CN111375415A - Catalyst for preparing olefin by low-carbon alkane dehydrogenation and preparation method thereof - Google Patents
Catalyst for preparing olefin by low-carbon alkane dehydrogenation and preparation method thereof Download PDFInfo
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- CN111375415A CN111375415A CN201811643427.8A CN201811643427A CN111375415A CN 111375415 A CN111375415 A CN 111375415A CN 201811643427 A CN201811643427 A CN 201811643427A CN 111375415 A CN111375415 A CN 111375415A
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- Prior art keywords
- preparing
- catalyst
- low
- carbon
- dehydrogenation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 116
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 27
- 238000006356 dehydrogenation reaction Methods 0.000 title claims description 75
- 239000002006 petroleum coke Substances 0.000 claims abstract description 102
- 238000001035 drying Methods 0.000 claims abstract description 75
- 238000002156 mixing Methods 0.000 claims abstract description 66
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 42
- 239000010703 silicon Substances 0.000 claims abstract description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 26
- 230000003213 activating effect Effects 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 130
- 239000000243 solution Substances 0.000 claims description 118
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 95
- 239000008367 deionised water Substances 0.000 claims description 69
- 229910021641 deionized water Inorganic materials 0.000 claims description 69
- 238000000034 method Methods 0.000 claims description 69
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 66
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 66
- 239000001569 carbon dioxide Substances 0.000 claims description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 58
- 238000005303 weighing Methods 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 48
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 27
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 26
- 238000001994 activation Methods 0.000 claims description 26
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 26
- 239000004254 Ammonium phosphate Substances 0.000 claims description 23
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 23
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 23
- 230000004913 activation Effects 0.000 claims description 21
- 239000000084 colloidal system Substances 0.000 claims description 21
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 230000007935 neutral effect Effects 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 15
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 14
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- 150000007524 organic acids Chemical class 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002210 silicon-based material Substances 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 239000012159 carrier gas Substances 0.000 claims description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical group OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 38
- 239000007787 solid Substances 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000000227 grinding Methods 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 229910052681 coesite Inorganic materials 0.000 description 11
- 229910052906 cristobalite Inorganic materials 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 229910052682 stishovite Inorganic materials 0.000 description 11
- 229910052905 tridymite Inorganic materials 0.000 description 11
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- -1 polypropylene Polymers 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 239000001282 iso-butane Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a catalyst for preparing olefin by dehydrogenating low-carbon alkane and a preparation method thereof, wherein the catalyst comprises an active component, an auxiliary agent and a carrier, the active component is one or more of Fe, Co, Ni, V, Mo, Cr, Mn, Cu or Zn, the auxiliary agent is one or more of IA group, IIA group, rare earth elements, Al, Ti, Zr, Nb and Ga, and the carrier is silicon-based modified petroleum coke-based activated carbon. The preparation method comprises the steps of (1) pretreating petroleum coke, (2) preparing silicon-based modified petroleum coke, and (3) preparing a composite oxide containing an active component and an auxiliary agent; (4) uniformly mixing the silicon-based modified petroleum coke, the composite oxide and the activating agent and then activating; and (4) washing and drying the sample obtained in the step (4) to obtain the catalyst. The prepared catalyst has the advantages of good dispersion of active components, high utilization rate, high selectivity of low-carbon olefin and the like.
Description
Technical Field
The invention belongs to the field of chemical catalysis, relates to a catalytic material and a preparation method thereof, and particularly relates to a catalyst for preparing olefin by dehydrogenation of low-carbon alkane and a preparation method thereof.
Background
The low-carbon olefin generally refers to an olefin having a carbon number of 4 or less, and is a very important organic chemical raw material. Ethylene is a very important intermediate in petrochemical industry and is a basic raw material of modern petrochemical industry. Propylene is an important chemical raw material, can be used for synthesizing materials such as polypropylene, polyacrylonitrile, acrolein, acrylic acid, propylene oxide and the like, and can also be used for producing products such as plastics, polypropylene, organic glass, epoxy resin and the like. Isobutene is currently used mainly for the synthesis of the gasoline additive methyl tert-butyl ether (MTBE) and in addition to this for the production of fine chemicals such as isoprene and methyl methacrylate, tert-butyl alcohol and elastomers such as butyl rubber, isoprene rubber and polyisobutylene rubber.
The production of light olefins mainly adopts light hydrocarbon (naphtha, light diesel oil and the like) cracking, and due to the gradual shortage of global petroleum resources and the long-term high-order operation of the price of crude oil, a new route for replacing the traditional olefin production method is urgently needed to be developed. The dehydrogenation preparation of the low-carbon olefin by utilizing the low-carbon alkane which is rich in source and low in price is one of the most promising methods. Dehydrogenation of light alkanes is a strong endothermic reaction, and the ideal olefin yield can be obtained only at a relatively high reaction temperature. However, too high a reaction temperature tends to bring about a series of side reactions, which decrease the selectivity of the olefin and aggravate the deactivation of the catalyst. Although oxidative dehydrogenation of oxygen can solve the above problems, deep oxidation of alkane inevitably occurs during the reaction, so that the reaction cannot obtain high selectivity at a desired conversion.
Carbon dioxide is a weaker oxidant than oxygen. Carbon dioxide is added into a reaction system for preparing olefin by dehydrogenating low-carbon alkane, (1) the equilibrium conversion rate can be improved; (2) partial energy is provided for dehydrogenation endothermic reaction, and the reaction temperature is reduced; (3) as a mild oxidant, deep oxidation of ethane does not occur, and the selectivity of the product ethylene is ensured; (4) carbon deposit is removed, and the stability of the catalyst is improved; (5) elimination of some greenhouse gas CO2And meets the current environmental protection requirement. Therefore, the method for preparing the olefin by dehydrogenating the low-carbon alkane in the carbon dioxide atmosphere is a green new process with great application prospect.
CN1339336A discloses a catalyst for preparing ethylene by dehydrogenation of carbon dioxide oxidized ethane at low temperature. The catalyst is prepared by an impregnation method, is composed of porous activated carbon loaded metal oxide, and has an ethylene yield of 14% at a temperature of 973K.
CN106563489A discloses a catalyst which takes small-grain all-silicon silicalite-1 with MFI structure as a carrier and chromium oxide as an active component. In the preparation process, soluble chromium salt is used as a precursor, silicalite-1 zeolite is introduced by an impregnation method, and the supported catalyst is prepared by roasting. The catalyst of the present invention is used in ethane dehydrogenation reaction in carbon dioxide atmosphere, and has high ethylene selectivity and yield. However, the active component chromium of the catalyst is a toxic metal, which is not environment-friendly.
CN101785993B discloses a catalyst for propane dehydrogenation to propylene under carbon dioxide atmosphere. The catalyst is prepared by adopting an impregnation method in the prior art by taking HZSM-5 molecular sieve with high silica-alumina ratio as a carrier and zinc oxide as an active component. The catalyst shows higher steady-state activity and has obvious promotion effect on carbon dioxide.
CN102485331A, CN102728364A, CN102631914A, CN104437568A and CN 104437456A, CN106311201A respectively construct Fe, Co, Ni, Ru, P, V, Cu, Sn, Pt and Ga catalysts loaded by mesoporous carbon by utilizing the characteristics of high specific surface area, large aperture and favorable diffusion of the mesoporous carbon, and the catalysts have better performance of selectively oxidizing isobutane by carbon dioxide to generate isobutene.
Disclosure of Invention
The applicant finds that the existing catalysts for preparing olefin by oxidizing low-carbon alkane with carbon dioxide are all prepared by adopting an impregnation method, and in the process of preparing the catalysts by adopting the impregnation method, the dispersibility of active metal on the surface of a carrier is poor due to the fact that active metal particles are easy to agglomerate, the oxidation capacity is limited when the catalysts are used in the alkane oxidative dehydrogenation process, the catalysts are easy to coke and lose activity due to carbon deposition, and the catalysts are difficult to popularize and apply on industrial devices.
Aiming at the problems in the prior art, the invention provides a catalyst for preparing low-carbon olefin by carbon dioxide oxidation and low-carbon alkane dehydrogenation and a preparation method thereof.
The invention provides a catalyst for preparing low-carbon olefin by carbon dioxide oxidation and dehydrogenation of low-carbon alkane, which comprises an active component, an auxiliary agent and a carrier, wherein the active component is one or more of Fe, Co, Ni, V, Mo, Cr, Mn, Cu or Zn, the auxiliary agent is one or more of IA group, IIA group, rare earth elements, Al, Ti, Zr, Nb and Ga, preferably one or more of Mg, K, Zr and Ce, and the carrier is silicon-based modified petroleum coke-based activated carbon, wherein based on the weight of the catalyst, the content of an active component oxide is 1-20%, preferably 3-15%, the content of the auxiliary agent oxide is 1-10%, preferably 3-8%, and the content of the carrier is 70-98%, preferably 77-94%.
The catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide has the following properties: the specific surface area is 500-1800 m2Preferably 700 to 1600 m/g2/g。
In the catalyst for preparing the low-carbon olefin by the dehydrogenation of the carbon dioxide oxidized low-carbon alkane, the active components and the auxiliary agent are embedded into the amorphous defects of the petroleum coke-based active carbon and the active carbon graphite microchip layer, and the size of active metal crystal grains is 1.5-5.8 nm, preferably 2.5-5 nm.
The second aspect of the invention provides a preparation method of a catalyst for preparing low-carbon olefin by carbon dioxide oxidation and low-carbon alkane dehydrogenation, which comprises the following steps:
(1) pretreating petroleum coke;
(2) preparing silicon-based modified petroleum coke;
(3) preparing a composite oxide containing an active component and an auxiliary agent;
(4) mixing the silicon-based modified petroleum coke obtained in the step (2), the composite oxide obtained in the step (3) and an activating agent, and activating after uniformly mixing;
(5) and (4) washing and drying the sample obtained in the step (4) to obtain the catalyst for preparing the low-carbon olefin by oxidizing the low-carbon alkane with carbon dioxide and dehydrogenating the low-carbon alkane.
In the preparation method of the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide, the pretreatment in the step (1) comprises the following steps:
(1.1) introducing ammonium phosphate salt into petroleum coke, and then drying;
(1.2) pretreating the sample obtained in the step (1.1) with water vapor-containing gas.
In the method, the ammonium phosphate salt in the step (1.1) is one or more of ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate, and is preferably ammonium phosphate.
In the above method, the method for introducing the ammonium phosphate salt into the petroleum coke in the step (1.1) is performed according to a method known in the art, and comprises one or more of an equal volume impregnation method, a supersaturated impregnation method and a kneading method, and is preferably a supersaturated impregnation method.
In the method, in the step (1.1), the drying temperature is 60-120 ℃, the preferable drying temperature is 80-100 ℃, the drying time is 2-8 hours, and the preferable drying time is 4-6 hours. The drying is further preferably carried out under vacuum conditions.
In the method, the weight ratio of the ammonium phosphate salt to the petroleum coke in the step (1.1) is 0.1-1: 1, preferably 0.3-0.8: 1.
in the method, the water vapor-containing gas in the step (1.2) is water vapor or a mixed gas of water vapor and a carrier gas, and the volume ratio of the water vapor to the carrier gas in the mixed gas is 1: 20-1: 1, preferably 1: 10-1: 2; the carrier gas is nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
In the method, the pretreatment in the step (1.2) comprises a first-stage pretreatment, a second-stage pretreatment and a cooling process, wherein the temperature of the first-stage pretreatment is 150-250 ℃, the pretreatment is preferably 180-220 ℃, the pretreatment time is 1-6 hours, and the pretreatment is preferably 2-4 hours; the second-stage pretreatment temperature is 300-500 ℃, preferably 350-450 ℃, the pretreatment time is 1-6 hours, preferably 2-4 hours, and the second-stage pretreatment is cooled to 20-100 ℃, preferably 40-80 ℃; the cooling process is preferably carried out under nitrogen protection.
In the method, the volume space velocity of the vapor-containing gas in the step (1.2) is 500-2000 h-1。
In the preparation method of the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide, the preparation method of the silicon-based modified petroleum coke in the step (2) comprises the following steps:
(2.1) uniformly mixing a surfactant, a solvent and deionized water to obtain a solution A;
and (2.2) uniformly mixing the petroleum coke pretreated in the step (1), the silicon-containing compound and the solution A, and then filtering, washing and drying to obtain the silicon-based modified petroleum coke.
In the above method, the surfactant in step (2.1) may be one or more of cetyltrimethylammonium bromide (CTAB), organic dicarboxylic acid, and fatty amine, preferably one or more of cetyltrimethylammonium bromide (CTAB), glutaric acid, and dodecylamine; the solvent can be one or more of hydrochloric acid, absolute ethyl alcohol and citric acid, wherein the concentration of the hydrochloric acid is 0.5-2.5M/L; the mass ratio of the surfactant to the solvent to the deionized water is 1: 1-10: 5 to 60. The mixing of step (2.1) may be carried out at room temperature.
In the above method, the silicon-containing compound in step (2.2) may be silica sol, water glass or tetraethoxysilane, preferably tetraethoxysilane; the mass ratio of the petroleum coke (calculated by the mass of the initially added petroleum coke) to the silicon-containing compound (calculated by the mass of the silicon element) after the pretreatment in the step (1) is 1: 0.01 to 0.05 of a silicon-containing compound (SiO)xMass) and the surfactant in the step (2.1) in a mass ratio of 1-1.5: 1
In the method, the mixing in the step (2.2) is carried out at 20-90 ℃, any operation in the field which can realize uniform mixing of two-phase materials can be adopted for mixing, such as mechanical stirring, electric stirring and the like, and the mixing time is 2-6 h.
In the method, in the step (2.2), the drying temperature is 100-150 ℃, and the drying time is 2-12 hours.
In the method, the washing in the step (2.2) is carried out by using a proper amount of deionized water until the pH value of the filtrate is neutral.
In the preparation method of the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide, the composite oxide containing the active component and the auxiliary agent in the step (3) is prepared by the following method:
(3.1) weighing a proper amount of active component soluble salt, assistant-containing metal soluble salt and deionized water to prepare a metal precursor salt solution A;
and (3.2) under the stirring condition, uniformly adding the metal precursor solution A obtained in the step (3.1) into an organic acid solution, adjusting the pH value to 1-4, heating at 50-90 ℃, preferably 60-80 ℃ until the solution becomes sticky colloid, drying and roasting to obtain the composite oxide.
In the above method, the active component soluble salt in step (3.1) may be one or more of nitrate, sulfate, hydrochloride, manganate, molybdate and vanadate, preferably nitrate, manganate, molybdate or vanadate, specifically may be one or more of iron nitrate, cobalt nitrate, nickel nitrate, ammonium metavanadate, ammonium molybdate, chromium nitrate, potassium permanganate, sodium permanganate, potassium molybdate, sodium molybdate, ammonium molybdate, molybdic acid, copper nitrate and zinc nitrate, and more preferably is one or more of iron nitrate, cobalt nitrate, nickel nitrate, ammonium metavanadate, ammonium molybdate, chromium nitrate, potassium permanganate, potassium molybdate, copper nitrate and zinc nitrate.
In the above method, the soluble salt containing an auxiliary agent metal in step (3.1) may be one or more of nitrate, sulfate, hydrochloride and oxalate, preferably nitrate, and specifically may be one or more of magnesium nitrate, cerium nitrate, potassium nitrate and zirconium nitrate.
In the above method, the organic acid in step (3.1) is a carboxyl group-containing organic acid, and the carboxyl group-containing organic acid is a hydroxycarboxylic acid composed of element C, H, O, and specifically may be one or more of maleic acid, citric acid, and fumaric acid, and more preferably is citric acid.
In the method, the mass ratio of the organic acid to the active component soluble salt (calculated by the mass of the active component oxide) to the auxiliary agent element-containing soluble salt (calculated by the mass of the auxiliary agent oxide) is 5-15: 1: 0.03 to 15, preferably 5 to 10: 1: 0.15 to 3.4.
In the method, nitric acid or ammonia water is used for adjusting the pH in the step (3.2), and the concentration of the nitric acid or the ammonia water is 0.05-0.5 mol/L; the drying temperature is 80-150 ℃, the drying time is 2-10 h, the preferred drying temperature is 100-120 ℃, and the drying time is 4-6 h; the roasting temperature is 300-800 ℃, the roasting time is 2-8 hours, the preferred roasting temperature is 400-600 ℃, and the roasting time is 4-6 hours.
In the preparation method of the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide, the activating agent in the step (4) is one or more of potassium hydroxide, sodium hydroxide, potassium bicarbonate and sodium bicarbonate, and the potassium hydroxide is preferred.
In the preparation method of the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide, the mass ratio of the composite oxide (calculated by the mass of the active component oxide), the activating agent and the silicon-based modified petroleum coke (calculated by the mass of the initially added petroleum coke) in the step (4) is 0.005-0.16: 0.5-4: 1, preferably 0.015 to 0.11: 1-3: 1.
in the preparation method of the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide, the activation process in the step (4) is as follows: uniformly mixing the composite oxide, the activating agent and the silicon-based modified petroleum coke, heating to an activation temperature in a nitrogen or inert atmosphere, cooling to 20-100 ℃ after activation, and performing subsequent treatment, wherein the inert atmosphere is one or more of helium or argon; the activation temperature is 400-900 ℃, preferably 600-800 ℃, and the activation time is 5-120 min, preferably 10-90 min. The activation process is further preferably carried out under microwave irradiation conditions, the microwave frequency being 2450MHz or 915 MHz; the microwave power is 1-10 kw per kg of petroleum coke, and preferably 2-4 kw. When the activation is carried out under the microwave radiation condition, the activation is further preferably carried out in two sections, the first section is activated for 10-60 min at 400-600 ℃ under the vacuum condition, inert gas or nitrogen is introduced to the atmosphere under the constant temperature condition, and the temperature is continuously increased to 700-900 ℃ under the microwave radiation condition for activation for 10-30 min.
In the preparation method of the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide, the washing in the step (5) is water washing, firstly, the sample obtained in the step (4) is mixed with deionized water, and after uniform mixing, solid-liquid separation is carried out until the pH value of the filtrate is neutral. The mass ratio of the sample obtained in the step (4) to the deionized water is 1: 5-1: 30, and preferably 1: 10-1: 20.
In the preparation method of the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide, the drying temperature in the step (5) is 100-200 ℃, the preferable drying temperature is 120-180 ℃, the drying time is 2-10 hours, and the preferable drying time is 4-8 hours. The drying is preferably carried out under vacuum.
The third aspect of the invention provides a catalyst for preparing low-carbon olefin by the dehydrogenation of low-carbon alkane oxidized by carbon dioxide, which is prepared by the method.
In the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide, the catalyst comprises an active component, an auxiliary agent and a carrier, wherein the active component is one or more of Fe, Co, Ni, V, Mo, Cr, Mn, Cu and Zn, the auxiliary agent is one or more of IA group, IIA group, rare earth elements, Al, Ti, Zr, Nb and Ga, preferably one or more of Mg, K, Zr and Ce, and the carrier is silicon-based modified petroleum coke-based activated carbon, wherein the content of an oxide of the active component is 1-20%, preferably 3-15%, the content of an oxide of the auxiliary agent is 1-10%, preferably 3-8%, and the content of the carrier is 70-98%, preferably 77-94% on the basis of the weight of the catalyst.
In the catalyst for preparing low carbon olefin by carbon dioxide oxidation and low carbon alkane dehydrogenation, the catalyst for preparing low carbon olefin by carbon dioxide oxidation and low carbon alkane dehydrogenation has the following properties: the specific surface area is 500-1800 m2Preferably 700 to 1600 m/g2/g。
In the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide, the active component and the auxiliary agent are embedded into the amorphous defect of the petroleum coke-based active carbon and the graphite microchip layer of the active carbon, and the size of the active metal crystal grain is 1.5-5.8 nm, preferably 2.5-5 nm.
The fourth aspect of the invention provides an application of the catalyst in preparation of low-carbon olefin by carbon dioxide oxidation and dehydrogenation of low-carbon alkane.
Compared with the prior art, the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide and the preparation method thereof have the following advantages:
1. in the preparation method of the catalyst, the petroleum coke is pretreated firstly, the ammonium phosphate is introduced into the petroleum coke, and then the petroleum coke is treated by adopting steam-containing gas, so that the ammonium phosphate is promoted to be decomposed in the petroleum coke to generate ammonia gas and phosphoric acid, the generated ammonia gas provides more primary pores for further activation of the petroleum coke, and meanwhile, the generated phosphoric acid can also be used as an activating agent to carry out primary activation on the petroleum coke, so that a developed pore structure is created. Solves the problems of serious equipment corrosion and higher production cost caused by that the petroleum coke in the prior art is compact in structure, high in crystallinity and lack of primary pores required by activation, and strong alkali with the alkali-coke ratio of more than 3/1 is usually adopted to activate pore-forming in an inert atmosphere.
2. In the preparation method of the catalyst, the phosphoric acid generated by decomposing the ammonium phosphate salt plays a primary activation role on petroleum coke, so that the dosage of a subsequent alkali activator can be reduced, and the catalyst is low in production cost and small in environmental pollution.
3. In the preparation method of the catalyst, SiO is introduced into pretreated petroleum cokexThe/surfactant compound is heated by microwave to decompose the surfactant to obtain the active carbon and the worm pore SiOxThe composite carrier improves the connectivity of carrier pore passages, is beneficial to the diffusion of reactants, intermediate products and products in pores, reduces the deep oxidation of the intermediate products and further improves the selectivity of the products.
4. According to the catalyst and the preparation method thereof, active metal and an auxiliary agent are introduced in the petroleum coke activation process, the active metal and the auxiliary agent enter a diffusion path generated by petroleum coke phase through an activating agent, and are combined with amorphous carbon defects or graphite carbon sheet layers under the action of microwave catalysis to form a high-dispersion and stable-state structure, so that the problem of uneven distribution of the active metal caused by weak action of the inert surface of a carbon-based carrier and the metal of a low-carbon alkane dehydrogenation catalyst taking active carbon as the carrier is solved, and the prepared catalyst has the advantages of good dispersion of active components, high utilization rate, high selectivity of low-carbon alkene and the like.
5. The preparation method of the catalyst improves the dispersion degree of active metal on the surface of the carrier, reduces carbon deposition in the reaction process, improves the diffusion rate of alkane oxidative dehydrogenation intermediate products and low-carbon olefin products, reduces deep oxidation of the intermediate products and the products, and further improves the selectivity of the olefin products.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples.
The specific surface and pore size distribution of the catalyst in the following examples and comparative examples are shown by using low temperature N2Measured by an adsorption method.
Example 1
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 110 ℃ for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (volume space velocity of water vapor gas is 500 h)-1) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
And uniformly mixing 8g of hexadecyl trimethyl ammonium bromide, 40g of citric acid and 200g of deionized water to obtain a solution B, weighing 22.25g of tetraethyl orthosilicate, uniformly mixing the tetraethyl orthosilicate with the pretreated petroleum coke and the solution B, stirring for 4 hours, and drying the obtained colloid at 120 ℃ for 4 hours to obtain the silicon-based modified petroleum coke.
31.45g of ferric nitrate and 1.36g of cerous nitrate are weighed and dissolved in 100mL of deionized water to obtain a solution C; weighing 50g of citric acid, and dissolving in 100mL of deionized water to obtain a solution D; and dropwise adding the solution C into the solution D under the stirring condition, adjusting the pH value of the obtained mixed solution to 2 by using a 0.2mol/L nitric acid solution, heating at 80 ℃ until the solution becomes a viscous colloid, drying for 5 hours in an oven at 110 ℃, and roasting the obtained sample for 5 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-based modified petroleum coke, the composite oxide and 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw to activate for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain Fe accounting for 10 percent of the mass of the catalyst in terms of oxide2O3、5%CeO2、4.8%SiO2The catalyst for the dehydrogenation of ethane to ethylene is denoted as C-1.
Example 2
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 110 ℃ for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (volume space velocity of water vapor gas is 800 h)-1) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Uniformly mixing 8g of glutaric acid, 40g of hydrochloric acid (the concentration is 1.5 moL/L) and 230g of deionized water to obtain a solution B, weighing 22.25g of tetraethyl orthosilicate, uniformly mixing the tetraethyl orthosilicate with the pretreated petroleum coke and the solution B, stirring for 4 hours, and drying the obtained colloid at 120 ℃ for 4 hours to obtain the silicon-based modified petroleum coke.
Weighing 11.3g of potassium permanganate and 2.07g of potassium nitrate, and dissolving in 100mL of deionized water to obtain a solution C; weighing 50g of citric acid, and dissolving in 100mL of deionized water to obtain a solution D; and dropwise adding the solution C into the solution D under the stirring condition, adjusting the pH value of the obtained mixed solution to 1 by using a 0.2mol/L nitric acid solution, heating at 80 ℃ until the solution becomes a viscous colloid, drying for 5 hours in an oven at 110 ℃, and roasting the obtained sample for 5 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-based modified petroleum coke, the composite oxide and 300g of sodium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 600 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 20min, introducing nitrogen to the normal pressure, and continuously heating to 900 ℃ under the condition that the microwave power is 0.3kw for activation for 10 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain MnO with the mass of 10 percent of the catalyst in terms of oxide2、5%K2O、4.8%SiO2The catalyst for the dehydrogenation of ethane to ethylene is denoted as C-2.
Example 3
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 110 ℃ for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (the volume space velocity of water vapor gas is 1200 h)-1) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Uniformly mixing 8g of dodecylamine, 40g of anhydrous ethanol and 230g of deionized water to obtain a solution B, weighing 22.25g of tetraethyl orthosilicate, uniformly mixing the tetraethyl orthosilicate with the pretreated petroleum coke and the solution B, stirring for 4 hours, carrying out solid-liquid separation, washing the obtained solid with deionized water until the filtrate is neutral, and drying at 120 ℃ for 4 hours to obtain the silicon-based modified petroleum coke.
Weighing 24.19g of nickel nitrate and 2.88g of zirconium nitrate, and dissolving in 100mL of deionized water to obtain a solution C; weighing 50g of citric acid, and dissolving in 100mL of deionized water to obtain a solution D; and dropwise adding the solution C into the solution D under the stirring condition, adjusting the pH value of the obtained mixed solution to 3 by using a 0.2mol/L nitric acid solution, heating at 80 ℃ until the solution becomes a viscous colloid, drying for 5 hours in an oven at 110 ℃, and roasting the obtained sample for 5 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-based modified petroleum coke, the composite oxide, 200g of potassium bicarbonate and 100g of potassium hydroxide, putting the mixture into a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 400 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 60min, introducing nitrogen to the normal pressure, and continuously heating to 700 ℃ under the condition that the microwave power is 0.3kw for activation for 30 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ under a vacuum conditionDrying for 6h to obtain NiO and ZrO with the mass percentage of 10 percent and 5 percent of the catalyst in terms of oxide2、4.8%SiO2The catalyst for producing propylene by dehydrogenation of propane is denoted as C-3.
Example 4
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 110 ℃ for 5 h. Pretreating the dried solid sample for 3h at 200 ℃ by using mixed gas of water vapor and argon gas in a volume ratio of 1:5 (the volume space velocity of the mixed gas is 1200 h)-1) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
And uniformly mixing 8g of hexadecyl trimethyl ammonium bromide, 40g of citric acid and 200g of deionized water to obtain a solution B, weighing 22.25g of tetraethyl orthosilicate, uniformly mixing the tetraethyl orthosilicate with the pretreated petroleum coke and the solution B, stirring for 4 hours, and drying the obtained colloid at 120 ℃ for 4 hours to obtain the silicon-based modified petroleum coke.
Weighing 9.24g of ammonium metavanadate and 19.77g of magnesium nitrate, and dissolving in 100mL of deionized water to obtain a solution C; weighing 50g of citric acid, and dissolving in 100mL of deionized water to obtain a solution D; and dropwise adding the solution C into the solution D under the stirring condition, adjusting the pH value of the obtained mixed solution to 2 by using a 0.2mol/L nitric acid solution, heating at 80 ℃ until the solution becomes a viscous colloid, drying for 5 hours in an oven at 110 ℃, and roasting the obtained sample for 5 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-based modified petroleum coke, the composite oxide, 100g of sodium bicarbonate and 200g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw to activate for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 is mixed with deionized water, fully stirred and then subjected to solid-liquid separationUntil the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain the catalyst with the mass percent of 10 percent V calculated by oxide2O5、5%MgO、4.8%SiO2The catalyst for producing propylene by dehydrogenation of propane is denoted as C-4.
Example 5
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 110 ℃ for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (the volume space velocity of water vapor gas is 1200 h)-1) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Uniformly mixing 8g of glutaric acid, 40g of hydrochloric acid (the concentration is 1.5 moL/L) and 230g of deionized water to obtain a solution B, weighing 22.25g of tetraethyl orthosilicate, uniformly mixing the tetraethyl orthosilicate with the pretreated petroleum coke and the solution B, stirring for 4 hours, and drying the obtained colloid at 120 ℃ for 4 hours to obtain the silicon-based modified petroleum coke.
Weighing 24.19g of nickel nitrate and 1.36g of cerium nitrate, and dissolving in 100mL of deionized water to obtain a solution C; weighing 50g of citric acid, and dissolving in 100mL of deionized water to obtain a solution D; and dropwise adding the solution C into the solution D under the stirring condition, adjusting the pH value of the obtained mixed solution to 3 by using a 0.2mol/L nitric acid solution, heating at 80 ℃ until the solution becomes a viscous colloid, drying for 5 hours in an oven at 110 ℃, and roasting the obtained sample for 5 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-based modified petroleum coke, the composite oxide and 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw to activate for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 with deionizationMixing water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain NiO and CeO with the mass percentage of 10 percent and 5 percent of the catalyst calculated by oxides2、4.8%SiO2The catalyst for preparing isobutene by isobutane dehydrogenation is marked as C-5.
Example 6
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 110 ℃ for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (the volume space velocity of water vapor gas is 1200 h)-1) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Uniformly mixing 8g of dodecylamine, 40g of anhydrous ethanol and 230g of deionized water to obtain a solution B, weighing 22.25g of tetraethyl orthosilicate, uniformly mixing the tetraethyl orthosilicate with the pretreated petroleum coke and the solution B, stirring for 4 hours, carrying out solid-liquid separation, washing the obtained solid with deionized water until the filtrate is neutral, and drying at 120 ℃ for 4 hours to obtain the silicon-based modified petroleum coke.
Weighing 17.53g of cupric nitrate and 2.07g of potassium nitrate, and dissolving in 100mL of deionized water to obtain a solution C; weighing 50g of citric acid, and dissolving in 100mL of deionized water to obtain a solution D; and dropwise adding the solution C into the solution D under the stirring condition, adjusting the pH value of the obtained mixed solution to be 4 by adopting a 0.2mol/L nitric acid solution, heating at 80 ℃ until the solution becomes a viscous colloid, then drying for 5 hours in an oven at 110 ℃, and roasting the obtained sample for 5 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-based modified petroleum coke, the composite oxide and 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 600 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 20min, introducing nitrogen to the normal pressure, and continuously heating to 900 ℃ under the condition that the microwave power is 0.3kw to activate for 10 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain the catalyst, wherein the mass of the solid sample is 10 percent of CuO and 5 percent of K in terms of oxides2O、4.8%SiO2The catalyst for preparing isobutene by dehydrogenating isobutane is marked as C-6.
Example 7
Weighing 50g of ammonium dihydrogen phosphate, and dissolving in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 110 ℃ for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (the volume space velocity of water vapor gas is 1200 h)-1) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Uniformly mixing 3g of hexadecyl trimethyl ammonium bromide, 13g of citric acid and 80g of deionized water to obtain a solution B, weighing 7.42g of tetraethyl orthosilicate, uniformly mixing the tetraethyl orthosilicate with the pretreated petroleum coke and the solution B, stirring for 4 hours, and drying the obtained colloid at 120 ℃ for 4 hours to obtain the silicon-based modified petroleum coke.
Weighing 12.97g of ferric nitrate and 0.67g of cerous nitrate, and dissolving in 100mL of deionized water to obtain a solution C; weighing 20g of citric acid, and dissolving in 100mL of deionized water to obtain a solution D; and dropwise adding the solution C into the solution D under the stirring condition, adjusting the pH value of the obtained mixed solution to 1 by using a 0.2mol/L nitric acid solution, heating at 80 ℃ until the solution becomes a viscous colloid, drying for 5 hours in an oven at 110 ℃, and roasting the obtained sample for 5 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-based modified petroleum coke, the composite oxide and 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 400 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 60min, introducing nitrogen to the normal pressure, and continuously heating to 700 ℃ under the condition that the microwave power is 0.3kw to activate for 30 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain Fe accounting for 5 percent of the mass of the catalyst in terms of oxide2O3、3%CeO2、2%SiO2The catalyst for the dehydrogenation of ethane to ethylene of (2) is denoted as C-7.
Example 8
Weighing 50g of ammonium hydrogen phosphate, and dissolving in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 90 ℃ for 8 h. Pre-treating the dried solid sample for 3h at 200 ℃ by using mixed gas with the volume ratio of water vapor to nitrogen being 1:2 (the volume space velocity of the mixed gas is 800 h)-1) And then raising the temperature to 400 ℃, continuing to pretreat for 3 hours, and then cooling to 40 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Uniformly mixing 11g of dodecylamine, 55g of anhydrous ethanol and 300g of deionized water to obtain a solution B, weighing 30g of tetraethyl orthosilicate, uniformly mixing the tetraethyl orthosilicate with the pretreated petroleum coke and the solution B, stirring for 4 hours, carrying out solid-liquid separation, washing the obtained solid with the deionized water until the filtrate is neutral, and drying for 4 hours at 120 ℃ to obtain the silicon-based modified petroleum coke.
Weighing 43.64g of nickel nitrate and 5.55g of zirconium nitrate, and dissolving in 100mL of deionized water to obtain a solution C; weighing 90g of citric acid, and dissolving in 150mL of deionized water to obtain a solution D; and dropwise adding the solution C into the solution D under the stirring condition, adjusting the pH value of the obtained mixed solution to 2 by using a 0.2mol/L nitric acid solution, heating at 80 ℃ until the solution becomes a viscous colloid, drying for 5 hours in an oven at 110 ℃, and roasting the obtained sample for 5 hours at 700 ℃ to obtain the composite oxide.
And uniformly mixing the silicon-based modified petroleum coke, the composite oxide and 300g of potassium hydroxide, placing the mixture in a tube furnace, and heating to 800 ℃ in a nitrogen atmosphere to activate for 40 min. .
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain NiO and ZrO with the mass percentage of 15 percent and 8 percent of the catalyst in terms of oxide2、5.35%SiO2The catalyst for producing propylene by dehydrogenation of propane is denoted as C-8.
Example 9
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 110 ℃ for 5 h. Pre-treating the dried solid sample for 3h at 200 ℃ by using mixed gas with the volume ratio of water vapor to helium gas being 1:10 (the volume space velocity of the mixed gas is 1500 h)-1) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Uniformly mixing 13g of glutaric acid, 65g of hydrochloric acid (the concentration is 1.5 moL/L) and 400g of deionized water to obtain a solution B, weighing 37.1g of tetraethyl orthosilicate, uniformly mixing the tetraethyl orthosilicate with the pretreated petroleum coke and the solution B, stirring for 4 hours, and drying the obtained colloid at 120 ℃ for 4 hours to obtain the silicon-based modified petroleum coke.
71.49g of nickel nitrate and 4.02g of cerium nitrate are weighed and dissolved in 150mL of deionized water to obtain a solution C; weighing 150g of citric acid, and dissolving in 200mL of deionized water to obtain a solution D; and dropwise adding the solution C into the solution D under the stirring condition, adjusting the pH value of the obtained mixed solution to 3 by using a 0.2mol/L nitric acid solution, heating at 80 ℃ until the solution becomes a viscous colloid, drying for 5 hours in an oven at 110 ℃, and roasting the obtained sample for 5 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-based modified petroleum coke, the composite oxide and 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, and heating to 900 ℃ in nitrogen atmosphere under the condition that the microwave power is 0.3kw for activation for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain the catalyst, wherein the mass of the solid sample is 20 percent of NiO and 10 percent of CeO in terms of oxides2、5.44%SiO2The catalyst for preparing isobutene by isobutane dehydrogenation is marked as C-9.
Comparative example 1
31.45g of ferric nitrate and 1.36g of cerous nitrate are weighed and dissolved in 100mL of deionized water to obtain a solution A; weighing 50g of citric acid, and dissolving in 100mL of deionized water to obtain a solution B; under the condition of stirring, dropwise adding the solution A into the solution B, adjusting the pH value of the obtained mixed solution to 2 by using a 0.2mol/L nitric acid solution, then heating at 80 ℃ until the solution becomes a sticky colloid, then drying for 5 hours in an oven at 110 ℃, and roasting the obtained sample for 5 hours at 700 ℃ to obtain the composite oxide.
Grinding 100g of petroleum coke into powder, then uniformly mixing the powder with the composite oxide and 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, then introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw to activate for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain Fe accounting for 10 percent of the mass of the catalyst in terms of oxide2O3、5%CeO2The catalyst for the dehydrogenation of ethane to ethylene is denoted as D-1.
Comparative example 2
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; grinding 100g petroleum coke into powder, adding into solution A, standing for 1.5 hr, filtering, placing the obtained solid sample in an oven at 110 deg.CDrying for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (the volume space velocity of water vapor gas is 1200 h)-1) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
And uniformly mixing 8g of hexadecyl trimethyl ammonium bromide, 40g of citric acid and 200g of deionized water to obtain a solution B, weighing 22.25g of tetraethyl orthosilicate, uniformly mixing the tetraethyl orthosilicate with the pretreated petroleum coke and the solution B, stirring for 4 hours, and drying the obtained colloid at 120 ℃ for 4 hours to obtain the silicon-based modified petroleum coke.
Grinding the silicon-based modified petroleum coke into powder, then uniformly mixing the powder with 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, then introducing nitrogen to the normal pressure, and continuing heating to 800 ℃ under the condition that the microwave power is 0.3kw to activate for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under the vacuum condition.
Weighing 31.45g of ferric nitrate and 1.36g of cerous nitrate, dissolving in 100mL of deionized water, adding into the sample obtained in the step of vacuum drying, stirring uniformly, aging for 2h, then placing in a vacuum drying oven, drying at 150 ℃ for 6h under a vacuum condition, roasting the dried sample at 700 ℃ for 6h under a nitrogen atmosphere, and thus obtaining Fe with the mass percentage of 10% of the catalyst in terms of oxide2O3、5%CeO2、4.8%SiO2The catalyst for the dehydrogenation of ethane to ethylene is denoted as D-2.
Comparative example 3
Uniformly mixing 8g of hexadecyl trimethyl ammonium bromide, 40g of citric acid and 200g of deionized water to obtain a solution A, weighing 22.25g of tetraethyl orthosilicate, uniformly mixing the tetraethyl orthosilicate with the pretreated petroleum coke and the solution A, stirring for 4 hours, and drying the obtained colloid at 120 ℃ for 4 hours to obtain the silicon-based modified petroleum coke.
31.45g of ferric nitrate and 1.36g of cerous nitrate are weighed and dissolved in 100mL of deionized water to obtain a solution B; weighing 50g of citric acid, and dissolving in 100mL of deionized water to obtain a solution C; and dropwise adding the solution B into the solution C under the stirring condition, adjusting the pH value of the obtained mixed solution to 2 by using a 0.2mol/L nitric acid solution, heating at 80 ℃ until the solution becomes a viscous colloid, drying for 5 hours in an oven at 110 ℃, and roasting the obtained sample for 5 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-based modified petroleum coke, the composite oxide and 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw to activate for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain Fe accounting for 10 percent of the mass of the catalyst in terms of oxide2O3、5%CeO2、4.8%SiO2The catalyst for the dehydrogenation of ethane to ethylene is denoted as D-3.
Evaluation conditions were as follows: the reaction for preparing olefin by dehydrogenating light alkane is carried out on a miniature reaction device of a normal pressure fixed bed. The reaction temperature is 500-700 ℃, and the dosage of the catalyst is 200 mg. Alkane in the raw material gas: CO 22：N2=1：1：4，GHSV=3000mL∙g-1∙h-1The reaction results are shown in Table 1.
TABLE 1 catalyst Properties and reaction Performance
Claims (32)
1. A catalyst for preparing low-carbon olefin by carbon dioxide oxidation and dehydrogenation of low-carbon alkane comprises an active component, an auxiliary agent and a carrier, wherein the active component is one or more of Fe, Co, Ni, V, Mo, Cr, Mn, Cu or Zn, the auxiliary agent is one or more of IA group, IIA group, rare earth elements, Al, Ti, Zr, Nb and Ga, preferably one or more of Mg, K, Zr and Ce, and the carrier is silicon-based modified petroleum coke-based activated carbon, wherein the content of the active component is 1-20%, preferably 3-15%, the content of the auxiliary agent element is 1-10%, preferably 3-8%, and the content of the carrier is 70-98%, preferably 77-94% on the basis of the weight of the catalyst.
2. The catalyst for preparing low-carbon olefin by the dehydrogenation of low-carbon alkane oxidized by carbon dioxide according to claim 1, which is characterized in that: the specific surface of the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide is 500-1800 m2Preferably 700 to 1600 m/g2/g。
3. The catalyst for preparing low-carbon olefin by the dehydrogenation of low-carbon alkane oxidized by carbon dioxide according to claim 1, which is characterized in that: in the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide, the active components and the auxiliary agent are embedded into the amorphous defects of the petroleum coke-based activated carbon and the activated carbon graphite microchip layer, and the size of the active metal crystal grains is 1.5-5.8 nm, preferably 2.5-5 nm.
4. A preparation method of a catalyst for preparing low-carbon olefin by carbon dioxide oxidation and low-carbon alkane dehydrogenation comprises the following steps:
(1) pretreating petroleum coke;
(2) preparing silicon-based modified petroleum coke;
(3) preparing a composite oxide containing an active component and an auxiliary agent;
(4) mixing the silicon-based modified petroleum coke obtained in the step (2), the composite oxide obtained in the step (3) and an activating agent, and activating after uniformly mixing;
(5) and (4) washing and drying the sample obtained in the step (4) to obtain the catalyst for preparing the low-carbon olefin by oxidizing the low-carbon alkane with carbon dioxide and dehydrogenating the low-carbon alkane.
5. The method for preparing the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide according to claim 4, which is characterized by comprising the following steps of: the pretreatment in the step (1) comprises the following steps:
(1.1) introducing ammonium phosphate salt into petroleum coke, and then drying;
(1.2) pretreating the sample obtained in the step (1.1) with water vapor-containing gas.
6. The method for preparing the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide according to claim 5, which is characterized by comprising the following steps of: in the step (1.1), the ammonium phosphate salt is one or more of ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate, and preferably ammonium phosphate.
7. The method for preparing the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide according to claim 5, which is characterized by comprising the following steps of: in the step (1.1), the drying temperature is 60-120 ℃, the preferred drying temperature is 80-100 ℃, the drying time is 2-8 hours, and the preferred drying time is 4-6 hours; the drying is further preferably carried out under vacuum conditions.
8. The method for preparing the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide according to claim 5, which is characterized by comprising the following steps of: in the step (1.1), the weight ratio of the ammonium phosphate to the petroleum coke is 0.1-1: 1, preferably 0.3-0.8: 1.
9. the method for preparing the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide according to claim 5, which is characterized by comprising the following steps of: in the step (1.2), the vapor-containing gas is vapor or a mixed gas of the vapor and a carrier gas, and the volume ratio of the vapor to the carrier gas in the mixed gas is 1: 20-1: 1, preferably 1: 10-1: 2; the carrier gas is nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
10. The method for preparing the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide according to claim 5, which is characterized by comprising the following steps of: the pretreatment in the step (1.2) comprises a first-stage pretreatment, a second-stage pretreatment and a cooling process, wherein the first-stage pretreatment is carried out at the temperature of 150-250 ℃, preferably 180-220 ℃, and the pretreatment time is 1-6 hours, preferably 2-4 hours; the second-stage pretreatment temperature is 300-500 ℃, preferably 350-450 ℃, the pretreatment time is 1-6 hours, preferably 2-4 hours, and the second-stage pretreatment is cooled to 20-100 ℃, preferably 40-80 ℃; the cooling process is preferably carried out under nitrogen protection.
11. The method for preparing the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide according to claim 5, which is characterized by comprising the following steps of: the volume space velocity of the vapor-containing gas in the step (1.2) is 500-2000 h-1。
12. The method for preparing the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide according to claim 4, which is characterized by comprising the following steps of: the preparation method of the silicon-based modified petroleum coke in the step (2) comprises the following steps:
(2.1) uniformly mixing a surfactant, a solvent and deionized water to obtain a solution A;
and (2.2) uniformly mixing the petroleum coke pretreated in the step (1), the silicon-containing compound and the solution A, and then filtering, washing and drying to obtain the silicon-based modified petroleum coke.
13. The method for preparing a catalyst for preparing light olefins by the dehydrogenation of light alkanes oxidized by carbon dioxide according to claim 12, which comprises the following steps: the surfactant in the step (2.1) is one or more of cetyl trimethyl ammonium bromide, organic dicarboxylic acid and fatty amine, preferably one or more of cetyl trimethyl ammonium bromide, glutaric acid and lauryl amine; the solvent is one or more of hydrochloric acid, absolute ethyl alcohol and citric acid.
14. The method for preparing a catalyst for preparing light olefins by the dehydrogenation of light alkanes oxidized by carbon dioxide according to claim 12, which comprises the following steps: the mass ratio of the surfactant to the solvent to the deionized water is 1: 1-10: 5 to 60.
15. The method for preparing a catalyst for preparing light olefins by the dehydrogenation of light alkanes oxidized by carbon dioxide according to claim 12, which comprises the following steps: in the step (2.2), the silicon-containing compound is silica sol, water glass or tetraethoxysilane, preferably tetraethoxysilane; the mass ratio of the petroleum coke pretreated in the step (1) to the silicon-containing compound is 1: 0.01-0.05, and the mass ratio of the silicon-containing compound to the surfactant in the step (2.1) is 1-1.5: 1.
16. The method for preparing a catalyst for preparing light olefins by the dehydrogenation of light alkanes oxidized by carbon dioxide according to claim 12, which comprises the following steps: and (3) mixing at 20-90 ℃ in the step (2.2).
17. The method for preparing a catalyst for preparing light olefins by the dehydrogenation of light alkanes oxidized by carbon dioxide according to claim 12, which comprises the following steps: and (2.2) drying at 100-150 ℃ for 2-12 h.
18. The method for preparing the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide according to claim 4, which is characterized by comprising the following steps of: the composite oxide containing the active component and the auxiliary agent in the step (3) is prepared by the following method:
(3.1) weighing active component soluble salt, assistant-containing metal soluble salt and deionized water to prepare a metal precursor salt solution A;
(3.2) under the stirring condition, uniformly adding the metal precursor salt solution A into an organic acid solution, adjusting the pH value to 1-4, then heating at 50-90 ℃, preferably 60-80 ℃ until the solution becomes a sticky colloid, and then drying and roasting to obtain the composite oxide.
19. The method for preparing a catalyst for preparing light olefins by the dehydrogenation of light alkanes oxidized by carbon dioxide according to claim 18, which is characterized in that: the active component soluble salt in the step (3.1) is one or more of nitrate, sulfate, hydrochloride, manganate, molybdate and vanadate, preferably nitrate, manganate, molybdate or vanadate, specifically one or more of ferric nitrate, cobalt nitrate, nickel nitrate, ammonium metavanadate, ammonium molybdate, chromic nitrate, potassium permanganate, sodium permanganate, potassium molybdate, sodium molybdate, ammonium molybdate, molybdic acid, copper nitrate or zinc nitrate, and further preferably one or more of ferric nitrate, cobalt nitrate, nickel nitrate, ammonium metavanadate, ammonium molybdate, chromic nitrate, potassium permanganate, potassium molybdate, copper nitrate and zinc nitrate.
20. The method for preparing a catalyst for preparing light olefins by the dehydrogenation of light alkanes oxidized by carbon dioxide according to claim 18, which is characterized in that: the soluble salt containing the auxiliary agent metal in the step (3.1) is one or more of nitrate, sulfate, hydrochloride and oxalate, preferably nitrate, and specifically one or more of magnesium nitrate, cerium nitrate, potassium nitrate and zirconium nitrate.
21. The method for preparing a catalyst for preparing light olefins by the dehydrogenation of light alkanes oxidized by carbon dioxide according to claim 18, which is characterized in that: the organic acid in the step (3.1) is an organic acid containing a carboxyl group, the organic acid containing a carboxyl group is a hydroxycarboxylic acid consisting of the element C, H, O, specifically one or more of maleic acid, citric acid and fumaric acid, and further preferably citric acid.
22. The method for preparing a catalyst for preparing light olefins by the dehydrogenation of light alkanes oxidized by carbon dioxide according to claim 18, which is characterized in that: the mol ratio of the organic acid to the active component soluble salt to the auxiliary agent element-containing soluble salt is 5-15: 1: 0.03 to 15, preferably 5 to 10: 1: 0.15 to 3.4.
23. The method for preparing a catalyst for preparing light olefins by the dehydrogenation of light alkanes oxidized by carbon dioxide according to claim 18, which is characterized in that: in the step (3.2), nitric acid or ammonia water is used for adjusting the pH, and the concentration of the nitric acid or the ammonia water is 0.05-0.5 mol/L; the drying temperature is 80-150 ℃, the drying time is 2-10 h, the preferred drying temperature is 100-120 ℃, and the drying time is 4-6 h; the roasting temperature is 300-800 ℃, the roasting time is 2-8 hours, the preferred roasting temperature is 400-600 ℃, and the roasting time is 4-6 hours.
24. The method for preparing the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide according to claim 4, which is characterized by comprising the following steps of: in the step (4), the activating agent is one or more of potassium hydroxide, sodium hydroxide, potassium bicarbonate and sodium bicarbonate, and preferably potassium hydroxide.
25. The method for preparing the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide according to claim 4, which is characterized by comprising the following steps of: the mass ratio of the composite oxide (calculated by the mass of the active metal elements), the activating agent and the silicon-based modified petroleum coke in the step (4) is 0.005-0.16: 0.5-4: 1, preferably 0.015 to 0.11: 1-3: 1.
26. the method for preparing the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide according to claim 4, which is characterized by comprising the following steps of: the activation process in the step (4) is as follows: uniformly mixing the composite oxide, the activating agent and the silicon-based modified petroleum coke, heating to an activation temperature in a nitrogen or inert atmosphere, cooling to 20-100 ℃ after activation, and performing subsequent treatment, wherein the activation temperature is 400-900 ℃, preferably 600-800 ℃, and the activation time is 5-120 min, preferably 10-90 min.
27. The method for preparing a catalyst for preparing light olefins by dehydrogenation of light alkanes oxidized by carbon dioxide according to claim 26, wherein the method comprises the following steps: the activation process is carried out under the condition of microwave radiation, and the microwave frequency is 2450MHz or 915 MHz; the microwave power is 1-10 kw per kg of petroleum coke, and preferably 2-4 kw.
28. The method for preparing a catalyst for preparing light olefins by dehydrogenation of light alkanes oxidized by carbon dioxide according to claim 27, wherein the method comprises the following steps: when the activation is carried out under the microwave radiation condition, two-stage activation is carried out, wherein the first stage is activated for 10-60 min at 400-600 ℃ under the vacuum condition, inert gas or nitrogen is introduced to the atmosphere under the constant temperature condition, and the temperature is continuously increased to 700-900 ℃ under the microwave radiation condition for activation for 10-30 min.
29. The method for preparing the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide according to claim 4, which is characterized by comprising the following steps of: washing in the step (5) is water washing, firstly, mixing the sample obtained in the step (4) with deionized water, uniformly mixing, and then carrying out solid-liquid separation until the pH value of the filtrate is neutral; the mass ratio of the sample obtained in the step (4) to the deionized water is 1: 5-1: 30, and preferably 1: 10-1: 20.
30. The method for preparing the catalyst for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane oxidized by the carbon dioxide according to claim 4, which is characterized by comprising the following steps of: the drying temperature in the step (5) is 100-200 ℃, the preferable drying temperature is 120-180 ℃, the drying time is 2-10 hours, and the preferable drying time is 4-8 hours; the drying is preferably carried out under vacuum.
31. A catalyst for preparing low-carbon olefin by carbon dioxide oxidation and low-carbon alkane dehydrogenation is characterized in that: the catalyst is prepared by the method of any one of claims 4 to 30.
32. Use of the catalyst of any one of claims 1-3 and 31 in the dehydrogenation of lower alkanes to lower olefins by oxidation with carbon dioxide.
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Effective date of registration: 20231114 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |