CN112570004B - Catalyst for gasoline catalytic conversion and high yield of BTX and preparation method thereof - Google Patents
Catalyst for gasoline catalytic conversion and high yield of BTX and preparation method thereof Download PDFInfo
- Publication number
- CN112570004B CN112570004B CN201910942733.XA CN201910942733A CN112570004B CN 112570004 B CN112570004 B CN 112570004B CN 201910942733 A CN201910942733 A CN 201910942733A CN 112570004 B CN112570004 B CN 112570004B
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- Prior art keywords
- catalyst
- oxide
- noble metal
- gasoline
- inorganic oxide
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 147
- 239000003502 gasoline Substances 0.000 title claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 78
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 127
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 91
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000002808 molecular sieve Substances 0.000 claims abstract description 73
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 50
- 239000011707 mineral Substances 0.000 claims abstract description 50
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- 239000010970 precious metal Substances 0.000 claims abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 113
- 239000002243 precursor Substances 0.000 claims description 58
- 239000012752 auxiliary agent Substances 0.000 claims description 53
- 238000002156 mixing Methods 0.000 claims description 44
- 150000003839 salts Chemical class 0.000 claims description 33
- 239000012265 solid product Substances 0.000 claims description 32
- 238000004537 pulping Methods 0.000 claims description 31
- 238000001694 spray drying Methods 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000011068 loading method Methods 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- 239000005995 Aluminium silicate Substances 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 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
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 4
- 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 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 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
- 238000010304 firing Methods 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 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 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
- 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 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium 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
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims 1
- 229910021417 amorphous silicon Inorganic materials 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 17
- 239000002002 slurry Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- 238000005470 impregnation Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 8
- 239000001099 ammonium carbonate Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 5
- 238000004523 catalytic cracking Methods 0.000 description 5
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010009 beating Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- -1 ethylene, propylene, butylene Chemical group 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 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
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- 101150003085 Pdcl gene Proteins 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000012084 conversion product Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
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- 201000010099 disease Diseases 0.000 description 1
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- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- 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
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
-
- 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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- 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
Abstract
The invention relates to the field of petrochemical industry, and discloses a catalyst for gasoline catalytic conversion and high yield of BTX, a preparation method thereof and a gasoline catalytic conversion method, wherein the catalyst comprises natural minerals, inorganic oxides, FAU structure molecular sieves and precious metals, wherein the content of the natural minerals is 15-70 wt%, the content of the inorganic oxides is 5-60 wt%, the content of the FAU structure molecular sieves is 10-70 wt%, and the content of the precious metals is 0.01-10 wt% calculated by elements. The method for catalytically converting gasoline comprises the following steps: gasoline, carbon dioxide and optional diluent gas are contacted with the catalyst for reaction. The catalyst provided by the invention can realize the catalytic conversion and CO of gasoline under mild conditions 2 The method has the advantages of effective utilization, high yield of low-carbon olefin and capability of producing more BTX.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a catalyst for gasoline catalytic conversion and high yield of BTX, a preparation method thereof and a gasoline catalytic conversion method.
Background
The low-carbon olefin and BTX are indispensable chemical raw materials. The lower olefins include ethylene, propylene, butylene, and BTX is benzene, toluene, and xylene. Wherein, ethylene is mainly used for producing polyethylene, ethylene oxide, dichloroethane and the like, propylene is mainly used for producing polypropylene, acrylonitrile, propylene oxide and other products, BTX is mainly used as a solvent of paint, dye, resin and the like, and for preparing medicines, pesticides and the like.
In recent years, the demand of low-carbon olefins and BTX is rapidly increased, and the productivity is continuously improved. Currently, the main ways of producing light olefins and BTX are steam cracking, catalytic cracking, propane dehydrogenation, MTO, catalytic reforming, and the like. Wherein, the proportion of the products of the low-carbon olefin produced by adopting a steam cracking mode can not be flexibly adjusted, the reaction temperature is up to 840-860 ℃, and the energy consumption is about 40 percent of the energy consumption of the petrochemical industry. Therefore, the method for increasing the yields of light olefins and BTX in large quantities by catalytic cracking is an efficient way for meeting the demand increase, wherein the catalytic cracking of gasoline fractions such as naphtha is promising because of the advantages of low reaction temperature, flexible and easily adjustable product distribution, small product pollution, and environmental protection. However, from the present results, further improvements and enhancements in process and catalyst performance are still needed.
As is well known, CO 2 Is an important greenhouse gas, the greenhouse effect of the greenhouse gas causes a series of problems such as land desertification, aggravation of plant diseases and insect pests, climate change, glacier melting and the like, and therefore, the international society calls for CO 2 And (5) emission reduction. But on the other hand, CO 2 It is also a cheap and rich C1 resource, which can react with hydrogen to produce CO, methanol, dimethyl ether, low carbon hydrocarbon, gasoline, etc., and can react with methane to produce synthetic gas and ethane to produce ethylene, etc. However, these reactions generally need to be carried out under high pressure, and the reaction conditions are relatively severe.
Disclosure of Invention
The invention aims to overcome the reaction conditions of gasoline catalytic conversion and CO in the prior art 2 The defect of harsh conditions is utilized to provide a catalyst for gasoline catalytic conversion and high yield of BTX, a preparation method thereof and a gasoline catalytic conversion method. The catalyst provided by the invention can realize the catalytic conversion and CO of gasoline under mild conditions 2 The yield of products (low-carbon olefin and BTX) is further improved.
In order to achieve the above object, the first aspect of the present invention provides a catalyst for catalytic conversion of gasoline to produce BTX in high yield, which comprises natural minerals, inorganic oxides, FAU-structured molecular sieves and noble metals, wherein the natural minerals are 15 to 70 wt%, the inorganic oxides are 5 to 60 wt%, the FAU-structured molecular sieves are 10 to 70 wt%, and the noble metals are 0.01 to 10 wt% calculated on elements, based on the total weight of the catalyst.
In a second aspect, the present invention provides a method for preparing the above catalyst for catalytic conversion of gasoline with high BTX yield, which comprises: mixing noble metal salt and/or supported noble metal, FAU structure molecular sieve, natural mineral, inorganic oxide and/or inorganic oxide precursor, pulping, spray drying, and roasting.
Preferably, the process further comprises introducing an adjunct to the catalyst.
Preferably, the introduction manner of the auxiliary agent comprises: mixing and pulping an auxiliary agent precursor, a noble metal salt and/or a supported noble metal, a FAU structure molecular sieve, a natural mineral substance, an inorganic oxide and/or an inorganic oxide precursor, and/or
Mixing and pulping the supported noble metal containing the auxiliary agent, the FAU structure molecular sieve, the natural mineral substance, the inorganic oxide and/or the inorganic oxide precursor.
In a third aspect, the present invention provides a method for preparing the above catalyst for catalytic conversion of gasoline with high BTX yield, which comprises:
(1) mixing noble metal salt and/or supported noble metal, partial natural mineral substance and partial inorganic oxide and/or inorganic oxide precursor, pulping, and spray drying to obtain a solid product I;
(2) mixing, pulping and spray-drying the FAU structure molecular sieve, the rest of natural mineral substances, the rest of inorganic oxide and/or inorganic oxide precursor to obtain a solid product II;
(3) and mixing the solid product I and the solid product II, and then roasting.
Preferably, the process further comprises introducing a promoter to the catalyst in step (1).
Preferably, step (1) comprises: mixing and pulping the auxiliary agent precursor, the noble metal salt and/or the supported noble metal, part of the natural mineral substance and part of the inorganic oxide and/or the inorganic oxide precursor, and/or
Mixing and pulping the supported noble metal containing the auxiliary agent, partial natural mineral substances and partial inorganic oxide and/or inorganic oxide precursor.
The fourth aspect of the present invention provides a method for preparing the above catalyst for catalytic conversion of gasoline to increase BTX yield, which comprises:
1) loading the noble metal on the FAU structure molecular sieve to obtain the FAU structure molecular sieve containing the noble metal;
2) mixing and pulping the FAU structure molecular sieve containing the noble metal, natural minerals and inorganic oxides and/or inorganic oxide precursors, spray drying, and then roasting.
Preferably, the process further comprises introducing a promoter to the catalyst.
Preferably, the method further comprises introducing an auxiliary agent into the catalyst in step 1), further preferably, step 1) comprises: and loading the noble metal and the auxiliary agent on the FAU structure molecular sieve to obtain the FAU structure molecular sieve containing the noble metal and the auxiliary agent.
The fifth aspect of the present invention provides a method for preparing the above catalyst for catalytic conversion of gasoline with high BTX yield, which comprises:
(I) mixing, pulping and spray-drying a FAU structure molecular sieve, natural minerals, precursors of inorganic oxides and/or precursors of inorganic oxides to obtain a solid product a;
(II) loading a noble metal on the solid product a, and then calcining.
Preferably, the process further comprises introducing an adjunct to the catalyst.
Preferably, the process further comprises introducing an adjunct to the catalyst in step (II), further preferably step (II) comprises: and loading the noble metal and the auxiliary agent on the solid product a.
The invention also provides a catalyst for gasoline catalytic conversion and high BTX yield, which is prepared by the method.
The seventh aspect of the present invention provides a method for catalytic conversion of gasoline, the method comprising: contacting gasoline, carbon dioxide and a catalyst and optionally a diluent gas for reaction, wherein the catalyst comprises the catalyst for catalytic conversion of the gasoline and high yield of BTX;
preferably, the conditions of the contact reaction include: the temperature is 350-850 ℃, the pressure is 0.1-2MPa, and the weight ratio of the carbon dioxide to the gasoline is 0.22-3: 1, the mass airspeed of the gasoline is 0.3-10h -1 ;
More preferably, the conditions of the contact reaction include: the temperature is 500-650 ℃, the pressure is 0.1-0.3MPa, and the weight ratio of the carbon dioxide to the gasoline is 0.2-2: 1, the mass airspeed of the gasoline is 0.5-5h -1 。
The invention can realize the catalytic conversion of gasoline under mild conditions by adopting the catalyst containing natural minerals, inorganic oxides, noble metals and FAU structure molecular sieves. The catalyst provided by the invention is used in the catalytic conversion process of gasoline, carbon dioxide and diluent gas are in contact reaction with the catalyst, and CO is utilized 2 The weak oxidation performance of the catalyst can be coupled with the catalytic cracking/thermal cracking reaction of the gasoline fraction, so that the yield of the low-carbon olefin can be improved in the normal pressure or lower pressure range, and particularly, the BTX can be produced in a large amount. In addition, the method for catalytically converting the gasoline can also fully utilize CO 2 Resources, reduces the problems caused by greenhouse gases, and has very good economic value and industrial application value.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a catalyst for catalytic conversion of gasoline and high yield of BTX, which comprises natural minerals, inorganic oxides, FAU structure molecular sieves and precious metals, wherein the natural minerals account for 15-70 wt%, the inorganic oxides account for 5-60 wt%, the FAU structure molecular sieves account for 10-70 wt%, and the precious metals account for 0.01-10 wt% of elements;
preferably, the content of the natural mineral matter is 20-60 wt%, the content of the inorganic oxide is 8-50 wt%, the content of the FAU structure molecular sieve is 10-55 wt%, and the content of the noble metal is 0.1-5 wt% calculated by element based on the total weight of the catalyst.
More preferably, the content of natural minerals is 20-55 wt%, the content of inorganic oxides is 10-45 wt%, the content of FAU structure molecular sieves is 30-40 wt%, and the content of noble metals is 1-3 wt% calculated on elements, based on the total weight of the catalyst.
In the present invention, the noble metal is preferably selected from one or more of Au, Ag, Ru, Rh, Pd, Pt, Ir, and Os; more preferably one or more selected from Au, Rh, Pd, Pt and Ir; further preferred is one or more of Au, Pd and Ru.
The catalyst for gasoline catalytic conversion and high yield of BTX is used in the gasoline catalytic conversion process, and has higher BTX yield.
In the invention, the molecular sieve is a molecular sieve with an FAU structure, wherein the structure type FAU refers to a molecular sieve structure named by International molecular sieve Association (IZA) and is used for describing a spatial topological structure of a pore channel in the molecular sieve. Preferably, the FAU molecular sieve is preferably a Y molecular sieve. The adoption of the Y molecular sieve is more beneficial to improving the yield of the target product.
In the present invention, the FAU molecular sieve 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 mineral may be selected conventionally in the art, and preferably, the natural mineral is 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 conventionally selected in the art, and preferably, the inorganic oxide is selected from one or more of silicon oxide, aluminum oxide-silicon oxide, zirconium oxide, titanium oxide, boron oxide, amorphous silica-alumina, aluminum phosphate, tungsten oxide-zirconium oxide, molybdenum oxide-zirconium 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, the inorganic oxide is selected from one or more of alumina, silica and alumina-silica.
In the present invention, preferably, the catalyst further comprises an auxiliary agent; the promoter may be present in the catalyst in the form of an oxide. The auxiliary agent is preferably selected from one or more of group IIA, group IIIA, group IVA, group VA, lanthanides, Sc, Y, Hf, Ta, Cr, Mn, Re, Fe and Cd, more preferably from one or more of Ca, Fe, Ga, In, Bi, La and Mn, and even more preferably Ga.
In the present invention, the content of the promoter is preferably 0.5 to 10 wt% in terms of oxide, based on the total weight of the catalyst. In the examples of the present invention, the example of 1.1% by weight is given as an example, and the present invention is not limited thereto.
The present invention provides a method for producing the catalyst, which is not particularly limited as long as the catalyst having the above composition can be produced, and a method for producing the catalyst is provided to further improve the catalytic performance of the catalyst.
In a second aspect, the present invention provides a method (denoted as method a) for preparing the above catalyst for catalytic conversion of gasoline with high BTX yield, the method comprising: mixing noble metal salt and/or supported noble metal, FAU structure molecular sieve, natural mineral, inorganic oxide and/or inorganic oxide precursor, pulping, spray drying, and roasting.
In the method provided by the invention, the noble metal can be introduced in the form of a noble metal salt or in the form of a supported noble metal.
In the present invention, the noble metal salt may be a water-soluble noble metal salt such as a nitrate and/or chloride of a noble metal, and the noble metal salt is preferably a chloride of a noble metal.
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, titania, molybdenum oxide-titania, tungsten oxide-titania, 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, the content of the noble metal is preferably 0.5-20% by element, and more preferably 5-20% by element based on the total weight of the supported noble metal.
The supported noble metal of the present invention may be prepared by a method conventionally used in the art, for example, by an impregnation method, and specifically, the support may be impregnated with a solution containing a noble metal salt, followed by drying and calcination. The drying and calcining conditions may be performed according to conventional conditions, and the present invention will not be described in detail herein.
In the preparation method of the catalyst of the present invention, unless otherwise specified, when the noble metal is mixed and beaten with other raw materials in the form of a supported noble metal, the weight content of the carrier of the supported noble metal is taken into account in the content of the inorganic oxide.
In the present invention, the inorganic oxide precursor may be a substance that can be converted into an inorganic oxide in a subsequent process (e.g., firing) of the method provided by the present invention, and the inorganic oxide precursor can be properly selected by those skilled in the art 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 aluminum sol, a peptized pseudo-boehmite, a silica-alumina sol, and a phosphorus-containing aluminum sol.
In the present invention, preferably, the method a further comprises introducing an auxiliary agent into the catalyst, wherein the kind of the auxiliary agent is as described above and is not described herein again.
Further preferably, the introduction manner of the auxiliary agent comprises: mixing and pulping an auxiliary agent precursor, a noble metal salt and/or a supported noble metal, a FAU structure molecular sieve, a natural mineral substance, an inorganic oxide and/or an inorganic oxide precursor; and/or
Mixing and pulping the supported noble metal containing the auxiliary agent, the FAU structure molecular sieve, the natural mineral substance, the inorganic oxide and/or the inorganic oxide precursor.
The auxiliary agent can be introduced in a form of mixing and pulping together with other materials in the form of an auxiliary agent precursor, or can be introduced in a form of loading the auxiliary agent and the noble metal on a carrier together and then mixing and pulping together with other materials.
In the present invention, the promoter precursor may be an oxide of a promoter element or a substance that can be converted into a promoter oxide in a subsequent process (e.g., firing) of the method provided by the present invention, and those skilled in the art can select the promoter precursor correctly based on the disclosure of the present invention. May be an oxide of an auxiliary element or a water-soluble salt of said auxiliary, for example a nitrate and/or chloride of the auxiliary.
The invention has no special limitation on the preparation method, the assistant and the noble metal can be introduced onto the carrier by adopting an impregnation method, the assistant precursor and the noble metal salt can be introduced onto the carrier together (co-impregnation) or introduced onto the carrier step by step (step-by-step impregnation), and when the assistant precursor and the noble metal salt are introduced onto the carrier step by step, the invention has no special limitation on the introduction sequence of the assistant precursor and the noble metal salt.
According to the method A provided by the invention, preferably, the method comprises the steps of adding water into the inorganic oxide and/or the inorganic oxide precursor and the natural mineral matter for mixing, then adding the FAU structure molecular sieve and the noble metal salt and/or the supported noble metal for mixing and pulping, spraying and drying, and then roasting.
According to a preferred embodiment of the invention: mixing inorganic oxide and/or inorganic oxide precursor, natural mineral and water, and stirring; adding a FAU structure molecular sieve and noble metal salt and/or 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; and then roasting the microspherical catalyst.
In a third aspect, the present invention provides a method (denoted as method B) for preparing the above catalyst for catalytic conversion of gasoline with high BTX production, the method comprising:
(1) mixing noble metal salt and/or supported noble metal, partial natural mineral substance and partial inorganic oxide and/or inorganic oxide precursor, pulping, and spray drying to obtain a solid product I;
(2) mixing, pulping and spray-drying the FAU structure molecular sieve, the rest of natural mineral substances, the rest of inorganic oxide and/or inorganic oxide precursor to obtain a solid product II;
(3) and mixing the solid product I and the solid product II, and then roasting.
According to the method B provided by the invention, preferably, the natural mineral substance in the step (1) accounts for 1-15% of the total weight of the natural mineral substances in the step (1) and the step (2).
According to method B provided herein, preferably, the inorganic oxide and/or inorganic oxide precursor of step (1) comprises 1 to 20% of the total weight of the inorganic oxide and/or inorganic oxide precursor of steps (1) and (2).
According to the method B provided by the present invention, preferably, the method further comprises introducing an auxiliary agent into the catalyst in step (1), wherein the kind of the auxiliary agent is as described above and is not described herein again; further preferably, step (1) comprises: mixing and pulping an auxiliary agent precursor, a noble metal salt and/or a supported noble metal, a part of natural mineral substances and a part of inorganic oxide and/or inorganic oxide precursor; and/or the presence of a gas in the gas,
the step (1) comprises the following steps: mixing and pulping the supported noble metal containing the auxiliary agent, partial natural mineral substances and partial inorganic oxide and/or inorganic oxide precursor.
The introduction manner of the auxiliary agent is as described in the method part a, and details are not repeated here.
According to the method B provided by the invention, the solid content of the slurry obtained by mixing and beating in the step (1) is preferably 30-40 wt%.
According to the method B provided by the invention, the solid content of the slurry obtained by mixing and beating in the step (2) is preferably 30-40 wt%.
In a fourth aspect, the present invention provides another method (denoted as method C) for preparing the above catalyst for catalytic conversion of gasoline with high BTX production, the method comprising:
1) loading the noble metal on the FAU structure molecular sieve to obtain the FAU structure molecular sieve containing the noble metal;
2) mixing and pulping the noble metal-containing FAU structure molecular sieve, natural minerals and inorganic oxides and/or inorganic oxide precursors, spray drying, and then roasting.
In step 1) of the present invention, the noble metal may be loaded on the FAU-structured molecular sieve by a conventional method in the art, and specifically, one of an impregnation method, an ion exchange method, a chemical deposition method and a plasma method may be used. The examples of the present invention are illustrated in part by the dipping method and the invention is not limited thereto.
According to an embodiment of the present invention, step 1) may be carried out by impregnating the FAU-structured molecular sieve with a solution containing a noble metal salt, followed by drying and calcination. The drying and calcining conditions may be carried out 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 kind of the auxiliary agent is as described in the foregoing, and is not described in detail herein; further preferably, the method further comprises introducing an auxiliary agent into the catalyst in step 1); even more preferably, step 1) comprises: and loading the noble metal and the auxiliary agent on the FAU structure molecular sieve to obtain the FAU structure molecular sieve containing the noble metal and the auxiliary agent. Specifically, the method C includes:
1) loading the noble metal and the auxiliary agent on the FAU structure molecular sieve to obtain the FAU structure molecular sieve containing the noble metal and the auxiliary agent;
2) mixing the FAU structure molecular sieve containing the noble metal and the auxiliary agent, natural mineral substances and inorganic oxide and/or inorganic oxide precursor, pulping, spray drying, washing sodium, and roasting.
The invention can adopt an impregnation method to load the auxiliary agent and the noble metal on the FAU structure molecular sieve, the auxiliary agent precursor and the noble metal salt can be jointly impregnated on the FAU structure molecular sieve (co-impregnation) or can be impregnated on the FAU structure molecular sieve step by step (step-by-step impregnation), and when the auxiliary agent precursor and the noble metal salt are impregnated on the FAU structure molecular sieve step by step, the invention has no special limitation on the introduction sequence of the auxiliary agent precursor and the noble metal salt.
According to the method C provided by the invention, the solid content of the slurry obtained by mixing and beating in the step 2) is preferably 30-40 wt%.
A fifth aspect of the present invention provides a method (denoted as method D) for preparing the above catalyst for catalytic conversion of gasoline with high BTX production, comprising:
(I) mixing, pulping and spray-drying a FAU structure molecular sieve, natural minerals and inorganic oxide precursors and/or inorganic oxide precursors to obtain a solid product a;
(II) loading a noble metal on the solid product a, and then calcining.
According to the method D provided by the invention, the solid content of the slurry obtained by mixing and beating in the step (I) is preferably 30-40 wt%.
According to an embodiment of the present invention, step (II) may impregnate the solid product a with a solution containing a noble metal salt, followed by drying and calcination. The drying and calcining conditions may be carried out according to conventional conditions, and the present invention will not be described herein. The noble metal salt is as described above.
According to the method D provided by the present invention, preferably, the method further comprises introducing an auxiliary agent into the catalyst, wherein the kind of the auxiliary agent is as described in the foregoing, and is not described herein again; further preferably, the process further comprises introducing an adjunct to the catalyst in step (II); still further preferably, step (II) comprises: and loading the noble metal and the auxiliary agent on the solid product a.
In the step (II) of the present invention, the noble metal may be supported on the solid product a by a conventional method in the art, and specifically, one of an impregnation method, an ion exchange method, a chemical deposition method and a plasma method may be used. The examples of the present invention are illustrated in part by the dipping method and the present invention is not limited thereto.
Specifically, the solid product a may be loaded with an auxiliary agent and a noble metal by an impregnation method, the auxiliary agent precursor and the noble metal salt may be impregnated together with the solid product a (co-impregnation) or may be impregnated stepwise into the solid product a (stepwise impregnation), and when the auxiliary agent precursor and the noble metal salt are impregnated stepwise into the solid product a, the order of introduction of the auxiliary agent precursor and the noble metal salt is not particularly limited in the present invention.
The spray drying in the above-mentioned method is not particularly limited in the present invention, and can be carried out according to a method conventionally used in the art, and the spray drying conditions in the above-mentioned methods may be the same or different. Preferably, the spray drying conditions are such that the average particle size of the spray dried particles is from 60 to 80 μm and the particle size distribution is predominantly from 40 to 100. mu.m, and more preferably, the spray drying conditions are such that more than 50% of the particles having a particle size of from 60 to 80 μm are present in the spray dried particles.
In the above method of the present invention, preferably, the roasting further comprises a step of washing sodium, which means that the catalyst particles obtained by spray drying are contacted with an ammonium salt solution to wash off sodium in the catalyst, wherein the ammonium salt may be an ammonium salt commonly used in the art, and is preferably one or more of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium acetate and ammonium nitrate.
In the present invention, the calcination conditions may be calcination conditions conventional in the art, and preferably, the calcination conditions in each of the above methods 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 present 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 sixth aspect of the invention also provides a catalyst prepared by the method for catalytic conversion of gasoline and capable of producing BTX in high yield.
The seventh aspect of the present invention provides a method for catalytic conversion of gasoline, wherein gasoline, carbon dioxide and catalyst, and optionally diluent gas are contacted and reacted, and the catalyst comprises the above catalyst for catalytic conversion of gasoline with high yield of BTX.
According to an embodiment of the present invention, the catalyst may be subjected to hydrothermal aging treatment before being used for catalytic conversion of gasoline. In the present invention, the conditions of the hydrothermal aging treatment are not particularly limited, and the hydrothermal aging treatment can be performed according to a conventional technique in the art. The hydrothermal aging treatment is more favorable for improving the stability of the catalyst. In the examples of the present invention, the aging is performed for 17 hours at 800 ℃ under 100% water vapor, but the present invention is not limited thereto.
In the inventionPreferably, the conditions of the contact reaction include: the temperature is 350-: 1, the gasoline mass space velocity is 0.3-10h -1 (ii) a More preferably, the conditions of the contact reaction include: the temperature is 500-650 ℃, the pressure is 0.1-0.3MPa, and the weight ratio of the carbon dioxide to the gasoline is 0.2-2: 1, the mass airspeed of the gasoline is 0.5-5h -1 。
In the invention, the gasoline mainly comprises aliphatic hydrocarbons and naphthenic hydrocarbons of C5-C12, and also comprises a certain amount of aromatic hydrocarbons, and specifically comprises one or more of catalytic cracking gasoline, coker gasoline, straight run gasoline, reformed gasoline, laminated gasoline and alkyl gasoline.
In the present invention, the diluent gas may be N 2 、H 2 O、O 2 Air, N 2 O、NO 2 、NO、 H 2 And SO 2 Preferably N, is preferably N 2 。
According to the present invention, it is preferable that the carbon dioxide is contained in an amount of 10 to 100% by volume, based on the total volume of the carbon dioxide and the diluent gas.
The present invention will be described in detail below by way of examples.
In the following examples:
the various parameters of the gasoline used are shown in table 1 below:
TABLE 1
Parameter(s) | Parameter value |
Density (20 ℃ C.), g/cm 3 | 0.7494 |
Vapor pressure/kPa | 21.9 |
Alkane/wt.% | 58.6 |
Cycloalkane/wt% | 31.1 |
Aromatic hydrocarbon/wt% | 10.3 |
C/wt% | 85.50 |
H/wt% | 14.48 |
S/wt% | 102 |
N/wt% | 0.64 |
Kaolin (purchased from suzhou china kaolin, having a solids content of 75% by weight);
rectorite (75 wt% solid content from Zhongxiang rectorite in Hubei province);
montmorillonite (obtained from red rock bentonite, Gekko city, Kogyo, Liaoning, with a solid content of 75 wt%);
alumina sol (available from zilu catalyst division, alumina content 22.5 wt%);
silica sol (purchased from Qingdao ocean chemical Co., Ltd., silica content of 25.5 wt%, pH 3.0);
y molecular sieve (purchased from zilu catalyst works);
the contents of the components in the following catalysts are calculated by the feeding amount.
Example 1
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
mixing 66.7g of alumina sol and 66.8g of kaolin, preparing the mixture into slurry by using decationized water, and uniformly stirring; after 1 hour, 32.9g of Y molecular sieve and 3.1g of AuCl were added 3 Stirring to form a catalyst slurry (solid content 32 wt%); continuously stirring, and spray drying to obtain microsphere catalyst (average particle diameter is 65 μm, particle with particle diameter of 60-80 μm accounts for 60%, the same below); and (3) carrying out sodium washing exchange on the microspherical catalyst and ammonium bicarbonate, and roasting the obtained solid product at 450 ℃ for 1.5 hours to obtain the catalyst C-1. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
aging the prepared catalyst for 17h at 800 ℃ under the condition of 100% of water vapor, and then adding gasoline, carbon dioxide and the catalyst at a temperature of 580 ℃, a pressure of 0.11MPa, a weight ratio of the carbon dioxide to the gasoline of 0.2: 1, the gasoline mass space velocity is 0.6h -1 The catalytic conversion product of the gasoline is obtained by the contact reaction under the condition of (1). The yields of the respective products were measured, and the results are shown in Table 3.
Example 2
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
1) will contain 1.6g of AuCl 3 The aqueous solution is dipped into 40.0g of Y molecular sieve, then dried for 2h at 100 ℃, and roasted for 4h at 300 ℃ to obtain the Y molecular sieve containing noble metal;
2) preparing the Y molecular sieve containing the noble metal, 66.7g of alumina sol and 58.7g of montmorillonite into slurry with the solid content of 32 weight percent by using decationized water; continuously stirring, and then spray-drying to prepare a microspherical catalyst; and (3) carrying out sodium washing exchange on the microspherical catalyst and ammonium bicarbonate, and roasting the microspherical catalyst for 2 hours at 450 ℃ to obtain the catalyst C-2. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of each product were tested and the results are shown in table 3.
Example 3
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
(1) preparing slurry with the solid content of 30 weight percent by using decationized water for 66.7g of alumina sol, 69.3g of kaolin and 30.0g of Y molecular sieve, uniformly stirring, and carrying out spray drying on the slurry to prepare a microspherical catalyst;
(2) with an AuCl containing 4.6g 3 The microsphere catalyst is soaked in the aqueous solution, and then the aqueous solution is dried for 2 hours at 100 ℃ and roasted for 4 hours at 450 ℃;
(3) and (3) performing sodium washing exchange on the roasted product obtained in the step (2) and ammonium bicarbonate, and then drying for 2 hours at 100 ℃ to obtain a catalyst C-3. The results of the contents of the components 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 measured, and the results are shown in Table 3.
Example 4
This example illustrates the catalyst and its preparation and the process for the catalytic conversion of gasoline according to the invention.
Preparing a catalyst:
mixing 66.7g of alumina sol and 66.0g of montmorillonite, preparing the mixture into slurry by using decationized water, and uniformly stirring; after 1 hour 35.0g of Y molecular sieves and 0.8g of PdCl were added 2 To form a catalyst slurry (solids content 32 wt%); continuously stirring, and then spray-drying to prepare a microspherical catalyst; and (3) carrying out sodium washing exchange on the microspherical catalyst and ammonium bicarbonate, and then roasting the microspherical catalyst for 1.5 hours at the temperature of 450 ℃ to obtain a catalyst C-4. The results of the contents of the components 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 measured, and the results are shown in Table 3.
Example 5
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
(1) 2.8g of AuCl 3 5.3g of rectorite and 6.3g of silica sol are prepared into slurry with the solid content of 32 weight percent by using decationized water; and continuously stirring, and then carrying out spray drying to obtain a solid product I.
(2) Preparing 25.0g of Y molecular sieve, 38.9g of rectorite and 150.6g of silica sol into slurry with the solid content of 32 weight percent by using decationized water; and continuously stirring, and then carrying out spray drying to obtain a solid product II.
(3) And mixing the solid product I and the solid product II, performing sodium washing exchange by using ammonium bicarbonate, and roasting at 360 ℃ for 1.5 hours to obtain the catalyst C-5. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of each product were tested and the results are shown in table 2.
Example 6
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
mixing 71.1g of alumina sol and 48.0g of kaolin, preparing the mixture into slurry by using decationized water, and uniformly stirring; after 2 hours 37.0 g of Y molecular sieve and 1.1g of Ga are added 2 O 3 And 10.0g of Ru (15% by weight)/Al 2 O 3 To form a catalyst slurry (35% solids by weight); continuously stirring, and then spray-drying to prepare a microspherical catalyst; and (3) carrying out sodium washing exchange on the microspherical catalyst and ammonium bicarbonate, and roasting the microspherical catalyst for 2 hours at 480 ℃ to obtain the catalyst C-6. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of each product were tested and the results are shown in table 3.
Example 7
The process of example 1 was followed except that carbon dioxide gas was not introduced during the catalytic conversion of gasoline. The yields of each product were tested and the results are shown in table 3.
Comparative example 1
This comparative example serves to illustrate a comparative catalyst and a method of making the same, as well as a method of catalytic conversion of gasoline.
Catalyst preparation and gasoline catalytic conversion the same as in example 1, except that no AuCl was added 3 (i.e., no noble metal is added).
The catalyst obtained was designated D-1. The results of the contents of the components in the catalyst are shown in Table 2. The results of yields of the various products obtained from gasoline catalytic conversion are shown in table 3.
Comparative example 2
This comparative example serves to illustrate a comparative catalyst and a method of making the same, as well as a method of catalytic conversion of gasoline.
Catalyst preparation and gasoline catalytic conversion the same as in example 1 except that no Y molecular sieve was added. The content of noble metal in the catalyst was calculated from the total weight and the amount of the catalyst to be finally obtained, and the results are shown in table 2.
The catalyst obtained was designated D-2. The results of the contents of the components in the catalyst are shown in Table 2. The results of the yields of the various products obtained by catalytic conversion of gasoline are shown in table 3.
TABLE 2
Note: the noble metal is calculated by element, the inorganic oxide is calculated by oxide, and the auxiliary oxide is calculated by oxide.
TABLE 3
Product yield (%) | Ethylene | Propylene (PA) | BTX | Coke | Diesel oil and oil slurry | Gasoline (R) and its preparation method | Liquefied gas | Dry gas |
Example 1 | 6.8 | 13.6 | 19.8 | 5.4 | 10.5 | 32.0 | 35.0 | 17.1 |
Example 2 | 6.7 | 13.2 | 18.8 | 6.2 | 12.3 | 29.9 | 34.8 | 16.8 |
Example 3 | 7.0 | 13.7 | 20.4 | 5.8 | 10.1 | 32.7 | 34.2 | 17.2 |
Example 4 | 6.2 | 12.3 | 18.3 | 5.6 | 11.2 | 31.5 | 34.6 | 17.1 |
Example 5 | 6.4 | 12.6 | 17.6 | 4.9 | 9.0 | 35.2 | 33.0 | 17.9 |
Example 6 | 7.1 | 14.3 | 20.7 | 5.3 | 10.1 | 30.4 | 36.6 | 17.6 |
Example 7 | 6.1 | 13.0 | 18.4 | 5.5 | 11.5 | 31.8 | 34.2 | 17.0 |
Comparative example 1 | 3.6 | 8.7 | 14.6 | 4.9 | 9.2 | 48.8 | 27.3 | 9.8 |
Comparative example 2 | 0.9 | 1.8 | 5.8 | 7.3 | 5.1 | 82.2 | 4.2 | 1.2 |
As can be seen from the data results in Table 3, the catalyst and CO provided by the present invention can be used 2 The catalyst is used in the catalytic conversion process of the gasoline in a matching way, can realize the effective catalytic conversion of the gasoline under mild conditions, has higher low-carbon olefin yield, can produce BTX in a high yield, and realizes CO 2 The effective utilization of the water is realized.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (35)
1. The catalyst for catalytic conversion of gasoline to produce BTX in high yield is characterized by comprising natural minerals, inorganic oxides, FAU structure molecular sieves and precious metals, wherein the FAU structure molecular sieves are Y molecular sieves, the content of the natural minerals is 20-60 wt%, the content of the inorganic oxides is 8-50 wt%, the content of the FAU structure molecular sieves is 10-55 wt%, and the content of the precious metals is 0.1-5 wt% calculated by elements.
2. The catalyst according to claim 1, wherein,
based on the total weight of the catalyst, the content of natural minerals is 20-55 wt%, the content of inorganic oxides is 10-45 wt%, the content of FAU structure molecular sieves is 30-40 wt%, and the content of noble metals is 1-3 wt% calculated by elements.
3. 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.
4. The catalyst according to claim 3,
the noble metal is selected from one or more of Au, Rh, Pd, Pt and Ir.
5. The catalyst of claim 4, wherein,
the noble metal is one or more of Au, Pd and Ru.
6. The catalyst according to any one of claims 1 to 5, wherein the natural mineral is selected from one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite.
7. The catalyst according to any one of claims 1 to 5,
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-zirconium oxide, molybdenum oxide-zirconium oxide, molybdenum oxide-titanium oxide, tungsten oxide-titanium oxide, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide, and niobium oxide.
8. The catalyst of any one of claims 1 to 5, wherein the catalyst further comprises a promoter selected from one or more of group IIA, group IIIA, group IVA, group VA, the lanthanide series, Sc, Y, Hf, Ta, Cr, Mn, Re, Fe and Cd.
9. The catalyst of claim 8, wherein,
the auxiliary agent is selected from one or more of Ca, Fe, Ga, In, Bi, La and Mn.
10. The catalyst of claim 8, wherein,
the content of the auxiliary agent is 0.5-10 wt% calculated by oxide based on the total weight of the catalyst.
11. A method for preparing the catalyst for gasoline catalytic conversion yielding BTX as claimed in any one of claims 1 to 10, the method comprising: mixing noble metal salt and/or supported noble metal, FAU structure molecular sieve, natural mineral, inorganic oxide and/or inorganic oxide precursor, pulping, spray drying, and roasting.
12. The method of claim 11, wherein,
the method further comprises introducing a promoter to the catalyst.
13. The method of claim 12, wherein,
the introduction mode of the auxiliary agent comprises the following steps: mixing and pulping an auxiliary agent precursor, a noble metal salt and/or a supported noble metal, a FAU structure molecular sieve, a natural mineral substance, an inorganic oxide and/or an inorganic oxide precursor, and/or
Mixing and pulping the supported noble metal containing the auxiliary agent, the FAU structure molecular sieve, the natural mineral substance, the inorganic oxide and/or the inorganic oxide precursor.
14. A method for preparing the catalyst for gasoline catalytic conversion yielding BTX as claimed in any one of claims 1 to 10, the method comprising:
(1) mixing noble metal salt and/or supported noble metal, partial natural mineral substance and partial inorganic oxide and/or inorganic oxide precursor, pulping, and spray drying to obtain a solid product I;
(2) mixing, pulping and spray-drying the FAU structure molecular sieve, the rest of natural mineral substances, the rest of inorganic oxide and/or inorganic oxide precursor to obtain a solid product II;
(3) mixing the solid product I and the solid product II, and then roasting.
15. The method of claim 14, wherein,
the natural mineral substance in the step (1) accounts for 1-15% of the total weight of the natural mineral substances in the step (1) and the step (2).
16. The method of claim 14, wherein,
the inorganic oxide and/or inorganic oxide precursor in the step (1) accounts for 1-20% of the total weight of the inorganic oxide and/or inorganic oxide precursor in the step (1) and the step (2).
17. The method of claim 14, wherein,
the process further comprises introducing a promoter to the catalyst in step (1).
18. The method of claim 14, wherein,
the step (1) comprises the following steps: mixing and pulping the auxiliary agent precursor, the noble metal salt and/or the supported noble metal, part of the natural mineral substance and part of the inorganic oxide and/or the inorganic oxide precursor, and/or
Mixing and pulping the supported noble metal containing the auxiliary agent, partial natural mineral substances and partial inorganic oxide and/or inorganic oxide precursor.
19. The method of claim 18, wherein the supported noble metal comprises a support and a noble metal supported on the support.
20. The method of claim 19, wherein,
the carrier is selected from one or more of alumina, silica, alumina-silica, zirconia, tungsten oxide-zirconia, molybdenum oxide-zirconia, titanium oxide, molybdenum oxide-titania, tungsten oxide-titania, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide and niobium oxide.
21. The method of claim 20, wherein,
the carrier is at least one of alumina, alumina-silica and tungsten oxide-zirconia.
22. The method of claim 19, wherein,
the content of the noble metal is 0.5-20% by element based on the total weight of the supported noble metal.
23. A method for preparing the catalyst for gasoline catalytic conversion yielding BTX as claimed in any one of claims 1 to 10, the method comprising:
1) loading noble metal on the FAU structure molecular sieve to obtain the FAU structure molecular sieve containing the noble metal;
2) mixing and pulping the noble metal-containing FAU structure molecular sieve, natural minerals and inorganic oxides and/or inorganic oxide precursors, spray drying, and then roasting.
24. The method of claim 23, wherein,
the method further comprises introducing a promoter to the catalyst.
25. The method of claim 24, wherein,
the process further comprises introducing a promoter to the catalyst in step 1).
26. The method of claim 25, wherein,
the step 1) comprises the following steps: and loading the noble metal and the auxiliary agent on the FAU structure molecular sieve to obtain the FAU structure molecular sieve containing the noble metal and the auxiliary agent.
27. A method for preparing the catalyst for catalytic conversion of gasoline with high BTX yield according to any one of claims 1 to 10, comprising:
(I) mixing, pulping and spray-drying a FAU structure molecular sieve, natural minerals, precursors of inorganic oxides and/or precursors of inorganic oxides to obtain a solid product a;
(II) loading a noble metal on the solid product a, and then calcining.
28. The method of claim 27, wherein,
the method further comprises introducing a promoter to the catalyst.
29. The method of claim 28, wherein,
the process further comprises introducing a promoter to the catalyst in step (II).
30. The method of claim 29, wherein,
the step (II) comprises the following steps: and loading the noble metal and the auxiliary agent on the solid product a.
31. The method of claim 27, 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 0.5-8 hours.
32. A catalyst for catalytic conversion of gasoline with high BTX yield prepared by the method of any one of claims 11-31.
33. A process for the catalytic conversion of gasoline, the process comprising: contacting gasoline, carbon dioxide and a catalyst and optionally a diluent gas for reaction, wherein the catalyst comprises the catalyst for catalytic conversion of gasoline and high yield of BTX in any one of claims 1-10 and 32.
34. The method of claim 33, wherein,
the conditions of the contact reaction include: the temperature is 350-The weight ratio of oil is 0.22-3: 1, the mass airspeed of the gasoline is 0.3-10h -1 。
35. The method of claim 34, wherein,
the conditions of the contact reaction include: the temperature is 500-650 ℃, the pressure is 0.1-0.3MPa, and the weight ratio of the carbon dioxide to the gasoline is 0.2-2: 1, the gasoline mass space velocity is 0.5-5h -1 。
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