CN104487164A - 制备羧酸和/或羧酸酐的催化剂 - Google Patents
制备羧酸和/或羧酸酐的催化剂 Download PDFInfo
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- CN104487164A CN104487164A CN201380037094.3A CN201380037094A CN104487164A CN 104487164 A CN104487164 A CN 104487164A CN 201380037094 A CN201380037094 A CN 201380037094A CN 104487164 A CN104487164 A CN 104487164A
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- Prior art keywords
- catalyst
- weight
- antimony
- content
- vanadium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 title claims abstract description 14
- 150000001735 carboxylic acids Chemical class 0.000 title abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 58
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001882 dioxygen Inorganic materials 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
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 45
- 239000002253 acid Substances 0.000 claims description 38
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 35
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 23
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 20
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 20
- 230000008025 crystallization Effects 0.000 claims description 20
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 3
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 abstract description 9
- 239000007789 gas Substances 0.000 abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 30
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 23
- 230000003197 catalytic effect Effects 0.000 description 21
- 239000000725 suspension Substances 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 17
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 14
- 239000004408 titanium dioxide Substances 0.000 description 13
- 229910052792 caesium Inorganic materials 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 239000000454 talc Substances 0.000 description 10
- 229910052623 talc Inorganic materials 0.000 description 10
- 235000012222 talc Nutrition 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 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
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- -1 antimony (V) compound Chemical class 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 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
- 239000005711 Benzoic acid Substances 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- RHDGNLCLDBVESU-UHFFFAOYSA-N but-3-en-4-olide Chemical compound O=C1CC=CO1 RHDGNLCLDBVESU-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 238000005755 formation reaction 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 238000012207 quantitative assay Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 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
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- WEHZNZTWKUYVIY-UHFFFAOYSA-N 3-oxabicyclo[3.2.2]nona-1(7),5,8-triene-2,4-dione Chemical compound O=C1OC(=O)C2=CC=C1C=C2 WEHZNZTWKUYVIY-UHFFFAOYSA-N 0.000 description 1
- LNYYKKTXWBNIOO-UHFFFAOYSA-N 3-oxabicyclo[3.3.1]nona-1(9),5,7-triene-2,4-dione Chemical compound C1=CC(C(=O)OC2=O)=CC2=C1 LNYYKKTXWBNIOO-UHFFFAOYSA-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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 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
- 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
- 229910021542 Vanadium(IV) oxide Inorganic materials 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 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
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 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
- 239000006227 byproduct Substances 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
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 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
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000006837 decompression Effects 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
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 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
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 239000008188 pellet 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
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- 230000035484 reaction time 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
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000005507 spraying 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
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 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
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- 238000002424 x-ray crystallography Methods 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
提供了一种制备羧酸和/或羧酸酐的催化剂,该催化剂具有多个串联排列的催化剂区且使用最大结晶锑华含量为5重量%的锑酸钒生产。本发明进一步提供了一种气相氧化方法,其中使包含至少一种烃和分子氧的气流通过具有多个串联排列的催化剂区且使用最大结晶锑华含量为5重量%的锑酸钒生产的催化剂。
Description
本发明涉及一种制备羧酸和/或羧酸酐的催化剂,该催化剂具有多个串联排列的催化剂区且使用最大结晶锑华含量为5重量%的锑酸钒生产。本发明进一步涉及一种气相氧化方法,其中使包含至少一种烃和分子氧的气流通过具有多个串联排列的催化剂区且使用最大结晶锑华含量为5重量%的锑酸钒生产的催化剂。
许多羧酸和/或羧酸酐在工业上通过烃如苯、二甲苯类、萘、甲苯或杜烯在固定床反应器中的催化气相氧化制备。以此方式可以得到例如苯甲酸、马来酸酐、邻苯二甲酸酐(PAn)、间苯二甲酸酐、对苯二甲酸酐或均苯四甲酸酐。通常使待氧化的含氧气体和原料的混合物通过其中存在催化剂床的管。为了调节温度,这些管被换热介质如盐浴包围。
已经发现其中已经以壳的形式将催化活性组合物施加于惰性载体材料如滑石上的涂敷催化剂可以用作这些氧化反应的催化剂。这些催化剂通常具有以壳形式施加的活性组合物层,该层具有基本均匀的化学组成。此外,也可以对载体依次施加两个或更多个不同的活性组合物层。此时将这称为两层或多层催化剂(例如见DE 19839001 A1)。
二氧化钛和五氧化二钒通常用作这些涂敷催化剂的催化活性组合物的催化活性成分。此外,可以在该催化活性组合物中少量包含许多用作促进剂以影响该催化剂的活性和选择性的其他氧化化合物,包括铯、磷和锑氧化物。
锑氧化物的存在导致PAn选择性提高,该效果被认为由钒位置的差别化造成。催化剂的活性组合物中所用锑氧化物可以是各种锑(III)、锑(IV)或锑(V)化合物;通常使用三氧化锑或五氧化二锑。EP 522871描述了使用五氧化二锑,US 2009/306409和EP 1636161公开了使用三氧化锑。根据EP 1636161,得到特别高PAn产率的催化剂可以在设定特定V2O5/Sb2O3比且三氧化锑具有限定的平均粒度时得到。
与四氧化二锑和五氧化二锑相比,三氧化锑能够更好地铺展在二氧化钛上,在该催化剂上实现显著更好的分布。三氧化锑存在两种不同的晶型,即立方晶系方锑矿和斜方晶系锑华(Golunski,S.E.等,Appl.Catal.,1989,第48卷,第123-135页)。通常将纯相方锑矿用作三氧化锑(参见Schubert,U.-A.等,Topics in Catalysis,2001,第15卷(2-4),第195-200页)。WO2012/014154描述了当使用锑华含量为至少2%的三氧化锑时的PAn产率提高。
为了生产该类催化剂,不仅可以使用锑和钒的纯氧化物,而且可以使用可以通过使合适的钒和锑化合物,例如氧化物反应而得到的锑酸钒(WO2011/61132)。在PAn催化剂的至少一个区中使用该锑酸钒在80-100g/标准m3的邻二甲苯负荷下导致较低的热点温度(<425℃)。PAn产率高于由没有结晶锑酸钒的类似催化剂所给出的那些。
在两个结晶相为形成另一混合相的化学反应,例如氧化钒与氧化锑为形成结晶锑酸钒的反应中,通常发生各原料的不完全反应。所得产物此时不是相纯的,而是包含一个或多个其他相。
持续需要以高选择性给出非常高转化率的气相氧化用催化剂。
本发明的目的是要开发一种制备羧酸和/或羧酸酐的催化剂,尤其用于将邻二甲苯和/或萘氧化成邻苯二甲酸酐的催化剂,其在低盐浴温度下使得高产率在副产物含量低下成为可能。
该目的由一种制备羧酸和/或羧酸酐的催化剂实现,该催化剂具有多个串联排列的催化剂区且在其生产中将最大结晶锑华含量为5重量%的锑酸钒加入至少一个区中。
对本发明而言,锑酸钒是一种包含结晶锑酸钒相(例如粉末衍射档案(PDF)号:01-81-1219,PDF:01-77-0331或PDF:37-1075)作为显著组分的物质。除了其他无定形材料外,该锑酸钒相还可以包含少量其他结晶组分,尤其是钒和/或锑的纯氧化物。
在该锑酸钒相中结晶锑华比例的定量测定例如可以借助X射线粉末衍射图案的Rietveld精修进行。
待根据本发明使用的最大结晶锑华含量为5重量%的锑酸钒可以用于生产一个或多个催化剂区。在本发明的优选实施方案中,该催化剂具有3、4或5个区,其中将最大结晶锑华含量为5重量%的锑酸钒用于生产至少一个区。
本发明催化剂具有多个串联排列的催化剂区且可以就其催化活性组合物的含量和化学构成而言以及还就其催化活性而言不同。通常优选其中各催化剂区的活性由反应器入口向反应器出口增加的催化剂。然而,还可以使用一个或多个活性比随后区要高的在前或中间催化剂区。
本发明催化剂例如可以用于避免高热点温度,包括与合适的上游和/或下游床结合以及还有与中间区一起,其中上游和/或下游床以及还有中间区通常可以包含催化钝性材料或催化活性更差材料。
本发明催化剂通常为其中已经将催化活性组合物以壳的形式施加于惰性载体材料上的涂敷催化剂。
作为惰性载体材料,可以使用基本上所有现有技术中的载体材料,这些载体材料有利地用于生产将芳族烃氧化成醛、羧酸和/或羧酸酐的涂敷催化剂,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。催化剂载体例如可以以球、环、粒料、螺旋物、管形物、挤出物或压碎材料形式使用。这些催化剂载体的尺寸对应于常用于生产芳烃气相氧化反应用涂敷催化剂的催化剂载体的那些。优选使用直径为3-6mm的球或内径为5-9mm、长度为3-8mm和壁厚为1-2mm的环形式的滑石。
本发明催化剂包含催化活性组合物,该组合物至少包含氧化钒或锑酸钒和二氧化钛并且可以以一层或多层施加于该载体材料上。各个层可以就其化学构成而言不同。
该催化活性组合物优选基于该催化活性组合物的总量包含1-40重量%以V2O5计算的钒化合物和60-99重量%以TiO2计算的二氧化钛。在优选实施方案中,该催化活性组合物可以额外包含至多1重量%以Cs计算的铯化合物,至多1重量%以P计算的磷化合物和至多10重量%以Sb2O3计算的锑化合物。所有涉及该催化活性组合物的化学构成的数字基于该组合物的煅烧状态,例如在将该催化剂在450℃下煅烧1小时之后。
二氧化钛通常以锐钛矿形式用于该催化活性组合物。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。所用二氧化钛可以由一种二氧化钛或二氧化钛的混合物构成。在后一情况下,BET表面积的值为各二氧化钛的贡献值的加权平均。所用二氧化钛有利地包含例如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。
特别合适的钒源是五氧化二钒、偏钒酸铵和锑酸钒。合适的锑源是各种三氧化锑和锑酸钒。将结晶锑酸钒中结晶锑华的含量限制到最大为5重量%的可能方式是多种多样的且为本领域熟练技术人员所已知。一种可能性是例如使用低锑华或无锑华的氧化锑作为锑源。诸如Selectipur 7835(来自Merck)、Triox White(来自Antraco)、ACC-BS(来自Antraco)或Zero锑华(来自Campine)的产品可市购。此外,结晶锑华的含量可以借助钒和锑化合物,优选相应氧化物的反应过程中的反应条件控制。在这里起作用的是诸如所用原料的粒度、反应时间、反应温度和热后处理以及V/Sb摩尔比的参数。
作为磷源,尤其可以使用磷酸、亚磷酸、次磷酸、磷酸铵或磷酸酯以及尤其是磷酸二氢铵。作为铯源可以使用氧化物或氢氧化物或可以热转化成氧化物的盐,例如羧酸盐,尤其是乙酸盐、丙二酸盐或草酸盐,碳酸盐,碳酸氢盐,硫酸盐或硝酸盐。
除了任选加入铯和磷外,可以在该催化活性组合物中以少量包含许多用作促进剂以例如通过降低或提高其活性而影响该催化剂的活性和选择性的其他氧化化合物。作为该类促进剂,例如可以提及通常以其氧化物或氢氧化物形式使用的碱金属,尤其除上述铯以外的锂、钾和铷,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。
在所述促进剂中,进一步优选铌和钨的氧化物作为添加剂,其量基于该催化活性组合物为0.01-0.50重量%。
该涂敷催化剂的层的施加有利地通过将TiO2和V2O5的悬浮液喷雾于流化载体上而进行,该悬浮液任选含有上述促进剂元素源。在涂敷操作之前,优选将该悬浮液搅拌足够长时间,例如2-30小时,尤其是12-25小时,以粉碎悬浮固体的附聚物并得到均相悬浮液。该悬浮液通常具有20-50重量%的固体含量。该悬浮介质通常为含水的,例如水本身或与水溶混性有机溶剂如甲醇、乙醇、异丙醇、甲酰胺等的含水混合物。
通常向该悬浮液中加入有机粘合剂,优选丙烯酸-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-乙烯的共聚物,有利地呈水分散体形式。粘合剂可以作为固体含量为例如35-65重量%的水分散体市购。所用该类粘合剂分散体的量基于该悬浮液的重量通常为2-45重量%,优选5-35重量%,特别优选7-20重量%。
例如在流化床设备中将该载体在上升的气体气流,尤其是空气流中流化。设备通常包括锥形或球形容器,流化气体经由浸入管从下面或从上面引入该容器中。该悬浮液经由喷嘴从上面、从侧面或从下面喷入该流化床中。使用绕该浸入管正中或同心设置的提升管是有利的。更高气速在该提升管中占优并将载体颗粒向上输送。在外环中,气速仅稍高于松散速度。由此将颗粒以圆周运动垂直输送。合适的流化床设备例如描述于DE-A4006935中。
在该催化活性组合物对催化剂载体的涂敷中通常使用20-500℃的涂敷温度,并且涂敷可以在大气压力或减压下进行。涂敷通常在0-200℃,优选20-150℃,尤其是60-120℃下进行。
该催化活性组合物的层厚通常为0.02-0.2mm,优选0.05-0.15mm。该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%。
由于在>200-500℃的温度下对以此方式得到的预催化剂进行热处理,该粘合剂通过热分解和/或燃烧与所施加的层分离。该热处理优选在该气相氧化反应器中就地进行。
本发明进一步提供了一种生产用于制备羧酸和/或羧酸酐的催化剂的方法,该催化剂具有多个串联排列的催化剂区,其中将最大结晶锑华含量为5重量%的锑酸钒加入至少一个区中。
本发明进一步提供了一种气相氧化方法,其中使包含至少一种烃和分子氧的气流通过具有多个串联排列的催化剂区且在其生产中将最大结晶锑华含量为5重量%的锑酸钒加入至少一个区中的催化剂。
本发明方法有利地适合将C6-C10芳烃如苯、二甲苯类、甲苯、萘或杜烯(1,2,4,5-四甲基苯)气相氧化成羧酸和/或羧酸酐如马来酸酐、邻苯二甲酸酐、苯甲酸和/或均苯四甲酸二酐。该方法特别适合由邻二甲苯和/或萘制备邻苯二甲酸酐。制备邻苯二甲酸酐的气相氧化反应通常是已知的且例如描述于WO 2004/103561第6页。
本发明的优选实施方案是一种将邻二甲苯和/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具有多个串联排列的催化剂区且在其生产中将最大结晶锑华含量为5重量%的锑酸钒加入至少一个区中的催化剂。
本发明进一步提供了具有多个串联排列的催化剂区且在其生产中将最大结晶锑华含量为5重量%的锑酸钒加入至少一个区中的催化剂在制备羧酸和/或羧酸酐中的用途。
实施例
三氧化锑和锑酸钒中锑华含量和方锑矿含量的X射线结晶学测定
该测定借助X射线粉末衍射法进行。为此在“D8Bruker AXSTheta/Theta”X射线粉末衍射仪中测量粉状样品。测量参数如下:
Sol-X检测器
步进宽度 0.02°2θ
步进模式 连续
测量时间 3.6s/步进
结晶材料(锑华、方锑矿和锑酸钒相)的定量测定借助Rietveld精修(Topas,Bruker AXS)进行。
催化剂合成:
催化剂区CZ1:
(锑华含量约3%的锑酸钒作为V和Sb源,本发明):
制备锑酸钒:
将1223.6g五氧化二钒和783.2g三氧化锑(Merck Selectipur 7835,16%锑华和84%方锑矿;Sb2O3≥99.8重量%;As 200重量ppm,Pb 200重量ppm,Fe≤100重量ppm Fe,平均粒度=2μm)悬浮于3.0l软化水中并将该悬浮液在回流下搅拌16小时。然后将该悬浮液在25℃下搅拌24小时,然后在在真空干燥箱中于100℃下干燥10小时。随后在研钵中研磨得到BET表面积为64m2/g且钒含量为32重量%和锑含量为30重量%的粉末。该产物具有下列结晶成分:锑华(PDF 11-0689):约3%;锑酸钒(PDF:01-81-1219):约97%。锑酸钒的平均晶粒尺寸为约12nm。
悬浮批料和涂敷:
在流化床设备中将2kg尺寸为7mm×7mm×4mm的滑石环(硅酸镁)用768g由4.44g碳酸铯、413.7g二氧化钛(Fuji TA 100CT;锐钛矿,BET表面积27m2/g)、222.1g二氧化钛(Fuji TA 100;锐钛矿,BET表面积7m2/g)、91.6g如上所述制备的锑酸钒、1869g软化水和78.4g有机粘合剂(乙酸乙烯酯和月桂酸乙烯酯的共聚物,呈浓度为50重量%的水分散体形式)构成的悬浮液涂敷。
在将该催化剂在450℃下煅烧1小时后,施加于滑石环上的活性组合物量为8.4重量%。该活性组合物的分析得到如下含量:7.1%V2O5,4.5%Sb2O3,0.50%Cs,余量TiO2。
催化剂区CZ2:
(锑华含量约7%的锑酸钒作为V和Sb源;非本发明):
制备锑酸钒:
将2855.1g五氧化二钒和1827.5g三氧化锑(Merck Selectipur 7835,16%锑华和84%方锑矿;Sb2O3≥99.8重量%;As 200重量ppm,Pb 200重量ppm,Fe≤100重量ppm Fe,平均粒度=2μm)悬浮于7.0l软化水中并将该悬浮液在回流下搅拌16小时。然后将该悬浮液冷却至90℃并借助喷雾干燥干燥。入口温度为340℃,出口温度为110℃。以此方式得到的喷雾干燥粉末具有的BET表面积为65m2/g且钒含量为32重量%和锑含量为30重量%。该产物具有下列结晶成分:锑华(PDF 11-0689):约7%;方锑矿(PDF:43-1071):约1%;锑酸钒(PDF:01-81-1219):约92%。锑酸钒的平均晶粒尺寸为约9nm。
悬浮批料和涂敷:
类似于CZ1生产,其中将CZ2中所述锑酸钒用于生产。
在将该催化剂在450℃下煅烧1小时后,施加于滑石环上的活性组合物量为8.3重量%。该活性组合物的分析得到如下含量:7.1%V2O5,4.5%Sb2O3,0.50%Cs,余量TiO2。
与CZ1和CZ2相反,在CZ3、CZ4、CZ5和CZ6中使用五氧化二钒和三氧化锑代替锑酸钒作为V和Sb源。代替Fuji TA 100CT类型的TiO2,在CZ3、CZ4和CZ5中使用Fuji TA 100C类型的TiO2(BET表面积:20m2/g)。
催化剂区CZ3:
(五氧化二钒和三氧化锑作为V和Sb源)
类似于CZ1生产,但改变该悬浮液的化学构成。在将该催化剂在450℃下煅烧1小时后,施加于滑石环上的活性组合物量为9.1重量%。该活性组合物的分析得到如下含量:7.1%V2O5,1.8%Sb2O3,0.38%Cs,余量TiO2。
催化剂区CZ4:
(五氧化二钒和三氧化锑作为V和Sb源)
类似于CZ1生产,但改变该悬浮液的化学构成。在将该催化剂在450℃下煅烧1小时后,施加于滑石环上的活性组合物量为8.5重量%。该活性组合物的分析得到如下含量:7.95%V2O5,2.7%Sb2O3,0.31%Cs,余量TiO2。
催化剂区CZ5:
类似于CZ1生产,但改变该悬浮液的化学构成。在将该催化剂在450℃下煅烧1小时后,施加于滑石环上的活性组合物量为8.5重量%。该活性组合物的分析得到如下含量:7.1%V2O5,2.4%Sb2O3,0.10%Cs,余量TiO2。
催化剂区CZ6:
类似于CZ1生产,但改变该悬浮液的化学构成。在将该催化剂在450℃下煅烧1小时后,施加于滑石环上的活性组合物量为9.1重量%。该活性组合物的分析得到如下含量:20%V2O5,0.38%P,余量TiO2。
在模型管规模上将邻二甲苯催化氧化成邻苯二甲酸酐
实施例1(本发明):
邻二甲苯催化氧化成邻苯二甲酸酐在管内径为25mm的盐浴冷却反应器中进行。由反应器入口到反应器出口将80cm CZ1,60cm CZ3,70cmCZ4,50cm CZ5和60cm CZ6引入内径为25mm的3.5m长铁管中。该铁管由盐浴包围以调节温度,并且外径为4mm的温度传感器护套和内置可拆卸元件用于测量催化剂温度。
使4.0标准m3/h负载有80g/标准m3浓度为99.2重量%邻二甲苯的空气由反应器入口到反应器出口通过该管。这得到总结于表1中的结果(“PAn产率”为以重量百分数得到的邻苯二甲酸酐,基于100%纯净邻二甲苯)。实施例2(在模型管规模上将邻二甲苯氧化成邻苯二甲酸酐,非本发明):
见实施例1,但使用从反应器入口至反应器出口由80cm CZ2,60cmCZ3,70cm CZ4,50cm CZ5和60cm CZ6构成的催化剂床。
表1
模型管结果 | 实施例1(本发明) | 实施例2(非本发明) |
空气量[标准m3/h] | 4.0 | 4.0 |
负荷[g/标准m3] | 80 | 80 |
操作时间[天] | 29 | 35 |
盐浴温度[℃] | 349 | 351 |
PAn产率[重量%] | 114.7 | 113.9 |
邻二甲苯含量[重量%] | 0.05 | 0.05 |
2-苯并[c]呋喃酮含量[重量%] | 0.09 | 0.12 |
热点温度[℃] | 421 | 420 |
在这两种情况下热点温度均低于425℃。
实施例1中PAn产率显著高于实施例2。实施例1中2-苯并[c]呋喃酮含量低于实施例2。
Claims (5)
1.一种制备羧酸和/或羧酸酐的催化剂,所述催化剂具有多个串联排列的催化剂区且在其生产中将最大结晶锑华含量为5重量%的锑酸钒加入至少一个区中。
2.一种生产用于制备羧酸和/或羧酸酐的催化剂的方法,所述催化剂具有多个串联排列的催化剂区,其中将最大结晶锑华含量为5重量%的锑酸钒加入至少一个区中。
3.一种气相氧化方法,其中使包含至少一种烃和分子氧的气流通过具有多个串联排列的催化剂区且在其生产中将最大结晶锑华含量为5重量%的锑酸钒加入至少一个区中的催化剂。
4.一种将邻二甲苯和/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具有多个串联排列的催化剂区且在其生产中将最大结晶锑华含量为5重量%的锑酸钒加入至少一个区中的催化剂。
5.根据权利要求1的催化剂在制备羧酸和/或羧酸酐中的用途。
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CN1054726A (zh) * | 1990-03-16 | 1991-09-25 | 日本触媒化学工业株式会社 | 用于制造邻苯二甲酸酐的催化剂 |
CN1302294A (zh) * | 1998-05-26 | 2001-07-04 | 巴斯福股份公司 | 邻二甲苯/萘混合物的气相催化氧化制备邻苯二甲酸酐的方法 |
US20110124885A1 (en) * | 2009-11-20 | 2011-05-26 | Basf Se | Multilayer catalyst having vanadium antimonate in at least one catalyst layer for preparing carboxylic acids and/or carboxylic anhydrides and process for preparing phthalic anhydride having a low hot spot temperature |
US20120029214A1 (en) * | 2010-07-30 | 2012-02-02 | Basf Se | Catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride |
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JPS57180430A (en) * | 1981-04-30 | 1982-11-06 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for production of phthalic acid anhydride |
EP2598238A4 (en) * | 2010-07-30 | 2014-08-20 | Basf Se | CATALYZER FOR OXIDIZING O-XYLENE AND / OR NAPHTHALINE TO PHTHALIC ACID ANHYDRIDE |
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- 2013-07-12 CN CN201380037094.3A patent/CN104487164A/zh active Pending
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CN1054726A (zh) * | 1990-03-16 | 1991-09-25 | 日本触媒化学工业株式会社 | 用于制造邻苯二甲酸酐的催化剂 |
CN1302294A (zh) * | 1998-05-26 | 2001-07-04 | 巴斯福股份公司 | 邻二甲苯/萘混合物的气相催化氧化制备邻苯二甲酸酐的方法 |
US20110124885A1 (en) * | 2009-11-20 | 2011-05-26 | Basf Se | Multilayer catalyst having vanadium antimonate in at least one catalyst layer for preparing carboxylic acids and/or carboxylic anhydrides and process for preparing phthalic anhydride having a low hot spot temperature |
US20120029214A1 (en) * | 2010-07-30 | 2012-02-02 | Basf Se | Catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride |
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WO2014013397A2 (de) | 2014-01-23 |
EP2872251A2 (de) | 2015-05-20 |
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