CN100503545C - 具有规定的氧化钒粒度分布的气相氧化催化剂 - Google Patents
具有规定的氧化钒粒度分布的气相氧化催化剂 Download PDFInfo
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- CN100503545C CN100503545C CNB2004800280469A CN200480028046A CN100503545C CN 100503545 C CN100503545 C CN 100503545C CN B2004800280469 A CNB2004800280469 A CN B2004800280469A CN 200480028046 A CN200480028046 A CN 200480028046A CN 100503545 C CN100503545 C CN 100503545C
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 16
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- 229910001935 vanadium oxide Inorganic materials 0.000 title claims description 9
- 238000009826 distribution Methods 0.000 title abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 33
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- 238000000034 method Methods 0.000 claims description 20
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- 239000004408 titanium dioxide Substances 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 17
- 238000000576 coating method Methods 0.000 abstract description 17
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
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- 150000001875 compounds Chemical class 0.000 description 5
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- 239000000454 talc Substances 0.000 description 5
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- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012041 precatalyst Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- PSDQQCXQSWHCRN-UHFFFAOYSA-N vanadium(4+) Chemical class [V+4] PSDQQCXQSWHCRN-UHFFFAOYSA-N 0.000 description 2
- JRIGVWDKYXCHMG-UHFFFAOYSA-N (5-arsoroso-2-hydroxyphenyl)azanium;chloride Chemical compound Cl.NC1=CC([As]=O)=CC=C1O JRIGVWDKYXCHMG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 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
- 238000004364 calculation method Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229950008475 oxophenarsine Drugs 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910003438 thallium oxide Inorganic materials 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
公开了一种制备气相氧化催化剂的方法，通过该方法将TiO2和V2O5颗粒的悬浮液施加到流化的惰性载体上，其中至少90体积%的V2O5颗粒具有20μm或更小的直径且至少95体积%的V2O5颗粒具有30μm或更小的直径。规定的V2O5粒度分布能够实现高涂敷效率。
Description
本发明涉及含有二氧化钛和氧化钒并且具有规定的氧化钒粒度分布的气相氧化催化剂，涉及制备该催化剂的方法，以及涉及该催化剂在由邻二甲苯、萘或其混合物制备邻苯二甲酸酐中的用途。
在工业上借助芳族烃如苯、二甲苯、萘、甲苯或均四甲苯在固定床反应器中的催化气相氧化而制备许多羧酸和/或羧酸酐。通过这种方法可以得到例如苯甲酸、马来酸酐、邻苯二甲酸酐、间苯二甲酸、对苯二甲酸或均苯四酸酐。通常，将含氧气体和待氧化原料的混合物通过其中存在催化剂床的管道。为了调节温度，管道周围是传热介质如盐熔体。
发现对这些氧化反应有用的催化剂是涂敷催化剂，在该涂敷催化剂中将催化活性组合物以壳的形式施加到惰性载体材料如滑石上。这些涂敷催化剂的催化活性组合物的催化活性成分通常是二氧化钛和五氧化二钒。该催化活性组合物还可以含有少量的用作促进剂的许多其它氧化物以影响催化剂的活性和选择性。
为了生产该涂敷催化剂，在升高的温度下将活性组合物组分和/或它们的前体化合物的水悬浮液喷涂到载体材料上直到达到在催化剂的活性组合物的总重量中的所需比例。
DE-A 2550686描述了一种将含有四氯化钛和钒(IV)盐的水溶液施加到载体上的方法。
在DE-A 1442590公开的生产方法中，将细碎的锐钛矿晶型的二氧化钛加入草酸氧钒、甲酰胺和水的溶液中。将所得的浆液施加到惰性催化剂载体上。
WO 00/12214描述了一种生产方法，其中通过在涂敷转鼓中喷涂、在流化床中涂敷或通过粉末涂敷而以两层同心涂层将二氧化钛、草酸氧钒、有机粘合剂和如果合适的话还有促进剂的混合物以壳状形式施加到惰性载体环上。
EP-A 539878描述了在气相中制备邻苯二甲酸酐的催化剂的生产方法。将偏钒酸铵溶解在草酸水溶液中并与促进剂一起搅拌。随后加入通过硫酸盐法由硫酸钛制备的TiO2。均化所得的悬浮液并且在升高的温度下将其喷涂到催化剂载体上。
根据DE-A 2106796和DE-A 19633757，将锐钛矿和水合二氧化钛、V2O5和有机粘合剂组分的水悬浮液施加到载体上。
根据使用的钒源可以将已知的生产工艺分成两类：在一种情况下，使用可溶性钒(IV)化合物如草酸氧钒作为钒源。借助有机还原剂如草酸还原钒(IV)。在另一种情况下，将不溶性钒(V)化合物如V2O5加入水悬浮液中。由于此时不再需要还原剂，因此原料的成本更低。然而，缺点是V2O5颗粒倾向于在流化床中的涂敷工艺中分层并且不完全沉积在待涂敷的载体上，而是例如部分由加工空气带出或作为沉积物沉积在涂敷设备上。为了弥补该损失，必须使用过量的V2O5。需要将要求的过量保持在尽可能少的程度。
本发明的目的是提供一种生产含有二氧化钛和氧化钒的气相氧化催化剂的经济方法，以及提供由此得到的催化剂。
现已发现涂敷操作的效率在很大程度上取决于涂敷悬浮液中悬浮的V2O5的粒度分布。
本发明提供了一种含有惰性载体和施加在惰性载体上的催化活性组合物的气相氧化催化剂，其中催化活性组合物含有1-40重量％的氧化钒，按照V2O5计算，以及60-99重量％的二氧化钛，按照TiO2计算，并且该催化剂可以通过将TiO2和V2O5颗粒的悬浮液施加到载体上而得到，其中至少90体积％的V2O5颗粒具有20μm或更小的直径且至少95体积％的V2O5颗粒具有30μm或更小的直径。
本发明另外提供了一种生产气相氧化催化剂的方法，其中将TiO2和V2O5颗粒的悬浮液施加到流化的惰性载体上，其中至少90体积％的V2O5颗粒具有20μm或更小的直径且至少95体积％的V2O5颗粒具有30μm或更小的直径。
优选至少90体积％的V2O5颗粒具有15μm或更小的直径且至少95体积％的V2O5颗粒具有20μm或更小的直径。
在特别优选的实施方案中，至少60体积％的V2O5颗粒具有4μm或更小的直径，至少80体积％的V2O5颗粒具有10μm或更小的直径，至少90体积％的V2O5颗粒具有15μm或更小的直径，以及至少95体积％的V2O5颗粒具有20μm或更小的直径。
优选至少50体积％的V2O5颗粒具有2μm以上的直径。基于体积的D50优选为2.0-2.5μm。
对于本申请而言，借助激光散射和Fraunhofer方法评价而适当地确定基于体积的粒度分布。在此方法中，颗粒散射平行激光。每个颗粒产生其尺寸所特有的散射谱图。借助检测器测量散射光谱并且借助微型计算机按照体积分布计算粒度分布。
可以通过在合适的磨机中研磨足够长的时间而生产具有合适粒度分布的钒氧化物。合适的磨机包括例如冲击磨机、辊压磨机、振动磨机、研磨介质磨机或转鼓磨机。优选研磨介质磨机。它们含有水平安装在轴承上并且围绕固定的旋转点旋转的圆柱形操作室。操作室装有通常具有不同尺寸的研磨介质。待研磨的材料存在于研磨介质之间的空隙中。作为研磨介质，使用耐磨的锻造或铸造钢珠、棒或小段的棒。根据磨机的旋转速度，将会形成特别是研磨介质的运动，以及由此在待研磨材料上产生不同应力如摩擦、震动、冲击和压力，结果导致待研磨材料的较大颗粒破裂。
基于催化活性组合物的总量，煅烧状态下的催化活性组合物优选含有1-40重量％的氧化钒，按照V2O5计算，以及60-99重量％的二氧化钛，按照TiO2计算。催化活性组合物还可以含有至多1重量％的铯化合物，按照Cs计算，至多1重量％的磷化合物，按照P计算，以及至多10重量％的氧化锑，按照Sb2O3计算。
除了任选的添加剂铯和磷以外，原则上在催化活性组合物中还可以存在少量的作为促进剂的许多其它氧化物以影响催化剂的活性和选择性，例如通过减小或增加其活性。该促进剂的实例是碱金属氧化物，特别是上述氧化铯以及锂、钾和铷的氧化物，氧化铊(I)、氧化铝、氧化锆、氧化铁、氧化镍、氧化钴、氧化锰、氧化锡、氧化银、氧化铜、氧化铬、氧化钼、氧化钨、氧化铱、氧化钽、氧化铌、氧化砷、氧化锑、氧化铈。从这组化合物中，通常使用铯作为促进剂。
此外，在上述促进剂中，基于催化活性组合物，优选用量为0.01-0.50重量％的铌和钨氧化物作为添加剂。作为增加活性而降低选择性的添加剂，特别有用的是磷氧化物，尤其是五氧化二磷。
使用的二氧化钛有利地由BET表面积为5-15m2/g的TiO2和BET表面积为15-50m2/g的TiO2的混合物组成。还可以使用BET表面积为5-50m2/g，优选13-28m2/g的单一二氧化钛。
作为惰性载体材料，实际上可以使用现有技术的所有载体材料，正如在芳族烃氧化形成醛、羧酸和/或羧酸酐的涂敷催化剂的生产中有利采用的那些，例如石英(SiO2)、瓷、氧化镁、二氧化锡、碳化硅、金红石、氧化铝(Al2O3)、硅酸铝、滑石(硅酸镁)、硅酸锆、硅酸铯或这些载体材料的混合物。该载体材料通常是无孔的。对于本发明而言，“无孔”的表述应当理解为“除了技术上不重要的孔数量以外是无孔的”的含意，因为少量的孔可能不可避免地存在于载体材料中，该载体材料在理想情况下应当不含有孔。作为有利的载体材料，可以特别提到滑石和碳化硅。对于本发明的预催化剂和涂敷催化剂而言，载体材料的形状通常不重要。例如可以使用球、环、丸、螺旋物、管、挤出物或压碎材料形式的催化剂载体。这些催化剂载体的尺寸对应于生产涂敷催化剂(用于芳族烃的气相部分氧化)的常用催化剂载体的尺寸。优选使用直径为3-6mm的球或外径为5-9mm、长度为3-8mm且壁厚为1-2mm的环形式的滑石。
在本发明方法中，通过将TiO2和V2O5的悬浮液(如果合适的话该悬浮液可以含有上述促进剂元素的来源)喷涂到流化的载体上而施加涂敷催化剂的涂层。在涂敷程序以前，优选搅拌悬浮液足够长的时间，例如2-30小时，特别是12-25小时，以破坏悬浮固体的附聚物并且得到均匀的悬浮液。悬浮液通常具有20-50重量％的固体含量。悬浮介质通常是含水介质，例如水本身或者水和与水混溶的有机溶剂如甲醇、乙醇、异丙醇、甲酰胺等的含水混合物。
通常，有利地以水悬浮液的形式将有机粘合剂，优选乙酸乙烯酯/月桂酸乙烯酯、乙酸乙烯酯/丙烯酸酯、苯乙烯/丙烯酸酯或乙酸乙烯酯/乙烯的共聚物加入悬浮液中。粘合剂可以作为例如具有35-65重量％固体含量的水悬浮液而市购。基于悬浮液的重量，该粘合剂分散体的用量通常为2-45重量％，优选5-35重量％，特别优选7-20重量％。
在流化床或移动床设备中，在上升的气流，特别是空气中流化载体。该设备通常含有圆锥形或球形容器，其中由向下延伸的管道将流化气体从下端或上端引入该容器中。借助喷嘴将悬浮液从上端、侧面或下端喷涂到流化床中。使用布置在中心位置或围绕向下延伸的管道而同心布置的升气管是有利的。在升气管中主要是较高的气体速度并且将载体颗粒向上输送。在外环中，气体流速仅略高于松弛速度。由此，以环形垂直运动输送颗粒。合适的流化床设备例如描述于DE-A 4006935。
用催化活性组合物涂敷催化剂载体通常在20-500℃的涂敷温度下在大气压或减压下进行。通常在0-200℃，优选20-150℃，特别是60-120℃下进行涂敷。
还可以以两层或更多层施加催化活性组合物，其中例如一个或多个内层具有至多15重量％的氧化锑含量，并且外层具有低50-100％的氧化锑含量。通常，催化剂的内层是含磷的且外层是低磷或无磷的。
催化活性组合物的层厚通常是0.02-0.2mm，优选0.05-0.15mm。催化剂中活性组合物的比例通常是5-25重量％，大多数是7-15重量％。
在>200至500℃的温度下热处理所得的预催化剂的结果导致粘合剂通过热分解和/或燃烧而从施加的层中排出。优选在气相氧化反应器中就地进行热处理。
本发明的催化剂总体上适合芳族C6-C10烃如苯、二甲苯、甲苯、萘或均四甲苯(1，2，4，5-四甲基苯)的气相氧化，形成羧酸和/或羧酸酐如马来酸酐、邻苯二甲酸酐、苯甲酸和/或均苯四酸酐。
为此，将根据本发明生产的催化剂引入反应管中，例如借助盐熔体从外部将该反应管恒温在反应温度下，并且在通常为300-450℃，优选320-420℃，特别优选340-400℃的温度和通常为0.1-2.5巴，优选0.3-1.5巴的表压下以通常为750-5000h-1的空速将反应气体通过制备的催化剂床。
供应给催化剂的反应气体通常通过将含有分子氧并且除此以外还可以含有合适的反应调节剂和/或稀释剂如蒸汽、二氧化碳和/或氮气的气体与待氧化的芳族烃混合而制备，其中含有分子氧的气体通常可以含有1-100摩尔％，优选2-50摩尔％，特别优选10-30摩尔％的氧，0-30摩尔％，优选0-10摩尔％的蒸汽，以及0-50摩尔％，优选0-1摩尔％的二氧化碳，余量为氮气。为了制备该反应气体，每标准m3的含有分子氧的气体通常载有30-150g的待氧化芳族烃。
发现特别有利的是使用催化活性不同的催化剂和/或催化剂床中的催化剂活性组合物的化学组成不同的催化剂。当采用两个反应区时，第一反应区，即最靠近反应气体入口的反应区中使用的催化剂比第二反应区，即最靠近气体出口的反应区中存在的催化剂优选具有更低的催化活性。通常，借助温度设定控制反应从而在第一区中以最大的产率使反应气体中存在的大部分芳族烃发生反应。优选使用3-5个区的催化剂体系，特别是3区和4区的催化剂体系。
通过下列实施例说明本发明。
使用Frisch粒度仪“Analysette 22”测量粒度分布，测量范围是0.3-300μm且分辨率是62信道。为了进行测量，将V2O5样品悬浮在水中并借助泵将其循环通过测量池。测量时间是2次扫描。通过Fraunhofer方法进行评价。
实施例1
将54.227kg锐钛矿(BET表面积＝9m2/g)、126.517kg锐钛矿(BET表面积＝20m2/g)、14.195kg V2O5、3.549kg Sb2O3、0.805kg碳酸铯悬浮在519.035kg去离子水中并且搅拌以达到均匀分布。该V2O5具有下列基于体积的粒度分布：10％≤0.58μm；20％≤0.87μm；30％≤1.20μm；40％≤1.61μm；50％≤2.21μm；60％≤3.26μm；70％≤5.52μm；80％≤9.46μm；90％≤14.92μm；95％≤19.51μm；99.9％≤169.33μm。以50％浓度分散体的形式将80kg含有乙酸乙烯酯和月桂酸乙烯酯的共聚物的有机粘合剂加入悬浮液中。将60kg悬浮液喷涂到150kg尺寸为7×7×4mm(外径×高度×内径)的滑石环(硅酸镁)上，并且在流化床涂敷设备中干燥。在80-120℃的温度下使用6000m3/h的空气流进行涂敷。
分析在400℃下煅烧的催化剂表明V2O5在活性组合物中的比例是6.85重量％。然而，点燃的活性组合物的V2O5理论计算含量是7.12重量％。有0.27％的损失量(绝对)。为了弥补在涂敷程序中的V2O5损失并且生产具有规定V2O5含量的催化剂，悬浮液中的V2O5用量必须增加0.543kg。
实施例2
使用具有下列基于体积的粒度分布的V2O5重复实施例1：10％≤0.62μm；20％≤0.93μm；30％≤1.25μm；40％≤1.63μm；50％≤2.10μm；60％≤2.76μm；70％≤3.84μm；80％≤6.27μm；90％≤24.24μm；95％≤46.58μm；99.9％≤300μm。
分析在400℃下煅烧的催化剂表明V2O5在活性组合物中的比例是5.55重量％。与7.12重量％的理论值相比，有1.57％的损失量(绝对)。为了弥补在涂敷程序中的V2O5损失并且生产具有规定V2O5含量的催化剂，悬浮液中的V2O5用量必须增加3.134kg。
上述实施例表明使用具有规定粒度分布的V2O5可以减少需要量。
Claims (9)
1.一种制备气相氧化催化剂的方法，其中将TiO2和V2O5颗粒的悬浮液喷涂到流化的惰性载体上，其中至少90体积％的V2O5颗粒具有20μm或更小的直径且至少95体积％的V2O5颗粒具有30μm或更小的直径。
2.根据权利要求1的方法，其中至少90体积％的V2O5颗粒具有15μm或更小的直径且至少95体积％的V2O5颗粒具有20μm或更小的直径。
3.根据权利要求1的方法，其中至少50体积％的V2O5颗粒具有2μm以上的直径。
4.根据权利要求2的方法，其中至少50体积％的V2O5颗粒具有2μm以上的直径。
5.根据权利要求1-4中任何一项的方法，其中该悬浮液还含有至少一种铯、磷和/或锑源。
6.根据权利要求1-4中任何一项的方法，其中催化活性组合物含有1-40重量％的氧化钒，按照V2O5计算，以及60-99重量％的二氧化钛，按照TiO2计算。
7.根据权利要求5的方法，其中催化活性组合物含有1-40重量％的氧化钒，按照V2O5计算，以及60-99重量％的二氧化钛，按照TiO2计算。
8.根据权利要求6的方法，其中基于催化活性组合物的总量，催化活性组合物还含有至多1重量％的铯化合物，按照Cs计算，至多1重量％的磷化合物，按照P计算，以及至多10重量％的氧化锑，按照Sb2O3计算。
9.根据权利要求7的方法，其中基于催化活性组合物的总量，催化活性组合物还含有至多1重量％的铯化合物，按照Cs计算，至多1重量％的磷化合物，按照P计算，以及至多10重量％的氧化锑，按照Sb2O3计算。
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| DE10344846A DE10344846A1 (de) | 2003-09-26 | 2003-09-26 | Gasphasenoxidationskatalysator mit definierter Vanadiumoxid-Teilchengrößenverteilung |
| DE10344846.2 | 2003-09-26 |
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| WO2006125468A1 (de) * | 2005-05-22 | 2006-11-30 | Süd-Chemie AG | Mehrlagen-katalysator zur herstellung von phthalsäureanhydrid |
| DE102004026472A1 (de) * | 2004-05-29 | 2005-12-22 | Süd-Chemie AG | Mehrlagen-Katalysator zur Herstellung von Phthalsäureanhydrid |
| WO2005115615A1 (de) * | 2004-05-29 | 2005-12-08 | Süd-Chemie AG | Katalysator sowie verfahren zur herstellung von phthalsäureanhydrid |
| MX2007010223A (es) * | 2005-03-02 | 2008-03-10 | Sued Chemie Ag | Metodo para producir un catalizador de varias capas para la produccion de anhidrido ftalico. |
| DE102005009473A1 (de) * | 2005-03-02 | 2006-09-07 | Süd-Chemie AG | Mehrlagen-Katalysator zur Herstellung von Phthalsäureanhydrid |
| KR100671978B1 (ko) | 2005-07-19 | 2007-01-24 | 한국과학기술연구원 | 탈질환원촉매 |
| DE102009041960A1 (de) | 2009-09-17 | 2011-04-07 | Süd-Chemie AG | Verfahren zur Herstellung einer Katalysatoranordnung für die Herstellung von Phthalsäureanhydrid |
| DE102010006854A1 (de) | 2010-02-04 | 2011-08-04 | Süd-Chemie AG, 80333 | Verfahren zur Gasphasenoxidation von Kohlenwasserstoffen |
| DE102010012090A1 (de) | 2010-03-19 | 2011-11-17 | Süd-Chemie AG | Verfahren zur katalytischen Gasphasenoxidation von Kohlenwasserstoffen und Katalysereaktionsvorrichtung |
| US8652988B2 (en) | 2011-04-27 | 2014-02-18 | Celanese International Corporation | Catalyst for producing acrylic acids and acrylates |
| US8642498B2 (en) * | 2011-05-11 | 2014-02-04 | Celanese International Corporation | Catalysts for producing acrylic acids and acrylates |
| CN104159670A (zh) * | 2012-03-13 | 2014-11-19 | 国际人造丝公司 | 用于产生丙烯酸和丙烯酸类的包含钒、钛和钨的催化剂 |
| ES2804521T3 (es) * | 2012-08-24 | 2021-02-08 | Tronox Llc | Materiales de apoyo a catalizadores, catalizadores, métodos de su fabricación y usos de los mismos |
| EP2704301B1 (en) * | 2012-08-31 | 2016-07-27 | Stichting IMEC Nederland | DC-DC converter and control method thereof |
| EP2781262B1 (en) | 2013-03-22 | 2020-05-27 | Clariant International Ltd | Removable protective coating for the receipt of a dust free catalyst |
| US9765046B2 (en) | 2013-06-26 | 2017-09-19 | Basf Se | Process for preparing phthalic anhydride |
| CN105339338B (zh) | 2013-06-26 | 2017-11-21 | 巴斯夫欧洲公司 | 起动气相氧化反应器的方法 |
| CN110871098A (zh) * | 2018-08-30 | 2020-03-10 | 中国石油化工股份有限公司 | 萘制苯酐的催化剂及其制备方法和应用 |
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| DE3125062C2 (de) * | 1981-06-26 | 1984-11-22 | Degussa Ag, 6000 Frankfurt | Verfahren zur Herstellung von abriebfesten Schalenkatalysatoren und Verwendung eines so erhaltenen Katalysators |
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| Publication number | Publication date |
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| TW200523020A (en) | 2005-07-16 |
| US7592294B2 (en) | 2009-09-22 |
| RU2006114066A (ru) | 2006-09-10 |
| KR20060113888A (ko) | 2006-11-03 |
| CN1860093A (zh) | 2006-11-08 |
| RU2314867C2 (ru) | 2008-01-20 |
| DE10344846A1 (de) | 2005-04-14 |
| EP1670741B1 (de) | 2010-03-03 |
| MXPA06002874A (es) | 2006-06-05 |
| WO2005030692A1 (de) | 2005-04-07 |
| JP4499729B2 (ja) | 2010-07-07 |
| IN2006CH01022A (zh) | 2007-06-29 |
| DE502004010857D1 (de) | 2010-04-15 |
| BRPI0414453A (pt) | 2006-11-14 |
| JP2007533424A (ja) | 2007-11-22 |
| EP1670741A1 (de) | 2006-06-21 |
| IL174130A0 (en) | 2006-08-01 |
| UA79056C2 (en) | 2007-05-10 |
| US20070093384A1 (en) | 2007-04-26 |
| ATE459593T1 (de) | 2010-03-15 |
| ZA200603259B (en) | 2008-09-25 |
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