EP3302793A1 - Verfahren zur herstellung eines bismut und wolfram enthaltenden multielementoxids durch co-präzipitation - Google Patents
Verfahren zur herstellung eines bismut und wolfram enthaltenden multielementoxids durch co-präzipitationInfo
- Publication number
- EP3302793A1 EP3302793A1 EP16726299.7A EP16726299A EP3302793A1 EP 3302793 A1 EP3302793 A1 EP 3302793A1 EP 16726299 A EP16726299 A EP 16726299A EP 3302793 A1 EP3302793 A1 EP 3302793A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- tungsten
- volume
- mixture
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 26
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000010937 tungsten Substances 0.000 title claims abstract description 24
- 238000000975 co-precipitation Methods 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 92
- 239000000203 mixture Substances 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 4
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims abstract description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 3
- 239000010931 gold Substances 0.000 claims abstract description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 239000004332 silver Substances 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000000465 moulding Methods 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical group O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005188 flotation Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000003856 thermoforming Methods 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 239000000047 product Substances 0.000 abstract description 9
- 238000001694 spray drying Methods 0.000 abstract description 9
- 238000001556 precipitation Methods 0.000 abstract 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 abstract description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 abstract description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 61
- 239000007858 starting material Substances 0.000 description 29
- 239000007789 gas Substances 0.000 description 27
- 238000007669 thermal treatment Methods 0.000 description 27
- 230000003647 oxidation Effects 0.000 description 24
- 238000007254 oxidation reaction Methods 0.000 description 24
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000012495 reaction gas Substances 0.000 description 17
- 229910001868 water Inorganic materials 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000012018 catalyst precursor Substances 0.000 description 14
- 238000009826 distribution Methods 0.000 description 14
- 238000007493 shaping process Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 9
- 229910001882 dioxygen Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000000314 lubricant Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 7
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- -1 alkali metal (hydrogen) carbonates Chemical class 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000005056 compaction Methods 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000004677 hydrates Chemical class 0.000 description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- XOBGMVXXJIHFNI-UHFFFAOYSA-N bismuth;oxotungsten Chemical compound [Bi].[W]=O XOBGMVXXJIHFNI-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000008240 homogeneous mixture Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000003701 inert diluent Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 125000005624 silicic acid group Chemical class 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- 239000001692 EU approved anti-caking agent Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical class O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000009997 thermal pre-treatment Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 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 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000003335 Production assurance Methods 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- NEOOEFDJRSCWOU-UHFFFAOYSA-N iron(2+);dinitrate;hydrate Chemical compound O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NEOOEFDJRSCWOU-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000275 quality assurance Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/24—Chromium, molybdenum or tungsten
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- 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
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J37/04—Mixing
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Definitions
- the present invention relates to a process for the preparation of shaped catalyst bodies which contain as active composition a bismuth and tungsten-containing multielement oxide.
- Multielement oxides which in addition to bismuth and tungsten contain other elements, such as molybdenum and iron, are used as catalysts for the gas phase oxidation of alkenes to unsaturated aldehydes, in particular the gas phase oxidation of propene to acrolein.
- Acrolein is further oxidized to acrylic acid, which is an important feedstock in the chemical industry.
- No. 4,537,874 discloses a process in which aqueous bismuth nitrate solution is mixed with ammonia and the resulting precipitate is filtered off and washed. The precipitate is mixed with tungsten trioxide, dried and calcined. The bismuth tungsten oxide thus obtained is mixed with a pulverulent mixture of further constituents, shaped into pellets and calcined.
- WO 2007/042369 describes a process for the preparation of
- Mixtures containing mixed oxide catalysts mixed produces coprecipitates, isolated the resulting solid, dried, calcined and optionally deformed.
- the mixed oxide catalysts are used to prepare aldehydes and acids by oxidation of olefins or methylated aromatics with air or oxygen.
- Spray drying is a preferred method of preparing the bismuth tungsten oxide precursor because the homogeneous distribution of bismuth and tungsten in the aqueous mixture is fixed by the sudden removal of water. During calcining, it is then possible to obtain a phase of the desired stoichiometry, which is largely free of foreign phases.
- Spray-drying is an energy-consuming process, which also requires a special spray-drying plant. It is therefore desirable to have alternative production routes. It is generally known to produce multielement oxide compositions by co-precipitation, whereby mixed solutions of water-soluble compounds of the elemental constituents are mixed with alkali and a precipitate of a mixed hydroxide and / or oxide is obtained.
- Bismuth oxide is an amphoteric oxide.
- the precipitation can lead to inhomogeneous precipitation products, wherein z. B. phases with more than stoichiometric tungsten content in addition to tungsten poorer phases or pure bismuth oxide can form.
- bismuth and tungsten oxides tend to precipitate in finely divided and / or difficult to filter form.
- the invention has for its object to provide a method which avoids the problems described above.
- the invention relates to a process for the preparation of shaped catalyst bodies which contain as active composition a multielement oxide of general stoichiometry I, [BhW b Ox] a [Moi 2 Z 1 cZ 2 dF ee Z 3 f Z 4 g Z 5 hO y ] i (I) With
- Z 1 one element or more than one element from the group consisting of nickel and cobalt,
- Z 2 one element or more than one element from the group consisting of the alkali metals, the alkaline earth metals,
- Z 3 one element or more than one element from the group consisting of zinc, phosphorus, arsenic, boron, antimony, tin, cerium, vanadium, chromium and bismuth
- Z 4 one element or more than one element from the group consisting of silicon, aluminum, titanium, tungsten and zirconium,
- x, y numbers determined by the valence and frequency of the elements other than oxygen in I, wherein a mixed oxide B WbOx is used and the precursor of the mixed oxide BhWbOx is a co-precipitate from an aqueous environment at a pH in Range of 1, 5 to 3, vorzugtical, 5 to 2.5, in particular about 2, and a separation of the precipitate by a mechanical separation method.
- Z 1 is preferred in the process according to the invention exclusively Co.
- Z 2 in the process according to the invention is preferably K, Cs and / or Sr, more preferably K.
- Z 4 is preferably Si in the process according to the invention.
- the stoichiometric coefficient a is advantageously 1.0 to 2.0.
- the stoichiometric coefficient b is advantageously 0.5 to 4 or 3, more preferably 1 to 2.5, and most preferably 1.5 to 2.5.
- the stoichiometric coefficient c is preferably 3 to 8, particularly advantageously 4 to 7 and very particularly advantageously 5 to 6.
- the stoichiometric coefficient d is advantageously 0.02 to 2 and particularly advantageously 0.03 to 1 or 0.05 to 0, 5th
- the stoichiometric coefficient e is advantageously 0.1 to 4.5, preferably 0.5 to 4 and particularly preferably 1 to 4 or 2 to 4.
- the stoichiometric coefficient g is preferably> 0 to 10, more preferably 0.1 to 8 or 0.2 to 7, even more preferably 0.3 to 6 or 0.4 to 5, and most preferably 0.5 to 3 or 1 to 3.
- the stoichiometric coefficients h and f can both be 0 at the same time, but can also independently of 0 assume different values.
- the fraction contains [Mo? Z 'C Z 2 (! Fe ö Z 3 fZ 4 B Z 5 h Oy] no Bi.
- is at least one source of the element Bi and at least one source of the element W are intimately mixed with one another in an aqueous medium and have a pH in the range from 1.5 to 3, preferably from 5 to 2.5, in particular about 2, to adjust.
- an aqueous preparation of a bismuth source having a pH of from 1.5 to 3, preferably from 1.5 to 2.5, in particular about 2, is present, an aqueous preparation is added to a tungsten source and keeps the pH of the mixture during the addition of the tungsten source in the range of 1, 5 to 3, preferably 1, 5 to 2.5, in particular about 2.
- Suitable sources of Bi and W are in principle those compounds which are already oxides of these elements, or compounds which can be converted into oxides by heating, at least in the presence of molecular oxygen.
- the bismuth source used is preferably water-soluble bismuth salts, such as nitrates, carbonates, hydroxides and / or acetates. It is preferable to use tungsten acid and / or tungsten oxide as the tungsten source.
- the tungstic acid which is essentially insoluble in water, is preferably used as finely divided powder whose dgo, in terms of application, is expediently .ltoreq.5 or .ltoreq.2 .mu.m, preferably from 0.1 to 1 .mu.m.
- the tungstic acid is suitably added in the form of an aqueous slurry.
- Sodium tungstate is another tungsten source.
- the sources of Bi and W are in completely dissolved form. It is also possible to start from aqueous slurries of the sources of Bi and / or W. The co-precipitation is carried out while redissolving the incompletely dissolved source of Bi and / or W.
- the adjustment of the pH in the stated range is carried out by adding suitable amounts of an acid or base, preferably in the form of an aqueous solution. If tungsten acid and / or tungsten oxide is used as the tungsten source, the pH of the mixture during the addition of the tungsten source by addition of a base is kept in the range from 1.5 to 3, preferably 1.5 to 2.5, in particular about 2.
- Suitable bases are alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, or alkali metal (hydrogen) carbonates, such as sodium carbonate.
- alkali metal hydroxide solutions of a concentration of 5 to 40 wt .-%, preferably 12 to
- the addition of the tungsten source and the addition of the base are carried out with suitable mixing, for. B. with stirring.
- the co-precipitation is usually carried out at a temperature of 10 C to 90 C, preferably at room temperature.
- the pressure is not critical and is preferably ambient pressure.
- hydrothermal conditions may also be used.
- the addition of the aqueous preparation of a tungsten source to a presented preparation of a bismuth source is preferably distributed in time, z. B. over a period of 1 to 40 minutes, in particular 10 to 30 minutes. After completion of the addition, the suspension obtained is preferably stirred, z. B. over a period of 1 to 5 hours, in particular 2 to 4 hours. It is characteristic of the process according to the invention that the separation of the precipitate takes place by a mechanical separation process.
- the mechanical separation process is z. B.
- Suitable filter elements include, for. As nonwovens, felts or sintered plates. Also suitable are filter cloths, which are inserted into filtration devices such as filter presses or centrifuges.
- filter cloths for chamber filter presses have two filter cloth halves to be arranged in parallel. They are thus placed on the individual filter plates of the filter presses. caused the two filter cloth halves to cover opposite faces of the filter plates. Several such filter plates covered with filter cloths are then pressed together. The suspension to be filtered is pumped into the cavity between the wipes and, leaving behind the filter cake, flows into the draining chamber behind the wipes and flows outward therefrom.
- the precipitate is washed salt-free with a suitable washing liquid.
- the washing liquid is usually deionized water.
- the washing can be done by slurrying in the washing liquid and decanting.
- the slurrying in the washing liquid and decanting can preferably be repeated one or more times.
- the washing may be carried out by flowing a filter cake of the precipitate with the washing liquid.
- the success of the washing can be traced by measuring the conductivity of the used washing liquid.
- the precipitate is considered to be salt-free when deionized water (pH 7.0) equilibrated with the washed precipitate (eg 1 L of water on 500 g of precipitate, calculated as dry mass of oxide) has a conductivity at 25 C of less than 800 pS has.
- the precipitate is then dried in a conventional manner, for. B. in a drying oven, tray oven, rotary dryer or the like.
- the resulting dry matter is calcined at temperatures in the range of 400 to 900 ° C (preferably 600 to 900 ° C and more preferably 700 to 900 ° C) (thermally treated).
- the thermal treatment usually takes place in the air stream (for example in a rotary kiln, as described in DE-A 103 25 487).
- the calcine obtained thereby is comminuted to obtain a finely divided starting material.
- the particle diameter d 50 is preferably 2.9 to 3.6 ⁇ m (unless stated otherwise, the particle size data refer to the values determined in aqueous suspension without preceding ultrasonic treatment by laser diffraction).
- the division of the calcined mixed oxide to a desired particle diameter will normally be effected by milling in mills. If necessary, the material to be ground is subsequently classified to the desired degree of division.
- application technology advantageous with the addition of up to 20 wt .-% of water anieret and z. B.
- Preferred mixed oxides BiiWbOx formed beforehand in the process according to the invention are the mixed oxides BiiW 2 , 5 0 9 (1/2 Bi 2 W 2 O 9 -1, 5 W0 3 ), BiiW 3 Oio, 5 (1/2 Bi 2 W 2 0 9 -2 W0 3 ), BiiW 4 0i3, 5 (1/2 Bi 2 W 2 0 9 -3 W0 3 ), BiiW 0 , 5 O 3 , BiiWi0 4 , 5 (1/2 Bi 2 W 2 0 9 ) BiiW 2 0 7 , 5 (1/2 Bi 2 W 2 0 9 -1 W0 3 ) and BiiWi, 5 0 6 (1/2 Bi 2 W 2 0 9 -1/2 W0 3 ), among which the BiiW 2 07.5 is very particularly preferred according to the invention.
- Mischoxids BiiWbOx applied thermal treatment to degrade gaseous escaping compounds and / or decomposed (chemically reacted).
- Such substances may, for example, function as pore formers and be included for the purpose of influencing the active inner surface of the mixed oxide BiiWbOx.
- auxiliary substances are, for example, NH 4 OH, (NH 4 ) 2 C03, NH 4 HC03, NH 4 N0 3 , urea, NH 4 CH0 2 , H 2 C0 3 , HN0 3 , H 2 S0 4 , NH 4 CH 3 C0 2, NH 4 HS0 4, NH 4 Cl, HCl, (NH 4) 2 S0 4, ammonium oxalate, hydrates of the aforementioned compounds as well as organic substances such.
- the preformed mixed oxide B WbO x is mixed with a pre-formed powdery precursor of the stoichiometry [Mo 2 Z 1 c Z 2 dFe e Z 3 fZ 4 gZ 5 hOy].
- a precursor of the stoichiometry is understood to mean a mixture of element sources in suitable relative amounts which, upon calcining, at least in the presence of molecular oxygen, a multielement oxide of stoichiometry [ Moi? Z * c Z d FeeZ 3 , Z 4 ⁇ ; Z s h O y ] returns.
- Suitable sources of the elements of the moiety [Moi 2 Z 1 c Z 2 dFe e Z 3 fZ 4 gZ 5 hOy] of the desired multielement oxide active composition according to the invention are, in principle, those compounds which are already oxides and / or are such Compounds which are convertible into oxides by heating, at least in the presence of molecular oxygen.
- suitable starting compounds are, in particular, halides, nitrates, formates, oxalates, citrates, acetates, carbonates, amine complexes, ammonium salts and / or hydroxides (and the hydrates of the abovementioned salts).
- a convenient Mo source is ammonium heptamolybdate tetrahydrate. Basically, but also z. B. molybdenum trioxide used.
- favorable Z 1 sources are the nitrates or nitrate hydrates of Z 1 elements. According to the invention advantageous
- Z 2 sources are the hydroxides and nitrates of the Z 2 elements or their hydrates.
- element iron an iron nitrate hydrate is advantageously used in the process according to the invention.
- Silica sol forms the preferred Si source according to the invention.
- Lanthanides which are preferred according to the invention are Er, Tb, Ho, Eu, Tm, Nd, Lu, Dy, Gd, Ce and Sm.
- the corresponding nitrate hydrates are preferably used as well as in the case of La and Y.
- the multielement oxide I can also be incorporated into the respective aqueous mixture also substances which at least under the Conditions of the thermal treatment of the geometric shaped bodies to form the geometric Kata- lysatorform Equity disintegrate to gaseous escaping compounds and / or decomposed (chemically reacted).
- Such substances may, for example, act as pore formers and be included for the purpose of adjusting the active inner surface.
- auxiliary substances examples include NH 4 OH, (NH 4 ) 2 CO 3 , NH 4 HC0 3 , NH 4 NO 3 , urea, NH 4 CHO 2 , H 2 CO 3 , HNO 3 , H 2 SO 4
- NH 4 CH 3 C0 2 NH 4 HSO 4 , NH 4 Cl, HCl, (NH 4 ) 2 SO 4 , ammonium oxalate, hydrates of the abovementioned compounds and organic substances, such as.
- stearic acid, malonic acid, ammonium salts of the aforementioned acids starches (eg, potato starch and corn starch), cellulose, ground nutshell, finely divided plastic flour (eg., Polyethylene, polypropylene), etc. into consideration.
- the production of the pulverulent precursor of the stoichiometry preferably takes place from an aqueous mixture
- the drying preferably takes place in the hot air stream.
- other hot gases can also be used for the abovementioned spray drying (for example nitrogen, or air diluted with nitrogen and other inert gases).
- the spray drying can take place both in cocurrent and in countercurrent of the droplets to the hot gas.
- it takes place in countercurrent of the droplets to the hot gas. It is particularly preferably carried out in hot air counterflow.
- Typical gas inlet temperatures are in the range of 250 to 450 ° C, preferably 270 to 370 ° C.
- Typical gas outlet temperatures are in the range of 100 to 160 ° C.
- the spray-drying is preferably carried out so that a desired particle diameter is set directly.
- the particle diameter d 50 is preferably 30 to 45 ⁇ m. If the degree of dispersion of the resulting spray powder is too small compared to the desired dso, the same can be achieved, for example. B. be coarsened by subsequent compacting to the desired degree of division.
- the spray powder resulting from spray-drying can be refined by grinding, if necessary, to a desired degree of dewatering.
- the intimate aqueous mixture can also first by conventional evaporation (preferably at reduced pressure, the drying temperature should not exceed 150 ° C generally) dried and the resulting dry matter can be adjusted by subsequent crushing to a required degree of separation. In principle, however, the drying of the aqueous mixture can also be effected by freeze-drying.
- Preferred stoichiometries [Mo i? Z? C z 2 ⁇ ; Fe e Z 3 fZ 4 B Z 5 hOy] are Mo 12 Co 6 Fe 3 O 3 Si 0.6 K 0.08, or Moi 2 Co 6.5 Fe 3, Osi, eco, o8, or Moi 2 Co 7 , o Fe 3, o Si, 6K 0 , o 8, or Moi 2 Co 5 .
- the finely divided shaping aids may also or only (only) be mixed into the finely divided mixture of mixed oxide B WbOx and the pulverulent precursor of the stoichiometry [Moi 2 Z 1 c Z 2 dFe e Z 3 fZ 4 gZ 5 hOy].
- the group of fine-particle shaping aids initially includes the so-called anti-caking agents.
- finely divided materials which are advantageously used concomitantly in terms of application, in order to produce, in the context of mixing z.
- a preferred group of finely divided anti-caking agents forms finely divided hydrophobized silicic acids, in particular finely divided hydrophobized synthetic silicic acids (silicon dioxides).
- synthetic silicic acids can be generated directly from sand and on the other hand by precipitation reactions from waterglass, in particular synthetic silicas are hydrophilic due to their surface-active OH groups, ie they are wetted by water, for example by reaction of these surface-active OH groups with chlorosilanes Hydrophobized products are produced from both the fumed and the precipitated silicas, and commercial products of hydrophobicized precipitated silicas form, for example, the SI PERNAT® grades.
- Sipernat® D17 from Degussa or from EVONI K Industries, 64293 Darmstadt, Germany, is preferably used as fine-particle anticaking agent. Based on its weight, Sipernat® D17 contains about 2% by weight of chemically bonded carbon and is not wetted by water. His shaking weight (ge ISO 787-1 1) is 150 g / l. Its dso value is 10 ⁇ m (laser diffraction according to ISO 13320-1) and the specific surface area (nitrogen adsorption according to ISO 5794-1, Annex D) is 100 m 2 / g.
- finely divided anti-caking agent such.
- the additional amount of finely divided anti-caking agent is from 0.1 to 3% by weight, based on the weight of the finely divided mixed oxide BiiWs, O x .
- anti-caking agent also reduces the energy input required for homogeneous mixing of the two starting materials.
- the starting material as further finely divided shaping aids lubricant such as graphite, carbon black, polyethylene glycol, polyacrylic acid, stearic acid, starch, mineral oil, vegetable oil, water, boron trifluoride and / or boron nitride.
- lubricant such as graphite, carbon black, polyethylene glycol, polyacrylic acid, stearic acid, starch, mineral oil, vegetable oil, water, boron trifluoride and / or boron nitride.
- the finely divided graphite (typical dgo values of suitable graphite according to the invention is 30 to 300 ⁇ ) only the mixture of mixed oxide BiiWs, O x with the precursor of the stoichiometry [Moi2Z 1 c Z 2 dFe e Z 3 f Z 4 gZ 5 h O y ] added.
- it can also be mixed in advance of the mixing of the two finely divided starting materials in each of them (or in only one of the two). Based on the weight of the finely divided mixture of this z. B. up to 15 wt .-% of finely divided lubricant. In most cases, however, the lubricant content in the finely divided mixture is included
- finely divided lubricant is graphite.
- the aforementioned additional amount ä 0.5 wt .-% usually> 2.5 wt .-%.
- finely divided reinforcing agents such as microfibers made of glass, asbestos, silicon carbide or potassium titanate can be added to the finely divided mixture as further shaping aids, which after completion of shaping by compaction have a beneficial effect on the cohesion of the resulting compact (of the resulting shaped body).
- shaping aids which are present can be retained both in the resulting shaped catalyst body and at least partly by thermal and / or chemical decomposition to gaseous compounds (eg CO, CO2) gaseous escape from these.
- gaseous compounds eg CO, CO2
- the forming apparatus to be used or the forming method to be used are subject to no restriction.
- the compacting shaping can take place by extrusion, tabletting or extrusion.
- the finely divided mixture is preferably used dry to the touch. It can, however, z. B.
- the finely divided mixture may contain up to 10% of its total weight substances added, which are liquid under normal conditions (25 ° C, 1 atm).
- the finely divided mixture may contain solid solvates (eg, hydrates) having such liquid substances in chemically and / or physically bound form.
- the finely divided mixture but also be completely free of such substances.
- a compression molding method preferred according to the invention is tableting.
- the basic features of tabletting are z. B. in "The Tablet", Handbook of Development, Production and Quality Assurance, WA Ritschel and A. Bauer-Brandl, 2nd edition, Edition Verlag Aulendorf, described in 2002 and in a completely corresponding manner transferable to a tabletting invention according to the invention tabletting according to the invention as in the publications
- first carry out intermediate compaction as a first shaping step in order to coarsen the finely divided mixture (generally to a particle diameter of 100) to 2000 ⁇ , preferably 150 to 1500 ⁇ , more preferably 400 to 1250 ⁇ , or 400 to 1000 ⁇ , or 400 to 800 ⁇ ).
- finely divided lubricant eg., Graphite
- the final shaping wherein if necessary again z.
- fine-particle lubricant eg., Graphite
- optionally further shaping and / or reinforcing aid can be added.
- the desired geometry of the resulting shaped bodies is not subject to any restriction in the method according to the invention.
- the catalyst precursor moldings (the moldings) can be formed both regularly and irregularly, with regularly shaped moldings are generally preferred according to the invention.
- the shaped body in the method according to the invention have ball geometry.
- the ball diameter z. B. 2 to 10 mm, or 4 to 8 mm.
- the geometry of the catalyst precursor shaped body can also be fully cylindrical or hollow cylindrical (annular).
- outer diameter (A) and height (H) can be z. B. 2 to 10 mm, or 2 or 3 to 8 mm.
- the outer diameter may also be 1 to 10 mm.
- hollow cylinders is usually a wall thickness of 1 to 3 mm appropriate.
- catalyst precursor geometry but also all those geometries come into consideration, which are disclosed and recommended in WO 02/062737.
- the molding pressures applied in the course of densification of the finely divided mixture will generally be 50 kg / cm 2 to 5000 kg / cm 2 in the process according to the invention.
- the forming pressures are from 200 to 3500 kg / cm 2 , more preferably from 600 to 25000 kg / cm 2 .
- the shaping compaction in the method according to the invention should be carried out according to the teaching of DE 10 2008 040093, DE 10 2008 040094 and WO 2005/030393 so that the Side crushing strength SD of the resulting annular shaped body V
- SD is> 13 N and ⁇ 24 N, or> 14 N and ⁇ 22 N, and very particularly preferably> 15 N and ⁇ 20 N.
- the experimental determination of lateral compressive strength is as described in WO 2005/030393 and WO 2007 / 017431 described.
- ring-like shaped bodies as recommended by DE 10 2008 040093, are very particularly preferred according to the invention.
- the end face of annular or ring-like shaped bodies V can be both curved and not curved in the method according to the invention (cf., in particular, DE 10 2007 004961, EP-A 184 790 and DE 10 2008 040093). When determining the height of such geometric shaped body, such a curvature is not taken into account.
- Catalyst moldings obtainable according to the invention which have been prepared by thermal treatment of moldings which have been obtained by compacting finely divided starting material, are referred to as full catalysts (solid catalyst moldings).
- the ratio I / A (where I is the inner diameter of the ring geometry) is 0.3 to 0.7, preferably 0.4 to 0.7.
- Possible ring geometries for the aforementioned annular shaped bodies are thus (A ⁇ H ⁇ I) 5 mm ⁇ 2 mm ⁇ 2 mm, or 5 mm ⁇ 3 mm ⁇ 2 mm, or 5 mm ⁇ 3 mm ⁇ 3 mm, or 5.5 mm ⁇ 3 mm ⁇ 3.5 mm, or 6 mm ⁇ 3 mm ⁇ 4 mm, or 6.5 mm ⁇ 3 mm ⁇ 4.5 mm, or 7 mm ⁇ 3 mm ⁇ 5 mm, or 7 mm ⁇ 7 mm ⁇ 3 mm, or 7 mm ⁇ 7 mm ⁇ 4 mm.
- the thermal treatment of moldings according to the invention while retaining the geometric shaped catalyst bodies is generally carried out at temperatures within the scope of the process according to the invention (this means the temperature within the calcination material ) exceeding 350 ° C. Normally, however, the temperature of 650 ° C is not exceeded during the thermal treatment.
- the temperature of 600 ° C. preferably the temperature of 550 ° C. and particularly preferably the temperature of 500 ° C., is not exceeded within the scope of the thermal treatment.
- the thermal treatment of the molded body preferably the temperature of 380 ° C, advantageously the temperature of 400 ° C, with particular advantage the temperature of 420 ° C and most preferably the temperature of 440 ° C exceeded.
- the thermal treatment can also be divided into several sections in their time sequence. For example, first a thermal treatment at a temperature (phase 1) of 150 to 350 ° C, preferably 220 to 290 ° C, and thereafter a thermal treatment at a temperature (phase 2) of 400 to 600 ° C, preferably 430 to 550 ° C are performed.
- the thermal treatment of the moldings takes several hours (often more than 5 h) to complete. In many cases, the total duration of the thermal treatment extends to more than 10 h. Treatment times of 45 hours and 25 hours are usually not exceeded within the scope of the thermal treatment of the molded bodies. Often the total treatment time is less than 20 hours. In principle, the thermal treatment can be carried out at higher temperatures for a shorter treatment time or at temperatures that are not too high during a longer treatment duration. In an advantageous embodiment of the invention, the thermal treatment of the moldings 465 ° C are not exceeded and the treatment time in the temperature window> 440 ° C extends to> 10 to 20 h.
- the thermal treatment (also called phase 1 (also called the decomposition phase)) of the shaped bodies V can be carried out both under inert gas and under an oxidative atmosphere such as As air (or other mixture of inert gas and oxygen) and under a reducing atmosphere (eg., A mixture of inert gas, NH3, CO and / or H2 or under methane, acrolein, methacrolein) take place.
- a reducing atmosphere eg., A mixture of inert gas, NH3, CO and / or H2 or under methane, acrolein, methacrolein
- the thermal treatment can also be carried out under vacuum.
- the calcination atmosphere can also be made variable over the calcination period.
- the thermal treatment of the shaped bodies preferably takes place in an oxidizing atmosphere. In terms of application technology, it consists predominantly of stagnant or agitated air.
- the thermal treatment of the moldings in a variety of furnace types such.
- B. heated convection chambers (convection ovens), Hordenöfen, rotary kilns, Bandkalzinierern or shaft furnaces are performed.
- the thermal treatment of the shaped bodies V takes place in a belt calcination device, as recommended by DE-A 10046957 and WO 02/24620.
- a hot spot formation within the calcination material is thereby largely avoided by promoting increased volume flows of calcination atmosphere through the calcination material with the aid of fans through a gas-permeable conveyor belt carrying the calcination material.
- the thermal treatment of the moldings below 350 ° C usually pursues the goal of thermal decomposition of the sources contained in the moldings of the elements (the elemental constituents) of the desired Multielementoxid-I active composition of the shaped catalyst body and optionally co-used molding aids. Frequently, this decomposition phase takes place during the heating of the calcination good to temperatures> 350 ° C.
- the thermal treatment can be carried out as described in US 2005/0131253.
- the lateral compressive strengths of annular unsupported catalyst bodies obtainable according to the invention are from 5 to 13 N, frequently from 8 to 11, N.
- Full-catalyst shaped bodies produced in accordance with the invention may also be subjected to grinding and may be extruded from the resulting finely divided material (optionally after classifying the resulting finely divided material) with the aid of a suitable liquid binder (eg water) onto the surface of a suitable, e.g. B. spherical or annular support body (geometric carrier molding) are applied (eg., Using the in DE-A 2909671, and DE-A 100 51 419 disclosed method principle).
- a suitable liquid binder eg water
- a suitable, e.g. B. spherical or annular support body (geometric carrier molding) are applied (eg., Using the in DE-A 2909671, and DE-A 100 51 419 disclosed method principle).
- the resulting coated catalyst can be used as a catalyst for the aforementioned heterogeneously catalyzed gas phase partial oxidation, as z. B. WO 02/49757 and the
- carrier materials in the above procedure conventional porous or nonporous aluminas, silica, zirconia, silicon carbide or silicates such as magnesium or aluminum silicate can be used.
- the carrier bodies can be formed regularly or irregularly, with regularly shaped carrier bodies having a clearly formed surface roughness (for example the already mentioned balls or rings) being preferred.
- substantially non-porous, surface-rough rings of steatite whose longitudinal extension (longest direct straight line connecting two befind Norway on the surface of the Sug stresses body points) typically 2 to 12 mm, often 4 to 10 mm (see also DE-A 4442346).
- the aforementioned longitudinal extents also come for other carrier moldings such. B. balls, solid cylinders and other rings into consideration.
- the carrier mass is suitably selected in the range 10 to 1000 ⁇ , preferably in the range 100 to 700 ⁇ and particularly preferably in the range 300 to 500 ⁇ lying. Possible shell thicknesses are also 10 to 500 ⁇ or 200 to 300 ⁇ .
- the surface roughness Rz of the carrier molded body is in the range from 40 to 200 ⁇ m, often in the range from 40 to 100 ⁇ m (determined in accordance with DIN 4768 Part 1 with a "Hommel tester for DIN-ISO surface measured sizes" from Hommeltechnike, DE).
- the carrier material is non-porous (total volume of the pores based on the volume of the carrier body ⁇ 1% by volume).
- O x can be the precursor of stoichiometry [M o 12Z 1 c Z 2 d Fe 0 Z 3 fZ 4 e Z 5 hO ⁇ ] take place at a mold body also by allowing the fine-particle Apply mixture with the aid of a suitable liquid binder to the surface of a geometric carrier shaped body as described above. After drying, the resultant precursor moldings can be thermally treated in the manner according to the invention to obtain molded-sheet shaped catalyst bodies according to the invention.
- active catalyst powder bodies produced according to the invention it is also possible, by grinding active catalyst powder bodies produced according to the invention, to prepare as an active mass powder as such in the fluidized bed for the sen writings addressed heterogeneously catalyzed partial Gasphasenoxidatio- nen be used.
- geometrically shaped catalyst bodies which are obtainable according to the invention are particularly suitable as catalysts for the partial oxidations of propene to acrolein and of isobutene and / or tert. Butanol to methacrolein. This applies in particular to inventive annular unsupported catalyst bodies.
- the partial oxidation can be z. As in DE-A 10 2007 004961, WO 02/49757, WO 02/24620, DE 10 2008 040093, WO 2005/030393, EP-A 575 897, WO 2007/082827, WO 2005/1 13127, WO 2005/047224, WO 2005/042459 and WO 2007/017431 are described.
- the propene content (isobutene content or tert-butanol content (or the methyl ether content)) in the reaction gas starting mixture is generally (ie essentially independent of the load) 4 to 20% by volume, frequently 5 to 15% by volume. , or 5 to 12% by volume, or 5 to 8% by volume (in each case based on the total volume of the reaction gas starting mixture).
- the gas phase partial oxidation process is carried out at a volume ratio of the partially oxidized (organic) compound (eg propene): oxygen: indifferent gases (including water vapor) in the reaction gas starting mixture of 1: (1, 0 to 3.0) :( 5 to 25), preferably 1: (1, 5 to 2.3) :( 10 to 20).
- a volume ratio of the partially oxidized (organic) compound eg propene
- oxygen indifferent gases (including water vapor) in the reaction gas starting mixture of 1: (1, 0 to 3.0) :( 5 to 25), preferably 1: (1, 5 to 2.3) :( 10 to 20).
- Indifferent gases are understood to mean those gases which remain chemically unchanged in the course of the partial oxidation to at least 95 mol%, preferably at least 98 mol%.
- the inert gas may be> 20% by volume, or> 30% by volume, or> 40% by volume, or too
- % consist of molecular nitrogen.
- the concomitant use of inert diluent gases such as propane, ethane, methane, pentane, butane, CO, CO, water vapor and / or noble gases is recommended for the starting gas of the reaction gas .
- these inert gases and their mixtures can also be used even at lower loads on the catalyst feed with the organic compound to be partially oxidized.
- recycle gas can be used as diluent gas become. Under circulating gas is understood to mean the residual gas which remains when the target compound is essentially selectively separated from the product gas mixture of the partial oxidation.
- annular catalyst shaped articles k K may be only the first stage of a two-stage partial oxidation to acrylic acid or methacrylic acid as the actual target compounds, so that the recycle gas then usually takes place only after the second stage.
- the product mixture of the first stage as such, if appropriate after cooling and / or secondary oxygen addition, is as a rule fed to the second partial oxidation stage.
- the former compositions are particularly suitable for propene loadings of> 130 Nl / l-h and the latter composition in particular at propene loads ⁇ 130 Nl / l-h, in particular ⁇ 100 Nl / l-h of the fixed catalyst bed.
- Suitable alternative compositions of the starting reaction gas mixture are those which have the following component contents: 4 to 25% by volume of propene,
- the reaction gas starting mixture may also be composed as follows:
- reaction gas starting mixture composition may include:
- composition grid 34% by volume of H 2 O.
- reaction gas starting mixture may in particular also be composed as described in DE-A 44 07 020.
- reaction temperature for the propene partial oxidation is when using the z.
- annular shaped catalyst body often at 300 to 380 ° C. The same is true in the case of methacrolein as the target compound.
- reaction pressure for the abovementioned partial oxidations is generally 0.5 or 1.5 to 3 or 4 bar (meant in this document, unless explicitly stated otherwise, always absolute pressures).
- the total charge of the catalyst charge with starting reaction gas mixture in the abovementioned partial oxidations is typically 1000 to 10000 Nl / lh, usually 1500 to 5000 Nl / lh and often 2000 to 4000 Nl / lh.
- propene are mainly polymer grade propene and chemical grade propene into consideration, as z. B. DE-A 102 32 748 describes.
- the source of oxygen is usually air.
- the partial oxidation using the z. B. annular shaped catalyst body K can in the simplest case z. B. be carried out in a one-zone Dahlutton fixed bed reactor, as described in DE-A 44 31 957, EP-A 700 714 and EP-A 700 893.
- the contact tubes are made of ferritic steel and typically have a wall thickness of 1 to 3 mm. Their inner diameter is usually 20 to 30 mm, often 21 to 26 mm. A typical contact tube length amounts to z. B. at 3.20 m.
- the number of catalyst tubes accommodated in the tube bundle container amounts to at least 1000, preferably to at least 5000. Often the number of catalyst tubes accommodated in the reaction container is 15000 to 35000. Tube bundle reactors having a number of contact tubes above 40000 tend to be the exception.
- the contact tubes are normally distributed homogeneously, the distribution is suitably chosen so that the distance between the central inner axes of closest contact tubes (the so-called contact tube pitch) is 35 to 45 mm (see.
- the partial oxidation can also be carried out in a multizone (eg, "two-zone") multi-contact-tube fixed-bed reactor, as described in DE-A 199 10 506, DE-A 103 13 213, DE-A 103 13 208 and EP-A 1 106 598, in particular in the event of increased loading of the catalyst charge with the organic compound to be partially oxidized
- a typical catalyst tube length in the case of a two-zone multi-contact fixed bed reactor is 3.50 m
- a heat exchange medium is conducted in each temperature control zone around the catalyst tubes within which the catalyst feed is located, such as, for example, melts of salts such as potassium nitrate, potassium nitrite, sodium nitrite and / or sodium nitrate.
- the flow rate of the heat exchange medium within the respective temperature control zone is usually chosen so that the temperature of the heat from 0 to 15 ° C, often 1 to 10 ° C, or 2 to 8 ° C, or 3 to 6 ° C increases from the point of entry into the temperature zone to the point of exit from the temperature zone.
- the inlet temperature of the heat exchange medium, which, viewed over the respective temperature control zone, can be conducted in cocurrent or in countercurrent to the reaction gas mixture is preferably as in the specifications EP-A 1,106,598, DE-A 199 48 523, DE-A 199 48 248 , DE-A 103 13 209, EP-A 700 714,
- the heat exchange medium is preferably guided in meandering fashion.
- the multi-contact fixed-bed reactor also has thermo tubes for determining the gas temperature in the catalyst bed.
- the inner diameter of the thermo tubes and the diameter of the inner receiving sleeve for the thermocouple is selected so that the ratio of heat of reaction developing volume to heat dissipating surface is the same or only slightly different in thermal tubes and work tubes.
- the pressure loss should be at work tubes and thermotubes, based on the same
- GHSV be the same.
- a pressure loss compensation in the thermal tube can be done by adding split catalyst to the shaped catalyst bodies. This compensation is expediently homogeneous over the entire thermal tube length.
- To prepare the catalyst charge in the catalyst tubes can, as already mentioned, only as described available z.
- B. annular shaped catalyst bodies and no active material having, with respect to the heterogeneously catalyzed partial gas phase oxidation substantially inert behaving moldings are used. As materials for such inert molded body z.
- Example porous or non-porous aluminum oxides, silica, zirconium oxide, silicon carbide, silicates such as magnesium or aluminum silicate and / or steatite (eg., Type C220 Fa. CeramTec, 73207 Plochingen, Germany) into consideration.
- the geometry of such inert shaped diluent bodies can in principle be arbitrary. D. h., It may, for example, balls, polygons, solid cylinders or else, such as. B. in the case of annular shaped catalyst body, rings. Often one will choose as inert diluent moldings whose geometry corresponds to that of the catalyst molding to be diluted with them.
- the active composition of the catalyst molding can also be changed along the catalyst charge.
- the catalyst feed is advantageously designed so that the volume-specific (i.e., normalized to the unit of volume) activity in the flow direction of the reaction gas mixture either remains constant or increases (continuous, discontinuous or stepwise).
- a reduction of the volume-specific activity can be easily z. B. be achieved by a uniform amount of inventively produced z.
- B. annular catalyst form bodies with inert diluent bodies homogeneously diluted. The higher the proportion of the diluent molding is selected, the lower is the active material or catalyst activity contained in a certain volume of the feed.
- a reduction can also be achieved by changing the geometry of the shaped catalyst bodies K obtainable according to the invention such that the amount of active mass contained in the unit of the inner volume of the reaction tube becomes smaller.
- the catalyst feed is preferably designed either uniformly over the entire length with only one type of full-catalyst ring molding or structured as follows.
- At the reactor inlet is at a length of 10 to 60%, preferably 10 to 50%, more preferably 20 to 40% and most preferably 25 to 35% (ie, for., On a length of 0.70 to 1.50 m, preferably 0.90 to 1, 20 m), in each case the total length of the catalyst charge, a substantially homogeneous mixture of erhern ringförmigen Vollkatalysatorform stresses and inert dilution molded body according to the invention (both preferably have substantially the same geometry) placed, wherein the weight fraction the diluent molding (the mass densities of shaped catalyst bodies and diluent moldings usually differ only slightly) usually 5 to 40 wt .-%, or 10 to 40 wt .-%, or 20 to 40 wt .-%, or 25 to 35 wt .-% is.
- the weight fraction the diluent molding usually 5 to 40 wt .-%, or 10 to 40 wt .-%, or 20 to
- annular unsupported catalyst body obtainable in accordance with the invention can be charged with an active mass density based on its space requirement
- an annular unsupported catalyst body obtainable according to the invention with high active mass density based on its space requirement eg 6.5 mm ⁇ 3 mm ⁇ 4.5 mm [A ⁇ H ⁇ I] in the first section, and 5 x 2 x 2 mm in the second section.
- annular shaped catalyst bodies carried out as catalysts partial oxidation for the preparation of acrolein or methacrolein the catalyst charge, the starting reaction gas mixture, the load and the reaction temperature usually chosen so that the single passage of the reaction gas mixture through the catalyst feed a conversion of the partially oxidized organic compound (Propene, isobutene, tert-butanol or its methyl ether) of at least 90 mol%, or at least 92 mol%, preferably of at least 94 mol% results.
- the selectivity of the acrolein or methacrolein formation will regularly be 80 mol% or> 85 mol%. In the natural way, the lowest possible hotspot temperatures are sought.
- the activity and selectivity of target product formation initially increase with the service life of the catalyst feed before its age-related degradation occurs.
- This formation can be accelerated by carrying out the reaction at substantially constant conversion under increased loading of the catalyst charge with reaction gas starting mixture and, after completion of the largely completed formation, reducing the charge to its target value.
- geometric shaped catalyst bodies obtainable according to the invention are very generally used as catalysts for gas-phase catalytic partial oxidations 3 to 6 (ie 3, 4, 5 or 6) C atoms containing alkanes (in particular propane), alkanols, alkanals, alkenes and alkenals to z.
- FIGS. 1 a and 1 b show the size distribution of the particles of the Bi-W precipitate
- FIGS. 2a and 2b show the particle size distributions of the calcined initial mass A1 as a function of the applied dispersion pressure
- FIGS. 3a and 3b show the particle size distributions of the calcined and ground starting mass A1 as a function of the duration of the ultrasonic wave pretreatment
- the dry particle diameter distributions were determined by laser diffraction as follows.
- the multielement oxide powder was passed through a dispersing trough into the dry disperser Scirocco 2000 (Malvern Instruments, Worcestershire WR 14 1AT, United Kingdom), there with compressed air (which had the respective dispersing pressure of 1, 2 or 2 or 4.5 bar abs.) dry dispersed and in free jet to the dry disperser Scirocco 2000 (Malvern Instruments, Worcestershire WR 14 1AT, United Kingdom), there with compressed air (which had the respective dispersing pressure of 1, 2 or 2 or 4.5 bar abs.) dry dispersed and in free jet to the
- volume-related particle size distributions in suspension were measured with the
- Ultrasonic bath Hydro 2000 G from Malvern Instruments treated at 100% ultrasound intensity over a period of 1, 3 and 5 minutes.
- the suspension was then pumped directly into the laser diffraction spectrometer via a pump
- the filter cake was washed repeatedly with demineralized water until a conductivity of ⁇ 400 ⁇ was reached.
- the resulting filter cake was dried in a circulating air drying oven of the type T5060E (Heraeus, 63450 Hanau, Germany) at 110 ° C. until after 16 hours a weight constancy was reached.
- the Na content of the dried filter cake which was determined by flame atomic adsorption spectroscopy on a flame atomic adsorption spectrometer SpectrAA-700 (Spectro Analytical Instruments GmbH, 47533 Kleve, Germany), was below the detection limit.
- the molar Bi / W ratio determined by means of X-ray fluorescence analysis using a Axios sequence-sonic spectrometer (PANalytical GmbH, 34123 Kassel, Germany), was 2: 1 in this catalyst.
- the dried starting material A1 was then calcined in a rotary kiln (brand: Eigenbau BASF SE). In each case, 200 g of the dried powder were placed in a 1 l round bottom flask and calcined under air (air flow: 50 l / h) at a constant rotation of 10 rpm. The temperature increases were essentially linear over time. Within 4 h was from 25 ° C to 300 ° C. heated. The temperature was maintained for 12 hours and then raised to 800 ° C over 5 hours and 40 minutes. The temperature was then maintained for 3 hours. This was followed by a linear cooling to 25 ° C under 50 Nl / h air flow. The resulting dried starting material had an ignition loss of 11% by weight under the calcination conditions.
- phase composition of the calcined, finely divided starting material A1 was determined by means of X-ray diffractometry on an Advance D8 series 2 with a multiple sample changer (Bruker AXS GmbH, 76187 Düsseldorf, Germany).
- FIG. 4 shows the XRD diffractogram of the ground calcined starting material A1.
- the abscissa shows the diffraction angle in the 29-shell (2 theta scale) and the ordinate shows the absolute intensity of the X-ray radiation.
- the existing phases were 43% monoclinic WO3 and 57% orthorhomatic B12W2O9.
- Preparation of a finely divided starting material A2 Moi2Co5.5 Fe3, oSii, 6Ko, o8)
- Sipernat ® D17 containing finely divided starting material A1 was washed with a 1: 1 stoichiometry with the finely divided starting material A2 (total amount: 580 g containing 0.39 g of Sipernat) (in a amixon mixer type VMT 1 special model for BASF SE, Fa. amixon GmbH, 33106 Paderborn, Germany, filling volume: 1 l, power: 0.7 kW) are mixed homogeneously within 15 min by means of a clockwise rotating insert with 2 blades (rotational speed: 1 1 1 rpm). Based on the existing total mass were to this in a Rhönradmischer
- thermocouples were found in DE 10 201 1 084 040 A1. Subsequently, while maintaining the air flow (including its inlet temperature), the temperature in
- Um Kunststoffschachtofen varies as follows, with the temperature increases over time were essentially linear. Within 72 min was heated from 25 ° C to 130 ° C. The temperature was maintained for 72 minutes and then increased to 190 ° C over 36 minutes. The 190 ° C was held for 72 minutes before the temperature was raised to 220 ° C within 36 minutes. The 220 ° C was held for 72 minutes before the temperature was increased to 265 ° C within 36 minutes. The 265 ° C was held for 72 minutes before the temperature was raised to 380 ° C over 93 minutes. The 380 ° C was held for 187 min before the temperature was increased to 430 ° C within 93 min.
- the 430 ° C was held for 187 min before being increased within 93 min to the final temperature of 456 ° C. This was maintained for 467 min. Then within 24 h cooled to 25 ° C. For this purpose, both the heating of the Um Kunststoffschachtofens and the air flow heating was switched off (the air flow of 1200 Nl / h as such was maintained, the inlet temperature of the air flow was then 25 ° C). The loss on ignition under the calcination conditions was 26% by weight.
- BET Brunnerauer-Emmet plate
- FIG. 5 shows the XRD diffractogram of the calcined unsupported catalyst precursor body ES.
- the abscissa shows the diffraction angle in the 29-shell (2 theta scale) and the ordinate shows the absolute intensity of the X-ray radiation.
- Bismuth nitrate solution was adjusted to a pH of 1.0, and this pH was kept constant during the addition of the tungstic acid slurry.
- the molar Bi / W ratio was 1.74: 1.
- Bismuth nitrate solution was adjusted to a pH of 4.0 and this pH was kept constant during the addition of the tungstic acid slurry.
- the molar Bi / W ratio was 0.89: 1.
- Comparative Examples 2 and 3 show that a pH of 1.5 to 3 is critical to achieve a stoichiometric precipitation (Bi / W ratio of 2: 1).
- Full Catalyst Precursor Moldings VS The preparation of the full catalyst precursor molded article VS was carried out as described under I) for the unsupported catalyst molded article VS.
- the loss on ignition under the calcination conditions was 26% by weight.
- BET Brunnerauer-Emmet plate
- FIG. 6 shows the XRD diffractogram of the calcined unsupported catalyst precursor body VS.
- the abscissa shows the diffraction angle in the 29-shell
- reaction tube V2A steel; 21, 3 mm outside diameter, 3.2 mm wall thickness, 14.9 mm inside diameter, length 125 cm
- Section 1 approx. 25 cm in length
- Section 2 about 70 cm in length Catalyst charge with 40 g of the respective annular Vollkatalysatorform stressess diluted with 80 g steatite (C220 steatite from. CeramTec, 73207 Plochingen, Germany) with a diameter of 2 to 3 mm.
- the temperature of the reaction tube was carried out by means of a molten salt-externally heated molten salt (mixture of 53 wt .-% potassium nitrate, 40 wt .-% sodium nitrite and 7 wt .-% sodium nitrate).
- the reactor was continuously charged with a feed gas mixture (mixture of air, polymer grade propylene and nitrogen) of the composition:
- the COx selectivity with the non-inventive comparative catalyst VS also comparable.
- the value product selectivity is similar to that of the comparative catalyst VS.
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Abstract
Description
Claims
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US201562166692P | 2015-05-27 | 2015-05-27 | |
DE102015209638.6A DE102015209638A1 (de) | 2015-05-27 | 2015-05-27 | Verfahren zur Herstellung eines Bismut und Wolfram enthaltenden Multielementoxids durch Co-Präzipitation |
PCT/EP2016/061729 WO2016189010A1 (de) | 2015-05-27 | 2016-05-25 | Verfahren zur herstellung eines bismut und wolfram enthaltenden multielementoxids durch co-präzipitation |
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US (1) | US20160346768A1 (de) |
EP (1) | EP3302793A1 (de) |
JP (1) | JP2018516750A (de) |
CN (1) | CN107666959A (de) |
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GB2562115B (en) | 2017-05-05 | 2022-02-16 | William Blythe Ltd | Tungsten oxide |
US11745161B2 (en) | 2017-11-03 | 2023-09-05 | Basf Corporation | Arsine adsorbents |
CN109225204A (zh) * | 2018-10-19 | 2019-01-18 | 上海纳米技术及应用国家工程研究中心有限公司 | 用于四环素废水处理的钨酸铋纳米片可见光催化剂的制备及产品和应用 |
CN110841626B (zh) * | 2019-10-24 | 2022-06-21 | 江苏大学 | 一种氧化钨/氧化铋网-片复合材料及制备方法与用途 |
CN116139881B (zh) * | 2023-03-28 | 2023-12-12 | 上海腾灵建设集团有限公司 | 纳米金负载多孔钨酸铋光催化材料的制备及产品和应用 |
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-
2015
- 2015-05-27 DE DE102015209638.6A patent/DE102015209638A1/de not_active Withdrawn
-
2016
- 2016-05-25 US US15/164,097 patent/US20160346768A1/en not_active Abandoned
- 2016-05-25 WO PCT/EP2016/061729 patent/WO2016189010A1/de unknown
- 2016-05-25 EP EP16726299.7A patent/EP3302793A1/de not_active Withdrawn
- 2016-05-25 JP JP2017561274A patent/JP2018516750A/ja active Pending
- 2016-05-25 CN CN201680030785.4A patent/CN107666959A/zh active Pending
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JP2018516750A (ja) | 2018-06-28 |
DE102015209638A1 (de) | 2016-07-07 |
US20160346768A1 (en) | 2016-12-01 |
WO2016189010A1 (de) | 2016-12-01 |
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