EP2379223A2 - Katalysatorformkörper und verfahren zur herstellung von maleinsäureanhydrid - Google Patents
Katalysatorformkörper und verfahren zur herstellung von maleinsäureanhydridInfo
- Publication number
- EP2379223A2 EP2379223A2 EP09801445A EP09801445A EP2379223A2 EP 2379223 A2 EP2379223 A2 EP 2379223A2 EP 09801445 A EP09801445 A EP 09801445A EP 09801445 A EP09801445 A EP 09801445A EP 2379223 A2 EP2379223 A2 EP 2379223A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- shaped
- geo
- volume
- pore
- 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- Withdrawn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
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 239000011148 porous material Substances 0.000 claims abstract description 31
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 17
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N malonic acid group Chemical group C(CC(=O)O)(=O)O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 16
- 238000007254 oxidation reaction Methods 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000012018 catalyst precursor Substances 0.000 description 29
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000001354 calcination Methods 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 16
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 14
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- -1 vanadyl pyrophosphate Chemical compound 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 150000003018 phosphorus compounds Chemical class 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 4
- 150000003682 vanadium compounds Chemical class 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 238000002459 porosimetry Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- LOUORYQQOPCXGD-UHFFFAOYSA-N 2-methylpropan-1-ol Chemical compound CC(C)CO.CC(C)CO LOUORYQQOPCXGD-UHFFFAOYSA-N 0.000 description 2
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 2
- IWTBVKIGCDZRPL-UHFFFAOYSA-N 3-methylpentanol Chemical compound CCC(C)CCO IWTBVKIGCDZRPL-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- MZNDIOURMFYZLE-UHFFFAOYSA-N butan-1-ol Chemical compound CCCCO.CCCCO MZNDIOURMFYZLE-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical compound CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 150000002835 noble gases Chemical class 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 2
- USGIERNETOEMNR-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO.CCCO USGIERNETOEMNR-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000001618 (3R)-3-methylpentan-1-ol Substances 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- QMMOXUPEWRXHJS-HWKANZROSA-N (e)-pent-2-ene Chemical compound CC\C=C\C QMMOXUPEWRXHJS-HWKANZROSA-N 0.000 description 1
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- XRMVWAKMXZNZIL-UHFFFAOYSA-N 2,2-dimethyl-1-butanol Chemical compound CCC(C)(C)CO XRMVWAKMXZNZIL-UHFFFAOYSA-N 0.000 description 1
- SXSWMAUXEHKFGX-UHFFFAOYSA-N 2,3-dimethylbutan-1-ol Chemical compound CC(C)C(C)CO SXSWMAUXEHKFGX-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- LCFKURIJYIJNRU-UHFFFAOYSA-N 2-methylhexan-1-ol Chemical compound CCCCC(C)CO LCFKURIJYIJNRU-UHFFFAOYSA-N 0.000 description 1
- DUXCSEISVMREAX-UHFFFAOYSA-N 3,3-dimethylbutan-1-ol Chemical compound CC(C)(C)CCO DUXCSEISVMREAX-UHFFFAOYSA-N 0.000 description 1
- ZXNBBWHRUSXUFZ-UHFFFAOYSA-N 3-methyl-2-pentanol Chemical compound CCC(C)C(C)O ZXNBBWHRUSXUFZ-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- PCWGTDULNUVNBN-UHFFFAOYSA-N 4-methylpentan-1-ol Chemical compound CC(C)CCCO PCWGTDULNUVNBN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- WEBQSTQBNIKKTK-UHFFFAOYSA-N bismuth;ethyl hexanoate Chemical compound [Bi+3].CCCCCC(=O)OCC WEBQSTQBNIKKTK-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- GKMQWTVAAMITHR-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O.CCC(C)O GKMQWTVAAMITHR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- GWEFHNYDRUAGGI-UHFFFAOYSA-N ethanolate silicon(4+) Chemical compound [Si+4].CC[O-].CC[O-].CC[O-].CC[O-] GWEFHNYDRUAGGI-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZAPKJNQWQKICPZ-UHFFFAOYSA-N ethyl hexanoate nickel(2+) Chemical compound [Ni+2].CCCCCC(=O)OCC ZAPKJNQWQKICPZ-UHFFFAOYSA-N 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- SYJRVVFAAIUVDH-UHFFFAOYSA-N ipa isopropanol Chemical compound CC(C)O.CC(C)O SYJRVVFAAIUVDH-UHFFFAOYSA-N 0.000 description 1
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 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 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ZSSVQAGPXAAOPV-UHFFFAOYSA-K molybdenum trichloride Chemical compound Cl[Mo](Cl)Cl ZSSVQAGPXAAOPV-UHFFFAOYSA-K 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- QHMGFQBUOCYLDT-RNFRBKRXSA-N n-(diaminomethylidene)-2-[(2r,5r)-2,5-dimethyl-2,5-dihydropyrrol-1-yl]acetamide Chemical compound C[C@@H]1C=C[C@@H](C)N1CC(=O)N=C(N)N QHMGFQBUOCYLDT-RNFRBKRXSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- GJVFBWCTGUSGDD-UHFFFAOYSA-L pentamethonium bromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCC[N+](C)(C)C GJVFBWCTGUSGDD-UHFFFAOYSA-L 0.000 description 1
- PRCNQQRRDGMPKS-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O.CC(=O)CC(C)=O PRCNQQRRDGMPKS-UHFFFAOYSA-N 0.000 description 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- DFOXKPDFWGNLJU-UHFFFAOYSA-N pinacolyl alcohol Chemical compound CC(O)C(C)(C)C DFOXKPDFWGNLJU-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- HTSABYAWKQAHBT-UHFFFAOYSA-N trans 3-methylcyclohexanol Natural products CC1CCCC(O)C1 HTSABYAWKQAHBT-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/31—Density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/653—500-1000 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
Definitions
- the present invention relates to a shaped catalyst body and a process for the preparation of maleic anhydride by heterogeneously catalyzed gas phase oxidation and a process for the preparation of the catalyst.
- Maleic anhydride is an important intermediate in the synthesis of ⁇ -butyrolactone, tetrahydrofuran and 1,4-butanediol, which in turn are used as solvents or are further processed, for example, to polymers such as polytetrahydrofuran or polyvinylpyrrolidone.
- VPO catalysts vanadium, phosphorus and oxygen-containing catalysts, in particular catalysts based on vanadyl pyrophosphate (VO) 2P2Ü7 (so-called VPO catalysts) are used.
- the reaction is usually carried out in a salt bath-cooled shell and tube reactor. Depending on the size of the plant this has a few thousand to several tens of thousands of catalyst-filled pipes.
- the heat of reaction formed is transferred and removed via the wall of the catalyst-filled tubes to the surrounding SaIz-, usually a eutectic mixture of potassium and sodium nitrate and nitrite.
- the individual tubes have a relatively small cross-section, so that the heat of reaction can be dissipated uniformly and an accurate temperature control over the tube cross-section can be ensured.
- the reactors are as slim as possible and built high, so that the thermal stresses can be absorbed by the tube sheets.
- a pressure loss occurs due to friction of the gas flow to the particles.
- the pressure loss determines the pressure gradient that must be overcome between the reactor inlet and the reactor outlet.
- the thin and long configuration of the reaction tubes necessarily means a comparatively high pressure loss. Too high pressure losses are disadvantageous; they result in the need for higher compressor power, which increases plant investment and operating costs, or reduces reactor productivity with limited available compressor power.
- One way to reduce the pressure loss is to use low pressure loss molded catalyst body geometries. The molded body geometry determines the resistance that the catalyst particles oppose to the gas flowing through. Larger catalyst particles generally have a lower pressure drop, but at the same time the outer surface and thus the activity of the catalyst decreases, so that the yield and productivity decrease.
- No. 5,168,090 describes shaped catalyst bodies whose outer surface has at least one cavity and whose geometric volume corresponds to 30 to 67% of the volume of the void-free geometric shape and which have a ratio of the outer geometric surface to the geometric volume of at least 20 cm -1 US 5,168,090 cylinder with 3 equidistant grooves in the outer surface, which are parallel to the cylinder axis.
- WO 01/68245 discloses a catalyst for the production of maleic anhydride by heterogeneously catalyzed gas phase oxidation, which has a substantially hollow cylindrical structure, wherein the hollow cylindrical structure has a certain ratio of the height to the diameter of the opening passing through and a certain ratio of the geometric surface to the geometric Has volume.
- WO 03/078057 describes a catalyst for the preparation of maleic anhydride which comprises a catalytically active composition comprising vanadium, phosphorus and oxygen and has a substantially hollow cylindrical structure whose geometric density d p satisfies certain conditions.
- WO 2007/051 602 describes shaped catalyst bodies for the preparation of maleic anhydride, wherein the geometric base body enclosing the shaped catalyst body is a prism and the shaped catalyst body is provided with three through openings. The shaped catalyst body should have a triangular cross-section with rounded vertices.
- the present invention has for its object to provide a method for producing maleic anhydride by heterogeneously catalyzed gas-phase oxidation of a hydrocarbon, which combines a lower pressure drop with a high yield.
- the object is achieved by a shaped catalyst body whose catalytically active composition comprises a vanadium and phosphorus-containing multielement oxide which is characterized in that the specific pore volume PV (in ml / g) of the shaped catalyst body, the bulk density p of the shaped catalyst body (in kg / l ), the geometric surface A geo (in mm 2 ) and the geometric volume V geo (in mm 3 ) of the shaped catalyst body satisfy the condition:
- bulk density p is the bulk density of the shaped catalyst body in a circular section tube having an inner diameter of 21 mm.
- the bulk density of the shaped catalyst body depends on the size and shape of the cross section of the reaction tube because the packing density of the material is lower on the walls (edge effect).
- Conventional reaction tubes generally have a diameter of 20 to 25 mm.
- the bulk density p is expediently determined by filling a model tube of known volume with shaped catalyst bodies and determining the weight of the shaped catalyst bodies.
- the bulk density determined in the present case using a model tube is a sufficient approximation to the bulk density of the shaped catalyst body in conventional reaction tubes.
- the bulk density p of the shaped catalyst body in the reaction tube influences the observed pressure loss, wherein the pressure loss generally increases with increasing bulk density.
- the bulk density p is less than 0.60 kg / l, preferably less than 0.55 kg / l, especially less than 0.50 kg / l, e.g. B. 0.40 to 0.50 kg / l.
- the specific pore volume PV is the (integral) specific pore volume determined by mercury porosimetry according to DIN No. 66133.
- Mercury behaves as a non-wetting liquid to most solids. Therefore, mercury is not spontaneously absorbed by the porous material, but penetrates into the pores of the solid sample only under an external pressure. The amount of pressure depends on the size of the pores. This behavior is exploited in Hg porosimetry to detect the pore radius when applied externally through the volumetrically detected intrusion.
- the specific pore volume PV is at least 0.30 ml / g, preferably at least 0.35 ml / g, e.g. From 0.38 to 0.50 ml / g.
- At least 15% of the specific pore volume is formed by pores of a size of 0.3 to 20 ⁇ m. It has been found that shaped catalyst bodies with a high proportion of pores in this size range lead to an increase in activity. These pores probably act as so-called transport pores.
- the geometric shape of the shaped catalyst bodies is not subject to any particular restrictions. It may be prisms, cylinders or other shaped body geometries that can be produced inexpensively, for. B. by extrusion or tabletting, and provide sufficient mechanical stability.
- the ratio of the geometric surface A geo to the geometric volume V geo is preferably at least 1, 50 mm- 1 , z. 1, 50 to 2.60 mm- 1 , more preferably at least 1.60 mm- 1 , in particular at least 1.85 mm- 1 .
- the geometric volume and the geometric surface can be calculated from corresponding measurements of the perfect underlying geometric shapes. For example, the geometric volume and the geometric surface of a hollow cylinder can be calculated based on the height h of the cylinder, the outer diameter di and the diameter of the inner bore 62.
- the geometric surface Ageo is an idealized size and does not take into account the increase in surface area due to the porosity or surface roughness of the moldings.
- the ratio A ge oA / geo can be increased by providing cavities or recesses on the outer surfaces of the molding or holes through the molding.
- the recesses can z. B. grooves, which extend parallel to the longitudinal axis or helically in the shell of a cylinder.
- Catalyst shaped bodies having a substantially cylindrical body with a longitudinal axis have proved successful, the cylindrical body having at least one, e.g. Having one to four, to the cylinder axis of the body substantially parallel, continuous inner bore.
- Particularly preferred shaped catalyst bodies have one or four internal bores.
- the term "substantially” indicates that deviations from the ideal geometry, such as slight deformations of the circular structure, non-plane parallel lid surfaces, chipped corners and edges, surface roughness or indentations in the lateral surface, the cover surfaces or the inner surface of the holes passing through Catalyst shaped bodies according to the invention are also included.
- the inner bores preferably have a round or oval cross section, in particular a round cross section. In general, all internal bores have the same cross-section.
- the central axes of the inner bores preferably lie equidistantly on a cylinder jacket which is concentric with the jacket of the cylindrical body.
- the ratio of the diameter 62 of an inner bore to the outer diameter di of the cylindrical body is 0.2 to 0.35.
- the ratio of the diameter dß of the cylinder jacket, on which the central axes of the inner bores lie, to the outer diameter di of the cylindrical body is 0.8 to 0.9.
- both the smallest distance of the inner bores with each other and the smallest distance of the inner bores to the outer surface of the body is at least 7% of the diameter di of the cylindrical body.
- the ratio of the height h of the cylindrical body to the diameter d2 of the inner bores is preferably at most 3.4, in particular 2.0 to 2.35.
- the lateral compressive strength of the shaped catalyst bodies is preferably at least 8 N, in particular at least 10 N. If the shaped body is not rotationally symmetrical and the lateral compressive strength depends on the orientation of the shaped body with respect to the applied force, then the lowest lateral compressive strength is considered as lateral compressive strength.
- the invention also relates to a process for producing a shaped catalyst body in which a vanadium and phosphorus-containing multielement oxide or a precursor therefor (hereinafter also referred to as catalyst precursor or precursor powder) is mixed with a pore former, the mixture is shaped into shaped bodies and the shaped bodies are calcined ,
- the pore-forming agent is particulate and in particular has a particle size distribution with an average particle diameter d 50 in the range of 1 to 80 microns.
- the determination of the particle size distribution is suitably carried out using a Malvern Mastersizer S laser diffraction meter from Malvern Instruments and a RODOS dry-dosing dispersing system from Sympatec.
- the multielement oxide or its precursor has a particle size distribution with an average particle diameter d 50 in the range of 50 to 70 microns.
- the mean particle size distribution can suitably be determined as a suspension in isobutanol by laser diffraction (Malvern Mastersizer S with wet dispersing unit MS1).
- the phosphorus / vanadium atomic ratio in the catalytically active composition of the catalyst is generally from 0.9 to 1.5, preferably from 0.9 to 1.2, in particular from 1.0 to 1.1.
- the average oxidation state of the vanadium is preferably +3.9 to +4.4 and preferably 4.0 to 4.3.
- Suitable active compounds are described, for example, in the patents US 5,275,996, US Pat. No. 5,641,722, US Pat. No. 5,137,860, US Pat. No. 5,095,125 or US Pat. No. 4,933,312.
- the catalysts of the invention may further contain so-called promoters.
- Suitable promoters are the elements of groups 1 to 15 of the periodic table and their compounds. Suitable promoters are described, for example, in the published specifications WO 97/12674 and WO 95/26817 and in the patents US 5,137,860, US 5,296,436, US 5,158,923 and US 4,795,818.
- Preferred promoters are compounds of the elements cobalt, molybdenum, iron, zinc, hafnium, zirconium, lithium, titanium, chromium, manganese, nickel, copper, boron, silicon,.
- the promoted catalysts of the invention may contain one or more promoters.
- the content of promoters in total in the finished catalyst is generally not more than about 5 wt .-%, each as Oxide calculated.
- Preferred catalysts are those which do not contain promoters and those which contain molybdenum or iron.
- VPO precursor vanadium, phosphorus, oxygen-containing catalyst precursor
- the dried, preferably tempered VPO precursor powder can then optionally powdered carrier material and / or a pore former may be mixed.
- the molding is preferably carried out by tabletting, preferably with prior sub-mixing of a so-called lubricant, such as graphite.
- the mechanical and catalytic properties of the catalyst can be influenced.
- pentavalent vanadium compounds oxides, acids and inorganic and organic salts containing pentavalent vanadium or mixtures thereof can be used.
- the pentavalent vanadium compounds present as solids are used in the form of a powder, preferably in a particle size range of 50 to 500 ⁇ m.
- phosphorus compounds As phosphorus compounds, reducing phosphorus compounds such as phosphorous acid, as well as pentavalent phosphorus compounds such as phosphorus pentoxide (P2O5), orthophosphoric acid (H3PO4), phosphoric acid (H4P2O7), polyphosphoric acids of the general formula H n + 2Pn ⁇ 3n + i with n> 3 or their mixtures are used.
- pentavalent phosphorus compounds is preferred.
- the content of said compounds and mixtures in wt .-%, based on H3PO4 on.
- the reducing solvent used is preferably a primary or secondary, noncyclic or cyclic, unbranched or branched, saturated alcohol having 3 to 6 carbon atoms and mixtures thereof. Preference is given to the use of a primary or secondary unbranched or branched C 3 to C 6 alkanol or the use of cyclopentanol or cyclohexanol.
- Suitable alcohols are n-propanol (1-propanol), isopropanol (2-propanol), n-butanol (1-butanol), sec-butanol (2-butanol), isobutanol (2-methyl-1-propanol), 1 Pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 2, 2-dimethyl-1-propanol, 1-hexanol, 2 Hexanol, 3-hexanol, 2-methyl-1-hexanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2, 2 Dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butano
- n-propanol (1-propanol), n-butanol (1-butanol), isobutanol (2-methyl-1-propanol), 1-pentanol, 2-methyl-1-butanol, 3-methyl-1 butanol and cyclohexanol, especially isobutanol.
- the assembly of the components can be done in different ways, for example in a stirred tank.
- the amount of reducing solvent should be greater than the stoichiometric amount required to reduce vanadium from +5 oxidation state to +3.5 to +4.5 oxidation state.
- the amount of the reducing solvent to be added is at least such that it is sufficient for the slurry of the pentavalent vanadium compound, which allows intensive mixing with the phosphorus compound to be added.
- the slurry is heated to react the said compounds and form the catalyst precursor.
- the temperature range to be selected depends on various factors, in particular the reduction effect and the boiling point of the components. In general, a temperature of 50 to 200 0 C, preferably from 100 to 200 0 C, a.
- the reaction at elevated temperature generally takes several hours.
- Promoter compounds can be added at any time.
- Suitable promoter compounds are, for example, the acetates, acetylacetonates, oxalates, oxides or alkoxides of the abovementioned promoter metals, such as cobalt acetate, cobalt (II) acetylacetonate, cobalt (II) chloride, molybdenum (VI) oxide, molybdenum (III ) - chloride, iron (III) acetylacetonate, iron (III) chloride, zinc (II) oxide, zinc (II) acetyl acetonate, lithium chloride, lithium oxide, bismuth (III) chloride, bismuth (III) - ethylhexanoate, nickel (II) ethylhexanoate, nickel (II) oxalate, zirconyl chloride, zirconium (IV) butoxide, silicon (IV) ethoxid
- the catalyst precursor formed is isolated, it being possible, if appropriate, to interpose a cooling phase and also a storage or aging phase of the cooled reaction mixture before isolation.
- the solid catalyst precursor is separated from the liquid phase. Suitable methods are for example filtering, decanting or centrifuging.
- the catalyst precursor is isolated by filtration.
- the isolated catalyst precursor can be further processed unwashed or washed.
- the isolated catalyst precursor is washed with a suitable solvent to remove, for example, still adhering reducing agent (eg alcohol) or its degradation products.
- suitable solvents are, for example, alcohols (eg methanol, ethanol, 1-propanol, 2-propanol), aliphatic and / or aromatic hydrocarbons (eg pentane, hexane, benzines, benzene, toluene, xylene), ketones (eg B.
- ethers eg, 1, 2-dimethoxyethane, tetrahydrofuran, 1, 4-dioxane
- 2-propanone and / or methanol and particularly preferably methanol preference is given to using 2-propanone and / or methanol and particularly preferably methanol.
- the solid is generally dried.
- the drying can be carried out under different conditions. In general, they are carried out under reduced pressure or atmospheric pressure.
- the drying temperature is usually 30 to 250 0 C.
- the drying is carried out at a pressure of 1 to 30 kPa abs and a temperature of 50 to 200 0 C under oxygen-containing or oxygen-free residual gas atmosphere, such as air or nitrogen.
- the catalyst precursor powder is thoroughly mixed with about 2 to 4% by weight of graphite and precompressed.
- the precompressed particles are tabletted into the shaped catalyst body.
- Precursor powder mixed intensively with a pore-forming agent and further treated and shaped as described above.
- it is carbon, hydrogen, oxygen and / or nitrogen-containing compounds, which are removed in the subsequent activation of the catalyst under sublimation, decomposition and / or evaporation for the most part again.
- the finished catalyst may contain residues or decomposition products of the pore-forming agent.
- Suitable pore formers are z.
- fatty acids such as palmitic acid or stearic acid
- dicarboxylic acids such as oxalic acid or malonic acid, cyclodextrins or polyethylene glycols.
- malonic acid is preferred.
- the shaping is preferably carried out by tableting.
- Tableting is a process of press agglomeration.
- a powdery bulk material is introduced into a pressing tool with a so-called die between two punches and compacted by uniaxial compression and formed into a solid compressed. This process is divided into four sections: dosage, compaction (elastic
- the upper punch and / or lower punch on outstanding spines.
- the molded VPO precursor is preformed (calcined) by heating in an atmosphere containing oxygen (O 2), hydrogen oxide (H 2 O) and / or inert gas in a temperature range of 250 to 600 ° C.
- oxygen O 2
- hydrogen oxide H 2 O
- inert gas inert gases are nitrogen, carbon dioxide and noble gases.
- the calcination can be carried out batchwise, for example in a shaft furnace, tray furnace, muffle furnace or heating cabinet or continuously, for example in a rotary tube, belt calciner or rotary ball furnace. It may successively contain various portions in terms of temperature such as heating, keeping the temperature constant or cooling and successively different portions with respect to the atmospheres such as oxygen-containing, water vapor-containing, oxygen-free gas atmospheres. Suitable preforming methods are described, for example, in US Pat. Nos. 5,137,860 and 4,933,312 and WO 95/29006. Particularly preferred is the continuous calcination in a Bandcalcinierofen with at least two, for example, two to ten calcination zones, which optionally have a different gas atmosphere and a different temperature. By suitable, adapted to the respective catalyst system combination of temperatures, treatment times and gas atmospheres, the mechanical and catalytic properties of the catalyst can be influenced and thus adjusted specifically.
- step (i) the catalyst precursor is reacted in an oxidizing atmosphere having a molecular oxygen content of generally 2 to 21% by volume and preferably 5 to 21% by volume at a temperature of 200 to 350 ° C and preferably from 250 to 350 ° C for a time effective to set the desired average oxidation state of the vanadium.
- oxidizing atmosphere having a molecular oxygen content of generally 2 to 21% by volume and preferably 5 to 21% by volume at a temperature of 200 to 350 ° C and preferably from 250 to 350 ° C for a time effective to set the desired average oxidation state of the vanadium.
- inert gases eg nitrogen or argon
- hydrogen oxide water vapor
- / or air and air are used. From the point of view of the catalyst precursor passed through the calcination zone (s), the temperature during the Calcination step (i) are kept constant, increase or decrease on average.
- step (i) Since the step (i) is generally preceded by a heating phase, the temperature will usually increase initially, and then settle at the desired final value. In general, therefore, the calcination zone of step (i) is preceded by at least one further calcination zone for heating the catalyst precursor.
- the period over which the heat treatment in step (i) is maintained is preferably selected in the process according to the invention such that a mean oxidation state of the vanadium has a value of +3.9 to +4.4, preferably +4 , 0 to +4,3.
- the period of time required is advantageously to be determined experimentally in preliminary experiments. As a rule, this is a series of measurements in which it is annealed under defined conditions, the samples after different times removed from the system, cooled and analyzed with respect to the mean oxidation state of the vanadium.
- the time required in step (i) is generally dependent on the nature of the catalyst precursor, the set temperature and the selected gas atmosphere, in particular the oxygen content.
- the period at step (i) extends to a duration of over 0.5 hours, and preferably over 1 hour.
- a period of up to 4 hours, preferably up to 2 hours is sufficient to set the desired average oxidation state.
- a period of over 6 hours may also be required.
- the catalyst intermediate obtained is stored in a non-oxidizing atmosphere containing ⁇ 0.5% by volume of molecular oxygen and 20 to 75% by volume, preferably 30 to 60%, of hydrogen oxide (water vapor) Vol .-% at a temperature of 300 to 500 0 C and preferably from 350 to 450 0 C over a period of> 0.5 hours, preferably 2 to 10 hours and more preferably 2 to 4 hours leave.
- the non-oxidizing atmosphere generally contains nitrogen and / or noble gases, such as, for example, argon, in addition to the abovementioned hydrogen oxide, although this is not intended to be limiting. Gases, such as carbon dioxide are suitable in principle.
- the non-oxidizing atmosphere preferably contains> 40% by volume of nitrogen.
- step (ii) From the point of view of cini mecanicszone (n) guided catalyst precursor, the temperature during the calcination step (ii) can be kept constant, average rise or fall. If step (ii) is carried out at a temperature which is higher or lower than step (i), there is generally a heating or cooling phase between steps (i) and (ii), which is optionally implemented in a further calcination zone . To facilitate improved separation to the oxygen-containing atmosphere of step (i), this further calcination zone may be purged between (i) and (ii), for example, for purging with inert gas, such as nitrogen. Preferably, step (ii) is carried out at a temperature higher by 50 to 150 ° C. than step (i).
- the calcination comprises a further step (iii) to be carried out after step (ii), in which the calcined catalyst precursor in an inert gas atmosphere to a temperature of ⁇ 300 0 C, preferably of ⁇ 200 0 C and especially preferably from ⁇ 150 0 C cools.
- further steps are possible in the calcination according to the inventive method.
- further steps include, for example, changes in temperature (heating, cooling), changes in the gas atmosphere (conversion of the gas atmosphere), further holding times, transfers of the catalyst intermediate into other apparatus or interruptions of the entire calcination process.
- the catalyst precursor usually has a temperature of ⁇ 100 ° C. before the beginning of the calcination, this is usually to be heated before step (i).
- the heating can be carried out using various gas atmospheres.
- the heating is carried out in an oxidizing atmosphere as defined under step (i) or in an inert gas atmosphere as defined under step (iii).
- a change of the gas atmosphere during the heating phase is possible.
- the heating in the oxidizing atmosphere which is also used in step (i).
- the invention further provides a process for the preparation of maleic anhydride, wherein a hydrocarbon having at least four carbon atoms in the presence of an oxygen-containing gas is brought into contact with a bed of shaped catalyst bodies according to the invention in at least one reaction tube.
- a hydrocarbon having at least four carbon atoms in the presence of an oxygen-containing gas is brought into contact with a bed of shaped catalyst bodies according to the invention in at least one reaction tube.
- reactors tube bundle reactors are generally used. Suitable tube bundle reactors are described for example in EP-B 1 261 424.
- Suitable hydrocarbons in the process according to the invention are aliphatic and aromatic, saturated and unsaturated hydrocarbons having at least four carbon atoms, for example 1,3-butadiene, 1-butene, 2-cis-butene, 2-trans-butene, n-butane, C 4 - Mixture, 1, 3-pentadiene, 1, 4-pentadiene, 1-pentene, 2-cis-pentene, 2-trans-pentene, n-pentane, cyclopentadiene, dicyclopentadiene, cyclopentene, cyclopentane, C 5 -mixture, hexenes , Hexanes, cyclohexane and benzene.
- propane, n-butane or benzene particularly preferred is the use of n-butane, for example as pure n-butane or as a component in n-butane-containing gases and liquids.
- n-butane used may, for example, come from natural gas, from steam crackers or FCC crackers.
- the addition of the hydrocarbon is generally quantity controlled, d. H. under constant specification of a defined amount per time unit.
- the hydrocarbon can be metered in liquid or gaseous form.
- the dosage in liquid form with subsequent evaporation before entering the tube bundle reactor unit.
- oxygen-containing gases such as air, synthetic air, an oxygen-enriched gas or so-called "pure", z. B. originating from the air separation oxygen. Also, the oxygen-containing gas is added volume controlled.
- the inventive method is carried out at a temperature of 250 to 500 0 C. Under the said temperature, regardless of the type of reactor, in each case the mean temperature of the heat transfer medium to understand.
- the inventive method is preferably carried out at a temperature of 380 to 460 0 C and more preferably 380 to 440 0 C performed.
- propane the inventive method is preferably carried out between 250 and 350 0 C.
- benzene the inventive method is preferably carried out between 330 and 450 0 C.
- the process according to the invention is advantageously carried out isothermally, with a temperature control increasing over the reactor length or with a combination of temperature control increasing over the reactor length and isothermal mode of operation.
- the process according to the invention is advantageously carried out at an oxygen partial pressure of from 0.6 bar to 50 bar, preferably from 2 bar to 50 bar, more preferably from 3 bar to 50 bar, in particular from 4 bar to 50 bar.
- the hydrocarbon concentration of the input stream fed to the reactor unit is 0.5 to 10% by volume, preferably 0.8 to 10% by volume, more preferably 1 to 10% by volume and very particularly preferably 2 to 10% by volume .-%.
- the hydrocarbon conversion per reactor passage is 40 to 100%, preferably 50 to 95%, particularly preferably 70 to 95% and in particular 85 to 95% of the hydrocarbon from the input stream.
- a GHSV gas hourly space velocity
- the process according to the invention can be carried out in two preferred process variants, the "straight through” variant and the “recirculation” variant.
- the "straight pass” maleic anhydride and optionally oxygenated hydrocarbon by-products are removed from the reactor effluent and the remaining gas mixture is discharged and optionally thermally recovered.
- the “recycling” is also removed from the reactor effluent maleic anhydride and optionally oxygenated hydrocarbon by-products, the remaining gas mixture containing unreacted hydrocarbon, completely or partially recycled to the reactor.
- Another variant of the "recycling" is the removal of the unreacted hydrocarbon and its return to the reactor.
- reaction products or the product stream can be diluted by adding substances which are inert under reaction conditions, such as, for example, water or nitrogen at the end of the reactor or at the reactor outlet, so that a non-explosive product stream is obtained.
- a non-explosive product stream can be achieved by a pressure stage.
- This product stream can then be processed with the conventional workup units.
- n-butane to provide a long catalyst life and further increase in conversion, selectivity, yield, catalyst loading, and space / time yield, the gas is advantageously fed to the gas in the process of this invention a volatile phosphorus compound.
- Volatile phosphorus compounds are understood as meaning all those phosphorus-containing compounds which are gaseous in the desired concentration under the conditions of use.
- the volatile phosphorus compound used is preferably triethyl phosphate or trimethyl phosphate.
- geometric surface A geo geometric surface of the moldings [mm 2 ]
- XTEP triethyl phosphate concentration of the input stream
- GHSV the amount of the input current based on the at 0 0 C and 0.1013 MPa abs volume normalized volume of the supplied input current and based on the reaction, which is filled with catalyst
- shaped catalyst bodies are freed from dust and debris by a slight sieve movement on a sieve with a mesh width of 5 mm. These moldings are filled via a vibrating trough in a period of 180 to 200 s in a reaction tube having a length of 650 cm and 21 mm inner diameter up to a filling height of 600 cm ⁇ 1 cm. Care is taken to ensure that it is filled evenly and that the filling time is within the defined range. When reaching the filling level (600 cm ⁇ 1 cm), the mass of the filled catalyst is determined.
- the bulk density m (catalyst) in kg / V (reactor) in L, where V (reactor) is the product of fill level and pipe cross section.
- the shaped catalyst bodies with the rounded side surface were respectively placed on the flat metal support plate of a corresponding measuring device in successive measurements.
- the two plane-parallel cover surfaces were thus in the vertical direction.
- a flat metal stamp was fed from above at a feed rate of 1, 6 mm / min to the shaped catalyst body and recorded the time course of the action of force on the shaped catalyst body until its breakage.
- the lateral compressive strength of the individual shaped catalyst body corresponds to the maximum force applied.
- the resulting dried powder was then tempered for 2 hours under air in a rotary tube having a length of 6.5 m, an inner diameter of 0.9 m and internal helical coils.
- the speed of the rotary tube was 0.4 U / min.
- the powder was fed into the rotary kiln at a rate of 60 kg / h.
- the air supply was 100 m 3 / h.
- the temperatures measured directly on the outside of the rotary tube of the five heating zones of the same length were 250 ° C., 300 ° C., 340 ° C., 340 ° C. and 340 ° C.
- the catalyst precursor was admixed with 1% by weight. Graphite intimately mixed and compacted in a roller compactor.
- the catalyst precursor powder was mixed with the amount of malonic acid as pore former indicated in the table.
- the catalyst precursor powder or the mixture with malonic acid was dissolved in a tabletting machine. machine to hollow cylinders or cylinders with four through holes of the dimensions indicated in the table (outer diameter di * height h * diameter of the bore (s) d2).
- the tableted catalyst precursor samples were added sequentially to a belt calciner and calcined as follows, with residence time in each zone of about 1.78 hours.
- the pilot plant was equipped with a feed unit and a reactor tube.
- the replacement of a tube bundle reactor by a reactor tube is very well possible on a laboratory or pilot plant scale, provided that the dimensions of the reactor tube are in the range of a technical reactor tube.
- the plant was operated in a "straight passage".
- the hydrocarbon was added in a controlled amount in liquid form via a pump. As an oxygen-containing gas, air was added volume controlled. Triethyl phosphate (TEP) was also added in a controlled amount, dissolved in water, in liquid form.
- TEP Triethyl phosphate
- the tube bundle reactor unit consisted of a tube bundle reactor with a reactor tube.
- the length of the reactor tube was 6.5 m, the inner diameter 22.3 mm.
- a multi-thermocouple with 20 temperature measuring points was located in a protective tube with an outer diameter of 6 mm.
- the temperature of the reactor was carried out by a heat transfer circuit with a length of 6.5 m.
- a molten salt was used.
- the reactor tube was flowed through by the reaction gas mixture from top to bottom.
- the upper 0.2 m of the 6.5 m long reactor tube remained unfilled. This was followed by a 0.3 meter preheat zone filled with steatite shaped bodies as inert material.
- the catalyst bed followed, which contained a total of 2173 ml of catalyst.
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DE102005061382A1 (de) * | 2005-12-21 | 2007-06-28 | Basf Ag | Umwandlung eines Präkatalysators in eine katalytisch aktive Silber-Vanadiumoxid-Bronze |
US8143461B2 (en) * | 2006-09-05 | 2012-03-27 | Huntsman Petrochemical Llc | Maleic anhydride catalyst and method for its preparation |
KR101392580B1 (ko) | 2007-01-19 | 2014-05-21 | 바스프 에스이 | 그의 활성 덩어리가 다원소 산화물인 촉매 성형체의 제조 방법 |
-
2009
- 2009-12-21 WO PCT/EP2009/067657 patent/WO2010072721A2/de active Application Filing
- 2009-12-21 US US13/141,179 patent/US20110257414A1/en not_active Abandoned
- 2009-12-21 EP EP09801445A patent/EP2379223A2/de not_active Withdrawn
- 2009-12-21 CN CN2009801572043A patent/CN102325593A/zh active Pending
Non-Patent Citations (1)
Title |
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SABRI ERGUN: "Fluid Flow Through Packed Columns", CHEMICAL ENGINEERING PROGRESS, vol. 48, no. 2, February 1952 (1952-02-01), pages 89 - 94, XP003030812 |
Also Published As
Publication number | Publication date |
---|---|
WO2010072721A2 (de) | 2010-07-01 |
US20110257414A1 (en) | 2011-10-20 |
WO2010072721A3 (de) | 2010-10-28 |
CN102325593A (zh) | 2012-01-18 |
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