor.The tablets were then crushed into smaller particles, which were charged into a tube reactor.
Den framställda katalysatorn användes vid ammon- oxidation av toluen vid 400°C. Under försöket upprätt- hölls konstanta partialtryck av ammoniak och toluen i ingående gasström av 2,58 kPa respektive 0,767 kPa.The catalyst prepared was used in the ammonium oxidation of toluene at 400 ° C. During the experiment, constant partial pressures of ammonia and toluene were maintained in the incoming gas stream of 2.58 kPa and 0.767 kPa, respectively.
Partialtrycket av syrgas varierades från 26 kPa ned till 9 kPa. Hastigheterna för bildning av bensonitril och C02 fig 2, kurvorna 1 och 2). var oberoende av syrgasens partialtryck (se 457 5 10 15 20 25 30 35 506 14 Efter en reduktiv behandling under l h med en gasström bestående av ammoniak och toluen (samma par- tialtryck som ovan) ökades syrgasens partialtryck.The partial pressure of oxygen varied from 26 kPa down to 9 kPa. The rates of formation of benzonitrile and CO2 (Fig. 2, curves 1 and 2). was independent of the partial pressure of the oxygen (see 457 5 10 15 20 25 30 35 506 14 After a reductive treatment for 1 hour with a gas stream consisting of ammonia and toluene (same partial pressure as above), the partial pressure of the oxygen increased.
Katalysatorn var nu selektiv för nitrilbildning upp till ett syrgaspartialtryck av 8,65 kPa. Reaktions- hastigheten för bildning av bensonitril var som högst 2.l0_5 mol/(min, m2 katalysatoryta) (fig 2, kurva 3).The catalyst was now selective for nitrile formation up to an oxygen partial pressure of 8.65 kPa. The reaction rate for the formation of benzonitrile was at most 2.10_5 mol / (min, m2 catalyst surface) (Fig. 2, curve 3).
Om syrgaspartialtrycket ökades mol/(min, m2 katalysatoryta). Denna hastig- het var 3-4 gånger högre än motsvarande hastighet före den reduktiva behandlingen.If the oxygen partial pressure increased, mol / (min, m2 catalyst surface area). This rate was 3-4 times higher than the corresponding rate before the reductive treatment.
Den använda katalysatorns sammansättning analyse- rades och befanns vara YBa2Cu3O6+¿ (0 § 6 3 1). Stökio- metrin, 6, var beroende av reaktionsbetingelserna och den reduktiva behandlingen. Den selektiva och mest aktiva katalysatorns sammansättning motsvarade 6'~ 0, och den effektivaste totalförbränningskatalysatorn hade en sammansättning motsvarande ett något större värde på 6.The composition of the catalyst used was analyzed and found to be YBa2Cu3O6 + ¿(0 § 6 3 1). The stoichiometry, 6, was dependent on the reaction conditions and the reductive treatment. The composition of the selective and most active catalyst corresponded to 6 '~ 0, and the most efficient total combustion catalyst had a composition corresponding to a slightly larger value of 6.
Exempel § YBa2Cu3O7 framställdes såsom beskrivits i exem- pel 5. Denna katalysator användes för totalförbränning av toluen till koloxider. Försökstemperaturen var 400°C och partialtrycken av toluen och 0,767 kPa respektive 17,3 kPa. av koloxider var 6,8.l0_6 Förhållandet C02/CO var ll syrgas var Hastigheten för bildning mol/(min, g katalysator).Example § YBa 2 Cu 3 O 7 was prepared as described in Example 5. This catalyst was used for the total combustion of toluene to carbon oxides. The test temperature was 400 ° C and the partial pressures of toluene and 0.767 kPa and 17.3 kPa, respectively. of carbon oxides was 6,8.10_6 The ratio CO 2 / CO was 11 oxygen was the rate of formation mol / (min, g catalyst).
Efter reduktiv behandling med toluen och ammo- niak (enligt exempel 5) ökade aktiviteten betydligt Hastigheten för bildning av koloxider var nu 50.l0_6 mol/(min, g katalysator) vid 400°C om partialtrycken för toluen och syrgas var 0,767 kPa respektive 4,3 kPa.After reductive treatment with toluene and ammonia (according to Example 5), the activity increased significantly. The rate of formation of carbon oxides was now 50.10_6 mol / (min, g catalyst) at 400 ° C if the partial pressures of toluene and oxygen were 0.767 kPa and 4, respectively. , 3 kPa.
Förhållandet C02/CO var större än 100. Katalysatorns stökiometri var YBa2Cu306+¿, varvid 5 > 0. I exempel 5 var hastigheten för totalförbränning i närvaro av 10 15 20 25 30 457 506 15 5 mol/(min, m2 katalysatoryta), vilket ammoniak 12.10" 6 g katalysator). Förbrän- motsvarar 12.10- mol/(min, ningshastigheten i frånvaro av ammoniak var alltså 4 gånger större. §rsm2sl_l En katalysator med sammansättningen YBa2Cu3O6 framställdes enligt den metod som beskrivs i exempel 5, med undantag av att den första sintringen genomfördes i luft vid 900°C och den andra sintringen genomfördes i ett argonflöde vid 700°C.The CO 2 / CO ratio was greater than 100. The stoichiometry of the catalyst was YBa 2 Cu 3 O 6 + ¿, where 5> 0. In Example 5, the rate of total combustion in the presence of 10 mol / (min, m2 of catalyst surface) 12.10 "6 g of catalyst). The combustion corresponds to 12.10 mol / min, the rate of reaction in the absence of ammonia was thus 4 times greater. §Rsm2sl_l A catalyst having the composition YBa2Cu3O6 was prepared according to the method described in Example 5, except that the the first sintering was performed in air at 900 ° C and the second sintering was performed in an argon flow at 700 ° C.
Krossad katalysator satsades i en tubreaktor.Crushed catalyst was charged to a tube reactor.
Partialtrycken av syrgas, ammoniak och toluen var 2,15 kPa, 2,58 kPa respektive 0,767 kPa. Katalysatorns selektivitet för bensonitril var större än 90%. Hastig- neten för bi1aning av bensonitril uppmättes ti11 3,s.1o" mol/(min, g katalysator).The partial pressures of oxygen, ammonia and toluene were 2.15 kPa, 2.58 kPa and 0.767 kPa, respectively. The catalyst selectivity for benzonitrile was greater than 90%. The rate of addition of benzonitrile was measured to be 3, s. 10 "mol / (min, g catalyst).
Försöket upprepades med följande partialtryck: syre 17,2 kPa, ammoniak 0 kPa och toluen 0,767 kPa.The experiment was repeated with the following partial pressures: oxygen 17.2 kPa, ammonia 0 kPa and toluene 0.767 kPa.
Selektiviteten för bildning av C02 översteg 99% och 5 mol/(min, hastigheten för bildning därav vara 20.10' g katalysator). §rsm2sl_§ En katalysator innehållande samarium i stället för yttrium satsades i en tubreaktor. Den kördes under totalförbränningsbetingelser med endast toluen, syrgas och inert kvävgas i ingående gasström. Aktiviteten för bildning av CC2 avtog med 30% under den första timmen och var därefter konstant.The selectivity for the formation of CO 2 exceeded 99% and 5 mol / (min, the rate of formation thereof being 20.10 g of catalyst). §Rsm2sl_§ A catalyst containing samarium instead of yttrium was charged to a tube reactor. It was run under total combustion conditions with only toluene, oxygen and inert nitrogen in the incoming gas stream. The activity of CC2 formation decreased by 30% during the first hour and was then constant.
För motsvarande katalysator innehållande yttrium tog det minst 6 h att uppnå konstant aktivitet. Sama- rium har alltså en stabiliserande inverkan. 6For the corresponding catalyst containing yttrium, it took at least 6 hours to achieve constant activity. Samaria thus has a stabilizing effect. 6
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