CN113548677A - Composite modified molecular sieve, preparation method thereof, catalytic cracking catalyst, preparation method and application thereof - Google Patents
Composite modified molecular sieve, preparation method thereof, catalytic cracking catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN113548677A CN113548677A CN202010333471.XA CN202010333471A CN113548677A CN 113548677 A CN113548677 A CN 113548677A CN 202010333471 A CN202010333471 A CN 202010333471A CN 113548677 A CN113548677 A CN 113548677A
- Authority
- CN
- China
- Prior art keywords
- sapo
- molecular sieve
- composite modified
- modified molecular
- content
- Prior art date
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Links
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 248
- 239000002131 composite material Substances 0.000 title claims abstract description 226
- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 90
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 57
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 61
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 50
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 48
- 239000002253 acid Substances 0.000 claims description 44
- 239000004927 clay Substances 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 42
- 238000010306 acid treatment Methods 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 33
- 239000011230 binding agent Substances 0.000 claims description 32
- 239000012752 auxiliary agent Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 23
- 229910052593 corundum Inorganic materials 0.000 claims description 23
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 19
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 19
- 239000012265 solid product Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 16
- 235000006408 oxalic acid Nutrition 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000006011 modification reaction Methods 0.000 claims description 14
- 239000005995 Aluminium silicate Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims description 12
- 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 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 238000004537 pulping Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052621 halloysite Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- -1 rectorite Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- 229940092782 bentonite Drugs 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 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
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 229910000275 saponite Inorganic materials 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 22
- 238000006317 isomerization reaction Methods 0.000 abstract description 12
- 150000001336 alkenes Chemical class 0.000 abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 229910052799 carbon Inorganic materials 0.000 description 21
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 17
- 239000008279 sol Substances 0.000 description 16
- 229910001868 water Inorganic materials 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 7
- 235000019838 diammonium phosphate Nutrition 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000006276 transfer reaction Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 241000269350 Anura Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000002149 hierarchical pore Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012521 purified sample Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
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Abstract
本发明涉及烃油催化裂解领域，公开了一种SAPO‑11及SAPO‑34复合改性分子筛，该分子筛包括SAPO‑11及SAPO‑34复合分子筛和碱土金属元素；以所述SAPO‑11及SAPO‑34复合改性分子筛的干基重量为基准，以氧化物计，所述碱土金属元素的含量为10‑30重量％；所述SAPO‑11及SAPO‑34复合改性分子筛中的SiO2、Al2O3与P2O5的摩尔比为(0.1‑2)：1：(0.1‑3)；所述复合改性分子筛的介孔体积占总孔体积的10‑50％。所述催化剂具有裂解性能好，异构能力强的特点，在催化裂解反应中，产物中的低碳烯烃和异构产物选择性更高。The invention relates to the field of hydrocarbon oil catalytic cracking, and discloses a SAPO-11 and SAPO-34 composite modified molecular sieve, the molecular sieve includes SAPO-11 and SAPO-34 composite molecular sieves and alkaline earth metal elements; The dry basis weight of the -34 composite modified molecular sieve is based on the oxide, and the content of the alkaline earth metal element is 10 - 30% by weight; SiO 2 , The molar ratio of Al 2 O 3 to P 2 O 5 is (0.1-2): 1: (0.1-3); the mesopore volume of the composite modified molecular sieve accounts for 10-50% of the total pore volume. The catalyst has the characteristics of good cracking performance and strong isomerization ability, and in the catalytic cracking reaction, the selectivity of light olefins and isomerized products in the product is higher.
Description
Technical Field
The invention relates to the field of catalytic cracking of hydrocarbon oil, in particular to an SAPO-11 and SAPO-34 composite modified molecular sieve, a preparation method thereof, a catalytic cracking catalyst, a preparation method and an application thereof.
Background
The propylene capacity of China is rapidly increased in recent years, and crude oil is heavier and light hydrocarbon and naphtha resources are poor in China, so that the development of a catalytic cracking technology for producing propylene and ethylene by using C4-rich olefin is suitable for the needs of the national conditions of China.
The catalytic cracking process has more than ten catalytic reactions such as cracking, hydrogen transfer, condensation, polymerization, alkylation and the like, and also has nearly ten non-catalytic reactions which are very complex. The C4 monomeric olefin is often polymerized (self-polymerized) to form an olefin having a large number of carbon atoms and then subjected to a reaction such as cracking. In the reaction process of catalytic cracking, the catalyst plays a crucial role. The catalyst used in the cracking reaction of C4 is capable of holding C4 olefin molecules, on the one hand, to allow ethylene and propylene to diffuse out, and on the other hand, to block the diffusion of dimer through the catalyst channels, thereby reducing coking within the channels.
The molecular sieve is used as a cracking C4 catalyst to obtain high-yield propylene, which has attracted high attention of domestic and foreign scholars. With the increasing market demand for high octane gasoline, the demand for Methyl Tertiary Butyl Ether (MTBE) as an octane enhancer to be incorporated increases. For example, in 2011 China, the gasoline yield is 8141.1 ten thousand tons, and the total required amount of MTBE exceeds 350 ten thousand tons based on the MTBE average blending ratio of 4.5 percent. The high market demand for MTBE tends to pull the demand for the feedstock isobutylene, which is difficult to meet with conventional catalytic cracking and ethylene cracking routes. On the other hand, the utilization rate of n-butene in carbon four after MTBE byproduct ether is low, and the n-butene is often mixed with civil liquefied gas to be burned.
The process for preparing isobutene by skeletal isomerization of n-butene can convert n-butene in the carbon four after etherification into isobutene, and recycle the isobutene as an MTBE raw material. The process has the characteristics of low and easily obtained raw materials, simple process and low investment. The method not only can convert the low-value n-butene in the etherified C4 of refineries and petrochemical plants into the isobutene with high added value, but also solves the problem of low utilization rate of the etherified C4. The existing method for preparing isobutene by n-butene skeletal isomerization adopts the technical scheme that a raw material containing n-butene is contacted with a catalyst under an isomerization condition, and the catalyst is the key of the technology.
CN103769208A discloses a preparation method of a phosphorus modified SAPO-11 molecular sieve catalyst: after the SAPO-11 molecular sieve is subjected to dipping treatment by a phosphorus-containing solution, the SAPO-11 molecular sieve is uniformly mixed with a binder and water, and the obtained mixture is molded, dried and roasted to obtain the final catalyst.
CN105800633A discloses SAPO-11 molecular sieve and hydrocarbon isomerization catalyst and preparation method thereof. The secondary crystallization preparation method of the SAPO-11 molecular sieve comprises the following steps: dissolving a phosphorus source and at least one aluminum source in water, and stirring; sequentially adding at least one template agent and at least one cosolvent, dissolving, and performing primary crystallization to obtain a crystallized solution; adding at least one cationic surfactant and at least one silicon source into the crystallized solution, aging, and performing secondary crystallization; cooling, centrifugally separating, washing and drying the crystallized product to obtain raw powder of the step-hole SAPO-11 molecular sieve; and (3) roasting the raw powder of the step pore SAPO-11 molecular sieve in an air atmosphere to obtain the SAPO-11 molecular sieve.
CN105819466A provides an SAPO-18/SAPO-34 eutectic molecular sieve, a preparation method and an application thereof. The preparation method of the SAPO-18/SAPO-34 eutectic molecular sieve comprises the steps of sequentially mixing a phosphorus source, water, an organic template, an aluminum source and a silicon source, crystallizing at the temperature of 150-.
CN104525250A discloses a SAPO-34 molecular sieve catalyst with a hierarchical pore structure, and a preparation method and an application thereof, wherein the catalyst is prepared by the following steps: at a molar ratio of 1Al2O3:(0.05～0.6)SiO2:(0.8～1.2)P2O5Mixing an aluminum source, a silicon source, a phosphorus source, triethylamine and water into a mixed solution according to the proportion of (0.2-5) triethylamine and (5-100) H2O, adding a pre-crushed SAPO-34 molecular sieve as a seed crystal, crystallizing, separating, washing, drying, roasting, and carrying out alkali treatment on a roasted product to obtain the SAPO-34 molecular sieve catalyst with the hierarchical pore structure. The catalyst is applied to the reaction of preparing olefin from methanol.
However, the performance of the SAPO molecular sieve in the prior art needs to be further improved, when the SAPO molecular sieve is applied to a catalytic cracking reaction of heavy and poor oil, the cracking performance still needs to be improved, and the improvement effect on the yield of low-carbon olefins in a reaction product and the selectivity of an isomeric product is not obvious.
Disclosure of Invention
The invention aims to overcome the problems of insufficient cracking capability of heavy and poor crude oil, low selectivity of low-carbon olefin and low selectivity of an isomeric product in the prior art, and provides a SAPO-11 and SAPO-34 composite modified molecular sieve, a preparation method thereof, a catalytic cracking catalyst, a preparation method and application thereof.
In order to achieve the above object, the invention provides a SAPO-11 and SAPO-34 composite modified molecular sieve, which comprises a SAPO-11 and SAPO-34 composite molecular sieve and an alkaline earth metal element; taking the dry basis weight of the SAPO-11 and SAPO-34 composite modified molecular sieve as a reference, and taking the oxide as a reference, the content of the alkaline earth metal element is 10-30 wt%;
SiO in the SAPO-11 and SAPO-34 composite modified molecular sieve2、Al2O3And P2O5In a molar ratio of (0.1-2): 1: (0.1-3);
the mesoporous volume of the SAPO-11 and SAPO-34 composite modified molecular sieve accounts for 10-50% of the total pore volume of the SAPO-11 and SAPO-34 composite modified molecular sieve;
the specific surface area of the SAPO-11 and SAPO-34 composite modified molecular sieve is 300-700m2/g。
Preferably, the SAPO-11 and SAPO-34 composite modified molecular sieve further comprises an auxiliary agent element, and the content of the auxiliary agent element is 1-15 wt%, preferably 5-10 wt%, and more preferably 7-10 wt% calculated by oxide.
The second aspect of the invention provides a preparation method of SAPO-11 and SAPO-34 composite modified molecular sieve, which comprises the following steps:
(1) contacting the SAPO-11 and SAPO-34 composite molecular sieves with compounds of alkali and alkaline earth metals in the presence of a first solvent;
(2) carrying out acid treatment on the solid product obtained in the step (1) by adopting an acid solution;
(3) roasting the product after acid treatment;
the dosage of the SAPO-11 and SAPO-34 composite molecular sieve and the alkaline earth metal compound is such that the content of the alkaline earth metal element in the prepared SAPO-11 and SAPO-34 composite modified molecular sieve is 10-30 wt% calculated by oxide based on the dry weight of the SAPO-11 and SAPO-34 composite modified molecular sieve;
SiO in the SAPO-11 and SAPO-34 composite modified molecular sieve2、Al2O3And P2O5In a molar ratio of (0.1-2): 1: (0.1-3).
In a third aspect, the present invention provides a catalytic cracking catalyst comprising: SAPO-11 and SAPO-34 composite modified molecular sieve, binder and optional clay; based on the dry weight of the catalyst, the content of the SAPO-11 and SAPO-34 composite modified molecular sieve is 20-60 wt% in terms of dry basis, the content of clay is 0-50 wt% in terms of dry basis, and the content of the binder is 10-40 wt% in terms of oxide;
the SAPO-11 and SAPO-34 composite modified molecular sieve is the SAPO-11 and SAPO-34 composite modified molecular sieve of the first aspect or the SAPO-11 and SAPO-34 composite modified molecular sieve prepared by the method of the second aspect.
The fourth aspect of the present invention provides a method for preparing a catalytic cracking catalyst, the method comprising:
(1) in the presence of a first solvent, contacting the SAPO-11 and SAPO-34 composite molecular sieves with compounds of alkali and alkaline earth metals, and then sequentially filtering and drying to obtain a solid product;
(2) carrying out acid treatment on the solid product obtained in the step (1) by adopting an acid solution;
(3) roasting the product after acid treatment to obtain the SAPO-11 and SAPO-34 composite modified molecular sieve;
(4) pulping the SAPO-11 and SAPO-34 composite modified molecular sieve, the binder and optional clay to obtain slurry, and performing spray drying and optional roasting on the slurry;
the dosage of the SAPO-11 and SAPO-34 composite modified molecular sieve, the adhesive and the optional clay is that in the prepared catalyst, on the basis of the dry weight of the catalyst, the content of the SAPO-11 and SAPO-34 composite modified molecular sieve is 20-60 wt% on a dry basis, the content of the clay is 0-50 wt% on a dry basis, and the content of the adhesive is 10-40 wt% on an oxide basis;
the dosage of the SAPO-11 and SAPO-34 composite molecular sieve and the alkaline earth metal compound is such that the content of the alkaline earth metal element in the prepared SAPO-11 and SAPO-34 composite modified molecular sieve is 10-30 wt% calculated by oxide based on the dry weight of the SAPO-11 and SAPO-34 composite modified molecular sieve;
the SAPO-11 and the SAPO-34 are compoundedSiO in synthetic modified molecular sieve2、Al2O3And P2O5In a molar ratio of (0.1-2): 1: (0.1-3).
In a fifth aspect, the present invention provides a catalyst prepared by the above method. The catalyst has the characteristics of strong cracking capability and strong isomerization capability, and can improve the selectivity of low-carbon olefin and an isomerization product in a catalytic cracking reaction.
Accordingly, a sixth aspect of the present invention provides the use of a catalyst as described above in catalytic cracking.
According to the technical scheme, the SAPO-11 and SAPO-34 composite molecular sieve is modified by alkaline earth metal, part of silicon in the molecular sieve is removed, and a framework and surface vacancies are formed, so that the mesoporous structure of the molecular sieve is enriched, wherein the alkaline earth metal has an alkaline site which can reduce strong acidity of the molecular sieve, so that hydrogen transfer reaction of generated olefin is inhibited, and the generated low-carbon olefin is stabilized. The modification is carried out by using acid, so that part of amorphous aluminum and impurities are removed, the pore structure of the molecular sieve is favorably improved, and the stability is improved.
The embodiment of the invention shows that when the catalyst prepared by the SAPO-11 and SAPO-34 composite modified molecular sieve is used for catalytic cracking, the catalyst has good cracking performance, strong isomerization capability, higher selectivity of ethylene and propylene and higher selectivity of isobutene. Under the preferable condition, the product obtained by acid treatment in the step (2) is modified by adopting the auxiliary agent element, so that the cracking performance of the catalyst is improved, and the yield of the low-carbon olefin is improved; under the preferable condition, the invention adopts the filtrate generated in the preparation process of the SAPO-11 and SAPO-34 composite modified molecular sieve to prepare the catalyst, thereby improving the utilization rate of raw materials, avoiding environmental pollution, reducing the preparation cost of the catalyst and simultaneously improving the problem of higher coke selectivity of the cracking catalyst.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the pore diameter refers to a diameter unless otherwise specified.
In the present invention, the dry weight refers to the weight after burning at 800 ℃ for 1 hour.
The invention provides a SAPO-11 and SAPO-34 composite modified molecular sieve, which comprises the SAPO-11 and SAPO-34 composite molecular sieve and alkaline earth metal elements; taking the dry basis weight of the SAPO-11 and SAPO-34 composite modified molecular sieve as a reference, and taking the oxide as a reference, the content of the alkaline earth metal element is 10-30 wt%;
SiO in the SAPO-11 and SAPO-34 composite modified molecular sieve2、Al2O3And P2O5In a molar ratio of (0.1-2): 1: (0.1-3);
the mesoporous volume of the SAPO-11 and SAPO-34 composite modified molecular sieve accounts for 10-50% of the total pore volume of the SAPO-11 and SAPO-34 composite modified molecular sieve;
the specific surface area of the SAPO-11 and SAPO-34 composite modified molecular sieve is 300-700m2/g。
In the invention, the mesoporous volume and the total pore volume are measured by AS-3 and AS-6 static nitrogen adsorbers produced by Quantachrome instruments.
According to the invention, preferably, the weight ratio of the SAPO-11 molecular sieve to the SAPO-34 molecular sieve in the SAPO-11 and SAPO-34 composite modified molecular sieve is 1-9: 1-9, more preferably 2-3: 2-3.
According to a preferred embodiment of the present invention, the content of the alkaline earth metal element is 12 to 20% by weight, more preferably 14 to 20% by weight, in terms of oxide. The inventor of the invention finds that under the preferable condition, the strong acidity of the molecular sieve is more favorably reduced, so that the generated olefin is inhibited from generating hydrogen transfer reaction in the catalytic cracking reaction, and the yield of the low-carbon olefin is more favorably improved.
According to a preferred embodiment of the invention, SiO in the SAPO-11 and SAPO-34 composite modified molecular sieve2、Al2O3And P2O5In a molar ratio of (0.1-0.5): 1: (0.5-2). In this preferred embodiment, it is more beneficial to improve the catalytic performance of the composite modified molecular sieve in catalytic cracking.
According to the invention, the mesoporous volume of the SAPO-11 and SAPO-34 composite modified molecular sieve is 15-45%, preferably 28-40% of the total pore volume of the SAPO-11 and SAPO-34 composite modified molecular sieve. In this preferred case, the production and diffusion of the isomerization reaction product are facilitated, thereby avoiding coking and deactivation of the composite modified molecular sieve.
According to a preferred embodiment of the present invention, in the composite modified molecular sieve, the volume of mesopores with a pore diameter of 5nm to 20nm accounts for more than 85%, preferably 90% and more, for example, 90% to 96% of the total mesopore volume. Under the preferable condition, the pore channel structure of the composite modified molecular sieve is beneficial to improving the catalytic performance of the molecular sieve in catalytic cracking reaction.
According to the invention, the specific surface area of the SAPO-11 and SAPO-34 composite modified molecular sieve is preferably 500-620m2G, preferably 520-600m2(ii) in terms of/g. In the preferable case, the catalytic performance of the composite modified molecular sieve in catalytic cracking reaction is improved. In the present invention, the specific surface area is measured by a BET adsorption method.
According to the invention, the strong acid content of the SAPO-11 and SAPO-34 composite modified molecular sieve is preferably 25-45%, preferably 28-40% of the total acid content. Under the preferable condition, the hydrogen transfer reaction generated by the generated olefin is inhibited in the catalytic cracking reaction, so that the yield of the low-carbon olefin is improved.
In the invention, NH is adopted as the proportion of the acid amount of the strong acid to the total acid amount3TPD method.
In the present invention, the strong acid means that the acid center is NH without specific description3The desorption temperature is higher than 300 ℃ of the corresponding acid center.
According to a preferred embodiment of the present invention, the SAPO-11 and SAPO-34 composite modified molecular sieve further contains an auxiliary element, and the content of the auxiliary element is 1 to 15 wt%, preferably 5 to 10 wt%, and more preferably 7 to 10 wt%, calculated as an oxide. Under the preferred embodiment, the cracking performance of the composite modified molecular sieve is improved, so that the selectivity of low-carbon olefin and an isomeric product in a cracking reaction product is improved.
According to the composite modified molecular sieve provided by the invention, the selection range of the auxiliary element is wide, and preferably, the auxiliary element comprises a first auxiliary element and/or a second auxiliary element.
In the present invention, the first auxiliary element is selected from a wide range, for example, a metal element, and preferably, the first auxiliary element is selected from at least one of group IB, group IIB, group IVB, group VIIB, group VIII, and a rare earth element. Further preferably, the first auxiliary element is at least one selected from Zr, Ti, Ag, La, Ce, Fe, Cu, Zn and Mn elements, more preferably at least one selected from Ti, Zr, Zn and Ce elements. Under the preferable condition, the composite modified sub-sieve has stronger catalytic activity in the catalytic cracking reaction, and is favorable for improving the selectivity of low-carbon olefin and an isomeric product.
The second auxiliary element is selected in a wide range, such as a nonmetal element, preferably, the second auxiliary element is at least one element selected from B, P and F, preferably, the second auxiliary element is a B element and/or a P element. Under the preferable condition, the composite modified molecular sieve has stronger catalytic activity in catalytic cracking reaction, and is favorable for improving the selectivity of low-carbon olefin and an isomeric product.
The content selection range of the first auxiliary element and the second auxiliary element is wide, and preferably, the content of the first auxiliary element is 1-10 wt%, preferably 5-10 wt%, and more preferably 7-9 wt% calculated by oxide based on the dry weight of the SAPO-11 and SAPO-34 composite modified molecular sieve; the content of the second auxiliary element is 0.1 to 10, preferably 0.1 to 5 wt%, and more preferably 1 to 3 wt%. Under the preferable condition, the composite modified molecular sieve has stronger cracking performance, and is favorable for improving the selectivity of low-carbon olefin and an isomeric product.
According to a preferred embodiment of the present invention, the alkaline earth metal element is at least one element selected from Mg, Ca, Sr and Ba elements, preferably Mg element. Under the preferred embodiment, the method is beneficial to improving the selectivity of the low-carbon olefin in the catalytic cracking reaction.
The second aspect of the invention provides a preparation method of SAPO-11 and SAPO-34 composite modified molecular sieve, which comprises the following steps:
(1) contacting the SAPO-11 and SAPO-34 composite molecular sieves with compounds of alkali and alkaline earth metals in the presence of a first solvent;
(2) carrying out acid treatment on the solid product obtained in the step (1) by adopting an acid solution;
(3) roasting the product after acid treatment;
the dosage of the SAPO-11 and SAPO-34 composite molecular sieve and the alkaline earth metal compound is such that the content of the alkaline earth metal element in the prepared SAPO-11 and SAPO-34 composite modified molecular sieve is 10-30 wt% calculated by oxide based on the dry weight of the SAPO-11 and SAPO-34 composite modified molecular sieve;
SiO in the SAPO-11 and SAPO-34 composite modified molecular sieve2、Al2O3And P2O5In a molar ratio of (0.1-2): 1: (0.1-3).
According to a preferred embodiment of the invention, the preparation method of the SAPO-11 and SAPO-34 composite modified molecular sieve comprises the following steps:
(1) contacting the SAPO-11 and SAPO-34 composite molecular sieves with compounds of alkali and alkaline earth metals in the presence of a first solvent;
(2) carrying out acid treatment on the solid product obtained in the step (1) by adopting an acid solution;
(3) roasting the product after acid treatment;
the amount of the alkaline earth metal compound is 10 to 35 parts by weight, preferably 12 to 20 parts by weight, and more preferably 14 to 20 parts by weight, in terms of oxide, relative to 100 parts by weight of the SAPO-11 and SAPO-34 composite modified molecular sieve;
SiO in the SAPO-11 and SAPO-34 composite modified molecular sieve2、Al2O3And P2O5In a molar ratio of (0.1-2): 1: (0.1-3).
The inventor of the invention finds that the alkaline earth metal is adopted to modify the SAPO-11 and SAPO-34 composite molecular sieve, so that part of silicon in the molecular sieve can be removed to form a framework and surface vacancies, and the mesoporous structure of the molecular sieve is favorably improved; the alkaline earth metal has an alkaline site which is beneficial to reducing strong acidity of the molecular sieve, so that hydrogen transfer reaction of generated olefin is inhibited in catalytic cracking reaction, and the selectivity of low-carbon olefin is improved.
According to the invention, preferably, the weight ratio of the SAPO-11 molecular sieve to the SAPO-34 molecular sieve in the SAPO-11 and SAPO-34 composite molecular sieve is 1-9: 1-9, more preferably 2-3: 2-3.
The first solvent in step (1) is selected in a wide range, as long as the environment for contacting the composite molecular sieve with alkali and alkaline earth metal elements can be provided. Preferably, the first solvent is water. The water used in the present invention is not particularly limited, and may be any water having various hardness, and any of tap water, distilled water, purified water and deionized water can be used. In one embodiment of the present invention, the first solvent is neutral water, which is also called distilled water.
The amount of the first solvent used in the present invention is selected from a wide range, and may be appropriately selected according to the amounts of the compound of the composite molecular sieve and the alkali and alkaline earth metals, as long as the contacting in step (1) can be smoothly performed.
Preferably, the first solvent is used in an amount of 100-1000 parts by weight relative to 100 parts by weight of the SAPO-11 and SAPO-34 molecular sieves.
In the present invention, in the step (1), the order of contacting the composite molecular sieve with the alkali and alkaline earth metal compound is not particularly limited, and the composite molecular sieve may be contacted with the alkali first, the alkaline earth metal compound first, or both the alkali and alkaline earth metal compound simultaneously.
In the present invention, the first solvent may be introduced alone or together with the alkali or alkaline earth metal compound. According to an embodiment of the present invention, the step (1) comprises: and contacting the first solvent, the SAPO-11 and the SAPO-34 composite molecular sieve with an alkali solution and an alkaline earth metal compound.
According to the present invention, preferably, the contacting conditions of step (1) include: the temperature is 50-90 ℃ and the time is 1-5 h; further preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
In the present invention, the filtration and drying in step (1) are all operations well known to those skilled in the art, and the present invention is not particularly limited.
According to a specific embodiment of the present invention, the method may further include, in step (1), sequentially filtering and drying the post-contact product to obtain a solid product, and then washing the solid product. In the present invention, the filtration, drying and washing are all conventional operations in the art, and the present invention is not particularly limited thereto, and thus, the details thereof are not repeated. The washing conditions are selected in a wide range, and preferably, the pH of the filtrate obtained after washing is 6.5-7.5, and preferably, the pH of the filtrate obtained after washing is more than 7.
According to a preferred embodiment of the present invention, the amounts of the SAPO-11 and SAPO-34 composite molecular sieve and the alkaline earth metal compound are such that the alkaline earth metal element is 12 to 20 wt%, more preferably 14 to 20 wt%, based on the dry weight of the SAPO-11 and SAPO-34 composite modified molecular sieve, in the SAPO-11 and SAPO-34 composite modified molecular sieve. Under the preferred embodiment, the method is more favorable for inhibiting the generated olefin from generating hydrogen transfer reaction in the catalytic cracking reaction, and improves the selectivity of the low-carbon olefin and the isomeric product.
According to the invention, the SAPO-11 and SAPO-34 are preferably combinedSiO in molecular sieve2、Al2O3And P2O5In a molar ratio of (0.1-0.5): 1: (0.5-2).
In the present invention, the SAPO-11 and SAPO-34 composite molecular sieves are commercially available or can be self-prepared according to any prior art method.
According to the present invention, preferably, the base is selected from at least one of sodium hydroxide, potassium carbonate, and sodium carbonate. From the viewpoint of cost reduction, the alkali is further preferably sodium hydroxide.
According to the present invention, preferably, in step (1), the base is introduced in the form of an alkaline solution. The concentration of the alkali solution is selected in a wide range, and the molar concentration of the alkali solution is preferably 0.1 to 2mol/L, and more preferably 0.3 to 0.9 mol/L.
According to the present invention, preferably, the alkali solution is used in an amount of 1 to 100 parts by weight, preferably 5 to 20 parts by weight, relative to 100 parts by weight of the SAPO-11 and SAPO-34 composite molecular sieves.
In the present invention, the selection range of the alkaline earth metal is as described above, and the present invention will not be described herein again.
The compound of the alkaline earth metal can be selected from a wide range, and the compound can be dissolved in a solvent or dissolved in the solvent under the action of a cosolvent. Preferably, the compound of the alkaline earth metal is selected from at least one of an oxide, a chloride, a nitrate and a sulfate of the alkaline earth metal, more preferably at least one of magnesium oxide, magnesium chloride, magnesium sulfate and magnesium nitrate.
The acid of the present invention can be selected from a wide range of acids, and can be any of those conventionally used in the art. Specifically, the acid is an organic acid and/or an inorganic acid. Preferably, the acid in step (2) is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, oxalic acid, citric acid and acetic acid, preferably sulfuric acid and/or oxalic acid, and more preferably sulfuric acid and oxalic acid. Under the optimal condition, part of amorphous aluminum and impurities are removed, and the pore structure of the composite molecular sieve is improved, so that the stability is improved, and the catalytic performance of the composite modified molecular sieve is improved.
According to the invention, preferably, the weight ratio of the sulfuric acid to the oxalic acid is 1: 1-4.
According to the invention, preferably, the acid treatment enables the prepared SAPO-11 and SAPO-34 composite modified molecular sieve to have sodium content of not more than 0.5 wt% calculated by oxide.
The weight content of the acid solution is selected from a wide range, and preferably, the weight content of the acid solution is 5 to 98 wt%, and more preferably, 10 to 30 wt%.
According to the present invention, preferably, the weight ratio of the acid to the solid product obtained in step (1) on a dry basis is from 0.1 to 5, more preferably from 0.2 to 2. In the preferable case, the catalytic performance of the composite modified molecular sieve in the catalytic cracking reaction is more favorably improved.
In the present invention, the acid treatment in step (2) is not particularly limited, and preferably, the reaction conditions of the acid treatment in step (2) include: the temperature is 50-90 ℃ and the time is 1-5 h; preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
According to a preferred embodiment of the present invention, the method further comprises modifying the product obtained by the acid treatment in step (2) after step (2) and before step (3), wherein the modification comprises: and (3) carrying out modification reaction on the product obtained by the acid treatment in the step (2) and a soluble compound of the auxiliary agent in the presence of a second solvent. Under the preferred embodiment, the cracking performance of the composite modified molecular sieve in the catalytic cracking reaction is improved, and the selectivity of the low-carbon olefin and the isomeric product is improved.
In the present invention, the manner of introducing the second solvent is not particularly limited, and specifically, for example, the second solvent may be introduced alone or may be introduced together with the soluble compound of the auxiliary. According to a particular embodiment of the invention, the modification comprises: and (3) contacting the product obtained by acid treatment in the step (2), the second solvent and a soluble compound of an auxiliary agent for modification reaction. The order of the contacting is not particularly limited in the present invention, and the product obtained by the acid treatment in the step (2) may be contacted with the second solvent first and then contacted with the soluble compound of the auxiliary agent; the product obtained by the acid treatment in the step (2) can also be contacted with the second solvent before being contacted with the soluble compound of the auxiliary agent.
In the present invention, the second solvent is selected from a wide range as long as it provides an environment in which the product obtained by the acid treatment in the step (2) and the soluble compound of the auxiliary are subjected to the modification reaction. Preferably, the second solvent is water. The water used in the present invention is not particularly limited, and may be any water having various hardness, and any of tap water, distilled water, purified water and deionized water can be used. In one embodiment of the present invention, the second solvent is neutral water, which is also called distilled water.
The amount of the second solvent is selected from a wide range, and may be appropriately selected according to the amounts of the soluble compound of the product obtained by the acid treatment in the step (2) and the auxiliary agent, as long as the modification reaction in the step (2) can be smoothly performed. Preferably, the second solvent is used in an amount of 100-1000 parts by weight based on 100 parts by weight of the product (dry basis weight) obtained in step (2).
According to the invention, the soluble compound of the auxiliary agent is preferably used in an amount such that the content of the auxiliary agent element in the prepared SAPO-11 and SAPO-34 composite modified molecular sieve is 1-15 wt%, preferably 5-10 wt%, and more preferably 7-10 wt% calculated by oxide based on the dry weight of the SAPO-11 and SAPO-34 composite modified molecular sieve. Under the optimal condition, the catalytic performance of the composite modified molecular sieve in catalytic cracking is improved, so that the selectivity of low-carbon olefin and an isomeric product is improved.
According to the invention, preferably, the auxiliary element comprises a first auxiliary element and/or a second auxiliary element.
In the present invention, the selection ranges of the first auxiliary element and the second auxiliary element are as described above, and the present invention is not described herein again.
Preferably, the conditions of the modification reaction include: the temperature is 50-90 ℃ and the time is 1-5 h; preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
According to an embodiment of the present invention, the method may further include: and (3) after the step (2), filtering, washing and drying the product obtained by the acid treatment in sequence before modifying the product obtained by the acid treatment in the step (2) to obtain the product after the acid treatment. The filtration, washing and drying are all operations well known to those skilled in the art, and the present invention is not particularly limited.
According to the present invention, it is preferable that after the modification reaction is carried out, the product obtained by the modification reaction is sequentially filtered and dried before the calcination in step (3). The filtration and drying are procedures well known to those skilled in the art, and the present invention is not particularly limited.
According to the present invention, preferably, the roasting conditions of step (3) include: the temperature is 500-800 ℃, preferably 550-650 ℃; the time is 1-10h, preferably 2-3 h.
In a third aspect, the present invention provides a catalytic cracking catalyst comprising: SAPO-11 and SAPO-34 composite modified molecular sieve, binder and optional clay; based on the dry weight of the catalyst, the content of the SAPO-11 and SAPO-34 composite modified molecular sieve is 20-60 wt% in terms of dry basis, the content of clay is 0-50 wt% in terms of dry basis, and the content of the binder is 10-40 wt% in terms of oxide;
the SAPO-11 and SAPO-34 composite modified molecular sieve is the SAPO-11 and SAPO-34 composite modified molecular sieve of the first aspect or the SAPO-11 and SAPO-34 composite modified molecular sieve prepared by the method of the second aspect.
According to the invention, preferably, the content of the SAPO-11 and SAPO-34 composite modified molecular sieve is 25-50 wt% on a dry basis, the content of the clay is 12-45 wt% on a dry basis, and the content of the binder is 12-38 wt% on an oxide basis, based on the dry weight of the catalyst.
Further preferably, the content of the SAPO-11 and SAPO-34 composite modified molecular sieve is 25-40 wt% on a dry basis, the content of the clay is 25-40 wt% on a dry basis, and the content of the binder is 20-35 wt% on an oxide basis, based on the dry weight of the catalyst.
In one embodiment, the total of the SAPO-11 and SAPO-34 composite modified molecular sieve content on a dry basis, the clay content on a dry basis, and the binder content on an oxide basis, based on the dry weight of the catalyst, is 100%.
In the present invention, the optional clay means that the catalyst may or may not contain clay, and preferably contains clay. The clay is selected from a wide range of materials known to those skilled in the art. Preferably, the clay is selected from at least one of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite, and further preferably kaolin and/or halloysite.
According to the present invention, the selection of the binder is not particularly limited, and may be a material known to those skilled in the art. Preferably, the binder is a refractory inorganic oxide, preferably one or more of alumina, silica, titania, magnesia, zirconia, thoria and beryllia, and/or a refractory inorganic oxide precursor, which is at least one of acidified pseudo-boehmite, alumina sol, silica sol, phosphor-alumina sol, silica-alumina sol, magnesium-alumina sol, zirconium sol and titanium sol, preferably acidified pseudo-boehmite and alumina sol.
The fourth aspect of the present invention provides a method for preparing a catalytic cracking catalyst, the method comprising:
(1) in the presence of a first solvent, contacting the SAPO-11 and SAPO-34 composite molecular sieves with compounds of alkali and alkaline earth metals, and then sequentially filtering and drying to obtain a solid product;
(2) carrying out acid treatment on the solid product obtained in the step (1) by adopting an acid solution;
(3) roasting the product after acid treatment to obtain the SAPO-11 and SAPO-34 composite modified molecular sieve;
(4) pulping the SAPO-11 and SAPO-34 composite modified molecular sieve, the binder and optional clay to obtain slurry, and performing spray drying and optional roasting on the slurry;
the dosage of the SAPO-11 and SAPO-34 composite modified molecular sieve, the adhesive and the optional clay is that in the prepared catalyst, on the basis of the dry weight of the catalyst, the content of the SAPO-11 and SAPO-34 composite modified molecular sieve is 20-60 wt% on a dry basis, the content of the clay is 0-50 wt% on a dry basis, and the content of the adhesive is 10-40 wt% on an oxide basis;
the dosage of the SAPO-11 and SAPO-34 composite molecular sieve and the alkaline earth metal compound is such that the content of the alkaline earth metal element in the prepared SAPO-11 and SAPO-34 composite modified molecular sieve is 10-30 wt% calculated by oxide based on the dry weight of the SAPO-11 and SAPO-34 composite modified molecular sieve;
in the SAPO-11 and SAPO-34 composite modified molecular sieve, SiO2、Al2O3And P2O5In a molar ratio of (0.1-2): 1: (0.1-3).
According to the invention, preferably, the weight ratio of the SAPO-11 molecular sieve to the SAPO-34 molecular sieve in the SAPO-11 and SAPO-34 composite molecular sieve is 1-9: 1-9, more preferably 2-3: 2-3.
According to a preferred embodiment of the present invention, the method for preparing the catalytic cracking catalyst comprises:
(1) in the presence of a first solvent, contacting the SAPO-11 and SAPO-34 composite molecular sieves with compounds of alkali and alkaline earth metals, and then sequentially filtering and drying to obtain a solid product;
(2) carrying out acid treatment on the solid product obtained in the step (1) by adopting an acid solution;
(3) roasting the product after acid treatment to obtain the SAPO-11 and SAPO-34 composite modified molecular sieve;
(4) pulping the SAPO-11 and SAPO-34 composite modified molecular sieve, the binder and optional clay to obtain slurry, and performing spray drying and optional roasting on the slurry;
the dosage of the SAPO-11 and SAPO-34 composite modified molecular sieve, the adhesive and the optional clay is that in the prepared catalyst, on the basis of the dry weight of the catalyst, the content of the SAPO-11 and SAPO-34 composite modified molecular sieve is 20-60 wt% on a dry basis, the content of the clay is 0-50 wt% on a dry basis, and the content of the adhesive is 10-40 wt% on an oxide basis;
the amount of the alkaline earth metal compound is 10 to 35 parts by weight, preferably 12 to 20 parts by weight, and more preferably 14 to 20 parts by weight, in terms of oxide, relative to 100 parts by weight of the SAPO-11 and SAPO-34 composite modified molecular sieve;
in the SAPO-11 and SAPO-34 composite modified molecular sieve, SiO2、Al2O3And P2O5In a molar ratio of (0.1-2): 1: (0.1-3).
According to the preparation method provided by the invention, the SAPO-11 and SAPO-34 composite molecular sieve, and the alkali, alkaline earth metal and alkaline earth metal compounds are selected as described above, and the details are not repeated herein.
According to the preparation method provided by the invention, the selection of the contacting condition in the step (1) is as described above, and the invention is not repeated herein.
The acid in step (2) is selected as described above, and is not described herein again.
The reaction conditions for the acid treatment in step (2) are selected as described above, and the present invention is not described herein again.
According to a preferred embodiment of the present invention, the method further comprises modifying the product obtained by the acid treatment in step (2) after step (2) and before step (3), wherein the modification comprises: and (3) carrying out modification reaction on the product obtained by the acid treatment in the step (2) and a soluble compound of the auxiliary agent in the presence of a second solvent. The conditions for the modification reaction of the present invention are selected as described above, and the present invention is not described herein in detail.
The selection of the auxiliary elements and the soluble compounds of the auxiliary is as described above, and the detailed description of the invention is omitted here.
According to the present invention, preferably, the roasting conditions of step (3) include: the temperature is 500-800 ℃, preferably 550-650 ℃; the time is 1-10h, preferably 2-3 h.
In the present invention, the optional clay in step (4) means that the clay may or may not be introduced during the beating.
In the present invention, the optional calcination in the step (4) means that the slurry may or may not be calcined after spray-drying. Preferably, the slurry is spray-dried and then calcined in step (4).
According to a preferred embodiment of the present invention, the step (4) comprises: and pulping the SAPO-11 and SAPO-34 composite modified molecular sieve, the binder and the clay to obtain slurry, and performing spray drying and roasting on the slurry.
The conditions for the calcination in the step (4) are not particularly limited in the present invention, and may be conventionally selected in the art. Specifically, for example, the conditions for the calcination in the step (4) include: the temperature is 300-800 ℃, preferably 400-700 ℃; the time is 0.5-10h, preferably 1-6 h.
According to the invention, preferably, the SAPO-11 and SAPO-34 composite modified molecular sieve, the binder and the optional clay are used in amounts such that the prepared catalyst has a SAPO-11 and SAPO-34 composite modified molecular sieve content of 25-50 wt.% on a dry basis, a clay content of 12-45 wt.% on a dry basis and a binder content of 12-38 wt.% on an oxide basis, based on the dry weight of the catalyst.
Further preferably, the content of the SAPO-11 and SAPO-34 composite modified molecular sieve is 25-40 wt% on a dry basis, the content of the clay is 25-40 wt% on a dry basis, and the content of the binder is 20-35 wt% on an oxide basis, based on the dry weight of the catalyst.
The binder and clay are selected in accordance with the present invention as described above, and the present invention will not be described in detail herein.
According to a preferred embodiment of the present invention, step (4) comprises pulping the filtrate obtained by filtration in step (1), the SAPO-11 and SAPO-34 composite modified molecular sieve, the binder and optionally the clay. In the preferred embodiment, the filtrate generated in the preparation process of the SAPO-11 and SAPO-34 composite modified molecular sieve is reused in the preparation process of the catalyst, and the filtrate contains Al, Si and Mg elements, so that the utilization rate of raw materials is improved, the environmental pollution is reduced, the energy consumption for preparing the catalyst is reduced, and the coke selectivity of the cracking reaction is reduced.
According to the present invention, it is preferred that the filtrate obtained by filtration in step (1) has a total content of silicon in terms of oxide, aluminum in terms of oxide and phosphorus in terms of oxide of 1 to 20% by weight, preferably 5 to 10% by weight;
according to the present invention, it is preferred that the filtrate obtained by filtration in step (1) is used in such an amount that SiO introduced into the resulting catalyst from the filtrate obtained by filtration in step (1) is introduced on a dry basis of the weight of the catalyst2、Al2O3And P2O5The total content of (A) is 5-10 wt%;
preferably, the slurry of step (4) has a solids content of 15 to 45 wt%, preferably 30 to 40 wt%.
According to a specific embodiment of the invention, the binder in step (4) is pseudo-boehmite and alumina sol, and the pulping process in step (4) comprises: mixing the aluminum sol and the pseudo-boehmite, adding the clay, adding acid for acidification, and finally adding the SAPO-11 and SAPO-34 composite modified molecular sieve.
The acidification in step (4) is not particularly limited in the present invention, and may be carried out according to a conventional technique in the art. The present invention has a wide choice of the acid used for the acidification in step (4), and may be, for example, a mineral acid conventionally used in the art, including but not limited to hydrochloric acid. The weight ratio of the acid to the pseudoboehmite in the step (4) is preferably 0.01 to 1.
The spray drying in the invention is the prior art, and the invention has no special requirements, and is not described in detail herein.
The fifth invention of the present invention provides the catalyst prepared by the above method. When the catalyst is applied to cracking reaction, the cracking performance is better, the isomerization capability is stronger, and the selectivity of low-carbon olefin and isobutene is higher.
Accordingly, a sixth aspect of the present invention provides the use of a catalyst as described above in catalytic cracking. Specifically, for example, a hydrocarbon oil may be contacted with the catalyst under catalytic cracking conditions to carry out a reaction.
In the present invention, the selection range of the hydrocarbon oil is wide, and the hydrocarbon oil can be selected conventionally in the field, and the present invention is not described herein again.
The reaction conditions for the catalytic cracking in the present invention are widely selected, and specifically, for example, the reaction conditions may include: the temperature is 250-350 ℃, preferably 280-330 ℃; the weight hourly space velocity is 1-15h-1Preferably 4-10h-1。
According to the present invention, preferably, the catalytic process further comprises: the catalyst is subjected to hydrothermal aging before the reaction is carried out. The invention has wider selection range of the conditions of the hydrothermal aging, and preferably, the hydrothermal aging is carried out by adopting 90-100% of water vapor. Further preferably, the hydrothermal aging conditions further include: the temperature is 700-900 ℃, preferably 750-850 ℃ and the time is 5-24h, preferably 10-16 h.
The present invention will be described in detail below by way of examples.
In the following examples, room temperature means 25 ℃ unless otherwise specified;
the specifications of the raw materials used in the examples are as follows:
kaolin: with a solids content of 72% by weight, manufactured by china kaolin, inc (suzhou).
Sulfuric acid, oxalic acid: analyzing and purifying;
aluminum sol: al (Al)2O322 wt%, produced by Qilu Branch of China petrochemical catalyst, Inc.;
pseudo-boehmite: solid content 72 wt%, Shandong aluminum industries, China;
SAPO-11 and SAPO-34 composite molecular sieves: tianjin Kaimeisi chemical Co., Ltd (weight ratio of SAPO-11 molecular sieve to SAPO-34 molecular sieve is 1: 1);
in the following examples, the following methods were used to evaluate the relevant parameters of the prepared SAPO-11 and SAPO-34 composite modified molecular sieves:
(1) comprises the following components:
and (3) adopting fluorescence spectrum analysis, and referring to the GB/T30905-2014 standard method for determination.
(2) Specific surface area (SBET), mesopore volume, total pore volume, mesopore volume of 5-20 nm:
the determination is carried out by adopting AS-3 and AS-6 static nitrogen adsorption instruments produced by Congta Quantachrome company of America, and the instrument parameters are AS follows: the sample was placed in a sample handling system and evacuated to 1.33X 10 at 300 deg.C-2Pa, keeping the temperature and the pressure for 4h, and purifying the sample. Testing the purified samples at different specific pressures P/P at a liquid nitrogen temperature of-196 DEG C0The adsorption quantity and the desorption quantity of the nitrogen under the condition are obtained to obtain N2Adsorption-desorption isotherm curve. Then, calculating the total specific surface area by utilizing a BET formula of two parameters; proportional pressure P/P0The adsorption capacity of 0.98 or less is the total pore volume of the sample; the pore size distribution of the mesoporous part is calculated by a BJH formula, and the mesoporous volume (5-50nm) and the mesoporous volume (5-20 nm) are calculated by an integration method.
(3) Total acid amount and strong acid amount:
the determination is carried out by adopting an Autochem II 2920 programmed temperature desorption instrument of Michman, USA, and the test conditions are as follows: weighing 0.2g of a sample to be detected, putting the sample into a sample tube, placing the sample tube in a thermal conductivity cell heating furnace, taking He gas as carrier gas (50mL/min), raising the temperature to 600 ℃ at the speed of 20 ℃/min, and purging for 60min to remove impurities adsorbed on the surface of the sample. Then cooling to 100 ℃, keeping the temperature for 30min, and switching to NH3-He mixed gas (10.02% NH)3+ 89.98% He) for 30min, and then continuing to purge with He gas for 90min until the baseline is stable, so as to desorb the physically adsorbed ammonia gas. And (4) heating to 600 ℃ at the heating rate of 10 ℃/min for desorption, keeping for 30min, and finishing desorption. Detecting gas component change by TCD detector, and automatically integrating by instrument to obtain total acid amount and strong acid amount, wherein acid center of strong acid is NH3The desorption temperature is higher than 300 ℃ of the corresponding acid center.
Example 1
The method for preparing the composite modified molecular sieve and the catalytic cracking catalyst comprises the following specific steps:
(1) taking SAPO-11 and SAPO-34 composite molecular Sieve (SiO)2、Al2O3And P2O5Is 0.45: 1: 1.1)100g (dry basis weight), adding 600g of neutral water (also called distilled water in the invention), 20g of NaOH solution (with the molar concentration of 0.833mol/L) and 20g of MgO, heating to 70 ℃, carrying out contact reaction for 2h, cooling to room temperature, and then sequentially filtering, washing and drying to obtain a solid product; the filtrate was obtained for future use, and the content of elements in the filtrate was measured by the ICP analytical method, and the total weight content of aluminum in terms of oxide, silicon in terms of oxide, and phosphorus in terms of oxide in the filtrate was 8.21 wt%, and the specific ingredients are shown in table 1.
(2) Taking 80g (dry basis weight) of the solid product obtained in the step (1), pulping with 640g of water, and then adding 40g of H with the weight content of 20 wt%2SO460g of oxalic acid, heating to 70 ℃, carrying out acid treatment for 2 hours, and then sequentially carrying out filtration, washing and drying;
(3) taking 50g (dry basis weight) of the product obtained in the step (2), adding 200g of neutral water, 5.23g of zirconium oxychloride, 4.33g of cerous chloride and 1.86g of diammonium hydrogen phosphate, heating to 70 ℃, carrying out contact reaction for 2h, sequentially filtering and drying, and then roasting at 650 ℃ for 2.5h to obtain SAPO-11 and SAPO-34 composite modified molecular sieve S1, wherein the specific physicochemical property data are listed in Table 2;
(4) pulping the SAPO-11 and SAPO-34 composite modified molecular sieve, pseudo-boehmite, alumina sol and kaolin obtained in the step (3) with hydrochloric acid with the weight concentration of 22 wt% to obtain slurry, wherein the solid content of the slurry is 35 wt%; spray drying the slurry to obtain a microspherical catalyst, roasting the microspherical catalyst at 500 ℃ for 1h to obtain a catalytic cracking catalyst C1, and specifically evaluating data are listed in Table 2;
the amount of hydrochloric acid having a weight concentration of 22% by weight was 10.28 parts by weight relative to 100 parts by weight of the composite modified molecular sieve;
calculated by alumina, the weight ratio of the used amount of the pseudo-boehmite to the used amount of the alumina sol is 2.25: 1; the usage amounts of the SAPO-11 and SAPO-34 composite modified molecular sieve, the pseudo-boehmite, the alumina sol and the kaolin are such that in the prepared catalyst, on the basis of the dry weight of the catalyst, the content of the SAPO-11 and SAPO-34 composite modified molecular sieve on a dry basis is 35 wt%, the content of the clay on a dry basis is 39 wt%, and the content of the binder on an oxide basis is 26 wt%.
Examples 1 to 1
The composite modified molecular sieve and the catalytic cracking catalyst are prepared according to the method of the invention, the steps (1), (2) and (3) are the same as the example (1), except that the step (4) is carried out according to the following process:
(4) pulping the filtrate obtained in the step (1), the SAPO-11 and SAPO-34 composite modified molecular sieve obtained in the step (3), pseudo-boehmite, alumina sol, kaolin and hydrochloric acid with the weight concentration of 22 wt% to obtain slurry, wherein the solid content of the slurry is 33 wt%; spray drying the slurry to obtain a microspherical catalyst, roasting the microspherical catalyst at 500 ℃ for 1h to obtain a catalytic cracking catalyst C1-1, wherein specific evaluation data are listed in Table 2;
the amount of hydrochloric acid having a weight concentration of 22% by weight was 10.28 parts by weight relative to 100 parts by weight of the composite modified molecular sieve; the amount of filtrate used was such that in the catalyst C1-1 obtained, SiO was introduced from the filtrate on a dry weight basis of the catalyst2、Al2O3And P2O5The total content of (a) is 8.21 wt%;
calculated by alumina, the weight ratio of the used amount of the pseudo-boehmite to the used amount of the alumina sol is 2.25: 1; in the catalyst, the weight ratio of the SAPO-11 and SAPO-34 composite modified molecular sieve, the total amount of the pseudoboehmite and the alumina sol counted by alumina and the kaolin counted by dry basis is 35: 26: 39.
comparative example 1
A composite modified molecular sieve and a catalytic cracking catalyst were prepared in the same manner as in example 1, except that 20g of MgO was not added in the step (1);
the steps (2), (3) and (4) are carried out according to the method of the example 1 to obtain the SAPO-11 and SAPO-34 composite modified molecular sieve SD1 and the catalyst D1, and the specific physicochemical properties and evaluation data are listed in Table 2.
Example 2
A composite modified molecular sieve and a catalytic cracking catalyst were prepared in the same manner as in example 1, except that, in the step (2), H was contained in an amount of 20% by weight2SO4The dosage of the oxalic acid is 80g, and the dosage of the oxalic acid is 120 g;
the steps (1), (3) and (4) are carried out according to the method of the example 1 to obtain the SAPO-11 and SAPO-34 composite modified molecular sieve S2 and the catalyst C2, and the specific physicochemical properties and evaluation data are listed in Table 2.
Example 3
A composite modified molecular sieve and a catalytic cracking catalyst were prepared in the same manner as in example 1, except that in step (3), 5.23g of zirconium oxychloride, 4.33g of cerous chloride, and 1.86g of diammonium hydrogen phosphate were replaced with 13.08g of zirconium oxychloride;
the steps (1), (2) and (4) are carried out according to the method of the example 1 to obtain the SAPO-11 and SAPO-34 composite modified molecular sieve S3 and the catalyst C3, and the specific physicochemical properties and evaluation data are listed in Table 2.
Example 4
A composite modified molecular sieve and a catalytic cracking catalyst were prepared in the same manner as in example 1, except that in step (3), 5.23g of zirconium oxychloride, 4.33g of cerous chloride, 1.86g of diammonium hydrogen phosphate were replaced with 10.83g of cerous chloride;
the steps (1), (2) and (4) are carried out according to the method of the example 1 to obtain the SAPO-11 and SAPO-34 composite modified molecular sieve S4 and the catalyst C4, and the specific physicochemical properties and evaluation data are listed in Table 2.
Example 5
A composite modified molecular sieve and a catalytic cracking catalyst were prepared in the same manner as in example 1, except that in step (3), 5.23g of zirconium oxychloride, 4.33g of cerous chloride, 1.86g of diammonium hydrogen phosphate was replaced with 9.3g of diammonium hydrogen phosphate;
the steps (1), (2) and (4) are carried out according to the method of the example 1 to obtain the SAPO-11 and SAPO-34 composite modified molecular sieve S5 and the catalyst C5, and the specific physicochemical properties and evaluation data are listed in Table 2.
Example 6
A composite modified molecular sieve and a catalytic cracking catalyst were prepared in the same manner as in example 1, except that in step (3), 5.23g of zirconium oxychloride, 4.33g of cerous chloride, and 1.86g of diammonium hydrogen phosphate were replaced with 2.62g of zirconium oxychloride, 2.17g of cerous chloride, 1g of titanium dioxide, 1.40g of diammonium hydrogen phosphate, and 1.33g of boric acid;
the steps (1), (2) and (4) are carried out according to the method of the example 1 to obtain the SAPO-11 and SAPO-34 composite modified molecular sieve S6 and the catalyst C6, and the specific physicochemical properties and evaluation data are listed in Table 2.
Example 7
A composite modified molecular sieve and a catalytic cracking catalyst were prepared in the same manner as in example 1, except that in the SAPO-11 and SAPO-34 composite molecular sieves in the step (1), SiO was contained in2、Al2O3And P2O5Is 0.25: 1: 1.8;
the steps (1), (2), (3) and (4) are carried out according to the method of the example 1 to obtain the composite modified molecular sieve S7 and the catalyst C7, and the specific physicochemical properties and the evaluation data are listed in Table 2.
Example 8
A composite modified molecular sieve and a catalytic cracking catalyst were prepared in the same manner as in example 1, and steps (1), (2) and (4) were carried out in the same manner as in example 1, except that no modification reaction was carried out in step (3), i.e., 50g of the product obtained in step (2) was calcined at 650 ℃ for 2 hours to obtain SAPO-11 and SAPO-34 composite modified molecular sieve S8 and catalyst C8, and the specific physicochemical properties and evaluation data are shown in Table 2.
Example 9
A composite modified molecular sieve and a catalytic cracking catalyst were prepared in the same manner as in example 1, except that MgO was replaced with CaO of the same mass in terms of oxide. SAPO-11 and SAPO-34 composite modified molecular sieve S9 and catalyst C9 are obtained, and the specific physicochemical properties and evaluation data are listed in Table 2.
Example 10
A composite modified molecular sieve and a catalytic cracking catalyst were prepared in the same manner as in example 1, except that the amount of the NaOH solution used in step (1) was 5g and the amount of MgO was 12 g. SAPO-11 and SAPO-34 composite modified molecular sieve S10 and catalyst C10 are obtained, and the specific physicochemical properties and evaluation data are listed in Table 2.
Example 11
A composite modified molecular sieve and a catalytic cracking catalyst were prepared in the same manner as in example 1, except that MgO was replaced with MgCl of the same mass in terms of oxide2. SAPO-11 and SAPO-34 composite modified molecular sieve S11 and catalyst C11 are obtained, and the specific physicochemical properties and evaluation data are listed in Table 2.
TABLE 1
| Element(s) | Al | Si | P | Na | Mg |
| content/(g.L)-1) | 0.24 | 3.19 | 0.41 | 1.06 | 0.21 |
Test example 1
This test example was used to evaluate the performance of the catalytic cracking catalysts prepared in the above examples.
The prepared catalyst is aged for 12 hours by 100 percent water vapor at 800 ℃ by adopting a fixed fluidized bed device. Cracking the raw material gas, wherein the reaction conditions comprise: the temperature is 300 ℃, the pressure (absolute pressure) is 0.25MPa, and the weight hourly space velocity is 10h-1. The volume content of 1-butene in the feed gas is 10 volume percent, and the balance is nitrogen. The reaction product was analyzed on-line by Agilent-7890 gas chromatography, and the physicochemical properties after the reaction are shown in Table 2.
TABLE 2
TABLE 2
Note: SiO 22:Al2O3:P2O5Represents SiO2、Al2O3And P2O5The molar ratio of (A) to (B);
Vmesoporous structure/VGeneral holeThe proportion of the mesoporous volume to the total pore volume of the SAPO-11 and SAPO-34 composite modified molecular sieve is shown;
V5nm-20nm/Vmesoporous structureRepresents the proportion of the mesoporous volume with the aperture of 5nm to 20nm in the total mesoporous volume;
the amount of strong acid/the total amount of acid indicates the ratio of the amount of strong acid to the total amount of acid.
The data in table 2 show that the alkaline earth metal element-containing SAPO-11 and SAPO-34 composite modified molecular sieve obtained by the method has richer mesopores, higher mesopore content between 5nm and 20nm, lower strong acid center proportion, and is beneficial to generation and diffusion of isomerization reaction intermediates and products under the synergistic action with the alkaline earth metal element, so that coking inactivation is reduced, and the hydrogen transfer reaction of the produced low-carbon olefin is inhibited, and the yield and selectivity of the low-carbon olefin are improved. The reaction result shows that when the catalyst prepared by the method is used for cracking reaction, the catalyst has better cracking performance, stronger isomerization capability, higher n-butene conversion rate and higher selectivity of ethylene, propylene and isobutene.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (26)
1. SAPO-11 and SAPO-34 composite modified molecular sieve, which comprises SAPO-11 and SAPO-34 composite molecular sieve and alkaline earth metal elements; taking the dry basis weight of the SAPO-11 and SAPO-34 composite modified molecular sieve as a reference, and taking the oxide as a reference, the content of the alkaline earth metal element is 10-30 wt%;
SiO in the SAPO-11 and SAPO-34 composite modified molecular sieve2、Al2O3And P2O5In a molar ratio of (0.1-2): 1: (0.1-3);
the mesoporous volume of the SAPO-11 and SAPO-34 composite modified molecular sieve accounts for 10-50% of the total pore volume of the SAPO-11 and SAPO-34 composite modified molecular sieve;
the specific surface area of the SAPO-11 and SAPO-34 composite modified molecular sieve is 300-700m2/g。
2. The SAPO-11 and SAPO-34 composite modified molecular sieve of claim 1, wherein the alkaline earth metal element is present in an amount of 12 to 20 wt.%, preferably 14 to 20 wt.%, calculated as oxide;
preferably, SiO in the SAPO-11 and SAPO-34 composite modified molecular sieve2、Al2O3And P2O5In a molar ratio of (0.1-0.5): 1: (0.5-2);
preferably, the mesoporous volume of the SAPO-11 and SAPO-34 composite modified molecular sieve accounts for 15-45%, preferably 28-40%, of the total pore volume of the SAPO-11 and SAPO-34 composite modified molecular sieve;
preferably, the mesopore volume with the pore diameter of 5nm to 20nm accounts for more than 85 percent of the total mesopore volume, preferably 90 percent and more;
preferably, the specific surface area of the SAPO-11 and SAPO-34 composite modified molecular sieve is 500-620m2G, preferably 520-600m2/g。
3. The SAPO-11 and SAPO-34 composite modified molecular sieve of claim 1 or 2, wherein the SAPO-11 and SAPO-34 composite modified molecular sieve has a strong acid content of 25-45%, preferably 28-40% of the total acid content.
4. The SAPO-11 and SAPO-34 composite modified molecular sieve of any one of claims 1 to 3, wherein the SAPO-11 and SAPO-34 composite modified molecular sieve further comprises an auxiliary element, and the auxiliary element comprises 1 to 15 wt%, preferably 5 to 10 wt%, and more preferably 7 to 10 wt% calculated as an oxide;
the auxiliary agent elements comprise a first auxiliary agent element and/or a second auxiliary agent element;
the first auxiliary element is selected from at least one of IB group, IIB group, IVB group, VIIB group, VIII group and rare earth elements, preferably the first auxiliary element is selected from at least one of Zr, Ti, Ag, La, Ce, Fe, Cu, Zn and Mn element, preferably at least one of Ti, Zr, Zn and Ce element;
the second auxiliary element is selected from at least one of B, P and F elements, preferably, the second auxiliary element is B element and/or P element;
preferably, the content of the first auxiliary element is 1-10 wt%, preferably 5-10 wt%, and more preferably 7-9 wt% calculated by oxide based on the dry weight of the SAPO-11 and SAPO-34 composite modified molecular sieve; the content of the second auxiliary element is 0.1 to 10, preferably 0.1 to 5 wt%, and more preferably 1 to 3 wt%.
5. The SAPO-11 and SAPO-34 composite modified molecular sieve of any one of claims 1 to 4,
the alkaline earth metal element is at least one element selected from Mg, Ca, Sr and Ba elements, and is preferably Mg element.
6. A preparation method of SAPO-11 and SAPO-34 composite modified molecular sieve comprises the following steps:
(1) contacting the SAPO-11 and SAPO-34 composite molecular sieves with compounds of alkali and alkaline earth metals in the presence of a first solvent;
(2) carrying out acid treatment on the solid product obtained in the step (1) by adopting an acid solution;
(3) roasting the product after acid treatment;
the dosage of the SAPO-11 and SAPO-34 composite molecular sieve and the alkaline earth metal compound is such that the content of the alkaline earth metal element in the prepared SAPO-11 and SAPO-34 composite modified molecular sieve is 10-30 wt% calculated by oxide based on the dry weight of the SAPO-11 and SAPO-34 composite modified molecular sieve;
SiO in the SAPO-11 and SAPO-34 composite modified molecular sieve2、Al2O3And P2O5In a molar ratio of (0.1-2): 1: (0.1-3).
7. The method as claimed in claim 6, wherein the SAPO-11 and SAPO-34 composite molecular sieves and the alkaline earth metal compound are used in an amount such that the obtained SAPO-11 and SAPO-34 composite modified molecular sieve contains the alkaline earth metal element in an amount of 12 to 20 wt%, more preferably 14 to 20 wt%, calculated as oxide, based on the dry weight of the SAPO-11 and SAPO-34 composite modified molecular sieve;
preferably, SiO in the SAPO-11 and SAPO-34 composite modified molecular sieve2、Al2O3And P2O5In a molar ratio of (0.1-0.5): 1: (0.5-2).
8. The method of claim 6, wherein the base is selected from at least one of sodium hydroxide, potassium carbonate, and sodium carbonate;
preferably, the base is introduced in the form of an alkaline solution having a molar concentration of 0.1 to 2mol/L, preferably 0.3 to 0.9 mol/L;
preferably, the alkali solution is used in an amount of 1-100 parts by weight, preferably 5-20 parts by weight, relative to 100 parts by weight of the SAPO-11 and SAPO-34 composite molecular sieve;
preferably, the alkaline earth metal is selected from at least one of Mg, Ca, Sr and Ba elements, more preferably Mg element;
preferably, the compound of the alkaline earth metal is selected from at least one of an oxide, a chloride, a nitrate and a sulfate of the alkaline earth metal, more preferably at least one of magnesium oxide, magnesium chloride, magnesium sulfate and magnesium nitrate;
preferably, the first solvent is used in an amount of 100-1000 parts by weight relative to 100 parts by weight of the SAPO-11 and SAPO-34 composite molecular sieve.
9. The method of any one of claims 6-8, wherein the contacting conditions of step (1) comprise: the temperature is 50-90 ℃ and the time is 1-5 h; preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
10. The method according to any one of claims 6 to 9, wherein the acid of step (2) is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, oxalic acid, citric acid and acetic acid, preferably sulfuric acid and/or oxalic acid, and further preferably sulfuric acid and oxalic acid;
preferably, the weight ratio of the sulfuric acid to the oxalic acid is 1: 1-4;
preferably, the acid solution has a weight content of 5-98 wt.%, preferably 10-30 wt.%;
preferably, the weight ratio of the acid to the solid product obtained in step (1) on a dry basis is from 0.2 to 2;
preferably, the reaction conditions of the acid treatment of step (2) include: the temperature is 50-90 ℃ and the time is 1-5 h; preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
11. The method according to any one of claims 6 to 10, wherein the method further comprises modifying the product obtained by the acid treatment in step (2) after step (2) and before step (3), wherein the modification comprises: carrying out modification reaction on the product obtained by acid treatment in the step (2) and a soluble compound of an auxiliary agent in the presence of a second solvent;
preferably, the soluble compound of the auxiliary agent is used in an amount such that in the prepared SAPO-11 and SAPO-34 composite modified molecular sieve, the content of the auxiliary agent element is 1 to 15 wt%, preferably 5 to 10 wt%, and more preferably 7 to 10 wt%, calculated by oxide, based on the dry weight of the SAPO-11 and SAPO-34 composite modified molecular sieve;
the auxiliary agent elements comprise a first auxiliary agent element and/or a second auxiliary agent element;
the first auxiliary element is selected from at least one of IB group, IIB group, IVB group, VIIB group, VIII group and rare earth elements, preferably the first auxiliary element is selected from at least one of Zr, Ti, Ag, La, Ce, Fe, Cu, Zn and Mn element, preferably at least one of Ti, Zr, Zn and Ce element;
the second auxiliary element is selected from at least one of B, P and F elements, preferably, the second auxiliary element is B element and/or P element;
preferably, the soluble compound of the auxiliary agent is used in an amount such that the content of the first auxiliary agent element in the prepared SAPO-11 and SAPO-34 composite modified molecular sieve is 1-10 wt%, preferably 5-10 wt%, and more preferably 7-9 wt% calculated by oxide; the content of the second auxiliary element is 0.1-10, preferably 0.1-5 wt%, and more preferably 1-3 wt%;
preferably, the conditions of the modification reaction include: the temperature is 50-90 ℃ and the time is 1-5 h; preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
12. The method of any one of claims 6-11, wherein the firing conditions of step (3) comprise: the temperature is 500-800 ℃, preferably 550-650 ℃; the time is 1-10h, preferably 2-3 h.
13. A catalytic cracking catalyst, the catalyst comprising: SAPO-11 and SAPO-34 composite modified molecular sieve, binder and optional clay; based on the dry weight of the catalyst, the content of the SAPO-11 and SAPO-34 composite modified molecular sieve is 20-60 wt% in terms of dry basis, the content of clay is 0-50 wt% in terms of dry basis, and the content of the binder is 10-40 wt% in terms of oxide;
the SAPO-11 and SAPO-34 composite modified molecular sieve is the SAPO-11 and SAPO-34 composite modified molecular sieve of any one of claims 1 to 5 or the SAPO-11 and SAPO-34 composite modified molecular sieve prepared by the method of any one of claims 6 to 12.
14. The catalyst of claim 13, wherein the SAPO-11 and SAPO-34 composite modified molecular sieves are present in an amount of 25 to 50 wt.% on a dry basis, the clay is present in an amount of 12 to 45 wt.% on a dry basis, and the binder is present in an amount of 12 to 38 wt.% on an oxide basis, based on the weight of the catalyst on a dry basis;
preferably, the content of the SAPO-11 and SAPO-34 composite modified molecular sieve is 25-40 wt% on a dry basis, the content of the clay is 25-40 wt% on a dry basis, and the content of the binder is 20-35 wt% on an oxide basis, based on the dry weight of the catalyst;
preferably, the clay is selected from at least one of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite, preferably kaolin and/or halloysite;
preferably, the binder is a refractory inorganic oxide, preferably one or more of alumina, silica, titania, magnesia, zirconia, thoria and beryllia, and/or a refractory inorganic oxide precursor, preferably at least one of acidified pseudo-boehmite, alumina sol, silica sol, phosphoalumina sol, silica-alumina sol, magnesium-alumina sol, zirconium sol and titanium sol, preferably acidified pseudo-boehmite and alumina sol.
15. A method of preparing a catalytic cracking catalyst, the method comprising:
(1) in the presence of a first solvent, contacting the SAPO-11 and SAPO-34 composite molecular sieves with compounds of alkali and alkaline earth metals, and then sequentially filtering and drying to obtain a solid product;
(2) carrying out acid treatment on the solid product obtained in the step (1) by adopting an acid solution;
(3) roasting the product after acid treatment to obtain the SAPO-11 and SAPO-34 composite modified molecular sieve;
(4) pulping the SAPO-11 and SAPO-34 composite modified molecular sieve, the binder and optional clay to obtain slurry, and performing spray drying and optional roasting on the slurry;
the dosage of the SAPO-11 and SAPO-34 composite modified molecular sieve, the adhesive and the optional clay is that in the prepared catalyst, on the basis of the dry weight of the catalyst, the content of the SAPO-11 and SAPO-34 composite modified molecular sieve is 20-60 wt% on a dry basis, the content of the clay is 0-50 wt% on a dry basis, and the content of the adhesive is 10-40 wt% on an oxide basis;
the dosage of the SAPO-11 and SAPO-34 composite molecular sieve and the alkaline earth metal compound is such that the content of the alkaline earth metal element in the prepared SAPO-11 and SAPO-34 composite modified molecular sieve is 10-30 wt% calculated by oxide based on the dry weight of the SAPO-11 and SAPO-34 composite modified molecular sieve;
SiO in the SAPO-11 and SAPO-34 composite modified molecular sieve2、Al2O3And P2O5In a molar ratio of (0.1-2): 1: (0.1-3).
16. The method as claimed in claim 15, wherein the SAPO-11 and SAPO-34 composite molecular sieves and the alkaline earth metal compound are used in an amount such that the resulting SAPO-11 and SAPO-34 composite modified molecular sieves have an alkaline earth metal element content of 12 to 20 wt.%, preferably 14 to 20 wt.%, calculated as oxide, based on the dry weight of the SAPO-11 and SAPO-34 composite modified molecular sieves;
preferably, SiO in the SAPO-11 and SAPO-34 composite modified molecular sieve2、Al2O3And P2O5In a molar ratio of (0.1-0.5): 1: (0.5-2).
17. The method of claim 16, wherein the base is selected from at least one of sodium hydroxide, potassium carbonate, and sodium carbonate;
preferably, the base is introduced in the form of an alkaline solution having a molar concentration of 0.1 to 2mol/L, preferably 0.3 to 0.9 mol/L;
preferably, the alkali solution is used in an amount of 1-100 parts by weight, preferably 5-20 parts by weight, relative to 100 parts by weight of the SAPO-11 and SAPO-34 composite molecular sieve;
preferably, the alkaline earth metal is selected from at least one of Mg, Ca, Sr and Ba elements, more preferably Mg element;
preferably, the compound of the alkaline earth metal is selected from at least one of an oxide, a chloride, a nitrate and a sulfate of the alkaline earth metal, more preferably at least one of magnesium oxide, magnesium chloride, magnesium sulfate and magnesium nitrate;
preferably, the first solvent is used in an amount of 100-1000 parts by weight relative to 100 parts by weight of the SAPO-11 and SAPO-34 composite molecular sieve.
18. The method of any one of claims 15-17, wherein the contacting conditions of step (1) comprise: the temperature is 50-90 ℃ and the time is 1-5 h; preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
19. The method according to any one of claims 15 to 18, wherein the acid of step (2) is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, oxalic acid, citric acid and acetic acid, preferably sulfuric acid and/or oxalic acid, further preferably sulfuric acid and oxalic acid;
preferably, the weight ratio of the sulfuric acid to the oxalic acid is 1: 1-4;
preferably, the acid solution has a weight content of 5-98 wt.%, preferably 10-30 wt.%;
preferably, the weight ratio of the acid to the solid product obtained in step (1) on a dry basis is from 0.5 to 2;
preferably, the reaction conditions of the acid treatment of step (2) include: the temperature is 50-90 ℃ and the time is 1-5 h; preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
20. The method according to any one of claims 15 to 19, wherein the method further comprises modifying the product obtained by the acid treatment of step (2) after step (2) and before step (3), wherein the modification comprises: carrying out modification reaction on the product obtained by acid treatment in the step (2) and a soluble compound of an auxiliary agent in the presence of a second solvent;
preferably, the soluble compound of the auxiliary agent is used in an amount such that in the prepared SAPO-11 and SAPO-34 composite modified molecular sieve, the content of the auxiliary agent element is 1 to 15 wt%, preferably 5 to 10 wt%, and more preferably 7 to 10 wt%, calculated by oxide, based on the dry weight of the SAPO-11 and SAPO-34 composite modified molecular sieve;
the auxiliary agent elements comprise a first auxiliary agent element and/or a second auxiliary agent element;
the first auxiliary element is selected from at least one of IB group, IIB group, IVB group, VIIB group, VIII group and rare earth elements, preferably the first auxiliary element is selected from at least one of Zr, Ti, Ag, La, Ce, Fe, Cu, Zn and Mn element, preferably at least one of Ti, Zr, Zn and Ce element;
the second auxiliary element is selected from at least one of B, P and F elements, preferably, the second auxiliary element is B element and/or P element;
preferably, the soluble compound of the auxiliary agent is used in an amount such that the content of the first auxiliary agent element in the prepared SAPO-11 and SAPO-34 composite modified molecular sieve is 1-10 wt%, preferably 5-10 wt%, and more preferably 7-9 wt% calculated by oxide; the content of the second auxiliary element is 0.1-10, preferably 0.1-5 wt%, and more preferably 1-3 wt%;
preferably, the conditions of the modification reaction include: the temperature is 50-90 ℃ and the time is 1-5 h; preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
21. The method of any one of claims 15-20, wherein the firing conditions of step (3) comprise: the temperature is 500-800 ℃, preferably 550-650 ℃; the time is 1-10h, preferably 2-3 h.
22. The method of any of claims 15-21, wherein the SAPO-11 and SAPO-34 composite modified molecular sieves, the binder, and optionally the clay are used in amounts such that the resulting catalyst comprises, on a dry basis, 25 to 50 wt.% of the SAPO-11 and SAPO-34 composite modified molecular sieves, 12 to 45 wt.% of the clay, and 12 to 38 wt.% of the binder, on an oxide basis, based on the weight of the catalyst on a dry basis;
preferably, the content of the SAPO-11 and SAPO-34 composite modified molecular sieve is 25-40 wt% on a dry basis, the content of clay is 25-40 wt% on a dry basis, and the content of the binder is 20-35 wt% on an oxide basis, based on the dry weight of the catalyst.
23. The method according to any one of claims 15-22, wherein the clay is selected from at least one of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite, preferably kaolin and/or halloysite;
preferably, the binder is a refractory inorganic oxide, preferably one or more of alumina, silica, titania, magnesia, zirconia, thoria and beryllia, and/or a refractory inorganic oxide precursor, which is at least one of acidified pseudo-boehmite, alumina sol, silica sol, phosphor-alumina sol, silica-alumina sol, magnesium-alumina sol, zirconium sol and titanium sol, preferably acidified pseudo-boehmite and alumina sol.
24. The method of any one of claims 15 to 23, wherein step (4) comprises slurrying the filtrate filtered in step (1), the SAPO-11 and SAPO-34 composite modified molecular sieves, the binder, and optionally the clay;
preferably, the filtrate obtained by filtration in step (1) has a total content of silicon in terms of oxides, aluminium in terms of oxides and phosphorus in terms of oxides of from 1 to 20% by weight, preferably from 5 to 10% by weight;
preferably, the filtrate obtained by filtering in the step (1) is used in an amount such that SiO introduced into the obtained catalyst from the filtrate obtained by filtering in the step (1) is introduced into the obtained catalyst based on the dry weight of the catalyst2、Al2O3And P2O5The total content of (A) is 5-10 wt%;
preferably, the slurry of step (4) has a solids content of 15 to 45 wt%, preferably 30 to 40 wt%.
25. A catalyst prepared by the process of any one of claims 15 to 24.
26. Use of a catalyst as claimed in any one of claims 13 to 14 and 25 in catalytic cracking.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6451316A (en) * | 1987-08-17 | 1989-02-27 | Agency Ind Science Techn | Aluminophosphosilicate containing alkali earth metal, its production and production of lower olefin by using same as catalyst |
| US6004898A (en) * | 1996-04-04 | 1999-12-21 | Exxon Chemicals Patent Inc. | Alkaline earth metal containing small pore non-zeolitic molecular sieve catalysts |
| CN1340488A (en) * | 2000-08-29 | 2002-03-20 | 中国石油化工集团公司 | Alkali-earth metal modified selective disproportionation catalyst of toluene |
| CN1504541A (en) * | 2002-12-03 | 2004-06-16 | 中国科学院大连化学物理研究所 | Hydrocarbon Catalytic Cracking to Produce Olefins and Co-produce Aromatics Catalyst, Preparation Method and Application |
| CN1749362A (en) * | 2004-09-15 | 2006-03-22 | 中国石油化工股份有限公司 | A kind of catalytic cracking auxiliary agent and preparation method thereof |
| CN101683621A (en) * | 2008-09-28 | 2010-03-31 | 中国石油化工股份有限公司 | Catalyst for producing low-carbon olefins through catalytic cracking by fixed bed |
| CN108264059A (en) * | 2017-01-04 | 2018-07-10 | 中国石油化工股份有限公司 | The method of modifying of silicoaluminophosphamolecular molecular sieves, modified molecular screen and application thereof |
-
2020
- 2020-04-24 CN CN202010333471.XA patent/CN113548677B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6451316A (en) * | 1987-08-17 | 1989-02-27 | Agency Ind Science Techn | Aluminophosphosilicate containing alkali earth metal, its production and production of lower olefin by using same as catalyst |
| US6004898A (en) * | 1996-04-04 | 1999-12-21 | Exxon Chemicals Patent Inc. | Alkaline earth metal containing small pore non-zeolitic molecular sieve catalysts |
| CN1340488A (en) * | 2000-08-29 | 2002-03-20 | 中国石油化工集团公司 | Alkali-earth metal modified selective disproportionation catalyst of toluene |
| CN1504541A (en) * | 2002-12-03 | 2004-06-16 | 中国科学院大连化学物理研究所 | Hydrocarbon Catalytic Cracking to Produce Olefins and Co-produce Aromatics Catalyst, Preparation Method and Application |
| CN1749362A (en) * | 2004-09-15 | 2006-03-22 | 中国石油化工股份有限公司 | A kind of catalytic cracking auxiliary agent and preparation method thereof |
| CN101683621A (en) * | 2008-09-28 | 2010-03-31 | 中国石油化工股份有限公司 | Catalyst for producing low-carbon olefins through catalytic cracking by fixed bed |
| CN108264059A (en) * | 2017-01-04 | 2018-07-10 | 中国石油化工股份有限公司 | The method of modifying of silicoaluminophosphamolecular molecular sieves, modified molecular screen and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李红彬等: "碱土金属改性SAPO-34催化甲醇制烯烃", 《催化学报》 * |
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