CN114471676B - Cracking auxiliary agent - Google Patents
Cracking auxiliary agent Download PDFInfo
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- CN114471676B CN114471676B CN202011169072.0A CN202011169072A CN114471676B CN 114471676 B CN114471676 B CN 114471676B CN 202011169072 A CN202011169072 A CN 202011169072A CN 114471676 B CN114471676 B CN 114471676B
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- China
- Prior art keywords
- phosphorus
- molecular sieve
- hierarchical pore
- cracking
- zsm
- Prior art date
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- 238000005336 cracking Methods 0.000 title claims abstract description 135
- 239000012752 auxiliary agent Substances 0.000 title claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 265
- 239000011574 phosphorus Substances 0.000 claims abstract description 262
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 261
- 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 255
- 239000002808 molecular sieve Substances 0.000 claims abstract description 254
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 175
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 58
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 46
- 238000004458 analytical method Methods 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 87
- 238000000034 method Methods 0.000 claims description 73
- 239000004927 clay Substances 0.000 claims description 54
- 239000011148 porous material Substances 0.000 claims description 52
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical group [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 claims description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 43
- 239000003921 oil Substances 0.000 claims description 43
- 238000002360 preparation method Methods 0.000 claims description 42
- 230000032683 aging Effects 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 29
- 239000002002 slurry Substances 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 18
- 238000003795 desorption Methods 0.000 claims description 17
- 239000005995 Aluminium silicate Substances 0.000 claims description 16
- 235000012211 aluminium silicate Nutrition 0.000 claims description 16
- 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 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000001228 spectrum Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- -1 1,3-xylene bis triethyl phosphonium Chemical compound 0.000 claims description 13
- 238000000921 elemental analysis Methods 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 238000002441 X-ray diffraction Methods 0.000 claims description 10
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 10
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000004537 pulping Methods 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 10
- 238000005004 MAS NMR spectroscopy Methods 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 239000004113 Sepiolite Substances 0.000 claims description 7
- 229960000892 attapulgite Drugs 0.000 claims description 7
- 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 7
- 239000003292 glue Substances 0.000 claims description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- 229910052625 palygorskite Inorganic materials 0.000 claims description 7
- 229910052624 sepiolite Inorganic materials 0.000 claims description 7
- 235000019355 sepiolite Nutrition 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 239000004254 Ammonium phosphate Substances 0.000 claims description 5
- 239000005909 Kieselgur Substances 0.000 claims description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 5
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 claims description 5
- 229910000149 boron phosphate Inorganic materials 0.000 claims description 5
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 238000003776 cleavage reaction Methods 0.000 claims description 4
- 230000007017 scission Effects 0.000 claims description 4
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- WTEPWWCRWNCUNA-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 WTEPWWCRWNCUNA-UHFFFAOYSA-M 0.000 claims description 3
- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 239000010779 crude oil Substances 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
- VLKRPMRVOKGQRE-UHFFFAOYSA-N dibenzyl(diethyl)phosphanium Chemical compound C=1C=CC=CC=1C[P+](CC)(CC)CC1=CC=CC=C1 VLKRPMRVOKGQRE-UHFFFAOYSA-N 0.000 claims description 3
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 239000011268 mixed slurry Substances 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 claims description 3
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 claims description 3
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 claims description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 3
- 229920006342 thermoplastic vulcanizate Polymers 0.000 claims 4
- 230000000052 comparative effect Effects 0.000 description 128
- 238000011156 evaluation Methods 0.000 description 48
- XXZCIYUJYUESMD-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(morpholin-4-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCOCC1 XXZCIYUJYUESMD-UHFFFAOYSA-N 0.000 description 46
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- 238000010304 firing Methods 0.000 description 20
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- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 14
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 6
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- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 3
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 3
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 3
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- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 101100426973 Caenorhabditis elegans ttr-3 gene Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 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
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 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
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910001682 nordstrandite Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B01J35/647—
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A cracking assistant is characterized in that the cracking assistant contains 5-75 wt% of phosphorus-containing hierarchical pore ZSM-5 molecular sieve based on the dry basis of the catalytic cracking assistant; in the surface XPS element analysis, n1/n2 of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is less than or equal to 0.08, wherein n1 represents the mole number of phosphorus, and n2 represents the total mole number of silicon and aluminum.
Description
Technical Field
The invention relates to a cracking assistant and a preparation method and application thereof, and further relates to a cracking assistant containing a ZSM-5 molecular sieve, a preparation method thereof and application thereof in catalytic cracking of hydrocarbon oil.
Background
ZSM-5 molecular sieves were a widely used zeolitic molecular sieve catalytic material developed in 1972 by Mobil corporation, USA. The molecular sieve has a three-dimensional crossed pore channel structure, wherein the pore channel along the axial direction a is a straight pore, the cross section dimension of the pore channel is 0.54 multiplied by 0.56nm and is approximately circular, and the pore channel along the axial direction b is a Z-shaped pore, the cross section dimension of the pore channel is 0.51 multiplied by 0.56nm and is oval. The pore opening is composed of ten-membered rings, and the size of the pore opening is between that of the small pore zeolite and that of the large pore zeolite, so that the catalyst has a unique shape-selective catalytic action. The ZSM-5 molecular sieve has a unique pore channel structure, has the characteristics of good shape-selective catalysis and isomerization performance, high thermal and hydrothermal stability, high specific surface area, wide silicon-aluminum ratio variation range, unique surface acidity and low carbon content, is widely used as a catalyst and a catalyst carrier, and is successfully used in production processes of alkylation, isomerization, disproportionation, catalytic cracking, gasoline preparation from methanol, olefin preparation from methanol and the like. The ZSM-5 molecular sieve is introduced into catalytic cracking and carbon four-hydrocarbon catalytic cracking, shows excellent catalytic performance, and can greatly improve the yield of low-carbon olefin by utilizing the shape selectivity of the molecule.
Since 1983, ZSM-5 molecular sieve was applied to catalytic cracking process as an octane number promoter for catalytic cracking, aiming at improving the octane number of catalytic cracking gasoline and the selectivity of low-carbon olefin. In US3758403 ZSM-5 was first reported as the active component for increasing the yield of propylene and REY was prepared into FCC catalyst, in US5997728 it was disclosed that ZSM-5 molecular sieve without any modification was used as the assistant for increasing the yield of propylene, and their propylene yields were all not high. Although ZSM-5 molecular sieve has good shape-selective performance and isomerization performance, the defects of the ZSM-5 molecular sieve are that the hydrothermal stability is poor, and the ZSM-5 molecular sieve is easy to inactivate under severe high-temperature hydrothermal conditions, so that the catalytic performance is reduced.
In the 80 s of the 20 th century, mobil company found that phosphorus can improve the hydrothermal stability of the ZSM-5 molecular sieve, and the phosphorus modifies the ZSM-5 molecular sieve to improve the yield of low-carbon olefin. Conventional additives typically contain ZSM-5 activated with phosphorus, which selectively converts primary cracking products (e.g., gasoline olefins) to C3 and C4 olefins. After being synthesized, the ZSM-5 molecular sieve is modified by introducing a proper amount of inorganic phosphorus compound, and can stabilize framework aluminum under severe hydrothermal conditions.
In CN106994364 a process is disclosed for phosphorus modification of ZSM-5 molecular sieves by first mixing a phosphorus-containing compound selected from one or more of phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate with a ZSM-5 molecular sieve having a high alkali metal ion content to obtain a mixture having a phosphorus loading of at least 0.1wt% as P2O5, drying and calcining the mixture, then subjecting the mixture to an ammonium cross-linking step and a water washing step to reduce the alkali metal ion content to below 0.10wt%, and then subjecting the mixture to drying and hydrothermal aging at 400-1000 ℃ and 100% steam. The phosphorus-containing ZSM-5 molecular sieve obtained by the method has high total acid content, excellent cracking conversion rate and propylene selectivity and higher liquefied gas yield.
In CN1506161a, a method for modifying a hierarchical porous ZSM-5 molecular sieve is disclosed, which comprises the following conventional steps: synthesizing → filtering → ammonium exchanging → drying → roasting to obtain the multi-stage hole ZSM-5 molecular sieve,and then modifying the hierarchical pore ZSM-5 molecular sieve with phosphoric acid, and then drying and roasting to obtain the phosphorus modified hierarchical pore ZSM-5 molecular sieve. Wherein, P 2 O 5 The loading is generally in the range from 1 to 7% by weight. However, phosphoric acid or ammonium phosphate can generate phosphorus species in different aggregation states by self-polymerization in the roasting process, and only phosphate radical entering pores is interacted with framework aluminum in the hydrothermal treatment process to keep B acid centers and reduce the distribution of the phosphorus species.
The hierarchical pore ZSM-5 molecular sieve is a ZSM-5 molecular sieve containing micropores and mesopores, and various hierarchical pore ZSM-5 molecular sieves with mesopore pore canals are prepared by a hard template method, a soft template method, an acid-base post-treatment method and the like.
Although the multilevel pore ZSM-5 molecular sieve is modified by adopting a proper amount of inorganic phosphide, the framework dealumination can be slowed down, the hydrothermal stability is improved, and phosphorus atoms can be combined with distorted four-coordination framework aluminum to generate weak B acid centers, so that the higher conversion rate of long paraffin cracking and the higher selectivity of light olefins are achieved, the excessive inorganic phosphide is used for modifying the multilevel pore ZSM-5 molecular sieve, so that the pore channels of the molecular sieve are blocked, the pore volume and the specific surface area are reduced, and a large amount of strong B acid centers are occupied. In addition, in the prior art, phosphoric acid or ammonium phosphate salts can generate phosphorus species in different aggregation states by self-polymerization in the roasting process, phosphorus is insufficiently coordinated with framework aluminum, the utilization efficiency of phosphorus is low, and phosphorus modification does not always obtain a satisfactory hydrothermal stability improvement result. Therefore, a new technology is urgently needed to promote the coordination of phosphorus and framework aluminum, improve the hydrothermal stability of the phosphorus-modified hierarchical pore ZSM-5 molecular sieve and further improve the cracking activity.
Disclosure of Invention
One of the objects of the present invention is to provide a cracking aid based on a phosphorus-containing hierarchical pore ZSM-5 molecular sieve having different physical characteristics from conventional phosphorus-containing hierarchical pore ZSM-5 molecular sieves and better hydrothermal stability as an active component; the other purpose is to provide a preparation method of the cracking assistant; the third purpose is to provide the application of the cracking assistant.
In order to achieve one of the above objects, the first aspect of the present invention provides a cracking assistant, wherein the catalytic cracking assistant comprises 5 to 75 wt% of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve based on a dry basis of the catalytic cracking assistant; in the surface XPS element analysis, n1/n2 of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is less than or equal to 0.08, wherein n1 represents the mole number of phosphorus, and n2 represents the total mole number of silicon and aluminum.
Preferably, in the surface XPS element analysis of the multistage pore ZSM-5 molecular sieve containing phosphorus, the n1/n2 is less than or equal to 0.07, the preferable n1/n2 is less than or equal to 0.06, and the more preferable n1/n2 is 0.02 to 0.05.
The phosphorus-containing hierarchical pore ZSM-5 molecular sieve, 27 in Al MAS-NMR, the ratio of the peak area of the resonance signal with the chemical shift of 39 +/-3 ppm to the peak area of the resonance signal with the chemical shift of 54ppm +/-3 ppm is more than or equal to 1, preferably more than or equal to 8, more preferably more than or equal to 12, and most preferably 14-25.
The phosphorus-containing hierarchical pore ZSM-5 molecular sieve is subjected to hydrothermal aging at 800 ℃ for 17 hours under the condition of 100 percent of water vapor, and then NH 3 In the TPD map, the proportion of the area of the strong acid central peak at the desorption temperature of more than 200 ℃ in the total acid central peak area is more than or equal to 45 percent, preferably more than or equal to 50 percent, more preferably more than or equal to 60 percent, and most preferably 60 to 80 percent.
The phosphorus-containing hierarchical pore ZSM-5 molecular sieve has the mesoporous volume accounting for more than 10 percent of the total pore volume and the average pore diameter of 2-20 nm.
When the phosphorus and the aluminum are both counted by mol, the ratio of the phosphorus to the aluminum is 0.01-2, the preferred ratio is 0.1-1.5, and the more preferred ratio is 0.2-1.5.
The cracking assistant also contains 1-40 wt% of binder and 0-65 wt% of second clay based on the dry basis of the cracking assistant. Preferably, the binder comprises a phosphorus-aluminum inorganic binder. More preferably, the phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or a phosphorus-aluminum inorganic binder containing first clay.
In order to achieve the second purpose, the preparation method of the cracking assistant provided by the invention comprises the steps of mixing and pulping the phosphorus-containing hierarchical pore ZSM-5 molecular sieve and the binder with the second clay which can be added optionally, and spray-drying the mixture to obtain the catalytic cracking assistant, wherein the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is obtained by contacting a phosphorus-containing compound solution with a hydrogen-type hierarchical pore ZSM-5 molecular sieve, performing hydrothermal roasting treatment under the external pressure and external water-adding atmosphere environment after drying treatment, and recovering a product; in the hydrogen-type hierarchical pore ZSM-5 molecular sieve, the proportion of the mesopore volume to the total pore volume is more than 10 percent, and the average pore diameter is 2-20 nm; the contact is that the water solution of the phosphorus-containing compound with the temperature of 0-150 ℃ and the HZSM-5 molecular sieve with the temperature of 0-150 ℃ are mixed and contacted for at least 0.1 hour at the basically same temperature by adopting an impregnation method, or the contact is that the phosphorus-containing compound, the HZSM-5 molecular sieve and water are mixed and pulped and then are kept for at least 0.1 hour at the temperature of 0-150 ℃; the atmosphere environment has an apparent pressure of 0.01-1.0 Mpa and contains 1-100% of water vapor.
The phosphorus-containing compound is selected from organic phosphide and/or inorganic phosphide. The organic phosphide is selected from trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium hydroxide, triphenyl ethyl phosphonium bromide, triphenyl butyl phosphonium bromide, triphenyl benzyl phosphonium bromide, hexamethyl phosphoric triamide, dibenzyl diethyl phosphonium, 1,3-xylene bis triethyl phosphonium; the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.
In the multistage Kong Qingxing ZSM-5 molecular sieve, na is added 2 O<0.1wt％。
The phosphorus-containing compound is calculated by phosphorus, the hydrogen type multi-stage hole ZSM-5 molecular sieve is calculated by aluminum, the molar ratio of the phosphorus-containing compound to the hydrogen type multi-stage hole ZSM-5 molecular sieve is 0.01-2, the preferred molar ratio is 0.1-1.5, and the more preferred molar ratio is 0.3-1.3.
The weight ratio of the water sieve to the contact is 0.5-1, and the contact is carried out for 0.5-40 hours at the temperature of 50-150 ℃, preferably 70-130 ℃.
The apparent pressure of the atmosphere environment is 0.1-0.8 Mpa, preferably 0.3-0.6 Mpa, and the atmosphere environment contains 30-100% of water vapor, preferably 60-100% of water vapor; the hydrothermal roasting treatment is carried out at 200 to 800 ℃, preferably 300 to 500 ℃.
The binder is a phosphorus-aluminum inorganic binder. The phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or a phosphorus-aluminum inorganic binder containing first clay; the phosphorus-aluminum inorganic binder containing the first clay takes Al as the basis weight on a dry basis 2 O 3 15-40% by weight, calculated as P, of an aluminium component 2 O 5 45-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay calculated on dry basis, wherein the P/Al weight ratio of the phosphorus-aluminum inorganic binder containing the first clay is 1.0-6.0, the pH is 1-3.5, and the solid content is 15-60 wt%; the first clay comprises at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomaceous earth; the other inorganic binder includes at least one of pseudo-boehmite, alumina sol, silica-alumina sol and water glass.
The second clay is at least one selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite and diatomite.
In the preparation method, the binder comprises 3-39 wt% of the phosphorus-aluminum inorganic binder in terms of dry basis and 1-30 wt% of the other inorganic binders in terms of dry basis based on the cracking assistant.
The preparation method also comprises the following steps: carrying out first roasting, washing and optional drying treatment on the product obtained by spray drying to obtain the cracking assistant; wherein the roasting temperature of the first roasting is 300-650 ℃, and the roasting time is 0.5-8 h; the drying temperature is 100-200 ℃, and the drying time is 0.5-24 h.
The preparation method further comprises the following steps of preparing the first clay-containing phosphorus-aluminum inorganic binder: pulping an alumina source, the first clay and water to disperse into slurry with solid content of 5-48 wt%; wherein the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, and the weight ratio of the aluminum hydroxide and/or the aluminum oxide is 15-40 partsWith Al 2 O 3 (ii) an alumina source in an amount greater than 0 parts by weight and not greater than 40 parts by weight of the first clay on a dry basis; adding concentrated phosphoric acid to the slurry in a weight ratio of P/Al =1-6 with stirring, and reacting the resulting mixed slurry at 50-99 ℃ for 15-90 minutes; in the P/Al, P is the weight of phosphorus in the phosphoric acid in terms of simple substance, and Al is the weight of aluminum in the alumina source in terms of simple substance.
In order to achieve the third object, the invention provides an application of cracking assistant, namely a method for catalytic cracking of hydrocarbon oil, which comprises the following steps: under the condition of catalytic cracking, the hydrocarbon oil is contacted with the cracking assistant for reaction. For example, the hydrocarbon oil is contacted and reacted with a catalytic mixture containing the cracking assistant and a catalytic cracking catalyst; in the catalytic mixture, the content of the cracking assistant is 0.1-30 wt%. Wherein the catalytic cracking conditions comprise: the reaction temperature is 500-800 ℃; the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residue oil, vacuum residue oil, atmospheric wax oil, vacuum wax oil, straight-run wax oil, propane light/heavy deoiled oil, coker wax oil and coal liquefaction products.
The cracking assistant provided by the invention has excellent cracking conversion rate and low-carbon olefin yield in the catalytic cracking reaction of petroleum hydrocarbon, and has higher liquefied gas yield.
Drawings
FIG. 1 shows a sample PAZ-1 of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid according to the invention 27 Al MAS-NMR spectrum.
FIG. 2 shows NH of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample PAZ-1 in the cracking aid after hydrothermal aging for 17h at 800 ℃ under the condition of 100% of water vapor 3 -TPD spectrum.
FIG. 3 is a graph of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample PBZ-1 in a cracking aid of the invention 27 Al MAS-NMR spectrum.
FIG. 4 is a graph showing comparative samples D1-1 27 Al MAS-NMR spectrum.
FIG. 5 shows NH of a comparative sample D1-1 after 17 hours of hydrothermal aging at 800 ℃ under 100% steam 3 -TPD spectrum.
Detailed Description
The cracking assistant provided by the invention takes the dry basis of the catalytic cracking assistant as a reference, and the catalytic cracking assistant contains 5-75 wt% of a multistage hole ZSM-5 molecular sieve containing phosphorus; in the surface XPS element analysis, n1/n2 is not more than 0.08, wherein n1 represents the mole number of phosphorus, and n2 represents the total mole number of silicon and aluminum.
In XPS (performance index) elemental analysis of the surface of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, n1/n2 is not more than 0.07, preferably n1/n2 is not more than 0.06, and more preferably n1/n2 is 0.02-0.05. The characterization parameters show that the content of surface phosphorus species in the molecular sieve is reduced, and also show that the surface phosphorus species are more migrated to the molecular sieve body phase, namely the numerical value of n1/n2 shows that the phosphorus species are dispersed on the surface of the molecular sieve and migrated from the surface of the ZSM-5 molecular sieve to the crystal, and the smaller the numerical value is, the content of the surface phosphorus species is reduced, the phosphorus species are well dispersed and migrated inwards, so that the hydrothermal stability of the molecular sieve is better.
Further, the cracking assistant of the invention, wherein the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, 27 in Al MAS-NMR, the ratio of the peak area of the resonance signal with the chemical shift of 39 +/-3 ppm to the peak area of the resonance signal with the chemical shift of 54ppm +/-3 ppm is more than or equal to 1, preferably more than or equal to 8, more preferably more than or equal to 12, and most preferably 14-25. 27 In Al MAS-NMR, a resonance signal at a chemical shift of 39. + -. 3ppm indicates a skeletal aluminum species coordinated to phosphorus (phosphorus-stabilized skeletal aluminum, i.e., distorted four-coordinate skeletal aluminum); a chemical shift of 54 ppm. + -.3 ppm of the resonance signal indicates a four-coordinate framework aluminum species.
Furthermore, the cracking assistant of the invention, wherein the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is subjected to hydrothermal aging at 800 ℃ and 100% of water vapor for 17h to obtain NH 3 In the TPD map, the proportion of the area of the strong acid central peak at the desorption temperature of more than 200 ℃ to the area of the total acid central peak is more than or equal to 45 percent, the preferred range is more than or equal to 50 percent, the more preferred range is more than or equal to 60 percent, and the most preferred range is 60 to 80 percent. Illustrating the inventionThe phosphorus-containing hierarchical-pore ZSM molecular sieve has high strong acid center retention after 17 hours of hydrothermal aging at 800 ℃ under the condition of 100% of water vapor, thereby having high cracking activity.
The cracking assistant of the invention, wherein the phosphorus content of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is 0.01-2 when the phosphorus and the aluminum are counted by mol; preferably, the ratio of the two is 0.1-1.5; more preferably, the ratio of the two is 0.2 to 1.5.
In the cracking assistant of the present invention, the cracking assistant may contain 1 to 40 wt% of a binder and 0 to 65 wt% of a second clay in addition to 5 to 75 wt%, preferably 8 to 60 wt% of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve, based on the dry basis of the cracking assistant. The binder may be an inorganic oxide binder, such as one or more of pseudo-boehmite, alumina sol, silica alumina sol, and water glass, conventionally used as a co-agent or catalyst binder component, as is well known to those skilled in the art. Preferably, the binder contains a phosphor-aluminum inorganic binder, i.e. a phosphor-aluminum inorganic binder or a mixture of a phosphor-aluminum inorganic binder and other inorganic binders.
The phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or a phosphorus-aluminum inorganic binder containing first clay. The phosphorus-aluminum inorganic binder containing the first clay contains Al based on the dry basis of the phosphorus-aluminum inorganic binder containing the first clay 2 O 3 15-40% by weight, calculated as P, of an aluminium component 2 O 5 45-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay calculated on dry basis, and the P/Al weight ratio of the phosphorus-aluminum inorganic binder containing first clay is 1.0-6.0, pH is 1-3.5, and solid content is 15-60 wt%.
In one embodiment of the phosphorus-aluminum inorganic binder, the phosphorus-aluminum inorganic binder may include Al based on the dry weight of the phosphorus-aluminum inorganic binder 2 O 3 15-40% by weight, calculated as P, of an aluminium component 2 O 5 45-80% by weight of a phosphorus component and 0-40% by weight, based on the weight of the dry basis, of a first clay, and having a P/Al weight ratio of 1.0-6.0, a pH value of 1-3.5,the solid content is 15-60 wt%; for example, including Al 2 O 3 15-40% by weight, calculated as P, of an aluminium component 2 O 5 45-80 wt% of a phosphorus component and 1-40 wt% of a first clay, based on dry weight; preferably contains Al 2 O 3 15-35% by weight, calculated as P, of an aluminium component 2 O 5 50-75 wt% of a phosphorus component and 8-35 wt% of a first clay, calculated on a dry basis, and preferably having a P/Al weight ratio of 1.2-6.0, more preferably 2.0-5.0 and a pH value of preferably 2.0-3.0.
In another embodiment of the phosphor-aluminum inorganic binder, the phosphor-aluminum inorganic binder comprises Al based on the dry weight of the phosphor-aluminum inorganic binder 2 O 3 20-40% by weight, calculated as P, of an aluminium component 2 O 5 60-80% by weight of a phosphorus component.
The first clay may be at least one selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomaceous earth; the additional inorganic binder may be selected from one or more of inorganic oxide binders conventionally used in catalytic cracking aids or catalyst binder components other than the aluminophosphate and aluminophosphate inorganic binders, preferably from at least one of pseudoboehmite, alumina sol, silica alumina sol, and water glass, more preferably from at least one of pseudoboehmite and alumina sol.
The cracking aid of the present invention further comprises 0 to 65 wt%, preferably 5 to 55 wt%, of a second clay, based on the dry weight of the cracking aid. The second clay is also well known to those skilled in the art, and is, for example, at least one selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite, and diatomaceous earth.
In one embodiment of the cracking aid of the present invention, the cracking aid comprises 20-60 wt% of the phosphorus-modified ZSM-5 molecular sieve, 5-35 wt% of the binder, and 5-55 wt% of the second clay, on a dry basis of the catalytic cracking aid.
The invention also provides a preparation method of the cracking assistant, which comprises the steps of mixing and pulping the phosphorus-containing hierarchical pore ZSM-5 molecular sieve and the binder with the second clay which can be added optionally, and spray-drying to obtain the catalytic cracking assistant, and is characterized in that the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is obtained by contacting a phosphorus-containing compound solution with a hydrogen-type hierarchical pore ZSM-5 molecular sieve, drying, carrying out hydrothermal roasting treatment under the external pressure and external water-adding atmosphere environment, and recovering the product; in the hydrogen-type hierarchical pore ZSM-5 molecular sieve, the proportion of the mesopore volume to the total pore volume is more than 10 percent, and the average pore diameter is 2-20 nm; the contact is that the water solution of the phosphorus-containing compound with the temperature of 0-150 ℃ and the HZSM-5 molecular sieve with the temperature of 0-150 ℃ are mixed and contacted for at least 0.1 hour at the basically same temperature by adopting an impregnation method, or the contact is that the phosphorus-containing compound, the HZSM-5 molecular sieve and water are mixed and pulped and then are kept for at least 0.1 hour at the temperature of 0-150 ℃; the atmosphere environment has an apparent pressure of 0.01-1.0 Mpa and contains 1-100% of water vapor.
The hierarchical pore means that the hierarchical pore contains both micropores and mesopores. In the preparation method, the hydrogen type hierarchical pore ZSM-5 molecular sieve Na is adopted 2 O<0.1wt%, the proportion of mesopore (2 nm-50 nm) volume in the total pore volume is more than 10%, usually 10-90%, and the average pore diameter is 2-20 nm. The silica to alumina ratio (molar ratio of silica to alumina) is in the range of 10 or more, usually 10 to 200.
The preparation steps adopted by the phosphorus-containing hierarchical pore ZSM-5 molecular sieve promote the migration of surface phosphorus species to the hierarchical pore ZSM-5 molecular sieve bulk phase; the coordination of phosphorus and the framework aluminum is sufficient, the framework aluminum is fully protected, and the molecular sieve has excellent hydrothermal stability.
In the preparation steps adopted by the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, the hydrogen type ZSM-5 molecular sieve is a microporous ZSM-5 molecular sieve for reducing sodium to Na by ammonium exchange 2 O<0.1wt% is obtained, and the silicon-aluminum ratio (the molar ratio of silicon oxide to aluminum oxide, the same applies hereinafter) is more than or equal to 10, and usually is 10 to 200.
The phosphorus-containing hierarchical pore ZSM-5 molecular sieve adopts the preparation steps that the phosphorus-containing compound is selected from organic phosphide and/or inorganic phosphide. The organic phosphide is selected from trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium hydroxide, triphenyl ethyl phosphonium bromide, triphenyl butyl phosphonium bromide, triphenyl benzyl phosphonium bromide, hexamethyl phosphoric triamide, dibenzyl diethyl phosphonium, 1,3-xylene bis triethyl phosphorus, and the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.
The multistage ZSM-5 molecular sieve containing phosphorus is prepared by a first mode of contacting an aqueous solution of a phosphorus-containing compound at a temperature of 0-150 ℃ with a hydrogen-type multistage ZSM-5 molecular sieve at a temperature of 0-150 ℃ for at least 0.1 hour by an impregnation method. For example, the contacting may be performed at a normal temperature range of 0 to 30 ℃, preferably, at a higher temperature range of 40 ℃ or higher, for example, 50 to 150 ℃, more preferably 70 to 130 ℃, so as to obtain a better effect, i.e., the phosphorus species are better dispersed, the phosphorus is easier to migrate into the crystal of the hydrogen-type hierarchical pore ZSM-5 molecular sieve to be combined with the framework aluminum, the coordination degree of the phosphorus and the framework aluminum is further improved, and finally, the hydrothermal stability of the molecular sieve is improved. The substantially same temperature means that the temperature difference between the aqueous solution of the phosphorus-containing compound and the hydrogen-type hierarchical pore ZSM-5 molecular sieve is within +/-5 ℃. For example, the temperature of the aqueous solution of the phosphorus-containing compound is 80 ℃ and the hydrogen-type hierarchical pore ZSM-5 molecular sieve is heated to 75-85 ℃.
In the preparation step of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, the second contact mode is to mix a phosphorus-containing compound, a hydrogen-type hierarchical pore ZSM-5 molecular sieve and water and then keep the mixture at 0-150 ℃ for at least 0.1 hour. For example, after mixing, the mixture is maintained at a normal temperature range of 0 to 30 ℃ for at least 0.1 hour, preferably, in order to obtain a better effect, i.e., in order to achieve better dispersion of phosphorus species, easier migration of phosphorus into molecular sieve crystals to be combined with framework aluminum, further increase the coordination degree of phosphorus and framework aluminum, and finally improve the hydrothermal stability of the molecular sieve, the phosphorus-containing compound, the hydrogen-type hierarchical pore ZSM-5 molecular sieve, and water are mixed, and then maintained at a higher temperature range of 40 ℃ or higher for 0.1 hour, for example, a temperature range of 50 to 150 ℃, more preferably a temperature range of 70 to 130 ℃.
In the preparation steps of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, when a phosphorus-containing compound is counted by phosphorus and a hydrogen-type hierarchical pore ZSM-5 molecular sieve is counted by aluminum, the molar ratio of the phosphorus-containing compound to the hydrogen-type hierarchical pore ZSM-5 molecular sieve is 0.01-2; preferably, the molar ratio of the two is 0.1-1.5; more preferably, the molar ratio of the two is 0.2 to 1.5. The weight ratio of the water sieve to the contact is 0.5-1, and the preferable contact time is 0.5-40 hours.
In the preparation steps of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, the hydrothermal roasting treatment is carried out under the atmosphere environment of externally applied pressure and externally added water. The atmospheric environment is obtained by externally applying pressure and water, and preferably has a superficial pressure of 0.1 to 0.8MPa, more preferably a superficial pressure of 0.3 to 0.6MPa, preferably 30 to 100% water vapor, more preferably 60 to 100% water vapor. The external pressure is applied to the hydrothermal roasting treatment of the prepared material from the outside, and for example, the external pressure may be applied by introducing an inert gas from the outside to maintain a certain back pressure. The amount of the externally added water is based on the condition that the atmosphere contains 1 to 100 percent of water vapor. The step of the hydrothermal roasting treatment is performed at 200 to 800 ℃, preferably 300 to 500 ℃.
In the preparation method of the cracking assistant, the binder contains a phosphorus-aluminum inorganic binder and other inorganic binders, and the weight and dosage ratio of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, the phosphorus-aluminum inorganic binder and the other inorganic binders can be (10-75): (3-39): (1 to 30), preferably (10 to 75): (8-35): (5-25); wherein the aluminophosphate inorganic binder can be an aluminophosphate glue and/or a aluminophosphate inorganic binder comprising a first clay; the other inorganic binder may include at least one of pseudoboehmite, alumina sol, silica alumina sol, and water glass. The preparation method can be mixing and pulping the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, the phosphorus-aluminum inorganic binder and other inorganic binders, and the order of adding the inorganic binders is not particularly required, for example, the phosphorus-aluminum inorganic binder, other inorganic binders, the phosphorus-containing hierarchical pore ZSM-5 molecular sieve and the second clay can be mixed (when the second clay is not contained, the relevant adding step can be omitted) and the mixture is pulped, preferably, the second clay, the phosphorus-containing hierarchical pore ZSM-5 molecular sieve and other inorganic binders are firstly mixed and pulped and then added into the phosphorus-aluminum inorganic binder, which is favorable for improving the activity and selectivity of the auxiliary agent.
The preparation method of the catalytic cracking assistant also comprises the step of spray drying the slurry obtained by pulping. Spray drying methods are well known to those skilled in the art and there is no particular requirement for the present invention. Optionally, the preparation method may further include: and carrying out first roasting, washing and optional drying treatment on the product obtained by spray drying to obtain the cracking aid. Wherein, the roasting temperature of the first roasting can be 300-650 ℃, for example 400-600 ℃, preferably 450-550 ℃, and the roasting time can be 0.5-8 hours; the washing can adopt one of ammonium sulfate, ammonium chloride and ammonium nitrate, and the washing temperature can be 40-70 ℃; the temperature of the drying treatment may be 100 to 200 ℃, for example, 100 to 150 ℃, and the drying time may be 0.5 to 24 hours, for example, 1 to 12 hours.
One specific embodiment of the preparation method of the cracking aid comprises the following steps: mixing a binder, second clay and water (such as decationized water and/or deionized water) to prepare slurry with the solid content of 10-50 wt%, uniformly stirring, adjusting the pH value of the slurry to 1-4 by using inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, keeping the pH value, standing and aging for 0-2 hours (such as 0.3-2 hours) at the temperature of 20-80 ℃, adding an inorganic binder such as alumina sol and/or silica sol, stirring for 0.5-1.5 hours to form colloid, then adding a molecular sieve, wherein the molecular sieve comprises the phosphorus-containing hierarchical pore ZSM-5 molecular sieve to form assistant slurry, the solid content of the assistant slurry is 20-45 wt%, continuously stirring, and then performing spray drying to prepare the microsphere assistant. The microsphere aid is then subjected to a first calcination, for example at 350 to 650 ℃ or 400 to 600 ℃, preferably 450 to 550 ℃, for 0.5 to 6 hours or 0.5 to 2 hours, washed with ammonium sulfate (wherein the washing temperature may be 40 to 70 ℃, ammonium sulfate: microsphere aid: water =0.2 to 0.8 (weight ratio) to a sodium oxide content of less than 0.25 wt%, washed with water and filtered, and then dried.
In the preparation method of the cracking assistant, the phosphorus-aluminum inorganic binder containing the first clay can also be prepared by the following steps: pulping an alumina source, the first clay and water to disperse into slurry with solid content of 5-48 wt%; wherein the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, and the weight of the alumina source is 15-40 parts by weight of Al 2 O 3 (ii) an alumina source in an amount greater than 0 parts by weight and not greater than 40 parts by weight of the first clay on a dry basis; adding concentrated phosphoric acid to the slurry in a weight ratio of P/Al =1-6 with stirring, and reacting the resulting mixed slurry at 50-99 ℃ for 15-90 minutes; in the P/Al, P is the weight of phosphorus in the phosphoric acid calculated by a simple substance, and Al is the weight of aluminum in the alumina source calculated by the simple substance. The alumina source may be at least one selected from the group consisting of rho-alumina, x-alumina, η -alumina, γ -alumina, κ -alumina, σ -alumina, θ -alumina, gibbsite, surge, nordstrandite, diaspore, boehmite, and pseudo-boehmite from which the aluminum component of the first clay-containing aluminophosphate inorganic binder is derived. The first clay can be one or more of high alumina, sepiolite, attapulgite, rectorite, montmorillonite and diatomite, and preferably rectorite. The concentrated phosphoric acid may be present in a concentration of 60 to 98 wt.%, more preferably 75 to 90 wt.%. The feed rate of phosphoric acid is preferably 0.01 to 0.10kg of phosphoric acid per minute per kg of alumina source, more preferably 0.03 to 0.07kg of phosphoric acid per minute per kg of alumina source.
In the embodiment, due to the introduction of the clay, the phosphorus-aluminum inorganic binder containing the first clay not only improves mass transfer and heat transfer among materials in the preparation process, but also avoids binder solidification caused by nonuniform local instant violent reaction and heat release and superstability of the materials, and the obtained binder has the same binding performance as the phosphorus-aluminum binder prepared by a method without the introduction of the clay; in addition, the method introduces clay, especially rectorite with a layered structure, improves the heavy oil conversion capability of the catalyst composition, and enables the obtained auxiliary agent to have better selectivity.
The invention further provides application of the cracking assistant, namely a method for catalytic cracking of hydrocarbon oil, which comprises the following steps: under the condition of catalytic cracking, the hydrocarbon oil is contacted and reacted with the cracking assistant agent.
The method for catalytic cracking of hydrocarbon oil of the present invention comprises: under the catalytic cracking condition, the hydrocarbon oil is in contact reaction with a catalytic mixture containing the cracking auxiliary agent and a catalytic cracking catalyst; in the catalytic mixture, the content of the cracking assistant is 0.1-30 wt%.
Optionally, the catalytic cracking conditions comprise: the reaction temperature is 500-800 ℃; the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residue oil, vacuum residue oil, atmospheric wax oil, vacuum wax oil, straight-run wax oil, propane light/heavy deoiled oil, coker wax oil and coal liquefaction products.
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The X-ray diffraction (XRD) pattern was measured on a Nippon Denshi TTR-3 powder X-ray diffractometer. The instrument parameters are as follows: copper target (tube voltage 40kV, tube current 250 mA), scintillation counter, step width 0.02 degree, scanning speed 0.4 (degree)/min. The ZSM-5 molecular sieve synthesized by the method of example 1 in CN1056818C is used as a standard sample, and the crystallinity of the molecular sieve is determined to be 100%. The relative crystallinity is expressed in percentage by the ratio of the sum of the peak areas of five characteristic diffraction peaks between 22.5 and 25.0 degrees in terms of 2 theta of the X-ray diffraction spectra of the obtained product and the standard sample.
27 The analysis of the Al MAS-NMR spectrum was carried out on a Bruker AVANCE III WB spectrometer. The instrument parameters are as follows: the diameter of the rotor is 4mm, the resonance frequency spectrum is 156.4MHz, the pulse width is 0.4 mus (corresponding to 15-degree pulling chamfer angle), the magic angle rotating speed is 12kHz, and the delay time is 1s. 27 The characteristic peak 1 at 54 + -3 pp m is attributed to the four-coordinate framework aluminum, and the characteristic peak 2 at 39 + -3 ppm is attributed to the phosphorus-stabilized framework aluminum (distortion four) in the Al MAS-NMR spectrumCoordination framework aluminum). And each peak area is calculated by adopting an integration method after peak-splitting fitting is carried out on the characteristic peak.
X-ray photoelectron spectroscopy (XPS) was used to analyze the surface of molecular sieves and examine the migration of phosphorus compounds using an ESCALB 250 model X-ray photoelectron spectrometer from Thermo Fisher-VG. The instrument parameters are as follows: the excitation source was a monochromatized AlK α X-ray of 150W power, and the charge shift was corrected for the C1s peak (284.8 eV) from the contaminating carbon.
Temperature programmed desorption analysis (NH) 3 TPD) characterization was carried out using an AutoChen II temperature programmed adsorption apparatus from Micromeritics. Weighing 0.1-0.2 g of sample, putting the sample into a quartz adsorption tube, introducing carrier gas (the flow rate of high-purity He. is 50 mL/min), raising the temperature to 600 ℃ at the speed of 20 ℃/min, keeping the temperature for 2 hours, and removing water and air adsorbed on the sample; reducing the temperature to 100 ℃ at the speed of 20 ℃/min, and keeping the temperature for 30min; switching the carrier gas to NH 3 Keeping the temperature for 30min by using-He mixed gas to ensure that the sample is saturated by absorbing ammonia; reacting NH 3 Switching the-He mixed gas into high-purity He carrier gas, and purging for 1h to desorb material resources and adsorb ammonia; then the temperature is raised to 600 ℃ at the speed of 10 ℃/min, and a temperature programmed desorption curve is obtained. The desorbed ammonia is detected by a thermal conductivity cell. Converting the temperature programmed desorption curve into NH 3 After the desorption rate-temperature curve, the acid center density data is obtained by the spectrum resolution of the peak pattern.
The instruments and reagents used in the examples of the present invention are those commonly used by those skilled in the art unless otherwise specified.
The micro-reaction device is adopted to evaluate the influence of the catalytic cracking auxiliary agent on the yield of the low-carbon olefin in the catalytic cracking of the petroleum hydrocarbon. The prepared catalytic cracking assistant sample is aged for 17 hours at 800 ℃ under 100 percent water vapor in a fixed bed aging device, and is evaluated in a micro-reaction device, wherein the raw material oil is VGO or naphtha, and the evaluation conditions are that the reaction temperature is 620 ℃, the regeneration temperature is 620 ℃ and the agent-oil ratio is 3.2. Microreflective activity is determined using the ASTM D5154-2010 standard method.
The RIPP standard method provided by the invention can be found in petrochemical analysis methods, yang Cui, and the like, 1990 edition.
Some of the raw materials used in the examples had the following properties:
the pseudoboehmite is an industrial product produced by Shandong aluminum industry company, and the solid content is 60 percent by weight; the alumina sol is an industrial product, al, produced by Qilu division of medium petrochemical catalyst 2 O 3 The content was 21.5 wt%; the silica sol is an industrial product, siO, produced by the middle petrochemical catalyst Qilu division 2 Content 28.9 wt%, na 2 The O content is 8.9%; the kaolin is kaolin specially used for a catalytic cracking catalyst produced by Suzhou kaolin company, and the solid content is 78 weight percent; the rectorite is produced by Taixiang famous stream rectorite development Limited company in Hubei province, and the content of the quartz sand<3.5 Weight% of Al 2 O 3 39.0 wt.% of Na 2 The O content was 0.03% by weight, and the solid content was 77% by weight; SB aluminum hydroxide powder, manufactured by Condex, germany, al 2 O 3 The content was 75% by weight; gamma-alumina, manufactured by Condex, germany, al 2 O 3 The content was 95% by weight. Hydrochloric acid, chemical purity, concentration 36-38 wt%, and is produced in Beijing chemical plant.
Example 1A
Example 1A illustrates a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid of the present invention and a method of preparation.
Dissolving 18.5g of diammonium hydrogen phosphate in 60g of deionized water, stirring for 0.5h to obtain a phosphorus-containing aqueous solution, adding 108g of a hydrogen-type hierarchical pore ZSM-5 molecular sieve (provided by Qilu division, china petrochemical catalyst, inc., with a relative crystallinity of 88.6 percent and a silica/alumina molar ratio of 20.8) 2 The content of O is 0.017 percent by weight, and the specific surface area is 373m 2 (g), the total pore volume is 0.256ml/g, the mesoporous volume is 0.119ml/g, the average pore diameter is 5.8nm, the same is applied below), the mixture is immersed at 20 ℃ for 2 hours, dried in an oven at 110 ℃, externally applied with pressure and added with water, and treated at 450 ℃, 0.4Mpa and 60% of water vapor atmosphere for 0.5 hour, and the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is marked as PAZ-1.
Example 1B
Example 1B illustrates a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid and a method of preparation according to the present invention.
The process is the same as the process of example 1A, except that diammonium hydrogen phosphate, a hydrogen-type hierarchical pore ZSM-5 molecular sieve and water are mixed and beaten into slurry, and the temperature is raised to 100 ℃ and kept for 2 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample is marked as PBZ-1.
Comparative examples 1 to 1
Comparative examples 1-1 illustrate the current industry conventional process and the resulting phosphorus containing hierarchical pore ZSM-5 comparative sample.
The same as example 1A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃ for 3 hours. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve comparison sample is marked as D1-1.
Comparative examples 1 to 2
Comparative examples 1-2 illustrate comparative samples of phosphorus-containing hierarchical pore ZSM-5 molecular sieves obtained by atmospheric hydrothermal calcination. The difference from example 1A is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparison sample of the ZSM-5 molecular sieve containing phosphorus was obtained and was designated as D1-2.
The XPS elemental analysis data for the surfaces of PAZ-1, PBZ-1, D1-1 and D1-2 are shown in Table 1-1.
XRD crystallinity and BET pore parameters of PAZ-1, PBZ-1, D1-1 and D1-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h are shown in Table 1-2.
Of PAZ-1, PBZ-1, D1-1 27 The Al MAS-NMR spectra are shown in FIG. 1, FIG. 3, FIG. 4, and D1-2, respectively 27 The Al MAS-NMR spectrum is characterized by the same figure 4, in which different treatment conditions have a great influence on the coordination degree of phosphorus and framework aluminum, chemical shifts are attributed to four-coordinate framework aluminum at 54ppm, and four-coordinate framework aluminum which is attributed to phosphorus-stabilized combination of phosphorus and aluminum is a characteristic peak at 39 ppm. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in tables 1-3.
NH of PAZ-1 and D1-1 after being treated by 100 percent of water vapor at 800 ℃ and hydrothermal aging for 17 hours 3 the-TPD spectra are shown in FIG. 2 and FIG. 5, respectively, NH of PBZ-1 and D1-2 3 TPD spectra are characterized as in figures 2 and 5, respectively; the specific gravity data of the strong acid central peak area accounting for the total acid central peak area at desorption temperature above 200 ℃ are shown in tables 1-4.
TABLE 1-1
Tables 1 to 2
As can be seen from tables 1-2, after hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the phosphorus-containing hierarchical porous ZSM-5 molecular sieve still has high crystallization retention and Kong Canshu retention, the crystallization retention and the pore parameters are obviously compared with a sample, the crystallization retention is improved by 6 percent at most, and the hydrothermal stability is obviously improved.
Tables 1 to 3
Tables 1 to 4
| Sample name | The ratio of the strong acid central peak area to the total acid central peak area |
| PAZ-1 | 45％ |
| PBZ-1 | 52％ |
| D1-1 | 16％ |
| D1-2 | 24％ |
Example 2A
Example 2A illustrates a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid and method of preparation of the present invention.
Dissolving 18.5g of diammonium hydrogen phosphate in 120g of deionized water, stirring for 0.5h to obtain a phosphorus-containing aqueous solution, adding 108g of a hydrogen-type hierarchical pore ZSM-5 molecular sieve, soaking at 20 ℃ for 2 hours by adopting a soaking method, drying in an oven at 110 ℃, externally applying pressure and adding water, and treating for 2h at 600 ℃, 0.4Mpa and 50% of water vapor atmosphere to obtain a phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample, wherein the sample is marked as PAZ-2.
Example 2B
Example 2B illustrates a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid and a method of preparation according to the present invention.
The process is the same as the process of example 2A, except that diammonium hydrogen phosphate, a hydrogen-type hierarchical pore ZSM-5 molecular sieve and water are mixed and beaten into slurry, and the slurry is heated to 70 ℃ and kept for 2 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample is marked as PBZ-2.
Comparative example 2-1
Comparative example 2-1 illustrates the prior art process and the resulting phosphorus containing hierarchical pore ZSM-5 comparative sample.
The same as example 2A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃ for 2 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve comparison sample is marked as D2-1.
Comparative examples 2 to 2
Comparative examples 2-2 illustrate comparative samples of phosphorus-containing hierarchical pore ZSM-5 molecular sieves obtained by atmospheric hydrothermal calcination.
The difference from example 2A is that the calcination conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of the phosphorous containing ZSM-5 molecular sieve was obtained and designated D2-2.
The XPS elemental analysis data for the surfaces of PAZ-2, PBZ-2, D2-1 and D2-2 are shown in Table 2-1.
XRD crystallinity and BET pore parameters of PAZ-2, PBZ-2, D2-1 and D2-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h are shown in Table 2-2.
Of PAZ-2, PBZ-2 27 The Al MAS-NMR spectrum has the characteristics of FIG. 1 and FIG. 3, respectively. Of D2-1, D2-2 27 The Al MAS-NMR spectrum has the characteristics of FIG. 4. 27 The data of the peak area ratio of the Al MAS-NMR spectrum are shown in tables 2-3.
NH of PAZ-2 and PBZ-2 treated by 100 percent of water vapor at 800 ℃ and 17 hours of hydrothermal aging 3 NH of-TPD spectrum characterized by the same pattern as in FIGS. 2, D2-1, D2-2 3 The characteristics of TPD spectrogram are shown in the same figure 5, and the specific gravity data of the strong acid central peak area accounting for the total acid central peak area at the desorption temperature of more than 200 ℃ are shown in tables 2-4.
TABLE 2-1
Tables 2 to 2
As can be seen from the table 2-2, after the phosphorus-containing hierarchical porous ZSM-5 molecular sieve is subjected to hydrothermal aging treatment at 800 ℃, 100% of water vapor and 17 hours, the phosphorus-containing hierarchical porous ZSM-5 molecular sieve still has high crystallization retention and Kong Canshu retention, the crystallization retention and the pore parameters are obviously compared with a sample, the crystallization retention is improved by 9 percentage points at most, and the hydrothermal stability is obviously improved.
Tables 2 to 3
Tables 2 to 4
Example 3A
Example 3A illustrates a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid of the present invention and a method of preparation.
Dissolving 11.8g of phosphoric acid in 60g of deionized water at normal temperature, stirring for 2 hours to obtain a phosphorus-containing aqueous solution, adding the phosphorus-containing aqueous solution into 108g of a hydrogen-type hierarchical pore ZSM-5 molecular sieve, soaking for 4 hours at 20 ℃ by adopting a soaking method, drying in an oven at 110 ℃, and treating for 2 hours at 430 ℃ under 0.4Mpa in a 100% water vapor atmosphere to obtain the phosphorus-modified hierarchical pore ZSM-5 molecular sieve, wherein the molecular sieve is marked as PAZ-3.
Example 3B
Example 3B illustrates a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid of the present invention and a method of preparation.
The same materials, proportioning, drying and calcining as in example 3A except that the phosphorus-containing aqueous solution at 80 ℃ was mixed and contacted with the hydrogen-type multi-stage pore ZSM-5 molecular sieve heated to 80 ℃ for 4 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve is marked as PBZ-3.
Comparative example 3-1
Comparative example 3-1 illustrates the prior art process and the resulting phosphorus containing hierarchical pore ZSM-5 comparative sample.
The same as example 3A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃ for 2 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve comparison sample is marked as D3-1.
Comparative examples 3 to 2
Comparative example 3-2 illustrates a comparative sample of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The difference from example 3A is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of the phosphorous containing ZSM-5 molecular sieve was obtained and was designated D3-2.
The XPS elemental analysis data for the surfaces of PAZ-3, PBZ-3, D3-1 and D3-2 are shown in Table 3-1.
XRD crystallinity and BET pore parameters of PAZ-3, PBZ-3, D3-1 and D3-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h are shown in Table 3-2.
Of PAZ-3, PBZ-3 27 The Al MAS-NMR spectrum has the characteristics of FIG. 1 and FIG. 3, respectively. Of D3-1, D3-2 27 The Al MAS-NMR spectrum has that of FIG. 4And (5) characterizing. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in tables 3-3.
NH of PAZ-3 and PBZ-3 treated by 100 percent of water vapor at 800 ℃ and 17 hours of hydrothermal aging 3 NH of TPD spectrum characterized by the same pattern as in FIGS. 3, D3-1, D3-2 3 The TPD spectrum is characterized as in figure 5, 27 the data of the peak area ratio of the Al MAS-NMR spectrum are shown in tables 3-3.
NH of PAZ-3, PBZ-3, D3-1 and D3-2 after 100 percent of water vapor and 17h of hydrothermal aging treatment at 800 DEG C 3 In a TPD spectrogram, specific gravity data of the area of the strong acid center peak occupying the total acid center peak area at the desorption temperature of more than 200 ℃ are shown in a table 3-4.
TABLE 3-1
TABLE 3-2
As can be seen from the table 3-2, after the phosphorus-containing hierarchical porous ZSM-5 molecular sieve is subjected to hydrothermal aging treatment at 800 ℃, 100% of water vapor and 17 hours, the phosphorus-containing hierarchical porous ZSM-5 molecular sieve still has high crystallization retention and Kong Canshu retention, the crystallization retention and the pore parameters are obviously compared with a sample, the crystallization retention is improved by 11 percentage points at most, and the hydrothermal stability is obviously improved.
Tables 3 to 3
Tables 3 to 4
Example 4A
Example 4A illustrates a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid of the present invention and a method of preparation.
Dissolving 9.3g of diammonium hydrogen phosphate in 120g of deionized water at normal temperature, stirring for 0.5h to obtain a phosphorus-containing aqueous solution, adding the phosphorus-containing aqueous solution into 108g of a hydrogen-type hierarchical pore ZSM-5 molecular sieve, soaking for 2 hours at 20 ℃ by adopting a soaking method, drying in an oven at 110 ℃, and treating for 2h at 350 ℃, 0.2Mpa and 100% steam atmosphere to obtain the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, wherein the molecular sieve is marked as PAZ-4.
Example 4B
Example 4B illustrates a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid and a method of preparation according to the present invention.
The material and the mixture ratio are the same as those of the example 4A, except that diammonium hydrogen phosphate, a hydrogen type hierarchical pore ZSM-5 molecular sieve and water are mixed and beaten into slurry, and then the temperature is raised to 70 ℃ and the slurry is kept for 2 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample is marked as PBZ-4.
Comparative example 4-1
Comparative example 4-1 illustrates the prior art process and the resulting phosphorus containing hierarchical pore ZSM-5 comparative sample.
The same as example 1A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃ for 2 hours. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve comparison sample is marked as D4-1.
Comparative examples 4 to 2
Comparative example 4-2 illustrates a comparative sample of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The difference from example 1A is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of the phosphorous containing ZSM-5 molecular sieve was obtained and was designated D4-2.
The XPS elemental analysis data for surfaces of PAZ-4, PBZ-4, D4-1 and D4-2 are shown in Table 4-1.
XRD crystallinity and BET pore parameters of PAZ-4, PBZ-4, D4-1 and D4-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h are shown in Table 4-2.
Of PAZ-4, PBZ-4 27 The Al MAS-NMR spectrum has the characteristics of FIG. 1 and FIG. 3, respectively. Of D4-1, D4-2 27 The Al MAS-NMR spectrum has the characteristics of FIG. 4. 27 The data of the peak area ratio of the Al MAS-NMR spectrum are shown in tables 4-3.
NH of PAZ-4 and PBZ-4 treated by 100 percent of water vapor at 800 ℃ and 17 hours of hydrothermal aging 3 NH of-TPD spectrum characterized by the same pattern as in FIGS. 2, D4-1 and D4-2 3 The characteristics of the TPD spectrogram are as shown in figure 5, and the specific gravity data of the area of the strong acid central peak occupying the total acid central peak area at the desorption temperature of more than 200 ℃ are shown in a table 4-4.
TABLE 4-1
TABLE 4-2
As can be seen from Table 4-2, after hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the phosphorus-containing hierarchical porous ZSM-5 molecular sieve still has high crystallization retention and Kong Canshu retention, the crystallization retention and the pore parameters are obviously compared with a sample, the crystallization retention is improved by 15 percent at most, and the hydrothermal stability is obviously improved.
Tables 4 to 3
Tables 4 to 4
Example 5A
Example 5A illustrates a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid of the present invention and a method of preparation.
Dissolving 9.7g of trimethyl phosphate in 80g of deionized water at 90 ℃, stirring for 1h to obtain a phosphorus-containing aqueous solution, adding the phosphorus-containing aqueous solution into 108g of a hydrogen-type hierarchical pore ZSM-5 molecular sieve, modifying by adopting an impregnation method, impregnating for 8 hours at 20 ℃, drying in an oven at 110 ℃, and carrying out pressurized hydrothermal roasting treatment for 4h at 500 ℃, 0.6Mpa and 40% of steam atmosphere to obtain a phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample, which is marked as PAZ-5.
Example 5B
Example 5B illustrates a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid of the present invention and a method of preparation.
The procedure of the same materials, mixing, drying and calcining as in example 5A is different in that trimethyl phosphate, hydrogen type multi-stage pore ZSM-5 molecular sieve and water are mixed and beaten into slurry, and then the temperature is raised to 120 ℃ and kept for 8 hours. And marking the obtained phosphorus modified hierarchical pore ZSM-5 molecular sieve as PBZ-5.
Comparative example 5-1
Comparative example 5-1 illustrates the prior art process and the resulting phosphorus containing hierarchical pore ZSM-5 comparative sample.
The same as example 5A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃ for 2 hours. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve comparison sample is marked as D5-1.
Comparative examples 5 to 2
Comparative example 5-2 illustrates a comparative sample of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The difference from example 5A is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of the phosphorous containing ZSM-5 molecular sieve was obtained and was designated D5-2.
The XPS elemental analysis data for surfaces of PAZ-5, PBZ-5, D5-1, and D5-2 are shown in Table 5-1.
XRD crystallinity and BET pore parameters of PAZ-5, PBZ-5, D5-1 and D5-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h are shown in Table 5-2.
Of PAZ-5, PBZ-5 27 The Al MAS-NMR spectrum has the characteristics of FIG. 1 and FIG. 3, respectively. Of D5-1, D5-2 27 The Al MAS-NMR spectrum has the characteristics of FIG. 4. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 5-3.
NH of PAZ-5 and PBZ-5 treated by 100 percent of water vapor at 800 ℃ and 17 hours of hydrothermal aging 3 NH of the TPD spectrum with the same characteristics as those of FIG. 2, D5-1 and D5-2 3 The characteristics of TPD spectrogram are as shown in figure 5, the desorption temperature is above 200 ℃, the peak area of the strong acid center isThe specific gravity data of the total acid center peak area are shown in the table 5-4.
TABLE 5-1
TABLE 5-2
As can be seen from Table 5-2, after hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the phosphorus-containing hierarchical porous ZSM-5 molecular sieve still has high crystal retention and Kong Canshu retention, the crystal retention and the pore parameters are obviously compared with a sample, the crystal retention is improved by 14 percent at most, and the hydrothermal stability is obviously improved.
Tables 5 to 3
Tables 5 to 4
Example 6A
Example 6A illustrates a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid and method of preparation of the present invention.
Dissolving 13.2g of boron phosphate in 100g of deionized water at 100 ℃, stirring for 3h to obtain a phosphorus-containing aqueous solution, adding the phosphorus-containing aqueous solution into 108g of a hydrogen-type hierarchical pore ZSM-5 molecular sieve, soaking for 2h at 20 ℃ by adopting a soaking method, drying in an oven at 110 ℃, and carrying out pressurized hydrothermal roasting treatment for 4h at 350 ℃, 0.4Mpa and 60% steam atmosphere to obtain a phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample, wherein the sample is marked as PAZ-6.
Example 6B
Example 6B illustrates a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid and a method of preparation according to the present invention.
The same materials and mixture ratio as in example 6A, except that boron phosphate, hydrogen type multi-stage hole ZSM-5 molecular sieve and water are mixed and beaten into slurry, and then the temperature is raised to 150 ℃ and kept for 2 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve is marked as PBZ-6.
Comparative example 6-1
Comparative example 6-1 illustrates the prior art process and the resulting phosphorus containing hierarchical pore ZSM-5 comparative sample.
The same as example 6A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃ for 2 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve comparison sample is marked as D6-1.
Comparative examples 6 to 2
Comparative example 6-2 illustrates a comparative sample of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The difference from example 6A is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparison sample of the ZSM-5 molecular sieve containing phosphorus was obtained and was designated as D6-2.
The XPS elemental analysis data for the surfaces of PAZ-6, PBZ-6, D6-1 and D6-2 are shown in Table 6-1.
XRD crystallinity and BET pore parameters of PAZ-6, PBZ-6, D6-1 and D6-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h are shown in Table 6-2.
Of PAZ-6, PBZ-6 27 The Al MAS-NMR spectrum has the characteristics of FIG. 1 and FIG. 3, respectively. Of D6-1, D6-2 27 The Al MAS-NMR spectrum has the characteristics of FIG. 4. 27 The data of the peak area ratio of the Al MAS-NMR spectrum are shown in Table 6-3.
NH of PAZ-6 and PBZ-6 treated by 100 percent of water vapor at 800 ℃ and 17 hours of hydrothermal aging 3 NH of-TPD spectrum characterized by the same pattern as in FIGS. 2, D6-1 and D6-2 3 The characteristics of the TPD spectrogram are shown in the same figure 5, and the proportion data of the strong acid center peak area accounting for the total acid center peak area at the desorption temperature of more than 200 ℃ are shown in a table 6-4.
TABLE 6-1
TABLE 6-2
As can be seen from Table 6-2, after hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the phosphorus-containing hierarchical porous ZSM-5 molecular sieve still has high crystal retention and Kong Canshu retention, the crystal retention and the pore parameters are obviously compared with a sample, the crystal retention is improved by 8 percent at most, and the hydrothermal stability is obviously improved.
Tables 6 to 3
Tables 6 to 4
Example 7A
Example 7A illustrates a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid of the present invention and a method of preparation.
Dissolving 16.3g of triphenyl phosphine in 80g of deionized water, stirring for 2 hours to obtain a phosphorus-containing aqueous solution, adding the phosphorus-containing aqueous solution into 108g of a hydrogen-type hierarchical pore ZSM-5 molecular sieve, modifying by adopting an impregnation method, impregnating for 4 hours at 20 ℃, drying in an oven at 110 ℃, carrying out pressurized hydrothermal roasting treatment for 2 hours at 600 ℃, 1.0Mpa and 50% steam atmosphere, and marking the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample as PAZ-7.
Example 7B
Example 7B illustrates a phosphorus-containing hierarchical pore ZSM-5 molecular sieve in a cracking aid of the present invention and a method of preparation.
The same materials and proportions as in example 7A except that the 80 ℃ phosphorus-containing aqueous solution was mixed with the 80 ℃ hydrogen-type multi-stage pore ZSM-5 molecular sieve and contacted for 4 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample is marked as PBZ-7.
Comparative example 7-1
Comparative example 7-1 illustrates the prior art process and the resulting phosphorus containing hierarchical pore ZSM-5 comparative sample.
The same as example 7A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃ for 2 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve comparison sample is marked as D7-1.
Comparative examples 7 and 2
Comparative example 7-2 illustrates a comparative sample of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The same as example 7A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of the phosphorous containing ZSM-5 molecular sieve was obtained and was designated D7-2.
The XPS elemental analysis data for the surfaces of PAZ-7, PBZ-7, D7-1, D7-2 are shown in Table 7-1.
XRD crystallinity and BET pore parameters of PAZ-7, PBZ-7, D7-1 and D7-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h are shown in Table 7-2.
Of PAZ-7, PBZ-7 27 The Al MAS-NMR spectrum has the characteristics of FIG. 1 and FIG. 3, respectively. Of D7-1, D7-2 27 The Al MAS-NMR spectrum has the characteristics of FIG. 4. 27 The data of the peak area ratio of the Al MAS-NMR spectrum are shown in Table 7-3.
NH of PAZ-7 and PBZ-7 treated by 100 percent of water vapor at 800 ℃ and 17 hours of hydrothermal aging 3 NH of the TPD spectrum with the same characteristics as those of FIG. 2, D7-1 and D7-2 3 The characteristics of the TPD spectrogram are as shown in figure 5, and the specific gravity data of the area of the strong acid central peak occupying the total acid central peak area at the desorption temperature of more than 200 ℃ are shown in a table 7-4.
TABLE 7-1
TABLE 7-2
As can be seen from Table 7-2, after hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the phosphorus-containing hierarchical porous ZSM-5 molecular sieve still has high crystal retention and Kong Canshu retention, the crystal retention and the pore parameters are obviously compared with a sample, the crystal retention is improved by 12 percent at most, and the hydrothermal stability is obviously improved.
Tables 7 to 3
Tables 7 to 4
Examples 8-11 illustrate the use of a phosphorus aluminum inorganic binder in the cleavage aid of the present invention.
Example 8
1.91 kg of pseudoboehmite (containing Al) 2 O 3 1.19 kg), 0.56 kg kaolin (0.5 kg on a dry basis) and 3.27 kg decationized water, stirring and adding 5.37 kg concentrated phosphoric acid (85% by mass) into the slurry, wherein the adding speed of the phosphoric acid is 0.04 kg phosphoric acid/min/kg alumina source, heating to 70 ℃, and then reacting for 45 minutes at the temperature to obtain the phosphorus-aluminum inorganic binder. The material ratios are shown in Table 8, sample number Binder1.
Examples 9 to 11
The phosphor-aluminum inorganic Binder was prepared by the method of example 8, and the material ratios are shown in Table 8, sample numbers Binder2, binder3, and Binder4.
TABLE 8
Examples 12-18 illustrate the cracking aids of the present invention, and comparative examples 12-18 illustrate the catalytic cracking comparative aids.
Example 12-1
The multistage containing phosphorus prepared in example 1A was takenAdding decationized water and aluminum sol into a porous molecular sieve PAZ-1, kaolin and pseudo-boehmite, pulping for 120 minutes to obtain slurry with the solid content of 30 weight percent, adding hydrochloric acid to adjust the pH value of the slurry to be 3.0, continuously pulping for 45 minutes, then adding the phosphorus-aluminum inorganic Binder Binder1 prepared in the example 8, stirring for 30 minutes, spray-drying the obtained slurry to obtain microspheres, roasting the microspheres for 1 hour at 500 ℃ to obtain a cracking assistant sample with the serial number CAZ1-1, wherein the mixture ratio of the molecular sieve to the kaolin to the pseudo-boehmite is 50 percent, and the mixture ratio of the cracking assistant sample to the pseudo-boehmite is 23 percent, 18 percent of the Binder1 to the pseudo-boehmite (Al is Al) 2 O 3 Calculated as Al) 5%, alumina sol (calculated as Al) 2 O 3 Calculated) is 4 percent.
The reaction performance evaluation of 100% of the balance agent and the cracking aid CAZ1-1 prepared by doping the balance agent into example 12-1 was performed by using a fixed bed micro-reactor to demonstrate the catalytic cracking reaction effect of the catalytic cracking aid provided by the present disclosure.
The auxiliary agent CAZ1-1 is aged for 17 hours at 800 ℃ under the condition of 100% steam atmosphere. Mixing aged CAZ1-1 with industrial FCC equilibrium catalyst (industrial FCC equilibrium catalyst of DVR-3, light oil with micro-reverse activity of 63). And (3) loading the mixture of the balancing agent and the auxiliary agent into a fixed bed micro-reactor, and carrying out catalytic cracking on the raw oil shown in the table 9 under the evaluation conditions of the reaction temperature of 620 ℃, the regeneration temperature of 620 ℃ and the agent-oil ratio of 3.2. The results of the reaction are given in Table 10, which includes the blank test cases.
TABLE 9
| Item | Raw oil |
| Density (20 ℃ C.), g/cm 3 | 0.9334 |
| Dioptric light (70 degree) | 1.5061 |
| Four components, m% | |
| Saturated hydrocarbons | 55.6 |
| Aromatic hydrocarbons | 30 |
| Glue | 14.4 |
| Asphaltenes | <0.1 |
| Freezing point, DEG C | 34 |
| Metal content, ppm | |
| Ca | 3.9 |
| Fe | 1.1 |
| Mg | <0.1 |
| Na | 0.9 |
| Ni | 3.1 |
| Pb | <0.1 |
| V | 0.5 |
| C m％ | 86.88 |
| H m％ | 11.94 |
| S m％ | 0.7 |
| M% of carbon residue | 1.77 |
Example 12-2
The difference from example 12-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-1 is replaced with the phosphorus-containing hierarchical pore molecular sieve PBZ-1 prepared in example 1B. Preparing a cracking assistant sample with the number of CAZ1-2.
The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 10.
Comparative example 12-1
The difference from example 12-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-1 was replaced with comparative sample D1-1 of comparative example 1-1. A comparative sample of the cracking aid was prepared and numbered DCAZ1-1.
The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 10.
Comparative examples 12 to 2
The difference from example 12-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-1 was replaced with comparative sample D1-2 of comparative example 1-2. A comparative sample of the cracking aid was prepared and numbered DCAZ1-2.
The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 10.
Watch 10
Example 13-1
The difference from example 12-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-1 was replaced with the phosphorus-containing hierarchical pore molecular sieve PAZ-2 prepared in example 2A. And preparing a cracking assistant sample with the number of CAZ2-1.
The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 11.
Example 13-2
The difference from example 13-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-2 therein is replaced with the phosphorus-containing hierarchical pore molecular sieve PBZ-2 prepared in example 2B. Preparing a cracking assistant sample with the number of CAZ2-2.
The evaluation was made in the same manner as in example 13-1, and the results are shown in Table 11.
Comparative example 13-1
The difference from example 13-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-2 was replaced with comparative sample D2-1 of comparative example 2-1. A comparative sample of the cracking aid was prepared and numbered DCAZ2-1.
The evaluation was made in the same manner as in example 13-1, and the results are shown in Table 11.
Comparative examples 13 to 2
The difference from example 13-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-2 is replaced with comparative sample D2-2 of comparative example 2-2. A comparative sample of cracking aid was prepared and numbered DCAZ2-2.
The evaluation was made in the same manner as in example 13-1, and the results are shown in Table 11.
TABLE 11
Example 14-1
The same as example 12-1 except that the phosphorus-containing hierarchical pore molecular sieve PAZ-1 was replaced with the phosphorus-modified molecular sieve PAZ-3 prepared in example 3A. Preparing a cracking assistant sample with the number of CAZ3-1.
The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 12.
Example 14-2
The difference from example 14-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-3 was replaced with the phosphorus-modified molecular sieve PBZ-3 prepared in example 3B. Preparing a cracking assistant sample with the number of CAZ3-2.
The evaluation was made in the same manner as in example 14-1, and the results are shown in Table 12.
Comparative example 14-1
The difference from example 14-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-3 was replaced with comparative sample D3-1 of comparative example 3-1. A comparative sample of the cracking aid was prepared and numbered DCAZ3-1.
The evaluation was made in the same manner as in example 14-1, and the results are shown in Table 12.
Comparative examples 14 to 2
The difference from example 14-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-3 was replaced with comparative sample D3-2 of comparative example 3-2. A comparative sample of the cracking aid was prepared and numbered DCAZ3-2.
The evaluation was made in the same manner as in example 14-1, and the results are shown in Table 12.
TABLE 12
Example 15-1
The difference from example 12-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-1 therein is replaced with the phosphorus-containing hierarchical pore molecular sieve PAZ-4 prepared in example 4A. Preparing a cracking assistant sample with the number of CAZ4-1.
The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 13.
Example 15-2
The difference from example 15-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-4 therein is replaced with the phosphorus-containing hierarchical pore molecular sieve PBZ-4 prepared in example 4B. Preparing a cracking assistant sample with the number of CAZ4-2.
The evaluation was made in the same manner as in example 15-1, and the results are shown in Table 13.
Comparative example 15-1
The difference from example 15-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-4 therein was replaced with comparative sample D4-1 of comparative example 4-1. A comparative sample of the cracking aid was prepared and numbered DCAZ4-1.
The evaluation was made in the same manner as in example 15-1, and the results are shown in Table 13.
Comparative examples 15 to 2
The difference from example 15-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-4 therein was replaced with comparative sample D4-2 of comparative example 4-2. A comparative sample of the cracking aid was prepared and numbered DCAZ4-2.
The evaluation was made in the same manner as in example 15-1, and the results are shown in Table 13.
Watch 13
Example 16-1
The difference from example 12-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-1 therein is replaced with the phosphorus-containing hierarchical pore molecular sieve PAZ-5 prepared in example 5A. A cracking assistant sample is prepared, and the number is CAZ5-1.
The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 14.
Example 16-2
The difference from example 16-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-5 therein is replaced with the phosphorus-containing hierarchical pore molecular sieve PBZ-5 prepared in example 5B. Preparing a cracking assistant sample with the number of CAZ5-2.
The evaluation was made in the same manner as in example 16-1, and the results are shown in Table 14.
Comparative example 16-1
The difference from example 16-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-5 therein was replaced with comparative sample D5-1 of comparative example 5-1. A comparative sample of the cracking aid was prepared and numbered DCAZ5-1.
The evaluation was made in the same manner as in example 16-1, and the results are shown in Table 14.
Comparative example 16-2
The difference from example 16-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-5 was replaced with comparative sample D5-2 of comparative example 5-2. A comparative sample of the cracking aid was prepared and numbered DCAZ5-2.
The evaluation was made in the same manner as in example 16-1, and the results are shown in Table 14.
TABLE 14
Example 17-1
The same as in example 12-1 except that the phosphorus-containing hierarchical pore molecular sieve PAZ-1 was replaced with the phosphorus-containing hierarchical pore molecular sieve PAZ-6 prepared in example 6A. Preparing a cracking assistant sample with the number of CAZ6-1.
The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 15.
Example 17-2
The difference from example 17-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-6 is replaced with the phosphorus-containing hierarchical pore molecular sieve PBZ-6 prepared in example 6B. Preparing a cracking assistant sample with the number of CAZ6-2.
The evaluation was made in the same manner as in example 17-1, and the results are shown in Table 15.
Comparative example 17-1
The difference from example 17-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-6 was replaced with comparative sample D6-1 of comparative example 6-1. A comparative sample of the cracking aid was prepared and numbered DCAZ6-1.
The evaluation was made in the same manner as in example 17-1, and the results are shown in Table 15.
Comparative examples 17 to 2
The difference from example 17-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-66 was replaced with comparative sample D6-2 of comparative example 6-2. A comparative sample of the cracking aid was prepared and numbered DCAZ6-2.
The evaluation was made in the same manner as in example 17-1, and the results are shown in Table 15.
Watch 15
Example 18-1
The difference from example 12-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-1 therein was replaced with the phosphorus-containing hierarchical pore molecular sieve PAZ-7 prepared in example 7A. Preparing a cracking assistant sample with the number of CAZ7-1.
The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 16.
Example 18-2
The difference from example 18-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-7 therein is replaced with the phosphorus-containing hierarchical pore molecular sieve PBZ-7 prepared in example 7B. Preparing a cracking assistant sample with the number of CAZ7-2.
The evaluation was made in the same manner as in example 18-1, and the results are shown in Table 16.
Comparative example 18-1
The difference from example 18-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-7 therein was replaced with comparative sample D7-1 of comparative example 7-1. A comparative sample of the cracking aid was prepared and numbered DCAZ7-1.
The evaluation was made in the same manner as in example 18-1, and the results are shown in Table 16.
Comparative example 18-2
The difference from example 18-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-7 was replaced with comparative sample D7-2 of comparative example 7-2. A comparative sample of the cracking aid was prepared and numbered DCAZ7-2.
The evaluation was made in the same manner as in example 18-1, and the results are shown in Table 16.
TABLE 16
Example 19-1
The difference from example 12-1 is that the phosphorus aluminum inorganic Binder was replaced with Binder2 prepared in example 9. The cracking assistant is prepared, and the number is CAZ8-1. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 17.
Example 19-2
The difference from example 12-2 is that the phosphorus aluminum inorganic Binder was replaced with Binder2 prepared in example 9. The cracking assistant is prepared, and the number is CAZ8-2. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 17.
Example 20-1
The difference from example 12-1 is that the phosphorous aluminum inorganic Binder was replaced with Binder3 prepared in example 10. The catalytic assistant is prepared, and the number is CAZ9-1. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 17.
Example 20-2
The difference from example 12-2 is that the phosphorous aluminum inorganic Binder was replaced with Binder3 prepared in example 10. The cracking assistant, number CAZ9-2, is prepared. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 17.
Example 21-1
The difference from example 12-1 is that the phosphorus aluminum inorganic Binder was replaced with Binder4 prepared in example 11. The cracking assistant is prepared, and the number is CAZ10-1. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 17.
Example 21-2
The difference from example 12-2 is that the phosphorus aluminum inorganic Binder was replaced with Binder4 prepared in example 11. The cracking assistant, number CAZ10-2, was prepared. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 17.
TABLE 17
Example 22-1
The same as example 12-1, except that the phosphorus-containing multistage pore ZSM-5 molecular sieve sample PAZ-1 wt%, kaolin clay 18 wt%, a aluminophosphate inorganic Binder Binder3 22 wt%, pseudoboehmite 10wt%, and alumina sol 5 wt%. The cracking assistant, number CAZ11-1, was prepared.
The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 18.
Example 22-2
The same as in example 22-1, except that PAZ-1 was replaced with PBZ-1. The cracking assistant, number CAZ11-2, is prepared.
The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 18.
Comparative example 22-1
The same as in example 23-1, except that PAZ-1 was replaced with D1-1. A comparative sample of the cracking aid was prepared and numbered DCAZ11-1. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 18.
Comparative example 22-2
The same as in example 22-1, except that PAZ-1 was replaced with D1-2. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ11-2. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 18.
Watch 18
Example 23-1
The same as example 12-1, except that the phosphorus-containing multistage pore ZSM-molecular sieve sample was PAZ-2 wt%, kaolin 24 wt%, aluminophosphate inorganic Binder Binder4 20 wt%, pseudoboehmite 6 wt%, and silica sol 10 wt%. The cracking assistant, number CAZ12-1, is prepared. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 19.
Example 23-2
The difference from example 12-1 is that the phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample PAZ-1 was replaced with PBZ-2. The cracking assistant is prepared, and the number is CAZ12-2. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 19.
Comparative example 23-1
The same as example 23-1, except that PAZ-2 was replaced with D2-1. A comparative sample of the cracking aid was prepared, numbered DCAZ12-1. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 19.
Comparative example 23 to 2
The same as example 23-1 except that PAZ-2 was replaced with D2-2. A comparative sample of the cracking aid was prepared, numbered DCAZ12-2. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 19.
Watch 19
Example 24-1
Mixing the binder alumina sol with kaolin, and making into a solid content of 30 wt% with decationized waterThe slurry is stirred uniformly, the pH value of the slurry is adjusted to 2.8 by hydrochloric acid, the slurry is kept stand and aged for 1 hour at 55 ℃, then the phosphorus-containing hierarchical pore molecular sieve PAZ-1 prepared in the example 1A is added to form catalyst slurry (the solid content is 35 weight percent), and the catalyst slurry is continuously stirred and then spray-dried to prepare the microspherical catalyst. The microspheroidal catalyst was then calcined at 500 ℃ for 1 hour, then washed with ammonium sulfate (where ammonium sulfate: microspheroidal catalyst: water = 0.5. The mixture ratio is 50% of molecular sieve, 23% of kaolin and aluminium sol (Al) 2 O 3 Calculated) 27 percent.
Example 24-2
The difference from example 24-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-1 therein is replaced with the phosphorus-containing hierarchical pore molecular sieve PBZ-1 prepared in example 1B. Preparing a cracking assistant sample with the number of CAZ13-2.
The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 20.
Comparative example 24-1
The difference from example 24-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-1 therein was replaced with comparative sample D1-1 of comparative example 1-1. A comparative sample of cracking aid was prepared, numbered DCAZ13-1.
The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 20.
Comparative example 24-2
The difference from example 24-1 is that the phosphorus-containing hierarchical pore molecular sieve PAZ-1 was replaced with comparative sample D1-2 of comparative example 1-2. A comparative sample of cracking aid was prepared, numbered DCAZ13-2.
The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 20.
Example 25-1 and example 25-2
Example 25-1 and example 25-2 used the cleavage assistants CAZ1-1 and CAZ1-2 of example 12-1 and example 12-2, respectively. The feed oil for catalytic cracking was naphtha shown in Table 21.
The evaluation conditions were a reaction temperature of 620 ℃, a regeneration temperature of 620 ℃ and an agent-to-oil ratio of 3.2.
The weight composition of each catalytic cracking assistant-containing catalyst mixture and the reaction results are given in Table 22.
Comparative examples 25-1 and 25-2
The comparative catalytic cracking aids DCAZ1-1 and DCAZ1-2 of comparative example 12-1 and comparative example 12-2 were used, respectively, in the same manner as in example 25-1.
The weight composition of each of the catalyst mixtures containing the comparative sample of catalytic cracking aid and the results of the reaction are shown in Table 22.
TABLE 21
| Raw materials | Naphtha (a) |
| Density (20 ℃ C.)/(g.m) -3 ) | 735.8 |
| Vapor pressure/kPa | 32 |
| Mass group composition/%) | |
| Alkane hydrocarbons | 51.01 |
| N-alkanes | 29.40 |
| Cycloalkanes | 38.24 |
| Olefins | 0.12 |
| Aromatic hydrocarbons | 10.52 |
| Distillation range/. Degree.C | |
| First run | 45.5 |
| 5％ | 72.5 |
| 10％ | 86.7 |
| 30％ | 106.5 |
| 50％ | 120.0 |
| 70％ | 132.7 |
| 90％ | 148.5 |
| 95％ | 155.2 |
| End point of distillation | 166.5 |
TABLE 22
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (38)
1. The cracking assistant is characterized by comprising 5-75 wt% of phosphorus-containing hierarchical pore ZSM-5 molecular sieve based on the dry basis of the cracking assistant; the phosphorus-containing hierarchical pore ZSM-5 molecular sieve has the advantages that the proportion of the mesopore volume to the total pore volume is more than 10%, the average pore diameter is 2-20 nm, the molar ratio of silicon oxide to aluminum oxide is more than or equal to 10, in surface XPS (X-ray diffraction) elemental analysis, n1/n2 is less than or equal to 0.08, n1 represents the mole number of phosphorus, and n2 represents the total mole number of silicon and aluminum.
2. The cracking aid of claim 1, wherein n1/n2 is 0.07 or less in XPS elemental analysis of the surface of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve.
3. The cracking aid of claim 1, wherein n1/n2 is 0.06 in XPS elemental analysis of the surface of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve.
4. The cracking aid of claim 1, wherein in the surface XPS elemental analysis of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, n1/n2 is 0.02-0.05.
5. The cracking aid of claim 1, wherein the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, 27 in Al MAS-NMR, the ratio of the peak area of the resonance signal with a chemical shift of 39. + -.3 ppm to the peak area of the resonance signal with a chemical shift of 54 ppm. + -.3 ppm is not less than 1.
6. The cracking aid of claim 1, wherein the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, 27 in Al MAS-NMR, the ratio of the peak area of the resonance signal with a chemical shift of 39. + -.3 ppm to the peak area of the resonance signal with a chemical shift of 54 ppm. + -.3 ppm is not less than 8.
7. The cracking aid of claim 1, wherein the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, 27 in Al MAS-NMR, the ratio of the peak area of the resonance signal with a chemical shift of 39. + -.3 ppm to the peak area of the resonance signal with a chemical shift of 54 ppm. + -.3 ppm is not less than 12.
8. The cracking aid of claim 1, wherein the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, 27 in the Al MAS-NMR, the ratio of the peak area of the resonance signal with a chemical shift of 39. + -.3 ppm to the peak area of the resonance signal with a chemical shift of 54 ppm. + -.3 ppm is 14 to 25.
9. The cracking aid of claim 1, wherein the phosphorus-containing hierarchical pore ZSM-5 molecular sieve has NH after 17h hydrothermal aging at 800 ℃ under 100% water vapor condition 3 In a TPD (thermoplastic vulcanizate) map, the proportion of the area of the strong acid central peak occupying the total acid central peak area at the desorption temperature of more than 200 ℃ is more than or equal to 45 percent.
10. The cracking aid of claim 1, wherein the phosphorus-containing hierarchical pore ZSM-5 molecular sieve has NH after 17h hydrothermal aging at 800 ℃ under 100% water vapor condition 3 In a TPD (thermoplastic vulcanizate) map, the proportion of the area of the strong acid central peak occupying the total acid central peak area at the desorption temperature of more than 200 ℃ is more than or equal to 50 percent.
11. The cracking aid of claim 1, wherein the phosphorus-containing hierarchical pore ZSM-5 molecular sieve has NH after 17h hydrothermal aging at 800 deg.C under 100% water vapor 3 In a TPD (thermoplastic vulcanizate) map, the proportion of the area of the strong acid central peak occupying the total acid central peak area at the desorption temperature of more than 200 ℃ is more than or equal to 60 percent.
12. The cracking aid of claim 1, wherein the phosphorus-containing hierarchical pore ZSM-5 molecular sieve has NH after 17h hydrothermal aging at 800 deg.C under 100% water vapor 3 In a TPD (thermoplastic vulcanizate) spectrum, the proportion of the area of a strong acid central peak occupying the area of a total acid central peak at the desorption temperature of more than 200 ℃ is 60 to 80 percent.
13. The cracking aid of claim 1, wherein the phosphorus-containing hierarchical pore ZSM-5 molecular sieve has a ratio of 0.01 to 2 when both phosphorus and aluminum are in molar terms.
14. The cracking aid of claim 1, wherein the phosphorus-containing hierarchical pore ZSM-5 molecular sieve has a ratio of 0.1 to 1.5 when both phosphorus and aluminum are in molar terms.
15. The cracking aid of claim 1, wherein the phosphorus-containing hierarchical pore ZSM-5 molecular sieve has a ratio of 0.2 to 1.5 when both phosphorus and aluminum are in molar terms.
16. A cracking aid according to claim 1, further comprising 1-40 wt% of a binder and 0-65 wt% of a second clay, based on the dry weight of the cracking aid.
17. A cleavage aid according to claim 16 wherein the binder comprises a phosphorus aluminium inorganic binder.
18. A cracking aid according to claim 17, wherein the aluminophosphate inorganic binder is an aluminophosphate glue and/or a first clay-containing aluminophosphate inorganic binder.
19. A preparation method of a cracking aid comprises the steps of mixing and pulping a phosphorus-containing hierarchical pore ZSM-5 molecular sieve and a binder with second clay which is optionally added, and spray-drying to obtain the cracking aid, and is characterized in that the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is obtained by contacting a phosphorus-containing compound solution with a hydrogen-type hierarchical pore ZSM-5 molecular sieve, drying, carrying out hydrothermal roasting treatment under external applied pressure and external water-added atmosphere environment, and recovering a product, wherein in surface XPS element analysis, n1/n2 is less than or equal to 0.08, wherein n1 represents the mole number of phosphorus, and n2 represents the total mole number of silicon and aluminum; in the hydrogen-type hierarchical pore ZSM-5 molecular sieve, the proportion of the mesopore volume to the total pore volume is more than 10%, the average pore diameter is 2-20 nm, and the molar ratio of silicon oxide to aluminum oxide is more than or equal to 10; the contact is that the water solution of the phosphorus-containing compound with the temperature of 0-150 ℃ and the hydrogen-type hierarchical pore ZSM-5 molecular sieve with the temperature of 0-150 ℃ are mixed and contacted for at least 0.1 hour at the basically same temperature by adopting an impregnation method, wherein the basically same temperature means that the temperature difference between the water solution of the phosphorus-containing compound and the hydrogen-type hierarchical pore ZSM-5 molecular sieve is +/-5 ℃; or, the contact is that after the phosphorus-containing compound, the hydrogen-type hierarchical pore ZSM-5 molecular sieve and water are mixed and beaten, the mixture is kept for at least 0.1 hour at the temperature of between 0 and 150 ℃; the apparent pressure of the atmosphere environment is 0.01-1.0 Mpa and contains 1-100% of water vapor; the hydrothermal roasting treatment is carried out at 200-800 ℃.
20. The method according to claim 19, wherein the phosphorus-containing compound is selected from an organic phosphide and/or an inorganic phosphide.
21. The method of claim 20, wherein the organophosphate is selected from the group consisting of trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium hydroxide, triphenylethyl phosphonium bromide, triphenylbutyl phosphonium bromide, triphenylbenzyl phosphonium bromide, hexamethylphosphoric triamide, dibenzyl diethyl phosphonium, 1,3-xylene bis triethyl phosphonium; the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.
22. The preparation method of claim 19, wherein the phosphorus-containing compound is calculated as phosphorus, the hydrogen-type hierarchical pore ZSM-5 molecular sieve is calculated as aluminum, and the molar ratio of the phosphorus-containing compound to the hydrogen-type hierarchical pore ZSM-5 molecular sieve is 0.01-2.
23. The preparation method of claim 19, wherein the phosphorus-containing compound is calculated as phosphorus, the hydrogen-type hierarchical pore ZSM-5 molecular sieve is calculated as aluminum, and the molar ratio of the phosphorus-containing compound to the hydrogen-type hierarchical pore ZSM-5 molecular sieve is 0.1-1.5.
24. The preparation method of claim 19, wherein the phosphorus-containing compound is calculated as phosphorus, the hydrogen-type hierarchical pore ZSM-5 molecular sieve is calculated as aluminum, and the molar ratio of the phosphorus-containing compound to the hydrogen-type hierarchical pore ZSM-5 molecular sieve is 0.3-1.3.
25. The method of claim 19, wherein the contacting is performed at 50 to 150 ℃ for 0.5 to 40 hours with a water sieve weight ratio of 0.5 to 1.
26. The method according to claim 19, wherein the atmosphere has an apparent pressure of 0.1 to 0.8MPa and contains 30 to 100% of water vapor.
27. The method according to claim 19, wherein the atmosphere has an apparent pressure of 0.1 to 0.8Mpa and contains 30 to 100% of water vapor; the hydrothermal roasting treatment is carried out at 300-500 ℃.
28. The method according to claim 19, wherein the atmosphere has an apparent pressure of 0.3 to 0.6MPa and contains 60 to 100% of water vapor.
29. The method of claim 19, wherein the binder is a phosphor-aluminum inorganic binder.
30. The method of claim 29, wherein the aluminophosphate inorganic binder is an aluminophosphate glue and/or a first clay-containing aluminophosphate inorganic binder; the phosphorus-aluminum inorganic binder containing the first clay contains Al based on the dry weight of the phosphorus-aluminum inorganic binder containing the first clay 2 O 3 15-40% by weight, calculated as P, of an aluminium component 2 O 5 45-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay calculated on dry basis, wherein the P/Al weight ratio of the phosphorus-aluminum inorganic binder containing the first clay is 1.0-6.0, the pH is 1-3.5, and the solid content is 15-60 wt%; the first clay comprises at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomaceous earth.
31. The method according to claim 19, wherein the second clay is at least one selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite, and diatomaceous earth.
32. The method of claim 19, wherein the binder comprises 3 to 39 wt% of the aluminophosphate inorganic binder on a dry basis and 1 to 30 wt% of the other inorganic binder on a dry basis, based on the total weight of the cracking aid.
33. The method of claim 19, wherein the method further comprises: carrying out first roasting, washing and optional drying treatment on a product obtained by spray drying to obtain the cracking assistant; wherein the roasting temperature of the first roasting is 300-650 ℃, and the roasting time is 0.5-8 h; the drying temperature is 100-200 ℃, and the drying time is 0.5-24 h.
34. The method of claim 30, further comprising: preparing the first clay-containing phosphorus-aluminum inorganic binder by adopting the following steps: pulping an alumina source, the first clay and water to disperse into slurry with solid content of 5-48 wt%; wherein the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, and the aluminum oxide source is 15 to 40 weight portions of Al 2 O 3 (ii) an alumina source in an amount greater than 0 parts by weight and not greater than 40 parts by weight of the first clay on a dry basis; adding concentrated phosphoric acid to the slurry in a weight ratio of P/Al =1-6 with stirring, and reacting the resulting mixed slurry at 50-99 ℃ for 15-90 minutes; in the P/Al, P is the weight of phosphorus in the phosphoric acid in terms of simple substance, and Al is the weight of aluminum in the alumina source in terms of simple substance.
35. A cleavage aid prepared by the method of any one of claims 19 to 34.
36. A method for catalytic cracking of hydrocarbon oil, comprising: a hydrocarbon oil is brought into contact with the cracking assistant according to any one of claims 1 to 18 and claim 35 under catalytic cracking conditions.
37. The method of claim 36, wherein the method comprises: under the catalytic cracking condition, the hydrocarbon oil is in contact reaction with a catalytic mixture containing the cracking auxiliary agent and a catalytic cracking catalyst; in the catalytic mixture, the content of the cracking assistant is 0.1-30 wt%.
38. The method of claim 36 or 37, wherein the catalytic cracking conditions comprise: the reaction temperature is 500-800 ℃; the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residue oil, vacuum residue oil, atmospheric wax oil, vacuum wax oil, straight-run wax oil, propane light/heavy deoiled oil, coker wax oil and coal liquefaction products.
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| CN202011169072.0A CN114471676B (en) | 2020-10-28 | 2020-10-28 | Cracking auxiliary agent |
| US17/996,178 US20230202851A1 (en) | 2020-04-13 | 2021-04-13 | Phosphorus-containing/phosphorus-modified zsm-5 molecular sieve, cracking auxiliary and cracking catalyst containing the same, process of preparing the same, and use thereof |
| TW110113299A TW202146336A (en) | 2020-04-13 | 2021-04-13 | Phosphorus-containing/phosphorus-modified zsm-5 molecular sieve, pyrolysis additive and pyrolysis catalyst containing same, preparation method therefor and application thereof |
| PCT/CN2021/086821 WO2021208884A1 (en) | 2020-04-13 | 2021-04-13 | Phosphorus-containing/phosphorus-modified zsm-5 molecular sieve, pyrolysis additive and pyrolysis catalyst containing same, preparation method therefor and application thereof |
| EP21788139.0A EP4137456A1 (en) | 2020-04-13 | 2021-04-13 | Phosphorus-containing/phosphorus-modified zsm-5 molecular sieve, pyrolysis additive and pyrolysis catalyst containing same, preparation method therefor and application thereof |
| KR1020227039663A KR20230002699A (en) | 2020-04-13 | 2021-04-13 | Phosphorus-containing/phosphorus-modified ZSM-5 molecular sieve, thermal decomposition additive and thermal decomposition catalyst including the same, manufacturing method thereof and application thereof |
| JP2022562488A JP2023523559A (en) | 2020-04-13 | 2021-04-13 | Phosphorus-Containing/Phosphorus-Modified ZSM-5 Molecular Sieves, Cracking Aids and Cracking Catalysts Containing The Same, Methods Of Making The Same, And Methods Of Using The Same |
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| CN103007990A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
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| CN107970999A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking containing phosphorous Beta molecular sieves and preparation method thereof |
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| CN101537365A (en) * | 2008-03-19 | 2009-09-23 | 中国石油天然气股份有限公司 | Modified method for improving hydrothermal stability of molecular sieve in FCC catalyst with high efficiency |
| CN103007990A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
| CN103785458A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
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