CN113546670A - Light gasoline cracking propylene yield-increasing catalyst containing silane modified hexagonal single crystal mesoporous material and preparation method and application thereof - Google Patents
Light gasoline cracking propylene yield-increasing catalyst containing silane modified hexagonal single crystal mesoporous material and preparation method and application thereof Download PDFInfo
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- CN113546670A CN113546670A CN202010328069.2A CN202010328069A CN113546670A CN 113546670 A CN113546670 A CN 113546670A CN 202010328069 A CN202010328069 A CN 202010328069A CN 113546670 A CN113546670 A CN 113546670A
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- mesoporous material
- catalyst
- hexagonal single
- single crystal
- oxide
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- 239000013335 mesoporous material Substances 0.000 title claims abstract description 138
- 239000013078 crystal Substances 0.000 title claims abstract description 130
- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 74
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 66
- 238000005336 cracking Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002808 molecular sieve Substances 0.000 claims abstract description 65
- 239000011148 porous material Substances 0.000 claims abstract description 65
- 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 65
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 46
- 239000010457 zeolite Substances 0.000 claims abstract description 46
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 18
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 28
- 238000000498 ball milling Methods 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 238000001125 extrusion Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- 239000012018 catalyst precursor Substances 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 12
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 12
- 235000011151 potassium sulphates Nutrition 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000007725 thermal activation Methods 0.000 claims description 10
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 9
- 241000219782 Sesbania Species 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001648 diaspore Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 17
- 150000001336 alkenes Chemical class 0.000 abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 238000000227 grinding Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- -1 olefin aromatic hydrocarbon Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
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- 238000002336 sorption--desorption measurement Methods 0.000 description 2
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- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003442 catalytic alkylation reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
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- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 239000001294 propane Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J29/405—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/615—100-500 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Oil, Petroleum & Natural Gas (AREA)
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- Catalysts (AREA)
Abstract
The invention relates to the field of petrochemical industry, and discloses a light gasoline cracking propylene yield-increasing catalyst containing a silane modified hexagonal single crystal mesoporous material, and a preparation method and application thereof. Wherein the catalyst comprises a zeolite molecular sieve with a high silica-alumina ratio and a silane modified hexagonal single crystal mesoporous material; wherein the silane modified hexagonal single crystal mesoporous material has a cubic body centered Im3m crystal phase structure, a pore channel structure is cubic cage-shaped, the average pore diameter is 4-15nm, the pore volume is 0.5-1.5mL/g, and the specific surface area is 400-600m2Per g, mean particle diameterThe diameter is 0.5-6 μm. The silane modified hexagonal single crystal mesoporous material provided by the invention is used for catalytic cracking reaction of light gasoline, not only can obtain more propylene, but also can reduce the olefin content of light gasoline products.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a light gasoline cracking propylene yield-increasing catalyst containing a silane modified hexagonal single crystal mesoporous material, and a preparation method and application thereof.
Background
In recent years, the demand for propylene, a very important basic organic chemical raw material, has been continuously increasing. Therefore, methods for increasing the yield of propylene have attracted general attention, including technologies for producing Propylene (PDH) by direct dehydrogenation of propane and producing low-carbon olefins (MTP) from coal. Compared with the new propylene yield increasing technology, the method for increasing the yield of the propylene by catalytic cracking of the olefin or the olefin-containing raw material has the characteristics of strong raw material adaptability, flexible product structure adjustment, high propylene/ethylene ratio and low production cost. The method for producing propylene by using light gasoline as cracking raw material is a very good way for increasing the yield of propylene. On the other hand, according to the requirements of environmental regulations, the requirements of China on the quality of vehicle fuels are gradually strict, and clean gasoline with high octane number and low olefin aromatic hydrocarbon content becomes the mainstream in the future. However, up to now, the quality of gasoline in China has a certain gap compared with that of other developed countries. Therefore, how to reduce the olefin content in light gasoline is also a technology that will be regarded as important in the future. The olefin above C4 in the light gasoline is converted into propylene through catalytic cracking reaction and separated, which is an effective way for reducing the olefin content in the light gasoline.
The zeolite molecular sieve is a catalyst with high selectivity and good heat resistance, and is widely used in the petrochemical fields of catalytic cracking, alkylation and the like. The main components of the light gasoline cracking catalyst disclosed in the prior art are microporous zeolite molecular sieves (including ZSM-5, ZSM-11, ZSM-35 or ZRP). Although unmodified zeolite molecular sieves have good initial activity in light gasoline cracking reactions, they are less stable. In order to improve the performance of the catalyst, many researchers have conducted intensive studies on the synthesis and modification of zeolite molecular sieves.
The zeolite molecular sieve used in the catalyst for cracking reaction of light gasoline belongs to the category of microporous molecular sieve, and although the microporous molecular sieve has an orderly and stable structure, the pore size is narrow, generally between 0.4 and 0.7 nm. In the olefin cracking reaction process, reactant molecules and product molecules with larger sizes are difficult to diffuse among narrow channels, contact between the reactants and active centers is influenced, and side reactions such as deep dehydrogenation and the like are easy to occur.
Therefore, the propylene selectivity of the light gasoline catalytic cracking yield-increasing propylene catalyst in the prior art is yet to be further improved.
Disclosure of Invention
The invention aims to overcome the defects of low propylene yield and poor stability of a light gasoline catalytic cracking yield-increasing propylene catalyst in the prior art, and provides a light gasoline cracking yield-increasing propylene catalyst containing a silane modified hexagonal single crystal mesoporous material, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides a light gasoline cracking propylene yield increasing catalyst, wherein the catalyst comprises a zeolite molecular sieve with a high silica-alumina ratio and a silane modified hexagonal single crystal mesoporous material; wherein the silane modified hexagonal single crystal mesoporous material has a cubic body centered Im3m crystal phase structure, a pore channel structure is cubic cage-shaped, the average pore diameter is 4-15nm, the pore volume is 0.5-1.5mL/g, and the specific surface area is 400-600m2(ii)/g, the average particle diameter is 0.5 to 6 μm.
The invention provides a preparation method of a light gasoline cracking propylene yield-increasing catalyst containing a silane modified hexagonal single-crystal mesoporous material, wherein the method comprises the following steps:
(1) mixing a high silica-alumina ratio zeolite molecular sieve, a silane modified hexagonal single crystal mesoporous material, a binder and an extrusion aid, then carrying out extrusion forming and carrying out first roasting treatment to obtain a catalyst precursor;
(2) in the presence of dilute nitric acid, dipping the catalyst precursor into an aqueous solution of an oxide precursor, and drying and carrying out second roasting treatment to obtain the light gasoline cracking propylene yield-increasing catalyst containing the silane modified hexagonal single crystal mesoporous material;
wherein the silane modified hexagonal single crystal mesoporous material has a cubic body centered Im3m crystal phase structure, a pore channel structure is cubic cage-shaped, the average pore diameter is 4-15nm, the pore volume is 0.5-1.5mL/g, and the specific surface area is 400-600m2(ii)/g, the average particle diameter is 0.5 to 6 μm.
The third aspect of the invention provides a light gasoline cracking propylene yield increasing catalyst containing the silane modified hexagonal single crystal mesoporous material, which is prepared by the method.
The invention provides an application of the light gasoline cracking propylene yield-increasing catalyst containing the silane modified hexagonal single crystal mesoporous material in catalytic cracking.
Through the technical scheme, compared with the prior art, the technical scheme provided by the invention has the following advantages:
(1) the main component of the light gasoline cracking catalyst provided by the invention is a mixture of a silane modified hexagonal single crystal mesoporous material and a zeolite molecular sieve with a high silica-alumina ratio, and a finished product catalyst simultaneously contains a microporous and mesoporous multistage ordered pore structure, so that rapid diffusion of reactant molecules and product molecules is facilitated, and side reactions are inhibited;
(2) the light gasoline cracking propylene yield-increasing catalyst provided by the invention is used for light gasoline cracking reaction, can effectively improve the conversion rate of olefin and the selectivity of propylene in light gasoline, and can effectively reduce the content of olefin in light gasoline;
(3) the preparation method of the light gasoline cracking propylene yield-increasing catalyst has the advantages of simple process, easily controlled conditions and good product repeatability.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an X-ray diffraction pattern of a silane-modified hexagonal single-crystal mesoporous material A prepared in example 1;
FIG. 2 is a nitrogen adsorption-desorption graph of the silane-modified hexagonal single-crystal mesoporous material A prepared in example 1;
FIG. 3 is a distribution diagram of the pore diameter of the silane-modified hexagonal single-crystal mesoporous material A prepared in example 1;
FIG. 4 is a TEM transmission electron micrograph of the silane-modified hexagonal single-crystal mesoporous material A prepared in example 1;
FIG. 5 is an SEM scanning electron micrograph of the silane-modified hexagonal single-crystal mesoporous material A prepared in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The light gasoline catalytic cracking catalyst disclosed in the prior art takes a zeolite molecular sieve or a modified zeolite molecular sieve as a main component. However, since the zeolite molecular sieve belongs to a microporous molecular sieve, the pore structure is narrow, which easily causes side reactions, thereby causing the selectivity of the target product propylene to be reduced.
The inventor of the invention discovers that when a certain amount of silane modified hexagonal single crystal mesoporous material is mixed and modified with a zeolite molecular sieve with a high silica-alumina ratio and used as a main component of a catalyst for a catalytic cracking reaction of light gasoline, the catalyst can not only effectively improve the selectivity of propylene, but also increase the conversion rate of olefin in the light gasoline. Compared with zeolite molecular sieves with narrow channels, the silane modified hexagonal single crystal mesoporous material used in the invention has the advantages of larger specific surface area, larger pore volume and larger average pore diameter, is beneficial to the diffusion of raw material molecules and product molecules in the reaction, and can effectively inhibit the occurrence of side reactions caused by the narrow channels of the zeolite molecular sieves.
The inventor of the invention discovers that the silane modified hexagonal single crystal mesoporous material prepared by the method has larger aperture and higher specific surface area due to the special cubic center Im3m crystal phase structure and hexagonal pore channel structure, and the surface hydrophobicity of the silane modified hexagonal single crystal mesoporous material is increased, so that the silane modified hexagonal single crystal mesoporous material is more beneficial to the conversion of olefin, and further the conversion rate of raw materials of the light gasoline cracking reaction is improved.
The invention provides a light gasoline cracking propylene yield-increasing catalyst, wherein the catalyst comprises a zeolite molecular sieve with a high silica-alumina ratio and a silane modified hexagonal single crystal mesoporous material; wherein the silane modified hexagonal single crystal mesoporous material has a cubic body centered Im3m crystal phase structure, a pore channel structure is cubic cage-shaped, the average pore diameter is 4-15nm, the pore volume is 0.5-1.5mL/g, and the specific surface area is 400-600m2(ii)/g, the average particle diameter is 0.5 to 6 μm.
According to the invention, the silane modified hexagonal single-crystal mesoporous material preferably has an average pore diameter of 6.8-8nm, a pore volume of 0.9-1.2mL/g, and a specific surface area of 461-546m2(ii)/g, the average particle diameter is 1 to 3 μm. Under the condition, the diffusion of raw material molecules and product molecules in the reaction can be facilitated, and the side reaction caused by the narrow pore channel of the zeolite molecular sieve can be effectively inhibited.
According to the invention, the zeolite molecular sieve with high silica-alumina ratio is a hydrogen type high silica ZSM-5 molecular sieve and/or a high silica ZRP molecular sieve; preferably, the Si/Al molar ratio of the high-Si/Al ratio zeolite molecular sieve is 80-800, more preferably 100-500, and still more preferably 300-500.
According to the invention, the weight ratio of the hydrogen-type high-silicon ZSM-5 molecular sieve to the silane-modified hexagonal single crystal mesoporous material is (1.5-6.5): 1, preferably (1.57-2.75): 1. in addition, the weight ratio of the high-silicon ZRP molecular sieve to the silane modified hexagonal single crystal mesoporous material is (9-12): 1, preferably (10-11): 1.
according to the invention, based on the total weight of the catalyst, the content of the zeolite molecular sieve with high silica-alumina ratio is 45-65 wt%, and the content of the silane modified hexagonal single crystal mesoporous material is 10-30 wt%; preferably, the content of the zeolite molecular sieve with high silica-alumina ratio is 47-63 wt%, and the content of the silane modified hexagonal single crystal mesoporous material is 12-30 wt%, based on the total weight of the catalyst.
According to the invention, the preparation method of the silane modified hexagonal single crystal mesoporous material comprises the following steps:
(a) contacting a template agent, potassium sulfate, an acidic aqueous solution and a silicon source, and crystallizing, filtering, washing and drying the obtained mixture to obtain hexagonal mesoporous material raw powder;
(b) carrying out demoulding agent treatment on the hexagonal mesoporous material raw powder to obtain a hexagonal mesoporous material;
(c) carrying out thermal activation treatment on the hexagonal mesoporous material to obtain a hexagonal single crystal mesoporous material;
(d) and mixing the hexagonal single crystal mesoporous material with dichlorodimethylsilane, and performing ball milling treatment to obtain the silane modified hexagonal single crystal mesoporous material.
According to the invention, in step (a), a template, potassium sulfate, an acidic aqueous solution and a silicon source are contacted in a mixing manner. The order of mixing and contacting is not particularly limited, and the template agent, the potassium sulfate, the acidic aqueous solution and the silicon source may be mixed simultaneously, or any two or three of them may be mixed, and then the other components may be added and mixed uniformly. According to a preferred embodiment, the template agent, potassium sulfate and the acidic aqueous solution are mixed uniformly, and then the silicon source is added and mixed uniformly.
According to the present invention, in step (a), the templating agent is a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, which may be prepared by methods known to those skilled in the art or may be obtained commercially, for example, from Fuka under the trade name Synperonic F108, having the formula EO132PO60EO132 and an average molecular weight Mn of 14600.
According to the present invention, in step (a), the acidic aqueous solution is an aqueous solution of an inorganic acid, including an aqueous solution of sulfuric acid, an aqueous solution of hydrochloric acid, an aqueous solution of hydrobromic acid, and an aqueous solution of nitric acid, and more preferably an aqueous solution of hydrochloric acid.
According to the invention, in step (a), the silicon source is selected from one or more of ethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate and silica sol, preferably ethyl orthosilicate.
According to the invention, in step (a), the molar ratio of the template, potassium sulfate, the silicon source, water and the inorganic acid is 1: 50-500: 50-300: 5000-50000: 200-2000, preferably 1: 100-300: 100-200: 10000-30000: 500-1500;
according to the invention, in step (a), the conditions of said contact are: the temperature is 25-60 deg.C, and the time is 10-200 min. In order to further facilitate uniform mixing between the substances, according to a preferred embodiment of the invention, the mixing contact is carried out under stirring conditions. Wherein, the stirring conditions comprise: the stirring rate was 200 and 900rpm (revolutions per minute).
According to the invention, in step (a), the crystallization conditions are: the temperature is 25-60 ℃, and the time is 10-72 h; preferably, the temperature is 30-55 ℃ and the time is 10-40 h. According to a preferred embodiment, the crystallization is carried out by hydrothermal crystallization.
According to the invention, in step (a), the drying conditions comprise: the drying temperature is 70-150 ℃, and the drying time is 3-20 h.
According to the present invention, in the step (a), the washing process may include: after filtration, a solid product is obtained, which is repeatedly washed with deionized water (the number of washing times can be 2-10), and then subjected to suction filtration.
According to the invention, the suction filtration separation is a well-known way of separating liquid from solid particles, which is to separate liquid from solid particles or a mixture of liquid and liquid by using air pressure.
According to the invention, in step (b), the method of the template removal treatment is typically a calcination method. The template agent removing treatment process comprises the following steps: calcining original hexagonal mesoporous material powder in air atmosphere; the temperature of the template removal agent is preferably 400-700 ℃, and the time of the template removal agent is preferably 8-20 h.
According to the invention, in step (c), the conditions of the thermal activation treatment comprise: roasting the product in nitrogen atmosphere to remove the template agent, wherein the thermal activation temperature is 450-800 ℃, and the time is 8-20 h.
According to the invention, in the step (d), the weight ratio of the hexagonal single-crystal mesoporous material to the dichlorodimethylsilane is (2-50): 1, preferably (5-20): 1.
according to the invention, in the step (d), the specific operation method and conditions of the ball milling treatment are subject to the condition that the pore channel structure of the hexagonal single crystal mesoporous material with the cubic center Im3m structure is not damaged or is not basically damaged. Specifically, the ball milling treatment may be performed in a ball mill, wherein the diameter of the milling balls in the ball mill may be 2-3 mm; the number of the grinding balls can be reasonably selected according to the size of the ball milling tank, and for the ball milling tank with the size of 50-150mL, 20-80 grinding balls can be generally used; the material of the grinding ball can be agate, polytetrafluoroethylene and the like, and agate is preferred. The ball milling conditions include: the rotation speed of the grinding balls can be 300-500r/min, the temperature in the ball milling tank can be 15-70 ℃, and the ball milling time can be 0.5-30 h.
According to the invention, the catalyst also comprises a first oxide, wherein the first oxide is an oxide obtained by roasting a binder, and is preferably silicon oxide and/or aluminum oxide; more preferably, the binder is selected from one or more of silica sol, alumina sol, pseudoboehmite, and diaspore.
According to the invention, the catalyst further comprises a second oxide selected from alkaline earth metal oxides and/or rare earth metal oxides; preferably, the second oxide is selected from one or more of magnesium oxide, calcium oxide, strontium oxide, barium oxide, cerium oxide and lanthanum oxide.
According to the present invention, the first oxide is contained in an amount of 10 to 30 wt% and the second oxide is contained in an amount of 1 to 11 wt%, based on the total weight of the catalyst; preferably, the first oxide is present in an amount of 15 to 22 wt% and the second oxide is present in an amount of 4 to 8 wt%, based on the total weight of the catalyst.
The invention provides a preparation method of a light gasoline cracking propylene yield-increasing catalyst containing a silane modified hexagonal single-crystal mesoporous material, wherein the method comprises the following steps:
(1) mixing a high silica-alumina ratio zeolite molecular sieve, a silane modified hexagonal single crystal mesoporous material, a binder and an extrusion aid, then carrying out extrusion forming and carrying out first roasting treatment to obtain a catalyst precursor;
(2) in the presence of dilute nitric acid, dipping the catalyst precursor into an aqueous solution of an oxide precursor, and drying and carrying out second roasting treatment to obtain the light gasoline cracking propylene yield-increasing catalyst containing the silane modified hexagonal single crystal mesoporous material;
wherein the silane modified hexagonal single crystal mesoporous material has a cubic body centered Im3m crystal phase structure, a pore channel structure is cubic cage-shaped, the average pore diameter is 4-15nm, the pore volume is 0.5-1.5mL/g, and the specific surface area is 400-600m2(ii)/g, the average particle diameter is 0.5 to 6 μm.
According to the invention, the silane modified hexagonal single-crystal mesoporous material preferably has an average pore diameter of 6.8-8nm, a pore volume of 0.9-1.2mL/g, and a specific surface area of 461-546m2(ii)/g, the average particle diameter is 1 to 3 μm.
According to the invention, in the step (2), relative to 100mL of dilute nitric acid, the dosage of the zeolite molecular sieve with high silica-alumina ratio is 300 parts by weight, the dosage of the silane modified hexagonal single-crystal mesoporous material is 20-120 parts by weight, the dosage of the binder is 150-350 parts by weight, and the dosage of the extrusion aid is 20-40 parts by weight; preferably, the amount of the zeolite molecular sieve with high silica-alumina ratio is 156.7-280 parts by weight, the amount of the silane modified hexagonal single crystal mesoporous material is 26.7-100 parts by weight, the amount of the binder is 178-322.5 parts by weight, and the amount of the extrusion aid is 23.3-35.6 parts by weight, relative to 100mL of dilute nitric acid.
Preferably, in the step (2), the catalyst precursor is used in an amount of 50 to 100 parts by weight and the oxide precursor is used in an amount of 12 to 25 parts by weight, relative to 100mL of water; preferably, the catalyst precursor is used in an amount of 70.7 to 106.7 parts by weight and the oxide precursor is used in an amount of 14.1 to 19.38 parts by weight, relative to 100mL of water.
According to the invention, the oxide precursor comprises an alkaline earth metal and/or a rare earth metal; preferably, the alkaline earth metal and rare earth metal are selected from one or more of magnesium, calcium, strontium, barium, cerium and lanthanum.
According to the invention, the extrusion aid is selected from one or more of sesbania powder, cellulose, polyethylene glycol, polyvinyl alcohol and starch, and is preferably sesbania powder and/or polyethylene glycol.
According to the invention, in the step (1), the zeolite molecular sieve with high silica-alumina ratio, the silane modified hexagonal single-crystal mesoporous material, the adhesive and the extrusion aid are uniformly mixed, diluted nitric acid is added, the mixture is uniformly stirred and then extruded and formed, and the mixture is dried at 70-140 ℃ for 5-30h and calcined at 500-700 ℃ for 3-20h to obtain the catalyst precursor.
According to the invention, in the step (2), the catalyst precursor obtained in the step is immersed in an aqueous solution of an oxide precursor, the solid product is dried for 5-30h at 70-130 ℃ after the moisture is removed, and is calcined for 3-16h at 550-650 ℃ to obtain the light gasoline cracking yield-increasing propylene catalyst.
According to the preparation method of the light gasoline cracking propylene yield-increasing catalyst, in the step (1), the zeolite molecular sieve with high silica-alumina ratio, the silane modified hexagonal single crystal mesoporous material, the adhesive and the extrusion aid are uniformly mixed, and then dilute nitric acid is added, and the mixture is uniformly stirred and then extruded and formed. Wherein, the extrusion molding is followed by cutting, for example, the extrusion molding can be followed by stirring to obtain a spherical, granular, strip-shaped or cylindrical shape, and the cutting can be carried out to a desired length, for example, the extrusion molding can be followed by cutting to obtain a cylinder with a diameter of 2mm and a length of 2-3 mm. In the present invention, it is to be noted that the nitric acid is added in the step (1) for the purpose of making the mixture into a slurry form and facilitating the molding.
The third aspect of the invention provides a light gasoline cracking propylene yield increasing catalyst containing the silane modified hexagonal single crystal mesoporous material, which is prepared by the method.
According to the invention, the specific surface area of the light gasoline cracking propylene yield-increasing catalyst is 150-400m2G, pore bodyThe product is 0.4-1.0cm3(ii)/g; preferably, the specific surface area is 267-340m2Per g, pore volume of 0.59-0.67cm3/g。
According to the invention, the light gasoline cracking propylene yield-increasing catalyst is spherical, granular, strip-shaped or cylindrical in shape.
The invention provides an application of the light gasoline cracking propylene yield-increasing catalyst containing the silane modified hexagonal single crystal mesoporous material in catalytic cracking.
According to the invention, the method comprises the following specific operations: at the temperature of 450 ℃ and 580 ℃, the pressure of 0.01-0.5MPa and the weight hourly space velocity of 1-30h-1Under the condition of (1), the raw material containing light gasoline is contacted with a light gasoline cracking yield-increasing propylene catalyst in a fixed bed adiabatic reactor.
According to the invention, the light gasoline feedstock may be selected from:
(1) light gasoline fraction obtained from the catalytic cracking unit;
(2) and (4) preparing a carbon five or more fraction of olefin from methanol.
The method provided by the invention can be used as a method for preparing propylene independently, and can also be used in combination with an FCC unit or a methanol-to-olefin unit in an oil refinery.
According to the invention, the surface of the microporous zeolite molecular sieve catalyst with low silicon-aluminum ratio has more acid sites, and the microporous zeolite molecular sieve catalyst used for the catalytic cracking reaction of light gasoline has the characteristics of high reaction speed, poor propylene selectivity and short service cycle. Relatively speaking, the zeolite molecular sieve catalyst with high silica-alumina ratio added with the modification component has certain improvement on the selectivity and stability of propylene, but is easy to have secondary reaction in the reaction process. The light gasoline cracking propylene yield-increasing catalyst provided by the invention adopts a mixture of the zeolite molecular sieve with high silica-alumina ratio and the silane-modified hexagonal single crystal mesoporous material as a main active component, and introduces a proper amount of oxide as a modification component, so that the conversion rate of olefin in light gasoline, the selectivity of propylene and the stability of the catalyst can be obviously improved.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the pore structure parameter analysis of the samples was carried out on an adsorption apparatus available from Micromeritics, USA, model ASAP2020-M + C; x-ray diffraction analysis of the samples was performed on an X-ray diffractometer, model D8 Advance, available from Bruker AXS, Germany; the scanning electron microscope picture of the sample is obtained on an XL-30 type field emission environment scanning electron microscope produced by FEI company in America; high-resolution Transmission Electron Microscope (TEM) images of the samples were obtained on a Tecnai F20 model high-resolution transmission electron microscope manufactured by FEIPhilips, Netherlands; the elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, USA.
The drying box is produced by Shanghai-Hengchang scientific instruments Co., Ltd, and is of a type DHG-9030A.
The muffle furnace is manufactured by CARBOLITE corporation, model CWF 1100.
The polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P108) used in the examples and comparative examples was purchased from Fuka corporation; ZSM-5 molecular sieves with different silica-alumina ratios were purchased from Shanghai Korea molecular sieves Co., Ltd; the ZRP zeolite molecular sieve is purchased from Hezhong Biochemical manufacturing company, Inc. in Wuhan City; the alumina sol and the silica sol are purchased from Zibo Jiarun chemical Co., Ltd; pseudoboehmite was purchased from Zibo Hengqi powder New Material Co., Ltd; other reagents were purchased from the national pharmaceutical group chemical reagents, ltd.
Example 1
This example illustrates a light gasoline cracking propylene yield increase catalyst containing silane-modified hexagonal single-crystal mesoporous material prepared by the method of the present invention.
(1) Preparation of silane modified hexagonal single crystal mesoporous material
20g (0.0014mol) of template F108, 52.4g (0.3mol) of potassium sulfate and 600g of hydrochloric acid aqueous solution (containing 1.2mol of HCl) are mixed and stirred at 38 ℃ until F108 is completely dissolved; adding 41.6g (0.2mol) of tetraethoxysilane into the solution, continuously stirring for 15min at 38 ℃, and standing and crystallizing for 24h at 38 ℃; washing the solid product obtained by filtering with deionized water for 4 times, and drying at 110 ℃ for 10h after suction filtration to obtain the hexagonal mesoporous material raw powder. Calcining the hexagonal mesoporous material raw powder for 10 hours at 500 ℃ in air atmosphere, and removing the template agent; then calcining the mixture for 10 hours at 550 ℃ under the protection of nitrogen to carry out thermal activation treatment, thus obtaining the thermally activated hexagonal single crystal mesoporous material.
And (2) putting 10g of the hexagonal single-crystal mesoporous material and 1g of dichlorodimethylsilane into a 100ml ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, grinding balls are made of agate, the diameter of each grinding ball is 3-15mm, the number of the grinding balls is 30, and the rotating speed is 400 rpm. And (3) sealing the ball milling tank, and carrying out ball milling for 8 hours in the ball milling tank at the temperature of 40 ℃ to obtain the silane modified hexagonal single crystal mesoporous material A.
The specific surface area of the silane modified hexagonal single crystal mesoporous material A is 509m2G, average pore diameter of 7.5nm, pore volume of 1.0 mL/g.
FIG. 1 is an X-ray diffraction pattern of a hexagonal single-crystal mesoporous material A modified by silane. From the XRD spectrum, it is evident that the hexagonal mesoporous material support C1 has 1 diffraction peak (2 θ ═ 0.6 °) of the (110) plane and a diffraction shoulder (2 θ ═ 1.2 °) of the (200) plane corresponding to the cubic center Im3m crystalline phase in the small angular region. (110) The diffraction peak intensity of the surface is high, the peak shape is narrow, which indicates that the material has a good long-range ordered structure, and the XRD spectrum of the material is consistent with that of the FDU-6 mesoporous material reported in the literature (Chengzhong Yu, Bozhi Tian, Jie Fan, Galen D. Stucky, Dongyuman Zhuao, J.Am.Chem.Soc.2002,124, 4556-4557);
FIG. 2 is a nitrogen adsorption-desorption curve diagram of a silane modified hexagonal single crystal mesoporous material A, wherein a nitrogen adsorption-desorption isotherm is a typical class IV adsorption-desorption isotherm and has H2The model hysteresis loop proves that the material has a cubic cage-shaped mesoporous structure. Desorption branches between 0.4 and 0.5 relative partial pressure also indicate that the material has a cage-like cavity structure;
FIG. 3 is a distribution diagram of the pore diameter of the hexagonal single-crystal mesoporous material A modified by silane. As can be seen from the pore size distribution diagram, the material has a narrow pore size distribution and the pores are very uniform;
FIG. 4 is a TEM transmission electron micrograph of the silane-modified hexagonal single-crystal mesoporous material A. The pore shape of the (100) crystal plane is clearly seen in fig. 3, and the material has a cubic-centered Im3m crystal phase structure;
FIG. 5 is an SEM scanning electron microscope image of a silane-modified hexagonal single-crystal mesoporous material A. As can be seen, the microscopic morphology of the material is hexagonal, the particle size is micron-scale, and the average particle diameter is 1.0-3.0 μm.
(2) Preparation of light gasoline cracking yield-increasing propylene catalyst
Uniformly mixing 40g of the silane modified hexagonal single crystal mesoporous material A prepared in the step with 110g of ZSM-5 molecular sieve (Si/Al is 300), 129g of 28% silica sol and 10g of sesbania powder, adding 40mL of 5% dilute nitric acid, uniformly stirring, and performing extrusion forming; drying at 110 ℃ for 10h and finally calcining at 550 ℃ for 8h to obtain the catalyst precursor A. 93g of the catalyst precursor A was taken, and 10.8g of calcium nitrate and 8.8g of lanthanum nitrate hexahydrate were dissolved in 110mL of water, dried at 110 ℃ for 16 hours, and fired at 600 ℃ for 5 hours to obtain a catalyst A.
Catalyst A had a specific surface area of 326m2Pore volume was 0.65 mL/g.
Based on the total weight of the catalyst a, the content of the ZSM-5 zeolite molecular sieve was 55 wt%, the content of the silane-modified hexagonal single crystal mesoporous material was 20 wt%, the content of silica derived from the binder was 18 wt%, the content of calcium oxide was 3.7 wt%, and the content of lanthanum oxide was 3.3 wt%.
Example 2
This example illustrates a light gasoline cracking propylene yield increase catalyst containing silane-modified hexagonal single-crystal mesoporous material prepared by the method of the present invention.
(1) Preparation of silane modified hexagonal single crystal mesoporous material
20g (0.0014mol) of template F108, 73.4g (0.42mol) of potassium sulfate and 833g of hydrochloric acid aqueous solution (containing 2.1mol of HCl) are mixed and stirred at 55 ℃ until F108 is completely dissolved; adding 58.2g (0.28mol) of tetraethoxysilane into the solution, continuously stirring for 10min at 55 ℃, and standing and crystallizing for 10h at 55 ℃; washing the solid product obtained by filtering with deionized water for 6 times, and drying at 150 ℃ for 3h after suction filtration to obtain the hexagonal mesoporous material raw powder. Calcining the hexagonal mesoporous material raw powder for 15 hours at 600 ℃ in air atmosphere, and removing the template agent; then calcining for 8 hours at 650 ℃ under the protection of nitrogen for heat activation treatment to obtain the heat-activated hexagonal single crystal mesoporous material.
And (2) putting 10g of the hexagonal single-crystal mesoporous material and 2g of dichlorodimethylsilane into a 100mL ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, grinding balls are made of agate, the diameter of each grinding ball is 3-15mm, the number of the grinding balls is 30, and the rotating speed is 400 rpm. And (3) sealing the ball milling tank, and carrying out ball milling for 1h in the ball milling tank at the temperature of 70 ℃ to obtain the silane modified hexagonal single crystal mesoporous material B.
The silane modified hexagonal single crystal mesoporous material B has a cubic-centered Im3m crystal phase structure, a pore channel structure is cubic cage-shaped, and the specific surface area is 461m2(iv)/g, average pore diameter of 6.8nm, pore volume of 0.9mL/g, and average particle diameter of 1.0-3.0. mu.m.
(2) Preparation of light gasoline cracking yield-increasing propylene catalyst
Uniformly mixing the silane modified hexagonal single crystal mesoporous material B12g prepared in the step with 126g of ZRP-5 molecular sieve (Si/Al is 300), 136g of 25% alumina sol and 16g of sesbania powder, adding 45mL of 5% dilute nitric acid, stirring uniformly, and then carrying out extrusion forming; drying at 140 ℃ for 5h and finally calcining at 650 ℃ for 4h gave catalyst precursor B. 96g of catalyst precursor B was taken, and 8.4g of magnesium nitrate and 4.3g of cerous nitrate hexahydrate were dissolved in 90ml of water, dried at 130 ℃ for 5 hours, and fired at 650 ℃ for 3 hours to obtain catalyst B.
The specific surface area of catalyst B was 267m2Pore volume was 0.59 mL/g.
Based on the total weight of the catalyst B, the content of the ZRP-5 zeolite molecular sieve is 63 weight percent, the content of the silane-modified hexagonal single crystal mesoporous material is 12 weight percent, the content of alumina derived from a binder is 22 weight percent, the content of magnesia is 2.3 weight percent, and the content of cerium oxide is 1.7 weight percent.
Example 3
This example illustrates a light gasoline cracking propylene yield increase catalyst containing silane-modified hexagonal single-crystal mesoporous material prepared by the method of the present invention.
(1) Preparation of silane modified hexagonal single crystal mesoporous material
20g (0.0014mol) of template F108, 24.5g (0.14mol) of potassium sulfate and 278g of hydrochloric acid aqueous solution (containing 0.7mol of HCl) are mixed and stirred at 30 ℃ until F108 is completely dissolved; adding 29.1g (0.14mol) of tetraethoxysilane into the solution, continuously stirring for 60min at 30 ℃, and standing and crystallizing for 40h at 30 ℃; washing the solid product obtained by filtering with deionized water for 8 times, and drying at 70 ℃ for 20 hours after suction filtration to obtain the hexagonal mesoporous material raw powder. Calcining the hexagonal mesoporous material raw powder for 20 hours at 400 ℃ in an air atmosphere, and removing the template agent; then calcining for 16h at 500 ℃ under the protection of nitrogen for thermal activation treatment to obtain the thermally activated hexagonal single crystal mesoporous material.
And (2) putting 10g of the hexagonal single-crystal mesoporous material and 0.5g of dichlorodimethylsilane into a 100mL ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, grinding balls are made of agate, the diameter of each grinding ball is 3-15mm, the number of the grinding balls is 30, and the rotating speed is 400 rpm. And (3) sealing the ball milling tank, and carrying out ball milling for 24 hours in the ball milling tank at the temperature of 15 ℃ to obtain the silane modified hexagonal single crystal mesoporous material C.
The silane modified hexagonal single crystal mesoporous material C has a cubic-centered Im3m crystal phase structure, a pore channel structure is cubic cage-shaped, and the specific surface area is 546m2(iv)/g, average pore diameter of 8.0nm, pore volume of 1.2mL/g, and average particle diameter of 1.0-3.0. mu.m.
(2) Preparation of light gasoline cracking yield-increasing propylene catalyst
Uniformly mixing 60g of the silane modified hexagonal single crystal mesoporous material C prepared in the step with 94g of ZSM-5 molecular sieve (Si/Al is 500), 107g of 28% silica sol and 14g of sesbania powder, adding 60mL of 5% dilute nitric acid, uniformly stirring, and performing extrusion forming; drying at 70 ℃ for 30h and finally calcining at 500 ℃ for 20h to obtain the catalyst precursor C. 92g of catalyst precursor C was taken, and 17.1g of strontium nitrate and 8.1g of cerium nitrate hexahydrate were dissolved in 130mL of water, dried at 150 ℃ for 3 hours, and fired at 600 ℃ for 6 hours to obtain catalyst C.
The specific surface area of catalyst C was 340m2Pore volume was 0.67 mL/g.
Based on the total weight of the catalyst C, the content of the ZSM-5 zeolite molecular sieve was 47 wt%, the content of the silane-modified hexagonal single crystal mesoporous material was 30 wt%, the content of silica derived from the binder was 15 wt%, the content of strontium oxide was 4.8 wt%, and the content of cerium oxide was 3.2 wt%.
Example 4
This example illustrates a light gasoline cracking propylene yield increase catalyst containing silane-modified hexagonal single-crystal mesoporous material prepared by the method of the present invention.
The light gasoline cracking propylene yield increase catalyst was prepared in the same manner as in example 1, except that:
(1) preparation of silane modified hexagonal single crystal mesoporous material
According to the molar ratio of the template agent, the potassium sulfate, the silicon source, the water and the inorganic acid being 1: 50: 50: 5000: 200 to obtain the hexagonal single crystal mesoporous material after thermal activation.
The weight ratio of the hexagonal single-crystal mesoporous material to the dichlorodimethylsilane is 2: 1, ball milling to obtain the silane modified hexagonal single crystal mesoporous material D.
The silane modified hexagonal single crystal mesoporous material has a cubic-centered Im3m crystal phase structure, a pore channel structure is cubic cage-shaped, the average pore diameter is 4-15nm, the pore volume is 0.5mL/g, and the specific surface area is 400m2(ii)/g, the average particle diameter is 0.5 to 6 μm.
(2) Preparation of light gasoline cracking yield-increasing propylene catalyst
According to the following steps: relative to 100mL of dilute nitric acid, the dosage of the zeolite molecular sieve with high silica-alumina ratio is 300 parts by weight, the dosage of the silane modified hexagonal single crystal mesoporous material is 20 parts by weight, the dosage of the adhesive is 350 parts by weight, and the dosage of the extrusion aid is 20 parts by weight; and the catalyst precursor is used in an amount of 50 parts by weight and the oxide precursor is used in an amount of 12 parts by weight with respect to 100mL of water; catalyst D was prepared.
The specific surface area of catalyst D was 150m2Per g, pore volume 0.4cm3/g。
Based on the total weight of the catalyst D, the content of the ZSM-5 zeolite molecular sieve was 65 wt%, the content of the silane-modified hexagonal single crystal mesoporous material was 10 wt%, the content of silica derived from the binder was 20 wt%, the content of calcium oxide was 2.5 wt%, and the content of lanthanum oxide was 2.5 wt%.
Example 5
This example illustrates a light gasoline cracking propylene yield increase catalyst containing silane-modified hexagonal single-crystal mesoporous material prepared by the method of the present invention.
The light gasoline cracking propylene yield increase catalyst was prepared in the same manner as in example 1, except that:
(1) preparation of silane modified hexagonal single crystal mesoporous material
According to the molar ratio of the template agent, the potassium sulfate, the silicon source, the water and the inorganic acid being 1: 500: 300: 50000: 2000 to obtain the hexagonal single crystal mesoporous material after thermal activation.
And (2) mixing the hexagonal single-crystal mesoporous material with dichlorodimethylsilane in a weight ratio of 50: 1, ball milling to obtain the silane modified hexagonal single crystal mesoporous material E.
The silane modified hexagonal single crystal mesoporous material has a cubic-centered Im3m crystal phase structure, a pore channel structure is cubic cage-shaped, the average pore diameter is 4-15nm, the pore volume is 1.5mL/g, and the specific surface area is 600m2(ii)/g, the average particle diameter is 0.5 to 6 μm.
(2) Preparation of light gasoline cracking yield-increasing propylene catalyst
According to the following steps: relative to 100mL of dilute nitric acid, the dosage of the zeolite molecular sieve with high silica-alumina ratio is 120 parts by weight, the dosage of the silane modified hexagonal single crystal mesoporous material is 120 parts by weight, the dosage of the adhesive is 150 parts by weight, and the dosage of the extrusion aid is 40 parts by weight; and the catalyst precursor is used in an amount of 100 parts by weight and the oxide precursor is used in an amount of 25 parts by weight, relative to 100mL of water; catalyst E was prepared.
The specific surface area of catalyst E was 400m2Per g, pore volume 1.0cm3/g。
Based on the total weight of the catalyst E, the content of the ZSM-5 zeolite molecular sieve was 45 wt%, the content of the silane-modified hexagonal single crystal mesoporous material was 30 wt%, the content of silica derived from the binder was 15 wt%, the content of calcium oxide was 2.3 wt%, and the content of lanthanum oxide was 7.7 wt%.
Comparative example 1
Catalyst D1 was prepared according to the method of example 1, except that step (1) was eliminated, only step (2) was retained, silane-modified hexagonal single crystalline mesoporous material A was not used, and only 150g of ZSM-5 molecular Sieve (SiO) was used2/Al2O3300) is provided.
Catalyst D1 had a specific surface area of 152m2Pore volume was 0.28 mL/g.
The ZSM-5 zeolite molecular sieve content was 75 wt%, the silica content from the binder was 18 wt%, the calcium oxide content was 3.7 wt%, and the lanthanum oxide content was 3.3 wt%, based on the total weight of catalyst D1.
Comparative example 2
Catalyst D2 was prepared by the method of example 1 except that the high silica to alumina ratio ZSM-5 zeolite molecular sieve (Si/Al of 300) in step (1) was replaced with the low silica to alumina ratio ZSM-5 zeolite molecular Sieve (SiO)2/Al2O3Is 25).
Catalyst D2 had a specific surface area of 254m2Pore volume was 0.50 mL/g.
Based on the total weight of the catalyst D2, the content of the ZSM-5 zeolite molecular sieve was 55 wt%, the content of the silane-modified hexagonal single crystal mesoporous material was 20 wt%, the content of silica derived from the binder was 18 wt%, the content of calcium oxide was 3.7 wt%, and the content of lanthanum oxide was 3.3 wt%.
Test example 1
Test of light gasoline cracking yield-increasing propylene catalyst in light gasoline catalytic cracking reaction
The test catalysts were example catalyst a, catalyst B, catalyst C, catalyst D, catalyst E, comparative catalyst D1, and catalyst D2, respectively.
The reaction raw materials are as follows: c5-C8Light steamThe oil raw material composition is as follows: 7.71 normal paraffin, 40.49 isoparaffin, 51.46 olefin, 0.36 naphthene.
The specific test method is as follows:
and (3) evaluating the catalytic cracking reaction performance of the light gasoline of the catalyst on a fixed bed reaction device. The loading of the catalyst is 5.0g, the reaction temperature is 540 ℃, the reaction pressure is 0.05MPa, and the weight space velocity of the raw material is 16h-1After cooling and gas-liquid separation of the product, the gas composition is prepared with Al2O3-agilent 6890 gas chromatograph analysis of S capillary chromatography column and hydrogen flame detector (FID), using programmed temperature, quantitative analysis with correction factors; the liquid composition was analyzed by Agilent 6890 gas chromatograph equipped with PONA chromatographic column, using programmed temperature rise, and quantitative analysis with light gasoline standard. The reaction results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the catalyst provided by the invention has excellent performance when used for preparing propylene by catalytic cracking of light gasoline. Comparing the data of catalysts A-E and D1, it can be seen that a portion of the silane-modified hexagonal single crystalline mesoporous material was added to catalysts A-E and no silane-modified hexagonal single crystalline mesoporous material was added to catalyst D1. Compared with catalyst D1, the light gasoline olefin conversion rate, propylene selectivity and catalyst stability of catalysts A-E are all improved significantly. The results show that the light gasoline cracking propylene yield-increasing catalyst provided by the invention has excellent performance because the catalyst contains a proper amount of all-silicon silane modified hexagonal single crystal mesoporous material.
Comparing the data of the catalysts A-E and the catalyst D2, it can be seen that the light gasoline cracking propylene-increasing catalyst prepared by using the hydrogen type ZSM-5 molecular sieve with lower silicon-aluminum ratio has poorer performance, and although the conversion rate of olefin in the light gasoline at the initial stage of reaction is higher, the propylene selectivity is low. In addition, the conversion and selectivity of catalyst D2 decreased significantly as the reaction proceeded, while catalysts A-E remained stable throughout the 100h reaction.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (17)
1. The light gasoline cracking propylene yield-increasing catalyst is characterized by comprising a zeolite molecular sieve with a high silica-alumina ratio and a silane modified hexagonal single crystal mesoporous material; wherein the silane modified hexagonal single crystal mesoporous material has a cubic body centered Im3m crystal phase structure, a pore channel structure is cubic cage-shaped, the average pore diameter is 4-15nm, the pore volume is 0.5-1.5mL/g, and the specific surface area is 400-600m2(ii)/g, the average particle diameter is 0.5 to 6 μm.
2. The catalyst as claimed in claim 1, wherein the silane-modified hexagonal single-crystal mesoporous material has an average pore diameter of 6.8-8nm, a pore volume of 0.9-1.2mL/g, and a specific surface area of 461-546m2(ii)/g, the average particle diameter is 1 to 3 μm.
3. The catalyst of claim 1, wherein the high silica to alumina ratio zeolite molecular sieve is a hydrogen-type high silica ZSM-5 molecular sieve and/or a high silica ZRP molecular sieve; preferably, the Si/Al molar ratio of the zeolite molecular sieve with high silica-alumina ratio is 80-800, more preferably 100-500;
preferably, the weight ratio of the hydrogen-type high-silicon ZSM-5 molecular sieve to the silane-modified hexagonal single-crystal mesoporous material is (1.5-6.5): 1;
preferably, the weight ratio of the high-silicon ZRP molecular sieve to the silane-modified hexagonal single-crystal mesoporous material is (9-12): 1.
4. the catalyst of any one of claims 1 to 3, wherein the content of the zeolite molecular sieve with high silica-alumina ratio is 45 to 65 wt% and the content of the silane-modified hexagonal single crystal mesoporous material is 10 to 30 wt%, based on the total weight of the catalyst.
5. The catalyst according to any one of claims 1 to 4, wherein the preparation method of the silane-modified hexagonal single-crystal mesoporous material comprises the following steps:
(a) contacting a template agent, potassium sulfate, an acidic aqueous solution and a silicon source, and crystallizing, filtering, washing and drying the obtained mixture to obtain hexagonal mesoporous material raw powder;
(b) carrying out demoulding agent treatment on the hexagonal mesoporous material raw powder to obtain a hexagonal mesoporous material;
(c) carrying out thermal activation treatment on the hexagonal mesoporous material to obtain a hexagonal single crystal mesoporous material;
(d) and mixing the hexagonal single crystal mesoporous material with dichlorodimethylsilane, and performing ball milling treatment to obtain the silane modified hexagonal single crystal mesoporous material.
6. The catalyst of claim 5, wherein in step (a), the acidic aqueous solution is an aqueous solution of a mineral acid;
preferably, the molar ratio of the template agent, the potassium sulfate, the silicon source, the water and the inorganic acid is 1: 50-500: 50-300: 5000-50000: 200-2000, preferably 1: 100-300: 100-200: 10000-30000: 500-1500;
preferably, the template agent is polyoxyethylene-polyoxypropylene-polyoxyethylene;
preferably, the conditions of said contacting are: the temperature is 25-60 deg.C, and the time is 10-200 min;
preferably, the crystallization conditions are: the temperature is 25-60 ℃, and the time is 10-72 h.
7. The catalyst of claim 5, wherein in step (b), the conditions for removing the template agent comprise: and roasting the hexagonal mesoporous material raw powder in an air atmosphere, wherein the temperature is 400-700 ℃, and the time is 8-20 h.
8. The catalyst of claim 5, wherein in step (c), the conditions of the thermal activation process comprise: in a nitrogen atmosphere, the thermal activation temperature is 450-800 ℃, and the time is 8-20 h;
preferably, in the step (d), the weight ratio of the hexagonal single-crystal mesoporous material to the dichlorodimethylsilane is (2-50): 1, preferably (5-20): 1;
preferably, in step (d), the ball milling conditions include: the temperature is 15-70 ℃ and the time is 0.5-30 h.
9. The catalyst according to claim 1, wherein the catalyst further comprises a first oxide which is an oxide obtained by calcining a binder, preferably silicon oxide and/or aluminum oxide;
more preferably, the binder is selected from one or more of silica sol, alumina sol, pseudoboehmite, and diaspore.
10. The catalyst of claim 1, wherein the catalyst further comprises a second oxide selected from an alkaline earth metal oxide and/or a rare earth metal oxide;
preferably, the second oxide is selected from one or more of magnesium oxide, calcium oxide, strontium oxide, barium oxide, cerium oxide and lanthanum oxide.
11. The catalyst of claim 9 or 10, wherein the first oxide is present in an amount of 10 to 30 wt% and the second oxide is present in an amount of 1 to 11 wt%, based on the total weight of the catalyst.
12. A preparation method of a light gasoline cracking propylene yield-increasing catalyst containing a silane modified hexagonal single crystal mesoporous material is characterized by comprising the following steps:
(1) mixing a high silica-alumina ratio zeolite molecular sieve, a silane modified hexagonal single crystal mesoporous material, a binder and an extrusion aid, then carrying out extrusion forming and carrying out first roasting treatment to obtain a catalyst precursor;
(2) in the presence of dilute nitric acid, dipping the catalyst precursor into an aqueous solution of an oxide precursor, and drying and carrying out second roasting treatment to obtain the light gasoline cracking propylene yield-increasing catalyst containing the silane modified hexagonal single crystal mesoporous material;
wherein the silane modified hexagonal single crystal mesoporous material has a cubic body centered Im3m crystal phase structure, a pore channel structure is cubic cage-shaped, the average pore diameter is 4-15nm, the pore volume is 0.5-1.5mL/g, and the specific surface area is 400-600m2(ii)/g, the average particle diameter is 0.5 to 6 μm.
13. The method as claimed in claim 12, wherein the amount of the zeolite molecular sieve with high silica-alumina ratio is 120-300 parts by weight, the amount of the silane modified hexagonal single-crystal mesoporous material is 20-120 parts by weight, the amount of the binder is 150-350 parts by weight, and the amount of the extrusion aid is 20-40 parts by weight, relative to 100mL of dilute nitric acid;
preferably, in the step (2), the catalyst precursor is used in an amount of 50 to 100 parts by weight and the oxide precursor is used in an amount of 12 to 25 parts by weight, relative to 100mL of water.
14. The method of claim 12 or 13, wherein the oxide precursor comprises an alkaline earth metal and/or a rare earth metal;
preferably, the alkaline earth metal and rare earth metal are selected from one or more of magnesium, calcium, strontium, barium, cerium and lanthanum;
preferably, the extrusion aid is selected from one or more of sesbania powder, cellulose, polyethylene glycol, polyvinyl alcohol and starch, and is more preferably sesbania powder and/or polyethylene glycol.
15. The method of claim 12, wherein, in step (1), the conditions of the first firing comprise: the temperature is 500-700 ℃, and the time is 3-20 h;
preferably, in the step (2), the conditions of the second firing include: the temperature is 550-650 ℃, and the time is 3-16 h.
16. The light gasoline cracking propylene yield increasing catalyst containing the silane modified hexagonal single crystal mesoporous material prepared by the method of any one of claims 12 to 15.
17. The use of the light gasoline cracking propylene production increasing catalyst containing the silane-modified hexagonal single crystalline mesoporous material of any one of claims 1 to 11 and 16 in catalytic cracking.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039183A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Metallocene catalyst-loaded hexagonal mesoporous material and preparation method thereof |
| CN102040688A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Application of metallocene catalyst-loaded hexagonal mesoporous material to olefinic polymerization |
| CN108786800A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN109382132A (en) * | 2017-08-07 | 2019-02-26 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN110496618A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN110614097A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with carrier being composite material containing silica gel and hexagonal mesoporous material, and preparation method and application thereof |
-
2020
- 2020-04-23 CN CN202010328069.2A patent/CN113546670A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039183A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Metallocene catalyst-loaded hexagonal mesoporous material and preparation method thereof |
| CN102040688A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Application of metallocene catalyst-loaded hexagonal mesoporous material to olefinic polymerization |
| CN108786800A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN109382132A (en) * | 2017-08-07 | 2019-02-26 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN110496618A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN110614097A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with carrier being composite material containing silica gel and hexagonal mesoporous material, and preparation method and application thereof |
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