JP4280797B2 - Method for producing composite oxide catalyst - Google Patents
Method for producing composite oxide catalyst Download PDFInfo
- Publication number
- JP4280797B2 JP4280797B2 JP2002330930A JP2002330930A JP4280797B2 JP 4280797 B2 JP4280797 B2 JP 4280797B2 JP 2002330930 A JP2002330930 A JP 2002330930A JP 2002330930 A JP2002330930 A JP 2002330930A JP 4280797 B2 JP4280797 B2 JP 4280797B2
- Authority
- JP
- Japan
- Prior art keywords
- producing
- composite oxide
- oxide catalyst
- bismuth
- molybdenum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 65
- 239000002131 composite material Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- 238000000034 method Methods 0.000 claims description 41
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 30
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 30
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 28
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 27
- 229910052750 molybdenum Inorganic materials 0.000 claims description 27
- 239000011733 molybdenum Substances 0.000 claims description 27
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 26
- 230000003197 catalytic effect Effects 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 239000012018 catalyst precursor Substances 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 19
- 229910052797 bismuth Inorganic materials 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 13
- -1 carbonate compound Chemical class 0.000 claims description 12
- 150000001622 bismuth compounds Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 8
- 230000010354 integration Effects 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 7
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 7
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 7
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 7
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 claims description 5
- 239000003125 aqueous solvent Substances 0.000 claims description 5
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 claims description 5
- 229940036358 bismuth subcarbonate Drugs 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229940036348 bismuth carbonate Drugs 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 238000012805 post-processing Methods 0.000 claims 1
- 239000006104 solid solution Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 36
- 239000002002 slurry Substances 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 18
- 239000012071 phase Substances 0.000 description 18
- 238000002156 mixing Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 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 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000005078 molybdenum compound Substances 0.000 description 4
- 150000002752 molybdenum compounds Chemical class 0.000 description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 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 3
- 229910052751 metal Inorganic materials 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 229910052701 rubidium Inorganic materials 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000003679 aging effect Effects 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 150000001621 bismuth Chemical class 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- LVAMVZXECCXUGI-UHFFFAOYSA-N acetic acid;thallium Chemical compound [Tl].CC(O)=O LVAMVZXECCXUGI-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate 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
- 150000002823 nitrates Chemical class 0.000 description 1
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 229910000344 rubidium sulfate Inorganic materials 0.000 description 1
- FOGKDYADEBOSPL-UHFFFAOYSA-M rubidium(1+);acetate Chemical compound [Rb+].CC([O-])=O FOGKDYADEBOSPL-UHFFFAOYSA-M 0.000 description 1
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 1
- JPDBEEUPLFWHAJ-UHFFFAOYSA-K samarium(3+);triacetate Chemical compound [Sm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JPDBEEUPLFWHAJ-UHFFFAOYSA-K 0.000 description 1
- QCZFMLDHLOYOQJ-UHFFFAOYSA-H samarium(3+);tricarbonate Chemical compound [Sm+3].[Sm+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QCZFMLDHLOYOQJ-UHFFFAOYSA-H 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
- LVSITDBROURTQX-UHFFFAOYSA-H samarium(3+);trisulfate Chemical compound [Sm+3].[Sm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LVSITDBROURTQX-UHFFFAOYSA-H 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- GBECUEIQVRDUKB-UHFFFAOYSA-M thallium monochloride Chemical compound [Tl]Cl GBECUEIQVRDUKB-UHFFFAOYSA-M 0.000 description 1
- DASUJKKKKGHFBF-UHFFFAOYSA-L thallium(i) carbonate Chemical compound [Tl+].[Tl+].[O-]C([O-])=O DASUJKKKKGHFBF-UHFFFAOYSA-L 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
この発明は、プロピレン、イソブテン又はターシャリーブタノールからアクロレイン又はメタクロレインを製造する気相接触酸化反応、プロピレン又はイソブテンからアクリロニトリル又はメタクリロニトリルを製造する気相接触アンモ酸化反応、及びブテンからブタジエンを製造する気相接触酸化的脱水素反応等の選択的反応に用いられる複合酸化物触媒の製造方法に関する。
【０００２】
【従来の技術】
プロピレン、イソブテン又はターシャリーブタノールからアクロレイン又はメタクロレインを製造する気相接触酸化反応、プロピレン又はイソブテンからアクリロニトリル又はメタクリロニトリルを製造する気相接触アンモ酸化反応、及びブテンからブタジエンを製造する気相接触酸化的脱水素反応等の選択的反応において、モリブデン−ビスマス系の複合酸化物触媒が有用な触媒であることは良く知られており、工業的にも広く実用化されている。
【０００３】
これら各種反応におけるモリブデン−ビスマス系複合酸化物触媒の組成及び製造方法に関しては、特許文献１〜５０等が知られている。
【０００４】
これらのうち、製造方法についていくつか例を挙げると、例えば、特許文献２７にはクエン酸ビスマス水溶液をモリブデン酸水溶液に添加する方法、特許文献２８、特許文献２９及び特許文献３０にはモリブデン酸水溶液に固体状態のビスマス化合物を添加する方法、特許文献３１にはｐＨが６〜８の範囲のモリブデン酸水溶液にビスマス塩の水溶液とアンモニア水を同時に添加する方法、特許文献３２にはモリブデン化合物の懸濁液にビスマス塩の水溶液を添加する方法、特許文献３３、特許文献２３及び特許文献３４には種々のモリブデイトを予め形成する方法、特許文献３５及び特許文献３６には種々のビスマス化合物を予め形成する方法、特許文献３７にはビスマス源として酸化ビスマスや、次炭酸ビスマスを用いる方法、特許文献３８には鉄、ビスマス及びテルルの少なくとも一つとモリブデン化合物とを含むスラリーをｐＨ７を越える範囲に調整する方法、特許文献３９にはシリカを含むモリブデン化合物含有スラリーにキレート剤を添加してｐＨ６以上に調整する方法、特許文献４０にはモリブデンを含むスラリーをｐＨ６以上とした後ビスマス化合物を混合する方法などが開示されている。
【０００５】
また、特許文献４１には、モリブデン酸鉄のゲルを添加する方法、特許文献４２にはモリブデンと鉄を予め混合する方法、特許文献４３にはモリブデン化合物と特定の金属化合物を特定の条件下で混合し、鉄化合物を混合して製造する方法が開示されている。
【０００６】
また、触媒の性能は、触媒を構成する成分及びその比率に強く支配されるが、とりわけ大規模な工業スケールでの触媒製造においては、触媒の構成成分やその比率だけでなく、触媒製造の生産性、安定性のみならず触媒性能の発現及び向上のために、触媒の製造方法が重要な役割を担っている。このため、上記触媒系に関しても、触媒の製造方法に関して多くの提案がなされている。例えば、特許文献４４には、触媒原料を混合したスラリーを微粒化処理後、オートクレーブ中、１００〜２００℃で処理することが有効である旨が開示されている。また、特許文献４５には、Ｍｏ，Ｂｉ，Ｆｅを必須成分として含有するスラリーを噴霧乾燥する旨が開示されている。さらに、特許文献４６には、噴霧乾燥前にホモジナイザー等で１０ミクロン以下に微細化処理することが開示されている。さらにまた、特許文献４７、特許文献４８、特許文献４９、特許文献５０には、成形助剤について開示されている。
【０００７】
【特許文献１】
特公昭３６−３５６３号公報
【特許文献２】
特公昭３９−３６７０号公報
【特許文献３】
特公昭４４−６２４５号公報
【特許文献４】
特公昭４７−２７４９０号公報
【特許文献５】
特公昭４７−２７４９０号公報
【特許文献６】
特公昭４７−４２２４１号公報
【特許文献７】
特公平７−８７３００号公報
【特許文献８】
特公昭４８−１６４５号公報
【特許文献９】
特公昭４８−４７６３号公報
【特許文献１０】
特公昭４８−１７２５３号公報
【特許文献１１】
特公昭４９−３４９８号公報
【特許文献１２】
特公昭５５−４１２１３号公報
【特許文献１３】
特公昭５６−１４６５９号公報
【特許文献１４】
特公昭５６−２３９６９号公報
【特許文献１５】
特公昭５６−５２０１３号公報
【特許文献１６】
特公昭５７−２６２４５号公報
【特許文献１７】
特開昭４８−５０３号公報
【特許文献１８】
特開昭４８−５１４号公報
【特許文献１９】
特開昭４８−５２７１３号公報
【特許文献２０】
特開昭４８−５４０２７号公報
【特許文献２１】
特開昭４８−５７９１６号公報
【特許文献２２】
特開昭５５−２０６１０号公報
【特許文献２３】
特開昭５５−４７１４４号公報
【特許文献２４】
特開昭５５−８４５４１号公報
【特許文献２５】
特開昭５９−７６５４１号公報
【特許文献２６】
特開昭６０−１２２０４１号公報
【特許文献２７】
特公昭４３−２２７４６号公報
【特許文献２８】
特開昭５３−１０３８７号公報
【特許文献２９】
特開昭５３−１０３８８号公報
【特許文献３０】
特公昭５５−１２２９８号公報
【特許文献３１】
特公昭５９−５１８４８号公報
【特許文献３２】
特公昭５９−５１８４９号公報
【特許文献３３】
特開昭５５−１３１８７号公報
【特許文献３４】
特公昭６０−２９５３６号公報
【特許文献３５】
特公昭５２−２２３５９号公報
【特許文献３６】
特公昭５２−４７４３５号公報
【特許文献３７】
特開昭６２−２３５４８号公報
【特許文献３８】
特開平２−５９０４６号公報
【特許文献３９】
特開平２−２１４５４３号公報
【特許文献４０】
特開平２−２５１２５０号公報
【特許文献４１】
特開平１−１６８３４４号公報
【特許文献４２】
特開平９−１０５８８号公報
【特許文献４３】
特開平１２−３７６３１号公報
【特許文献４４】
特開平７−２８９９０２号公報
【特許文献４５】
特開平９−１１７６６４号公報
【特許文献４６】
特開平１０−２５８２３３号公報
【特許文献４７】
特開平６−３８０号公報
【特許文献４８】
特開平７−１６４６３号公報
【特許文献４９】
特開平７−１６４６４号公報
【特許文献５０】
特開平７−１８５３４９号公報
【０００８】
【発明が解決しようとする課題】
このように触媒の性能向上を図るためにモリブデン水溶液とビスマス化合物を混合する方法を工夫したり、モリブデンと鉄との混合方法を工夫したり、種々の方法が提案されている。しかし、これらの方法を二価の金属元素ならびに三価の金属元素からなる群から選ばれた少なくとも一種の金属元素を含むモリブデン−ビスマス含有複合酸化物触媒の製造に適用した場合、目的とする酸化生成物収率は必ずしも満足すべきものではなかった。
【０００９】
そこで、この発明は、プロピレン、イソブテン又はターシャリーブタノールからアクロレイン又はメタクロレインを製造する気相接触酸化反応、プロピレン又はイソブテンからアクリロニトリル又はメタクリロニトリルを製造する気相接触アンモ酸化反応、及びブテンからブタジエンを製造する気相接触酸化的脱水素反応のいずれかの反応に用いられる触媒の製造方法として、より効率的かつ安定的に高性能触媒を製造する方法を提供することを目的とする。
【００１０】
【課題を解決するための手段】
この発明は、上記の課題を解決するために、下記一般式（１）で表される複合酸化物触媒を、各成分元素の供給源化合物の水性系での一体化及び加熱を含む工程を経て製造する方法において、モリブデン、鉄、ニッケル又はコバルトの少なくとも一つ、及びシリカを含む原料塩水溶液又はこれを乾燥して得た乾燥物を加熱処理して触媒前駆体を製造する前工程、該触媒前駆体、モリブデン及びビスマス化合物とを水性溶媒とともに一体化し、乾燥、焼成する後工程を経て調製することにより、高活性で、かつ目的とする酸化生成物を高い収率で与える複合酸化物触媒が得られることを見出したのである。
ＭｏaＢｉbＣｏcＮｉdＦｅeＸfＹgＺhＳｉiＯj （１）
（式中、Ｘはマグネシウム（Ｍｇ）、カルシウム（Ｃａ）、亜鉛（Ｚｎ）、セリウム（Ｃｅ）及びサマリウム（Ｓｍ）からなる群から選ばれる少なくとも１種の元素であり、Ｙはナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）及びタリウム（Ｔｌ）からなる群から選ばれる少なくとも１種の元素であり、Ｚはホウ素（Ｂ）、リン（Ｐ）、砒素（Ａｓ）及びタングステン（Ｗ）からなる群から選ばれる少なくとも１種の元素である。また、ａ〜ｊはそれぞれの元素の原子比を表わし、ａ＝１２のとき、ｂ＝０．５〜７、ｃ＝０〜１０、ｄ＝０〜１０（但しｃ＋ｄ＝１〜１０）、ｅ＝０．０５〜３、ｆ＝０〜２、ｇ＝０．０４〜２、ｈ＝０〜３、ｉ＝５〜４８の範囲にあり、またｊは他の元素の酸化状態を満足させる数値である。）
【００１１】
この発明の複合酸化物触媒の製造方法においては、前記前工程で用いられるモリブデンが、モリブデンの全原子比（ａ）の内の一部の原子比（ａ1）相当のモリブデンであり、前記後工程で用いられるモリブデンが、モリブデンの全原子比（ａ）からａ1を差し引いた残りの原子比（ａ2）相当のモリブデンであることが好ましい。
また、前記ａ1が１<ａ1／（ｃ＋ｄ＋ｅ）<３を満足する値であることが好ましい。
さらに、前記ａ2が０<ａ2／ｂ<８を満足する値であることが好ましい。
【００１２】
この発明の複合酸化物触媒の製造方法においては、前記触媒前駆体の灼熱減量が、０．５〜５重量％であることが好ましい。
但し、灼熱減量は、次式により与えられる値である。
灼熱減量（％）＝［（Ｗ0−Ｗ1）／Ｗ0］×１００
Ｗ0：触媒前駆体を１５０℃で３時間乾燥して付着水分を除いたものの重量（ｇ）
Ｗ1：付着水分を除いた前記触媒前駆体を更に５００℃で２時間熱処理した後の重量（ｇ）
【００１３】
この発明の複合酸化物触媒の製造方法においては、前工程の一体化における熟成温度が、６０〜９０℃であることが好ましい。
【００１４】
また、前工程における触媒前駆体製造のための加熱温度が２００〜４００℃であることが好ましい。
【００１５】
この発明の複合酸化物触媒の製造方法においては、Ｘ、Ｙ、及びＺの各成分を後工程において添加することが好ましい。
【００１６】
さらに、後工程において、触媒前駆体、モリブデン及びビスマス化合物の水性溶媒中での一体化の際にアンモニア水を添加することができる。
【００１７】
また、後工程の焼成温度は、４５０〜６５０℃の範囲であることが好ましい。
【００１８】
ビスマスの供給源としては、酸化ビスマス又は次炭酸ビスマスの少なくとも一方を用いることができる。
【００１９】
また、ビスマスの供給源として、所要のＮａの少なくとも一部を固溶した次炭酸ビスマスを用いることができる。
【００２０】
また、ビスマスの供給源として、Ｘ成分の少なくとも一部を含むＢｉとＸとの複合炭酸塩化合物を用いることができる。
【００２１】
また、ビスマスの供給源として、所要のＮａ及びＸ成分のそれぞれ少なくとも一部を含むＢｉとＮａとＸとの複合炭酸塩化合物を用いることができる。
【００２２】
この発明により、プロピレン、イソブテン又はターシャリーブタノールからアクロレイン又はメタクロレインを製造する気相接触酸化反応、プロピレン又はイソブテンからアクリロニトリル又はメタクリロニトリルを製造する気相接触アンモ酸化反応、及びブテンからブタジエンを製造する気相接触酸化的脱水素反応のいずれかに用いることができる、高性能な複合酸化物触媒を効率的かつ安定的に製造することができる。
【００２３】
プロピレンを原料とするアクロレイン及び／又はアクリル酸の製造する場合、この発明より製造された複合酸化物触媒は、触媒組成物として少なくとも一部含有すればよい。
【００２４】
【発明の実施の形態】
以下、この発明を詳細に説明する。
なお、この発明において、モリブデン（Ｍｏ）、ビスマス（Ｂｉ）、ケイ素（Ｓｉ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、鉄（Ｆｅ）、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、亜鉛（Ｚｎ）、セリウム（Ｃｅ）、サマリウム（Ｓｍ）、ナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）、タリウム（Ｔｌ）、ホウ素（Ｂ）、リン（Ｐ）、砒素（Ａｓ）、タングステン（Ｗ）の各元素は、適宜、括弧内の元素記号を用いて表記する。
【００２５】
上記成分元素の供給源化合物としては、成分元素の酸化物、硝酸塩、炭酸塩、アンモニウム塩、水酸化物、カルボン酸塩、カルボン酸アンモニウム塩、ハロゲン化アンモニウム塩、水素酸、アセチルアセトナート、アルコキシド等があげられる。
【００２６】
上記成分元素の供給源化合物の具体例としては、下記のようなものがあげられる。Ｍｏの供給源化合物としては、パラモリブデン酸アンモニウム、三酸化モリブデン、モリブデン酸、リンモリブデン酸アンモニウム、リンモリブデン酸等があげられる。さらに、Ｆｅの供給源化合物としては、硝酸第二鉄、硫酸第二鉄、塩化第二鉄、酢酸第二鉄等があげられる。
【００２７】
また、Ｃｏの供給源化合物としては、硝酸コバルト、硫酸コバルト、塩化コバルト、炭酸コバルト、酢酸コバルト等があげられる。さらに、Ｎｉの供給源化合物としては、硝酸ニッケル、硫酸ニッケル、塩化ニッケル、炭酸ニッケル、酢酸ニッケル等があげられる。
【００２８】
また、Ｓｉの供給源化合物としては、シリカ、粒状シリカ、コロイダルシリカ、ヒュームドシリカ等をあげることができる。
【００２９】
さらに、Ｂｉの供給源化合物としては、塩化ビスマス、硝酸ビスマス、酸化ビスマス、次炭酸ビスマス等があげられる。また、Ｘ成分（Ｍｇ，Ｃａ，Ｚｎ，Ｃｅ及び／又はＳｍ）やＹ成分（Ｎａ，Ｋ，Ｒｂ，Ｃｓ及び／又はＴｌ）を固溶させた、ＢｉとＸ成分やＹ成分との複合炭酸塩化合物として供給することもできる。
【００３０】
例えば、Ｙ成分としてＮａを用いた場合、ＢｉとＮａとの複合炭酸塩化合物は、炭酸ナトリウム又は重炭酸ナトリウムの水溶液等に、硝酸ビスマス等の水溶性ビスマス化合物の水溶液を滴下混合し、得られた沈殿を水洗、乾燥することによって製造することができる。
【００３１】
また、ＢｉとＸ成分との複合炭酸塩化合物は、炭酸アンモニウム又は重炭酸アンモニウムの水溶液等に、硝酸ビスマス及びＸ成分の硝酸塩等の水溶性化合物からなる水溶液を滴下混合し、得られた沈殿を水洗、乾燥することによって製造することができる。上記炭酸アンモニウム又は重炭酸アンモニウムの代わりに、炭酸ナトリウム又は重炭酸ナトリウムを用いると、Ｂｉ、Ｎａ及びＸ成分との複合炭酸塩化合物を製造することができる。
【００３２】
その他の成分元素の供給源化合物としては、下記のものがあげられる。Ｋの供給源化合物としては、硝酸カリウム、硫酸カリウム、塩化カリウム、炭酸カリウム、酢酸カリウム等をあげることができる。Ｒｂの供給源化合物としては、硝酸ルビジウム、硫酸ルビジウム、塩化ルビジウム、炭酸ルビジウム、酢酸ルビジウム等をあげることができる。Ｃｓの供給源化合物としては、硝酸セシウム、硫酸セシウム、塩化セシウム、炭酸セシウム、酢酸セシウム等をあげることができる。Ｔｌの供給源化合物としては、硝酸第一タリウム、塩化第一タリウム、炭酸タリウム、酢酸第一タリウム等をあげることができる。
【００３３】
さらに、Ｂの供給源化合物としては、ホウ砂、ホウ酸アンモニウム、ホウ酸等をあげることができる。Ｐの供給源化合物としては、リンモリブデン酸アンモニウム、リン酸アンモニウム、リン酸、五酸化リン等をあげることができる。Ａｓの供給源化合物としては、ジアルセノ十八モリブデン酸アンモニウム、ジアルセノ十八タングステン酸アンモニウム等をあげることができる。Ｗの供給源化合物としては、パラタングステン酸アンモニウム、三酸化タングステン、タングステン酸、リンタングステン酸等をあげることができる。
【００３４】
また、Ｍｇの供給源化合物としては、硝酸マグネシウム、硫酸マグネシウム、塩化マグネシウム、炭酸マグネシウム、酢酸マグネシウム等があげられる。Ｃａの供給源化合物としては、硝酸カルシウム、硫酸カルシウム、塩化カルシウム、炭酸カルシウム、酢酸カルシウム等があげられる。Ｚｎの供給源化合物としては、硝酸亜鉛、硫酸亜鉛、塩化亜鉛、炭酸亜鉛、酢酸亜鉛等があげられる。Ｃｅの供給源化合物としては、硝酸セリウム、硫酸セリウム、塩化セリウム、炭酸セリウム、酢酸セリウム等があげられる。Ｓｍの供給源化合物としては、硝酸サマリウム、硫酸サマリウム、塩化サマリウム、炭酸サマリウム、酢酸サマリウム等があげられる。
【００３５】
この発明の製造方法における前工程において用いる原料塩水溶液は、触媒成分として少なくともモリブデン（全原子比ａの内のａ1相当）、鉄、ニッケル又はコバルトの少なくとも一方、及びシリカを含む水溶液、水スラリー又はケーキである。
【００３６】
この原料水溶液の調製は、供給源化合物の水性系での一体化により行われる。この発明において、各成分元素の供給源化合物の水性系での一体化とは、各成分元素の供給源化合物の水溶液あるいは水分散液を一括に、あるいは段階的に混合又は熟成処理、混合及び熟成処理を行うことをいう。即ち、（イ）上記の各供給源化合物を一括して混合する方法、（ロ）上記の各供給源化合物を一括して混合し、そして熟成処理する方法、（ハ）上記の各供給源化合物を段階的に混合する方法、（ニ）上記の各供給源化合物を段階的に混合・熟成処理を繰り返す方法、及び（イ）〜（ニ）を組み合わせる方法のいずれもが、各成分元素の供給源化合物の水性系での一体化という概念に含まれる。ここで、熟成とは、工業原料もしくは半製品を、一定時間、一定温度等の特定条件のもとに処理して、必要とする物理性、化学性の取得、上昇あるいは所定反応の進行等を図る操作をいい、この発明における一定時間とは、通常１０分〜２４時間の範囲であり、一定温度とは通常室温〜水溶液又は水分散液の沸点範囲をいう。
【００３７】
上記の一体化の具体的な方法としては、例えば、触媒成分から選ばれた酸性塩を混合して得られた溶液と、触媒成分から選ばれた塩基性塩を混合して得られた溶液とを混合する方法等が挙げられ、具体例としてモリブデン化合物の水溶液に、鉄化合物とニッケル化合物及び／又はコバルト化合物との混合物を加温下添加し、シリカを混合する方法等が挙げられる。
【００３８】
このようにして得られたシリカを含む原料塩水溶液（スラリー）を６０〜９０℃に加温し、熟成する。
【００３９】
この熟成とは、上記触媒前駆体用スラリーを所定温度で所定時間、撹拌することをいう。この熟成により、スラリーの粘度が上昇し、スラリー中の固体成分の沈降を緩和し、とりわけ次の乾燥工程での成分の不均一化を抑制するのに有効となり、得られる最終製品である複合酸化物触媒の原料転化率や選択率等の触媒活性がより良好となる。
【００４０】
上記熟成における温度は、６０〜９０℃がよく、７０〜８５℃が好ましい。熟成温度が６０℃未満では、熟成の効果が十分ではなく、良好な活性を得られない場合がある。一方、９０℃を超えると、熟成時間中の水の蒸発が多く、工業的な実施には不利である。更に１００℃を超えると、溶解槽に耐圧容器が必要となり、また、ハンドリングも複雑になり、経済性及び操作性の面で著しく不利となる。
【００４１】
上記熟成にかける時間は、２〜１２時間がよく、３〜８時間が好ましい。熟成時間が２時間未満では、触媒の活性及び選択性が十分に発現しない場合がある。一方、１２時間を超えても熟成効果が増大することはなく、工業的な実施には不利である。
【００４２】
上記撹拌方法としては、任意の方法を採用することができ、例えば、撹拌翼を有する撹拌機による方法や、ポンプによる外部循環による方法等があげられる。
【００４３】
熟成されたスラリーは、そのままで、又は乾燥した後、加熱処理を行う。乾燥する場合の乾燥方法及び得られる乾燥物の状態については特に限定はなく、例えば、通常のスプレードライヤー、スラリードライヤー、ドラムドライヤー等を用いて粉体状の乾燥物を得てもよいし、また、通常の箱型乾燥器、トンネル型焼成炉を用いてブロック状又はフレーク状の乾燥物を得てもよい。
【００４４】
上記の原料塩水溶液又はこれを乾燥して得た顆粒あるいはケーキ状のものは空気中で２００〜４００℃、好ましくは２５０〜３５０℃の温度域で短時間の熱処理を行う。その際の炉の形式及びその方法については特に限定はなく、例えば、通常の箱型加熱炉、トンネル型加熱炉等を用いて乾燥物を固定した状態で加熱してもよいし、また、ロータリーキルン等を用いて乾燥物を流動させながら加熱してもよい。
【００４５】
加熱処理後に得られた触媒前駆体の灼熱減量は、０．５〜５重量％であることが好ましく、１〜３重量％であるのがより好ましい。灼熱減量をこの範囲とすることで、原料転化率や選択率が高い触媒を得ることができる。なお、灼熱減量は、前記のように、次式により与えられる値である。
灼熱減量（％）＝［（Ｗ0−Ｗ1）／Ｗ0］×１００
Ｗ0：触媒前駆体を１５０℃で３時間乾燥して付着水分を除いたものの重量（ｇ）
Ｗ1：付着水分を除いた前記触媒前駆体を更に５００℃で２時間熱処理した後の重量（ｇ）
【００４６】
この発明の製造方法における後工程では、上記の前工程において得られる触媒前駆体とモリブデン（全原子比ａからａ1相当を差し引いた残りのａ2相当）とビスマス化合物の一体化を、水性溶媒下で行う。この際、アンモニア水を添加するのが好ましい。Ｘ、Ｙ、Ｚ成分の添加もこの後工程で行うのが好ましい。また、この発明のビスマス供給源化合物は、水に難溶性〜不溶性のビスマスである。この化合物は、粉末の形態で使用することが好ましい。触媒製造原料としてのこれら化合物は粉末より大きな粒子のものであってもよいが、その熱拡散を行わせるべき加熱工程を考えれば小さい粒子である方が好ましい。従って、原料としてのこれらの化合物がこのように粒子の小さいものでなかった場合は、加熱工程前に粉砕を行うべきである。
【００４７】
次に、得られたスラリーを充分に撹拌した後、乾燥する。このようにして得られた乾燥品を、押出し成型、打錠成型、あるいは担持成型等の方法により任意の形状に賦形する。次に、このものを、好ましくは４５０〜６５０℃の温度条件にて１〜１６時間程度の最終熱処理に付す。
以上のようにして、高活性で、かつ目的とする酸化生成物を高い収率で与える複合酸化物触媒が得られる。
【００４８】
この方法で製造された複合酸化物触媒は、分子状酸素の存在下に行なわれる各種の気相接触酸化反応、具体的には、プロピレン、イソブテン又はターシャリーブタノールからアクロレイン又はメタクロレインを製造する気相接触酸化反応、プロピレン又はイソブテンからアクリロニトリル又はメタクリロニトリルを製造する気相接触アンモ酸化反応、及びブテンからブタジエンを製造する気相接触酸化的脱水素反応のいずれかの反応に使用することができる。
【００４９】
【実施例】
この発明に係る複合酸化物触媒のより具体的な製造方法と、得られた複合酸化物触媒を用いてプロピレンの酸化反応を実施した結果を以下に示す。なお、使用した各薬品は、原則として、試薬特級のものを使用した。
【００５０】
＜実施例１＞
（複合酸化物触媒の調製）
パラモリブデン酸アンモン５４ｇを純水２５０ｍｌに加温して溶解させる。次に硝酸第二鉄７．１８ｇ、硝酸コバルト３１．８ｇ及び硝酸ニッケル３１．８ｇを純水６０ｍｌに加温して溶解させる。これらの溶液を、充分に撹拌しながら徐々に混合する。
次に、シリカ６４ｇを加えて、充分に攪拌する。このスラリーを７５℃に加温し、５時間熟成する。その後、スラリーを加熱乾燥した後、空気雰囲気で３００℃／１時間の熱処理に付す。得られた触媒前駆体の粒状固体（灼熱減量：１．４重量％）を粉砕し、パラモリブデン酸アンモン４０．１ｇを純水１５０ｍｌにアンモニア水１０ｍｌを加え溶解した溶液に分散する。次に、純水４０ｍｌにホウ砂０．８５ｇ及び硝酸カリウム０．３６ｇを加温下に溶解させて、上記スラリーに加える。次に、Ｎａを０．４５％固溶した次炭酸ビスマス５８．１ｇを加えて、撹拌混合する。
このスラリーを加熱乾燥した後、得られた粒状固体を小型成形機にて径５ｍｍ、高さ４ｍｍの錠剤に打錠成型し、次に５００℃／４時間の焼成を行って、触媒とした。
仕込み原料から計算される触媒は、次の原子比を有する複合酸化物である。
Ｍｏ：Ｂｉ：Ｃｏ：Ｎｉ：Ｆｅ：Ｎａ：Ｂ：Ｋ：Ｓｉ＝１２：５：２．５：２．５：０．４：０．３５：０．２：０．０８：２４
調製の際のモリブデンの原子比ａ1とａ2は、それぞれ６．９と５．１である。
【００５１】
（プロピレンの酸化反応）
上記のようにして調製した複合酸化物触媒を使用して、プロピレンの酸化反応を実施し、プロピレン転化率、アクロレイン収率、アクリル酸収率を計算した。
複合酸化物触媒２０ｍｌを内径１５ｍｍのステンレス鋼製ナイタージャケット付反応管に充填し、プロピレン濃度１０％、スチーム濃度１７％、及び空気濃度７３％の原料ガスを常圧にて接触時間１．８秒にて通過させて、プロピレンの酸化反応を実施したところ、反応浴温３０５℃にて表１に示す結果が得られた。
【００５２】
＜比較例１＞
実施例１と同一組成の触媒を次のように調製した。パラモリブデン酸アンモン９４．１ｇを純水４００ｍｌに加温して溶解させる。次に硝酸第二鉄７．１８ｇ、硝酸コバルト３１．８ｇ及び硝酸ニッケル３１．８ｇを純水６０ｍｌに加温して溶解させる。これらの溶液を、充分に撹拌しながら徐々に混合する。
次に、純水４０ｍｌにホウ砂０．８５ｇ及び硝酸カリウム０．３６ｇを加温下に溶解させて、上記スラリーに加える。次に、シリカ６４ｇを加えて、充分に撹拌する。このスラリーを７５℃に加温し、５時間熟成させる。その後、スラリーを加熱乾燥した後、空気雰囲気で３００℃／１時間の熱処理に付す。得られた粒状固体を粉砕し、純水１５０ｍｌにアンモニア水１０ｍｌを加え分散する。次に、Ｎａを０．４５％固溶した次炭酸ビスマス５８．１ｇを加えて、撹拌混合する。このスラリーを加熱乾燥した後、得られた粒状固体を小型成形機にて径５ｍｍ、高さ４ｍｍの錠剤に打錠成型し、次に５００℃／４時間の焼成を行って、触媒とした。このように、モリブデン成分の供給源を分けずにＸ、Ｙ、Ｚ成分と同時に添加したこと以外は、実施例１と同様にして製造した複合酸化物触媒を用いて、実施例１と同様にプロピレンの酸化反応を実施した結果を表１に示した。
【００５３】
＜比較例２＞
実施例１において、熟成温度を室温とし、熟成時間を２時間として触媒を調製した。実施例１と同様にプロピレンの酸化反応を行い、結果を表１に示した。
【００５４】
【表１】
ここで、プロピレン転化率、アクロレイン収率、アクリル酸収率の定義は、次の通りである。
プロピレン転化率（モル％）＝（反応したプロピレンのモル数／供給したプロピレンのモル数）×１００
アクロレイン収率（モル数）＝（生成したアクロレインのモル数／供給したプロピレンのモル数）×１００
アクリル酸収率（モル数）＝（生成したアクリル酸のモル数／供給したプロピレンのモル数）×１００
【００５６】
【発明の効果】
以上のように、この発明によれば、プロピレン、イソブテン又はターシャリーブタノールからアクロレイン又はメタクロレインを製造する気相接触酸化反応、プロピレン又はイソブテンからアクリロニトリル又はメタクリロニトリルを製造する気相接触アンモ酸化反応、及びブテンからブタジエンを製造する気相接触酸化的脱水素反応等の選択的反応に用いられる触媒として、原料転化率や選択率等の触媒性能がより向上した触媒を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a gas phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, a gas phase catalytic ammoxidation reaction for producing acrylonitrile or methacrylonitrile from propylene or isobutene, and butadiene from butene. The present invention relates to a method for producing a composite oxide catalyst used for a selective reaction such as vapor phase catalytic oxidative dehydrogenation.
[0002]
[Prior art]
Gas phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, gas phase catalytic ammoxidation reaction for producing acrylonitrile or methacrylonitrile from propylene or isobutene, and gas phase contact for producing butadiene from butene In selective reactions such as oxidative dehydrogenation, it is well known that molybdenum-bismuth-based composite oxide catalysts are useful catalysts, and they are widely used industrially.
[0003]
For the composition and production method of the molybdenum-bismuth-based composite oxide catalyst in these various reactions, Patent Documents 1 to 50 are known.
[0004]
Among these, for example, Patent Document 27 discloses a method of adding a bismuth citrate aqueous solution to a molybdic acid aqueous solution. Patent Document 28, Patent Document 29, and Patent Document 30 include a molybdic acid aqueous solution. A method of adding a bismuth compound in a solid state to Patent Document 31; a method of simultaneously adding an aqueous solution of bismuth salt and aqueous ammonia to a molybdic acid aqueous solution having a pH of 6 to 8; A method of adding an aqueous solution of a bismuth salt to a suspension, Patent Document 33, Patent Document 23 and Patent Document 34 are pre-formed with various molybdates, Patent Document 35 and Patent Document 36 are pre-formed with various bismuth compounds. Patent Document 37 discloses a method using bismuth oxide or bismuth carbonate as a bismuth source, Patent Document 37 No. 8 is a method of adjusting a slurry containing at least one of iron, bismuth and tellurium and a molybdenum compound to a range exceeding pH 7, and Patent Document 39 discloses adding a chelating agent to a molybdenum compound-containing slurry containing silica to make the pH 6 or more. A method of adjusting, Patent Document 40 discloses a method of mixing a bismuth compound after setting the slurry containing molybdenum to pH 6 or higher.
[0005]
Patent Document 41 includes a method of adding iron molybdate gel, Patent Document 42 includes a method of premixing molybdenum and iron, and Patent Document 43 includes a molybdenum compound and a specific metal compound under specific conditions. A method of mixing and producing an iron compound is disclosed.
[0006]
In addition, the performance of the catalyst is strongly governed by the components constituting the catalyst and the ratio thereof. Especially in the production of a catalyst on a large-scale industrial scale, not only the components and ratio of the catalyst but also the production of the catalyst production. The catalyst production method plays an important role for the expression and improvement of the catalyst performance as well as the stability and stability. For this reason, many proposals have been made with respect to the above catalyst system as well as a method for producing the catalyst. For example, Patent Document 44 discloses that it is effective to treat a slurry mixed with a catalyst raw material at 100 to 200 ° C. in an autoclave after atomization. Patent Document 45 discloses that a slurry containing Mo, Bi, and Fe as essential components is spray-dried. Further, Patent Document 46 discloses that a finer treatment is performed to 10 microns or less with a homogenizer or the like before spray drying. Furthermore, Patent Literature 47, Patent Literature 48, Patent Literature 49, and Patent Literature 50 disclose molding aids.
[0007]
[Patent Document 1]
Japanese Patent Publication No. 36-3563
[Patent Document 2]
Japanese Examined Patent Publication No. 39-3670
[Patent Document 3]
Japanese Patent Publication No. 44-6245
[Patent Document 4]
Japanese Patent Publication No. 47-27490
[Patent Document 5]
Japanese Patent Publication No. 47-27490
[Patent Document 6]
Japanese Examined Patent Publication No. 47-42241
[Patent Document 7]
Japanese Patent Publication No. 7-87300
[Patent Document 8]
Japanese Patent Publication No. 48-1645
[Patent Document 9]
Japanese Patent Publication No. 48-4863
[Patent Document 10]
Japanese Patent Publication No. 48-17253
[Patent Document 11]
Japanese Patent Publication No.49-3498
[Patent Document 12]
Japanese Patent Publication No.55-41213
[Patent Document 13]
Japanese Examined Patent Publication No. 56-14659
[Patent Document 14]
Japanese Patent Publication No. 56-23969
[Patent Document 15]
Japanese Patent Publication No. 56-52013
[Patent Document 16]
Japanese Patent Publication No.57-26245
[Patent Document 17]
JP-A-48-503
[Patent Document 18]
JP-A-48-514
[Patent Document 19]
JP-A-48-52713
[Patent Document 20]
JP-A-48-54027
[Patent Document 21]
JP-A-48-57916
[Patent Document 22]
Japanese Patent Laid-Open No. 55-20610
[Patent Document 23]
JP 55-47144 A
[Patent Document 24]
JP-A-55-84541
[Patent Document 25]
JP 59-76541 A
[Patent Document 26]
JP-A-60-122201
[Patent Document 27]
Japanese Patent Publication No. 43-22746
[Patent Document 28]
Japanese Patent Laid-Open No. 53-10387
[Patent Document 29]
Japanese Patent Laid-Open No. 53-10388
[Patent Document 30]
Japanese Patent Publication No.55-12298
[Patent Document 31]
Japanese Examined Patent Publication No.59-51848
[Patent Document 32]
Japanese Patent Publication No.59-51849
[Patent Document 33]
Japanese Patent Laid-Open No. 55-13187
[Patent Document 34]
Japanese Patent Publication No. 60-29536
[Patent Document 35]
Japanese Examined Patent Publication No. 52-22359
[Patent Document 36]
Japanese Examined Patent Publication No. 52-47435
[Patent Document 37]
Japanese Patent Laid-Open No. 62-23548
[Patent Document 38]
JP-A-2-59046
[Patent Document 39]
JP-A-2-214543
[Patent Document 40]
JP-A-2-251250
[Patent Document 41]
JP-A-1-168344
[Patent Document 42]
Japanese Patent Laid-Open No. 9-10588
[Patent Document 43]
JP-A-12-37631
[Patent Document 44]
JP-A-7-289902
[Patent Document 45]
Japanese Patent Laid-Open No. 9-117664
[Patent Document 46]
JP 10-258233 A
[Patent Document 47]
JP-A-6-380
[Patent Document 48]
Japanese Patent Laid-Open No. 7-16463
[Patent Document 49]
Japanese Unexamined Patent Publication No. 7-16464
[Patent Document 50]
JP-A-7-185349
[0008]
[Problems to be solved by the invention]
Thus, in order to improve the performance of the catalyst, various methods have been proposed, such as devising a method of mixing an aqueous molybdenum solution and a bismuth compound, devising a mixing method of molybdenum and iron, or the like. However, when these methods are applied to the production of a molybdenum-bismuth-containing composite oxide catalyst containing at least one metal element selected from the group consisting of divalent metal elements and trivalent metal elements, the target oxidation is achieved. The product yield was not always satisfactory.
[0009]
Therefore, the present invention relates to a gas phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, a gas phase catalytic ammoxidation reaction for producing acrylonitrile or methacrylonitrile from propylene or isobutene, and butadiene from butene. An object of the present invention is to provide a method for producing a high-performance catalyst more efficiently and stably as a method for producing a catalyst used in any of the reactions in the gas phase catalytic oxidative dehydrogenation reaction for producing NO.
[0010]
[Means for Solving the Problems]
In order to solve the above-described problems, the present invention is a process in which a composite oxide catalyst represented by the following general formula (1) is integrated and heated in an aqueous system of source compounds of each component element. A pre-process for producing a catalyst precursor by heat-treating a raw salt aqueous solution containing at least one of molybdenum, iron, nickel or cobalt and silica, or a dried product obtained by drying the same, in the production method, the catalyst A composite oxide catalyst that integrates a precursor, molybdenum, and a bismuth compound together with an aqueous solvent, and is prepared through a post-process that is dried and calcined, thereby providing a highly active and desired oxidation product in a high yield. I found out that I could get it.
Mo a Bi b Co c Ni d Fe e X f Y g Z h Si i O j (1)
Wherein X is at least one element selected from the group consisting of magnesium (Mg), calcium (Ca), zinc (Zn), cerium (Ce) and samarium (Sm), and Y is sodium (Na) , Potassium (K), rubidium (Rb), cesium (Cs) and at least one element selected from the group consisting of thallium (Tl), and Z is boron (B), phosphorus (P), arsenic (As) And at least one element selected from the group consisting of tungsten (W), and a to j represent atomic ratios of the respective elements, and when a = 12, b = 0.5 to 7, c = 0-10, d = 0-10 (where c + d = 1-10), e = 0.05-3, f = 0-2, g = 0.04-2, h = 0-3, i = 5 48, and j satisfies the oxidation state of other elements That is a number.)
[0011]
In the method for producing a composite oxide catalyst of the present invention, the molybdenum used in the preceding step is a partial atomic ratio (a) of the total atomic ratio (a) of molybdenum. 1 ) Equivalent molybdenum, and the molybdenum used in the subsequent step is a from the total atomic ratio of molybdenum (a) 1 The remaining atomic ratio (a 2 ) It is preferable that it is an equivalent molybdenum.
In addition, a 1 Is 1 <a 1 / (C + d + e) A value satisfying <3 is preferred.
Furthermore, said a 2 Is 0 <a 2 / B A value satisfying <8 is preferred.
[0012]
In the method for producing the composite oxide catalyst of the present invention, the ignition loss of the catalyst precursor is preferably 0.5 to 5% by weight.
However, the loss on ignition is a value given by the following equation.
Burning loss (%) = [(W 0 -W 1 ) / W 0 ] × 100
W 0 : Weight (g) of catalyst precursor dried at 150 ° C. for 3 hours to remove adhering moisture
W 1 : Weight (g) after heat-treating the catalyst precursor excluding adhering moisture at 500 ° C. for 2 hours
[0013]
In the method for producing a composite oxide catalyst of the present invention, the aging temperature in the integration of the previous step is preferably 60 to 90 ° C.
[0014]
Moreover, it is preferable that the heating temperature for catalyst precursor manufacture in a pre-process is 200-400 degreeC.
[0015]
In the method for producing a composite oxide catalyst of the present invention, it is preferable to add each component of X, Y, and Z in a subsequent step.
[0016]
Furthermore, ammonia water can be added during the integration of the catalyst precursor, molybdenum, and bismuth compound in an aqueous solvent in a subsequent step.
[0017]
Moreover, it is preferable that the baking temperature of a post process is the range of 450-650 degreeC.
[0018]
As a supply source of bismuth, at least one of bismuth oxide and bismuth subcarbonate can be used.
[0019]
Further, as a bismuth supply source, bismuth carbonate in which at least a part of required Na is dissolved can be used.
[0020]
Further, as a bismuth supply source, a complex carbonate compound of Bi and X containing at least a part of the X component can be used.
[0021]
As a bismuth supply source, a complex carbonate compound of Bi, Na and X containing at least a part of each of the required Na and X components can be used.
[0022]
According to this invention, gas phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, gas phase catalytic ammoxidation reaction for producing acrylonitrile or methacrylonitrile from propylene or isobutene, and butadiene production from butene Thus, a high-performance composite oxide catalyst that can be used in any of the gas phase catalytic oxidative dehydrogenation reactions can be produced efficiently and stably.
[0023]
When producing acrolein and / or acrylic acid using propylene as a raw material, the composite oxide catalyst produced from the present invention may be at least partially contained as a catalyst composition.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
In this invention, molybdenum (Mo), bismuth (Bi), silicon (Si), cobalt (Co), nickel (Ni), iron (Fe), magnesium (Mg), calcium (Ca), zinc (Zn) , Cerium (Ce), samarium (Sm), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), boron (B), phosphorus (P), arsenic (As) Each element of tungsten (W) is appropriately described using element symbols in parentheses.
[0025]
Source compounds of the above component elements include oxides, nitrates, carbonates, ammonium salts, hydroxides, carboxylates, carboxylic acid ammonium salts, ammonium halide salts, hydrogen acids, acetylacetonates, alkoxides of the component elements. Etc.
[0026]
Specific examples of the source compound for the component elements include the following. Examples of Mo supply source compounds include ammonium paramolybdate, molybdenum trioxide, molybdic acid, phosphomolybdate, and phosphomolybdic acid. Furthermore, examples of Fe source compounds include ferric nitrate, ferric sulfate, ferric chloride, and ferric acetate.
[0027]
Examples of the Co source compound include cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt carbonate, and cobalt acetate. Further, examples of the Ni source compound include nickel nitrate, nickel sulfate, nickel chloride, nickel carbonate, nickel acetate and the like.
[0028]
Examples of Si supply source compounds include silica, granular silica, colloidal silica, and fumed silica.
[0029]
Furthermore, examples of Bi source compounds include bismuth chloride, bismuth nitrate, bismuth oxide, and bismuth subcarbonate. Also, a composite carbonic acid of Bi and X component or Y component in which X component (Mg, Ca, Zn, Ce and / or Sm) or Y component (Na, K, Rb, Cs and / or Tl) is dissolved. It can also be supplied as a salt compound.
[0030]
For example, when Na is used as the Y component, a complex carbonate compound of Bi and Na can be obtained by dropping an aqueous solution of a water-soluble bismuth compound such as bismuth nitrate into an aqueous solution of sodium carbonate or sodium bicarbonate. The precipitate can be produced by washing with water and drying.
[0031]
In addition, the complex carbonate compound of Bi and X component is prepared by mixing an aqueous solution of a water-soluble compound such as bismuth nitrate and nitrate of X component with an aqueous solution of ammonium carbonate or ammonium bicarbonate, etc. It can be produced by washing with water and drying. When sodium carbonate or sodium bicarbonate is used instead of the above ammonium carbonate or ammonium bicarbonate, a complex carbonate compound with Bi, Na and X components can be produced.
[0032]
Examples of other component element source compounds include the following. Examples of the source compound for K include potassium nitrate, potassium sulfate, potassium chloride, potassium carbonate, and potassium acetate. Examples of the source compound for Rb include rubidium nitrate, rubidium sulfate, rubidium chloride, rubidium carbonate, and rubidium acetate. Examples of Cs supply source compounds include cesium nitrate, cesium sulfate, cesium chloride, cesium carbonate, cesium acetate, and the like. Examples of the source compound of Tl include thallium nitrate, thallium chloride, thallium carbonate, and thallium acetate.
[0033]
Furthermore, examples of the source compound for B include borax, ammonium borate, and boric acid. Examples of the P source compound include ammonium phosphomolybdate, ammonium phosphate, phosphoric acid, and phosphorus pentoxide. Examples of As source compounds include dialsenooctammonium molybdate, dialsenooctammonium tungstate, and the like. Examples of the source compound for W include ammonium paratungstate, tungsten trioxide, tungstic acid, phosphotungstic acid, and the like.
[0034]
Examples of Mg source compounds include magnesium nitrate, magnesium sulfate, magnesium chloride, magnesium carbonate, and magnesium acetate. Examples of the Ca source compound include calcium nitrate, calcium sulfate, calcium chloride, calcium carbonate, calcium acetate and the like. Examples of Zn source compounds include zinc nitrate, zinc sulfate, zinc chloride, zinc carbonate, and zinc acetate. Examples of the Ce source compound include cerium nitrate, cerium sulfate, cerium chloride, cerium carbonate, and cerium acetate. Examples of Sm source compounds include samarium nitrate, samarium sulfate, samarium chloride, samarium carbonate, and samarium acetate.
[0035]
The raw material salt aqueous solution used in the previous step in the production method of the present invention contains at least molybdenum (a of the total atomic ratio a) as a catalyst component. 1 Equivalent), an aqueous solution, a water slurry or a cake containing at least one of iron, nickel or cobalt and silica.
[0036]
This raw material aqueous solution is prepared by integrating the source compound in an aqueous system. In the present invention, the integration of each component element source compound in an aqueous system means that an aqueous solution or an aqueous dispersion of each component element source compound is mixed or aged in stages or mixed and aged. It means performing processing. (B) a method of mixing the above-mentioned source compounds in a lump, (b) a method of mixing the above-mentioned source compounds in a lump and aging, and (c) a method of mixing each of the above-mentioned source compounds. Supply of each component element is a method of stepwise mixing, (d) a method of repeatedly mixing and aging the above-mentioned source compounds stepwise, and a method of combining (b) to (d). It is included in the concept of integration of the source compound in an aqueous system. Here, aging refers to the processing of industrial raw materials or semi-finished products under specific conditions such as constant temperature for a certain period of time to obtain the required physical and chemical properties, increase or advance the prescribed reaction, etc. The fixed time in the present invention is usually in the range of 10 minutes to 24 hours, and the fixed temperature is usually in the range of room temperature to the boiling point of the aqueous solution or aqueous dispersion.
[0037]
As a specific method of the above integration, for example, a solution obtained by mixing an acidic salt selected from catalyst components, and a solution obtained by mixing a basic salt selected from catalyst components, Specific examples include a method of adding a mixture of an iron compound and a nickel compound and / or a cobalt compound to an aqueous solution of a molybdenum compound while heating, and mixing silica.
[0038]
The raw material salt aqueous solution (slurry) containing silica thus obtained is heated to 60 to 90 ° C. and aged.
[0039]
The aging means that the catalyst precursor slurry is stirred at a predetermined temperature for a predetermined time. This aging increases the viscosity of the slurry, reduces the sedimentation of the solid components in the slurry, and is particularly effective in suppressing the heterogeneity of components in the subsequent drying process. The catalytic activity such as the raw material conversion rate and selectivity of the product catalyst becomes better.
[0040]
The temperature in the aging is preferably 60 to 90 ° C, and preferably 70 to 85 ° C. When the aging temperature is less than 60 ° C., the aging effect is not sufficient, and good activity may not be obtained. On the other hand, when it exceeds 90 ° C., the water is often evaporated during the aging time, which is disadvantageous for industrial implementation. Further, if the temperature exceeds 100 ° C., a pressure vessel is required for the dissolution tank, and handling becomes complicated, which is extremely disadvantageous in terms of economy and operability.
[0041]
The aging time is preferably 2 to 12 hours, and preferably 3 to 8 hours. If the aging time is less than 2 hours, the activity and selectivity of the catalyst may not be sufficiently developed. On the other hand, the aging effect does not increase even if it exceeds 12 hours, which is disadvantageous for industrial implementation.
[0042]
Any method can be adopted as the stirring method, and examples thereof include a method using a stirrer having a stirring blade and a method using external circulation using a pump.
[0043]
The aged slurry is subjected to heat treatment as it is or after drying. There is no particular limitation on the drying method in the case of drying and the state of the dried product to be obtained. For example, a powdery dried product may be obtained using a normal spray dryer, slurry dryer, drum dryer, etc. Alternatively, a block-like or flake-like dried product may be obtained using a normal box-type dryer or a tunnel-type firing furnace.
[0044]
The raw material salt aqueous solution or granules or cakes obtained by drying the aqueous salt solution are heat-treated in air at a temperature of 200 to 400 ° C., preferably 250 to 350 ° C. for a short time. There are no particular limitations on the type and method of the furnace at that time, and for example, it may be heated with a dry matter fixed using a normal box-type furnace, tunnel-type furnace, etc., or a rotary kiln. It is possible to heat the dried product while flowing it.
[0045]
The ignition loss of the catalyst precursor obtained after the heat treatment is preferably 0.5 to 5% by weight, more preferably 1 to 3% by weight. By setting the ignition loss within this range, a catalyst having a high raw material conversion rate and high selectivity can be obtained. Note that the loss on ignition is a value given by the following equation as described above.
Burning loss (%) = [(W 0 -W 1 ) / W 0 ] × 100
W 0 : Weight (g) of catalyst precursor dried at 150 ° C. for 3 hours to remove adhering moisture
W 1 : Weight (g) after heat-treating the catalyst precursor excluding adhering moisture at 500 ° C. for 2 hours
[0046]
In the post-process in the production method of the present invention, the catalyst precursor and molybdenum obtained in the pre-process described above (from the total atomic ratio a to a 1 The remaining a minus 2 And the bismuth compound are integrated in an aqueous solvent. At this time, it is preferable to add ammonia water. The addition of the X, Y, and Z components is also preferably performed in the subsequent step. The bismuth source compound of the present invention is bismuth that is hardly soluble or insoluble in water. This compound is preferably used in the form of a powder. These compounds as the catalyst production raw material may be particles larger than the powder, but are preferably smaller particles in view of the heating step in which thermal diffusion should be performed. Therefore, if these compounds as raw materials are not such particles, they should be pulverized before the heating step.
[0047]
Next, the obtained slurry is sufficiently stirred and then dried. The dried product thus obtained is shaped into an arbitrary shape by a method such as extrusion molding, tableting molding or support molding. Next, this is preferably subjected to a final heat treatment for about 1 to 16 hours under a temperature condition of 450 to 650 ° C.
As described above, a composite oxide catalyst having a high activity and a desired oxidation product in a high yield can be obtained.
[0048]
The composite oxide catalyst produced by this method is used for various gas phase catalytic oxidation reactions carried out in the presence of molecular oxygen, specifically, for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol. It can be used for any of the phase catalytic oxidation reaction, the gas phase catalytic ammoxidation reaction for producing acrylonitrile or methacrylonitrile from propylene or isobutene, and the gas phase catalytic oxidative dehydrogenation reaction for producing butadiene from butene. .
[0049]
【Example】
A more specific method for producing the composite oxide catalyst according to the present invention and results of carrying out an oxidation reaction of propylene using the obtained composite oxide catalyst are shown below. As a general rule, chemicals of special grade were used.
[0050]
<Example 1>
(Preparation of composite oxide catalyst)
54 g of ammonium paramolybdate is dissolved in 250 ml of pure water. Next, 7.18 g of ferric nitrate, 31.8 g of cobalt nitrate and 31.8 g of nickel nitrate are heated and dissolved in 60 ml of pure water. These solutions are gradually mixed with good stirring.
Next, 64 g of silica is added and stirred thoroughly. This slurry is heated to 75 ° C. and aged for 5 hours. Thereafter, the slurry is heated and dried, and then subjected to a heat treatment at 300 ° C./1 hour in an air atmosphere. The obtained catalyst precursor granular solid (ignition loss: 1.4% by weight) is pulverized, and 40.1 g of ammonium paramolybdate is dispersed in a solution obtained by adding 10 ml of ammonia water to 150 ml of pure water. Next, 0.85 g of borax and 0.36 g of potassium nitrate are dissolved in 40 ml of pure water under heating, and added to the slurry. Next, 58.1 g of bismuth subcarbonate in which Na is dissolved in 0.45% is added and mixed with stirring.
After the slurry was heat-dried, the obtained granular solid was tableted into a tablet having a diameter of 5 mm and a height of 4 mm with a small molding machine, and then calcined at 500 ° C. for 4 hours to obtain a catalyst.
The catalyst calculated from the charged raw materials is a complex oxide having the following atomic ratio.
Mo: Bi: Co: Ni: Fe: Na: B: K: Si = 12: 5: 2.5: 2.5: 0.4: 0.35: 0.2: 0.08: 24
Molybdenum atomic ratio a during preparation 1 And a 2 Are 6.9 and 5.1, respectively.
[0051]
(Propylene oxidation reaction)
The composite oxide catalyst prepared as described above was used to carry out an oxidation reaction of propylene, and the propylene conversion rate, acrolein yield, and acrylic acid yield were calculated.
20 ml of a composite oxide catalyst was filled in a stainless steel nighter jacketed reaction tube with an inner diameter of 15 mm, and a contact time of 1.8 seconds at a normal pressure of a raw material gas having a propylene concentration of 10%, a steam concentration of 17% and an air concentration of 73% When the propylene oxidation reaction was carried out, the results shown in Table 1 were obtained at a reaction bath temperature of 305 ° C.
[0052]
<Comparative Example 1>
A catalyst having the same composition as in Example 1 was prepared as follows. 94.1 g of ammonium paramolybdate is dissolved in 400 ml of pure water by heating. Next, 7.18 g of ferric nitrate, 31.8 g of cobalt nitrate and 31.8 g of nickel nitrate are heated and dissolved in 60 ml of pure water. These solutions are gradually mixed with good stirring.
Next, 0.85 g of borax and 0.36 g of potassium nitrate are dissolved in 40 ml of pure water under heating, and added to the slurry. Next, 64 g of silica is added and stirred thoroughly. The slurry is warmed to 75 ° C. and aged for 5 hours. Thereafter, the slurry is heated and dried, and then subjected to a heat treatment at 300 ° C./1 hour in an air atmosphere. The obtained granular solid is pulverized, and 10 ml of ammonia water is added to 150 ml of pure water and dispersed. Next, 58.1 g of bismuth subcarbonate in which Na is dissolved in 0.45% is added and mixed with stirring. After the slurry was heat-dried, the obtained granular solid was tableted into a tablet having a diameter of 5 mm and a height of 4 mm with a small molding machine, and then calcined at 500 ° C. for 4 hours to obtain a catalyst. Thus, using the composite oxide catalyst produced in the same manner as in Example 1 except that it was added simultaneously with the X, Y and Z components without dividing the supply source of the molybdenum component, it was the same as in Example 1. The results of the oxidation reaction of propylene are shown in Table 1.
[0053]
<Comparative example 2>
In Example 1, the catalyst was prepared by setting the aging temperature to room temperature and the aging time to 2 hours. The oxidation reaction of propylene was carried out in the same manner as in Example 1, and the results are shown in Table 1.
[0054]
[Table 1]
Here, the definitions of propylene conversion rate, acrolein yield, and acrylic acid yield are as follows.
Propylene conversion rate (mol%) = (number of moles of reacted propylene / number of moles of supplied propylene) × 100
Acrolein yield (number of moles) = (number of moles of acrolein produced / number of moles of propylene supplied) × 100
Acrylic acid yield (number of moles) = (number of moles of produced acrylic acid / number of moles of supplied propylene) × 100
[0056]
【The invention's effect】
As described above, according to the present invention, the gas phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, and the gas phase catalytic ammoxidation reaction for producing acrylonitrile or methacrylonitrile from propylene or isobutene. As a catalyst used for a selective reaction such as a gas phase catalytic oxidative dehydrogenation reaction for producing butadiene from butene, a catalyst with improved catalytic performance such as raw material conversion and selectivity can be obtained.
Claims (12)
モリブデン、鉄、ニッケル又はコバルトの少なくとも一つ、及びシリカを含む原料塩水溶液又はこれを乾燥して得た乾燥物を加熱処理して触媒前駆体を製造する前工程、該触媒前駆体、モリブデン及びビスマス化合物とを水性溶媒とともに一体化し、乾燥、焼成する後工程を経て調製する複合酸化物触媒の製造方法であって、
前記前工程で用いられるモリブデンが、モリブデンの全原子比（ａ）の内の一部の原子比（ａ１）相当のモリブデンであり、前記後工程で用いられるモリブデンが、モリブデンの全原子比（ａ）からａ１を差し引いた残りの原子比（ａ２）相当のモリブデンであり、前記ａ１が１＜ａ１／（ｃ＋ｄ＋ｅ）＜３を満足する値であり、
前記前工程で製造された、下記式（２）により与えられる触媒前駆体の灼熱減量が、０．５〜５重量％であり、
前工程の一体化における熟成温度が、６０〜９０℃であることを特徴とする複合酸化物触媒の製造方法。
ＭｏａＢｉｂＣｏｃＮｉｄＦｅｅＸｆＹｇＺｈＳｉｉＯｊ （１）
（式中、Ｘはマグネシウム（Ｍｇ）、カルシウム（Ｃａ）、亜鉛（Ｚｎ）、セリウム（Ｃｅ）及びサマリウム（Ｓｍ）からなる群から選ばれる少なくとも１種の元素であり、Ｙはナトリウム（Ｎａ）及びカリウム（Ｋ）であり、Ｚはホウ素（Ｂ）である。また、ａ〜ｊはそれぞれの元素の原子比を表わし、ａ＝１２のとき、ｂ＝０．５〜７、ｃ＝０〜１０、ｄ＝０〜１０（但しｃ＋ｄ＝１〜１０）、ｅ＝０．０５〜３、ｆ＝０〜２、ｇ＝０．０４〜２、ｈ＝０〜３、ｉ＝５〜４８の範囲にあり、またｊは他の元素の酸化状態を満足させる数値である。）
灼熱減量（％）＝［（Ｗ ０ −Ｗ １ ）／Ｗ ０ ］×１００ （２）
（Ｗ ０ ：触媒前駆体を１５０℃で３時間乾燥して付着水分を除いたものの重量（ｇ）、Ｗ １ ：付着水分を除いた前記触媒前駆体を更に５００℃で２時間熱処理した後の重量（ｇ）） In a method for producing a composite oxide catalyst represented by the following general formula (1) through a process including integration and heating of an aqueous source system of each component element,
A pre-process for producing a catalyst precursor by heat-treating a raw salt solution containing at least one of molybdenum, iron, nickel or cobalt and silica or a dried product obtained by drying the raw salt solution, the catalyst precursor, molybdenum and A method for producing a composite oxide catalyst, wherein a bismuth compound is integrated with an aqueous solvent, dried and calcined and then prepared through post-processing steps,
Molybdenum used in the previous step is molybdenum corresponding to a partial atomic ratio (a 1 ) of the total atomic ratio (a) of molybdenum, and the molybdenum used in the subsequent step is the total atomic ratio of molybdenum ( atomic ratio obtained by subtracting a 1 from a) (a 2) a corresponding molybdenum, Ri value der wherein a 1 satisfies 1 <a 1 / (c + d + e) <3,
The ignition loss of the catalyst precursor produced by the following formula (2) produced in the previous step is 0.5 to 5% by weight,
A method for producing a composite oxide catalyst, wherein the aging temperature in the integration of the previous step is 60 to 90 ° C.
Mo a Bi b Co c Ni d Fe e X f Y g Z h Si i O j (1)
Wherein X is at least one element selected from the group consisting of magnesium (Mg), calcium (Ca), zinc (Zn), cerium (Ce) and samarium (Sm), and Y is sodium (Na) And potassium (K), Z is boron (B), and a to j represent atomic ratios of the respective elements, and when a = 12, b = 0.5 to 7, c = 0 to 0. 10, d = 0 to 10 (where c + d = 1 to 10), e = 0.05 to 3, f = 0 to 2, g = 0.04 to 2, h = 0 to 3, i = 5 to 48 And j is a numerical value that satisfies the oxidation state of other elements.)
Burning loss (%) = [(W 0 −W 1 ) / W 0 ] × 100 (2)
(W 0 : weight (g) of the catalyst precursor dried at 150 ° C. for 3 hours to remove adhering water, W 1 : after further heat-treating the catalyst precursor excluding adhering water for 2 hours at 500 ° C. Weight (g)
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