WO2013086766A1 - 一种高轻收重油催化裂化催化剂及其制备方法 - Google Patents
一种高轻收重油催化裂化催化剂及其制备方法 Download PDFInfo
- Publication number
- WO2013086766A1 WO2013086766A1 PCT/CN2012/000507 CN2012000507W WO2013086766A1 WO 2013086766 A1 WO2013086766 A1 WO 2013086766A1 CN 2012000507 W CN2012000507 W CN 2012000507W WO 2013086766 A1 WO2013086766 A1 WO 2013086766A1
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- WO
- WIPO (PCT)
- Prior art keywords
- exchange
- rare earth
- molecular sieve
- magnesium
- weight
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000295 fuel oil Substances 0.000 title claims abstract description 21
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 190
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 165
- 239000002808 molecular sieve Substances 0.000 claims abstract description 147
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 131
- 239000011734 sodium Substances 0.000 claims abstract description 36
- 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 claims abstract description 33
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 33
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- 239000011777 magnesium Substances 0.000 claims abstract description 29
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 25
- 159000000003 magnesium salts Chemical group 0.000 claims abstract description 22
- 238000012986 modification Methods 0.000 claims abstract description 22
- 230000004048 modification Effects 0.000 claims abstract description 22
- 239000003921 oil Substances 0.000 claims abstract description 20
- 150000003863 ammonium salts Chemical group 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 8
- 239000004927 clay Substances 0.000 claims abstract description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 102
- -1 rare earth compound Chemical class 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 58
- 239000010457 zeolite Substances 0.000 claims description 53
- 229910021536 Zeolite Inorganic materials 0.000 claims description 52
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 51
- 239000002002 slurry Substances 0.000 claims description 41
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 239000012065 filter cake Substances 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 18
- 229910002651 NO3 Inorganic materials 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 17
- 229910052684 Cerium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000007921 spray Substances 0.000 claims description 14
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 12
- 239000005995 Aluminium silicate Substances 0.000 claims description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims description 11
- 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 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 229960004889 salicylic acid Drugs 0.000 claims description 6
- 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 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 229910052621 halloysite Inorganic materials 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 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
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 239000010451 perlite Substances 0.000 claims description 3
- 235000019362 perlite Nutrition 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 229910052715 tantalum Inorganic materials 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 70
- 239000008367 deionised water Substances 0.000 description 33
- 229910021641 deionized water Inorganic materials 0.000 description 33
- 238000010438 heat treatment Methods 0.000 description 23
- 239000004005 microsphere Substances 0.000 description 19
- 238000005336 cracking Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 229940091250 magnesium supplement Drugs 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 9
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 7
- 235000011130 ammonium sulphate Nutrition 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910052665 sodalite Inorganic materials 0.000 description 6
- KWVFUTDPKIKVQW-UHFFFAOYSA-N [Sr].[Na] Chemical compound [Sr].[Na] KWVFUTDPKIKVQW-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229960002337 magnesium chloride Drugs 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012013 faujasite Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- YZQOWXDLAGPZOW-UHFFFAOYSA-N cerium sodium Chemical compound [Na].[Ce] YZQOWXDLAGPZOW-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NZFWOBIOVKFUTL-UHFFFAOYSA-N lanthanum sodium Chemical compound [Na][La] NZFWOBIOVKFUTL-UHFFFAOYSA-N 0.000 description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005048 flame photometry Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 159000000008 strontium salts Chemical group 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- 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
-
- 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
-
- 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
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
-
- 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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J2029/062—Mixtures of different aluminosilicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
Definitions
- the invention relates to a high light weight oil catalytic cracking catalyst capable of high heavy oil conversion capacity and a preparation method thereof, and more particularly to a high-light recovery catalytic cracking catalyst suitable for blending residual oil and a preparation method thereof.
- Catalytic cracking unit is an important secondary processing method for crude oil. Its comprehensive product distribution, especially the high value-added light oil yield determines the economic benefits of the refinery. In recent years, the FCC catalyst is required as the heavy oil product tends to become heavier. It has stronger heavy oil conversion capacity and higher light oil yield. As a key active component in determining the selectivity of heavy oil cracking catalysts, high-product selectivity and high activity stability of Y-type molecular sieves have been the core technical issues in the field of catalysis.
- Patent CN1683474A describes a preparation method for improving the target product diesel yield cocatalyst, which is characterized by in-situ crystallization of 900 or more calcined kaolin into Y-type zeolite promoter, followed by exchange of magnesium, rare earth and/or ammonium salts. The catalyst is thus obtained to obtain a high diesel yield, and the method does not describe the stability.
- Patent CN1217231A describes a preparation method for improving the target product diesel oil yield phosphorus-containing faujasite catalyst, which is characterized by containing or not containing rare earth, and Na 2 0 is less than 5 weight%.
- the faujasite is uniformly mixed with the aqueous solution of the phosphorus-containing compound, allowed to stand for 0-8 hours, dried, and calcined to obtain a phosphorus-containing faujasite, and then a semi-synthesis process is used to prepare a catalyst for obtaining a high diesel yield, and the method is also Stability is explained.
- the more consistent viewpoint is to make the rare earth ions locate the sodalite cage as much as possible in the rare earth modification process of the molecular sieve, thereby inhibiting the dealuminization of the molecular sieve skeleton during the water vapor aging process, and improving the structural stability and activity stability of the molecular sieve framework.
- Patent ZL200410058089.3 introduces a preparation method of rare earth modified Y type molecular sieve, which is to adjust the pH value of the system to 8 ⁇ 11 by using lye after the end of the rare earth exchange reaction, and then carry out a conventional subsequent treatment process according to the method.
- the prepared molecular sieve rare earth ions are all located in Xiaocang (sodium soda cage); the reaction performance of the molecular sieve in patent ZL200410058089.3 is introduced in ZL200410058090.6.
- the catalyst reaction results in this patent indicate that the rare earth ions are located in the sodalite cage. Improve the structural stability and activity stability of the molecular sieve, which is manifested in the conversion of heavy oil from the catalyst The ability is significantly improved, but the catalyst selectivity of the catalyst is poor.
- the Y-type molecular sieve modification method is described in the U.S. Patent No. 5,340,957 and U.S. Patent No. 4,584,287, which is based on the use of NaY molecular sieves as raw materials, exchange modification with rare earth and/or VDI elements, and then hydrothermal treatment to obtain high
- the stability of the ultra-stable rare earth Y-type molecular sieve, 3 ⁇ 4 method does not explain the rare earth ion localization and grain dispersion.
- Chinese patent ZL97122039.5 describes a preparation method of ultra-stable Y zeolite, which comprises contacting a Y-type zeolite with an acid solution and a solution containing ammonium ions, and performing high-temperature steam treatment.
- the acid is used in an amount of 1.5 to 6 moles of hydrogen ion per mole of the framework aluminum, the acid solution concentration is 0.1 to 5 equivalents per liter, and the temperature at which the Y-type zeolite is contacted with the acid solution is 5 to 100 ° C, and the contact time is 0.5 to 72 hours.
- the weight ratio of the Y-type zeolite to the ammonium ion is 2 to 20.
- the modification method involved in the patent requires the addition of an ammonium ion-containing solution for the purpose of reducing the sodium oxide content in the molecular sieve or reducing the damage of the molecular gas structure by the acid gas during the calcination process, but the technique has the following technical defects: 1) Preparation The process adds a large amount of hinge ions, and the ammonium ions finally enter the atmosphere or sewage, increasing the ammonia nitrogen pollution and pollution control costs; 2) The patented method can not effectively solve the problem of molecular sieve particle agglomeration, and the particle agglomeration reduces the specific surface and pore volume of the molecular sieve.
- the patent also mentions that the Y-type zeolite can be used simultaneously with or after the contact with the ammonium ion-containing solution.
- the ion exchange method introduces rare earth ions. During the exchange process, the ammonium ions compete with the rare earth ions. The ammonium ions preferentially occupy the rare earth ion sites, increase the resistance of the rare earth ions to enter the molecular sieve cage, and reduce the rare earth ions. Utilization rate.
- Chinese patent ZL02103909.7 describes a preparation method of rare earth-containing ultra-stable Y molecular sieve, which is prepared by subjecting NaY molecular sieve to one-time roasting once, and is characterized in that NaY molecular sieve is placed in ammonium ion solution at 25 ⁇ Chemical dealuminization treatment at 100 ° C, oxalic acid and / or oxalate in the chemical dealumination complexing agent, treatment time 0.5 ⁇ 5 hours, then adding rare earth solution, stirring, to produce rare earth precipitate containing rare earth oxalate, by It is filtered, washed with water to form a filter cake, and then hydrothermally treated to obtain a molecular sieve product.
- the molecular sieve prepared by the method has certain anti-vanadium pollution ability, its activity stability and cracking activity are low, and the development trend of heavy oil quality and inferior quality of the raw material oil cannot be satisfied.
- This is mainly related to the positional distribution of rare earth ions in the molecular sieve super cage and sodalite cage during molecular sieve modification.
- the method clarifies that the rare earth ions exist in the molecular sieve system in two forms, that is, some rare earth ions enter the sodalite cage in the form of ions, and the other rare earth ions are rare earth oxides (the precursor is rare earth oxalate, which is converted into oxidation by subsequent calcination).
- the rare earth is dispersed on the surface of the molecular sieve, which reduces the stable supporting effect of the rare earth ions on the molecular sieve structure. At the same time, there is a large amount of ammonia nitrogen pollution in the method, and the added oxalic acid and or oxalate are more harmful to the environment and human body. .
- Chinese Patent No. 200510114495.1 describes a method for increasing the rare earth content of ultra-stable Y-type zeolite by using an ultra-stable Y-type zeolite and an acid solution having a concentration of 0.01 to 2 N at a liquid-solid ratio of 4 to 20 at a ratio of 20 to 100. °C temperature
- the mixture is thoroughly mixed under the range of 10 to 300 minutes, washed, filtered, and then rare earth ion exchange is carried out by adding a rare earth salt solution, followed by washing, filtering, and drying to obtain a rare earth super-stable Y-type zeolite.
- the invention uses a Y-type molecular sieve which has been supercooled by water vapor as a raw material, and undergoes secondary exchange and secondary calcination chemical modification, and does not involve the study of molecular sieve particle dispersibility.
- Chinese patent CN200410029875.0 introduces a preparation method of rare earth ultra-stable Y-type zeolite, which is characterized in that firstly, NaY molecular sieve is ion-exchanged with an inorganic cerium salt solution, and then subjected to water vapor ultra-stable treatment to obtain "one-to-one baking".
- the present invention adopts a rare earth ion precise positioning technology to prepare a ruthenium molecular sieve with high activity stability and structural stability, and is modified by magnesium element to regulate it. It has a suitable acidity to control the proportion of different reactions in the cracking process and increase the yield of light oil.
- the object of the present invention is to provide a high-light heavy oil high-efficiency conversion catalytic cracking catalyst and a preparation method thereof, the catalyst is characterized by strong heavy oil conversion ability, high light oil yield and moderate coke selectivity.
- the invention provides a high-light weight oil high-efficiency conversion catalytic cracking catalyst, which is characterized in that the catalyst composition contains 2 ⁇ 50% by weight of magnesium modified ultra-stable rare earth cerium type molecular sieve, 0.5 ⁇ 30% by weight of one or several other Molecular sieve, 0.5 to 70% by weight of clay, 1.0 to 65% by weight of high temperature resistant inorganic oxide and 0.01 to 12.5% by weight of oxidized rare earth, wherein the magnesium modified ultra-stable rare earth cerium type molecular sieve refers to magnesium modified ultra-stable rare earth cerium
- the molecular sieve contains 0.2 ⁇ 5 wt% of magnesium oxide, 1 ⁇ 20 wt% of rare earth oxide, sodium oxide not more than 1.2 wt%, crystallinity 46 ⁇ 63%, unit cell parameter 2.454 nm ⁇ 2.471 nm; magnesium modified super
- the preparation process of stable rare earth Y-type molecular sieve comprises dispersion pre-exchange, rare earth exchange and magnesium salt exchange modification, where
- the powder is subjected to dispersion pre-exchange, the exchange temperature is 0-100 Torr, and the exchange time is 0.1-1.5 hours; the dispersion pre-exchange process is selected from the group consisting of phthalocyanine powder, boric acid, urea, ethanol, polyacrylamide, acetic acid, oxalic acid, One or more of diacid, formic acid, hydrochloric acid, nitric acid, citric acid, salicylic acid, tartaric acid, benzoic acid, starch; no rare earth salt used in rare earth exchange and dispersion pre-exchange.
- the invention also provides a preparation method of a heavy oil catalytic cracking catalyst:
- (1) Preparation of magnesium-modified ultra-stable rare earth Y-type molecular sieve The NaY molecular sieve (preferably having a silicon-aluminum ratio greater than 4.0 and a knot degree greater than 70%) is used as a raw material. After rare earth exchange and dispersion pre-exchange, the molecular sieve slurry is filtered. , washing with water and roasting for the first time, obtaining "one-and-one-baked" rare earth sodium Y molecular sieve, wherein the order of rare earth exchange and dispersion pre-exchange is not limited; then the "one-and-one-baked" rare earth sodium Y molecular sieve is exchanged by ammonium salt.
- the magnesium salt exchange modification can be carried out either in the second calcination f3 ⁇ 4- or after the second calcination, or simultaneously before and after the second calcination;
- the molecular sieve slurry can be washed without washing. , filtration, washing and filtration.
- the RE 2 03/Y zeolite (mass) is preferably 0.005 to 0.25, preferably 0.01 to 0.20; the exchange temperature is 0 to 100 ° C, preferably 60 to 95 ° C; 2.5 ⁇ 6.0, preferably 3.5 ⁇ 5.5, the exchange time is 0.1 ⁇ 2 hours, preferably 0.3 ⁇ 1.5 hours; When dispersing pre-exchange, the dispersant is added in an amount of 0.2% by weight to 7% by weight, preferably 0.2% by weight. % ⁇ 5 ⁇ %; exchange temperature is 0 ⁇ 10 (TC, optimally 60 ⁇ 95 °C; exchange time is 0.1 ⁇ 1.5 hours.
- the modified molecular sieve slurry is filtered, washed with water to obtain filter cake, and the obtained filter cake Flash drying to make the moisture content of 30% ⁇ 50%, and finally roasting, the calcination conditions can be used under common conditions, such as 35 (TC ⁇ 700 ° C, 0 ⁇ 100% water vapor roasting 0.3 ⁇ 3.5 hours, preferably at 450T : ⁇ 650 ° C, 15 ⁇ 100% water vapour roasting 0.5 ⁇ 2.5 hours, that is, "one Jiaoyi baking"'ultra-stable rare earth sodium Y molecular sieve.
- the second exchange and the second calcination in the present invention are the ammonium salt exchange sodium reduction and ultra-stable processes which are familiar in the industry, and the present invention is not limited thereto.
- the "one-and-one-baked" rare earth sodium Y molecular sieve may be firstly modified by ammonium salt exchange and sodium reduction, followed by or without filtering water washing, followed by magnesium salt exchange modification, second baking, or "one After the exchange of the rare earth sodium Y molecular sieve by the ammonium salt exchange sodium reduction and the second calcination, the "two cross two baking" ultra-stable rare earth Y type molecular sieve is used as the raw material and then the magnesium salt exchange modification is carried out, followed by or not.
- Mg-REUSY molecular sieve also known as magnesium modified ultra-stable rare earth Y-type molecular sieve.
- the magnesium salt exchange modification process may be a magnesium salt exchange modification method familiar in the industry, such as Yes: Add "--one baking" ultra-stable rare earth sodium cerium molecular sieve to deionized water, the solid content is adjusted to 100 ⁇ 400g/L, NH /Y zeolite (mass) is 0.02 ⁇ 0.40, preferably 0.02 ⁇ 0.30; Mg The 2+ /Y zeolite (mass) is 0.002 to 0.08, preferably 0.002 to 0.04; the pH is 2.5 to 5.0, preferably 3.0 to 4.5, and the reaction is carried out at 60 to 95 ° C for 0.3 to 1.5 hours.
- Yes Add "--one baking" ultra-stable rare earth sodium cerium molecular sieve to deionized water, the solid content is adjusted to 100 ⁇ 400g/L, NH /Y zeolite (mass) is 0.02 ⁇ 0.40, preferably 0.02 ⁇ 0.30; Mg The 2+ /Y zeolite (mass) is 0.002
- the molecular sieve slurry is filtered and washed with water, and the obtained filter cake is calcined at 450 ° C to 700 ° C, 0 to 100% water vapor for 0.3 to 3.5 hours, preferably 0.5 to 2.5 hours, to finally obtain the magnesium modified super provided by the present invention.
- Stable rare earth Y molecular sieve is
- the strontium salt exchange modification process may also be: adding "one-to-one baking" ultra-stable rare earth sodium cerium molecular sieve to deionized water, the solid content is adjusted to 100 ⁇ 400g/L, and the Mg 2+ /Y zeolite (mass) is 0.002 ⁇ 0.08, preferably 0.002 to 0.04; pH value of 2.5 to 5.0, preferably 3.0 to 4.5, after reacting at 60 ° C to 95 ° C for 0.3 to 1.5 hours, filtering or washing the molecular sieve slurry, or not Filtered and washed with water; then modified by ammonium salt to reduce sodium, the solid content is adjusted to 100 ⁇ 400g/L, NH 4 + /Y zeolite (mass) is 0.02 ⁇ 0.40, preferably 0.02-0.30; pH is 2.5 ⁇ 5.0 Preferably, it is 3.0 to 4.5, and after reacting at 60 ° C to 95 ° C for 0.3 to 1.5 hours, the molecular sieve slurry is filtered
- the magnesium salt exchange modification process may also be: adding "one-to-one baking" ultra-stable rare earth sodium Y molecular sieve to deionized water, the solid content is adjusted to 100 ⁇ 400g/L, and the NH 4 +/Y zeolite (mass) is 0.02 ⁇ 0.40, preferably 0.02 ⁇ 0.30; pH 2.5 ⁇ 5.0, preferably 3.0 ⁇ 4.5, after reacting at 60 ° C ⁇ 95 ° C for 0.3 ⁇ 1.5 hours, filtering the molecular sieve slurry, washing with water, or not Filtered with water; then modified by magnesium, Mg 2+ Y zeolite (mass) is 0.002 ⁇ 0.08, preferably 0.002 ⁇ 0.04; pH is 2.5 ⁇ 5.0, preferably 3.0 ⁇ 4.5, at 60 °C ⁇ 95 After reacting at ° C for 0.3 to 1.5 hours, the molecular sieve slurry is filtered and washed with water, and the obtained filter cake is calcined at 450 ° C to 70 (TC, 0 to 100% water
- the magnesium salt exchange modification process may also be: adding "one-to-one baking" ultra-stable rare earth sodium Y molecular sieve to deionized water, the solid content is adjusted to 100 ⁇ 400g/L, and the NH/Y zeolite (mass) is 0.02 ⁇ 0.40. Preferably, it is 0.02 to 0.30; the pH is 2.5 to 5.0, preferably 3.0 to 4.5, and after reacting at 60 to 95 ° C for 0.3 to 1.5 hours, the molecular sieve slurry is filtered and washed with water, and the obtained filter cake is 450.
- the rare earth Y molecular sieve is added with deionized water, the solid content is adjusted to 100 ⁇ 400g/L, the Mg 2+ Y zeolite (mass) is 0.002 ⁇ 0.08, preferably 0.002 ⁇ 0.04; the pH is 2.5 ⁇ 5.0, preferably 3.0 ⁇ 4.5, after reacting at 60 ° C to 95 ° C for 0.3 to 1.5 hours, the molecular sieve slurry is filtered, washed with water, or washed without filtering, thereby obtaining the magnesium-modified ultra-stable rare earth cerium type molecular sieve provided by the present invention.
- rare earth exchange and dispersion pre-exchange The exchange process can be carried out by tank exchange, belt exchange and/or filter cake exchange; in the case of rare earth exchange, it can be carried out in the following manner, that is, the rare earth compound solution can be divided into several parts under the constant total amount of rare earth , tank exchange, belt exchange and / or filter cake exchange, that is, multiple exchanges.
- the dispersant in the process of dispersing the pre-exchange process, can be divided into several parts under the premise of the total amount of dispersant, for tank exchange, belt exchange and/or filter cake exchange; rare earth exchange and dispersion pre-pretreatment When switching to multiple exchanges, the two types of exchanges can be crossed.
- the rare earth compound of the present invention is a rare earth chloride or a rare earth nitrate or a rare earth sulfate, preferably a rare earth chloride or a rare earth nitrate.
- the rare earth of the present invention may be a cerium-rich or cerium-rich rare earth, or may be a pure cerium or a pure cerium rare earth.
- the magnesium salt of the present invention may be magnesium chloride or magnesium nitrate or magnesium sulfate, preferably magnesium chloride or magnesium nitrate.
- the dispersing agent in the dispersion pre-exchange process of the present invention is selected from the group consisting of phthalocyanine powder, boric acid, urea, ethanol, polyacrylamide, acetic acid, oxalic acid, adipic acid, formic acid, hydrochloric acid, nitric acid, citric acid, salicylic acid.
- phthalocyanine powder boric acid, urea, ethanol, polyacrylamide, acetic acid, oxalic acid, adipic acid, formic acid, hydrochloric acid, nitric acid, citric acid, salicylic acid.
- tartaric acid, benzoic acid, and starch preferably two or more.
- the other molecular sieves in the catalyst composition of the present invention are one or more selected from the group consisting of Y-type zeolite and L-zeolite.
- the clay according to the present invention is one or more selected from the group consisting of kaolin, halloysite, montmorillonite, sepiolite, perlite, etc.; said high temperature resistant inorganic oxide is one or more selected from the group consisting of A1 2 0 3, Si0 2, Si0 2 -Al 2 0 3, A1P0 4, its precursor comprising a silica-alumina gel, silica sol, alumina sol, silica-alumina composite sol, boehmite and pseudoboehmite.
- the spraying conditions of the present invention are conventional operating conditions for preparing a cracking catalyst, and the present invention is not limited thereto; the post-treatment process is the same as the prior art, and includes catalyst calcination, water washing, drying, etc., wherein the roasting is preferably a spray microsphere.
- the sample is calcined at 200 ° C ⁇ 700 ° C, preferably 300 ° C ⁇ 650 ° C, time 0. 05 ⁇ 4 hours, preferably 0. 1 ⁇ 3. 5 hours; water washing conditions are best: water / catalyst weight is 0 ⁇ 5. 3 ⁇ 0. 5 ⁇ 35, The washing temperature is 20 ° C ⁇ 10 (TC, time is 0. 1 ⁇ 0. 3 hours.
- NaY molecular sieve NaY-1 (silicon to aluminum ratio 4.8, crystallinity 92%), NaY-2 (silicon to aluminum ratio 4.1, crystallinity)
- Ultra-stable one-to-one baking molecular sieve sample Crystallinity 60%, sodium oxide 4.3m%, produced by Lanzhou Petrochemical Company Catalyst Factory.
- Rare earth solution rare earth chloride (rare earth oxide 277.5 g / liter), rare earth nitrate (rare earth oxide 252 g / liter), All are industrial products, taken from the catalyst factory of Lanzhou Petrochemical Company.
- ffl cyanine powder, boric acid, urea, ethanol, polyacrylamide, oxalic acid, adipic acid, acetic acid, formic acid, hydrochloric acid, nitric acid, citric acid, salicylic acid, tartaric acid, starch, magnesium chloride, magnesium nitrate are all chemically pure; Ammonium chloride, cerium nitrate, barium sulfate, ammonium oxalate are industrial products.
- Pseudo-boehmite (36.2% reduction), kaolin (16.4% reduction), halloysite (21.4% reduction), montmorillonite (15.8% reduction), perlite (17.6% reduction) , solid; aluminum sol, containing alumina 23.0% by weight; silica sol, containing silica 4.5% by weight, are all industrial qualified products.
- the system was adjusted to pH 3.6, heated to 90 ° C, exchanged for 1.2 hours, then filtered, washed, and the cake was calcined at 20% water vapor and 60 CTC for 0.5 hour to obtain a "two-baked-baked" rare earth super-stable.
- the band exchange conditions were as follows: The rare earth solution was heated to 88 ° C, the exchange pH was 4.7, the rare earth nitrate was added in a RE 2 03/Y zeolite (mass) of 0.04, and the belt filter vacuum was 0.03; the resulting filter cake was then flash dried to make it The moisture content is 30% ⁇ 50%, and finally calcined at 80% water vapor and 53CTC for 1.5 hours to obtain "one-to-one baking" ultra-stable rare earth sodium Y"-crossing one baking" ultra-stable rare earth sodium strontium.
- modified molecular sieve C-1 After drying at 15 CTC for 3 hours, it was calcined at 60% water vapor and 620 °C for 2 hours to obtain a "two-two-baked" rare earth super-stable enthalpy, which was designated as modified molecular sieve C-1.
- modified molecular sieve C-1 In a reaction kettle heated with a water bath, 4.804 liters of water, 1125 g of halloysite, 825 g of pseudoboehmite, and 51.4 ml of hydrochloric acid were added and mixed uniformly, and stirred for 1 hour, and then 456 g of modified molecular sieve C-1 was sequentially added. 903 g of USY, uniformly mixed, and slowly added 1224 g of silica sol to form a gel.
- Example 4 After spray molding, the obtained microspheres were calcined at 600 ° C for 0.3 hours. 2 kg of calcined microspheres were taken, 15 kg of deionized water was added, and the mixture was washed at 80 ° C for 30 minutes, and dried by filtration to obtain a cracking catalyst prepared by the present invention, which was designated as C.
- Example 4
- the rare earth nitrate is added in a RE 2 03/Y zeolite (mass) of 0.12, and the belt filter has a vacuum of 0.05; then the obtained filter cake is flash dried to a moisture content of 30% to 50%, and finally at 100% water vapor. It was calcined at 580 Torr for 2 hours to obtain "one-and-one-baked" ultra-stable rare earth sodium strontium. In a reaction kettle with a heating jacket, 500 g (dry basis) and deionized water of "one-and-one-baked" ultra-stable rare earth sodium Y molecular sieve were added to prepare a slurry having a solid content of 150 g/L, and 160 g of ammonium sulfate was added.
- the method for preparing REUSY molecular sieve is similar to the method shown in Example 2 except that polyacrylamide and salicylic acid are not added, and the other ultra-stable rare earth Y type molecular sieve number is E-1, and the obtained catalyst number is E. Comparative example 2
- the comparative example uses the molecular sieve preparation method described in CN200510114495.1 to examine the reaction performance of the molecular sieve, and the catalyst preparation process is the same as in the second embodiment.
- This comparative example uses the molecular sieve preparation method described in CN97122039.5, and the catalyst preparation process is the same as in Example 3.
- deionized water and 3000 g (dry basis) of NaY-1 molecular sieve were added to prepare a slurry having a solid content of 90 g/L, and the mixture was heated to 80 ° C with stirring, and 59 g of hydrochloric acid was added thereto, and the temperature was adjusted.
- the comparative molecular sieve sample was designated as G-1.
- the belt exchange conditions were as follows: Raise the rare earth nitrate solution to At 88 ° C, the exchange pH is 4.7, the rare earth nitrate is added in a RE 2 0 3 /Y zeolite (mass) of 0.04, and the belt filter has a vacuum of 0.03; then the obtained filter cake is flash dried to have a moisture content of 30% ⁇ 50%, finally calcined at 80% water vapor and 530 Torr for 1.5 hours, and obtained "one-and-one-baked" ultra-stable rare earth sodium Y"-cross-baked” ultra-stable rare earth sodium strontium.
- the strip exchange conditions were as follows: The temperature was raised to 88 °C, the exchange pH was 4.7, the rare earth nitrate was added in a RE 2 ⁇ 3/Y zeolite (mass) of 0.04, and the belt filter vacuum was 0.03. The resulting filter cake was then flash dried to make it moisture. The content is 30% ⁇ 50%, and finally calcined at 80% water vapor and 53CTC for 1.5 hours to obtain "one-and-one-baked" ultra-stable rare earth sodium Y"-cross-baked” ultra-stable rare earth sodium Y.
- the belt exchange conditions were as follows: The rare earth citrate solution was heated to 88 V, the exchange pH was 4.7, the rare earth nitrate was added in an amount of RE 2 03/Y zeolite (mass) of 0.04, and the belt filter vacuum was 0.03; the resulting filter cake was then flash dried. The moisture content is 30% ⁇ 50%, and finally calcined at 80% water vapor and 53CTC for 1.5 hours to obtain "one-to-one baking" ultra-stable rare earth sodium Y"-cross-baking" ultra-stable rare earth sodium strontium.
- Micro-reaction activity The sample was pretreated at 80 (TC, 100% water vapor for 4 hours.
- the reaction material was Dagang light diesel oil, reaction temperature was 460 ° C, reaction time was 70 seconds, catalyst loading was 5.0 g, ratio of solvent to oil 3.2, the total conversion rate as the micro-reaction activity.
- ACE heavy microreactor The reaction temperature is 530 ° C, the ratio of solvent to oil is 5, and the raw material oil is 30% vacuum residue of Xinjiang oil blending.
- the physicochemical properties of the ultra-stable rare earth Y type molecular sieve obtained in the examples and comparative examples of the present invention are shown in Table 1.
- the analysis results show that: Compared with the comparative example, the new molecular sieve has the characteristics of good structural stability and small particle size.
- the catalyst prepared by the method of the present invention has excellent heavy oil conversion ability and coke selectivity, and the total liquid yield and light oil yield are significantly higher than that of the comparative catalyst.
- Table 4 shows the evaluation results of the catalyst B riser. Compared with the comparative catalyst G, the total liquid recovery of the catalyst of the present invention is increased by 1.03 percentage points, and the light oil yield is increased by 0.95 percentage points, and the gasoline property is equivalent.
- One of the main active components of the novel heavy oil catalyst of the present invention is a high cracking active stability magnesium modified rare earth super stable Y type molecular sieve, and the molecular sieve is predispersed by using a dispersing agent to disperse the NaY molecular sieve in the rare earth modification preparation process.
- the degree of agglomeration between the molecular sieve particles is reduced, the surface of the molecular sieve is more contacted with the rare earth ions, the resistance of the rare earth ions in the exchange process is reduced, the rare earth ions are more exchanged into the molecular sieve cage, and migrated in the subsequent steam roasting process.
- the structural stability and activity stability of the molecular sieve are improved.
- the rare earth ions are located in the molecular sieve sodalite cage.
- the ultra-cage and surface have no rare earth ions, which reduces the acid strength and density at the position, reduces the biofocus rate of the active site, and better solves the heavy oil conversion capacity and coke of the catalyst. Selective contradiction.
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AU2012351265A AU2012351265B2 (en) | 2011-12-15 | 2012-04-13 | High light received heavy oil catalytic cracking catalyst and preparation method therefor |
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US14/364,652 US9889439B2 (en) | 2011-12-15 | 2012-04-13 | High light received heavy oil catalytic cracking catalyst and preparation method therefor |
JP2014546273A JP5996667B2 (ja) | 2011-12-15 | 2012-04-13 | 高軽質収率の重質油接触分解触媒およびその製造方法 |
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US9889439B2 (en) | 2011-12-15 | 2018-02-13 | Petrochina Company Limited | High light received heavy oil catalytic cracking catalyst and preparation method therefor |
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US9889439B2 (en) | 2011-12-15 | 2018-02-13 | Petrochina Company Limited | High light received heavy oil catalytic cracking catalyst and preparation method therefor |
CN104888840A (zh) * | 2015-01-14 | 2015-09-09 | 任丘市华北石油科林环保有限公司 | 一种高骨架硅铝比原位晶化fcc重油转化助剂的制备方法 |
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CN110652998B (zh) * | 2018-06-29 | 2021-01-08 | 中国石油化工股份有限公司 | 一种多产异构烃的高稳定性改性y型分子筛及其制备方法 |
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CN111744528B (zh) * | 2019-03-27 | 2023-04-07 | 中国石油化工股份有限公司 | 一种多金属修饰的复合材料的制备方法 |
CN112717985A (zh) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | 一种滤渣及其制备方法以及一种催化裂化催化剂及其制备方法 |
CN112717985B (zh) * | 2019-10-28 | 2023-04-07 | 中国石油化工股份有限公司 | 一种滤渣及其制备方法以及一种催化裂化催化剂及其制备方法 |
CN114132977A (zh) * | 2021-11-30 | 2022-03-04 | 华中科技大学 | 一种天然水体净化剂及其制备方法和应用 |
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CA2862131A1 (en) | 2013-06-20 |
AU2012351265B2 (en) | 2016-03-31 |
CN103157506A (zh) | 2013-06-19 |
US9889439B2 (en) | 2018-02-13 |
JP5996667B2 (ja) | 2016-09-21 |
AU2012351265A1 (en) | 2014-08-07 |
SG11201404087VA (en) | 2014-10-30 |
JP2015502252A (ja) | 2015-01-22 |
US20150011378A1 (en) | 2015-01-08 |
CN103157506B (zh) | 2015-09-23 |
CA2862131C (en) | 2018-03-13 |
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