WO2012101567A2 - Catalyst support produced by flame spray pyrolysis and catalyst for autothermal propane dehydrogenation - Google Patents
Catalyst support produced by flame spray pyrolysis and catalyst for autothermal propane dehydrogenation Download PDFInfo
- Publication number
- WO2012101567A2 WO2012101567A2 PCT/IB2012/050303 IB2012050303W WO2012101567A2 WO 2012101567 A2 WO2012101567 A2 WO 2012101567A2 IB 2012050303 W IB2012050303 W IB 2012050303W WO 2012101567 A2 WO2012101567 A2 WO 2012101567A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- pyrolysis
- particles
- carrier
- zirconium
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims description 22
- 238000006356 dehydrogenation reaction Methods 0.000 title claims description 16
- 239000001294 propane Substances 0.000 title claims description 11
- 238000005118 spray pyrolysis Methods 0.000 title description 7
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 37
- 238000000197 pyrolysis Methods 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000443 aerosol Substances 0.000 claims abstract description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 229910052792 caesium Inorganic materials 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 5
- 239000001273 butane Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 1
- YJZXDFOVSQRRHO-UHFFFAOYSA-N C(CCCCC)(=O)OCC.[Zr+4] Chemical compound C(CCCCC)(=O)OCC.[Zr+4] YJZXDFOVSQRRHO-UHFFFAOYSA-N 0.000 claims 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 2
- 229910052845 zircon Inorganic materials 0.000 abstract 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 239000007789 gas Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001694 spray drying Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 239000012159 carrier gas Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000002737 fuel gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 3
- TVCBSVKTTHLKQC-UHFFFAOYSA-M propanoate;zirconium(4+) Chemical compound [Zr+4].CCC([O-])=O TVCBSVKTTHLKQC-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 2
- OFYFURKXMHQOGG-UHFFFAOYSA-J 2-ethylhexanoate;zirconium(4+) Chemical compound [Zr+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O OFYFURKXMHQOGG-UHFFFAOYSA-J 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- -1 siloxanes Chemical class 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- BGGIUGXMWNKMCP-UHFFFAOYSA-N 2-methylpropan-2-olate;zirconium(4+) Chemical compound CC(C)(C)O[Zr](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BGGIUGXMWNKMCP-UHFFFAOYSA-N 0.000 description 1
- IJEFAHUDTLUXDY-UHFFFAOYSA-J 7,7-dimethyloctanoate;zirconium(4+) Chemical compound [Zr+4].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O IJEFAHUDTLUXDY-UHFFFAOYSA-J 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- CDXSJGDDABYYJV-UHFFFAOYSA-N acetic acid;ethanol Chemical compound CCO.CC(O)=O CDXSJGDDABYYJV-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 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 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- ASBGGHMVAMBCOR-UHFFFAOYSA-N ethanolate;zirconium(4+) Chemical compound [Zr+4].CC[O-].CC[O-].CC[O-].CC[O-] ASBGGHMVAMBCOR-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- KGDJAQAMSDMZCD-UHFFFAOYSA-M hydrogen carbonate lanthanum(3+) oxygen(2-) Chemical compound C([O-])(O)=O.[O-2].[La+3] KGDJAQAMSDMZCD-UHFFFAOYSA-M 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- OXHNIMPTBAKYRS-UHFFFAOYSA-H lanthanum(3+);oxalate Chemical compound [La+3].[La+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OXHNIMPTBAKYRS-UHFFFAOYSA-H 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- PLOSEKHZRPLNLO-UHFFFAOYSA-K lanthanum(3+);triformate Chemical compound [La+3].[O-]C=O.[O-]C=O.[O-]C=O PLOSEKHZRPLNLO-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- VRQWWCJWSIOWHG-UHFFFAOYSA-J octadecanoate;zirconium(4+) Chemical compound [Zr+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O VRQWWCJWSIOWHG-UHFFFAOYSA-J 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- BPYXFMVJXTUYRV-UHFFFAOYSA-J octanoate;zirconium(4+) Chemical compound [Zr+4].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O BPYXFMVJXTUYRV-UHFFFAOYSA-J 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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- B01J38/00—Regeneration or reactivation of catalysts, in general
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- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
- C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
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- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the invention relates to oxidic catalyst supports and catalyst particles prepared therefrom, to a process for their preparation and to the use of the catalyst particles as dehydrogenation catalyst.
- DE-A 196 54 391 describes the preparation of a dehydrogenation catalyst by impregnation of essentially monoclinic ZrO 2 with a solution of Pt (NO 3 ) 2 and Sn (OAc) 2 or by impregnation of ZrO 2 with a first solution of Pt (NO 3 ) 2 and then a second solution of La (NO 3 ) 3 .
- the impregnated carriers are dried and then calcined.
- the catalysts thus obtained are used as dehydrogenation catalysts, for example for the dehydrogenation of propane to propene.
- the preparation of the catalyst support is usually carried out by the sol-gel method, precipitation of the salts, dewatering of the corresponding acids, dry mixing, slurrying or spray drying.
- a ZrO AI 2 0 3 "Si0 2 mixed oxide can first a water-rich zirconia of the general formula ZrO xH 2 0 containing by precipitation of a suitable zirconium precursor be prepared. Suitable precursors of the zirconium are, for example, Zr (NO 3 ) 4 , ZrOCl 2 , or ZrCl 4 .
- the precipitation itself is carried out by adding a base such as NaOH, KOH, Na 2 C0 3 and NH 3 and is described for example in EP-A 0 849 224.
- the zirconium-containing precursor can be mixed with a precursor containing silicon.
- a precursor containing silicon for example, hydrous sols of Si0 2 such as Ludox TM.
- the mixture of the two components can be carried out, for example, by simple mechanical mixing or by spray-drying in a spray tower.
- a known process for the preparation of metal catalysts by flame spray pyrolysis is described in Pisduangnawakij et al., Applied Catalysis A: General 370 1-6, 2009.
- a solution containing precursor compounds of platinum and tin and of alumina as a carrier in xylene is converted into an aerosol, this treated in an inert carrier gas in a pyrolysis reactor at a temperature above the decomposition temperature of the precursor compounds and then separated the finely divided metal formed from the carrier gas ,
- the object of the present invention is to provide a cost-effective and time-saving process for the preparation of oxidic supports for dehydrogenation catalysts, wherein the resulting dehydrogenation catalysts should be comparable in activity and selectivity with the prior art catalysts prepared exclusively by impregnation or spray drying.
- the object is achieved by a method for producing catalyst carrier particles containing zirconium dioxide and optionally silicon oxide, comprising the steps
- the oxide-forming precursor compounds are fed to the pyrolysis zone as an aerosol. It is expedient to supply to the pyrolysis zone an aerosol which has been obtained by nebulization of only one solution which contains all oxide-forming precursor compounds. In this way, it is ensured in each case that the composition of the particles produced is homogeneous and constant.
- the individual components are therefore preferably selected so that the oxide-forming precursors present in the solution are present in homogeneously dissolved state until the solution has been atomized.
- the solution or solutions may contain both polar and non-polar solvents or solvent mixtures.
- the temperature in the pyrolysis zone is at a sufficient temperature for oxide formation, usually in the range between 500 and 2000 ° C.
- the pyrolysis is carried out at a temperature of 900 to 1500 ° C.
- the pyrolysis reactor can be indirectly heated from the outside, for example by means of an electric furnace. Because of the temperature gradient from outside to inside required for indirect heating, the furnace must be much hotter than the temperature required for pyrolysis. Indirect heating requires a temperature-stable furnace material and a complex reactor design, the required total amount of gas is, on the other hand, lower than in the case of a flame reactor.
- the pyrolysis zone is heated by a flame (flame spray pyrolysis).
- the pyrolysis zone then comprises an ignition device.
- conventional fuel gases can be used, but preferably hydrogen, methane or ethylene are used.
- the temperature can be adjusted in the pyrolysis zone targeted.
- the pyrolysis zone instead of air as a source of 0 2 for the combustion of the fuel gas and pure oxygen can be supplied.
- the total amount of gas also includes the carrier gas for the aerosol and the vaporized solvent of the aerosol.
- the one or more of the pyrolysis zone supplied aerosols are conveniently passed directly into the flame. While air is usually preferred as the carrier gas for the aerosol, it is also possible to use nitrogen, CO 2 , O 2 or a fuel gas, for example hydrogen, methane, ethylene, propane or butane.
- the pyrolysis zone is heated by an electrical plasma or an inductive plasma.
- a flame spray pyrolysis device generally comprises a reservoir for the liquid to be atomized, feed lines for carrier gas, fuel gas and oxygen-containing gas, a central aerosol nozzle and an annular burner arranged around it, a device for gas-solid separation comprising a filter element and a removal device for the solid and an outlet for the exhaust gas.
- the cooling of the particles is carried out by means of a quenching gas, e.g. Nitrogen or air.
- the combustion chamber which is preferably tubular, is thermally insulated.
- a pyrolysis gas containing spherical particles of varying specific surface area is obtained.
- the size distribution of the particles obtained gives inter alia from the droplet size spectrum of the aerosol supplied to the pyrolysis zone and the concentration of the solution or solutions used.
- the pyrolysis gas is cooled sufficiently before deposition of the particles formed from the pyrolysis gas, so that sintering of the particles is excluded.
- the pyrolysis zone preferably comprises a cooling zone which adjoins the combustion chamber of the pyrolysis reactor.
- a cooling of the pyrolysis gas and the catalyst particles contained therein to a temperature of about 100 - 500 ° C is required, depending on the filter element used.
- a cooling to about 100 - 150 ° C instead.
- the pyrolysis gas containing the catalyst particles and partially cooled, after leaving the pyrolysis zone, enters an apparatus for separating the particles from the pyrolysis gas, which comprises a filter element.
- a quenching gas for example nitrogen, air or a water humidified gas is introduced.
- Suitable zirconia-forming precursor compounds are alcoholates, such as zirconium (IV) ethanolate, zirconium (IV) n-propoxide, zirconium (IV) isopropoxide, zirconium (IV) n-butoxide and zirconium (IV) -tert butoxide.
- zirconium (IV) propoxide which is preferably in the form of a solution in n-propanol, is used as the ZrO 2 precursor compound.
- Suitable zirconia-forming precursor compounds are also carboxylates such as zirconium acetate, zirconium propionate, zirconium oxalate, zirconium octoate, zirconium 2-ethylhexanoate, zirconium acetate, zirconium propionate, zirconium oxalate, zirconium octanoate, zirconium 2-ethylhexanoate, zirconium neodecanoate, zirconium stearate and zirconium propionate.
- zirconium (IV) acetylacetonate is used as precursor compound.
- the precursor compounds additionally comprise a silica precursor compound.
- Suitable precursors for silicon dioxide are organosilanes and reaction products of SiCl 4 with lower alcohols or lower carboxylic acids. It is also possible to use condensates of the stated organosilanes or silanols with Si-O-Si members. Preference is given to using siloxanes. The use of Si0 2 is also possible.
- the precursor compounds comprise, as the precursor compound which forms the silica, hexamethyldisiloxane. To prepare the solution or solutions required for aerosol formation, it is possible to use both polar and apolar solvents or solvent mixtures.
- Preferred polar solvents are water, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, n-propanone, n-butanone, diethyl ether, tert-butyl methyl ether, tetrahydrofuran, CrC 8 -Carboxylic acids, ethyl acetate and mixtures thereof.
- one or more precursor compounds are dissolved in a mixture of acetic acid, ethanol and water.
- this mixture contains 30 to 75 wt .-% acetic acid, 30 to 75 wt .-% ethanol and 0 to 20 wt .-% water.
- zirconium (IV) acetylacetonate, hexamethyldisiloxane are dissolved in a mixture of acetic acid, ethanol and water.
- Preferred apolar solvents are toluene, xylene, n-heptane, n-pentane, octane, isooctane, cyclohexane, methyl, ethyl or butyl acetate or mixtures thereof. Hydrocarbons or mixtures of hydrocarbons with 5 to 15 carbon atoms are also suitable. Especially preferred is xylene.
- Zr (IV) -ethylhexanoate and hexamethyldisiloxane are dissolved in xylene.
- the catalyst carrier particles obtained by spray pyrolysis preferably have a specific surface area of 36 to 70 m 2 / g.
- the resulting catalyst support particles are then impregnated with one or more solutions containing compounds of platinum, tin and at least one other element selected from lanthanum and cesium.
- the impregnated catalyst support particles are dried and calcined.
- the invention thus also provides a process for the preparation of catalyst particles comprising platinum and tin and at least one further element selected from lanthanum and cesium on a zirconium dioxide-containing support, the process comprising steps (i) to (v) and additionally the steps
- precursor compounds are usually used compounds which can be converted by calcination in the corresponding oxides. Suitable examples are hydroxides, carbonates, oxalates, acetates, chlorides or mixed hydroxycarbonates of the corresponding metals.
- the application of the dehydrogenating component is usually carried out by impregnation. Instead of impregnation, however, the dehydrogenating component can also be carried out by other methods, such as, for example, spraying on the metal salt precursor.
- Platinum is preferably used as H 2 PtCl 6 or Pt (NO 3 ) 2 .
- Suitable solvents are water as well as organic solvents. Particularly suitable are water and lower alcohols such as methanol and ethanol.
- Suitable precursors in the use of noble metals as the dehydrogenating component are also the corresponding noble metal sols, which can be prepared by one of the known methods, for example by reduction of a metal salt in the presence of a stabilizer such as PVP with a reducing agent.
- a stabilizer such as PVP with a reducing agent.
- the manufacturing technique is discussed in detail in the German patent application DE 195 00 366.
- the content of platinum in the catalyst as the dehydrogenating component is from 0.01 to 5% by weight, preferably from 0.05 to 1% by weight, particularly preferably from 0.05 to 0.5% by weight.
- the catalyst contains at least tin in amounts of 0.01 to 10 wt .-%, preferably 0.05 to 2 wt .-%.
- Suitable tin compounds are carboxylates such as tin (II) acetate, tin 2-ethylhexanoate or tin (II) chloride.
- the loading with Pt is 0.05 to 1 wt .-% and the loading with Sn 0.05 to 2 wt .-%.
- the active composition may contain the following further components, wherein at least cesium or lanthanum are contained:
- Cesium and optionally potassium with a content between 0.1 and 10% by weight are included in cesium or Kalimoxidprecursoren using compounds that are can be converted by calcination in the oxides, for example, the hydroxides, carbonates, oxalates, acetates or formates.
- the precursor salts suitable are, for example, lanthanum oxide carbonate, La (OH) 3 , La 2 (CO 3 ) 3, La (NO 3 ) 3, lanthanum formate, lanthanum acetate and lanthanum oxalate.
- the calcination takes place at temperatures of 400 to 1000 ° C, preferably from 500 to 700 ° C, more preferably at 550 to 650 ° C.
- the present invention also provides the carrier and catalyst particles obtainable by the process according to the invention. These preferably have a specific surface area of 20 to 70 m 2 / g.
- the catalyst supports have the following percentage composition: 30 to 99.5% by weight Zr0 2 , 0.5 to 25% by weight Si0 2 .
- the catalyst particles further contain 0.1 to 1 wt .-% Pt, 0.1 to 10 wt .-% Sn, La and / or Cs, based on the mass of the carrier, wherein at least Sn and at least La or Cs are included.
- the present invention also relates to the use of the catalyst particles as hydrogenation catalysts or dehydrogenation catalysts.
- Alkanes such as butane and propane, but also ethylbenzene are preferably dehydrated.
- catalysts of the invention for the dehydrogenation of propane to propene.
- HMDSO Hexamethyldisiloxane
- the solvent is HoAc: EtOH: H 2 O in the mass ratio 4.6 to 4.6 to 1.
- the acetic acid-ethanol mixture is freshly prepared. This dissolves the precursor compounds for Si and Zr. Alternatively, xylene is used.
- Table 1 Compositions of solutions of precursor compounds for apolar
- the solution containing the precursor compounds was fed by means of a piston pump via a two-fluid nozzle and sprayed with an appropriate amount of air.
- a support flame was partially used from an ethylene-air mixture, which was metered via a ring burner located around the nozzle.
- the pressure drop was kept constant at 1, 1 bar.
- Table 2 summarizes the flame synthesis conditions.
- Xylene 1 310 3500 1200 A baghouse filter was used to separate the particles. To clean these filters, the filter bags were subjected to 5 bar pressure surges of nitrogen.
- the impregnation was carried out according to Example 4 of EP 1 074 301.
- the flame-synthesized Si0 2 / Zr0 2 support of the 1 to 2 mm sieve fraction was poured over a solution of SnCl 2 and H 2 PtCl 6 in ethanol.
- the excess solution was removed on a rotary evaporator, the solid dried and calcined.
- An aqueous solution of CsN0 3 and La (NO 3 ) 3 was added thereto and the supernatant was removed.
- the catalyst was obtained after drying and calcining with a BET surface area of 23 m 2 .
- the reference catalyst according to EP 1 074 301 consists of 95% by weight Zr0 2 , 5% by weight Si0 2 (carrier), 0.5% by weight Pt, 1% by weight Sn, 3% La, 0, 5 wt .-% Cs and 0.2 wt .-% K (active and promoter metals based on the mass of the carrier) prepared according to Example 4 by wet-chemical means.
- the support was prepared by spray-drying the oxide mixture obtained by precipitation by the sol / gel process.
- the propane dehydrogenation was carried out at about 600 ° C. 21 Nl / h of total gas (20 Nl / h of propane, 1 Nl / h of nitrogen as internal standard), 5 g / h of water.
- the regeneration is carried out at 400 ° C: 2 hours 21 Nl / h N 2 + 4 Nl / h air; 2 hours 25 Nl / h air; 1 hour 25 Nl / h of hydrogen.
- FIG. 1 shows for comparison the activities and selectivities of the reference catalyst (-) with support prepared by precipitation and spray-drying and the catalyst according to the invention whose support originates from the flame synthesis ( ⁇ ), the other elements being applied in each case by impregnation.
- the results for a flame-only synthesized catalyst of the same composition (A) are also shown.
- the abscissa shows the time in hours the ordinate shows conversions (40 to 50%) and selectivities (> 80%) for the autothermal dehydrogenation of propane to propene.
- the reference catalyst has lower initial selectivities. However, it is similar to the test cycles of a few weeks.
- the flame-synthesized catalyst and the flame-synthesized carrier after wet-chemical application of the other elements behave like an aged catalyst whose carrier was prepared by spray-drying.
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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EP12739435.1A EP2667968A2 (en) | 2011-01-25 | 2012-01-23 | Catalyst support produced by flame spray pyrolysis and catalyst for autothermal propane dehydrogenation |
JP2013549930A JP2014511259A (en) | 2011-01-25 | 2012-01-23 | Catalyst support from spray flame pyrolysis and autothermal propane dehydrogenation catalyst |
CN2012800086618A CN103379957A (en) | 2011-01-25 | 2012-01-23 | Catalyst support produced by flame spray pyrolysis and catalyst for autothermal propane dehydrogenation |
BR112013019047A BR112013019047A2 (en) | 2011-01-25 | 2012-01-23 | catalyst support particle production method, catalyst support particle, catalyst particle production method, catalyst particle, and use thereof. |
KR1020137022258A KR20140006909A (en) | 2011-01-25 | 2012-01-23 | Catalyst support from flame spray pyrolysis and catalyst for autothermal propane dehydrogenation |
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EP11151958 | 2011-01-25 | ||
EP11151958.3 | 2011-01-25 |
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EP (1) | EP2667968A2 (en) |
JP (1) | JP2014511259A (en) |
KR (1) | KR20140006909A (en) |
CN (1) | CN103379957A (en) |
BR (1) | BR112013019047A2 (en) |
WO (1) | WO2012101567A2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103566933A (en) * | 2012-08-08 | 2014-02-12 | 中国石油化工股份有限公司 | Catalyst for preparing alcohol by acetate hydrogenation as well as preparation method thereof |
CN104248953A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Catalyst for preparation of ethanol by acetate hydrogenation and preparation method thereof |
US8933262B2 (en) | 2011-05-24 | 2015-01-13 | Basf Se | Process for preparing polyisocyanates from biomass |
US11040333B2 (en) | 2015-11-10 | 2021-06-22 | Heesung Catalysts Corporation | Method for preparing dehydrogenation catalyst for straight chain-type light hydrocarbon using stabilized active material complex |
US11266979B2 (en) | 2015-11-10 | 2022-03-08 | Heesung Catalysts Corporation | Method for preparing dehydrogenation catalyst for straight chain-type light hydrocarbon using stabilized active metal composite |
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CN106753391A (en) * | 2016-11-28 | 2017-05-31 | 新沂市中诺新材料科技有限公司 | A kind of nano material and preparation method for being passivated heavy metal in rehabilitating soil |
CN111821996B (en) * | 2019-04-18 | 2022-11-29 | 清华大学 | Efficient hydrothermal-resistant and sulfur-resistant demercuration catalyst and preparation method and application thereof |
CN115069246B (en) * | 2021-03-15 | 2023-08-15 | 中国石油化工股份有限公司 | Supported silver catalyst and preparation method and application thereof |
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US3701805A (en) * | 1971-09-27 | 1972-10-31 | Pfizer | Preparation of citraconic and itaconic acids |
US6057030A (en) * | 1997-07-21 | 2000-05-02 | Kanebo Ltd. | Porous ceramic body and kiln furniture made from a porous ceramic body |
CN1513600A (en) * | 2003-08-19 | 2004-07-21 | 丁章云 | Catalyst active carrier and its preparation |
CN101204654A (en) * | 2006-12-20 | 2008-06-25 | 中国科学院生态环境研究中心 | Supported noble metal catalyst for low-temperature catalytic oxidation benzene series and preparation method thereof |
CN101433863A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Composite oxide carrier and preparation method thereof |
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DE19937107A1 (en) * | 1999-08-06 | 2001-02-08 | Basf Ag | Catalyst with bimodal pore radius distribution |
-
2012
- 2012-01-23 CN CN2012800086618A patent/CN103379957A/en active Pending
- 2012-01-23 KR KR1020137022258A patent/KR20140006909A/en not_active Application Discontinuation
- 2012-01-23 WO PCT/IB2012/050303 patent/WO2012101567A2/en active Application Filing
- 2012-01-23 BR BR112013019047A patent/BR112013019047A2/en not_active IP Right Cessation
- 2012-01-23 JP JP2013549930A patent/JP2014511259A/en not_active Withdrawn
- 2012-01-23 EP EP12739435.1A patent/EP2667968A2/en not_active Withdrawn
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US3701805A (en) * | 1971-09-27 | 1972-10-31 | Pfizer | Preparation of citraconic and itaconic acids |
US6057030A (en) * | 1997-07-21 | 2000-05-02 | Kanebo Ltd. | Porous ceramic body and kiln furniture made from a porous ceramic body |
CN1513600A (en) * | 2003-08-19 | 2004-07-21 | 丁章云 | Catalyst active carrier and its preparation |
CN101204654A (en) * | 2006-12-20 | 2008-06-25 | 中国科学院生态环境研究中心 | Supported noble metal catalyst for low-temperature catalytic oxidation benzene series and preparation method thereof |
CN101433863A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Composite oxide carrier and preparation method thereof |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8933262B2 (en) | 2011-05-24 | 2015-01-13 | Basf Se | Process for preparing polyisocyanates from biomass |
CN103566933A (en) * | 2012-08-08 | 2014-02-12 | 中国石油化工股份有限公司 | Catalyst for preparing alcohol by acetate hydrogenation as well as preparation method thereof |
CN104248953A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Catalyst for preparation of ethanol by acetate hydrogenation and preparation method thereof |
US11040333B2 (en) | 2015-11-10 | 2021-06-22 | Heesung Catalysts Corporation | Method for preparing dehydrogenation catalyst for straight chain-type light hydrocarbon using stabilized active material complex |
US11266979B2 (en) | 2015-11-10 | 2022-03-08 | Heesung Catalysts Corporation | Method for preparing dehydrogenation catalyst for straight chain-type light hydrocarbon using stabilized active metal composite |
Also Published As
Publication number | Publication date |
---|---|
BR112013019047A2 (en) | 2017-03-28 |
EP2667968A2 (en) | 2013-12-04 |
JP2014511259A (en) | 2014-05-15 |
KR20140006909A (en) | 2014-01-16 |
CN103379957A (en) | 2013-10-30 |
WO2012101567A3 (en) | 2013-01-03 |
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