CN115869995A - Catalyst for preparing low-carbon olefin by catalytic cracking and preparation method thereof - Google Patents
Catalyst for preparing low-carbon olefin by catalytic cracking and preparation method thereof Download PDFInfo
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- CN115869995A CN115869995A CN202111156504.9A CN202111156504A CN115869995A CN 115869995 A CN115869995 A CN 115869995A CN 202111156504 A CN202111156504 A CN 202111156504A CN 115869995 A CN115869995 A CN 115869995A
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- molecular sieve
- catalyst
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- aluminum
- alumina
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- 239000003054 catalyst Substances 0.000 title claims abstract description 160
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 65
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 179
- 239000002808 molecular sieve Substances 0.000 claims abstract description 173
- 238000006243 chemical reaction Methods 0.000 claims abstract description 104
- 239000011159 matrix material Substances 0.000 claims abstract description 79
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000005336 cracking Methods 0.000 claims abstract description 40
- 239000011148 porous material Substances 0.000 claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 22
- 238000012546 transfer Methods 0.000 claims abstract description 18
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 239000004927 clay Substances 0.000 claims abstract description 9
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 97
- 239000000243 solution Substances 0.000 claims description 88
- 229910001868 water Inorganic materials 0.000 claims description 63
- 230000032683 aging Effects 0.000 claims description 61
- 238000003756 stirring Methods 0.000 claims description 60
- 238000004537 pulping Methods 0.000 claims description 59
- 238000001035 drying Methods 0.000 claims description 44
- 238000001694 spray drying Methods 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 37
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- 230000000694 effects Effects 0.000 claims description 28
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 23
- 239000005995 Aluminium silicate Substances 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 235000012211 aluminium silicate Nutrition 0.000 claims description 21
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- -1 carbon olefin Chemical class 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 238000010306 acid treatment Methods 0.000 claims description 4
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 229910052621 halloysite Inorganic materials 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims 1
- 239000010779 crude oil Substances 0.000 abstract description 75
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 33
- 235000011114 ammonium hydroxide Nutrition 0.000 description 33
- 238000001914 filtration Methods 0.000 description 33
- 239000003921 oil Substances 0.000 description 29
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 25
- 238000011156 evaluation Methods 0.000 description 24
- 239000000463 material Substances 0.000 description 24
- 150000005671 trienes Chemical class 0.000 description 24
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 20
- 150000002430 hydrocarbons Chemical class 0.000 description 19
- 229930195733 hydrocarbon Natural products 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000002131 composite material Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000643 oven drying Methods 0.000 description 13
- 239000002872 contrast media Substances 0.000 description 12
- 235000012239 silicon dioxide Nutrition 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 239000002283 diesel fuel Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 7
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000020477 pH reduction Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006276 transfer reaction Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000002149 hierarchical pore Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- VFYUVMGJOFRPRT-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-dimethyl-nonylazanium Chemical compound CCCCCCCCC[N+](C)(C)C1CC(C)(C)N([O])C(C)(C)C1 VFYUVMGJOFRPRT-UHFFFAOYSA-N 0.000 description 1
- 102100029272 5-demethoxyubiquinone hydroxylase, mitochondrial Human genes 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 101100219344 Arabidopsis thaliana CAT7 gene Proteins 0.000 description 1
- 101100494447 Arabidopsis thaliana CAT9 gene Proteins 0.000 description 1
- 101150013917 CAT8 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 1
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 1
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 1
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 101000770593 Homo sapiens 5-demethoxyubiquinone hydroxylase, mitochondrial Proteins 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 108091006231 SLC7A2 Proteins 0.000 description 1
- 108091006230 SLC7A3 Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000009096 changqing Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing low-carbon olefin by catalytic cracking, which comprises the following components: 5-20 wt% of high silica alumina ratio Y-type molecular sieve, 20-60 wt% of modified ZSM-5 molecular sieve, 0.5-25 wt% of macroporous matrix material, 0.5-15 wt% of hydrogen transfer inhibiting component, 15-60 wt% of clay, 2-20 wt% of binder, and the silica alumina ratio of the high silica alumina ratio Y-type molecular sieve is more than 9; the modified element of the modified ZSM-5 molecular sieve comprises at least one of alkaline earth metal, rare earth metal and phosphorus element; the pore volume of the macroporous matrix material is 1.0-2.5 cm 3 (ii)/g, the average pore diameter is 5-100 nm; hydrogen rotorThe transfer component is a transition metal oxide. The invention also relates to a preparation method of the catalyst. The catalyst provided by the invention is used for preparing low-carbon olefin by directly catalyzing and cracking crude oil, and has the characteristics of high crude oil conversion rate and high low-carbon olefin yield.
Description
Technical Field
The invention belongs to the field of oil refining catalysts, and particularly relates to a catalyst suitable for preparing low-carbon olefin by catalytic cracking and a preparation method thereof, in particular to a catalyst suitable for preparing low-carbon olefin by directly catalytic cracking crude oil.
Background
The oil refining capacity of China is continuously increased by 2018, and the oil refining capacity of China already reaches 8.31 hundred million tons/year and is the second place in the world. The actual processing amount of crude oil is 6.04 hundred million tons, the processing load is less than 73 percent, the productivity is over 2 hundred million tons, and the market competition of the finished oil is strong. Meanwhile, the demand of low-carbon olefins mainly comprising ethylene, propylene and butylene keeps higher acceleration and becomes a main driving force for the increase of the demand of crude oil. This requires the refinery to adjust the product structure, reduce the production of oil products and increase the production of light olefins.
The low-carbon olefin is an important basic organic chemical raw material and has wide application. At present, the mainstream way for preparing low-carbon olefin in China is still through naphtha steam cracking process, and naphtha used as raw material faces serious shortage situation, and energy consumption and raw material cost are high. On the other hand, the Daqing and Changqing paraffin-based crude oil in China has high alkane content, high characteristic factor and low density, and is particularly suitable to be used as a raw material for producing low-carbon olefin by catalytic cracking. Under the situation, the direct catalytic cracking of crude oil to prepare low-carbon olefin becomes one of the main means for conversion upgrading from oil refining to chemical industry, quality improvement and efficiency improvement of refining enterprises.
At present, the research related to the technology of preparing low carbon olefins by direct catalytic cracking of crude oil is rising. The ExxonMobil company has developed a process for converting crude oil directly to light olefins without the need for a refining process, which bypasses the conventional atmospheric and vacuum distillation process, and supplies crude oil directly to a cracking furnace, and adds a flash tank between the convection section and the radiation section of the cracking furnace, respectively, preheats the crude oil to separate lighter components by flash evaporation, and then returns the extracted oil gas to the radiation section coil in the furnace and cracks it in the usual manner, and the heavy liquid components collected at the bottom of the flash tank are sent to a refinery or are sold on the market. According to the Saudi and Saudi basic industries, a project for directly converting crude oil which is built for 2000 ten thousand tons/year into various petrochemical products is declared in 2017, and the project is expected to be put into operation in 2025. This technology is a $ 200/ton lower production cost compared to conventional naphtha cracking technology, but hydrocracking and catalytic cracking units will add capital costs that are comparable to current sauter naphtha cracking costs at 15% pre-tax return on investment. In order to achieve higher chemical conversion and commercialize the technology, a joint development agreement was signed by satd amai and siberia (CB & I) and chevrons (Lummus Global) in 2018, aiming to improve the conversion rate of chemical products directly produced from crude oil to 70-80% by developing hydrocracking technology, and once the technology is successfully commercialized, at least 1400 million tons of chemical products are produced every year, taking 2000 million tons of crude oil as an example of annual processed quantity, compared with the new ethylene production capacity of an ethane cracking plant of only 1100 million tons/year in north america-2016-2022, the technology will severely impact the whole petrochemical industry.
In the development process of the technology for preparing low-carbon olefin by directly catalyzing and cracking crude oil, the development of a novel high-efficiency catalyst plays a crucial role, and the performance of the catalyst determines the conversion rate of raw materials and the selectivity of products to a great extent and determines the economic benefit of a device. Unlike naphtha and heavy oil, when crude oil is directly used as catalytic cracking raw material, the main characteristic is that the distillation range of crude oil is wide, and the catalyst needs to convert micromolecular hydrocarbon and macromolecular hydrocarbon in crude oil at the same time, thus providing extremely high requirements for the performance of the catalyst. The cracking conditions of micromolecule hydrocarbon and macromolecule hydrocarbon are different, and relatively speaking, the activation energy of the micromolecule hydrocarbon cracking is high, the cracking difficulty is large, and the catalyst is required to have a strong acid active center; the activation energy of cracking macromolecular hydrocarbons is low, cracking is easy, but the molecular size is large, and the catalyst is required to have better diffusion performance. Therefore, from the perspective of molecular management, the direct catalytic cracking of wide-cut crude oil to produce light olefins requires the development of catalysts with different structures and high conversion efficiency of hydrocarbon molecules, and requires that the catalysts have both strong acid active centers and appropriate-proportion hierarchical pore structures.
CN108097303A discloses a preparation method of a catalyst for preparing low-carbon olefins by catalytic cracking of diesel oil, which comprises the following steps: (1) Mixing aluminum hydroxide, phosphoric acid and water, pulping, heating to 75-95 ℃, and reacting for 1-3 hours for later use; (2) Mixing and pulping the ZSM-5 molecular sieve, water, zinc chloride and ferric chloride, filtering, and roasting at 550-650 ℃ for 0.5-2 hours to prepare the ZSM-5 modified molecular sieve; (3) Mixing and pulping the colloid prepared in the step (1), water and the ZSM-5 modified molecular sieve prepared in the step (2) and kaolin; (4) Pulping the modified Y-type molecular sieve, the pseudo-boehmite and water, adding hydrochloric acid for acidification, and uniformly stirring; (5) And (3) quickly adding the slurry obtained in the step (3) into the slurry obtained in the step (4), uniformly mixing, spraying for granulation, washing with water, and drying to obtain the catalyst, wherein the modified molecular sieve improves the selectivity of low-carbon olefin and the abrasion index of the catalyst.
CN1222558A discloses a catalyst for preparing low-carbon olefins by catalytic thermal cracking, which has the following composition (by weight of the catalyst): 10 to 70 percent of clay, 5 to 85 percent of inorganic oxide and 1 to 50 percent of zeolite, wherein the zeolite is 0 to 25 percent of Y-type zeolite and 75 to 100 percent of pentasil zeolite with a five-membered ring structure containing phosphorus, aluminum, magnesium or calcium, the high-silica zeolite is ZSM-5, -8 or-11 type zeolite containing 2 to 8 percent of phosphorus and 0.3 to 3 percent of aluminum, magnesium or calcium (calculated by oxide), and the silica-alumina ratio is 15 to 60. The catalyst has excellent hydrothermal activity stability and low carbon olefin yield, especially ethylene yield, and can reach the same level of low carbon olefin yield as thermal cracking at a lower reaction temperature.
CN111203225A discloses a catalyst for preparing olefin by catalytic cracking of hydrocarbon, which comprises an active component, an acidity adjusting component and a carrier, wherein the active component comprises one or more oxides of Mn, fe, co, ni, cu, zn, mo, la, ce and Ti, and the carrier comprises SiO 2 、Al 2 O 3 One or more of kaolin and montmorillonite, and the acidity adjusting component comprises alkali metal oxides such as K and Na and alkaline earth metal oxides such as Ca, mg and Ba. The metal oxide of the active component accounts for 5 to 60 weight percent of the total mass of the catalyst, the alkali metal oxide or/and the alkaline earth metal accounts for 0.01 to 10 weight percent, and the rest is the carrier. The catalyst has good hydrocarbon catalytic cracking activity and ethylene and propylene selectivity.
CN102600890A discloses a gas phase catalyst for diesel oil regenerated from waste oil by catalytic cracking method and a preparation method thereof, wherein the catalyst comprises 10-50 wt% of Y-type molecular sieve, 0-20 wt% of high-silicon ZSM-5 molecular sieve, 10-40 wt% of active alumina, 30-70 wt% of carrier and 10-20 wt% of binder. The catalyst has the advantages of moderate activity, high selectivity, good stability, strong metal pollution resistance, long service life and renewable use, and meets the requirement of regenerating diesel oil from waste oil by a catalytic cracking method.
ZL201510635009.4 discloses a catalyst for preparing ethylene and propylene by naphtha catalytic cracking and a preparation method thereof, which comprises the steps of (1) preparing a ZSM-5 molecular sieve with isomorphous replacement metal, wherein all or part of the metal replaces Al in the ZSM-5 molecular sieve, and the replacement metal is one or more of magnesium, calcium, zinc, gallium and the like; (2) dissolving a proper amount of heteropoly acid in water, and uniformly stirring; (3) Adding a proper amount of alcohol solvent and a silicon-containing precursor into the solution obtained in the step (2), uniformly stirring the solution, and adjusting the pH value of the solution to 2-5; (4) Adding the synthesized metal isomorphous displacement ZSM-5 molecular sieve into the solution obtained in the step (3), stirring at constant temperature until the solution is converted into sol, and then aging at room temperature to obtain gel; (5) And (5) drying the gel obtained in the step (4) to constant weight, and grinding to obtain the final catalytic cracking catalyst. The catalyst for preparing olefin by catalytic cracking has the advantages of high olefin yield, low reaction temperature, good catalyst stability and the like.
In a word, most of the existing catalysts for preparing low-carbon olefins by catalytic cracking use naphtha, diesel oil and heavy oil as raw materials, and the related reports of the catalysts for preparing low-carbon olefins by directly catalytically cracking crude oil and the preparation method thereof are few.
Disclosure of Invention
Based on the above, the present invention aims to provide a catalyst for preparing low carbon olefins by catalytic cracking and a preparation method thereof, wherein the catalyst is particularly suitable for taking paraffin-based crude oil as a reaction raw material, and can directly convert the crude oil into low carbon olefins such as ethylene, propylene, butylene, etc. with high efficiency through a catalytic cracking process, and the catalyst has high gas yield and low gasoline and diesel oil yield.
Therefore, the invention provides a catalyst for preparing low-carbon olefin by catalytic cracking, which comprises the following components:
5 to 20 weight percent of Y-type molecular sieve with high silica-alumina ratio, preferably 7 to 15 weight percent;
20 to 60 weight percent of modified ZSM-5 molecular sieve, preferably 25 to 50 weight percent;
0.5 to 25wt%, preferably 3 to 10wt% of macroporous matrix material;
hydrogen transfer inhibiting component, 0.5 to 15wt%, preferably 0.5 to 5wt%;
clay, 15 to 60wt%, preferably 20 to 55wt%;
binder, 2 to 20 wt.%, preferably 5 to 15 wt.%;
wherein the silicon-aluminum ratio of the high silicon-aluminum ratio Y-type molecular sieve is more than 9, preferably 15-90; the modified ZSM-5 molecular sieve comprises at least one, preferably at least two of alkaline earth metal, rare earth metal and phosphorus element; the pore volume of the macroporous matrix material is 1.0-2.5 cm 3 (ii)/g, the average pore diameter is 5-100 nm; the hydrogen transfer inhibiting component is a transition metal oxide.
In particular, the invention selects the Y-type molecular sieve with high silica-alumina ratio. The silicon-aluminum ratio of the Y-type molecular sieve directly influences the acid property of the Y-type molecular sieve, and the higher the silicon-aluminum ratio is, the higher the acid strength is, and the lower the acid density is. Different from naphtha, diesel oil, heavy oil and other distillate oil, the crude oil has the basic characteristics of wide distillation range, larger hydrocarbon structure difference, high activation energy of cracking of micromolecule hydrocarbon, large cracking difficulty and higher acid strength of a catalyst; the macromolecular hydrocarbons are easy to generate hydrogen transfer reaction to form coke, and the catalyst is required to have lower acid density. Compared with the conventional Y-type molecular sieve, the high-silicon aluminum Y-type molecular sieve can provide stronger acid centers and better promote the conversion of small molecular hydrocarbons; meanwhile, the high-silicon aluminum Y-type molecular sieve has lower acid density than the conventional Y-type molecular sieve, can inhibit hydrogen transfer reaction and reduce macromolecule coking.
In the catalyst, the high silica-alumina ratio Y-type molecular sieve is preferably selected from one or more of HY, USY, REY, REHY and REUSY. The present invention is not particularly limited in kind of rare earth, and rare earth commonly used in the art may be used.
The catalyst of the invention is preferably obtained by acid treatment and hydrothermal treatment of the high silica-alumina ratio Y-type molecular sieve, wherein the acid is selected from one or more of hydrochloric acid, phosphoric acid, acetic acid, oxalic acid, citric acid and tartaric acid, and the acid treatment conditions are as follows: adding acid with the mass of 10-30 wt% of the Y-type molecular sieve, adjusting the pH value of the solution to 3.2-4.5, controlling the temperature to 100-200 ℃, further preferably 150-195 ℃, and keeping the time to 1-6 h; the conditions of the hydrothermal treatment are as follows: 5 to 100 percent of water vapor, the temperature is 550 to 850 ℃, the further optimization is 650 to 810 ℃, and the time is 1 to 3 hours.
In the catalyst of the present invention, preferably, the modified ZSM-5 molecular sieve is an H-type molecular sieve having a silica-alumina ratio of 25 to 400, more preferably 25 to 180, and the content of the modifying element is 0.1 to 20wt%, more preferably 0.5 to 5wt%, in terms of oxide.
Specifically, ZSM-5 is one of the most main active components of the catalyst for preparing the low-carbon olefin by catalytic cracking. The unmodified HZSM-5 molecular sieve has poor hydrothermal stability and cannot bear the harsh hydrothermal conditions (generally, the reaction temperature is over 600 ℃ and the regeneration temperature is over 700 ℃) in the catalytic cracking reaction-regeneration process of crude oil. Through the modification of specific elements, the hydrothermal stability of the ZSM-5 can be greatly improved, so that the activity of the catalyst is ensured not to be obviously attenuated in the repeated reaction-regeneration process; in addition, the specific element modified ZSM-5 can effectively improve the cracking activity and the selectivity of the low-carbon olefin. Therefore, the element modified ZSM-5 molecular sieve can meet the comprehensive requirements of various aspects of the stability of the active components of the catalyst, the cracking activity and the selectivity of low-carbon olefin in the catalytic cracking reaction process of crude oil. The same modification elements are added into the ZSM-5 molecular sieve for modification, and the modification elements are different from the modification elements directly added as functional components during the preparation of the catalyst: when the modified molecular sieve is added into a ZSM-5 molecular sieve for modification, elements interact with framework aluminum of the molecular sieve in an atomic or ionic form to modulate the stability and the acid property of the molecular sieve; when the catalyst is directly added as a functional component during the preparation of the catalyst, the element exists in the whole catalyst in a compound form and interacts with hydrocarbon molecules to promote the desorption of olefin molecules and inhibit the generation of hydrogen transfer reaction.
The catalyst of the invention, wherein, preferably, the preparation process of the modified ZSM-5 molecular sieve comprises the following steps: soaking the ZSM-5 molecular sieve in the mixed solution containing the modified elements for 0.5 to 4 hours, drying, and roasting at the temperature of between 450 and 550 ℃ for 1 to 3 hours; wherein the mass concentration of the modifying element in the mixed solution is 5-30% in terms of oxide.
In the catalyst of the present invention, preferably, the macroporous matrix material is silica alumina or alumina; further preferably, the micro-back cracking activity of the macroporous matrix material after 17h of steam aging at 800 ℃ is 10-50%.
Specifically, for producing low-carbon olefins from wide-cut crude oil, catalysts for high-efficiency conversion of hydrocarbon molecules with different structures need to be developed, and the catalysts are required to have a hierarchical pore structure with a proper proportion. The function of adding the macroporous matrix material is to increase the mesopore structure of the catalyst, so that the diffusion performance of the catalyst can be improved; meanwhile, the macroporous matrix material with certain cracking activity can improve the pre-cracking performance of the catalyst; the two components act together to improve the conversion rate of macromolecular hydrocarbons in the crude oil.
In the catalyst of the present invention, preferably, when the macroporous matrix material is silica-alumina, the silicon source is solid silica, the aluminum source is one or more selected from aluminum sulfate, aluminum nitrate and aluminum chloride, and the preparation conditions are as follows: the gelling temperature is 60-95 ℃, the pH value after gelling is 7.0-9.5, the aging time is 2-12 h, preferably 2-6 h, and after removing by-products by washing, drying is carried out at 110-150 ℃; when the macroporous matrix material is alumina, the aluminum source is one or more selected from aluminum sulfate, aluminum nitrate and aluminum chloride, and the preparation conditions are as follows: the gelling temperature is 30-90 ℃, the pH value after gelling is 7.0-9.5, the aging time is 4-24 h, preferably 4-12 h, washing with water to remove by-products, and drying at 110-150 ℃.
The catalyst of the present invention, wherein preferably, the hydrogen transfer inhibiting component is selected from Cr 2 O 3 、V 2 O 5 、ZnO、Fe 2 O 3 、MoO 3 、ZrO 2 、MnO 2 One or more of them.
Specifically, in order to increase the yield of low-carbon olefins, the crude oil is catalytically cracked to generate sufficient olefin precursors, and the generated low-carbon olefins are prevented from generating hydrogen transfer secondary reaction to generate alkanes. The added transition metal oxide interacts with the molecular sieve, the acid property of the molecular sieve is adjusted by changing the electronic structure, the hydrogen transfer reaction is inhibited, and the selectivity of the low-carbon olefin is improved.
In the catalyst of the present invention, preferably, the clay is selected from one or more of kaolin, halloysite, montmorillonite, diatomite, and sepiolite. The role of the clay is to protect the stability of the active ingredient as a heat carrier.
In the catalyst of the invention, preferably, the binder is one or more selected from silica sol, aluminum sol, silica-alumina sol, phospho-alumina sol and acidified pseudo-boehmite. The binder has the function of binding the active component and the matrix component, so that the catalyst microspheres are formed and certain mechanical strength is ensured.
Specifically, when the binder comprises acidified boehmite, inorganic acid is added in the pulping process of the matrix (comprising the pseudoboehmite) for acidification, the added inorganic acid can be one or more of hydrochloric acid, nitric acid and phosphoric acid, the acidification temperature is 25-70 ℃, and the pH value of the acidified matrix slurry is 4.2-5.5.
In the catalyst composition, a high-silica-alumina-ratio Y-type molecular sieve and an element modified ZSM-5 molecular sieve are used as main active components, wherein the Y-type molecular sieve cracks paraffin-based crude oil to generate enough low-carbon olefin precursor, the ZSM-5 molecular sieve continuously and selectively converts the low-carbon olefin precursor into low-carbon olefins such as ethylene, propylene, butylene and the like, and the low-carbon olefin precursor are subjected to relay catalysis to jointly complete the conversion from the crude oil to the low-carbon olefin. The catalyst is added with a macroporous matrix material, so that a mesoporous structure is increased, the conversion rate of macromolecular hydrocarbons in the crude oil is improved, more cleavable raw materials are provided for the Y-type molecular sieve, and the macroporous matrix material and the Y-type molecular sieve are combined to jointly complete the task of simultaneously and efficiently converting macromolecular hydrocarbons and micromolecular hydrocarbons in the crude oil; the transition metal oxide is added into the catalyst, and the transition metal oxide is unexpectedly found to be capable of modulating the acid properties of the Y-type molecular sieve and the ZSM-5 molecular sieve by changing the electronic structure, inhibiting the occurrence of hydrogen transfer secondary reaction and improving the selectivity of the low-carbon olefin. The components are matched with each other and cooperate with each other, so that the catalyst is particularly suitable for preparing low-carbon olefin by directly catalyzing and cracking crude oil, and has the characteristics of high crude oil conversion rate and high low-carbon olefin yield.
The invention also provides a preparation method of the catalyst for preparing the low-carbon olefin by catalytic cracking, which comprises the following steps:
(1) Adding water, a binder and clay into a reaction kettle for pulping, uniformly stirring, adjusting the pH value to 4.2-5.5, and adding a macroporous matrix material to form matrix slurry;
(2) Adding water, the high silica-alumina ratio Y-type molecular sieve and the modified ZSM-5 molecular sieve into another reaction kettle, pulping, uniformly stirring, and adding a hydrogen transfer inhibiting component to form molecular sieve slurry;
(3) And transferring the molecular sieve slurry to matrix slurry, homogenizing to form catalyst slurry, and spray drying, roasting and curing to obtain the catalyst for preparing the low-carbon olefin by catalytic cracking.
In the method for preparing the catalyst of the present invention, it is preferable that in the step (2), the hydrogen transfer inhibiting component is added in the form of an oxide or a nitrate.
In the preparation method of the catalyst, preferably, in the step (2), the temperature of the spray drying is 370-450 ℃ and the time is 0.05-10 min; the roasting temperature is 450-530 ℃, and the roasting time is 0.5-2 h.
In conclusion, the components of the catalyst provided by the invention are mutually matched and have synergistic effect, so that the catalyst is particularly suitable for preparing low-carbon olefin by directly catalyzing and cracking crude oil, and has the characteristics of high crude oil conversion rate and high low-carbon olefin yield.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
1. The main raw material sources are as follows:
USY molecular sieves: commercial product, relative crystallinity 70%, unit cell constant
Commercially available, siO 2 /Al 2 O 3 ＝6.8。
REUSY molecular sieve: commercial product, relative crystallinity 65%, unit cell constant
RE 2 O 3 Commercial SiO 2% by weight 2 /Al 2 O 3 ＝7.2。
HZSM-5 molecular sieve: industrial product, relative crystallinity 93%, siO 2 /Al 2 O 3 =36, commercially available.
Citric acid: analytically pure, density 1.54g/mL, commercially available.
Oxalic acid: analytically pure, density 1.65g/mL, commercially available.
Ammonia water: analytically pure, density 0.91g/L, mass concentration 25%, commercially available.
Lanthanum nitrate: analytically pure, RE 2 O 3 The mass content is 44%, and the product is commercially available.
Zinc nitrate: analytically pure, znO mass content of 27%, commercially available.
Magnesium nitrate: analytically pure, mgO mass content of 27%, commercially available.
Phosphoric acid: analytically pure, density 1.87g/L, mass concentration 85%, commercially available.
Silicon dioxide: industrial products, siO 2 The resulting mixture had a mass content of 92% and an average particle diameter D (V, 0.5) of 6.5 μm, and was commercially available.
Aluminum sulfate: industrial products, al 2 O 3 The mass content is 90g/L, and the Lanzhou petrochemical production is realized.
Silica sol: industrial products, siO 2 The mass content is 30%, and the product is commercially available.
Aluminum sol: industrial products, al 2 O 3 The mass content is 21 percent, and the Lanzhou petrochemical production is carried out.
Pseudo-boehmite: the industrial product has a peptization index of more than 95 percent and is sold in the market.
Hydrochloric acid: analytically pure, density 1.19g/mL, mass concentration 36.5%, commercially available.
2. The main analysis and evaluation methods used in the examples and comparative examples:
the content of the molecular sieve element is tested by adopting an X-ray fluorescence spectrometry method, and the method standard is Q/SY LS1050-2014. The crystallinity of the molecular sieve is tested by an X-ray powder diffraction method, and the method standard is Q/SYLS0596-2002. The unit cell constant (Si/Al ratio) of the molecular sieve is measured by X-ray powder diffraction method with the standard of SH/T0339-92.
The micro-reaction activity of the macroporous matrix material is measured by a small fixed bed micro-reaction evaluation device produced by Beijing Whitchen Sanji green chemistry science and technology limited, the addition amount of the macroporous material is 5g, the reaction raw material is Hongkong light diesel oil, the reaction temperature is 460 ℃, the reaction time is 70s, the oil inlet amount of the diesel oil is 1.56mL, and the product is analyzed by a gas chromatograph; before activity evaluation, hydrothermal aging treatment is required, and the aging conditions are 100% water vapor, 800 ℃ and 17h.
The evaluation of the catalyst reaction performance was carried out using an advanced catalytic cracking evaluation unit (ACE) developed by KTI technologies, inc., USA. Before the evaluation of the catalyst, hydrothermal aging treatment is required, wherein the aging conditions are as follows: 800 ℃, 100 percent of water vapor and 17 hours. Other reaction conditions were: the reaction raw material is Daqing crude oil, the catalyst loading is 9g, the reaction temperature is 650 ℃, the regeneration temperature is 730 ℃, and the catalyst-oil ratio is 7.5. And analyzing the gas composition, the liquid composition and the coke content generated by the reaction on line.
Example 1
Taking 1kg of USY molecular sieve (commercially available, siO) 2 /Al 2 O 3 Dry basis weight, the same as below) of 5L of deionized water, adding 750g of a 20wt% citric acid solution, adjusting the pH to 4.0 with an ammonia solution in the adding process, reacting at 180 ℃ for 2h under the self pressure of steam in a closed container, filtering, washing, drying, placing in a muffle furnace, and roasting at 780 ℃ for 2h under the condition of introducing steam to obtain the high silica-alumina ratio (SiO 2) 2 /Al 2 O 3 = 30) Y molecular sieve, denoted Y1;
taking 1kg of HZSM-5 molecular sieve (dry basis weight, the same below), adding 458g of magnesium nitrate solution with the concentration of 20wt%, adding 316g of phosphoric acid solution with the concentration of 20wt%, uniformly stirring, soaking for 2h, drying, and roasting in a muffle furnace at 500 ℃ for 2h to obtain a composite modified ZSM-5 molecular sieve, wherein the mark is Z1;
1kg of solid silica was taken and 1.6L of aluminum sulfate solution (Al) was slowly added 2 O 3 The mass content is 90g/L, the same below), ammonia water is added to adjust the pH value to 8, the gelling temperature is 95 ℃, the aging is carried out for 2h, and after the filtration, the water washing and the drying at 110 ℃, the macroporous silicon-aluminum substrate material is obtained, the pore volume is 1.4cm 3 The micro-cracking activity per se of the material after 17h steam ageing at 800 ℃ per gram, with an average pore diameter of 40nm, is 29%, and is designated M1.
Adding 1.3kg of water, 400g of alumina sol and 570g of kaolin into a reaction kettle, pulping, uniformly stirring, adjusting the pH value to 4.5, and adding 50g of M1 to form matrix slurry; adding 100g of Y1 and 26 to 0.7kg of water0g of Z1 is added into another reaction kettle for pulping, evenly stirred and added with 20g of functional component Cr 2 O 3 Forming a molecular sieve slurry; transferring the molecular sieve slurry to a matrix slurry, homogenizing to form a catalyst slurry, and performing spray drying, roasting and curing (spray drying conditions: 400 ℃,1min; roasting conditions: 500 ℃,2 h) to obtain the low-carbon olefin catalyst prepared by catalytic cracking of crude oil, which is marked as CAT1.
After the catalyst is subjected to hydrothermal aging at 800 ℃ for 17h, the ACE evaluation result shows that the catalyst has the following characteristics at the reaction temperature of 650 ℃ and the catalyst-oil ratio of 7.5: the crude oil conversion was 91wt% and the single pass yield of trienes (ethylene + propylene + butylene, same below) was 49wt%.
Example 2
Taking 1kg of USY molecular sieve, pulping with 5L of deionized water, adding 1kg of oxalic acid solution with the concentration of 10wt%, adjusting the pH to 4.0 by using ammonia water solution in the adding process, reacting for 3h at 170 ℃ under the self pressure of steam in a closed container, filtering, washing, drying, putting into a muffle furnace, roasting for 2h at 800 ℃ under the condition of introducing steam to obtain high silicon-aluminum ratio (SiO) 2 /Al 2 O 3 = 90) Y molecular sieve, denoted Y2;
taking 1kg of HZSM-5 molecular sieve, adding 760g of 20wt% lanthanum nitrate solution, adding 158g of 20wt% phosphoric acid solution, uniformly stirring, dipping for 3h, drying, and roasting in a muffle furnace at 530 ℃ for 1.5h to obtain a composite modified ZSM-5 molecular sieve, wherein the Z2 is marked;
slowly adding 3.2L aluminum sulfate solution into 1kg solid silicon dioxide, adding ammonia water to adjust pH to 9, gelatinizing temperature to 85 deg.C, aging for 4 hr, filtering, washing with water, and oven drying at 120 deg.C to obtain macroporous silicon-aluminum matrix material with pore volume of 1.2cm 3 The intrinsic micro-cracking activity of the material after 17h steam ageing at 800 ℃ per gram, with a mean pore diameter of 32nm, is 25%, and is designated M2.
Adding 1.2kg of water, 420g of silica sol and 540g of kaolin into a reaction kettle, pulping, uniformly stirring, adjusting the pH value to 4.5, and adding 40g of M2 to form matrix slurry; adding 0.8kg of water, 120g of Y2 and 280g of Z2 into another reaction kettle for pulping, uniformly stirring, and adding 20g of functional component V 2 O 5 Forming a molecular sieve slurry; will be divided intoTransferring the sub-sieve slurry to matrix slurry, homogenizing to form catalyst slurry, spray drying, roasting and curing (spray drying condition: 410 deg.C, 1.5min; roasting condition: 480 deg.C, 2 h) to obtain crude oil catalytic cracking to prepare low carbon olefin catalyst, and recording as CAT2.
After the catalyst is subjected to hydrothermal aging at 800 ℃ for 17h, the ACE evaluation result shows that the catalyst has the following characteristics at the reaction temperature of 650 ℃ and the catalyst-oil ratio of 7.5: the crude oil conversion was 90wt% and the triene single pass yield was 47wt%.
Example 3
Taking 1kg REUSY molecular sieve (SiO, petrochemical production in Lanzhou) 2 /Al 2 O 3 Dry basis weight, the same as below) of the mixture, pulping the mixture with 6L of deionized water, adding 1kg of citric acid solution with the concentration of 20wt%, adjusting the pH to 3.8 by using an ammonia water solution in the adding process, reacting the mixture for 4 hours at 160 ℃ under the self pressure of water vapor in a closed container, filtering, washing and drying the mixture, putting the mixture into a muffle furnace, and roasting the mixture for 2 hours at 750 ℃ under the condition of introducing the water vapor to obtain the high silica-alumina ratio (SiO) of the mixture 2 /Al 2 O 3 = 21) Y molecular sieve, denoted Y3;
taking 1kg of HZSM-5 molecular sieve, adding 230g of 25wt% lanthanum nitrate solution, adding 617g of 20wt% magnesium nitrate solution, uniformly stirring, dipping for 4h, drying, and roasting in a muffle furnace at 510 ℃ for 2h to obtain a composite modified ZSM-5 molecular sieve, wherein the label is Z3;
1kg of solid silica was taken and 3.2L of aluminum nitrate solution (Al) was slowly added 2 O 3 Mass content of 90g/L, the same as below), adding ammonia water to adjust pH value to 7.5, gelatinizing temperature to 90 deg.C, aging for 6h, filtering, washing with water, and oven drying at 130 deg.C to obtain macroporous silicon-aluminum matrix material with pore volume of 1.3cm 3 The micro-cracking activity per se of the material after 17h steam aging at 800 ℃ was 31%, which was expressed as M3, per g and with an average pore diameter of 42nm.
Adding 1.2kg of water, 440g of alumina sol and 500g of kaolin into a reaction kettle, pulping, uniformly stirring, adjusting the pH value to 5, and adding 45g of M3 to form matrix slurry; adding 0.8kg of water, 90g of Y3 and 340g of Z3 into another reaction kettle for pulping, uniformly stirring, and adding 90g of functional component Zn (NO) 3 ) 2 ·6H 2 O, forming a molecular sieve slurryLiquid; transferring the molecular sieve slurry to a matrix slurry, homogenizing to form a catalyst slurry, and performing spray drying, roasting and curing (spray drying conditions: 390 ℃,0.5min; roasting conditions: 460 ℃,1.5 h) to obtain a catalyst for preparing low-carbon olefin by catalytic cracking of crude oil, wherein the catalyst is marked as CAT3.
After the catalyst is subjected to hydrothermal aging at 800 ℃ for 17 hours, the ACE evaluation result shows that: the crude oil conversion was 92wt% and the triene single pass yield was 48wt%.
Example 4
Pulping 1kg REUSY molecular sieve with 4L deionized water, adding 500g oxalic acid solution with concentration of 15wt%, adjusting pH to 3.6 with ammonia water solution, reacting at 165 deg.C under the pressure of water vapor in a sealed container for 4h, filtering, washing, oven drying, placing in a muffle furnace, and calcining at 800 deg.C for 1h under the condition of introducing water vapor to obtain high silica-alumina ratio (SiO) 2 /Al 2 O 3 = 15) Y molecular sieve, denoted Y4;
taking 1kg of HZSM-5 molecular sieve, adding 316g of phosphoric acid solution with the concentration of 30wt%, adding 617g of calcium nitrate solution with the concentration of 15wt%, uniformly stirring, dipping for 3.5h, drying, and roasting in a muffle furnace at 520 ℃ for 1h to obtain a composite modified ZSM-5 molecular sieve, wherein the label is Z4;
slowly adding 1kg of solid silicon dioxide into 6.4L of aluminum nitrate solution, adding ammonia water to adjust the pH value to 8.5, gelatinizing at 80 ℃, aging for 10h, filtering, washing with water, and drying at 150 ℃ to obtain a macroporous silicon-aluminum substrate material with a pore volume of 1.1cm 3 The micro-cracking activity per se of the material after 17h steam aging at 800 ℃ was 24%, which was measured as M4, per g and had an average pore diameter of 34nm.
Adding 1.3kg of water, 460g of alumina sol and 560g of kaolin into a reaction kettle for pulping, uniformly stirring, adjusting the pH value to 5, and adding 40g of M4 to form matrix slurry; adding 0.7kg of water, 150g of Y4 and 220g of Z4 into another reaction kettle for pulping, uniformly stirring, and adding 30g of functional component MoO 3 Forming a molecular sieve slurry; transferring the molecular sieve slurry to the matrix slurry, homogenizing to obtain catalyst slurry, spray drying, calcining for curing (spray drying at 380 deg.C for 1min; calcining at 520 deg.C),1h) To obtain the catalyst for preparing low-carbon olefin by catalytic cracking of crude oil, which is marked as CAT4.
After the catalyst is subjected to hydrothermal aging at 800 ℃ for 17h, the ACE evaluation result shows that the catalyst has the following characteristics at the reaction temperature of 650 ℃ and the catalyst-oil ratio of 7.5: the crude oil conversion was 90.5wt% and the triene single pass yield was 47wt%.
Example 5
Pulping 1kg USY molecular sieve with 5.5L deionized water, adding 500g citric acid solution with concentration of 20wt%, adjusting pH to 3.7 with ammonia water solution, reacting at 180 deg.C under the pressure of water vapor in a sealed container for 4 hr, filtering, washing, oven drying, placing in a muffle furnace, and calcining at 790 deg.C for 1.5 hr under the condition of introducing water vapor to obtain high silica-alumina ratio (SiO) 2 /Al 2 O 3 = 45) Y molecular sieve, denoted Y5;
taking 1kg of HZSM-5 molecular sieve, adding 350g of a 15wt% lanthanum nitrate solution, adding 500g of a 15wt% phosphoric acid solution and 450g of a 25wt% magnesium nitrate solution, uniformly stirring, dipping for 1.5h, drying, and roasting in a muffle furnace at 510 ℃ for 2.5h to obtain a composite modified ZSM-5 molecular sieve, wherein the record is Z5;
1kg of solid silica was taken and 0.9L of aluminum chloride solution (Al) was slowly added 2 O 3 The mass content is 90g/L, the same below), ammonia water is added to adjust the pH value to 8.5, the gelling temperature is 70 ℃, the aging is carried out for 8h, and after the filtration, the water washing and the drying at 140 ℃, the macroporous silicon-aluminum substrate material is obtained, the pore volume is 1.0cm 3 The intrinsic micro-cracking activity of the material after 17h steam ageing at 800 ℃ per gram, with a mean pore diameter of 43nm, is 22%, and is designated M5.
Adding 0.9kg of water, 380g of silica sol and 360g of kaolin into a reaction kettle, pulping, uniformly stirring, adjusting the pH value to 4.7, and adding 60g of M5 to form matrix slurry; adding 1.1kg water, 80g Y5, 480g Z5 into another reaction kettle, pulping, stirring, adding 100g functional component Fe (NO) 3 ) 3 ·9H 2 O, forming a molecular sieve slurry; transferring the molecular sieve slurry to the matrix slurry, homogenizing to obtain catalyst slurry, spray drying, roasting and curing (spray drying at 390 deg.C for 1min; roasting at 510 deg.C for 0.5 hr) to obtain crude oil as catalystThe catalyst is used for preparing low-carbon olefin by cracking, and is marked as CAT5.
After the catalyst is subjected to hydrothermal aging at 800 ℃ for 17h, the ACE evaluation result shows that the catalyst has the following characteristics at the reaction temperature of 650 ℃ and the catalyst-oil ratio of 7.5: the crude oil conversion was 91.5wt% and the triene single pass yield was 49.5wt%.
Example 6
Pulping 1kg of REUSY molecular sieve with 6.5L of deionized water, adding 800g of 10wt% oxalic acid solution, adjusting pH to 3.8 with ammonia water solution during the addition process, reacting at 175 ℃ for 3h under the self pressure of steam in a closed container, filtering, washing, drying, placing in a muffle furnace, and roasting at 770 ℃ for 2.5h under the condition of introducing steam to obtain high silica-alumina ratio (SiO) 2 /Al 2 O 3 = 27) Y molecular sieve, denoted Y6;
taking 1kg of HZSM-5 molecular sieve, adding 500g of 20wt% calcium nitrate solution, 510g of 20wt% yttrium nitrate solution and 400g of 25wt% diammonium phosphate solution, uniformly stirring, soaking for 1h, drying, and roasting at 530 ℃ in a muffle furnace for 3h to obtain a composite modified ZSM-5 molecular sieve, wherein the Z6 is recorded;
slowly adding 1.8L of aluminum chloride solution into 1kg of solid silicon dioxide, adding ammonia water to adjust the pH value to 8.0, gelatinizing at 60 ℃, aging for 3h, filtering, washing with water, and drying at 120 ℃ to obtain a macroporous silicon-aluminum substrate material with a pore volume of 1.5cm 3 The intrinsic micro-cracking activity of the material after 17h steam ageing at 800 ℃ per gram, with an average pore diameter of 47nm, is 35%, and is designated M6.
Adding 1.2kg of water, 410g of alumina sol and 535g of halloysite into a reaction kettle, pulping, uniformly stirring, and adding 50g of M6 to form matrix slurry; adding 0.8kg of water, 50g of Y6 and 240g of Z6 into another reaction kettle for pulping, uniformly stirring, and adding 25g of functional component ZrO 2 Forming a molecular sieve slurry; transferring the molecular sieve slurry to matrix slurry, homogenizing to form catalyst slurry, spray drying, roasting and curing (spray drying conditions: 380 deg.C, 1.5min; roasting conditions: 510 deg.C, 1 h) to obtain crude oil catalytic cracking to prepare low carbon olefin catalyst, and recording as CAT6.
After the catalyst is subjected to hydrothermal aging at 800 ℃ for 17h, the ACE evaluation result shows that the catalyst has the following characteristics at the reaction temperature of 650 ℃ and the catalyst-oil ratio of 7.5: the crude oil conversion was 92wt% and the triene single pass yield was 48wt%.
Example 7
Taking 1kg of USY molecular sieve, pulping with 7L of deionized water, adding 750g of citric acid solution with the concentration of 25wt%, adjusting the pH to 4.0 by using an ammonia water solution in the adding process, reacting for 2h at 185 ℃ under the self pressure of water vapor in a closed container, filtering, washing, drying, putting into a muffle furnace, and roasting for 3h at 760 ℃ under the condition of introducing the water vapor to obtain the high silica-alumina ratio (SiO) 2 /Al 2 O 3 = 60) Y molecular sieve, denoted Y7;
taking 1kg of HZSM-5 molecular sieve, adding 300g of phosphoric acid solution with the concentration of 25wt%, adding 600g of cerium nitrate solution with the concentration of 15wt%, uniformly stirring, soaking for 1.5h, drying, and roasting in a muffle furnace at 530 ℃ for 1.5h to obtain a composite modified ZSM-5 molecular sieve, wherein the notation is Z7;
slowly adding 4.8L aluminum sulfate solution into 1kg solid silicon dioxide, adding ammonia water to adjust pH to 8.0, gelatinizing at 80 deg.C, aging for 5 hr, filtering, washing with water, and oven drying at 140 deg.C to obtain macroporous silicon-aluminum matrix material with pore volume of 1.0cm 3 The intrinsic micro-cracking activity of the material after 17h steam ageing at 800 ℃ per gram, with an average pore diameter of 29nm, is 20%, and is designated M7.
Adding 1.3kg of water, 180g of pseudo-boehmite and 545g of halloysite into a reaction kettle for pulping, adding 36g of hydrochloric acid for acidification, uniformly stirring, adjusting the pH value to 4.8, and adding 50g of M7 to form matrix slurry; adding 0.7kg of water, 105g of Y7, 265g of Z7 into another reaction kettle for pulping, uniformly stirring, adding 35g of functional component MnO 2 Forming a molecular sieve slurry; transferring the molecular sieve slurry to matrix slurry, homogenizing to form catalyst slurry, spray drying, roasting and curing (spray drying condition: 420 deg.C, 1.5min; roasting condition: 490 deg.C, 1.5 h) to obtain crude oil catalytic cracking to prepare low carbon olefin catalyst, and recording as CAT7.
After the catalyst is subjected to hydrothermal aging at 800 ℃ for 17h, the ACE evaluation result shows that the catalyst has the following characteristics at the reaction temperature of 650 ℃ and the catalyst-oil ratio of 7.5: the crude oil conversion was 91.5wt% and the triene single pass yield was 48wt%.
Example 8
Pulping 1kg REUSY molecular sieve with 5.5L deionized water, adding 900g citric acid solution with concentration of 15wt%, adjusting pH to 3.7 with ammonia water solution during the addition process, reacting at 175 deg.C under the self pressure of water vapor in a sealed container for 2h, filtering, washing, oven drying, placing into a muffle furnace, and calcining at 750 deg.C for 2.5h under the condition of introducing water vapor to obtain high silica-alumina ratio (SiO) 2 /Al 2 O 3 = 19) Y molecular sieve, denoted Y8;
taking 1kg of HZSM-5 molecular sieve, adding 450g of 25wt% magnesium nitrate solution, adding 600g of 15wt% yttrium nitrate solution, uniformly stirring, soaking for 2.5h, drying, and roasting in a muffle furnace at 510 ℃ for 2h to obtain a composite modified ZSM-5 molecular sieve, wherein the Z8 is recorded;
slowly adding 1kg of solid silicon dioxide into 2.4L of aluminum chloride solution, adding ammonia water to adjust pH value to 8.5, gelatinizing at 70 deg.C, aging for 7h, filtering, washing with water, and oven drying at 150 deg.C to obtain macroporous silicon-aluminum matrix material with pore volume of 1.1cm 3 The micro-cracking activity per se of the material after 17h steam aging at 800 ℃ and a mean pore diameter of 35nm was 26%, and was designated as M8.
Adding 1.2kg of water, 190g of pseudo-boehmite and 520g of diatomite into a reaction kettle for pulping, adding 38g of nitric acid for acidification, uniformly stirring, and adding 55g of M8 to form matrix slurry; adding 0.8kg of water, 140g of Y8 and 250g of Z8 into another reaction kettle for pulping, uniformly stirring, adding 25g of Cr serving as a functional component 2 O 3 And 10g Fe 2 O 3 Forming a molecular sieve slurry; transferring the molecular sieve slurry to matrix slurry, homogenizing to obtain catalyst slurry, spray drying, roasting and curing (spray drying at 405 deg.C for 0.5min; roasting at 530 deg.C for 1 hr) to obtain crude oil catalytic cracking catalyst for preparing low-carbon olefin, and recording as CAT8.
After the catalyst is subjected to hydrothermal aging at 800 ℃ for 17h, the ACE evaluation result shows that the catalyst has the following characteristics at the reaction temperature of 650 ℃ and the catalyst-oil ratio of 7.5: the crude oil conversion was 92wt% and the triene single pass yield was 47wt%.
Example 9
Taking 1kg of USY molecular sievePulping with 5L deionized water, adding 1kg of 10wt% acetic acid solution, adjusting pH to 3.8 with ammonia water solution, reacting at 180 deg.C under the pressure of water vapor in a sealed container for 2h, filtering, washing, oven drying, placing in a muffle furnace, and calcining at 700 deg.C for 2h under the condition of introducing water vapor to obtain high silica-alumina ratio (SiO) 2 /Al 2 O 3 = 53) Y molecular sieve, denoted Y9;
taking 1kg of HZSM-5 molecular sieve, adding 780g of a 15wt% cerium nitrate solution, adding 200g of a 20wt% phosphoric acid solution, uniformly stirring, soaking for 2h, drying, and roasting in a muffle furnace at 530 ℃ for 1.5h to obtain a composite modified ZSM-5 molecular sieve, wherein the Z9 is marked;
adding ammonia water into 1L of aluminum nitrate solution to adjust pH to 8.5, gelatinizing temperature to 70 deg.C, aging for 10 hr, filtering, washing with water, and drying at 110 deg.C to obtain macroporous alumina matrix material with pore volume of 0.7cm 3 The micro-cracking activity per se of the material after 17h of steam aging at 800 ℃ is 31%, which is recorded as M9, and the average pore diameter is 8 nm.
Adding 0.6kg of water, 450g of alumina sol and 210g of kaolin into a reaction kettle, pulping, uniformly stirring, adjusting the pH value to 5.1, and adding 50g of M9 to form matrix slurry; adding 1.4kg of water, 120g of Y9, 590g of Z9 into another reaction kettle for pulping, uniformly stirring, and adding 20g of Cr serving as a functional component 2 O 3 And 10g MoO 3 Forming a molecular sieve slurry; transferring the molecular sieve slurry to matrix slurry, homogenizing to form catalyst slurry, spray drying, roasting and curing (spray drying condition: 415 deg.C, 0.5min; roasting condition: 460 deg.C, 2 h) to obtain crude oil catalytic cracking to prepare low carbon olefin catalyst, and recording as CAT9.
After the catalyst is subjected to hydrothermal aging at 800 ℃ for 17h, the ACE evaluation result shows that the catalyst has the following characteristics at the reaction temperature of 650 ℃ and the catalyst-oil ratio of 7.5: the crude oil conversion was 90wt% and the triene single pass yield was 48.5wt%.
Example 10
Taking 1kg of REUSY molecular sieve, pulping with 5L of deionized water, adding 800g of tartaric acid solution with the concentration of 15wt%, adjusting the pH to 3.6 by using ammonia water solution in the adding process, sealing the container under the self pressure of water vapor,reacting at 190 deg.C for 2h, filtering, washing, drying, placing in muffle furnace, and calcining at 750 deg.C for 1.5h under the condition of introducing water vapor to obtain high silica-alumina ratio (SiO) 2 /Al 2 O 3 = 22) Y molecular sieve, denoted Y10;
taking 1kg of HZSM-5 molecular sieve, adding 770g of 20wt% yttrium nitrate solution, adding 317g of 15wt% phosphoric acid solution, uniformly stirring, soaking for 2h, drying, and roasting in a muffle furnace at 540 ℃ for 2.5h to obtain a composite modified ZSM-5 molecular sieve, wherein the Z10 is recorded;
adding ammonia water into 1L of aluminum sulfate solution to adjust pH to 9, gelatinizing temperature to 65 deg.C, aging for 7 hr, filtering, washing with water, and oven drying at 110 deg.C to obtain macroporous alumina matrix material with pore volume of 1.0cm 3 The micro-cracking activity of the material itself after 17h steam ageing at 800 ℃ per gram, with an average pore diameter of 12nm, is 36%, and is designated M10.
Adding 0.8kg of water, 430g of alumina sol and 310g of kaolin into a reaction kettle, pulping, uniformly stirring, adjusting the pH value to 5.3, and adding 40g of M9 to form matrix slurry; adding 1.2kg of water, 120g of Y10 and 500g of Z9 into another reaction kettle for pulping, uniformly stirring, adding 20g of Cr serving as a functional component 2 O 3 And 10g MoO 3 Forming a molecular sieve slurry; transferring the molecular sieve slurry to matrix slurry, homogenizing to form catalyst slurry, spray drying, roasting and curing (spray drying conditions: 385 ℃,2min; roasting conditions: 520 ℃,1.5 h) to obtain the low-carbon olefin catalyst prepared by catalytic cracking of crude oil, and marking as CAT10.
After the catalyst is subjected to hydrothermal aging at 800 ℃ for 17h, the ACE evaluation result shows that the catalyst has the following characteristics at the reaction temperature of 650 ℃ and the catalyst-oil ratio of 7.5: the crude oil conversion was 91wt% and the triene single pass yield was 47.5wt%.
Example 11
Pulping 1kg of USY molecular sieve with 6L of deionized water, adding 850g of oxalic acid solution with the concentration of 10wt%, adjusting the pH to 3.8 by using an ammonia water solution in the adding process, reacting at 170 ℃ for 2h under the self pressure of steam in a closed container, filtering, washing, drying, putting into a muffle furnace, and roasting at 740 ℃ for 3h under the condition of introducing steam to obtain the high silica-alumina ratio (SiO) 2 /Al 2 O 3 = 45) Y molecular sieve, denoted Y11;
taking 1kg of HZSM-5 molecular sieve, adding 158g of 20wt% phosphoric acid solution, uniformly stirring, soaking for 3h, drying, and roasting in a muffle furnace at 530 ℃ for 2h to obtain a single-element modified ZSM-5 molecular sieve, wherein the mark is Z11;
adding ammonia water into 1L of aluminum chloride solution, adjusting pH to 9, gelatinizing temperature to 65 deg.C, aging for 4 hr, filtering, washing with water, and drying at 110 deg.C to obtain macroporous alumina matrix material with pore volume of 1.3cm 3 The micro-cracking activity per se of the material after 17h steam aging at 800 ℃ and an average pore diameter of 14nm was 37%, and was designated as M11.
Adding 1.2kg of water, 400g of alumina sol and 430g of kaolin into a reaction kettle, pulping, uniformly stirring, adjusting the pH value to 4.9, and adding 60g of M11 to form matrix slurry; adding 0.8kg of water, 130g of Y11 and 300g of Z11 into another reaction kettle for pulping, uniformly stirring, and adding 20g of Cr serving as a functional component 2 O 3 And 10g ZnO to form a molecular sieve slurry; transferring the molecular sieve slurry to a matrix slurry, homogenizing to form a catalyst slurry, and performing spray drying, roasting and curing (spray drying conditions: 405 ℃,1.5min; roasting conditions: 450 ℃,3 h) to obtain a catalyst for preparing low-carbon olefin by catalytic cracking of crude oil, wherein the catalyst is marked as CAT11.
After the catalyst is subjected to hydrothermal aging at 800 ℃ for 17h, the ACE evaluation result shows that the catalyst has the following characteristics at the reaction temperature of 650 ℃ and the catalyst-oil ratio of 7.5: the crude oil conversion was 90wt% and the triene single pass yield was 45wt%.
Example 12
Pulping 1kg of REUSY molecular sieve with 6L of deionized water, adding 700g of 15wt% acetic acid solution, adjusting pH to 3.7 with ammonia water solution during the addition process, reacting at 185 ℃ for 2h under the self pressure of steam in a closed container, filtering, washing, drying, placing in a muffle furnace, and roasting at 730 ℃ for 2h under the condition of introducing steam to obtain high silica-alumina ratio (SiO) 2 /Al 2 O 3 = 36) Y molecular sieve, denoted Y12;
taking 1kg of HZSM-5 molecular sieve, adding 617g of lanthanum nitrate solution with the concentration of 20wt%, uniformly stirring, soaking for 2h, drying, and roasting in a muffle furnace at 500 ℃ for 2h to obtain a single-element modified ZSM-5 molecular sieve, wherein the mark is Z12;
adding ammonia water into 1L of aluminum sulfate solution to adjust pH to 8, gelatinizing temperature to 70 deg.C, aging for 9 hr, filtering, washing with water, and oven drying at 110 deg.C to obtain macroporous alumina matrix material with pore volume of 1.9cm 3 The micro-cracking activity per se of the material after 17h steam aging at 800 ℃ and a mean pore diameter of 21nm was 39%, and this was designated as M12.
Adding 1.2kg of water, 420g of alumina sol and 420g of kaolin into a reaction kettle, pulping, uniformly stirring, adjusting the pH value to 5.2, and adding 65g of M12 to form matrix slurry; adding 0.8kg of water, 140g of Y12 and 290g of Z12 into another reaction kettle for pulping, uniformly stirring, adding 20g of Cr serving as a functional component 2 O 3 And 10g MnO 2 Forming a molecular sieve slurry; transferring the molecular sieve slurry to matrix slurry, homogenizing to form catalyst slurry, spray drying, roasting and curing (spray drying condition: 395 deg.C, 1min; roasting condition: 510 deg.C, 2 h) to obtain crude oil catalytic cracking low-carbon olefin catalyst, and recording as CAT12.
After the catalyst is subjected to hydrothermal aging at 800 ℃ for 17h, the ACE evaluation result shows that the catalyst has the following characteristics at the reaction temperature of 650 ℃ and the catalyst-oil ratio of 7.5: the crude oil conversion was 90wt% and the triene single pass yield was 45.5wt%.
Comparative example 1
USY molecular sieve, without any treatment; adding 458g of 20wt% magnesium nitrate solution into 1kg of HZSM-5 molecular sieve, adding 316g of 20wt% phosphoric acid solution, uniformly stirring, soaking for 2h, drying, and roasting in a muffle furnace at 500 ℃ for 2h to obtain a composite modified ZSM-5 molecular sieve, wherein the notation is Z1;
slowly adding 1.6L aluminum sulfate solution into 1kg solid silicon dioxide, adding ammonia water to adjust pH to 8, gelatinizing at 95 deg.C, aging for 2 hr, filtering, washing with water, and oven drying at 110 deg.C to obtain macroporous silicon-aluminum matrix material with pore volume of 1.4cm 3 The micro-cracking activity per se of the material after 17h steam aging at 800 ℃ was 29%, which was 40nm per gram and was designated as M1.
Adding 1.3kg of water, 400g of alumina sol and 570g of kaolin into a reaction kettle for pulping, uniformly stirring and adjusting the pH valueAt 4.5, 50g M1 was added to form a matrix slurry; adding 0.7kg water, 100g USY (commercially available, untreated), 260g Z1 into another reaction kettle, pulping, stirring, adding 20g functional component Cr 2 O 3 Forming a molecular sieve slurry; transferring the molecular sieve slurry to a matrix slurry, homogenizing to form a catalyst slurry, and performing spray drying, roasting and curing (spray drying conditions: 400 ℃,1min; roasting conditions: 500 ℃,2 h) to obtain the low-carbon olefin catalyst prepared by catalytic cracking of crude oil, wherein the D-CAT1 is recorded.
After the contrast agent is subjected to hydrothermal aging at 800 ℃ for 17 hours, the ACE evaluation result shows that the contrast agent has the following characteristics under the conditions that the reaction temperature is 650 ℃ and the agent-oil ratio is 7.5: the crude oil conversion was 90wt% and the triene single pass yield was 40wt%.
Comparative example 1 except that conventional USY (SiO) 2 /Al 2 O 3 = 6.8) instead of high silica alumina ratio USY (SiO) 2 /Al 2 O 3 = 30), other conditions are consistent, and the experimental results show that: in the catalyst preparation scheme, conventional USY is adopted to replace USY with high silica-alumina ratio, and the one-way yield of triene is reduced by 9wt%.
Comparative example 2
Pulping 1kg of USY molecular sieve with 5L of deionized water, adding 750g of citric acid solution with the concentration of 20wt%, adjusting the pH to 4.0 by using an ammonia water solution in the adding process, reacting at 180 ℃ for 2h under the self pressure of steam in a closed container, filtering, washing, drying, putting into a muffle furnace, and roasting at 780 ℃ for 2h under the condition of introducing the steam to obtain the high silica-alumina ratio (SiO) 2 /Al 2 O 3 = 30) Y molecular sieve, denoted Y1; HZSM-5 molecular sieve, without any treatment; 1kg of solid silicon dioxide, slowly adding 1.6L of aluminum sulfate solution, adding ammonia water to adjust the pH value to 8, gelling at 95 ℃, aging for 2h, filtering, washing with water, and drying at 110 ℃ to obtain a macroporous silicon-aluminum substrate material with a pore volume of 1.4cm 3 The micro-cracking activity per se of the material after 17h steam aging at 800 ℃ and 40nm per g was 29%, and this was designated M1.
Adding 1.3kg of water, 400g of alumina sol and 570g of kaolin into a reaction kettle, pulping, uniformly stirring, adjusting the pH value to 4.5, and adding 50g of M1 to form matrix slurry;adding 0.7kg of water, 100g of Y1, 260g of HZSM-5 (commercially available, unmodified) into another reaction kettle, pulping, uniformly stirring, adding 20g of functional component Cr 2 O 3 Forming a molecular sieve slurry; transferring the molecular sieve slurry to a matrix slurry, homogenizing to form a catalyst slurry, and performing spray drying, roasting and curing (spray drying conditions: 400 ℃,1min; roasting conditions: 500 ℃,2 h) to obtain the low-carbon olefin catalyst prepared by catalytic cracking of crude oil, which is marked as D-CAT2.
After the contrast agent is subjected to hydrothermal aging at 800 ℃ for 17h, the ACE evaluation result shows that the contrast agent has the following characteristics at the reaction temperature of 650 ℃ and the agent-oil ratio of 7.5: the crude oil conversion was 87wt% and the triene single pass yield was 31wt%.
Comparative example 1 except that unmodified ZSM-5 was used in place of the element modified ZSM-5, the other conditions were the same, and the experimental results show that: in the catalyst preparation scheme, unmodified ZSM-5 is adopted to replace element modified ZSM-5, and the one-way yield of triene is reduced by 18wt%.
Comparative example 3
Pulping 1kg USY molecular sieve with 5L deionized water, adding 750g citric acid solution with concentration of 20wt%, adjusting pH to 4.0 with ammonia water solution, reacting at 180 deg.C under the pressure of steam in a sealed container for 2 hr, filtering, washing, oven drying, and calcining at 780 deg.C for 2 hr under the condition of introducing steam to obtain high silica-alumina ratio (SiO) 2 /Al 2 O 3 = 30) Y molecular sieve, denoted Y1; adding 458g of 20wt% magnesium nitrate solution into 1kg of HZSM-5 molecular sieve, adding 316g of 20wt% phosphoric acid solution, uniformly stirring, dipping for 2h, drying, and roasting in a muffle furnace at 500 ℃ for 2h to obtain the composite modified ZSM-5 molecular sieve, wherein the record is Z1.
Adding 1.3kg of water, 400g of alumina sol and 620g of kaolin into a reaction kettle for pulping, uniformly stirring, adjusting the pH value to 4.5, and taking the mixture as matrix slurry without enlarging a hole matrix material; adding 0.7kg of water, 100g of Y1 and 260g of Z1 into another reaction kettle for pulping, uniformly stirring, and adding 20g of functional component Cr 2 O 3 Forming a molecular sieve slurry; transferring the molecular sieve slurry to a matrix slurry, homogenizing to form a catalyst slurry, spray drying, roasting, and solidifying(spray drying condition: 400 ℃,1min; roasting condition: 500 ℃,2 h) to obtain the catalyst for preparing the low-carbon olefin by catalytic cracking of the crude oil, which is marked as D-CAT3.
After the contrast agent is subjected to hydrothermal aging at 800 ℃ for 17 hours, the ACE evaluation result shows that the contrast agent has the following characteristics under the conditions that the reaction temperature is 650 ℃ and the agent-oil ratio is 7.5: the crude oil conversion was 85wt% and the triene single pass yield was 42wt%.
In comparative example 1, except that the macroporous matrix material is not added, that is, the inert kaolin is used to replace the macroporous matrix material, the other conditions are consistent, and the experimental result shows that: in the catalyst preparation scheme, a high-activity macroporous matrix material is not added, the crude oil conversion rate is reduced by 6wt%, and the triene single-pass yield is reduced by 7wt%.
Comparative example 4
Pulping 1kg of USY molecular sieve with 5L of deionized water, adding 750g of citric acid solution with the concentration of 20wt%, adjusting the pH to 4.0 by using an ammonia water solution in the adding process, reacting at 180 ℃ for 2h under the self pressure of steam in a closed container, filtering, washing, drying, putting into a muffle furnace, and roasting at 780 ℃ for 2h under the condition of introducing the steam to obtain the high silica-alumina ratio (SiO) 2 /Al 2 O 3 = 30) Y molecular sieve, denoted Y1; adding 458g of 20wt% magnesium nitrate solution into 1kg of HZSM-5 molecular sieve, adding 316g of 20wt% phosphoric acid solution, uniformly stirring, soaking for 2h, drying, and roasting in a muffle furnace at 500 ℃ for 2h to obtain a composite modified ZSM-5 molecular sieve, wherein the notation is Z1; slowly adding 1.6L aluminum sulfate solution into 1kg solid silicon dioxide, adding ammonia water to adjust pH to 8, gelatinizing temperature to 95 deg.C, aging for 2 hr, filtering, washing with water, and oven drying at 110 deg.C to obtain macroporous silicon-aluminum matrix material with pore volume of 1.4cm 3 The micro-cracking activity per se of the material after 17h steam aging at 800 ℃ was 29%, which was 40nm per gram and was designated as M1.
Adding 1.3kg of water, 400g of alumina sol and 570g of kaolin into a reaction kettle, pulping, uniformly stirring, adjusting the pH value to 4.5, and adding 50g of M1 to form matrix slurry; adding 0.7kg of water, 100g of Y1 and 260g of Z1 into another reaction kettle for pulping, uniformly stirring, and adding no hydrogen transfer inhibiting component to serve as molecular sieve slurry; transferring the molecular sieve slurry to a matrix slurry, homogenizing to form a catalyst slurry, and performing spray drying, roasting and curing (spray drying conditions: 400 ℃,1min; roasting conditions: 500 ℃,2 h) to obtain the low-carbon olefin catalyst prepared by catalytic cracking of crude oil, wherein the low-carbon olefin catalyst is marked as D-CAT4.
After the contrast agent is subjected to hydrothermal aging at 800 ℃ for 17 hours, the ACE evaluation result shows that the contrast agent has the following characteristics under the conditions that the reaction temperature is 650 ℃ and the agent-oil ratio is 7.5: the crude oil conversion was 90wt% and the triene single pass yield was 41.5wt%.
Comparative example 1 except that the hydrogen transfer inhibiting component was not added, i.e., inert kaolin was used instead of the hydrogen transfer inhibiting component Cr 2 O 3 And other conditions are consistent, and the experimental result shows that: in the catalyst preparation scheme, no hydrogen transfer inhibiting component is added, and the one-way yield of triene is reduced by 7.5wt%.
Comparative example 5
REUSY molecular sieve, without any treatment; taking 1kg of HZSM-5 molecular sieve, adding 230g of 25wt% lanthanum nitrate solution, adding 617g of 20wt% magnesium nitrate solution, uniformly stirring, dipping for 4h, drying, and roasting in a muffle furnace at 510 ℃ for 2h to obtain a composite modified ZSM-5 molecular sieve, wherein the label is Z3; slowly adding 1kg of solid silicon dioxide into 3.2L of aluminum nitrate solution, adding ammonia water to adjust the pH value to 7.5, gelatinizing at 90 ℃, aging for 6h, filtering, washing with water, and drying at 130 ℃ to obtain a macroporous silicon-aluminum substrate material with a pore volume of 1.3cm 3 The micro-cracking activity per se of the material after 17h steam aging at 800 ℃ was 31%, which was expressed as M3, per g and with an average pore diameter of 42nm.
Adding 1.2kg of water, 440g of alumina sol and 500g of kaolin into a reaction kettle, pulping, uniformly stirring, adjusting the pH value to 5, and adding 45g of M3 to form matrix slurry; adding 0.8kg water, 90g REUSY (untreated in Lanzhou petrochemical production) and 340g Z3 into another reaction kettle, pulping, stirring, adding 90g functional component Zn (NO) 3 ) 2 ·6H 2 O, forming a molecular sieve slurry; transferring the molecular sieve slurry to matrix slurry, homogenizing to obtain catalyst slurry, spray drying, roasting and curing (spray drying condition: 390 deg.C, 0.5min; roasting condition: 460 deg.C, 1.5 h) to obtain crude oil catalytic cracking catalyst for preparing low carbon olefin,denoted D-CAT5.
After the contrast agent is subjected to hydrothermal aging at 800 ℃ for 17h, the ACE evaluation result shows that the contrast agent has the following characteristics at the reaction temperature of 650 ℃ and the agent-oil ratio of 7.5: the crude oil conversion was 91wt% and the triene single pass yield was 42wt%.
Comparative example 3 except that conventional REUSY was used instead of high silica to alumina ratio REUSY (SiO) 2 /Al 2 O 3 = 21), other conditions are consistent, and the experimental results show that: in the catalyst preparation scheme, conventional REUSY is adopted to replace REUSY with high silica-alumina ratio, and the one-way yield of triene is reduced by 6wt%.
Comparative example 6
Taking 1kg of REUSY molecular sieve, pulping with 6L of deionized water, adding 1kg of citric acid solution with the concentration of 20wt%, adjusting the pH to 3.8 by using an ammonia water solution in the adding process, reacting for 4h at 160 ℃ under the self pressure of steam in a closed container, filtering, washing, drying, putting into a muffle furnace, and roasting for 2h at 750 ℃ under the condition of introducing steam to obtain the high silica-alumina ratio (SiO) 2 /Al 2 O 3 = 21) Y molecular sieve, denoted Y3; and (2) adding 230g of 25wt% lanthanum nitrate solution into 1kg of HZSM-5 molecular sieve, adding 617g of 20wt% magnesium nitrate solution into the mixture, uniformly stirring the mixture, dipping the mixture for 4 hours, drying the mixture, and roasting the dried mixture in a muffle furnace at 510 ℃ for 2 hours to obtain the composite modified ZSM-5 molecular sieve, wherein the mark is Z3.
Adding 1.2kg of water, 440g of alumina sol and 500g of kaolin into a reaction kettle for pulping, uniformly stirring, adjusting the pH value to 5, and adding 45g of non-porous inert silicon dioxide to form matrix slurry; adding 0.8kg of water, 90g of Y3 and 340g of Z3 into another reaction kettle for pulping, uniformly stirring, and adding 90g of functional component Zn (NO) 3 ) 2 ·6H 2 O, forming a molecular sieve slurry; transferring the molecular sieve slurry to a matrix slurry, homogenizing to form a catalyst slurry, and performing spray drying, roasting and curing (spray drying conditions: 390 ℃,0.5min; roasting conditions: 460 ℃,1.5 h) to obtain a catalyst for preparing low-carbon olefin by catalytic cracking of crude oil, wherein the catalyst is marked as D-CAT6.
After the contrast agent is subjected to hydrothermal aging at 800 ℃ for 17h, the ACE evaluation result shows that the contrast agent has the following characteristics at the reaction temperature of 650 ℃ and the agent-oil ratio of 7.5: the crude oil conversion was 88wt% and the triene single pass yield was 42wt%.
This comparative example, comparative example 3, only uses non-porous inert silica instead of the large pore active silica-alumina matrix material, the other conditions are consistent, and the experimental results show that: in the preparation scheme of the catalyst, the non-porous inert silicon dioxide is used for replacing a macroporous active silicon-aluminum substrate material, the conversion rate of crude oil is reduced by 4 percent, and the once-through yield of triene is reduced by 6 weight percent.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (13)
1. The catalyst for preparing the low-carbon olefin by catalytic cracking is characterized by comprising the following components:
5 to 20 weight percent of Y-type molecular sieve with high silica-alumina ratio, preferably 7 to 15 weight percent;
20 to 60 weight percent of modified ZSM-5 molecular sieve, preferably 25 to 50 weight percent;
0.5 to 25wt%, preferably 3 to 10wt% of macroporous matrix material;
hydrogen transfer inhibiting component, 0.5 to 15wt%, preferably 0.5 to 5wt%;
clay, 15 to 60wt%, preferably 20 to 55wt%;
binder, 2 to 20 wt.%, preferably 5 to 15 wt.%;
wherein the silicon-aluminum ratio of the high silicon-aluminum ratio Y-type molecular sieve is more than 9, preferably 15-90; the modified ZSM-5 molecular sieve comprises at least one of alkaline earth metal, rare earth metal and phosphorus, preferably at least two of the elements; the pore volume of the macroporous matrix material is 1.0-2.5 cm 3 (iv) g, the average pore diameter is 5-100 nm; the hydrogen transfer inhibiting component is a transition metal oxide.
2. The catalyst of claim 1, wherein the high silica to alumina ratio Y-type molecular sieve is selected from one or more of HY, USY, REY, REHY and REUSY.
3. The catalyst according to claim 2, wherein the high silica-alumina ratio Y-type molecular sieve is obtained by acid treatment and hydrothermal treatment, the acid is selected from one or more of hydrochloric acid, phosphoric acid, acetic acid, oxalic acid, citric acid and tartaric acid, and the acid treatment conditions are as follows: adding acid with the mass of 10-30 wt% of the Y-type molecular sieve, adjusting the pH value of the solution to 3.2-4.5, controlling the temperature to 100-200 ℃, preferably 150-195 ℃, and the time to 1-6 h; the conditions of the hydrothermal treatment are as follows: 5 to 100 percent of water vapor, 550 to 850 ℃, preferably 650 to 810 ℃ and 1 to 3 hours.
4. The catalyst according to claim 1, wherein the modified ZSM-5 molecular sieve is an H-type molecular sieve having a silica to alumina ratio of 25 to 400, preferably 25 to 180, and the content of modifying elements is 0.1 to 20wt%, preferably 0.5 to 5wt%, calculated as oxides.
5. The catalyst of claim 4, wherein the modified ZSM-5 molecular sieve is prepared by the process of: soaking the ZSM-5 molecular sieve in the mixed solution containing the modified elements for 0.5 to 4 hours, drying, and roasting at the temperature of between 450 and 550 ℃ for 1 to 3 hours; wherein the mass concentration of the modifying element in the mixed solution is 5-30% in terms of oxide.
6. The catalyst of claim 1, wherein the macroporous matrix material is silica alumina or alumina; preferably, the micro-reverse cracking activity of the macroporous matrix material after 17h of steam aging at 800 ℃ is 10-50%.
7. The catalyst according to claim 6, wherein when the macroporous matrix material is silica alumina, the silicon source is solid silica, and the aluminum source is one or more selected from aluminum sulfate, aluminum nitrate and aluminum chloride, and the preparation conditions are as follows: the gelling temperature is 60-95 ℃, the pH value after gelling is 7.0-9.5, the aging time is 2-12 h, preferably 2-6 h, after removing by-products by washing, drying at 110-150 ℃; when the macroporous matrix material is alumina, the aluminum source is one or more selected from aluminum sulfate, aluminum nitrate and aluminum chloride, and the preparation conditions are as follows: the gelling temperature is 30-90 ℃, the pH value after gelling is 7.0-9.5, the aging time is 4-24 h, preferably 4-12 h, the by-product is removed by washing with water, and then the drying is carried out at 110-150 ℃.
8. The catalyst of claim 1 wherein the hydrogen transfer inhibiting component is selected from Cr 2 O 3 、V 2 O 5 、ZnO、Fe 2 O 3 、MoO 3 、ZrO 2 、MnO 2 One or more of them.
9. The catalyst according to claim 1, wherein the clay is selected from one or more of kaolin, halloysite, montmorillonite, diatomaceous earth and sepiolite.
10. The catalyst according to claim 1, wherein the binder is selected from one or more of silica sol, aluminum sol, silica-alumina sol, phospho-alumina sol and acidified pseudo-boehmite.
11. A method for preparing the catalyst for preparing the low carbon olefin by catalytic cracking according to any one of claims 1 to 10, which is characterized by comprising the following steps:
(1) Adding water, a binder and clay into a reaction kettle for pulping, uniformly stirring, adjusting the pH value to 4.2-5.5, and adding a macroporous matrix material to form matrix slurry;
(2) Adding water, the high silica-alumina ratio Y-type molecular sieve and the modified ZSM-5 molecular sieve into another reaction kettle, pulping, uniformly stirring, and adding a hydrogen transfer inhibiting component to form molecular sieve slurry;
(3) And transferring the molecular sieve slurry to matrix slurry, homogenizing to form catalyst slurry, and spray drying, roasting and curing to obtain the catalyst for preparing the low-carbon olefin by catalytic cracking.
12. The method for preparing a catalyst according to claim 11, wherein in the step (2), the hydrogen transfer inhibiting component is added in the form of an oxide or a nitrate.
13. The method for preparing the catalyst according to claim 11, wherein in the step (2), the temperature of the spray drying is 370 to 450 ℃ and the time is 0.05 to 10min; the roasting temperature is 450-530 ℃, and the roasting time is 0.5-2 h.
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