CN103025424B - 用于使邻二甲苯和/或萘氧化成邻苯二甲酸酐的催化剂 - Google Patents
用于使邻二甲苯和/或萘氧化成邻苯二甲酸酐的催化剂 Download PDFInfo
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- CN103025424B CN103025424B CN201180035813.9A CN201180035813A CN103025424B CN 103025424 B CN103025424 B CN 103025424B CN 201180035813 A CN201180035813 A CN 201180035813A CN 103025424 B CN103025424 B CN 103025424B
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- Prior art keywords
- catalyst
- antimony
- xylene
- oxide
- ortho
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 title claims abstract description 18
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 30
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 28
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 27
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 5
- 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 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 31
- 239000000203 mixture Substances 0.000 description 30
- 230000003197 catalytic effect Effects 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- 239000004408 titanium dioxide Substances 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000454 talc Substances 0.000 description 8
- 235000012222 talc Nutrition 0.000 description 8
- 229910052623 talc Inorganic materials 0.000 description 8
- -1 cesium compound Chemical class 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- RHDGNLCLDBVESU-UHFFFAOYSA-N but-3-en-4-olide Chemical compound O=C1CC=CO1 RHDGNLCLDBVESU-UHFFFAOYSA-N 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 description 3
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadistibetane 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 238000010438 heat treatment Methods 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
- 229910052742 iron Inorganic materials 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
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000012041 precatalyst Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 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
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- CRSXUEWOSGRGNR-UHFFFAOYSA-N [Sb+4] Chemical compound [Sb+4] CRSXUEWOSGRGNR-UHFFFAOYSA-N 0.000 description 1
- TXTQARDVRPFFHL-UHFFFAOYSA-N [Sb].[H][H] Chemical compound [Sb].[H][H] TXTQARDVRPFFHL-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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 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
- 150000001462 antimony Chemical class 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- 230000001174 ascending effect Effects 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
- 235000010233 benzoic acid Nutrition 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
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- ORWFSDJNQHQQQD-UHFFFAOYSA-N cerium silicic acid Chemical compound [Ce].[Si](O)(O)(O)O ORWFSDJNQHQQQD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 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
- 239000007859 condensation product Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- 238000009826 distribution Methods 0.000 description 1
- UXAYDBNWIBJTRO-UHFFFAOYSA-N ethenyl acetate;ethenyl dodecanoate Chemical compound CC(=O)OC=C.CCCCCCCCCCCC(=O)OC=C UXAYDBNWIBJTRO-UHFFFAOYSA-N 0.000 description 1
- CYKDLUMZOVATFT-UHFFFAOYSA-N ethenyl acetate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=O)OC=C CYKDLUMZOVATFT-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002505 iron Chemical class 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
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 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 compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 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
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-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
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000006187 pill Substances 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
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 238000000926 separation method Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229910003438 thallium oxide Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
-
- 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
- B01J23/18—Arsenic, antimony or bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
提供了一种用于使邻二甲苯和/或萘氧化成邻苯二甲酸酐的催化剂,该催化剂具有多个串联设置于反应管中的催化剂区,并且使用包含显著比例的锑华的三氧化二锑生产。还公开了一种气相氧化的方法,其中使包含至少一种烃和分子氧的气流通过使用包含显著比例的锑华的三氧化二锑生产的催化剂。
Description
本发明涉及一种用于使邻二甲苯和/或萘氧化成邻苯二甲酸酐的催化剂,该催化剂具有多个串联设置于反应管中的催化剂区,并且使用包含显著比例的锑华的三氧化二锑生产。本发明进一步涉及一种气相氧化的方法,其中包含至少一种烃和分子氧的气流通过使用包含显著比例的锑华的三氧化二锑生产的催化剂。
在工业上很多羧酸和/或羧酸酐通过在固定床反应器中催化气相氧化烃如苯、二甲苯、萘、甲苯或杜烯制备。以此方法,可得到例如苯甲酸、马来酸酐、邻苯二甲酸酐、间苯二甲酸、对苯二甲酸或苯均四酸酐。通常使含氧气体和待氧化的原料的混合物通过其中存在催化剂床的管。为了调节温度,这些管由传热介质如盐熔体所环绕。
已发现其中催化活性组合物以壳的形式施加于惰性载体材料如滑石的经涂覆催化剂可用作这些氧化反应的催化剂。通常,这些催化剂具有活性组合物层,其基本具有均匀化学组成且以壳的形式施加。此外,可向载体连续施加两个或更多个不同的活性组合物层。这些称为双层或多层催化剂(参见例如DE19839001A1)。
作为这些经涂覆催化剂的催化活性组合物的催化剂活性成分,使用通常由二氧化钛和五氧化二钒制成的那些。此外,少量的许多其他作为促进剂影响催化剂活性和选择性的氧化化合物(包括氧化铯、氧化磷和氧化锑)可存在于催化活性组合物中。
根据EP1636161,当设定特定V2O5/Sb2O3比且三氧化二锑具有预定平均粒度时,可获得提供特别高PAn产率的催化剂。
锑氧化物的存在导致PAn选择性提高;其效果被认为是钒位置的分离。
催化剂的活性组合物中使用的锑氧化物可为各种锑(III)、锑(IV)和锑(V)的化合物;通常使用三氧化二锑或五氧化二锑。EP522871描述了五氧化二锑的用途,US2009/306409和EP1636161公开了三氧化二锑的用途。
与四氧化二锑和五氧化二锑相比,三氧化二锑可更好分散于二氧化钛上,从而获得明显改善的催化剂分布。三氧化二锑通常作为纯方锑矿相使用(参见Schubert,U.-A.等,TopicsinCatalysis,2001,第15(2-4)卷,第195-200页)。除立方锑矿外,还存在三氧化二锑的斜方晶型,称为锑华(Golunski,S.E.等.,Appl.Catal.,1989,第48卷,第123-135页)。
气相氧化持续需要催化剂,该催化剂以高选择性得到非常高的转化率。
本发明目的为开发一种用于使邻二甲苯和/或萘氧化成邻苯二甲酸酐的催化剂,该催化剂使得在低盐浴温度下由低含量邻二甲苯和2-苯并[c]呋喃酮可获得高邻苯二甲酸酐产率。
该目的通过一种用于使邻二甲苯和/或萘氧化成邻苯二甲酸酐的催化剂实现,该催化剂使用包含显著比例的锑华的三氧化二锑生产。
本发明目的为提供一种用于使邻二甲苯和/或萘氧化成邻苯二甲酸酐的催化剂,该催化剂使用三氧化二锑生产,其中X射线粉末衍射图中在2-θ=28.4°的信号高度与在2-θ=27.7°和28.4°的信号高度总和之比至少为0.02。
在2-θ=27.7°的信号为方锑矿的特征(参见ASTMIndex,No.5-0534/7)且在2-θ=28.4°的信号为锑华(参见ASTMIndex,No.11-689)。信号高度通过相应信号的最大强度与所测定背景之差得到。
在本发明优选实施方案中,该催化剂使用三氧化二锑生产,其中X射线粉末衍射图中在2-θ=28.4°的信号高度与在2-θ=27.7°和28.4°的信号高度总和之比至少为0.03,尤其优选至少0.05。
根据本发明要使用的具有显著锑华含量的三氧化二锑可用于产生一个或更多个催化剂区。在本发明的优选实施方案中,该催化剂具有3、4或5个区,其中使用具有显著锑华含量的三氧化二锑产生至少一个区。
本发明催化剂也与合适的上游和/或下游床组合以及和中间区一起组合可例如避免高热点温度,其中该上游和/或下游床和中间区通常可包含催化惰性或活性较低的物质。
本发明催化剂通常为经涂覆催化剂,其中催化剂活性组合物以壳的形式施加至惰性载体材料。
关于惰性载体材料,实际上可使用有利地用于生产将芳烃氧化成醛、羧酸和/或羧酸酐的经涂覆催化剂的现有技术的所有载体材料,例如石英(SiO2)、瓷、氧化镁、二氧化锡、碳化硅、金红石、矾土(Al2O3)、硅酸铝、滑石(硅酸镁)、硅酸锆、硅酸铈或这些载体材料的混合物。这些催化剂载体可例如以球体、环、丸剂、螺旋形物、管、挤出物或压碎物质的形式使用。这些催化剂载体的尺寸对应于通常用于生产芳烃的气相反应用经涂覆催化剂的催化剂载体的尺寸。优选使用呈具有3-6mm直径的球形形式或具有5-9mm外径和3-8mm长度以及1-2mm壁厚的环形形式的滑石。
本发明催化剂包含催化活性组合物,该催化活性组合物至少包含氧化钒和二氧化钛并且可以一层或多层施加于载体材料。此时各层的化学组成可不同。
该催化活性组合物优选基于催化活性组合物总量包含1-40重量%的氧化钒(以V2O5计算)和60-99重量%的二氧化钛(以TiO2计算)。在优选实施方案中,该催化活性组合物可额外包含至多1重量%的铯化合物(以Cs计算)、至多1重量%的磷化合物(以P计算)和至多10重量%的氧化锑(以Sb2O3计算)。关于催化活性组合物的化学组成的所有数值基于催化活性组合物的煅烧状态,例如,在将催化剂在450℃下煅烧1小时后。
二氧化钛通常以锐钛矿形式用于催化活性组合物。二氧化钛优选具有15-60m2/g,尤其是15-45m2/g,特别优选13-28m2/g的BET表面积。所用二氧化钛可为单独二氧化钛或二氧化钛的混合物。在后者情况下,该BET表面积的加权平均值决定单独二氧化钛的贡献。所用二氧化钛例如有利地为具有5-15m2/g的BET表面积的TiO2和具有15-50m2/g的BET表面积的TiO2的混合物。
合适钒源尤其是五氧化二钒或偏钒酸铵。合适锑源为各种具有显著锑华含量的三氧化二锑。可能的磷源尤其是磷酸、亚磷酸、次磷酸、磷酸铵或磷酸酯且尤其是磷酸二氢铵。合适铯源为氧化物或氢氧化物或可热转化成氧化物的盐,例如羧酸盐,特别是乙酸盐、丙二酸盐或草酸盐、碳酸盐、碳酸氢盐、硫酸盐或硝酸盐。
除任选添加铯和磷外,催化活性组合物可包含少量的许多其他作为促进剂影响催化剂的活性和选择性(例如通过降低或提高其活性)的氧化化合物。该类促进剂的实例为碱金属,特别是,除上述铯以外的锂、钾和铷(其通常以其氧化物或氢氧化物形式使用),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、四氧化二锑、五氧化二锑和氧化铈。
此外,在上述促进剂中,进一步优选含量基于催化活性组合物为0.01-0.50重量%的铌和钨的氧化物作为添加剂。
经涂覆催化剂层的施加有利地通过将TiO2和V2O5的悬浮液(其任选包含上述促进剂元素源)喷于流化载体上而进行。在涂覆前,优选将该悬浮液搅拌充分长时间,例如,2-30小时,尤其是12-25小时,以打碎悬浮固体的凝聚物并获得均匀悬浮液。悬浮液通常具有20-50重量%的固体含量。悬浮介质通常为水性,例如,水本身或与水混溶性有机溶剂如甲醇、乙醇、异丙醇、甲酰胺等的水性混合物。
通常,有机粘合剂,优选共聚物,有利地以丙烯酸-马来酸、乙酸乙烯酯-月桂酸乙烯酯、乙酸乙烯酯-丙烯酸酯、苯乙烯-丙烯酸酯和乙酸乙烯酯-乙烯的水性分散体的形式加入悬浮液中。可市购固体含量为例如35-65重量%的水性分散体的粘合剂。该粘合剂分散体的用量基于悬浮液重量通常为2-45重量%,优选5-35重量%,尤其优选7-20重量%。
将该载体在例如流体化床装置或移动床装置中在上升气流(尤其是空气)中流化。该装置通常包括圆锥形或球形容器,将流化气体经由沉管由下或由上引入其中。该悬浮液通过喷嘴由上、侧或下喷入流体化床。提升管以中心或同心环绕沉管设置使用是有利的。在提升管中向上运输载体颗粒的较高气流速度占主导。在外环中,气流速度仅稍高于松动速度。因此,这些颗粒以环状方式垂直移动。合适的流体化床装置描述于例如DE-A4006935中。
在涂覆有催化活性组合物的催化剂载体中通常使用20-500℃的涂覆温度,其中涂覆可在大气压或减压下进行。通常,涂覆在0-200℃,优选20-150℃,尤其是60-120℃下进行。
催化活性组合物的层厚通常为0.02-0.2mm,优选0.05-0.15mm。催化剂中活性组合物的比例通常为5-25重量%,大多数为7-15重量%。
在温度为大于200℃至500℃下热处理以此方式得到的预催化剂(precatalyst)导致粘合剂由于热分解和/或燃烧而由该施加层中放出。该热处理优选在气相氧化反应器中原位进行。
本发明进一步提供气相氧化的方法,其中使包含至少一种烃和分子氧的气流通过使用三氧化二锑生产的催化剂,其中X射线粉末衍射图中在2-θ=28.4°的信号高度与在2-θ=27.7°和28.4°的信号高度总和之比至少为0.02。
本发明优选实施方案为用于将邻二甲苯和/或萘气相氧化成邻苯二甲酸酐的方法,其中使包含邻二甲苯和/或萘和分子氧的气流通过使用三氧化二锑生产的催化剂,其中X射线粉末衍射图中在2-θ=28.4°的信号高度与在2-θ=27.7°和28.4°的信号高度总和之比至少为0.02。
实施例
三氧化二锑中锑华含量和方锑矿含量的测定:
此测定通过X射线粉末衍射进行。为此,三氧化二锑粉末在来自Siemens的“D5000θ/θ”X射线粉末衍射仪中测量。该测量参数如下:
直径 | 435mm |
X辐射 | CuK-α(λ=1.54·10-10m) |
管电压 | 40kV |
管电流 | 30mA |
孔径 | 变量V20 |
散射辐射孔 | 变量V20 |
次级单色仪(secondary monochromator) | 石墨 |
单色仪孔径 | 0.1mm |
闪烁计数器 | |
探测器孔径 | 0.6mm |
步长 | 0.02°2Θ |
步进模式 | 连续 |
测量时间 | 2.4s/步 |
测量速率 | 0.5°2Θ/min |
信号高度通过相应信号的最大强度与所测定背景之差得到。为测定锑华含量,使用在2-θ=27.7°(方锑矿,信号高度a)和28.4°(锑华,信号高度b)的信号。该锑华含量为b/(a+b),且该方锑矿含量为a/(a+b)。
实施例1(本发明):
催化剂区CZ1:
将3.38g碳酸铯,459.3g二氧化钛(FujiTA100C,锐钛矿,BET表面积20m2/g),196.9g二氧化钛(FujiTA100,锐钛矿,BET表面积7m2/g)和51.4g五氧化二钒以及13.2g三氧化二锑(MerckSelectipur7835,锑华含量=0.18,方锑矿含量=0.82,99.5%Sb2O3含量,300重量ppm的As,500重量ppm的Pb,50重量ppm的Fe,平均粒度2μm)悬浮于1869g去离子水中且搅拌18小时以获得均匀分布。将78.4g包含乙酸乙烯酯和月桂酸乙烯酯的共聚物的有机粘合剂以浓度为50重量%的水分散体形式加入该悬浮液中。在流化床装置中,将820g该悬浮液喷到2kg呈7mm×7mm×4mm尺寸的环形式的滑石(硅酸镁)上并干燥。在450℃下煅烧该催化剂1小时后,施加于滑石环的活性组合物的量为9.1%。该活性组合物的分析化学组成为7.1%的V2O5,1.8%的Sb2O3,0.38%的Cs,余量为TiO2。
催化剂区CZ2:
生产类似于CZ1,其中该悬浮液的化学组成变化。在450℃下煅烧该催化剂1小时后,施加于滑石环的活性组合物的量为8.5%。该活性组合物的分析化学组成包含7.95%的V2O5,2.7%的Sb2O3,0.31%的Cs,余量为平均BET表面积为18m2/g的TiO2。
催化剂区CZ3:
生产类似于CZ1,其中该悬浮液的化学组成变化。在450℃下煅烧该催化剂1小时后,施加于滑石环的活性组合物的量为8.5%。该活性组合物的分析化学组成包含7.1%的V2O5,2.4%的Sb2O3,0.10%的Cs,余量为平均BET表面积为17m2/g的TiO2。
催化剂区CZ4:
生产类似于CZ1,其中该悬浮液的化学组成变化且使用FujiTA100CT(锐钛矿,BET表面积27m2/g)代替FujiTA100C。在450℃下煅烧该催化剂1小时后,施加于滑石环的活性组合物的量为9.1%。该活性组合物的分析化学组成包含20%的V2O5,0.38%的P,其余为平均BET表面积为23m2/g的TiO2。
实施例2(非本发明):
催化剂区CZ5:
生产类似于CZ1,但使用具有降低锑华含量的三氧化二锑级(例如,白色Triox,来自Antraco,锑华含量=0.015,方锑矿含量=0.985,99.3%Sb2O3含量,0.3重量%的As2O3,0.18重量%的PbO,0.02重量%的氧化铁,平均粒度1.5μm)。
催化剂区CZ6:
生产类似于CZ2,但使用具有降低锑华含量的三氧化二锑级(例如,白色Triox,来自Antraco,锑华含量=0.015,方锑矿含量=0.985,99.3%Sb2O3含量,0.3重量%的As2O3,0.18重量%的PbO,0.02重量%的氧化铁,平均粒度1.5μm)。
催化剂区CZ7:
生产类似于CZ3,但使用具有降低锑华含量的三氧化二锑级(例如,白色Triox,来自Antraco,锑华含量=0.015,方锑矿含量=0.985,99.3%Sb2O3含量,0.3重量%的As2O3,0.18重量%的PbO,0.02重量%的氧化铁,平均粒度1.5μm)。
实施例3(本发明,邻二甲苯以模型管规模氧化成邻苯二甲酸酐):
邻二甲苯的催化氧化成邻苯二甲酸酐在具有内径为25mm的管的盐浴冷却管式反应器中进行。由反应器进口至反应器出口,将130cm的CZ1、70cm的CZ2、60cm的CZ3和60cm的CZ4引入到具有3.5m的长度和25mm的内径的铁管中。该铁管由调节温度的盐熔体,具有4mm外径的热电偶套管和用于测量催化温度的内建可抽出元件所环绕。
将载荷为30-100克/标准立方米的浓度为99.2重量%的邻二甲苯的4.0标准立方米/小时的空气由顶端向下通过管。这得到概括在表1中的结果(“PAn产率”获得的邻苯二甲酸酐量的基于浓度为100%的邻二甲苯的重量百分数)。
实施例4(非本发明,邻二甲苯以模型管规模氧化成邻苯二甲酸酐):
参见实施例3,但具有的催化剂床包括(从反应器进口至反应器出口)130cm的CZ5、70cm的CZ6、60cm的CZ7和60cm的CZ4。
表1
表1中实施例3和4的比较显示实施例3的催化剂催化活性高于实施例4。为此可进一步降低实施例3(本发明)中的盐浴温度,且具有低邻二甲苯和2-苯并[c]呋喃酮含量的PAn产率显著高于实施例4(非本发明)。
实施例5(本发明,邻二甲苯以工业规模氧化成邻苯二甲酸酐):
邻二甲苯的催化氧化成邻苯二甲酸酐在具有15105支内径为25mm的管的盐浴冷却管式反应器中进行。从反应器进口至反应器出口,引入130cm的CZ1、90cm的CZ2、60cm的CZ3和60cm的CZ4。为记录温度曲线,一些反应管装有热电偶。将具有0-100克/标准立方米的邻二甲苯载荷(纯度为约99重量%)的4.0标准立方米/小时空气通过该管。PAn产率在反应器出口气体中测量且在表2中以基于浓度为100%的邻二甲苯的重量%记录(每千克反应邻二甲苯的PAn千克)。
实施例6(非本发明,邻二甲苯以工业规模氧化成邻苯二甲酸酐):
参见实施例5,但具有的催化剂床包括(从反应器进口至反应器出口)130cm的CZ5、90cm的CZ6、60cm的CZ7和60cm的CZ4。
表2
工业规模 | 实施例5(本发明) | 实施例6(非本发明) |
气体量[标准立方米/h] | 4.0 | 4.0 |
载荷[g/标准立方米] | 95 | 95 |
运行时间[天] | 79 | 76 |
盐浴温度[℃] | 343.4 | 346.2 |
PAn产率[重量%] | 114.5 | 112.9 |
邻二甲苯含量[重量%] | 0.08 | 0.06 |
2-苯并[c]呋喃酮含量[重量%] | 0.01 | 0.01 |
表2中实施例5和6的比较显示实施例5的催化剂催化活性高于实施例6。为此可进一步降低实施例5(本发明)中的盐浴温度,且具有低邻二甲苯和2-苯并[c]呋喃酮含量的PAn产率显著高于实施例6(非本发明)。
Claims (3)
1.一种用于使邻二甲苯和/或萘氧化成邻苯二甲酸酐的催化剂,所述催化剂使用三氧化二锑生产,其中X射线粉末衍射图中在2-θ=28.4°的信号高度与在2-θ=27.7°和28.4°的信号高度总和之比至少为0.02,
其中在2-θ=27.7°的信号为方锑矿的特征,在2-θ=28.4°的信号为锑华的特征。
2.一种气相氧化方法,其中使包含至少一种烃和分子氧的气流通过使用三氧化二锑生产的催化剂,其中X射线粉末衍射图中在2-θ=28.4°的信号高度与在2-θ=27.7°和28.4°的信号高度总和之比至少为0.02,
其中在2-θ=27.7°的信号为方锑矿的特征,在2-θ=28.4°的信号为锑华的特征。
3.如权利要求2的方法,其中所述烃为邻二甲苯和/或萘。
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US9029289B2 (en) | 2012-07-16 | 2015-05-12 | Basf Se | Catalyst for preparing carboxylic acids and/or carboxylic anhydrides |
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EP2987552A1 (en) * | 2014-08-22 | 2016-02-24 | Basf Se | Catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride |
EP3107653B1 (en) * | 2014-02-17 | 2023-08-16 | Basf Se | Catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride |
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DE102014203725A1 (de) | 2014-02-28 | 2015-09-03 | Basf Se | Oxidationskatalysator mit sattelförmigem Trägerformkörper |
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DE102017202351A1 (de) * | 2017-02-14 | 2018-08-16 | Clariant International Ltd | Katalysatormaterial zur Oxidation von Kohlenwasserstoffen mit antimondotiertem Titandioxid |
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