CN112742385B - Catalyst for catalytic conversion of gasoline, preparation method thereof and catalytic conversion method of gasoline - Google Patents
Catalyst for catalytic conversion of gasoline, preparation method thereof and catalytic conversion method of gasoline Download PDFInfo
- Publication number
- CN112742385B CN112742385B CN202010906429.2A CN202010906429A CN112742385B CN 112742385 B CN112742385 B CN 112742385B CN 202010906429 A CN202010906429 A CN 202010906429A CN 112742385 B CN112742385 B CN 112742385B
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- oxide
- catalyst
- gasoline
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- noble metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 134
- 238000000034 method Methods 0.000 title claims abstract description 94
- 239000003502 gasoline Substances 0.000 title claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 73
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 86
- 239000011973 solid acid Substances 0.000 claims abstract description 70
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 45
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 30
- 239000011707 mineral Substances 0.000 claims abstract description 30
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 20
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 19
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 19
- 238000001694 spray drying Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 15
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 14
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 11
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000005995 Aluminium silicate Substances 0.000 claims description 8
- 235000012211 aluminium silicate Nutrition 0.000 claims description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 6
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 6
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011787 zinc oxide Substances 0.000 claims description 6
- 238000010009 beating Methods 0.000 claims description 4
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- OSYXMIHEWBABNJ-UHFFFAOYSA-N [Mo+2]=O.[O-2].[Ti+4].[O-2].[O-2] Chemical compound [Mo+2]=O.[O-2].[Ti+4].[O-2].[O-2] OSYXMIHEWBABNJ-UHFFFAOYSA-N 0.000 claims description 2
- DMHKMMLZKROINL-UHFFFAOYSA-N [O-2].[Ti+4].[W+2]=O.[O-2].[O-2] Chemical compound [O-2].[Ti+4].[W+2]=O.[O-2].[O-2] DMHKMMLZKROINL-UHFFFAOYSA-N 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- ZEYLTQYYYOQOJR-UHFFFAOYSA-N [Mo+2]=O.[O-2].[Zr+4].[O-2].[O-2] Chemical compound [Mo+2]=O.[O-2].[Zr+4].[O-2].[O-2] ZEYLTQYYYOQOJR-UHFFFAOYSA-N 0.000 claims 1
- XKNZTYYAKKNCDJ-UHFFFAOYSA-N [O-2].[Zr+4].[W+2]=O.[O-2].[O-2] Chemical compound [O-2].[Zr+4].[W+2]=O.[O-2].[O-2] XKNZTYYAKKNCDJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052762 osmium Inorganic materials 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 19
- 239000002002 slurry Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- 239000002808 molecular sieve Substances 0.000 description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000004005 microsphere Substances 0.000 description 7
- 101150003085 Pdcl gene Proteins 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- -1 ethylene, propylene Chemical group 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
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- 238000007796 conventional method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
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- 241000607479 Yersinia pestis Species 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
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- 230000008018 melting Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
-
- 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
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- 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
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention relates to the field of petrochemical industry, and discloses a catalyst for catalytic conversion of gasoline, a preparation method thereof and a catalytic conversion method of gasoline, wherein the catalyst comprises natural mineral substances, inorganic oxide, composite oxide solid acid and noble metal, the content of the natural mineral substances is 15-70wt% based on the total weight of the catalyst, the content of the inorganic oxide is 5-60wt%, the content of the composite oxide solid acid is 10-65wt%, and the content of the noble metal is 0.1-10wt% based on elements. The method for catalytic conversion of gasoline comprises the following steps: gasoline, carbon dioxide and optionally diluent gas are contacted with the catalyst. The catalyst provided by the invention has high activity, and can realize the catalytic conversion and CO of gasoline under very mild conditions 2 Effectively utilizing the catalyst to produce the low-carbon olefin.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a catalyst for catalytic conversion of gasoline, a preparation method thereof and a method for catalytic conversion of gasoline.
Background
The low-carbon olefin is an indispensable chemical raw material. The low-carbon olefin comprises ethylene, propylene and butylene. Wherein, ethylene is mainly used for producing polyethylene, ethylene oxide, dichloroethane and the like, and propylene is mainly used for producing polypropylene, acrylonitrile, propylene oxide and the like.
In recent years, the demand for low-carbon olefins has increased rapidly, driving the production capacity to increase continuously. Currently, the main modes for producing low-carbon olefins are steam cracking, catalytic cracking, propane dehydrogenation, MTO, catalytic reforming and the like. Wherein, the ratio of the products of the low-carbon olefin produced by adopting a steam cracking mode can not be flexibly adjusted, the reaction temperature is as high as 840-860 ℃, and the energy consumption accounts for about 40% of the energy consumption in petrochemical industry. Therefore, the catalytic cracking of the gasoline fractions such as naphtha and the like is very promising because of the advantages of low reaction temperature, flexible and easily-adjusted product distribution, small pollution of the product, environmental protection and the like. However, from the current results, further improvements and improvements in process and catalyst performance are still needed.
As is well known, CO 2 Is an important greenhouse gas, and causes a series of problems such as desertification of land, aggravation of plant diseases and insect pests, climate change, glacier melting and the like, thus the international society is calling for CO 2 And emission reduction. On the other hand, however, CO 2 And the catalyst is also a cheap and abundant C1 resource, can react with hydrogen to generate CO, methanol, dimethyl ether, low-carbon hydrocarbon, gasoline and the like, and can also react with methane to generate synthetic gas, ethane to generate ethylene and the like.However, these reactions are generally carried out under high pressure, and the reaction conditions are relatively severe.
Disclosure of Invention
The invention aims to overcome the reaction conditions and CO of the catalytic conversion of gasoline in the prior art 2 By utilizing the defect of harsh conditions, the catalyst for the catalytic conversion of gasoline, the preparation method thereof and the catalytic conversion method of gasoline are provided. The catalyst provided by the invention can realize the catalytic conversion of gasoline and CO under very mild conditions 2 And the yield of the product (low-carbon olefin) is further improved.
In order to achieve the above object, a first aspect of the present invention provides a catalyst for catalytic conversion of gasoline, the catalyst comprising natural minerals, inorganic oxides, complex oxide solid acids and noble metals, the content of the natural minerals being 15 to 70wt%, the content of the inorganic oxides being 5 to 60wt%, the content of the complex oxide solid acids being 10 to 65wt%, the content of the noble metals being 0.1 to 10wt%, based on the elements, based on the total weight of the catalyst.
Preferably, the complex oxide solid acid is selected from at least two of tungsten oxide, zirconium oxide, and molybdenum oxide.
In a second aspect, the present invention provides a method for preparing the above catalyst for catalytic conversion of gasoline, comprising: noble metal salt and/or supported noble metal, composite oxide solid acid, natural mineral, inorganic oxide and/or inorganic oxide precursor are mixed, beaten, spray dried and then calcined.
In a third aspect, the present invention provides a method for preparing the catalyst for catalytic conversion of gasoline, comprising:
1) Loading noble metal on the composite oxide solid acid to obtain the composite oxide solid acid containing the noble metal;
2) And mixing, pulping, spray-drying and roasting the noble metal-containing composite oxide solid acid, the natural mineral and the inorganic oxide and/or the inorganic oxide precursor.
In a fourth aspect the invention provides a catalyst for the catalytic conversion of gasoline produced by the process described above.
In a fifth aspect, the present invention provides a method for catalytic conversion of gasoline, the method comprising: the gasoline, carbon dioxide and catalyst, and optionally diluent gas, are contacted to react, the catalyst comprising the catalyst for catalytic conversion of gasoline described above.
The invention can realize the catalytic conversion of gasoline under mild conditions by adopting the catalyst containing natural minerals, inorganic oxides, noble metals and complex oxide solid acid. The catalyst provided by the invention is used in the catalytic conversion process of gasoline, carbon dioxide and diluent gas are contacted and reacted with the catalyst, and CO is utilized 2 The weak oxidation performance of the catalyst is coupled with the catalytic cracking/thermal cracking reaction of the gasoline fraction, so that the yield of ethylene, propylene and butylene can be improved in the normal pressure range. In addition, the method for catalytic conversion of gasoline provided by the invention can fully utilize CO under mild conditions 2 The resource reduces the problems caused by greenhouse gases, and has very good economic value and industrial application value.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a catalyst for catalytic conversion of gasoline, the catalyst comprising natural minerals, inorganic oxides, composite oxide solid acids and noble metals, wherein the content of the natural minerals is 15-70wt%, the content of the inorganic oxides is 5-60wt%, the content of the composite oxide solid acids is 10-65wt%, and the content of the noble metals is 0.1-10wt% in terms of elements.
Preferably, the content of natural minerals is 20 to 60wt%, the content of inorganic oxides is 10 to 55wt%, the content of composite oxide solid acids is 10 to 55wt%, and the content of noble metals is 0.1 to 5wt% on an elemental basis, based on the total weight of the catalyst.
More preferably, the content of natural minerals is 30 to 55wt%, the content of inorganic oxides is 10 to 43wt%, the content of complex oxide solid acids is 25 to 40wt%, and the content of noble metals is 1.2 to 4wt% on an elemental basis, based on the total weight of the catalyst.
In the present invention, the noble metal may be various noble metals conventionally used in the art, for example, the noble metal may be selected from one or more of Au, pd, and Rh.
According to one embodiment of the present invention, the complex oxide solid acid is selected from at least two of transition metal oxides; preferably, the complex oxide solid acid is selected from at least two of tungsten oxide, zirconium oxide, molybdenum oxide, titanium oxide, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide, and niobium oxide; preferably, the complex oxide solid acid is selected from at least two of tungsten oxide, zirconium oxide, and molybdenum oxide.
According to a preferred embodiment of the present invention, the composite oxide solid acid includes tungsten oxide and zirconium oxide, or the composite oxide solid acid includes molybdenum oxide and zirconium oxide.
Further preferably, the composite oxide solid acid includes tungsten oxide and zirconium oxide, and still further preferably, the molar ratio of tungsten oxide to zirconium oxide is 0.05 to 0.5:1, more preferably 0.1 to 0.4:1. preferably, the tungsten oxide and the zirconium oxide are used in combination in a specific ratio, which is more advantageous in improving the yield of the target product.
Further preferably, the composite oxide solid acid includes molybdenum oxide and zirconium oxide, and still further preferably, the molar ratio of molybdenum oxide to zirconium oxide is 0.05 to 0.5:1, more preferably 0.1 to 0.4:1. preferably, the molybdenum oxide and the zirconium oxide are used in a specific ratio, which is more favorable for improving the yield of the target product.
In the present invention, the complex oxide solid acid may be obtained commercially or may be prepared according to a conventional method in the art, and the present invention is not particularly limited thereto.
In the present invention, the natural minerals may be selected conventionally in the art, and preferably, the natural minerals are selected from one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite; more preferably, the natural mineral is selected from one or more of kaolin, halloysite, rectorite and montmorillonite.
In the present invention, the inorganic oxide may be a conventional choice in the art, preferably, the inorganic oxide is selected from one or more of silicon oxide, aluminum oxide-silicon oxide, zirconium oxide, titanium oxide, boron oxide, amorphous silicon aluminum, aluminum phosphate, tungsten oxide, molybdenum oxide, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide, and niobium oxide; more preferably, the inorganic oxide is selected from one or more of alumina, silica, and alumina-silica.
In the present invention, preferably, the catalyst further contains an auxiliary agent; the promoter may be present in the catalyst in the form of an oxide. The auxiliary agent is selected from at least one of group IIA, group IIIA, group IVA, group VA, lanthanide, Y, cr, mn, re, fe and Cd, preferably from at least one of Ca, fe, ga, in, bi, la and Mn.
The group IIA element can be Mg and/or Ca; the group IIIA element may be at least one of B, al and Ga; the group IVA element may be at least one of Si, ge and Sn; the VA group element may be at least one of N, P, as, sb and Bi.
Further preferably, the auxiliary is selected from at least one of Ca, fe, ga, in, bi, la and Mn, and even further preferably Ga.
In the present invention, the content of the auxiliary agent is preferably 0.5 to 9wt% in terms of oxide based on the total weight of the catalyst.
In the present invention, the catalyst may further contain a molecular sieve, which may be a conventional choice in the art. For example, the molecular sieve may be selected from one or more of FAU structure molecular sieve, BEA structure molecular sieve, MFI structure molecular sieve, FER structure molecular sieve, MCM molecular sieve, MTT structure molecular sieve, TON structure molecular sieve, MEL structure molecular sieve, SBA molecular sieve and silicoaluminophosphate molecular sieve.
The method for preparing the catalyst is not particularly limited as long as the catalyst with the composition can be prepared, and the invention further provides a method for preparing the catalyst in order to further improve the catalytic performance of the catalyst.
In a second aspect, the present invention provides a process (denoted as process a) for preparing the above catalyst for catalytic conversion of gasoline, the process comprising: noble metal salt and/or supported noble metal, composite oxide solid acid, natural mineral, inorganic oxide and/or inorganic oxide precursor are mixed, beaten, spray dried and then calcined.
In the method provided by the invention, the noble metal can be introduced in the form of noble metal salt or in the form of supported noble metal.
In the present invention, the noble metal salt may be a water-soluble noble metal salt, such as nitrate and/or chloride of noble metal, which may be selected from, but not limited to (NH 4 ) 3 RhCl 6 、PdCl 2 And AuCl 3 At least one of them.
In the method provided by the invention, preferably, the supported noble metal comprises a carrier and a noble metal supported on the carrier; preferably, the support is selected from one or more of alumina, silica, alumina-silica, zirconia, tungsten oxide-zirconia, molybdenum oxide-zirconia, titanium oxide, molybdenum oxide-titanium oxide, tungsten oxide-titanium oxide, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide and niobium oxide, more preferably alumina.
In the method provided by the invention, preferably, the content of the noble metal is 0.5-20wt% in terms of elements based on the total weight of the supported noble metal.
The supported noble metals of the present invention may be prepared by conventional means in the art, for example, by impregnation, and in particular, the support may be impregnated with a solution containing a noble metal salt, followed by drying and calcination. The drying and firing conditions may be performed according to conventional conditions, and the present invention will not be described herein.
In the preparation method of the catalyst, when the noble metal is mixed and pulped with other raw materials in the form of a supported noble metal, the weight content of the carrier of the supported noble metal is counted into the content of the inorganic oxide without special description.
According to the method provided by the present invention, the inorganic oxide precursor may be a substance that can be converted into an inorganic oxide during the subsequent process (e.g., calcination) provided by the present invention, and the skilled person will be able to correctly select the inorganic oxide precursor based on the disclosure of the present invention. Specifically, the inorganic oxide precursor may be a sol of an inorganic oxide, for example, at least one of a silica sol, an alumina sol, a peptized pseudo-boehmite, a silica-alumina sol, and a phosphorus-containing alumina sol.
According to the present invention, preferably, the method a further comprises introducing an auxiliary agent into the catalyst, wherein the auxiliary agent is as described above, and is not described herein.
Further preferably, the introduction mode of the auxiliary agent comprises: mixing and pulping auxiliary precursors, noble metal salts and/or supported noble metals, composite oxide solid acid, natural minerals, inorganic oxides and/or inorganic oxide precursors; and/or mixing and pulping the supported noble metal, the composite oxide solid acid, the natural mineral, the inorganic oxide and/or the inorganic oxide precursor containing the auxiliary agent.
That is, the auxiliary agent of the invention can be introduced in the form of mixing and beating the auxiliary agent precursor and other materials together, or in the form of loading the auxiliary agent and noble metal on a carrier together and mixing and beating the auxiliary agent and other materials together.
According to the method provided by the invention, the auxiliary precursor may be an oxide of the auxiliary and/or a substance which can be converted into an oxide of the auxiliary during a subsequent process (e.g. calcination) of the method provided by the invention, which auxiliary precursor can be properly selected by a person skilled in the art on the basis of the disclosure of the invention. May be an oxide and/or a water-soluble salt of the adjuvant (e.g., nitrate and/or chloride of the adjuvant).
The preparation method of the supported noble metal containing the auxiliary agent is not particularly limited, the auxiliary agent and the noble metal can be introduced onto the carrier by adopting an impregnation method, the auxiliary agent precursor and the noble metal salt can be jointly introduced onto the carrier (co-impregnation) or can be introduced onto the carrier step by step (step impregnation), and when the auxiliary agent precursor and the noble metal salt are introduced onto the carrier step by step, the introduction sequence of the auxiliary agent precursor and the noble metal salt is not particularly limited.
According to the method A provided by the invention, preferably, the method comprises the steps of mixing inorganic oxide and/or inorganic oxide precursor and natural mineral with water, adding composite oxide solid acid, noble metal salt and/or supported noble metal, mixing, pulping, spray drying and roasting.
According to a preferred embodiment of the present invention, inorganic oxide and/or inorganic oxide precursor, natural mineral and water are mixed and stirred uniformly to obtain slurry; adding the composite oxide solid acid, the noble metal salt and/or the supported noble metal into the mixture after 0.5 to 2 hours, and stirring the mixture to obtain catalyst slurry with the solid content of 30 to 40 weight percent; spray drying to obtain microsphere catalyst; the microspheroidal catalyst is then calcined.
In a third aspect, the present invention provides a process (denoted as process B) for preparing the above catalyst for catalytic conversion of gasoline, the process comprising:
1) Loading noble metal on the composite oxide solid acid to obtain the composite oxide solid acid containing the noble metal;
2) And mixing, pulping, spray-drying and roasting the noble metal-containing composite oxide solid acid, the natural mineral and the inorganic oxide and/or the inorganic oxide precursor.
In step 1) of the present invention, the noble metal may be supported on the complex oxide solid acid by a method conventional in the art, and specifically, one of a dipping method, an ion exchange method, a chemical deposition method and a plasma method may be used. The present invention is illustrated in the examples section by the impregnation method, and the present invention is not limited thereto.
According to one embodiment of the present invention, step 1) may impregnate the complex oxide solid acid with a solution containing a noble metal salt, followed by drying and calcination. The drying and firing conditions may be performed according to conventional conditions, and the present invention will not be described herein. The noble metal salt is as described above.
In the present invention, preferably, the method further comprises introducing an auxiliary agent into the catalyst, wherein the type of the auxiliary agent is as described above and is not described herein; further preferably, the process further comprises introducing an auxiliary agent into the catalyst in step 1); still more preferably, step 1) includes: and loading the noble metal and the auxiliary agent on the composite oxide solid acid to obtain the composite oxide solid acid containing the noble metal and the auxiliary agent. Specifically, the method B includes:
1) Loading noble metal and an auxiliary agent on the composite oxide solid acid to obtain the composite oxide solid acid containing the noble metal and the auxiliary agent;
2) And mixing, pulping, spray-drying and roasting the composite oxide solid acid containing noble metal and auxiliary agent, natural mineral and inorganic oxide and/or inorganic oxide precursor.
The present invention can adopt an impregnation method to load the auxiliary agent and the noble metal onto the composite oxide solid acid, the auxiliary agent precursor and the noble metal salt can be impregnated together onto the composite oxide solid acid (co-impregnation), or can be impregnated stepwise onto the composite oxide solid acid (stepwise impregnation), and when the auxiliary agent precursor and the noble metal salt are impregnated stepwise onto the composite oxide solid acid, the order of introduction of the auxiliary agent precursor and the noble metal salt is not particularly limited.
According to the method C provided by the invention, preferably, the slurry obtained by mixing and pulping in the step 2) has a solid content of 30-40 wt%.
The present invention is not particularly limited to the above-described spray drying method, and may be carried out according to a conventional technique in the art, and the spray drying conditions of the above-described respective methods may be the same or different. Preferably, the spray-drying is performed under such conditions that the average particle diameter of the particles obtained by the spray-drying is 60 to 80 μm and the particle diameter distribution is mainly in the range of 40 to 100. Mu.m, and more preferably, the spray-drying is performed under such conditions that the particles obtained by the spray-drying have a particle diameter of 60 to 80. Mu.m, optionally 50% or more.
In the present invention, the conditions of the firing may be conventional firing conditions in the art, and preferably, the conditions of the firing of the above-described respective methods each independently include: the roasting atmosphere is air atmosphere, inert atmosphere or steam atmosphere, the roasting temperature is 400-800 ℃, preferably 400-600 ℃, and the roasting time is 0.5-8 hours, preferably 1-5 hours. According to a preferred embodiment of the invention, the calcination is carried out under an air atmosphere.
In the present invention, the inert atmosphere may be provided by at least one of nitrogen, argon, helium and neon, preferably nitrogen.
The fourth aspect of the invention also provides a catalyst for catalytic conversion of gasoline produced by the above process.
In a fifth aspect the present invention provides a process for the catalytic conversion of gasoline by contacting gasoline, carbon dioxide with a catalyst, and optionally a diluent gas, the catalyst comprising a catalyst according to the invention as described above for the catalytic conversion of gasoline.
According to one embodiment of the invention, the catalyst may be subjected to a hydrothermal aging treatment prior to use in catalytic conversion of gasoline. The conditions for the hydrothermal aging treatment are not particularly limited, and the hydrothermal aging treatment can be carried out by a conventional means in the art. The hydrothermal aging treatment is more beneficial to improving the stability of the catalyst. In the embodiment of the present invention, aging for 10 hours at 800 ℃ under 100% steam is exemplified, and the present invention is not limited thereto.
The conditions of the contact reaction according to the present invention are selected in a wide range, and preferably the temperature of the contact reaction is not higher than 700 ℃. The catalyst provided by the invention can be suitable for low-temperature gasoline catalytic conversion reaction, and the preferred embodiment provided by the invention is more beneficial to saving energy consumption, and can realize effective utilization of carbon dioxide by treatment under mild conditions.
In the present invention, preferably, the conditions of the contact reaction include: the temperature is 350-700 ℃, the pressure is 0.1-2MPa, and the weight ratio of carbon dioxide to gasoline is 0.22-3:1, the gasoline mass airspeed is 0.3-10h -1 The method comprises the steps of carrying out a first treatment on the surface of the More preferably, the conditions of the contact reaction include: the temperature is 400-600 ℃, the pressure is 0.1-0.3MPa, and the weight ratio of carbon dioxide to gasoline is 0.25-2:1, the gasoline mass airspeed is 0.5 to 5 hours -1 。
In the present invention, the gasoline may mainly contain aliphatic hydrocarbons and naphthenes of C5 to C12, may further include a certain amount of aromatic hydrocarbons, and may specifically include one or more of catalytically cracked gasoline, coker gasoline, straight run gasoline, reformed gasoline, folded gasoline, and alkyl gasoline.
In the gasoline catalytic conversion method provided by the invention, the diluent gas can be introduced or not introduced in the reaction process, and the invention is not particularly limited to the method, and the diluent gas can be N 2 、H 2 O、O 2 Air, N 2 O、NO 2 、NO、H 2 And SO 2 One or more of the following.
According to the present invention, it is preferable that the content of carbon dioxide is 10 to 100% by volume based on the total volume of carbon dioxide and diluent gas.
The present invention will be described in detail by examples.
In the following examples:
the parameters of the gasolines used are shown in table 1 below:
TABLE 1
| Parameters (parameters) | Parameter value |
| Density (20 ℃), g/cm 3 | 0.7494 |
| Vapor pressure/kPa | 21.9 |
| Alkane/wt% | 58.6 |
| Naphthenes/wt% | 31.1 |
| Aromatic hydrocarbon/wt% | 10.3 |
| C/wt％ | 85.50 |
| H/wt％ | 14.48 |
| S/wt％ | 102 |
| N/wt％ | 0.64 |
Kaolin was purchased from china kaolin company, su zhou, with a solids content of 75 wt%;
montmorillonite was purchased from red stone bentonite company, the division of Kogyang, liaoning, with a solids content of 75% by weight;
the rectorite is purchased from Hubei's lucky rectorite ore, and the solid content is 75 weight percent;
alumina sol was purchased from zilu catalyst division and had an alumina content of 22.5 wt.%;
silica sol was purchased from Qingdao ocean chemical Co., ltd, with a silica content of 25.5 wt% and a pH of 3.0;
WO 3 /ZrO 2 the preparation method of the composite solid acid (molar ratio is 0.2) comprises the following steps: in ZrOCl 2 Ammonia was added to the aqueous solution of (a) to adjust ph=9.6, stirring was continued for 3 hours, then filtration was performed, and the precipitate was washed with deionized water until no chloride ions could be detected. Then drying overnight in an oven at 110 ℃ to obtain Zr (OH) 4 . Zr (OH) 4 Adding the mixture into an ammonium metatungstate solution to enable the molar ratio of W/Zr to be 0.2, stirring for 3 hours, heating and evaporating the water, and then placing the mixture into an oven for drying at 110 ℃ overnight. The dried sample was placed in a muffle furnace and baked at 800℃for 3 hours.
MoO 3 /ZrO 2 Preparation method of composite solid acid (molar ratio of 0.1) is the same as WO 3 /ZrO 2 The preparation method of the composite solid acid is to replace ammonium metatungstate with ammonium paramolybdate, and the mole ratio of Mo/Zr is 0.1.
The content of each component in the following catalyst is calculated by the feeding amount.
Example 1
This example is intended to illustrate the catalyst of the present invention, its method of preparation, and the method of catalytic conversion of gasoline.
And (3) preparing a catalyst:
71.1g of aluminum sol and 72.5g of kaolin are mixed, and are prepared into slurry by using decationized water, and the slurry is uniformly stirred; after 1 hour 27.2g of WO were added 3 /ZrO 2 Complex solid acids (WO) 3 And ZrO(s) 2 The molar ratio of (2) is 0.2: 1) And 4.0g of PdCl 2 Stirring to form a catalyst slurry (solid content: 32% by weight); continuously stirring and spray drying to obtain microsphere catalyst (60% of particles with average particle diameter of 65 μm and particle diameter of 60-80 μm, the same applies below); roasting at 450 ℃ for 1.5 hours to obtain the catalyst C-1. The results of the content of each component in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
aging the prepared catalyst for 10 hours at 800 ℃ under the condition of 100% water vapor, and then mixing gasoline, carbon dioxide and the catalyst at 550 ℃ under the pressure of 0.11MPa, wherein the weight ratio of the carbon dioxide to the gasoline is 0.6:1, the gasoline mass airspeed is 1.0h -1 And (3) carrying out contact reaction under the condition of obtaining the gasoline catalytic conversion product. The yields of the respective products were tested and the results are shown in table 3.
Example 2
This example is intended to illustrate the catalyst of the present invention, its method of preparation, and the method of catalytic conversion of gasoline.
And (3) preparing a catalyst:
1) Will contain 2.0g of PdCl 2 40.0g of WO 3 /ZrO 2 Complex solid acids (WO) 3 And ZrO(s) 2 The molar ratio of (2) is 0.2: 1) Drying at 100deg.C for 2h, and calcining at 300deg.C for 4h to obtain WO containing noble metal 3 /ZrO 2 A complex solid acid;
2) WO containing noble metals as described above 3 /ZrO 2 Preparing a slurry with a solid content of 32 weight percent by using decationized water, wherein the slurry contains composite solid acid, 71.1g of aluminum sol and 57.1g of montmorillonite; continuously stirring and then spray-drying to prepare a microsphere catalyst; the microspherical catalyst was calcined at 450℃for 2 hours to give catalyst C-2. The results of the content of each component in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of the respective products were tested and the results are shown in table 3.
Example 3
This example is intended to illustrate the catalyst of the present invention, its method of preparation, and the method of catalytic conversion of gasoline.
And (3) preparing a catalyst:
mixing 66.7g of aluminum sol with 74.7g of kaolin, preparing slurry by using decationized water, and uniformly stirring; after 1 hour 25g of WO are added 3 /ZrO 2 Complex solid acids (WO) 3 And ZrO(s) 2 The molar ratio of (2) is 0.2: 1) And 6.7g of PdCl 2 Stirring to form a catalyst slurry (solid content: 32% by weight); continuously stirring and then spray-drying to prepare a microsphere catalyst; roasting at 450 ℃ for 1.5 hours to obtain the catalyst C-3. The results of the content of each component in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of the respective products were tested and the results are shown in table 3.
Example 4
This example is intended to illustrate the catalyst of the present invention, its method of preparation, and the method of catalytic conversion of gasoline.
And (3) preparing a catalyst:
71.1g of aluminum sol and 65.5g of montmorillonite are mixed, and are prepared into slurry by using decationized water, and the slurry is uniformly stirred; 29.3g of WO are added after 1 hour 3 /ZrO 2 Complex solid acids (WO) 3 And ZrO(s) 2 The molar ratio of (2) is 0.2: 1) And 5.6g Rh/Al 2 O 3 (Rh weight content 16%) to form a catalyst slurry (solid content 32 wt%); continuously stirring and then spray-drying to prepare a microsphere catalyst; the microspherical catalyst was calcined at 450℃for 1.5 hours to give catalyst C-4. The results of the content of each component in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of the respective products were tested and the results are shown in table 3.
Example 5
This example is intended to illustrate the catalyst of the present invention, its method of preparation, and the method of catalytic conversion of gasoline.
And (3) preparing a catalyst:
164.7g of silica sol and 53.2g of rectorite are mixed, and are prepared into slurry by using decationized water, and the slurry is uniformly stirred; after 1 hour 16.1g of WO are added 3 /ZrO 2 Complex solid acids (WO) 3 And ZrO(s) 2 The molar ratio of (2) is 0.2: 1) And 3.3g of AuCl 3 Forming a catalyst slurry (solids content 32 wt%); continuously stirring and then spray-drying to prepare a microsphere catalyst; the microspherical catalyst was calcined at 450℃for 1.5 hours to give catalyst C-5. Each of the catalystsThe results of the component contents are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of the respective products were tested and the results are shown in table 3.
Example 6
This example is intended to illustrate the catalyst of the present invention, its method of preparation, and the method of catalytic conversion of gasoline.
And (3) preparing a catalyst:
71.1g of aluminum sol and 63.1g of kaolin are mixed, and are prepared into slurry by using decationized water, and the slurry is uniformly stirred; after 2 hours 31.9g of WO are added 3 /ZrO 2 Complex solid acids (WO) 3 And ZrO(s) 2 The molar ratio of (2) is 0.2: 1) 2.8 g Ga 2 O 3 And 3.3g of PdCl 2 Forming a catalyst slurry (solid content 35 wt%); continuously stirring and then spray-drying to prepare a microsphere catalyst; the microspherical catalyst was calcined at 480℃for 2 hours to give catalyst C-6. The results of the content of each component in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of the respective products were tested and the results are shown in table 3.
Example 7
According to the method of example 1, except that WO is used 3 /ZrO 2 Replacement of complex solid acids with MoO 3 /ZrO 2 Composite solid acid (MoO) 3 And ZrO(s) 2 The molar ratio of (2) is 0.1: 1). Catalyst C-7 was obtained. The results of the content of each component in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of the respective products were tested and the results are shown in table 3.
Example 8
The procedure of example 1 was followed except that carbon dioxide gas was not introduced during the catalytic conversion of gasoline. The yields of the respective products were tested and the results are shown in table 3.
Comparative example 1
This comparative example is intended to illustrate a comparative catalyst, a process for its preparation, and a process for catalytic conversion of gasoline.
Catalyst preparation and gasoline catalytic conversion were the same as in example 1 except that PdCl was not added 2 (i.e., no noble metal is added).
Wherein the prepared catalyst is named as D-1. The results of the content of each component in the catalyst are shown in Table 2. The results of the gasoline catalytic conversion to yield the respective products are shown in table 3.
Comparative example 2
This comparative example is intended to illustrate a comparative catalyst, a process for its preparation, and a process for catalytic conversion of gasoline.
Catalyst preparation and gasoline catalytic conversion were the same as in example 1 except that no WO was added 3 /ZrO 2 And (3) compounding solid acid.
The noble metal content of the catalyst was calculated from the total weight and the amount of the catalyst fed, and the results are shown in Table 2. The results of the gasoline catalytic conversion to yield the respective products are shown in table 3.
TABLE 2
TABLE 3 Table 3
As can be seen from the data in Table 3, the catalyst provided by the invention has high activity, and can realize effective catalytic conversion of gasoline under very mild conditions to produce low-carbon olefin. In addition, the catalyst and CO provided by the invention 2 Is matched in the catalytic conversion process of gasoline, is more beneficial to improving the yield of low-carbon olefin and realizes CO 2 Is effectively utilized.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (30)
1. The catalyst for the catalytic conversion of gasoline is characterized by comprising natural minerals, inorganic oxides, composite oxide solid acids and noble metals, wherein the content of the natural minerals is 15-70wt%, the content of the inorganic oxides is 5-60wt%, the content of the composite oxide solid acids is 10-65wt%, and the content of the noble metals is 0.1-10wt% in terms of elements;
the composite oxide solid acid is selected from at least two of tungsten oxide, zirconium oxide, molybdenum oxide, titanium oxide, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide and niobium oxide.
2. The catalyst according to claim 1, wherein the content of natural minerals is 20 to 60wt%, the content of inorganic oxides is 10 to 55wt%, the content of complex oxide solid acids is 10 to 55wt%, and the content of noble metals is 0.1 to 5wt% on an elemental basis, based on the total weight of the catalyst.
3. The catalyst according to claim 2, wherein,
based on the total weight of the catalyst, the content of natural minerals is 30-55wt%, the content of inorganic oxides is 10-43wt%, the content of composite oxide solid acid is 25-40wt%, and the content of noble metals is 1.2-4wt% based on elements.
4. The catalyst of claim 1, wherein the noble metal is selected from one or more of Au, ag, ru, rh, pd, pt, ir and Os.
5. The catalyst according to claim 4, wherein,
the noble metal is selected from one or more of Au, pd and Rh.
6. The catalyst according to any one of claims 1 to 5, wherein,
the complex oxide solid acid is selected from at least two of tungsten oxide, zirconium oxide, and molybdenum oxide.
7. The catalyst according to claim 6, wherein,
the complex oxide solid acid includes tungsten oxide and zirconium oxide.
8. The catalyst according to claim 7, wherein,
the mol ratio of the tungsten oxide to the zirconium oxide is 0.05-0.5:1.
9. the catalyst according to claim 8, wherein,
the mol ratio of the tungsten oxide to the zirconium oxide is 0.1-0.4:1.
10. the catalyst of any one of claims 1-5, wherein the natural mineral is selected from one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, and rectorite.
11. The catalyst according to any one of claims 1 to 5, wherein,
the inorganic oxide is selected from one or more of silicon oxide, aluminum oxide-silicon oxide, zirconium oxide, titanium oxide, boron oxide, amorphous silicon aluminum, tungsten oxide, molybdenum oxide, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide and niobium oxide.
12. The catalyst of any one of claims 1-5, further comprising an adjunct selected from at least one of group IIA, group IIIA, group IVA, group VA, lanthanide series, Y, cr, mn, re, fe, and Cd.
13. The catalyst according to claim 12, wherein,
the auxiliary agent is at least one selected from Ca, fe, ga, in, bi, la and Mn.
14. The catalyst of claim 13, wherein,
the content of the auxiliary agent is 0.5-9wt% based on the total weight of the catalyst and calculated by oxide.
15. A process for preparing the catalyst for catalytic conversion of gasoline of any one of claims 1 to 14, which comprises: noble metal salt and/or supported noble metal, composite oxide solid acid, natural mineral, inorganic oxide and/or inorganic oxide precursor are mixed, beaten, spray dried and then calcined.
16. The method of claim 15, wherein,
the method further comprises introducing an adjunct to the catalyst.
17. The method of claim 16, wherein,
the introduction mode of the auxiliary agent comprises the following steps: mixing and beating auxiliary precursors, noble metal salts and/or supported noble metals, complex oxide solid acids, natural minerals, inorganic oxides and/or inorganic oxide precursors, and/or mixing and beating auxiliary-containing supported noble metals, complex oxide solid acids, natural minerals, inorganic oxides and/or inorganic oxide precursors.
18. The method of claim 15, wherein the supported noble metal comprises a support and a noble metal supported on the support.
19. The method of claim 18, wherein,
the carrier is selected from one or more of aluminum oxide, silicon oxide, aluminum oxide-silicon oxide, zirconium oxide, tungsten oxide-zirconium oxide, molybdenum oxide-zirconium oxide, titanium oxide, molybdenum oxide-titanium oxide, tungsten oxide-titanium oxide, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide and niobium oxide.
20. The method of claim 19, wherein,
the carrier is alumina.
21. The method of claim 18, wherein,
the content of the noble metal is 0.5-20wt% based on the total weight of the supported noble metal.
22. A process for preparing the catalyst for catalytic conversion of gasoline of any one of claims 1 to 14, which comprises:
1) Loading noble metal on the composite oxide solid acid to obtain the composite oxide solid acid containing the noble metal;
2) And mixing, pulping, spray-drying and roasting the noble metal-containing composite oxide solid acid, the natural mineral and the inorganic oxide and/or the inorganic oxide precursor.
23. The method of claim 22, wherein,
the method further comprises introducing an adjunct to the catalyst.
24. The method of claim 23, wherein,
the method further comprises introducing an auxiliary agent into the catalyst in step 1).
25. The method of claim 24, wherein,
step 1) comprises: and loading the noble metal and the auxiliary agent on the composite oxide solid acid to obtain the composite oxide solid acid containing the noble metal and the auxiliary agent.
26. The method of any of claims 15-25, wherein the firing conditions include: the roasting atmosphere is air atmosphere, inert atmosphere or steam atmosphere, the roasting temperature is 400-800 ℃, and the roasting time is 0.5-10 hours.
27. A catalyst for catalytic conversion of gasoline prepared by the method of any one of claims 15-26.
28. A method for catalytic conversion of gasoline, the method comprising: contacting gasoline, carbon dioxide with a catalyst, and optionally a diluent gas, the catalyst comprising the catalyst for catalytic conversion of gasoline of any one of claims 1-14 and 27.
29. The method of claim 28, wherein,
the conditions of the contact reaction include: the temperature is 350-700 ℃, the pressure is 0.1-2MPa, and the weight ratio of carbon dioxide to gasoline is 0.22-3:1, the gasoline mass airspeed is 0.3-10h -1 。
30. The method of claim 29, wherein,
the conditions of the contact reaction include: the temperature is 400-600 ℃, the pressure is 0.1-0.3MPa, and the weight ratio of carbon dioxide to gasoline is 0.25-2:1, the gasoline mass airspeed is 0.5 to 5 hours -1 。
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| CN101811045A (en) * | 2009-02-25 | 2010-08-25 | 中国科学院大连化学物理研究所 | Catalyst for preparing acetic acid through direct oxidation of ethylene gaseous phase and preparation method thereof |
| CN105498830A (en) * | 2014-10-20 | 2016-04-20 | 中国石油化工股份有限公司 | Desulfurization catalyst, preparation method thereof and method for desulfurizing hydrocarbon oil by employing same |
| CN109952152A (en) * | 2016-10-10 | 2019-06-28 | 埃克森美孚化学专利公司 | The carbon monoxide-olefin polymeric that heavy aromatic substance is converted to the method for BTX and uses |
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| CN101811045A (en) * | 2009-02-25 | 2010-08-25 | 中国科学院大连化学物理研究所 | Catalyst for preparing acetic acid through direct oxidation of ethylene gaseous phase and preparation method thereof |
| CN105498830A (en) * | 2014-10-20 | 2016-04-20 | 中国石油化工股份有限公司 | Desulfurization catalyst, preparation method thereof and method for desulfurizing hydrocarbon oil by employing same |
| CN109952152A (en) * | 2016-10-10 | 2019-06-28 | 埃克森美孚化学专利公司 | The carbon monoxide-olefin polymeric that heavy aromatic substance is converted to the method for BTX and uses |
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