CN112047358A - Zinc or/and nickel-containing ZSM-5 molecular sieve with multi-stage structure and preparation method and application thereof - Google Patents
Zinc or/and nickel-containing ZSM-5 molecular sieve with multi-stage structure and preparation method and application thereof Download PDFInfo
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- CN112047358A CN112047358A CN201910491377.4A CN201910491377A CN112047358A CN 112047358 A CN112047358 A CN 112047358A CN 201910491377 A CN201910491377 A CN 201910491377A CN 112047358 A CN112047358 A CN 112047358A
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- nickel
- zinc
- molecular sieve
- zsm
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 127
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000011701 zinc Substances 0.000 title claims abstract description 93
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 88
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 86
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 83
- 239000010703 silicon Substances 0.000 claims abstract description 83
- 238000002425 crystallisation Methods 0.000 claims abstract description 50
- 230000008025 crystallization Effects 0.000 claims abstract description 47
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 45
- 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 45
- 239000010457 zeolite Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 33
- 150000001336 alkenes Chemical class 0.000 claims abstract description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 238000000967 suction filtration Methods 0.000 claims abstract description 12
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000011164 primary particle Substances 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 66
- 239000000047 product Substances 0.000 claims description 60
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 56
- 229910052782 aluminium Inorganic materials 0.000 claims description 55
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 55
- 238000003756 stirring Methods 0.000 claims description 39
- 239000011148 porous material Substances 0.000 claims description 37
- 239000000741 silica gel Substances 0.000 claims description 31
- 229910002027 silica gel Inorganic materials 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 30
- 230000032683 aging Effects 0.000 claims description 28
- 229910001868 water Inorganic materials 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 10
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000009825 accumulation Methods 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 238000005899 aromatization reaction Methods 0.000 abstract description 13
- 238000011068 loading method Methods 0.000 abstract description 12
- 238000006722 reduction reaction Methods 0.000 abstract description 12
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 239000000376 reactant Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000006317 isomerization reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 73
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 229910052751 metal Inorganic materials 0.000 description 28
- 239000002184 metal Substances 0.000 description 28
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 5
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 5
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- -1 zinc metals Chemical class 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- 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
- 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
-
- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
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Abstract
The invention relates to a zinc or/and nickel-containing ZSM-5 molecular sieve with a multi-stage structure, and a preparation method and application thereof. In particular to a zinc or/and nickel containing ZSM-5 zeolite molecular sieve with a multilevel structure and hydrothermal synthesis and application thereof. The low-silicon multi-stage structure ZSM-5 zeolite molecular sieve containing zinc or/and nickel has a lower silicon-aluminum ratio, higher zinc or/and nickel loading capacity and more mesoporous structures, wherein the primary particles are 100nm-2 mu m, and the secondary stacked particles are about 2 mu m-8 mu m. The preparation method of the invention has the advantages of simple preparation crystallization and convenient suction filtration and separation in the whole process. The mesoporous structure containing more ZSM-5 molecular sieves with zinc or/and nickel in the multilevel structure not only improves the diffusion rate of macromolecular reactants or products, but also increases the carbon capacity of the molecular sieves, so that the molecular sieves have higher selectivity and longer service life in the reactions of olefin reduction, aromatization and isomerization of catalytic gasoline.
Description
Technical Field
The invention relates to a zeolite molecular sieve, in particular to a hydrothermal synthesis method and application of a zinc-nickel containing hierarchical structure ZSM-5 zeolite molecular sieve for reducing olefins in gasoline.
Background
The ZSM-5 molecular sieve is a zeolite molecular sieve with a unique pore channel structure and acid property, has high hydrothermal stability and oleophylic hydrophobicity, is a good catalyst, and is often used as a solid acid catalyst to be widely applied to alkylation, catalytic cracking, alcohol dehydration and other reactions. Meanwhile, it is also an excellent carrier for metal ions or metal compounds having catalytic activity because it has a high specific surface area and excellent ion exchange properties. The ZSM-5 molecular sieve loaded iron, silver, copper and other catalysts show excellent catalytic performance in reactions such as benzene oxidation reaction, selective catalytic reduction reaction of oxynitride, methanol oxidation and carbonylation and the like. In the aromatization reaction, the ZSM-5 molecular sieve has the pore diameter equivalent to the benzene molecular scale and has special shape-selective catalytic performance, so that the ZSM-5 molecular sieve is widely applied to the oxygen-free aromatization reaction of hydrocarbons, the aromatization reaction of alcohols and the like. In the olefin aromatization reaction, the characteristics of ZSM-5 molecular sieve in various aspects are utilized to greatly improve the yield of aromatic hydrocarbon. However, the conventional ZSM-5 molecular sieve has a pore size of less than 0.6nm, resulting in diffusion limitation which seriously affects its catalytic application. In addition, when ZSM-5 is used for olefin aromatization reaction, modification of one or more metals is mostly needed, and the modification mode relates to the length of the operation period and the cost, so that the industrial application is influenced.
The problems of small pore passage and diffusion limitation of the traditional ZSM-5 molecular sieve are solved by adopting a method for preparing the ZSM-5 with a multistage structure at present. At present, the preparation method of the multistage structure ZSM-5 molecular sieve mainly comprises a post-treatment method, a hard template method and a soft template method. The post-treatment method includes a dealumination method and a desilication method. The dealumination method generally removes aluminum atoms from a zeolite framework by a high-temperature hydrothermal treatment and an acid treatment to generate mesopores. The desilication method similar to this method is mainly to remove silicon atoms in the skeleton by alkali treatment to obtain mesopores. Hard template methods often employ carbon materials as templates, which can produce a variety of mesoporous structures. The charge density matching between the surfactant and the inorganic substance at the interface is found in the preparation process of the soft template method, which is the key for the successful assembly of the mesoporous material. However, the post-treatment method of desiliconization and dealuminization has different effects of post-treatment when treating zeolite with different silica-alumina ratios; the hard template method can obtain highly ordered multi-level structure zeolite, but the route is high in cost and long in period; the product mesopores obtained by the soft template method are highly controllable, but expensive structure directing agents are needed, the steps are complicated, and the industrialization is difficult.
For the metal loading, the current loading methods are mainly classified into hydrothermal loading, impregnation, ion exchange, mechanical mixing, and the like. The hydrothermal method is to directly add a metal salt solution in the hydrothermal synthesis process, load the metal salt solution on a catalyst in the subsequent crystallization process, and transfer most of the metal salt solution to the surface of a molecular sieve pore channel after roasting. The preparation method can uniformly load the metal oxide, is very simple and convenient to operate, and the loaded metal is not easy to run off. The impregnation method is to impregnate the molecular sieve in the metal inorganic salt solution, and the metal ions adsorbed on the pore path of the molecular sieve are roasted to obtain the active components such as metal oxide, etc., and the method has the disadvantages of troublesome operation and long preparation time. The ion exchange method is to put the molecular sieve into a metal salt solution to perform the exchange and substitution of metal ions and framework aluminum atoms under the conditions of certain temperature and pH. This method is also cumbersome and does not allow control of the amount of metal loading. The mechanical mixing method is to physically mix and stir metal salt and molecular sieve, and although the method is simple, metal ions of the metal salt are difficult to enter the surfaces of the pore channels to achieve the synergistic effect with the acid sites of the surfaces of the pore channels. Although the hydrothermal loading mode is simple, green, short in operation period and low in cost, and is more beneficial to industrialization, the metal-loaded ZSM-5 molecular sieve for olefin aromatization reaction is prepared by adopting an impregnation method. This is mainly because the low silica alumina ratio ZSM-5 molecular sieves are used mainly in the olefin aromatization reaction, whereas it is very difficult to synthesize pure ZSM-5 zeolite molecular sieves with lower silica alumina ratio by a liquid phase hydrothermal synthesis method. If one or more metal salts are added, the gel concentration will tend to be further increased, making synthesis more difficult. Therefore, the hydrothermal synthesis of the zinc-containing nickel-containing low-silicon ZSM-5 molecular sieve with a multistage structure has great significance, but the synthesis challenge is greater, and no relevant literature report exists before.
Disclosure of Invention
The invention aims to provide a ZSM-5 zeolite molecular sieve with a low-silicon multi-stage structure and containing zinc or/and nickel, which has higher external surface area, mesoporous volume, acid content and zinc and nickel content.
The invention also aims to provide a preparation method of the zinc or/and nickel containing ZSM-5 zeolite molecular sieve with the low-silicon multi-stage structure by adopting a hydrothermal synthesis method.
The invention further aims to provide application of the zinc or/and nickel containing ZSM-5 molecular sieve with the multilevel structure as a catalyst in olefin reduction of gasoline.
The purpose of the invention is realized by adopting the following technical scheme:
the invention provides a zinc or/and nickel-containing ZSM-5 molecular sieve with a multi-stage structure, which is a ZS with a silicon-aluminum atomic ratio of 10-50 obtained by a hydrothermal synthesis methodAn M-5 zeolite, wherein: zinc or/and nickel is/are contained in the pore channel of the zeolite, the atomic ratio of the zinc to the silicon is 0-0.04:1, the atomic ratio of the nickel to the silicon is 0-0.03:1, the ZSM-5 molecular sieve with the multilevel structure has a mesoporous structure formed by secondary accumulation of crystal grains of the molecular sieve, and the mesoporous volume is not less than 0.09cm3Per g, specific surface area greater than 240cm2(ii)/g, wherein the primary particles of the molecular sieve have a size of about 100nm to 2 μm and the secondary packing particles of the molecular sieve have a size of 2 μm to 8 μm.
The invention also provides a preparation method of the zinc or/and nickel-containing ZSM-5 molecular sieve with the multilevel structure, wherein: mixing a silicon-containing source solution and an aluminum-containing source solution by a hydrothermal synthesis method, and then carrying out hydrothermal synthesis, crystallization, post-treatment and roasting to obtain the zinc or/and nickel-containing ZSM-5 molecular sieve with the multilevel structure;
wherein, in the hydrothermal synthesis, a silicon Source (SiO)2Meter): template agent: water: the molar ratio of alkali metal is 1: 0.05-0.3: 7.9-16.7: 0.1-0.4;
aluminum source (with Al)2O3Meter): zinc source (in ZnO): nickel source (as NiO): silicon source (with SiO)2In terms of) is 0.01 to 0.05: 0-0.04: 0-0.03:1,
and the adding amount of the zinc source (calculated by ZnO) and the nickel source (calculated by NiO) is not zero at the same time.
The invention also provides an application of the ZSM-5 molecular sieve with the multilevel structure containing zinc or/and nickel as a catalyst in the olefin reduction of gasoline, wherein: the ZSM-5 molecular sieve containing zinc or/and nickel with a multi-stage structure is used as a catalyst for catalyzing the reaction of reducing the olefin of the gasoline. Wherein, the catalytic heavy gasoline (more than 70 ℃) is used as a reaction raw material, the hydrogen is used as a carrier gas, the reaction temperature is 360-420 ℃, the pressure is 1-3 MPa, the hydrogen-oil ratio is 100-400: 1, and the space velocity is 1-3 h-1The olefins in the heavy gasoline are converted into high octane components under the process conditions of (1).
Compared with the prior art, the zinc or/and nickel-containing ZSM-5 molecular sieve and the preparation method thereof have the following advantages:
1. the synthesized ZSM-5 molecular sieve has a plurality of mesoporous structures and excellent diffusion performance and reaction activity. The mesoporous template agent or organic additive is not needed to be added in the synthesis process, so that the cost is saved and the environmental pollution is reduced.
2. Compared with the prior art, the zinc and nickel containing ZSM-5 molecular sieve with the multilevel structure has the advantages of lower silica-alumina ratio which can reach 10-50, high metal loading rate and excellent modification effect.
3. The preparation method is simple to operate, and the prepared zinc-nickel-containing low-silicon multi-level structure molecular sieve has the advantages of higher crystallinity, good test repeatability, larger secondary particle aggregate and low industrial separation cost.
4. The zinc or/and nickel-containing ZSM-5 molecular sieve with the multilevel structure prepared by the hydrothermal synthesis system can be used for catalyzing gasoline desulfurization-olefin reduction reaction.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a zinc-containing hierarchical ZSM-5 molecular sieve obtained in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the ZSM-5 molecular sieve containing nickel multi-stage structure obtained in example 2;
FIG. 3 is an XRD pattern of a zinc-nickel containing multi-stage ZSM-5 molecular sieve obtained in example 3;
FIG. 4 is a Scanning Electron Microscope (SEM) image of the ZSM-5 molecular sieve containing zinc and nickel in a multi-stage structure obtained in example 3;
FIG. 5 is an XRD pattern of a zinc-nickel containing multi-stage ZSM-5 molecular sieve obtained in example 4;
FIG. 6 is a Scanning Electron Microscope (SEM) image of the ZSM-5 molecular sieve containing zinc and nickel in a multi-stage structure obtained in example 4;
FIG. 7 is a Scanning Electron Microscope (SEM) image of the metal-free ZSM-5 molecular sieve having a multi-stage structure obtained in comparative example 1.
Detailed Description
The ZSM-5 molecular sieve with the multilevel structure is obtained by adopting a hydrothermal synthesis method to obtain ZSM-5 zeolite with the silicon-aluminum atomic ratio of 10-50, wherein zinc or/and nickel is/are contained in pore channels of the zeolite, the atomic ratio of the zinc or/and nickel to silicon is 0-0.04 and 0-0.03 respectively, the catalyst has a mesoporous structure formed by twice accumulation of molecular sieve grains, and the mesoporous volume is not less than 0.09cm3Per g, specific surface area greater than 240cm2(ii)/g, wherein the molecular sieve has a primary particle size of about 100nm to 2 μm and a secondary bulk particle size of 2 μm to 8 μm.
The invention also provides a preparation method of the zinc or/and nickel-containing ZSM-5 molecular sieve, wherein a silicon source-containing solution and an aluminum source-containing solution are mixed, hydrothermally synthesized, crystallized, post-treated and roasted to obtain a finished product molecular sieve; SiO in hydrothermal synthesis system2The molar ratio of the template agent to the water to the alkali metal is 1: 0.05-0.3: 7.9-16.7: 0.1-0.4, preferably 1: 0.1-0.2: 8-12: 0.2 to 0.3; al in hydrothermal synthesis system2O3ZnO, NiO and SiO2In a molar ratio of 0.01 to 0.05: 0-0.04: 0-0.03:1, preferably in the range of 0.02-0.04:0.01-0.02:0.01-0.02: 1.
The preparation method of the zinc or/and nickel containing ZSM-5 molecular sieve with the multilevel structure comprises the steps of mixing a silicon source-containing solution and an aluminum source-containing solution by a hydrothermal synthesis method, and then carrying out hydrothermal synthesis, crystallization, post-treatment and roasting to obtain the zinc or/and nickel containing ZSM-5 molecular sieve with the multilevel structure; wherein, in the hydrothermal synthesis, a silicon Source (SiO)2Meter): template agent: water: the molar ratio of alkali metal is 1: 0.05-0.3: 7.9-16.7: 0.1-0.4; aluminum source (with Al)2O3Meter): zinc source (in ZnO): nickel source (as NiO): silicon source (with SiO)2In terms of) is 0.01 to 0.05: 0-0.04: 0-0.03:1, and wherein the added amounts of the zinc source (calculated as ZnO) and the nickel source (calculated as NiO) are not zero at the same time.
Adding a silicon source or a silicon source and a nickel source into a template agent solution, and stirring to form a silicon source-containing solution; and mixing and stirring the aluminum source or the aluminum source and the zinc source to form an aluminum-containing source solution. And (3) dropwise adding the finally obtained aluminum-containing source solution into the finally obtained silicon-containing source solution, and aging to obtain the hydrothermal synthesis system.
The preferred mode of the invention is that the silicon-containing source solution and the aluminum-containing source solution are subjected to aging treatment before being mixed, and the preferred aging treatment conditions of the silicon-containing source solution are as follows: aging at 50-90 deg.C for 2-10 hr; the aging treatment conditions of the aluminum source containing solution are as follows: aging at 30-90 deg.C for 5-10 hr; the aging treatment conditions after mixing the silicon-containing source solution and the aluminum-containing source solution are as follows: aging at 30-90 deg.C for 2-5 hr, preferably at 30-70 deg.C.
The preparation of the preferred hydrothermal synthesis system of the invention comprises the following steps:
(1) treating the silicon source-containing solution:
adding a template into water at the temperature of 20-50 ℃, stirring and dispersing to obtain a clear template solution, then adding a silicon source or a silicon source and a nickel source into the template solution, stirring to obtain a silicon source-containing solution, and then aging for 2-10 hours at the temperature of 50-90 ℃ to obtain a uniform solution;
(2) and (3) treating the aluminum source-containing solution:
dissolving an aluminum source or an aluminum source and a zinc source in water at the temperature of 20-50 ℃, adjusting the pH value, uniformly stirring to be clear to obtain an aluminum source-containing solution, and then aging for 5-10 hours at the temperature of 30-90 ℃ to obtain a uniform solution;
and finally, dropwise adding the finally obtained aluminum-containing source solution into the finally obtained silicon-containing source solution, and aging for 2-5 hours at the temperature of 30-90 ℃ to obtain a hydrothermal synthesis system.
The crystallization process of the present invention is preferably a two-stage crystallization method: the hydrothermal synthesis system is placed in a reaction kettle, the temperature is raised to 100-120 ℃ for pre-crystallization for 12-48 hours, and then the temperature is adjusted to 160-180 ℃ for secondary crystallization for 12-24 hours.
The preferred post-treatment and calcination processes of the present invention are: and (3) carrying out suction filtration and separation on the crystallized product, washing the crystallized product by using an ammonium chloride solution until the pH value of a product eluent is 7-8, then drying the product for 8-12 hours at the temperature of 60-100 ℃, continuously roasting the product for 4-6 hours at the temperature of 500-600 ℃, and repeating washing and roasting for three times to finally obtain the ZSM-5 zeolite molecular sieve.
The preferred roasting process of the invention is to roast for 4-6 hours at the speed of 1-4 ℃/min and the temperature of 500-600 ℃, repeatedly wash and roast for three times, and finally obtain the ZSM-5 zeolite molecular sieve.
The present invention is not particularly limited to silicon, aluminum, zinc and nickel sources, and may be those commonly used in the art, and preferred embodiments are: the silicon source is coarse silica gel or white carbon black; the aluminum source is aluminum isopropoxide or pseudo-boehmite or sodium metaaluminate; the zinc source is zinc nitrate or zinc sulfate; the nickel source is nickel nitrate or nickel chloride; the template agent is tetrapropylammonium hydroxide or tetrapropylammonium bromide; the alkali metal is provided by an alkali metal compound.
The ZSM-5 molecular sieve with the multi-stage structure can be directly used as a catalyst after being formed. The prepared catalyst is especially suitable for gasoline desulfurizing-olefin reducing process.
The invention also provides the application of the catalyst in the olefin reduction of gasoline. The catalyst is particularly suitable for the catalytic heavy gasoline olefin reduction reaction, the catalytic heavy gasoline (more than 70 ℃) is used as a reaction raw material, hydrogen is used as a carrier gas, the reaction temperature is 360-420 ℃, the pressure is 1-3 MPa, the hydrogen-oil ratio is 100-400: 1, and the space velocity is 1-3 h-1Under the process conditions of (1), the olefins in the gasoline are converted into high octane components.
The ZSM-5 zeolite molecular sieve has a large number of mesoporous structures besides low silica-alumina ratio and high content of metal, and has high acid content, high L acid/B acid ratio and excellent mass transfer and diffusion performance due to the synergistic effect of the zinc source and the nickel source introduced into zeolite channels. The prepared catalyst has higher performances of desulfurization and olefin direction-selective conversion into isoparaffin and aromatic hydrocarbon, and in addition, the mesoporous structure also increases the carbon capacity of the molecular sieve and prolongs the service life of the molecular sieve.
The method also realizes that the ZSM-5 molecular sieve successfully carries a large amount of metals in a hydrothermal mode under low silicon, the metals are uniformly distributed, and the repeatability of the experiment is high by adjusting the addition of the raw materials and other methods.
The invention also successfully and reasonably designs the sequence of the treatment and the addition of the raw materials to prepare the ZSM-5 zeolite molecular sieve with the zinc-nickel low-silicon multi-stage structure, in the treatment of the silicon source and the nickel source, as the nickel is non-amphoteric metal, only a certain amount of water can be added without adding alkali metal, so that the solution of the silicon source and the nickel source can be kept at a neutral condition with the pH of about 7, and the metallic nickel ions can be dissolved and uniformly dispersed in the SiO to the maximum extent2In (1). In the treatment of an aluminum source and a zinc source, a small amount of aluminum and zinc metals can be added because both are amphoteric metalsAnd a certain amount of alkali metal, so that the aluminum source and the zinc source are kept at a higher alkalinity, and the aluminum source and the zinc source can be fully dissolved and uniformly mixed in an ionic state.
The invention also preferably mixes the silicon-containing source solution and the aluminum-containing source solution and then ages for 2-5 hours. The physical properties of different metal ions are considered in the whole process, and the adding sequence and adding conditions are reasonably adjusted, so that the two metal ions with different physical properties can be successfully loaded on the low-silicon ZSM-5 molecular sieve.
The preferred two-stage crystallization method of the invention firstly limits the crystal growth at low temperature and promotes the crystal nucleus generation, when the number of the crystal nuclei is generated sufficiently, the temperature is rapidly raised, the crystals rapidly grow into small particles at high temperature in short time, and the small particles spontaneously aggregate to form the large-particle multi-level structure molecular sieve due to high surface activation energy of the small particles. The ZSM-5 molecular sieve with the multi-stage structure can be successfully prepared by adopting a two-stage temperature crystallization method, so that the energy and the time are saved.
In the preparation method, firstly, different metal salt precursors and silicon sources or aluminum sources are specifically mixed and aged to construct a proper pH value, the hydrolysis and condensation reaction rates of the metal salt precursors and the silicon sources or the aluminum sources are controlled, the precipitation process and the crystallization of silicon-aluminum gel can be synchronized in the hydrothermal synthesis process of transition metal ions and the silicon sources or the aluminum sources, the generation of large-particle metal hydroxides or oxides is avoided, the large-particle metal hydroxides or oxides cannot enter pore channels of zeolite, and the sizes of metal salt hydrolysis and condensation products are small enough to enter the pore channels of the zeolite to be uniformly dispersed.
Secondly, by using the proportion of specific silicon-aluminum gel, ZSM-5 zeolite can generate a hierarchical pore structure with nanocrystal accumulation, and intergranular mesopores generated by nanocrystal accumulation can be used, so that the size and the number of generation spaces of metal hydroxide or oxide in the synthesis process are increased, the problem of pore blocking between metal and the inside of zeolite pore channels is solved, the problem of surplus reactants and products in the reaction process is solved, and the performance of the catalyst is improved.
The invention combines the control of the crystallization process, and further provides a crystallization theory which utilizes low temperature to be beneficial to nucleation, controls the metal salt precursor and the silicon-aluminum gel to generate crystal nuclei with smaller particle size at low temperature, and then utilizes the rapid growth at high temperature to realize the growth of the silicon-aluminum gel on the crystal nuclei, realize that the metal oxide can be coated inside the zeolite pores, and ensure that the transition metal is more uniformly dispersed on the zeolite molecular sieve.
By adopting the scheme of the invention, the zinc-nickel-containing low-silicon ZSM-5 molecular sieve with a multistage structure is finally synthesized by hydrothermal synthesis, so that the uniform distribution of transition metal species is ensured, and the accessibility problem of reactants and the active center of the catalyst is improved by utilizing the characteristics of the multistage structure, thereby improving the performance of the catalyst.
The invention also provides application of the zinc-nickel-containing low-silicon multi-stage structure ZSM-5 zeolite molecular sieve in the aspects of gasoline desulfurization and olefin reduction.
In conclusion, the zinc or/and nickel-containing low-silicon multi-stage structure ZSM-5 zeolite molecular sieve has a lower silicon-aluminum ratio, higher zinc or/and nickel loading and a more mesoporous structure, wherein the primary particles are 300nm-800nm, and the secondary stacked particles are about 2 μm-8 μm. The preparation method of the invention has the advantages of simple preparation crystallization and convenient suction filtration and separation in the whole process. The mesoporous structure containing more ZSM-5 molecular sieves with zinc or/and nickel in the multilevel structure not only improves the diffusion rate of macromolecular reactants or products, but also increases the carbon capacity of the molecular sieves, so that the molecular sieves have higher selectivity and longer service life in the reactions of olefin reduction, aromatization and isomerization of catalytic gasoline.
Example 1: preparation of zinc-containing ZSM-5 zeolite molecular sieve with multi-stage structure
(1) And (3) treating a silicon source:
2g of tetrapropylammonium bromide (0.0075mol, corresponding to 0.06 time of the coarse silica gel) was added to 10g of water (0.556mol, corresponding to 4.444 times of the coarse silica gel) at 25 ℃ respectively, and after stirring uniformly, 7.5g of coarse silica gel (0.125mol) was added, and stirring was continued for about 30min to obtain a silicon source solution.
(2) Treating an aluminum source and a zinc source:
adding 0.57g of sodium metaaluminate (0.0025mol, which is equivalent to 0.02 time of the coarse-pore silica gel) into 8.75g of water (0.486mol, which is equivalent to 3.889 times of the coarse-pore silica gel) at 25 ℃, stirring for 5min, adding 0.80g of zinc sulfate (0.0049mol, which is equivalent to 0.04 time of the coarse-pore silica gel) and 0.8g of sodium hydroxide (0.02mol, which is equivalent to 0.16 time of the coarse-pore silica gel) to adjust the pH value to be about 13.1, continuously stirring for about 40min to be in a clear state to obtain an aluminum source and a zinc source solution, and then aging for 5 hours at 70 ℃ to obtain a uniform solution;
and finally, adding the silicon source solution into the aluminum source and zinc source solution, stirring for 2 hours, and aging for 4 hours at 70 ℃ to obtain a hydrothermal synthesis system.
(3) And (3) crystallization process: the raw material preparation liquid is transferred to a reaction kettle and placed in an oven with the temperature of 100 ℃ for pre-crystallization for 36 hours, and then the temperature is raised to 170 ℃ for crystallization for 24 hours.
(4) And (3) post-treatment process: and (3) performing conventional suction filtration on the crystallized product, washing the crystallized product by using 1mol/L ammonium chloride solution until the pH value of a product leacheate is 7-8, drying the product in an oven at 60 ℃ for 12 hours, heating the product to 550 ℃ at the speed of 1.7 ℃/min in a muffle furnace, continuously roasting the product for 6 hours, and repeatedly washing and roasting the product for three times to obtain the zinc-containing multi-stage structure ZSM-5 zeolite molecular sieve.
SEM test (see figure 1) is carried out on the obtained sample to show that the sample is a multi-stage structure formed by stacking nanosheets ZSM-5, the nanosheets are about 300-500 nm, and the aggregated particles are about 3 microns;
example 2: preparation of ZSM-5 zeolite molecular sieve containing nickel multi-stage structure
(1) Treating a silicon source and a nickel source:
respectively adding 3g of tetrapropylammonium bromide (0.0113mol, which is equivalent to 0.09 time of white carbon black) into 10g of water (0.556mol, which is equivalent to 4.444 times of white carbon black) at 25 ℃, uniformly stirring, adding 7.5g of white carbon black (0.125mol) and 0.76g of nickel chloride hexahydrate (0.0032mol, which is equivalent to 0.026 time of white carbon black), continuously stirring for about 30min to obtain a silicon source and nickel source solution, and aging for 10 hours at 50 ℃ to obtain a uniform solution.
(2) And (3) treating an aluminum source:
1.02g of aluminium isopropoxide (0.0025mol, corresponding to 0.02 times of white carbon) was added to 8.75g of water (0.486mol, corresponding to 3.889 times of white carbon) at 25 ℃ and 0.9g of sodium hydroxide (0.0225mol, corresponding to 0.18 times of white carbon) was added to adjust the pH to about 13.2, and the mixture was stirred for about 40min to a clear state to obtain an aluminium source solution, which was then aged at 30 ℃ for 10 hours to obtain a homogeneous solution.
And finally, adding the silicon source solution and the nickel source solution into the aluminum source solution, and aging for 5 hours at 30 ℃ to obtain a hydrothermal synthesis system.
(3) And (3) crystallization process: the raw material preparation liquid is transferred to a reaction kettle and placed in an oven with the temperature of 100 ℃ for pre-crystallization for 48 hours, and then the temperature is raised to 160 ℃ for crystallization for 48 hours.
(4) And (3) post-treatment process: and (3) performing conventional suction filtration on the crystallized product, washing the crystallized product by using 1mol/L ammonium chloride solution until the pH value of a product eluent is 7-8, drying the product in an oven at 60 ℃ for 12 hours, heating the product to 550 ℃ at the speed of 1.7 ℃/min in a muffle furnace, continuously roasting the product for 6 hours, and repeatedly washing and roasting the product for three times to finally obtain the nickel-containing ZSM-5 zeolite molecular sieve with the multilevel structure.
SEM test (see FIG. 2) of the obtained sample shows that the sample is a multi-stage structure ZSM-5 with large particles of about 2-3 μm formed by stacking particles of about 200-300 nm.
Example 3: preparation of zinc-nickel-containing low-silicon multi-stage structure ZSM-5 zeolite molecular sieve
(1) Treating a silicon source and a nickel source:
respectively taking 3g of tetrapropylammonium bromide (0.0188mol, which is equivalent to 0.15 time of the coarse-pore silica gel) at 25 ℃, adding the tetrapropylammonium bromide into 10g of water (0.556mol, which is equivalent to 4.444 times of the coarse-pore silica gel), uniformly stirring, adding 7.5g of coarse-pore silica gel (0.125mol) and 0.41g of nickel nitrate hexahydrate (0.0014mol, which is equivalent to 0.011 time of the coarse-pore silica gel), continuously stirring for about 30min to obtain a silicon source and a nickel source solution, and aging for 2 hours at 90 ℃ to obtain a uniform solution.
(2) Treating an aluminum source and a zinc source:
adding 1.02g of aluminum isopropoxide (0.0025mol, which is equivalent to 0.02 time of the coarse-pore silica gel) into 8.75g of water (0.486mol, which is equivalent to 3.889 times of the coarse-pore silica gel) at 25 ℃, stirring for 5min, adding 0.95g of zinc nitrate hexahydrate (0.0032mol, which is equivalent to 0.026 time of the coarse-pore silica gel) and 1.2g of sodium hydroxide (0.03mol, which is equivalent to 0.24 time of the coarse-pore silica gel), adjusting the pH value to about 13.2, continuously stirring for about 40min to a clear state to obtain an aluminum source and a zinc source solution, and then aging for 5 hours at 90 ℃ to obtain a uniform solution;
and finally, adding the silicon source solution into the aluminum source, zinc source and molybdenum source solution, and aging for 2 hours at 90 ℃ to obtain a hydrothermal synthesis system.
(3) And (3) crystallization process: transferring the raw material preparation liquid to a reaction kettle, placing the reaction kettle in a 120 ℃ oven for pre-crystallization for 12 hours, and then heating to 180 ℃ for crystallization for 12 hours.
(4) And (3) post-treatment process: and (3) performing conventional suction filtration on the crystallized product, washing the crystallized product by using 1mol/L ammonium chloride solution until the pH value of a product leacheate is 7-8, drying the product in an oven at 60 ℃ for 12 hours, heating the product to 550 ℃ at the speed of 1.7 ℃/min in a muffle furnace, continuously roasting the product for 6 hours, and repeatedly washing and roasting the product for three times to finally obtain the ZSM-5 zeolite molecular sieve with the zinc and nickel containing multilevel structure.
XRD testing of the resulting sample (see fig. 3) showed that the sample had a typical ZSM-5 molecular sieve MFI topology and higher crystallinity. Thus successfully preparing the ZSM-5 molecular sieve with the zinc-nickel low-silicon multi-stage structure; SEM tests (see FIG. 4) of the obtained sample showed that the sample was a 2 μm-3 μm multi-stage structure ZSM-5 molecular sieve formed by stacking nano-strip-shaped plate-shaped particles having a length of about 500nm and a width of about 200 nm.
Example 4: preparation of zinc-nickel-containing ultra-low silicon multi-stage structure ZSM-5 zeolite molecular sieve
(1) Treating a silicon source and a nickel source:
5g of tetrapropylammonium bromide (0.0188mol, equivalent to 0.15 time of the coarse silica gel) is added into 10g of water (0.556mol, equivalent to 4.444 times of the coarse silica gel) at 30 ℃ respectively, and after uniform stirring, 7.5g of coarse silica gel (0.125mol) and 0.24g of nickel nitrate hexahydrate (0.0008mol, equivalent to 0.007 time of the coarse silica gel) are added, stirring is continued for about 30min to obtain a silicon source and a nickel source solution, and then aging is carried out for 6 hours at 70 ℃ to obtain a uniform solution.
(2) Treating an aluminum source and a zinc source:
adding 2.55g of aluminum isopropoxide (0.00625mol, which is equivalent to 0.05 time of the coarse-pore silica gel) into 8.75g of water (0.486mol, which is equivalent to 3.889 times of the coarse-pore silica gel) at 30 ℃, stirring for 5min, adding 0.47g of zinc nitrate hexahydrate (0.0016mol, which is equivalent to 0.0127 time of the coarse-pore silica gel) and 1.5g of sodium hydroxide (0.0375mol, which is equivalent to 0.3 time of the coarse-pore silica gel) to adjust the pH value to be about 13.3, continuously stirring for about 40min to be in a clear state to obtain an aluminum source solution and a zinc source solution, and then aging for 6 hours at 70 ℃ to obtain a uniform solution;
and finally, adding the silicon source solution and the nickel source solution into the aluminum source solution and the zinc source solution, and aging for 5 hours at 70 ℃ to obtain a hydrothermal synthesis system.
(3) And (3) crystallization process: and transferring the raw material preparation liquid to a reaction kettle, placing the reaction kettle in an oven at 120 ℃ for pre-crystallization for 36 hours, and then heating to 170 ℃ for crystallization for 24 hours.
(4) And (3) post-treatment process: and (3) performing conventional suction filtration on the crystallized product, washing the crystallized product by using 1mol/L ammonium chloride solution until the pH value of a product leacheate is 7-8, drying the product in an oven at 60 ℃ for 12 hours, heating the product to 550 ℃ at the speed of 1.7 ℃/min in a muffle furnace, continuously roasting the product for 6 hours, and repeatedly washing and roasting the product for three times to finally obtain the ZSM-5 zeolite molecular sieve containing zinc and nickel.
XRD (X-ray diffraction) tests (see figure 5) are carried out on the obtained sample, so that the sample has a typical MFI topological structure of the ZSM-5 molecular sieve, and the successful preparation of the ZSM-5 molecular sieve with the zinc-containing and nickel-containing ultra-low silicon multi-stage structure is shown; SEM tests (see FIG. 6) of the obtained sample showed that the sample was a large-particle ZSM-5 molecular sieve containing zinc and nickel multilevel structure of 2-4 μm formed by stacking nano-strip particles of about 700nm in length and about 200-300nm in width.
Comparative example 1: preparation of zinc, nickel or zinc-nickel loaded ZSM-5 zeolite molecular sieve with multi-stage structure
(1) And (3) treating a silicon source:
3g of tetrapropylammonium bromide (0.0113mol, which is equivalent to 0.09 time of the coarse silica gel) is added into 10g of water (0.556mol, which is equivalent to 4.444 times of the coarse silica gel) at 25 ℃ respectively, and then 7.5g of coarse silica gel (0.125mol) is added after uniform stirring, and the stirring is continued for about 30min to obtain a silicon source solution.
(2) And (3) treating an aluminum source:
adding 1.02g of aluminum isopropoxide (0.0025mol, corresponding to 0.02 times of the coarse silica gel) into 8.75g of water (0.486mol, corresponding to 3.889 times of the coarse silica gel) at 25 ℃, adding 0.9g of sodium hydroxide (0.0225mol, corresponding to 0.18 times of the coarse silica gel) to adjust the pH value to about 13.2, and continuously stirring for about 40min until the solution is clear to obtain an aluminum source solution;
and finally, adding the silicon source solution into the aluminum source solution, and stirring for 2 hours to obtain a hydrothermal synthesis system.
(3) And (3) crystallization process: the raw material preparation liquid is transferred to a reaction kettle and placed in an oven with the temperature of 100 ℃ for pre-crystallization for 36h, and then the temperature is raised to 170 ℃ for crystallization for 24 h.
(4) And (3) post-treatment process: and (3) performing conventional suction filtration on the crystallized product, washing the crystallized product by using 1mol/L ammonium chloride solution until the pH value of a product eluent is 7-8, drying the product in an oven at 60 ℃ for 12 hours, heating the product to 550 ℃ at the speed of 1.7 ℃/min in a muffle furnace, continuously roasting the product for 6 hours, and repeatedly washing and roasting the product for three times to obtain the ZSM-5 zeolite molecular sieve with the multilevel structure.
SEM test (see figure 7) of the obtained sample shows that the sample is of a multi-stage structure formed by stacking nano ZSM-5 particles, the primary particles are about 50-150 nm, and the secondary aggregates are about 1-1.5 um.
(5) Preparation of ZSM-5 zeolite molecular sieve catalyst loaded with zinc, nickel or zinc-nickel: by adopting an equal-volume impregnation method, 7.83g of ZSM-5 zeolite molecular sieve synthesized by the method is used as a carrier, and the preparation of the metal impregnation liquid is carried out according to the water absorption of the molecular sieve carrier. 1) Zinc supported catalyst: weighing 0.95g of zinc nitrate, adding a small amount of deionized water, stirring and dissolving, and then fixing the volume by using the deionized water; 2) nickel supported catalyst: 0.41g of nickel nitrate hexahydrate is weighed, a small amount of deionized water is added, and after stirring and dissolving, the volume is determined by using the deionized water. 3) Zinc and nickel supported catalyst: weighing 0.95g of zinc nitrate, adding a small amount of deionized water, stirring to dissolve, adding 0.41g of nickel nitrate hexahydrate, stirring to dissolve, and finally fixing the volume by using the deionized water. The carrier is impregnated by an isometric impregnation method, and after the carrier is placed for 6 hours, the catalyst is dried for 4 hours at 120 ℃ and roasted for 4 hours at 550 ℃. The ZSM-5 molecular sieve catalyst with the multilevel structure loaded with zinc, nickel or zinc-nickel is prepared.
Comparative example 2
According to the method for preparing a hydrothermal synthesis system, crystallizing, filtering and the like according to CN104556135B example 3 and the published feeding molar ratio range, the method refers to the examples of the invention, and specifically comprises the following steps:
1. adding 1.18g of sodium hydroxide and 4g of tetrapropylammonium bromide into 10g of water, stirring for dissolving, adding 1.13g of sodium metaaluminate, clarifying the solution, adding 25g of silica sol, 0.95g of zinc nitrate hexahydrate and 0.41g of nickel nitrate hexahydrate, and continuously stirring for 3 hours, wherein the molar ratio of SiO to nickel nitrate is SiO2、Al2O3ZnO, NiO, template agent, sodium hydroxide and H2O is 1: 0.04: 0.026: 0.011: 0.09: 0.2: 8.4 of the total weight of the mixture;
2. and (3) crystallization process: the raw material preparation liquid is transferred to a reaction kettle and placed in an oven with the temperature of 100 ℃ for pre-crystallization for 36 hours, and then the temperature is raised to 170 ℃ for crystallization for 24 hours.
3. And (3) post-treatment process: and carrying out conventional suction filtration or centrifugal separation on the crystallized product, washing the crystallized product by using 1mol/L ammonium chloride solution until the pH value of the product leacheate is 7-8, then drying the product in an oven at 60 ℃ for 12 hours, finally heating the product to 550 ℃ at the speed of 1.7 ℃/min in a muffle furnace, continuing roasting the product for 6 hours, and repeatedly washing and roasting the product for three times to finally obtain the ZSM-5 zeolite molecular sieve.
The method comprises the steps of preparing a hydrothermal system by adopting CN104556135B example 3 and the published feeding molar ratio range, then adding a zinc source and a nickel source, and performing crystallization, separation, drying and roasting by adopting the steps 2 and 3, and the results show that the prepared ZSM-5 molecular sieve has extremely low crystallinity, almost cannot be synthesized, is mostly of a block structure with a smooth surface and has no stacking phenomenon. The method is greatly different from the zinc and nickel-containing ZSM-5 molecular sieve in a multi-stage structure, and firstly, the zinc and nickel-containing low-silicon ZSM-5 molecular sieve prepared by the method has higher crystallinity and no mixed crystal; secondly, the zinc-nickel-containing ultralow-silicon ZSM-5 molecular sieve prepared by the invention is a large-particle multistage-structure ZSM-5 molecular sieve with 3-7 mu m formed by stacking 100-300nm small particles or nanosheets.
Comparative example 3:
according to the methods of preparing hydrothermal synthesis systems, crystallization, filtration and the like and the feeding molar ratio published by CN608990A in example 7 and example 11, the aluminum source is added in the synthesis of examples 7 and 11 by combining the application examples of the invention. The method specifically comprises the following steps:
1. adding sodium hydroxide, sodium nitrate, zinc nitrate, tetrapropylammonium hydroxide and sodium metaaluminate into 10g of water, stirring the mixed solution to clarify, dripping 25% white carbon black into the clarified solution, stirring for 30 minutes, putting the solution into a stainless steel reaction kettle, sealing and crystallizing at the crystallization temperature of 110 ℃ for 4 days. In addition, stirring crystallization and standing crystallization are divided in the crystallization process. In the reaction system, the relative molar ratio is as follows: SiO 22/Zn2O3＝84,NaOH/Zn2O3＝9,NaNO3/Zn2O3＝100,H2O//Zn2O3＝5000,TPAOH/Zn2O3＝10,SiO2/Al2O340. And carrying out suction filtration, washing and drying on the product. The product is amorphous through XRD diffraction measurement, which shows that the zeolite molecular sieve can not be synthesized under the system due to the introduction of the aluminum source.
2. Adding sodium hydroxide, potassium nitrate, nickel nitrate, tetrapropylammonium bromide and sodium metaaluminate into 10g of water, stirring the mixed solution to clarify, dripping 25% white carbon black into the clarified solution, stirring for 30 minutes, putting the solution into a stainless steel reaction kettle, sealing and crystallizing at the crystallization temperature of 110 ℃ for 4 days. In addition, stirring crystallization and standing crystallization are divided in the crystallization process. In the reaction system, the relative molar ratio is as follows: SiO 22/Ni2O3＝84,NaOH/Ni2O3＝20，NaNO3/Ni2O3＝112,H2O/Ni2O3＝4500,TPABr/Ni2O3＝15,SiO2/Al2O350. And carrying out suction filtration, washing and drying on the product. The product is amorphous through XRD diffraction measurement, which shows that the zeolite molecular sieve can not be synthesized under the system due to the introduction of the aluminum source.
The comparison example shows that in the hydrothermal system process, transition metal ions and silicon-aluminum gel are introduced to carry out hydrothermal synthesis crystallization together, and the synergistic crystallization of the transition metal ions and the silicon-aluminum gel is very important and needs special raw materials and crystallization process treatment.
Experimental example 1:
BET tests were performed on inventive examples 1-4; the results are shown in Table 1. Wherein the specific surface and pore volume are obtained by a nitrogen adsorption and desorption method, and the data is given by a detection device (nitrogen adsorption and desorption analyzer).
Table 1: specific surface and pore volume of the sample
Table 1 the results show that: (examples 1-4) ZSM-5 molecular sieves with significantly reduced surface area but still higher external surface area with decreasing silica to alumina ratio and increasing metal loading: (>80cm3Per g) and pore volume>0.19cm3Per gram) and the mesoporous content of the molecular sieve is higher and accounts for about 50 percent of the pore volume.
Experimental example 2: study on aromatization Performance of 1-octene
The evaluation reaction apparatus was a small fixed-bed microreactor having reaction tube dimensions of 530 mm. times.8 mm. The reaction uses 0.1g of ultra-low silicon multi-stage structure ZSM-5 molecular sieve catalyst with the size of 20-40 meshes, nitrogen is taken as carrier gas, 1-octene is taken as reaction raw material, and N2The volume ratio of the 1-octene is 300, and the space velocity is 2h-1And the reaction is carried out for 4 hours at the reaction temperature of 350 ℃. The reaction product was examined and analyzed by GC-8706 chromatography to evaluate the reactivity of the catalyst.
Table 2: aromatization performance test of zinc-nickel-containing low-silicon multi-stage structure ZSM-5 molecular sieve 1-octene
Table 2 shows that in the non-hydrogenation condition, the hydrothermally synthesized zinc-containing, nickel-containing and zinc-nickel-containing low-silicon multi-stage structure ZSM-5 molecular sieve has 100% of 1-octene conversion rate and high selectivity of aromatic hydrocarbon compared with the catalyst loaded with zinc, nickel and zinc-nickel by the traditional impregnation method.
The result shows that the ZSM-5 molecular sieve provided by the invention is a ZSM-5 molecular sieve containing zinc and nickel multilevel structures, has rich mesoporous structures, higher metal loading capacity and lower silica-alumina ratio, and shows extremely high activity and aromatic hydrocarbon yield in olefin aromatization reaction.
Experimental example 3: research on olefin reduction reaction performance of catalytic gasoline
The evaluation of the catalytic gasoline olefin reduction reaction is carried out on the ZSM-5 with the ultra-low silicon multi-stage structure obtained in the experimental example 1 of the invention.
The evaluation reaction apparatus was a 20mL small fixed-bed microreactor. The reaction uses 20-40 mesh ultra-low silicon ZSM-5 molecular sieve catalyst with multi-stage structure, uses hydrogen as carrier gas and catalytic gasoline as reaction raw material, and has the reaction pressure of 2MPa, the temperature of 380 ℃ and the reaction temperature of H2The volume ratio of the catalytic gasoline is 300:1 and the space velocity is 1.5h-1The reaction is carried out under the process conditions of (1). The product composition was analyzed by GC-7890A gas chromatograph to evaluate the reactivity of the catalyst.
Table 3: test for olefin reduction performance of zinc-nickel-containing low-silicon multi-stage structure ZSM-5 molecular sieve catalytic gasoline
Table 3 shows that the hydrothermally synthesized zinc, nickel and zinc-nickel containing low-silicon multi-stage ZSM-5 molecular sieve has higher desulfurization and olefin reduction performance in the presence of hydrogen, compared with the conventional impregnation method for loading zinc, nickel and zinc-nickel catalysts, and also has high selectivity and lower octane number loss for high octane number products such as isoparaffin and aromatic hydrocarbon.
The result shows that the ZSM-5 molecular sieve provided by the invention is a ZSM-5 molecular sieve containing zinc and nickel multilevel structures, has rich mesoporous structures, higher metal loading capacity and lower silica-alumina ratio, and shows extremely high activity and aromatic hydrocarbon yield in olefin aromatization reaction.
Although the present invention has been described in detail with respect to the general description and the specific embodiments, it is apparent that modifications or improvements can be made to the invention based on the present invention, which is apparent to those skilled in the art. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A zinc or/and nickel-containing ZSM-5 molecular sieve with a multilevel structure is ZSM-5 zeolite with a silicon-aluminum atomic ratio of 10-50 obtained by a hydrothermal synthesis method, and is characterized in that: zinc or/and nickel is/are contained in the pore channel of the zeolite, the atomic ratio of the zinc to the silicon is 0-0.04:1, the atomic ratio of the nickel to the silicon is 0-0.03:1, the ZSM-5 molecular sieve with the multilevel structure has a mesoporous structure formed by secondary accumulation of crystal grains of the molecular sieve, and the mesoporous volume is not less than 0.09cm3Per g, specific surface area greater than 240cm2(ii)/g, wherein the primary particles of the molecular sieve have a size of about 100nm to 2 μm and the secondary packing particles of the molecular sieve have a size of 2 μm to 8 μm.
2. A method for preparing a zinc or/and nickel containing multi-stage structured ZSM-5 molecular sieve according to claim 1, characterized in that: mixing a silicon-containing source solution and an aluminum-containing source solution by a hydrothermal synthesis method, and then carrying out hydrothermal synthesis, crystallization, post-treatment and roasting to obtain the zinc or/and nickel-containing ZSM-5 molecular sieve with the multilevel structure;
wherein, in the hydrothermal synthesis, a silicon Source (SiO)2Meter): template agent: water: the molar ratio of alkali metal is 1: 0.05-0.3: 7.9-16.7: 0.1-0.4;
aluminum source (with Al)2O3Meter): zinc source (in ZnO): nickel source (as NiO): silicon source (with SiO)2In terms of) is 0.01 to 0.05: 0-0.04: 0-0.03:1,
and the adding amount of the zinc source (calculated by ZnO) and the nickel source (calculated by NiO) is not zero at the same time.
3. The method of claim 2, wherein: the silicon source is SiO2Meter): template agent:water: the molar ratio of alkali metal is 1: 0.1-0.2: 8-12: 0.2-0.3.
4. The method of claim 2, wherein: the aluminum source (as Al)2O3Meter): zinc source (in ZnO): nickel source (as NiO): silicon source (with SiO)2In terms of) is 0.02 to 0.04:0.01-0.02:0.01-0.02: 1.
5. the method of claim 2, wherein:
the silicon source-containing solution is obtained by adding the silicon source or the silicon source and the nickel source into the template agent solution and stirring;
the aluminum-containing source solution is obtained by mixing and stirring the aluminum source or the aluminum source and the zinc source.
6. The method of claim 5, wherein:
performing an aging treatment on the silicon-containing source solution and the aluminum-containing source solution before or after mixing;
wherein, before mixing, the aging treatment conditions of the silicon source-containing solution are as follows: aging at 50-90 deg.C for 2-10 hr;
before mixing, the aging treatment conditions of the aluminum source-containing solution are as follows: aging at 30-90 deg.C for 5-10 hr;
after mixing, the aging treatment conditions of the silicon-containing source solution and the aluminum-containing source solution are as follows: aging at 30-90 deg.C for 2-5 hr.
7. The method of claim 2, wherein:
the crystallization is two-stage crystallization, comprising: heating the obtained product after the hydrothermal synthesis to 100-120 ℃, and performing pre-crystallization for 12-48 hours; then the temperature is raised to 160-180 ℃, and crystallization is carried out again for 12-24 hours.
8. The method of claim 2, wherein:
the post-treatment and the firing include: performing suction filtration separation on the crystallized product, washing the crystallized product by using an ammonium chloride solution until the pH value of leacheate is 7-8, drying the filtrate for 8-12 hours at the temperature of 60-100 ℃, and then heating to 600 ℃ for roasting for 4-6 hours; the washing and the baking were repeated three times.
9. The method of claim 2, wherein:
the silicon source is coarse-pore silica gel or white carbon black;
the aluminum source is aluminum isopropoxide or pseudo-boehmite or sodium metaaluminate;
the zinc source is zinc nitrate or zinc sulfate;
the nickel source is nickel nitrate or nickel chloride;
the template agent is tetrapropylammonium hydroxide or tetrapropylammonium bromide.
10. Use of a zinc or/and nickel containing multi-stage structure ZSM-5 molecular sieve as claimed in claim 1 or a zinc or/and nickel containing multi-stage structure ZSM-5 molecular sieve as prepared according to the preparation process of any of claims 2 to 9 as a catalyst in the olefin reduction of gasoline characterized in that: the ZSM-5 molecular sieve containing zinc or/and nickel and having a multi-stage structure is used as a catalyst in a reaction for catalyzing gasoline to reduce olefin, wherein heavy catalytic gasoline (more than 70 ℃) is used as a reaction raw material, hydrogen is used as a carrier gas, and the reaction temperature is 360-420 ℃, the pressure is 1-3 MPa, the hydrogen-oil ratio is 100-400: 1, and the airspeed is 1-3 h-1The olefins in the heavy gasoline are converted into high octane components under the process conditions of (1).
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Application publication date: 20201208 |