CN102196859A - Catalyst for the catalytic gas phase oxidation of aromatic hydrocarbons to form aldehydes, carboxylic acids and/or carboxylic acid anhydrides, in particular phthalic acid anhydride, and method for producing said type of catalyst - Google Patents
Catalyst for the catalytic gas phase oxidation of aromatic hydrocarbons to form aldehydes, carboxylic acids and/or carboxylic acid anhydrides, in particular phthalic acid anhydride, and method for producing said type of catalyst Download PDFInfo
- Publication number
- CN102196859A CN102196859A CN2009801427961A CN200980142796A CN102196859A CN 102196859 A CN102196859 A CN 102196859A CN 2009801427961 A CN2009801427961 A CN 2009801427961A CN 200980142796 A CN200980142796 A CN 200980142796A CN 102196859 A CN102196859 A CN 102196859A
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- Prior art keywords
- catalyst
- oxide
- vanadium
- weight
- silver
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- 239000003054 catalyst Substances 0.000 title claims abstract description 446
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 31
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 28
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 25
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 title claims description 12
- 150000001735 carboxylic acids Chemical class 0.000 title abstract 2
- 235000019256 formaldehyde Nutrition 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 151
- 229910052709 silver Inorganic materials 0.000 claims abstract description 86
- 239000004332 silver Substances 0.000 claims abstract description 86
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 86
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 150000001875 compounds Chemical class 0.000 claims abstract description 81
- 239000000725 suspension Substances 0.000 claims abstract description 80
- 239000000203 mixture Substances 0.000 claims abstract description 70
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 65
- 239000002243 precursor Substances 0.000 claims abstract description 58
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000002994 raw material Substances 0.000 claims abstract description 42
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 34
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 33
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 32
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011733 molybdenum Substances 0.000 claims abstract description 30
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010937 tungsten Substances 0.000 claims abstract description 30
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 26
- 239000010955 niobium Substances 0.000 claims abstract description 26
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 24
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 carboxylic acid hydrides Chemical class 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 23
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 23
- 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 claims abstract description 22
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011149 active material Substances 0.000 claims description 76
- 239000007789 gas Substances 0.000 claims description 53
- 238000002360 preparation method Methods 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims description 27
- 239000011574 phosphorus Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 239000013543 active substance Substances 0.000 claims description 18
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052792 caesium Inorganic materials 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 239000011135 tin Substances 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000012876 carrier material Substances 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 229910052701 rubidium Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000012797 qualification Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 229910052702 rhenium Inorganic materials 0.000 claims description 8
- 229910052716 thallium Inorganic materials 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- 230000000630 rising effect Effects 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011133 lead Substances 0.000 claims description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 239000000454 talc Substances 0.000 claims description 6
- 235000012222 talc Nutrition 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 6
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910000765 intermetallic Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229940100890 silver compound Drugs 0.000 claims description 3
- 150000003379 silver compounds Chemical class 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- MHLYOTJKDAAHGI-UHFFFAOYSA-N silver molybdate Chemical compound [Ag+].[Ag+].[O-][Mo]([O-])(=O)=O MHLYOTJKDAAHGI-UHFFFAOYSA-N 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims 4
- 239000011734 sodium Substances 0.000 claims 3
- 229910052748 manganese Inorganic materials 0.000 claims 2
- 239000011572 manganese Substances 0.000 claims 2
- 229910052715 tantalum Inorganic materials 0.000 claims 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910000416 bismuth oxide Inorganic materials 0.000 claims 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims 1
- 229920000620 organic polymer Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 62
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- 238000000576 coating method Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract 1
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- 230000000694 effects Effects 0.000 description 43
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000000126 substance Substances 0.000 description 13
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 10
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- 238000012360 testing method Methods 0.000 description 9
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- 229910001882 dioxygen Inorganic materials 0.000 description 8
- 150000001339 alkali metal compounds Chemical class 0.000 description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 6
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 description 6
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
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- 229910002651 NO3 Inorganic materials 0.000 description 3
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- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 3
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- 238000012805 post-processing Methods 0.000 description 3
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 2
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- 229910002915 BiVO4 Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229930194542 Keto Natural products 0.000 description 2
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003658 tungsten compounds Chemical class 0.000 description 2
- 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
- JJKXSKYMMKUVNH-UHFFFAOYSA-N C1(=O)OCC2=CC=CC=C12.O1C(CC=C1)=O Chemical compound C1(=O)OCC2=CC=CC=C12.O1C(CC=C1)=O JJKXSKYMMKUVNH-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- ZDINGUUTWDGGFF-UHFFFAOYSA-N antimony(5+) Chemical class [Sb+5] ZDINGUUTWDGGFF-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- FVKGRHSPCZORQC-UHFFFAOYSA-N formaldehyde;toluene Chemical compound O=C.CC1=CC=CC=C1 FVKGRHSPCZORQC-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 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
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- UKHWJBVVWVYFEY-UHFFFAOYSA-M silver;hydroxide Chemical compound [OH-].[Ag+] UKHWJBVVWVYFEY-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011282 treatment 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
Classifications
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- 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
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
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- 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
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- 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
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
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- B01J37/0215—Coating
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- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/08—Formation or introduction of functional groups containing oxygen of carboxyl groups or salts, halides or anhydrides thereof
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- 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
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract
The present invention relates to a catalyst for catalytic gas phase oxidation of aromatic hydrocarbons to form aldehydes, carboxylic acids and/or carboxylic acid hydrides, in particular phthalic acid anhydride. The active mass comprises vanadium oxide, preferably vanadium pentoxide, titanium dioxide, preferably in the anatas-modification, and at least one silver mixing element oxide with defined elements, preferably vanadium and/or molybdenum and/or tungsten and/or niobium and/or antimony, and/or a vanadium mixing element oxide with defined elements, preferably bismuth and/or molybdenum and/or tungsten and/or antimony and/or niobium. When producing the catalyst, in particular during the production of a catalyst suspension or a powder mixture necessary for coating a carrier, at least one silver and/or vanadium mixing element oxide and/or at least one precursor compound, in particular at least one multi-core precursor compound, of at least one silver and/or vanadium mixing element oxide is used as a raw material source.
Description
In fixed bed reactors, preferably for example benzene, dimethylbenzene, naphthalene, toluene or durene (Durol) of catalytic vapor phase oxidation aromatic hydrocarbon in bundled tube reactor is known for a long time, and repeatedly record in the literature.Prepared for example benzoic acid in this way, maleic anhydride, phthalic anhydride, M-phthalic acid, terephthalic acid (TPA) and 1,2,4,5-pyromellitic anhydride.
For this reason, usually will be and remain mixture guiding that the hydrocarbon (for example ortho-xylene or naphthalene) of oxidation forms by being arranged on a plurality of pipes in the reactor by the gas that contains molecular oxygen (for example air), in described pipe, there is the windrow of at least a catalyst.
In order to regulate temperature or to derive for the heat that will produce in exothermic reaction, the pipe of filling with catalyst is for example washed away around the molten salt bath by heat-carrying agent.
The adjustment of even now, in the catalyst windrow, still may cause forming local temperature peak value (" focus "), this may cause unacceptable effect, and the complete oxidation of raw material or the formation accessory substance that is difficult to separate for example is until causing limited raw material throughput.
For fear of this class focus, to transfer in practice so to carry out, the catalyst that will have different activities and chemical composition is stratiform and is arranged on position adjacent one another are in the described reaction tube.Wherein, according to prior art, have extremely low activity usually at the highest temperature peak zone catalyst, and the subsequent catalyst layer on the gas vent direction has the activity of raising.
At this, mention so-called shell catalyst (Schalenkatalysator), it is made up of the non-porous carrier material of inertia usually, is at least one thin layer that shelly is applied with catalytic active substance on this inert support material.
For the catalytic performance of associated catalysts, the composition of catalytic active substance has material impact.
For setting out by in gas phase, preparing phthalic anhydride by ortho-xylene and/or naphthalene on the fixed bde catalyst, many kinds of catalyst have been proposed in the past with the gas cyaniding that contains molecular oxygen.
According to prior art, the phthalic anhydride-catalyst of all industrial uses contains titanium dioxide, vanadic anhydride and other component of compound anatase variant form or is a spot of promoter that is used to improve the long-time stability of activity, conversion ratio, productive rate, selectivity and associated catalysts mostly in the practice in its catalytic active substance.
These additives for example are caesium, antimony, phosphorus, boron, molybdenum, tungsten, tin, bismuth, silver, niobium, iron, potassium, rubidium, chromium and caesium.
Therefore, strive adding effectiveness and the stability that different material further improves the PSA-catalyst by measuring targetedly.This means, As time goes on,, develop the catalyst formulation that becomes increasingly complex and the combination of different catalysts in order to address this problem.
Also use people's said " multilayer " catalyst more and more, this catalyst is different aspect active and selectivity because its different active material is formed.At this, in the catalyst windrow, multiple different catalyst is arranged in a plurality of layers (Lage), to notice tasks different in catalyst bed according to the difference of layer adjacent to each other.Wherein, relate generally to following requirements, also promptly under the situation of high raw material throughput, control exothermic reaction reliably, have high catalyst selectivity and stability simultaneously.
EP A 21 325 has put down in writing the catalyst that is used to prepare phthalic anhydride, and its active material is by the titanium dioxide of 60-99 weight %, 1-40 weight % vanadic anhydride and based on TiO
2And V
2O
5Total amount 2 weight % phosphorus and 1.5 weight % rubidium and/or caesiums at the most at the most, wherein catalytic active substance is applied on the carrier with bilayer.Wherein, the phosphorus that internal layer contains 0-2.0 weight % does not contain rubidium and/or caesium, and skin contains 0-0.20 weight % phosphorus and 0.02-1.5 weight % rubidium and/or caesium.The catalytic active substance of this catalyst can also contain other material except mentioned component, the metal molybdenum of 10 weight % at the most for example, tungsten, niobium, tin, silicon, antimony, the oxide of hafnium.Use talcum as inert support material.
EP A 286448 has put down in writing the method that is used to prepare phthalic anhydride, wherein uses to have two kinds of different catalysts of similar titanium dioxide and pentoxide content.Their difference mainly is, a kind of catalyst contains the cesium compound of 2-5 weight % in addition, cesium sulfate particularly, but not phosphorous, tin, antimony, bismuth, tungsten-or molybdenum compound, and second kind of catalyst contains phosphorus, tin, antimony, bismuth, tungsten or the molybdenum compound of 0.1-3.0 weight % in addition.
US 4,864, and 036 relates to the catalyst that is used to prepare phthalic anhydride, and it prepares with a plurality of steps.Wherein in first step with the metallic compound of the 6th subgroup, preferred molybdenum-or tungsten compound be applied on the titanium dioxide of anatase variant form and calcine then.Then, in second step, add vfanadium compound to precursor (Vorstufe), and calcine this precursor once more through calcining.
GB 1140264 relates to the oxidation catalyst that is used for being obtained by aromatics and non-aromatic hydrocarbon carboxylic acid, and it is made up of the non-porous carrier of inertia and the active material layer of 0.02-2 mm thickness, described active material layer and then by 1-15% V
2O
5Form with 85-99% titanium dioxide, wherein the content of vanadium of total body catalyst is 0.05-3%.Put down in writing such catalyst, wherein this active material also contains at least a metal oxide that 0.1-3 weight % derives from silver, iron, cobalt, nickel, chromium, molybdenum or tungsten except titanium dioxide and vanadic anhydride.
EP 0,447 267 has put down in writing the catalyst that is used to prepare phthalic anhydride, and this catalyst comprises the following material as catalytic active substance: 1-20 weight %V
2O
5With anatase variant form and the BET surface area of 99-80 weight % be 10-60m
2The titanium dioxide of/g and (B), based on this mixture (A) of 100 weight portions, at least a K that is selected from of 0.05-1.2 weight portion as oxide, Cs, the silver of the element of Rb and Tl and 0.05-2 weight portion calculates with silver oxide.
EP 0,522 871 B1 relates to a kind of catalyst, this catalyst is except titanium dioxide and vanadic anhydride, the niobium that also contains 0.01-1 weight % as niobium pentaoxide, 0.05-2 at least a potassium that is selected from of weight % as oxide, caesium, the element of rubidium or thallium, the phosphorus of 0.2-1.2 weight % as P2O5, with the antimony oxide of 0.55-5.5 weight % and the silver of 0.05-2 weight %, wherein use pentavalent antimony compounds as the antimony source as Ag2O.
CN1108996 relates to a kind of catalyst that has based on two layers of titanium dioxide/V2O5, it contains at least a rare earth compound and at least a element antimony in addition, phosphorus, the oxide of zinc and silver wherein contains at least a alkali metal compound in addition near the position of gas access.
Silver-vanadium oxide-the compound of atomic ratio Ag:V＜1 is known as silver bronze (Silberbronzen).Silver-vanadium bronze is known in the document as the purposes of oxidation catalyst.
DE 198 51 786 A1 have put down in writing general formula Ag
A-bM
bV
2O
x* c H
2The poly-metal deoxide of O, wherein a is the value of 0.3-1.9, M is the metal that is selected from Li, Na, K, Rb, Cs Tl, Mg, Ca, Sr, Ba, Cu, Zn, Cd, Pb, Cr, Au, Al, Fe, Co, Ni and/or Mo, and b is the value of 0-0.5, and wherein a-b is equal to or greater than 0.1.Put down in writing related poly-metal deoxide and be used to prepare the pre-catalyst that the gaseous oxidation of aromatic hydrocarbon uses and the purposes of catalyst as precursor compound.
At last, in WO 2005/092496 A1, put down in writing a kind of catalyst that is used to prepare aldehyde, carboxylic acid and/or carboxylic acid anhydrides, its active material contains phase A and B mutually with the form of three-dimensional extension confined area, and wherein phase A contains silver-vanadium oxide-bronze and B mutually and contains based on the complex element oxide of titanium dioxide and vanadic anhydride mutually.The mol ratio of Ag:V is 0.15-0.95 in phase A.
Prior art mentioned above is known has the catalyst that different active materials forms or can not reach gratifying selectivity, yield or activity, or has low service life, or its industrial production is accompanied by huge expending or expense.
Therefore, continue to exist selectivity and the yield with further improvement had the demand of high raw material throughput and the catalyst of long life simultaneously, this catalyst can recently be produced with acceptable expense-effectiveness industrial.
Therefore, the objective of the invention is to, develop be used for from the aromatic hydrocarbon to aldehyde, carboxylic acid and/or carboxylic acid anhydrides, particularly arrive the improvement catalyst of phthalic anhydride, this catalyst obtains improved selectivity and with service life of duration under the situation of high raw material throughput.In addition, the technology of big this catalyst of industrial production and economic drain keep low as far as possible.
This task realizes by the feature of claim 1.Embodiment preferred is the theme of dependent claims, and their disclosure is clearly introduced in this specification.
According to claim 1, claimed being used for becomes aldehyde with the aromatic hydrocarbon catalytic vapor phase oxidation, carboxylic acid and/or carboxylic acid anhydrides, the catalyst of phthalic anhydride particularly, wherein said active material contains vanadium oxide, preferred vanadic anhydride, titanium dioxide, the titanium dioxide of preferred anatase variant form and at least a silver and the complex element oxide that limits element, preferred vanadium of described qualification element and/or molybdenum and/or tungsten and/or niobium and/or antimony; And/or the complex element oxide of vanadium and qualification element, preferred bismuth of described qualification element and/or molybdenum and/or tungsten and/or antimony and/or niobium.In this Preparation of catalysts, particularly in catalyst suspension or the preparation for the required mixture of powders of coated carrier, use at least a complex element oxide of silver and/or vanadium, and/or at least a precursor compound of the complex element oxide of at least a silver and/or vanadium, particularly at least a multinuclear precursor compound is as raw material source.
Unexpectedly find, use the complex element oxide, the preferred mixed-metal oxides that uses, silver and for example vanadium, molybdenum, tungsten, niobium and/or antimony, and/or use the complex element oxide, the preferred mixed-metal oxides that uses, vanadium and for example bismuth, molybdenum, tungsten, niobium and/or antimony, perhaps the conduct of their precursor compound is preparing catalyst suspension or the raw material source when preparation is used for the mixture of powders of coating procedure, and/or as the composition except component titanium dioxide and vanadium oxide as the catalyst activity material, causes optionally to significantly improve.
Its reason also is not very clear, but what expect easily is, silver is highly effective in fact with the interaction of other catalytic active component (for example titanium dioxide/vanadium oxide individual layer), therefore considers the promoter effect (suppress Organic Ingredients and all be oxidized to carbon monoxide (Kohlenoxiden)) of silver own better.
In the art, silver is repeatedly put down in writing as the purposes of the composition of active material.At this, except silver oxide, also use corresponding salt as the silver material source that is used to prepare catalyst suspension, for example silver nitrate, silver sulfate, silver halide, silver sulfide, silver orthophosphate, organic acid silver salt, silver hydroxide, silver-colored ammonium salt and silver-colored amine complex.Monokaryon changed silver oxide into when these raw material source of great majority heated this catalyst in this reactor, and in this active material, exist thus as silver oxide, and for example silver orthophosphate and silver halide do not exist in active material with changing and do not change silver oxide into when heat treatments.
The main aspect of catalyst of the present invention is, typical catalyst contains titanium dioxide and vanadium oxide at least in active material, contain the silver of dopant of conduct and vanadium and/or other limits the complex element oxide of element, with or vanadium and other limit the complex element oxide of element, wherein add silver and/or at least a complex element oxide of vanadium and/or the corresponding precursor compound of at least a these complex element compounds at the preparation catalyst suspension or when preparation applies the used mixture of powders of this carrier.
The present invention refers explicitly to be used to prepare the method for described catalyst of the present invention just now in addition, the mixture that has wherein prepared catalyst suspension or different component, they contain the titanium dioxide of anatase variant form and at least a complex element oxide of vfanadium compound and silver and/or vanadium and qualification element at least, and the corresponding precursor compound of perhaps at least a these complex element oxides is as raw material source.
All components advantageously is incorporated in the water-bearing media each other, and is applied on the ceramic monolith by spray-on process (preferred fluid bed or drum process) subsequently.At this, the complex element oxide of silver and/or vanadium mutually or its complex element oxide precursor compounds advantageously directly add catalyst suspension to together with main component titanium dioxide and vanadium oxide and other promoter, and usually not as and the phase of forming by titanium dioxide and vanadium oxide of separating in the space.Thus, all the components of catalyst suspension forms consistent phase, and it also contains relevant complex element oxide and other optional component except component titanium dioxide and vanadium oxide.
But, it is also conceivable that such system, the layer that differs from one another that wherein will have different chemical compositions is applied on the inert carrier, and wherein at least one layer contains at least a complex element oxide of silver and/or vanadium and qualification element.Wherein, each coating of catalyst of the present invention also can be made up of the combination of of the present invention and non-composition of the present invention.
Relevant complex element oxide can individually or to be used in one or more coatings with other combination of compounds, described coating contain titanium dioxide and/or vanadium oxide in active material yet.
According to the present invention, can realize thus being used for containing molecule (molaren) oxygen gas gas-phase partial oxidation aromatic hydrocarbon catalyst or be used to produce and prepare the precursor of this catalyst, described catalyst is made of inertia, non-porous carrier material and one or more shelly layers that applies thereon, wherein at least one such layer contains one or more above-mentioned complex element oxide or its precursor compounds of 0.01-15 weight %, based on the gross weight of this layer.
In addition; claimed be used to prepare carboxylic acid and or the concrete grammar scheme of carboxylic acid anhydrides; it carries out in catalyst top oxidation aromatic hydrocarbon in the temperature that raises by the gas with molecule-containing keto in gas phase; this activity of such catalysts material is shelly and is applied on the inert carrier; it is characterized in that; shell catalyst; its catalytic active substance; based on its gross weight meter; the silver and the complex element oxide of vanadium and/or the complex element oxide of silver and other qualification element that contain 0.01-15 weight %; and/or the complex element oxide of the complex element oxide of the vanadium of 0.01-10 weight % and bismuth and/or vanadium and other qualification element; the titanium dioxide and the vfanadium compound (preferred V2O5) that contain the anatase variant form simultaneously; wherein complex element oxide-compound or its precursor compound have been used to prepare catalyst suspension and/or mixture of powders, form described active material by described mixture of powders by heat treatment after applying described carrier.
Wherein, (it contains the vanadium oxide as neccessary composition at least a non-shell catalyst of the present invention in its active material, vanadic anhydride particularly, and titanium dioxide, particularly with the titanium dioxide of anatase variant form, but do not contain hereinafter described complex element oxide or its precursor compound) when being oxidized to carboxylic acid and/or carboxylic acid anhydrides, aromatic hydrocarbon can exist or not exist, and use at the catalyst of combination windrow (this means in the single or multiple lift mixture) together with one or more the invention described above.
Preferably, with the bed of gaseous stream guiding through at least two catalyst layers, wherein the catalyst that is provided with near the gas access contains catalyst of the present invention, the bed of the catalyst that the flow direction downstream is provided with contains at least a catalyst, and its catalytic active substance contains the titanium dioxide of vanadium oxide and anatase variant form, but argentiferous and element vanadium for example not, molybdenum, tungsten, niobium, the complex element oxide of antimony and/or do not contain vanadium and element bismuth for example, molybdenum, tungsten, niobium, the complex element oxide of antimony.
Can also use the catalyst windrow of being made up of at least two layers, wherein all catalyst layers contain catalyst of the present invention.Wherein, used catalyst of the present invention can be distinguished type and the quantity that is the relevant complex element oxide in the active material.
Preferably, at least a portion, the catalyst layer (comprising catalyst of the present invention) that preferably all uses in catalyst bed should contain catalytic active substance, and it contains 1-40 weight % vanadium oxide (as V
2O
5Calculate), 50-99 weight % titanium dioxide is (as TiO
2Calculate), the alkali metal compound of 1 weight % (preferred cesium compound calculates as alkali metal) at the most, at the most the phosphorus compound of 1.5 weight % (calculating) as P and at the most the antimonial of 10 weight % (as Sb
2O
3Calculate).
According to a particularly advantageous embodiment, catalyst of the present invention preferably comprises silver and at least a at least a complex element oxide that is selected from following element of 0.01-15 weight %: vanadium, niobium, thallium, titanium, zirconium, chromium, molybdenum, tungsten, cerium, lanthanum, aluminium, boron, manganese, iron, cobalt, nickel, copper, zinc, gold, cadmium, tin, plumbous, bismuth, antimony, arsenic, hafnium, rhenium, ruthenium, rhodium and palladium, and/or preferably comprise vanadium and at least a at least a complex element oxide that is selected from following element of 0.01-10 weight %: bismuth, antimony, niobium, thallium, titanium, zirconium, chromium, molybdenum, tungsten, cerium, lanthanum, aluminium, boron, manganese, iron, cobalt, nickel, copper, zinc, gold, cadmium, tin, plumbous, arsenic, hafnium, rhenium, ruthenium, rhodium and palladium.
In preferred embodiments, silver is 0.01-15 % weight % with the content of the complex element oxide that limits element (particularly with for example vanadium and/or tungsten and/or molybdenum and/or niobium and/or antimony) in the catalyst activity material, be 0.01-10 weight % and in a further preferred embodiment in particularly preferred embodiments for 0.01-5 weight %.In preferred embodiments, in the catalyst activity material, the complex element oxide of vanadium and qualification element is (except silver, referring to of the argumentation of above-mentioned just silver) with the complex element oxide of vanadium, particularly with the complex element oxide of for example tungsten and/or molybdenum and/or niobium and/or antimony, content be 0.01-10 % weight %, be 0.01-5 weight % in particularly preferred embodiments.
In preferred embodiments, use catalyst of the present invention in first catalyst layer that is provided with near the gas access, wherein this catalyst layer is the layer with hottest point simultaneously.Next be at least one other catalyst layer on the gas vent direction, this catalyst layer has the activity higher than first catalyst layer usually, and wherein this catalyst layer normally corresponding to the catalyst of prior art.At this, catalyst of the present invention contains at least a complex element oxide of silver, the complex element oxide of preferred vanadic acid silver and preferred vanadium, preferred pucherite.
Same advantageously verified; under the multi-layer catalyst system situation that comprises at least one layer before being arranged at the focus catalyst layer on the direction of gas access; contain catalyst of the present invention from the gas access at least one catalyst layer that comprises layer with hot spots; and use common catalyst for follow-up layer, and/or in active material, use catalyst of the present invention with the complex element oxide required for protection that reduces content corresponding to prior art.
In another particularly preferred embodiment, at least one catalyst layer (it is positioned at before the layer with hottest point) has the complex element oxide of silver, the complex element oxide of preferred silver and molybdenum and/or tungsten, the complex element oxide of preferred especially silver and vanadium, and the layer that has the layer of hottest point and be arranged on its downstream complex element oxide of argentiferous not.At this, the layer with hottest point advantageously contains the complex element oxide of vanadium and bismuth.On the gas vent direction, at the catalyst layer in focus catalyst layer downstream preferably corresponding to prior art and do not contain catalyst of the present invention usually.
In the particularly preferred embodiment of catalyst, when the preparation catalyst suspension, use and/or inclusion compound AgVO in the activity of such catalysts material
3And/or Ag
2MoO
4And/or Ag
2WO
4And/or BiVO
4
In the case importantly, the content of complex element oxide that plays " promoter " effect is selected as both only low high only.If the complex element oxide content of silver is low excessively, can not bear fully so and improve optionally effectiveness, and if the complex element oxide content of silver is too high, then observe the activity of rising, this since the complete oxidation that raises to CO and CO
2And cause the selectivity that reduces.
In addition, advantageously, particularly near the catalyst layer that is provided with in the gas access until comprising that the layer with hottest point uses catalyst of the present invention because otherwise no longer can reach the effectiveness that selectivity completely raises because allowed at least a portion raw material unreacted.
The too high amount of the complex element oxide of bismuth has negative effect and also may cause forming increasedly accessory substance simultaneously for selection of catalysts equally, and this causes the relatively poor colour stability of required product phthalic anhydride.Different therewith, the low content of crossing of the complex element oxide of bismuth does not cause optionally significantly improving.
By at least two, but favourable, the combination (wherein at least one deck contain of the present invention catalyst) of more a plurality of catalyst layers in windrow can realize than only using the overall significantly higher yield of the multi-layer catalyst system that contains under the non-catalyst situation of the present invention.
At this, according to prior art, in many cases, the catalyst activity of first catalyst layer that uses in the gas access progressively increases until the catalyst activity near the final layer of gas vent.Active adjusting can realize by various methods well known to those skilled in the art.For example, in described layer from the gas access until gas vent by progressively reducing the alkali metal content the active material, improve the average BET-surface area of used titanium dioxide or also have the activity substance content that improves in total catalyst weight, improve catalyst activity.Can also use the various combinations that are used for the active measure of regulating.
Catalyst of the present invention advantageously contains the titanium dioxide of at least one class anatase form in active material, at least a vfanadium compound (preferred V2O5), at least a complex element oxide of silver and/or vanadium and optional antimonial, alkali metal compound and/or phosphorus compound.
The titanium dioxide total content is 50-99 weight % and preferred especially 80-99 weight % in activity of such catalysts material of the present invention.
In the case, can also only use the titanium dioxide of the anatase variant form with specific physical property, perhaps multiple mixture with titanium dioxide of different physical characteristics prepares catalyst suspension and/or activity of such catalysts material.
At this, under the situation of one or more titanium dioxide types, the average BET-surface area of the titanium dioxide of catalyst of the present invention advantageously is 10-60 m
2/ g and particularly advantageously be 12-30 m
2/ g, and the BET-surface area of each kind is 3-300 m
2/ g.
At this, the average BET-surface area of used titanium dioxide is calculated by the quantity and the BET-surface area of each used type.The preferred titanium dioxide of at least a its particle mean size that uses as 0.3-0.8 μ m.
The content of vanadium oxide is (as V in active material
2O
5Calculate) be in the preferable range of 1-40 weight % and be 1-20 weight % in particularly preferred embodiment.
In order to prepare catalyst of the present invention, advantageously use vanadic anhydride and/or vanadium oxalate raw material source.Suitable in principle other vfanadium compound especially in addition is the mixture in ammonium metavanadate, many vanadic acid or various sources for example.
Usually, these precursor compounds of vanadium or raw material source change vanadic anhydride in the presence of molecular oxygen when the heating of the heat treatment of catalyst or catalyst in reactor, make that vanadium exists with pentavalent oxidation valency substantially in active material.
Depend on each catalyst of the present invention position in catalyst bed, described activity of such catalysts material is except titanium dioxide, outside the vanadium oxide, also contain one or more silver and/or vanadium and another or the multiple complex element oxide that is selected from alkali-metal element.
These add in the catalyst suspension as salt (for example sulfate, carbonate, nitrate, phosphate) usually, and when this catalyst of heating, be transformed into corresponding oxide, and (after the heat treatment of catalyst) is not present in the active material still with changing.
Alkali metal compound is used to active adjusting and improves selection of catalysts simultaneously.
In preferred embodiments, the alkali metal content in active material is 0-1.0 weight % and is preferably 0-0.6 weight % especially.Particularly advantageously, use for example cesium sulfate of solubility cesium compound in order to prepare catalyst suspension.
In addition, catalyst of the present invention particularly in the active material of focus catalyst layer, advantageously contains antimonial and is used to improve heat endurance as the active material composition.The content of antimony in active material advantageously is that 0-10 weight % is (as Sb
2O
3Calculate) and be preferably 0-5 weight % especially, depend on the position of related catalyst in overall catalyst bed and the thermic load that depends on catalyst related in each layer.
Can use the antimonic salt or the sb oxide of for example different oxidation valencys of various antimonials as the parent material that is used to prepare catalyst suspension or is used for the mixture of powders of the required catalyst of the present invention of coated carrier.
In the embodiment preferred of catalyst of the present invention, when the preparation catalyst suspension, use antimony-III-oxide.
Similarly, catalyst of the present invention can contain phosphorus compound or can add phosphorus compound as raw material source in preparing the used mixture of powders of catalyst suspension or coated carrier in catalytic active substance.Wherein, in the particularly advantageous embodiment of catalyst of the present invention, the phosphorus content of active material is 0-1.5 weight % (calculating as P).
Particularly advantageously, have in a plurality of layers the catalyst system that contains one or more of the present invention and/or one or more non-catalyst of the present invention, phosphorus content raises from the gas access to gas vent in windrow.Be suitable as the preferably ammonium dihydrogen phosphate (ADP) of the raw material source of catalyst of the present invention.
In addition, can contain multiple other compound with low amount in activity of such catalysts material of the present invention, it reduces as promoter or the activity that raises, and/or influences selection of catalysts.
Record in the literature, in order to improve activity or in order to weaken or to avoid so-called " hot spot " (focus) industrial then use multi-layer catalyst, described multi-layer catalyst is arranged in the catalyst windrow with stratiform, the particularly catalyst layer with a plurality of settings adjacent one another are, wherein in the prior art usually the catalyst that activity is minimum be arranged near the place, gas access, and successively increase activity along the gas vent direction.
Wherein, each layer catalyst has different chemical compositions, described chemical composition and then have different activity and selectivity.
Enough for the present invention is, in the multi-layer catalyst system at least one deck contain catalyst of the present invention, the latter is contained at least a related complex element oxide.
Preferably, particularly ground floor contains catalyst of the present invention, and wherein this ground floor is positioned to approach most the gas access and is the layer with hottest point.Particularly advantageously be, all layers in catalyst bed, the layer that has a hottest point until (comprising) from the gas access contains catalyst of the present invention.Wherein, for example the content of the complex element oxide of silver can change in different related layers with type.Wherein advantageously, in catalyst bed according to they the layer and other composition of adaptive active material.
In preferred embodiments, particularly have the highest local temperature peak value the layer contain silver the complex element oxide and/or the complex element oxide of bismuth and vanadium.
Especially, using the combination of complex element oxide of AgVO3 and BiVO4 verified in having the layer of hottest point is to improve optionally in catalyst of the present invention.
Find that unexpectedly particularly advantageous is that at least a active material of catalyst layer (it is arranged in before the layer with hottest point with sailing against the current) has the antimony content of reduction at active material with respect to the layer with hottest point in the direction of gas access.
In another advantageous embodiment of the catalyst with multilayer in one or more windrows, at least one catalyst layer (it is arranged at before the focus catalyst layer) contains at least a complex element oxide of silver and element mentioned above (particularly advantageously being silver and vanadium and/or molybdenum and/or tungsten).
In the special embodiment of catalyst of the present invention, from the gas access until the complex element oxide that contains one of at least silver of layer with hottest point, the complex element oxide of silver and vanadium and/or molybdenum and/or tungsten particularly, and the layer with hottest point contains the complex element oxide, particularly vanadium of vanadium and the complex element oxide of bismuth.
In other particularly preferred embodiment, the layer that contains the complex element oxide of silver and only have a hottest point until all layers of the layer with hottest point from the gas access contains the complex element oxide of extra vanadium and bismuth.
Particularly advantageously, use multinuclear complex element oxide or its precursor compound when the preparation catalyst suspension or when preparation is used for the mixture of powders of coated carrier material as the source.
In addition, compare silver-colored complex element oxide with the AgVO3 situation and also can be used to prepare catalyst suspension and/or active material with lower or higher atomic ratio to silver.According to atoms of elements ratio difference in the related complex element oxide, amount at the complex element oxide of catalyst suspension or the mixture of powders that is used to apply and/or its precursor compound must be suitable, to obtain the optimum content of the silver in the activity of such catalysts material that makes.
Advantageously, described complex element oxide phase or its precursor compound formed before they being added to the used mixture of powders of catalyst suspension or coated carrier.But can also add one or more corresponding precursor compound or mixture of powders of catalyst suspension, it changes corresponding complex element oxide then into when the heat treatment of catalyst.
As what above described, in preparation during catalyst suspension (use) or in activity of such catalysts material of the present invention (existence), not only can use the complex element oxide of the silver that exists with the integer mol ratio and other element and/or its precursor compound as raw material source, and can use the double-core or the multinuclear complex element oxide of the silver that contains thick atom amount of owing or excessive silver.According to the general formula of complex element oxide or its silver-colored composition, must raise or be reduced in complex element oxide content related in catalyst suspension and/or the active material.
The silver-colored complex element oxide of double-core or multinuclear is described by the following general formula according to claim 11:
Ag
xM
yN
zO
n(formula I)
The x of the mixed-metal oxides of formula I especially preferably has the value of 0.1-5, and the value of variable y is preferably 0-0.3.
Particularly preferably be mixed-metal oxides with following general formula:
Ag
x?N
z?O
n
Wherein
Ag=silver
The value of x=0.1-5
N=group's vanadium, molybdenum, tungsten, niobium, the element of antimony
z=?1
N=number, it is determined by the valence state and the frequency that are different from the element of oxygen in this formula I.
Feasible in principle be with the present invention clearly comprises, the catalyst of the present invention that also uses one or more precursor compounds and/or its initial compounds of related complex element oxide during catalyst suspension and have a related complex element mixture in preparation in reactor by just forming in the calcining of rising temperature or in the heating period of catalyst reactor.
In the embodiment preferred of described catalyst, particularly use complex element oxide AgVO3, Ag2MoO4, Ag2WO4 and/or these elements cause the improvement of this catalyst with the complex element oxide of other atomic ratio.
Have now found that, with in active material not argentiferous and/or therein argentiferous as oxide (AgO or Ag2O) or as salt (nitrate, phosphate, sulfate, chloride, ammonium salt, acylate) or in addition add to as hydroxide or as amine complex and contain silver in catalyst suspension or the active material as oxide (AgO or Ag2O) or as salt (nitrate, phosphate, sulfate, chloride, ammonium salt, acylate) or in addition compare as hydroxide or as the catalyst of amine complex, add silver and preference such as vanadium, the complex element oxide of tungsten and molybdenum to catalyst suspension replaces " monokaryon " silver compound to cause optionally significantly improvement.
Exemplary but nonrestrictive, on this position, mention the composition of compd A gVO3 as catalyst of the present invention, it uses as additive when preparation catalyst suspension or active material, and wherein this active material at least also contains the titanium dioxide and the vfanadium compound of anatase variant form.Preferably, catalyst of the present invention also contains at least a compound of first major element.According to the position of catalyst of the present invention in the catalyst bed, catalyst of the present invention also contains antimonial (particularly Sb2O3) and optional phosphorus compound in active material.
Unexpectedly find, multi-layer catalyst has special advantage aspect the raising selectivity, use at least a complex element oxide or its precursor compound of silver and vanadium and/or tungsten and/or molybdenum during described catalyst in preparation, wherein advantageously using catalyst of the present invention from the gas access to the one or more catalyst layers that (comprising) have a layer of hottest point.
In particularly preferred embodiments, have catalyst layer one or more or that all are above-mentioned the layer of hottest point from gas access to (comprising) and in active material, contain 0.01 weight %-15 weight %, particularly 0.01-10.0 weight % and the especially preferably silver of 0.01-5 weight % and the complex element oxide of vanadium and/or tungsten and/or molybdenum.
In the special embodiment of catalyst of the present invention, silver-vanadium-complex element oxide is that mol ratio Ag:V is the compound of 1:1, particularly complex element oxide AgVO3.Wherein, it is not so-called silver-vanadium-bronze, and wherein the molar ratio of Ag:V is by defining less than 1:1.
Have been found that in addition the complex element oxide that uses vanadium and bismuth, molybdenum, tungsten, antimony, arsenic, lead, tin, zinc, copper, nickel, cobalt, iron, manganese, chromium, niobium, zirconium, titanium, gold, rhenium, lanthanum, cerium, thallium, rhenium as raw material source in Preparation of Catalyst or play improvement as the composition of active material and optionally act on.
Especially, use pucherite when the preparation catalyst suspension or as the composition of active material, to cause improving selectivity as raw material source.Wherein advantageously, catalyst of the present invention contains the composition of BiVO4 as active material one or more layers of the layer that has hottest point from gas access to (comprising).
Wherein, catalyst of the present invention can also contain the complex element oxide of at least a silver and one or more above-mentioned elements and at least a complex element oxide of vanadium and one or more above-mentioned elements simultaneously except titanium dioxide and vanadium oxide.In particularly preferred embodiments, in order to prepare the catalyst suspension of catalyst of the present invention, use vanadic acid silver and pucherite, and/or be present in adjacent to each other in the activity of such catalysts material.
The position difference of catalyst according to the invention in the catalyst windrow, catalyst of the present invention also contains at least a alkali metal compound in addition, preferred cesium compound, antimonial, preferred antimony-III-oxide and optional phosphorus compound.
In the case, preparation during catalyst suspension (use) or (existence) not only can use vanadium and other element or its precursor compound in the activity of such catalysts material of the present invention complex element oxide that exists with the integer atomic ratio and can use the double-core or the multinuclear complex element oxide of atom amount of owing with big vanadium or excessive vanadium as raw material source.According to general formula or its content of vanadium of complex element oxide, in catalyst suspension and/or active material, must improve or reduce the content of related complex element oxide.
The double-core of vanadium or multinuclear complex element oxide are described by the following general formula according to claim 12:
M
aN
bV
cO
d(formula II)
For catalyst of the present invention, advantageously consider so-called shell catalyst, wherein be applied to usually at the carrier material that is inertia under the reaction condition for example on the mixture of porcelain, magnesia, tin ash, carborundum, silicic acid cerium, magnesium silicate (talcum), zirconium silicate, aluminium oxide, quartz or these carrier materials with shelly with one or more layer this catalytic active substance.In industry, mention the carrier material that constitutes by talcum or carborundum especially.
In order to prepare this class shell catalyst, usually be applied on the carrier material with fluidized bed process (DE-A 2106796) at the solution moisture and/or that contain organic solvent or the suspension (being called " catalyst suspension ") of the temperature that raises, until reaching the required activity substance content that accounts for total catalyst weight at this with active material composition and/or its precursor compound.Be coated on inertia, the non-porous carrier material as suspension or mixture of powders with active material composition or its precursor compound and can implement through the sugared cylinder (Dragiertrommel) of wrapping up in of heating in the temperature that raises equally.
Because in wrapping up in sugared cylinder spraying wherein contain active material component and/or its precursor compound or in fluid bed during the coated inert carrier material since catalyst suspension haze and/or because high loss takes place in the part wearing and tearing of the carrier that has applied sometimes, in industry, turn to the catalyst suspension of organic bond (preferred copolymer), advantageously with vinyl acetate/vinyl laurate, vinyl acetate/acrylate, phenylethylene ethylene/propenoic acid ester, the aqueous dispersion form of vinyl acetate/maleate and vinyl acetate/ethene etc. is added, wherein use the amount of binder of 10-20 weight % usually, based on the solids content of catalyst suspension.Adding under the above-mentioned adhesive case, application temperature advantageously is 50-450 ℃.Adhesive therefor decomposes after the initial operation at catalyst when catalyst filling is the operating temperature reactor heating mostly after reactor or at the latest and removes from catalyst fully in the case.
The catalytic active component that is retained on the inert support material as shell is called active material in the case.The component of active material may partly be distinguished and be the component or raw material source or the precursor compound that use in described catalyst suspension, because these materials heat treatment generation chemical transformation by catalyst sometimes and be transformed into corresponding metal oxide under the situation mostly.
Allow the people be surprised to find now, the efficient of catalyst not only depends on the composition and the quantity of activity of such catalysts material (behind the catalytic activity compound that heating or temperature conditioning exist), and the raw material source of using at catalyst suspension or at the mixture of powders that is used for coated carrier is to there being appreciable impact in selection of catalysts, activity and service life.
The present invention relates in addition and is used to prepare aldehyde, and the method for carboxylic acid and/or carboxylic acid anhydrides wherein allows gaseous stream contact at the catalyst of the temperature that raises with the preamble definition, and wherein said gaseous stream contains the gas of aromatic hydrocarbon and molecule-containing keto.
The complex element oxide that uses as the raw material source of catalyst suspension can prepare in a different manner, and as compound independently or directly add in the catalyst suspension as reactant mixture.Can add the corresponding precursor compound of the mixed-metal oxides of catalyst suspension equally.Wherein, it is multinuclear complex element compound or mixed-metal oxides compound advantageously, its have usually with in active material, exist compare different crystal structures and can also contain the crystallization water in addition through heat treatment complex element oxide.
For suitable (favourable in many cases) that prepare complex element oxide used in catalyst of the present invention and/or its precursor compound is that the suspension of solution of metal compound and metal oxide reacts in moisture or non-aqueous solvent in the rising temperature.Used silver-vanadium-the oxide of catalyst like this, for example of the present invention can advantageously prepare in the following way: the silver nitrate in the aqueous solution reacts with corresponding required atomic ratio in rising temperature and vanadic anhydride.Wherein corresponding reactant mixture can directly add in this catalyst suspension together with wherein contained mixed-metal compounds, and perhaps corresponding mixed-metal compounds is also through separation in advance with randomly through heat treatment.
As solvent, except water, can also use polar organic solvent for example polyalcohol, polyethers or amine.A kind of metal oxide or multiple metal oxide (for example vanadic anhydride and molybdenum trioxide) can carry out in room temperature or rising temperature usually with the silver compound and the reaction of the additional compounds of choosing wantonly (for example phosphorus compound).Preferably, the described 50-100 of being reflected at ℃ temperature is carried out, and continues 20 minutes to 5 days according to used raw material is different with reaction condition.
The mixed-metal compounds of Xing Chenging can be separated and randomly stored until further use or directly add catalyst suspension to as suspension solution by reactant mixture like this, and the latter is also contained titanium dioxide and vfanadium compound at least.What obtain by reaction can also carry out post processing in the temperature that raises with the mixed-metal compounds that separates before being added into catalyst suspension, with the effect that runs up the twin crystal structure and remove the crystallization water.
Under the situation of separating mixed-metal compounds in advance, can implement by the solid of filtering suspension liquid and dry gained, wherein said drying can be implemented by diverse ways.Advantageously implement the drying of hybrid metal-suspension by spray-drying or freeze-drying.
Alternative as what in solution, react, can also produce mixed-metal compounds by fusion, for example as follows: the metal oxide powder of different thin mixing reacts with the solid reaction form 400-800 ℃ rising temperature.
The component of described catalyst suspension is used with the form of oxide form and/or compound (for example salt) usually, and it changes oxide into when heating under the oxygen existence condition.For example phosphate or halide are in this catalyst suspension can also to add slaine, and it is not present in the activity of such catalysts material after heat treatment with changing.
Preparation of catalysts of the present invention is undertaken by the precursor of final catalyst usually, and described precursor can be stored with former state.Wherein, described precursor is the inactive ceramic carrier, and the raw material that will use in catalyst suspension by spray-on process is applied on this inactive ceramic carrier, and advantageously uses organic bond to fix.
Active catalyst has produced when heating this catalyst by the heat treatment of these precursors or in reactor usually.In the case, used metallic compound changes corresponding metal oxide usually into.For example, vanadium oxalate decomposes and changes V into
2O
5Equally, other compound contained in catalyst suspension can change its oxide compound into when this catalyst of heating.Like this, set out thus, ammonium dihydrogen phosphate (ADP) changes P into
2O
5, and be present in the active material with former state.For the moisture mixed-metal oxides of preparation and when the preparation of catalyst suspension as the situation of raw material source, set out the loss crystallization water and randomly change its crystal structure when this catalyst of heat treatment usually thus.
The transformation of used raw material source is preferably at 200-500 ℃ with carry out particularly preferably in 300-500 ℃ temperature in catalyst suspension.
The form of inert support material is not conclusive for the efficient of catalyst of the present invention, yet verified in the prior art ball and ring are particularly advantageous as formed body.
The bed thickness of active material or the bed thickness sum that contains the shell of active material are generally 20-400 μ m, and the position of catalyst according to the invention in catalyst bed is different and change.
Also find surprisingly, separate with the catalyst that be improved usually optional with used mixed-metal oxides space each component of catalyst suspension.All components of using in catalyst suspension are mixed or blending with corresponding complex element oxide usually, and mixed uniformly suspension is applied on the inert carrier.Equally also can consider such catalyst, wherein the catalyst suspension that difference is formed successively is applied to the inactive ceramic carrier, and wherein one deck contains catalyst of the present invention and produces of the present invention through improved catalyst thus at least.
In addition, can consider the catalyst that improves, wherein non-catalyst suspension of the present invention (it contains titanium dioxide, vfanadium compound at least and advantageously goes back alkali metal-containing compound) is at first through separating and randomly through heat treatment, with the powder that produces with relief usually again with powder (advantageously in water) (it is obtained by catalyst suspension in advance, and it is made up of titanium dioxide, vfanadium compound and at least a mixed-metal oxides or its precursor compound at least).This new catalyst suspension can be used as layer and is applied to individually on the inactive ceramic carrier, perhaps to be used in combination according to coating of the present invention of the present invention and/or non-with other.
It is aldehyde, carboxylic acid and/or carboxylic acid anhydrides that catalyst of the present invention is generally used for the gaseous oxidation of aromatic hydrocarbon part.In the case, these catalyst are particularly suitable for the gas that contains molecular oxygen ortho-xylene and/or naphthalene gaseous oxidation being become phthalic anhydride.
Catalyst of the present invention can be as previously discussed, in the catalyst windrow, use separately for this purpose or with other different activities catalyst for example the catalyst of prior art (not indistinct alloy belong to oxide component and based on vanadic anhydride/anatase) be used in combination.
At this, in the separated catalyst windrow, use different catalyst of the present invention of the present invention and non-usually, they are arranged at least one catalyst bed.In the case, advantageously all use catalyst of the present invention until layer with hottest point at the catalyst layer that is provided with near the gas access.
Although use catalyst of the present invention to have good effect equally at layer follow-up catalyst layer with in being arranged on more and more near the catalyst layer of gas vent with hottest point, but use catalyst of the present invention to compare with the catalyst layer that is provided with near the gas access, caused remarkable lower good effect aspect selectivity.Catalyst of the present invention and/or its preceding body catalyst of the present invention are filled in the reaction tube of reactor with stratiform.At this, each layer can be made up of the present invention and non-catalyst of the present invention.
What can consider equally is, in layer, use the windrow of the mixture of forming by at least a catalyst of the present invention and at least a non-catalyst of the present invention and use described windrow separately or with other being used in combination by the catalyst layer of the present invention and/or non-catalyst of the present invention.
At this, reaction tube is by outside constant temperature, and it is implemented by the molten salt bath that washes away this pipe around usually.
Precursor by this catalyst when heating has the reaction tube of newly filling by catalyst and/or with this catalyst of after-baking the time produces actual active catalyst, wherein burn organic bond and each raw material source of using changes corresponding oxide compound usually in catalyst suspension.In addition, according to the type of mixed-metal compounds, can also change its chemical composition and/or its crystal structure.
Reacting gas 250-550 ℃, particularly be conducted through this class of forming by at least a catalyst of the present invention through heat treated catalyst windrow 330-500 ℃ temperature with in the overvoltage of 0.1-2.5 bar, preferred 0.3-1.5 bar usually, wherein air speed (Raumgeschwindigkeit) is generally 1000-5000 h (1).
Be directed containing the gas of molecular oxygen, preferred air (it can also contain suitable reaction control agent and or diluent for example steam, nitrogen and/or carbon dioxide except oxygen) by mixing usually and remaining the aromatic hydrocarbon of oxidation producing through the reacting gas of catalyst, the gas that wherein contains molecular oxygen can contain 1-100 volume % and preferred especially 10-30 volume % oxygen usually, 0-30 volume steam, preferred 0-20 volume % steam and 0-50% volume %, preferred 0-1 volume % carbon dioxide, the nitrogen of surplus.In order to form reacting gas, the gas that contains molecular oxygen usually mixes with the aromatics hydrocarbon phase of oxidation of remaining of 20-200 g/Nm3 and preferred especially and 60-120 g/Nm3.
In the preferred embodiment of this method, for the aromatic hydrocarbon partial oxygen is changed into aldehyde, carboxylic acid and/or carboxylic acid anhydrides, this is particularly advantageous for ortho-xylene and/or naphthalene are oxidized to phthalic anhydride, wherein at first on catalyst windrow of the present invention, only partly change aromatic hydrocarbon into form reactant mixture by raw material, intermediate product and end product, with this mixture and at least a other catalyst reaction, the latter can be according to of the present invention or can be catalyst corresponding to prior art equally.
Described reaction can also be by carrying out more than a reactor, and wherein each reactor can be through constant temperature to different reaction temperatures, and contain at least one the catalyst windrow with at least one catalyst layer.At this, for the inventive method enough be, these reactors contain one of at least layer with catalyst of the present invention.
For prepared phthalic anhydride by ortho-xylene for, the reacting gas that part transforms also contains the unconverted ortho-xylene of significant quantity and intermediate product for example o-methyl-benzene formaldehyde and o-toluic acid and 2-benzo [c] furanone (Phthalid) except required product phthalic anhydride after through the one or more catalyst layers that contain catalyst of the present invention.
In addition, usually with this product mixtures without further post processing at least one other catalyst layer of promptly passing through, described catalyst layer its chemical composition with active aspect different with catalyst of the present invention, raw material are all transformed or the oxidation of oxygen debtization product are obtained phthalic anhydride guaranteeing.
Wherein, after by the catalyst windrow that contains catalyst of the present invention, can consider to separate unconverted ortho-xylene, then this reacting gas be guided to one or more other catalyst windrows.But this flexible program industrial only can be with the high relatively realization that expends.
It is therefore preferable that described reactant mixture does not experience raw material or intermediate product and separates by guiding subsequently through a plurality of catalyst layers, wherein one of at least (preferably being arranged on the layer near the gas access) of these catalyst layers contains the windrow of catalyst of the present invention.
Usually, extra or a plurality of catalyst layers use catalyst of the present invention together with at least one, wherein from the gas access to (comprising) have a catalyst layer that the layer of hottest point is provided with one of at least contain catalyst of the present invention, it is usually by 1-40 weight % vanadic anhydride, as V
2O
5Calculate, 50-99 weight % titanium dioxide is as TiO
2Calculate, the alkali metal compound of 1 weight % calculates with alkali metal at the most, preferred caesium, and the phosphorus compound of 1.5 weight % calculates as P at the most, and the antimonial of 10 weight % at the most is as Sb
2O
3Calculate and silver and at least a complex element oxide of at least a element mentioned above and/or the complex element oxide composition of 10 weight % vanadium and at least a element mentioned above at the most of 15 weight % at the most.
Yet, usually near the catalyst based on titanium dioxide/V205 (mostly based on non-catalyst of the present invention) that is used for this with combining form with use in the layer after the hottest point layer of the gas vent setting complex element oxide of argentiferous and/or vanadium not.But, also can in all layers, only use catalyst of the present invention.In this case, the difference of catalyst is to be present in the type and the quantity of the mixed-metal oxides in the active material usually.
The catalyst non-of the present invention that derives from prior art that uses with catalyst combination of the present invention contains 60-99 weight % content of titanium dioxide usually, 1-40 weight % vanadium oxide content, 1 weight % alkali metal content at the most, 1.5 weight % phosphorus contents and 10 weight % antimony contents at the most at the most.
Without detriment to above-mentioned composition, activity of such catalysts material of the present invention of the present invention and/or non-can also contain a spot of other and be used for improving active and oxide compound optionally.
Embodiment
The preparation catalyst
The various components of catalyst suspension are successively added in the deionized water as solution and/or powder, and advantageously stir the suspension that produces at least 12 hours.Advantageously use the titanium dioxide of anatase variant form, V2O5 or oxalic acid vanadyl, cesium sulfate as the raw material source of the contained component of catalyst of the present invention, ammonium dihydrogen phosphate (ADP), antimony oxide, pucherite and vanadic acid silver, silver molybdate, other mixed-metal oxides of wolframic acid silver and/or silver and vanadium.
Then, add the organic bond of the aqueous dispersion form of vinyl acetate to aqueous catalyst suspension, and stir altogether the suspension 30 minutes of about 20-25% again.
Then, the aqueous suspension (it contains active material and/or its precursor compound and organic bond) of respective amount is applied on the inert carrier (being of a size of the talcum ring of 7x7x4 mm or 8x6x5 mm) with spraying process, until on ring, applying the suspension that contains adhesive of specified quantitative, make the active material that after calcining, is provided in an embodiment.
Activity substance content (content of catalytic active substance does not contain adhesive) under each situation based on the catalytic active substance in each catalyst layer account for total catalyst weight (comprising carrier) (400 ℃ the calcining 4 hours after) content.
Given phosphorus content is based on the amount of the phosphorus compound that adds in the catalyst suspension preparation.The actual content that it be known to those skilled in the art that phosphorus in active material can depart from therewith mutually, depends on degree that used TiO2 polluted by phosphorus compound how.
Oxidation reaction
At internal diameter is that 25 mm and length are to fill related multi-layer catalyst system in the tubular reactor of iron reactor tube (it is washed away around by salt bath) of 3.7 m, wherein in described embodiment, under each situation, the R1 layer is provided with near the gas access, and R4 layer or R5 layer are provided with near gas vent.
The center is provided with the 2mm thermal sleeve of the tractive element (Zugelement) with embedding to measure temperature in reaction tube.Per hour guide from top to down 4 Nm3 air and approximately 30-70g/ ortho-xylene/Nm3 air at 340-380 ℃ salt temperature by this reaction tube.
In order to measure the catalyst efficiency data, to leave the reacting gas guiding of reaction tube through oil cooled condenser, wherein particularly formed phthalic anhydride deposits substantially fully, and accessory substance benzoic acid for example, maleic anhydride and 2-benzo [c] furanone be the part deposition only.Rough-the PSA that in condenser, deposits by the deep fat fusion, capture and weigh, then by GC-assay determination phthalic anhydride content.
Rough-PSA-the yield that provides in an embodiment calculates in the following way:
Rough-PSA-yield (weight %)=(rough-PSA purity (%) that rough-PSA measures (g) x)/(ortho-xylene charging (g) x ortho-xylene purity (%))
Although still counting, the wherein contained accessory substance of measured solid PSA content removal makes rough-PSA-yield, because make pure PSA at hot preliminary treatment and the product meter that the distillation post processing obtains usually.This is well-known to those skilled in the art equally.
The conversion ratio of ortho-xylene is almost 100% under each situation, and the rough yield that so records is directly corresponding to the selectivity of catalyst system.
Embodiment 1 (Comparative Examples):
Catalyst system A (4 layers)
This catalyst system is the multilayer system with four different layers.Each windrow of this comparative catalyst is the complex element oxide of argentiferous not.
50-65g ortho-xylene every Nm3 air carrying capacity and altogether under 4.0 Nm3 air capacity hourly and the 344-347 ℃ of SBT situation test at the catalyst system A described in the embodiment 1.
In the case, on average rough-PSA-yield (based on 100% ortho-xylene purity) of realizing 113.4 weight % after the test run stage and in rough-PSA 2-benzo [c] furanone content be 0.01 weight %.
Embodiment 2 (the present invention):
Catalyst system B (4 layers)
In 58-63g ortho-xylene every Nm3 air carrying capacity with altogether under 4.0 Nm3 air capacity hourly and the 346-352 ℃ of SBT situation, tested the catalyst system B of record in embodiment 2.At this, on average rough-PSA-yield of having realized 114.0 weight % after the test run stage (based on 100% ortho-xylene purity) and in rough-PSA 2-benzo [c] furanone content be 0.06 weight %.
Embodiment 3 (the present invention):
Catalyst system C (4 layers)
In 58-65g ortho-xylene every Nm3 air carrying capacity with altogether under 4.0 Nm3 air capacity hourly and the 346-347 ℃ of SBT situation, tested the catalyst system C of record in embodiment 3.At this, on average rough-PSA-yield of having realized 115.3 weight % after the test run stage (based on 100% ortho-xylene purity) and in rough-PSA 2-benzo [c] furanone content be 0.04 weight %.
Embodiment 4 (the present invention):
Catalyst system D (4 layers)
In 57-69g ortho-xylene every Nm3 air carrying capacity with altogether under 4.0 Nm3 air capacity hourly and the 346-348 ℃ of SBT situation, tested catalyst system D in embodiment 4 records.At this, on average rough-PSA-yield of having realized 113.9 weight % after the test run stage (based on 100% ortho-xylene purity) and in rough-PSA 2-benzo [c] furanone content be average 0.02 weight %.
Embodiment 5 (the present invention):
Catalyst system E (4 layers)
In 52-62g ortho-xylene every Nm3 air carrying capacity with altogether under 4.0 Nm3 air capacity hourly and the 347-348 ℃ of SBT, tested the catalyst system E of record in embodiment 5.At this, on average rough-PSA-yield of having realized 114.2 weight % after the test run stage (based on 100% ortho-xylene purity) and in rough-PSA 2-benzo [c] furanone content be average 0.01 weight %.
Embodiment 6 (Comparative Examples):
Catalyst system F (5 layers)
58-61 ortho-xylene every Nm3 air carrying capacity and altogether 4 Nm3 tested the catalyst system F of record in embodiment 6 per hour under air capacity and the 350-354 ℃ of SBT situation.At this, on average rough-PSA-yield of having realized 113.1 weight % after the test run stage (based on 100% ortho-xylene purity) and in rough-PSA 2-benzo [c] furanone content be 0.01 weight %.
Embodiment 6 (the present invention):
Catalyst system G (5 layers)
58-75 g ortho-xylene every Nm3 air carrying capacity and altogether 4 Nm3 tested the catalyst system G of record in embodiment 6 per hour under air capacity and the 348-350 ℃ of SBT situation.At this, on average rough-PSA-yield of having realized 114.8 weight % after the test run stage (based on 100% ortho-xylene purity) and in rough-PSA 2-benzo [c] furanone content be 0.03 weight %.
Table 1:
The efficiency data of catalyst of the present invention
| Catalyst system | Salt temperature ℃ | -rough-PSA-yield (after the test run stage) (weight %) | 2-benzo [c] furanone content (weight %) among rough-PSA |
| A (contrast) | 344-347 | 113.4 | 0.01 |
| B | 346-352 | 114.0 | 0.06 |
| C | 346-347 | 115.3 | 0.04 |
| D | 346-348 | 113.9 | 0.02 |
| E | 347-348 | 114.2 | 0.01 |
| F (contrast) | 350-354 | 113.1 | 0.01 |
| G | 348-350 | 114.8 | 0.03 |
By the contrast of embodiment 2-5 and Comparative Examples 1 as can be seen, the complex element oxide that uses silver prepares the catalyst suspension that is used to be arranged near the catalyst of first catalyst layer of gas access as raw material source and causes significant selectivity to improve.
By the contrast of embodiment 7 and Comparative Examples 6 as can be seen, in the active material of focus-catalyst layer, use the application of vanadic acid silver at least one follow-up catalyst layer of first catalyst layer also to cause improving selectivity.
Claims (38)
1. be used for the aromatic hydrocarbon catalytic vapor phase oxidation to obtain aldehyde, carboxylic acid and/or carboxylic acid anhydrides particularly obtain phthalic anhydride, catalyst,
Wherein said active material contains vanadium oxide, preferred vanadic anhydride, titanium dioxide, preferably with the titanium dioxide of anatase variant form, with at least a silver and the complex element oxide that limits element, the complex element oxide of preferred silver and vanadium and/or molybdenum and/or tungsten and/or niobium and/or antimony, and/or the complex element oxide of vanadium and qualification element, the complex element oxide of preferred vanadium and bismuth and/or molybdenum and/or tungsten and/or antimony and/or niobium and
Wherein at the preparation catalyst, particularly at the preparation catalyst suspension or when being the required mixture of powders of coated carrier, use at least a complex element oxide of silver and/or vanadium, and/or at least a precursor compound of at least a complex element oxide of silver and/or vanadium, particularly at least a multinuclear precursor compound is as raw material source.
2. the catalyst of claim 1 is characterized in that, described active material contains 0.01-15 weight %, preferred 0.01-10 weight %, most preferably the complex element oxide of the silver of 0.01-5 weight %.
3. claim 1 or 2 catalyst, it is characterized in that at least a complex element oxide of described silver is to contain at least a complex element oxide that is selected from other following element: vanadium, molybdenum, tungsten, niobium, thallium, chromium, titanium, manganese, iron, cobalt, nickel, copper, zinc, cadmium, gold, tin, zirconium, antimony, arsenic, cerium, lanthanum, bismuth, hafnium, lead, boron, aluminium, ruthenium, rhenium, palladium, rhodium.
4. the catalyst of one of claim 1-3 is characterized in that, described active material contains 0.01-10 weight %, the complex element oxide of the vanadium of preferred 0.01-5 weight %.
5. the catalyst of one of claim 1-4, it is characterized in that at least a complex element oxide of described vanadium is to contain at least a complex element oxide that is selected from other following element: bismuth, antimony, molybdenum, tungsten, chromium, lanthanum, cerium, iron, manganese, niobium, thallium, rhenium, cobalt, nickel, copper, zinc, gold, cadmium, lead, tin, boron, titanium, zirconium, hafnium, aluminium, arsenic, ruthenium, rhodium, palladium.
6. the catalyst of one of claim 1-5 is characterized in that, the vanadium oxide content of described active material is 1-40 weight %, as V
2O
5The content of titanium dioxide of calculating and described active material is 50-99 weight %, as TiO
2Calculate.
7. the catalyst of one of claim 1-6 is characterized in that, described active material contains the antimonial of 0-10 weight %, as Sb
2O
3Calculate, and/or the compound that is selected from following at least a element of 0-1 weight %: lithium, sodium, potassium, rubidium, caesium calculates as alkali metal under each situation, and/or the phosphorus compound of 0-1.5 weight %, calculates as P.
8. the catalyst of one of claim 1-7 is characterized in that, described active material contains AgVO
3And/or Ag
2MoO
4And/or Ag
2WO
4And/or BiVO
4
9. the catalyst of claim 8 is characterized in that, uses the AgVO of above-mentioned amount when the described catalyst of preparation
3And/or Ag
2MoO
4And/or Ag
2WO
4And/or BiVO
4And/or at least a precursor compound of these compounds is as raw material source.
10. the catalyst of one of claim 1-9, it is characterized in that, separate from reactant mixture in the preparation at them before the complex element oxide-precursor compound of the complex element oxide of complex element oxide that preparation is used during described catalyst and/or this complex element oxide or silver and/or vanadium uses as raw material source during in Preparation of Catalyst as raw material source, perhaps related reactant mixture directly uses when the Preparation of Catalyst as raw material source.
11. the catalyst of one of claim 1-10 is characterized in that, the complex element oxide of silver has following formula (I):
Ag
xM
yN
zO
n(formula I)
Wherein
Ag=silver
X=0.01-100, particularly 0.1-10,
M=be selected from following element: Li, Na, K, Rb, Cs, P, Mg, Ca, Sr, Ba, Tl,
y?=?0-1
N=at least a following element: V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ni, Pd, Cu, Au, Zn, Cd, Sn, Pb, B, Al, Bi, Sb, As, Ti, Zr, Hf, Ce, the La of being selected from
z?=?1
O=oxygen
N=number, it is determined by the valence state and the frequency that are different from the element of oxygen in this formula I.
12. the catalyst of one of claim 1-11 is characterized in that, the complex element oxide of described vanadium has following formula (II):
M
aN
bV
cO
d(formula II)
Wherein
M=at least a following element: Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ni, Pd, Cu, Au, Zn, Cd, Sn, Pb, B, Al, Bi, Sb, As, Ti, Zr, Hf, Ce, the La of being selected from
a?=?0.01-100
N=at least a following element: Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Tl, the P of being selected from
b?=?0-1，
V=vanadium
c?=?1
O=oxygen
D=number, it is determined by the valence state and the frequency that are different from the element of oxygen in this formula II.
13. the catalyst of one of claim 1-12 is characterized in that, as the vanadium source use V that is used to prepare catalyst
2O
5And/or vanadium oxalate and/or V
6O
13And/or NH
4VO
3And/or many vanadic acid, wherein in described active material, after catalyst heat treatment, exist to the small part vanadium as vanadic anhydride.
14. the catalyst of one of claim 1-13 is characterized in that, uses the titanium dioxide of at least a anatase variant form to prepare catalyst, and former state is present in the described active material, wherein the average BET surface area of overall titanium dioxide is 10-60 m
2/ g is calculated by all types of quantity ratio and surface area ratio.
15. the catalyst of claim 14, it is characterized in that, in described active material, use the mixture of the multiple different titanium dioxide types of anatase variant form, wherein at least a titanium dioxide type of anatase variant form have the BET surface area of the particle mean size of 0.3 μ m-0.8 μ m and 13-60 m2/g and wherein at least a other titanium dioxide type of anatase variant form have the BET-surface area of 2-15 m2/g.
16. the catalyst of one of claim 1-15, it is characterized in that, for the antimonial for preparing catalyst suspension or use for the required mixture of powders of coated carrier and/or the antimonial that exists in the described active material of catalyst are antimony-III-oxide and/or antimony-V-oxide.
17. the catalyst of one of claim 1-16, it is characterized in that, described catalyst is formed by at least three layers, and wherein the antimony content of the antimony content specific heat site catalyst layer of at least one layer before being arranged at the focus catalyst layer on the direction of gas access reduces 20-100%.
18. the catalyst of one of claim 1-17 is characterized in that, the described active material of described catalyst in the lasting hourage that limits of 400 ℃ of warps, preferably continues a few hours at this catalyst, particularly has following composition after the temperature adjustment of lasting about 4 hour time:
Vanadium oxide: % is (as V for 1-40 weight
2O
5Calculate)
Titanium dioxide: % is (as TiO for 50-99 weight
2Calculate)
AgxMyNzOn:0.01-15 weight % (calculating) as AgxMyNzOn
MaNbVcOd:0-10 weight % (calculating) as MaNbVcOd
Alkali metal: 0-1.0 weight % (calculating) as alkali metal
Antimony oxide: % is (as Sb for 0-10 weight
2O
3Calculate)
Phosphorus: 0-1.5 weight % (calculating) as P.
19. the catalyst of claim 18 is characterized in that, the described active material of described catalyst in the lasting hourage that limits of 400 ℃ of warps, preferably continues a few hours at this catalyst, particularly has following composition after the temperature adjustment of lasting about 4 hour time:
% is (as V for vanadium oxide 1-20 weight
2O
5Calculate)
Titanium dioxide: % is (as TiO for 80-99 weight
2Calculate)
Vanadic acid silver: % is (as AgVO for 0-5 weight
3Calculate)
Wolframic acid silver: % is (as Ag for 0-5 weight
2WO
4Calculate)
Silver molybdate: % is (as Ag for 0-5 weight
2MoO
4Calculate)
Pucherite: % is (as BiVO for 0-3 weight
4Calculate)
Caesium: 0-1 weight % (calculating) as Cs
Antimony oxide: % is (as Sb for 0-5 weight
2O
3Calculate)
Phosphorus: 0-1.5 weight % (calculating) as P
Wherein Yin at least a complex element oxide and/or pucherite are the compositions of the described active material of described catalyst.
20. the catalyst of one of claim 1-19 is characterized in that, the described active material of described catalyst this catalyst at least 400 ℃ and at least after the time temperature adjustment of 4h the content in this total catalyst weight be 2-25 weight %.
21. the catalyst of one of claim 1-20, it is characterized in that, the bed thickness of the described active material on inert support material is 20-400 μ m, with described catalytic active substance is applied on the non-porous carrier of inertia, the carrier, particularly talcum ring that preferably constitute of this carrier wherein by talcum.
22. the catalyst of one of claim 1-21 is characterized in that, at least two different layers are on the carrier that shelly is applied to preferred inertia, wherein at least one described layer contains titanium dioxide, the complex element oxide of vanadium oxide and silver and/or vanadium.
23. the catalyst of one of claim 1-22, it is characterized in that, at least two different layers are on the carrier that shelly is applied to preferably ceramic, wherein at least one layer contains titanium dioxide at least, vanadium oxide, contain the complex element oxide of at least a silver and/or vanadium with at least one other layer, contain or do not contain extra titanium dioxide and vanadium oxide.
24. the catalyst of one of claim 1-23, it is characterized in that, until at least one catalyst layer of the layer with hottest point, using shell catalyst from the gas access, its active material contains the complex element oxide of the vanadium of the complex element oxide of silver of claim 11 and/or claim 12, be used to prepare the raw material source use silver of catalyst and/or the complex element oxide of vanadium with conduct under this catalyst situation, and/or the precursor compound of the complex element oxide of silver and/or vanadium, with until at least one catalyst layer, be used for the shell catalyst of oxidation aromatic hydrocarbon from layer under this catalyst situation at the layer of gas vent with hottest point, this shell catalyst contains vanadic anhydride and titanium dioxide as main component in its active material.
25. the catalyst of one of claim 1-24 is characterized in that, the adhesive that is used to prepare at least one catalyst layer is organic polymer or copolymer, particularly vinyl acetate copolymer, and described polymer uses with the form of aqueous dispersion especially.
26. the catalyst of one of claim 1-25 is characterized in that, described catalytic active substance, based on its gross weight, contain the complex element oxide of the silver of 0.01-15 weight % and vanadium and wherein the Ag:V ratio greater than 0.95 (〉 0.95): 1-10:1.
27. the precursor of catalyst, the precursor of the catalyst of one of claim 1-26 particularly, the non-porous carrier material and one or more layers that is applied thereto with shelly that it is characterized in that inertia, wherein at least one layer contains the general formula I of with good grounds claim 11 or according at least a precursor compound of the complex element oxide of the general formula I I of claim 12, titanium dioxide, and vfanadium compound and wherein these precursor compounds when the heat treatment of the precursor of this catalyst, change the complex element oxide of silver or vanadium into.
28. the precursor of catalyst, the precursor of the catalyst of one of claim 1-26 particularly, it is characterized in that, at least two different layers are on the carrier that shelly is applied to preferably ceramic, wherein at least one layer contains titanium dioxide and vfanadium compound at least, other layer contains at least a precursor compound that mixes element oxide with at least one, described precursor compound contains or does not contain extra titanium dioxide and contains or do not contain extra vfanadium compound and wherein said precursor compound change silver or vanadium into when catalyst heat treatment complex element oxide.
29. be used to prepare the method for the catalyst of one of claim 1-26, it is characterized in that, preparation powder or suspension, aqueous suspension and it is applied on the inert carrier particularly, described suspension contains titanium dioxide at least, at least a complex element compound of vfanadium compound and silver and/or vanadium, and/or at least a precursor compound of the complex element compound of silver and/or vanadium.
30. be used to prepare the precursor of complex element oxide of claim 11 or the method for complex element oxide, it is characterized in that, will be at liquid, preferably in water, metal oxide N through suspending, preferred vanadic anhydride and/or molybdenum trioxide and/or tungstic acid, and/or metallic compound N through dissolving, preferred ammonium metavanadate, with the suspension of silver compound or solution, preferred aqueous solution, with the solution or the suspension heating of the oxide of optional metallic compound M, and reaction product isolated and the raw material source used as catalyst.
31. the method for claim 30 is characterized in that, the reactant mixture that produced or separated product are used to prepare the catalyst that the gaseous oxidation aromatic hydrocarbon uses or are used to prepare the catalyst precarsor that the gaseous oxidation aromatic hydrocarbon is used.
32. be used to prepare the precursor of complex element oxide of claim 12 or the method for complex element oxide, it is characterized in that, to suspend and/or be dissolved in the liquid, preferably in water, vfanadium compound, preferred vanadic anhydride and/or ammonium vanadate and/or vanadium (IV, V) oxide, metallizing thing M, preferred bismuth and/or molybdenum and/or tungsten and/or niobium and/or antimony, salt or the solution or the suspension of oxide, the suspension of the salting liquid of the oxide of preferred aqueous solution and optional metal N or the oxide of metal N is through heating, and reaction product isolated, perhaps as the raw material source of reactant mixture as catalyst.
33. the method for claim 32 is characterized in that, the reactant mixture of separated product and/or generation is used to prepare the catalyst that the gaseous oxidation aromatic hydrocarbon uses or is used to prepare the precursor of the catalyst that the gaseous oxidation aromatic hydrocarbon uses.
34. be used to prepare the method for the complex element oxide of claim 11, it is characterized in that, with at least a metal oxide N, preferred vanadic anhydride and/or molybdenum trioxide and/or tungstic acid, and/or at least a slaine N and silver-colored oxide or salt, preferred AgO and/or Ag
2The oxide of O and the metal M of choosing wantonly or salt merge with dried forms or solution form, and described mixture heats time that limits and the raw material source that described product is used as catalyst 200-900 ℃ of temperature after optional drying in advance.
35. the method for claim 34 is characterized in that, the reactant mixture of described product or generation is used to prepare the catalyst that the gaseous oxidation aromatic hydrocarbon uses or is used to prepare the precursor of the catalyst that the gaseous oxidation aromatic hydrocarbon uses.
36. be used to prepare the method for the complex element oxide of claim 12, it is characterized in that, at least a salt or the oxide of vanadium, preferred vanadic anhydride and/or ammonium vanadate and/or vanadium (IV, V) oxide, at least a oxide and/or salt with metal M, preferred bismuth oxide, oxide or salt with the metal N that chooses wantonly, merge with dried forms or solution form, and this mixture randomly after drying in advance subsequently in time that 200-900 ℃ temperature heating limits and the raw material source of using this product catalyst that gaseous oxidation is used as aromatic hydrocarbon.
37. be used to prepare aldehyde, the method of carboxylic acid and/or carboxylic acid anhydrides, this method is by carrying out in rising temperature section oxidation aromatic hydrocarbon on catalyst, the catalytic active substance of described catalyst is applied to inertia, on the non-porous carrier, it is characterized in that, the shell catalyst of described catalytic active substance, based on its gross weight, contain the complex element oxide of the vanadium of the complex element oxide of the silver of 0.01-15 weight % and vanadium and/or molybdenum and/or tungsten and/or niobium and/or antimony and/or 0.01-10 weight % and bismuth and/or molybdenum and/or niobium and/or antimony and contain titanium dioxide and vfanadium compound simultaneously, preferred V
2O
5Wherein complex element oxide-compound or its precursor compound, exist or do not exist under at least a other shell catalyst situation, preparation during catalyst suspension and/or preparation use when being used for the mixture of powders of follow-up active material, described other shell catalyst contains in its active material as the vanadic anhydride of main component and the titanium dioxide of anatase variant form.
38. be used to prepare the method for the catalyst of one of claim 1-26, it is characterized in that, described catalytic active substance or catalyst suspension or in mixture of powders contained compound with thermopnore or preferably be applied on the inert carrier with fluid bed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102008044890.7 | 2008-08-29 | ||
| DE102008044890.7A DE102008044890B4 (en) | 2008-08-29 | 2008-08-29 | Catalyst for the catalytic gas phase oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and/or carboxylic anhydrides, in particular to phthalic anhydride, and process for producing such a catalyst |
| PCT/EP2009/005372 WO2010022830A2 (en) | 2008-08-29 | 2009-07-24 | Catalyst for the catalytic gas phase oxidation of aromatic hydrocarbons to form aldehydes, carboxylic acids and/or carboxylic acid anhydrides, in particular phthalic acid anhydride, and method for producing said type of catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102196859A true CN102196859A (en) | 2011-09-21 |
| CN102196859B CN102196859B (en) | 2014-08-06 |
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|---|---|---|---|
| CN200980142796.1A Active CN102196859B (en) | 2008-08-29 | 2009-07-24 | Catalyst for the catalytic gas phase oxidation of aromatic hydrocarbons to form aldehydes, carboxylic acids and/or carboxylic acid anhydrides, in particular phthalic acid anhydride, and method for producing said type of catalyst |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP2321045A2 (en) |
| KR (1) | KR101706790B1 (en) |
| CN (1) | CN102196859B (en) |
| BR (1) | BRPI0913160B1 (en) |
| DE (1) | DE102008044890B4 (en) |
| TW (1) | TWI518079B (en) |
| WO (1) | WO2010022830A2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107999107A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of maleic anhydride catalyst and its preparation method and application |
| CN109158119A (en) * | 2018-09-14 | 2019-01-08 | 中海油天津化工研究设计院有限公司 | A kind of catalyst and preparation method for durol oxidation |
| CN109369544A (en) * | 2018-12-05 | 2019-02-22 | 兰州大学 | A kind of method that catalysis oxidation prepares 5-Methylpyrazine-2-carboxylic acid |
| CN110290869A (en) * | 2017-02-14 | 2019-09-27 | 科莱恩国际有限公司 | The catalyst material for oxygenated hydrocarbon of titanium dioxide with Sb doped |
| CN114100651A (en) * | 2020-08-25 | 2022-03-01 | 中国石油化工股份有限公司 | Catalyst for preparing maleic anhydride through benzene oxidation and preparation method and application thereof |
| CN114539207A (en) * | 2020-11-24 | 2022-05-27 | 万华化学(四川)有限公司 | Method and catalyst for preparing lactide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011061132A1 (en) * | 2009-11-20 | 2011-05-26 | Basf Se | Multilayer catalyst for producing carboxylic acids and/or carboxylic acid anhydrides with vanadium antimonate in at least one catalyst layer, and method for producing phthalic acid anhydride with a low hot-spot temperature |
| DE102013202048A1 (en) * | 2013-02-07 | 2013-04-18 | Basf Se | Preparing catalytically active composition useful for preparing a catalyst, comprises e.g. thermally treating geometrical precursor bodies formed by a mixture obtained by uniformly mixing e.g. a spray-dried powder and molybdenum oxide |
| EP3047904A1 (en) | 2015-01-22 | 2016-07-27 | Basf Se | Catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride |
| NL2018890B1 (en) * | 2017-05-10 | 2018-11-15 | Admatec Europe B V | Additive manufacturing of metal objects |
| CN109110910A (en) * | 2018-08-31 | 2019-01-01 | 江苏新亿源环保科技有限公司 | A kind of preparation method of high catalytic property suspension step biofilter material |
| CN114682278B (en) * | 2020-12-29 | 2023-09-01 | 中国石油化工股份有限公司 | Anti-phosphorus loss vanadium phosphorus oxide catalyst |
| IT202100021746A1 (en) | 2021-08-11 | 2023-02-11 | Polynt S P A | Multilayer catalytic bed for the production of phthalic anhydride. |
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| EP0522871A1 (en) * | 1991-07-10 | 1993-01-13 | Nippon Shokubai Co., Ltd. | Catalyst and process for producing phthalic anhydride |
| CN1938086A (en) * | 2004-03-26 | 2007-03-28 | 巴斯福股份公司 | Catalyst having a silver-vanadium oxide phase and a promoter phase |
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-
2008
- 2008-08-29 DE DE102008044890.7A patent/DE102008044890B4/en active Active
-
2009
- 2009-07-24 CN CN200980142796.1A patent/CN102196859B/en active Active
- 2009-07-24 EP EP09777410A patent/EP2321045A2/en not_active Withdrawn
- 2009-07-24 WO PCT/EP2009/005372 patent/WO2010022830A2/en active Application Filing
- 2009-07-24 KR KR1020117006837A patent/KR101706790B1/en active IP Right Grant
- 2009-07-24 BR BRPI0913160-4A patent/BRPI0913160B1/en not_active IP Right Cessation
- 2009-08-04 TW TW098126162A patent/TWI518079B/en not_active IP Right Cessation
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| EP0522871A1 (en) * | 1991-07-10 | 1993-01-13 | Nippon Shokubai Co., Ltd. | Catalyst and process for producing phthalic anhydride |
| CN1938086A (en) * | 2004-03-26 | 2007-03-28 | 巴斯福股份公司 | Catalyst having a silver-vanadium oxide phase and a promoter phase |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107999107A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of maleic anhydride catalyst and its preparation method and application |
| CN110290869A (en) * | 2017-02-14 | 2019-09-27 | 科莱恩国际有限公司 | The catalyst material for oxygenated hydrocarbon of titanium dioxide with Sb doped |
| CN109158119A (en) * | 2018-09-14 | 2019-01-08 | 中海油天津化工研究设计院有限公司 | A kind of catalyst and preparation method for durol oxidation |
| CN109369544A (en) * | 2018-12-05 | 2019-02-22 | 兰州大学 | A kind of method that catalysis oxidation prepares 5-Methylpyrazine-2-carboxylic acid |
| CN109369544B (en) * | 2018-12-05 | 2022-06-03 | 兰州大学 | Method for preparing 5-methylpyrazine-2-carboxylic acid by catalytic oxidation |
| CN114100651A (en) * | 2020-08-25 | 2022-03-01 | 中国石油化工股份有限公司 | Catalyst for preparing maleic anhydride through benzene oxidation and preparation method and application thereof |
| CN114100651B (en) * | 2020-08-25 | 2023-12-08 | 中国石油化工股份有限公司 | Catalyst for preparing maleic anhydride by benzene oxidation and preparation method and application thereof |
| CN114539207A (en) * | 2020-11-24 | 2022-05-27 | 万华化学(四川)有限公司 | Method and catalyst for preparing lactide |
| CN114539207B (en) * | 2020-11-24 | 2023-09-19 | 万华化学(四川)有限公司 | Method for preparing lactide and catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI518079B (en) | 2016-01-21 |
| EP2321045A2 (en) | 2011-05-18 |
| KR101706790B1 (en) | 2017-02-15 |
| DE102008044890A1 (en) | 2010-03-04 |
| DE102008044890B4 (en) | 2023-09-14 |
| BRPI0913160B1 (en) | 2018-03-27 |
| CN102196859B (en) | 2014-08-06 |
| WO2010022830A3 (en) | 2010-05-20 |
| BRPI0913160A2 (en) | 2016-07-26 |
| TW201012805A (en) | 2010-04-01 |
| WO2010022830A2 (en) | 2010-03-04 |
| KR20110050694A (en) | 2011-05-16 |
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