CN113042094A - Lanthanum-containing and nickel or/and zinc-containing ZSM-5 molecular sieve with multi-stage structure and preparation method and application thereof - Google Patents
Lanthanum-containing and nickel or/and zinc-containing ZSM-5 molecular sieve with multi-stage structure and preparation method and application thereof Download PDFInfo
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- CN113042094A CN113042094A CN201911367038.1A CN201911367038A CN113042094A CN 113042094 A CN113042094 A CN 113042094A CN 201911367038 A CN201911367038 A CN 201911367038A CN 113042094 A CN113042094 A CN 113042094A
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- lanthanum
- molecular sieve
- nickel
- zinc
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 189
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 122
- 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 122
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 107
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000011701 zinc Substances 0.000 title claims abstract description 105
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 100
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 78
- 239000010457 zeolite Substances 0.000 claims abstract description 43
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 42
- 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 42
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 claims abstract description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000009825 accumulation Methods 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 239000011164 primary particle Substances 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 87
- 239000010703 silicon Substances 0.000 claims description 87
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 72
- 229910052782 aluminium Inorganic materials 0.000 claims description 62
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 56
- 238000002425 crystallisation Methods 0.000 claims description 47
- 230000008025 crystallization Effects 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 39
- 239000000741 silica gel Substances 0.000 claims description 35
- 229910002027 silica gel Inorganic materials 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 31
- 230000032683 aging Effects 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910001868 water Inorganic materials 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 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
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 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
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 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 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 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 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 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 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
- 239000012159 carrier gas Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical group Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- 238000009792 diffusion process Methods 0.000 abstract description 8
- 238000006477 desulfuration reaction Methods 0.000 abstract description 5
- 230000023556 desulfurization Effects 0.000 abstract description 5
- 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
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000006011 modification reaction Methods 0.000 abstract description 2
- 238000012856 packing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 78
- 239000000047 product Substances 0.000 description 57
- 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 238000011068 loading method Methods 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000499 gel Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000005899 aromatization reaction Methods 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 150000003839 salts 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
- 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
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910001428 transition metal ion Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229910052593 corundum Inorganic materials 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
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000003912 environmental pollution 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
- 239000002159 nanocrystal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000006259 organic additive 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
- 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
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000000903 blocking effect Effects 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
- 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
- 238000011156 evaluation 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
- 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
- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000007935 neutral effect Effects 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
- 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
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 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
- 238000005303 weighing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- 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
-
- 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
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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
- B01J35/61—Surface area
- B01J35/613—10-100 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
- B01J35/61—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/695—Pore distribution polymodal
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- 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
- C10G45/12—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 containing crystalline alumino-silicates, e.g. molecular sieves
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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Abstract
The invention relates to a lanthanum-containing and nickel or/and zinc-containing ZSM-5 molecular sieve with a multi-stage structure, a preparation method thereof and application thereof in catalyzing gasoline to reduce olefin. The molecular sieve is ZSM-5 zeolite with the silicon-aluminum atomic ratio of 10-50, which is obtained by a hydrothermal synthesis method, wherein: the channels in the zeolite contain lanthanum, and contain zinc or/and nickel; the multi-stage junctionThe structural ZSM-5 molecular sieve has a mesoporous structure formed by secondary accumulation of crystal grains of the molecular sieve, and the volume of a mesoporous is not less than 0.09cm3Per g, specific surface area greater than 200cm2(ii)/g, wherein the molecular sieve has a primary particle size of about 300nm to 2 μm and a secondary packing particle size of 2 μm to 8 μm. The lanthanum-containing and nickel or/and zinc-containing ZSM-5 molecular sieve has higher acid content and L acid/B acid ratio, and more mesoporous structures improve the diffusion rate of macromolecular reactants or products, so that the carbon-containing capacity of the catalyst is enhanced, and the catalyst has higher desulfurization and olefin-octane number reduction recovery activity and long-period stability in the catalytic gasoline olefin reduction-modification reaction.
Description
Technical Field
The invention belongs to the technical field of catalytic materials and catalytic chemistry, and particularly relates to a hydrothermal synthesis method and application of a gasoline olefin reduction-modified ZSM-5 zeolite molecular sieve with a multilevel structure.
Background
The ZSM-5 molecular sieve is used as a good catalyst due to the unique pore channel structure and acid property, high hydrothermal stability and oleophilic hydrophobicity, and is often used as a solid acid catalyst to be widely applied to alkylation, catalytic cracking, alcohol dehydration and other reactions. Meanwhile, because the catalyst has high specific surface area and excellent ion exchange performance and is an excellent carrier of metal ions or metal compounds with catalytic activity, the catalyst loaded by the ZSM-5 molecular sieve, such as iron, silver, copper and the like, has 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 alcohol aromatization reaction 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.
The traditional ZSM-5 molecular sieve has the pore size smaller than 0.6nm, so that the catalytic application of the molecular sieve is seriously influenced by the diffusion limitation, meanwhile, when the ZSM-5 molecular sieve is used for olefin aromatization reaction, one or more metals are required to be modified, 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 path and diffusion limitation of the traditional ZSM-5 molecular sieve are solved by adopting a method for preparing the ZSM-5 with the multilevel structure at present, and the preparation method of the ZSM-5 molecular sieve with the multilevel structure at present mainly comprises a post-treatment method, a hard template method and a soft template method. The post-treatment method comprises a dealumination method and a desilication method, wherein the dealumination method usually adopts high-temperature hydrothermal treatment and acid treatment to remove aluminum atoms from a zeolite framework so as to generate mesopores, the desilication method mainly adopts alkali treatment to remove silicon atoms in the framework so as to obtain the mesopores, and the two post-treatment methods have different effects when treating the zeolites with different silicon-aluminum ratios. Hard template methods often use carbon materials as templates, which can produce a variety of mesoporous structures, but this route is costly and long-lived. In the preparation process of the soft template method, the charge density matching between the surfactant and the inorganic substance at the interface is found to be the key for successful assembly of the mesoporous material, and the obtained product has high controllability of mesopores, but needs an expensive structure directing agent, has more complicated steps and is difficult to industrialize.
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 a metal inorganic salt solution, and the metal ions adsorbed on the pore channels of the molecular sieve are roasted to obtain active components such as metal oxide and the like, so the operation steps are complicated and the preparation time is long. The ion exchange method is to place the molecular sieve in a metal salt solution to perform the exchange and substitution of metal ions and framework aluminum atoms under certain temperature and pH conditions, and has complicated operation steps and no control of metal loading. The mechanical mixing method is to physically mix and stir the metal salt and the molecular sieve, the operation steps are simple, but metal ions are difficult to enter the surface of the pore channel to achieve the synergistic effect with the acid sites on the surface of the pore channel. Therefore, the method adopting hydrothermal load is simple, convenient and green, has short operation period and low cost and is more beneficial to industrialization. However, the metal-loaded ZSM-5 molecular sieves currently used for olefin aromatization reactions are essentially prepared by impregnation. This is mainly because the ZSM-5 molecular sieve with low silica-alumina ratio is mainly used in the aromatization reaction of olefin, and the synthesis of pure ZSM-5 zeolite molecular sieve with low silica-alumina ratio by liquid phase hydrothermal synthesis method is very difficult. If one or more metal salts are added, the gel concentration tends to be further increased, making synthesis more difficult. Therefore, the hydrothermal synthesis of the zinc, nickel and lanthanum containing low-silicon ZSM-5 molecular sieve with a multilevel structure has great significance, but the synthesis challenge is greater, and no relevant patent report exists at present.
Disclosure of Invention
The invention aims to provide a multistage-structure ZSM-5 molecular sieve containing lanthanum, nickel or/and zinc, which has more mesoporous structures and more excellent diffusion performance and reaction activity.
The invention also aims to provide a lanthanum-containing and nickel-containing or/and zinc-containing ZSM-5 molecular sieve with a multistage structure, which has a lower silica-alumina ratio, a high metal loading rate and an excellent modification effect.
The invention also aims to provide the ZSM-5 molecular sieve containing lanthanum, nickel or/and zinc and having a multistage structure, wherein the secondary particle aggregate is large, and the industrial separation cost is low.
The invention also aims to provide a preparation method of the ZSM-5 molecular sieve containing lanthanum, nickel or/and zinc and having the multilevel structure by adopting a hydrothermal synthesis method, and the obtained low-silicon ZSM-5 zeolite molecular sieve containing lanthanum, nickel or/and zinc and having the multilevel structure has higher external surface area, mesoporous volume and acid content and zinc, nickel and lanthanum content.
The invention further aims to provide application of the multistage-structure ZSM-5 molecular sieve containing lanthanum and nickel or/and zinc in catalyzing gasoline to reduce olefin.
The purpose of the invention can be realized by adopting the following technical scheme:
the invention provides a lanthanum-containing and nickel or/and zinc-containing ZSM-5 molecular sieve with a multilevel structure, which is ZSM-5 zeolite with a silicon-aluminum atomic ratio of 10-50 obtained by a hydrothermal synthesis method, wherein: the channels in the zeolite contain lanthanum and contain zinc or/and nickel, and the atomic ratio of said zinc to said silicon is 0-0.04, the atomic ratio of said nickel to said silicon is 0-0.03, and the atomic ratio of said lanthanum to said silicon is 0.001-0.02; 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 volume of the mesopores is not less than 0.09cm3Per g, specific surface area greater than 200cm2(ii)/g, wherein the primary particles of the molecular sieve have a size of about 300nm to 2 μm and the secondary packed particles of the molecular sieve have a size of 2 μm to 8 μm.
The invention also provides a preparation method of the multistage-structure ZSM-5 molecular sieve containing lanthanum and nickel or/and zinc, wherein the preparation method comprises the following steps: mixing a silicon-containing source solution and an aluminum-containing source solution by a hydrothermal synthesis method, and then carrying out hydrothermal crystallization, post-treatment and roasting to obtain the lanthanum-containing and nickel-or/and zinc-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)2O3): zinc source (in ZnO): nickel source (as NiO): lanthanum source (with La)2O3Meter): silicon source (with SiO)2In terms of) is 0.01 to 0.05: 0-0.04: 0-0.03: 0.01-0.15: 1.
the invention also provides lanthanum-containing and nickel-containing compositionsOr/and zinc, and the application of the ZSM-5 molecular sieve with the multilevel structure as a catalyst in the desulfurization-olefin reduction of gasoline, wherein: the lanthanum-containing and nickel or/and zinc-containing ZSM-5 molecular sieve with the multi-stage structure is used as a catalyst in a reaction for catalyzing heavy gasoline to reduce olefin, wherein 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-1The olefins in the heavy gasoline are converted into high octane components under the process conditions of (1).
Compared with the prior art, the low-silicon multi-stage structure ZSM-5 molecular sieve containing zinc, nickel and lanthanum and the synthesis 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, nickel and lanthanum containing ZSM-5 molecular sieve prepared by the hydrothermal method 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 and lanthanum-containing low-silicon molecular sieve with the multilevel structure has the advantages of higher crystallinity, good test repeatability, larger secondary particle aggregate and low industrial separation cost.
4. The ZSM-5 molecular sieve with the zinc, nickel and lanthanum multi-stage structure prepared by the hydrothermal synthesis system can be used for catalyzing gasoline desulfurization-olefin reduction reaction.
Drawings
FIG. 1: a Scanning Electron Microscope (SEM) image of the ZSM-5 molecular sieve containing the zinc and lanthanum multistage structure obtained in the example 1;
FIG. 2: a Scanning Electron Microscope (SEM) picture of the ZSM-5 molecular sieve containing the nickel and lanthanum multistage structure obtained in the example 2;
FIG. 3: XRD pattern of zinc, nickel and lanthanum containing hierarchical structure ZSM-5 molecular sieve obtained in example 3;
FIG. 4: scanning Electron Microscope (SEM) images of the ZSM-5 molecular sieve containing zinc, nickel and lanthanum in the multi-stage structure obtained in example 3;
FIG. 5: XRD pattern of zinc, nickel and lanthanum containing hierarchical structure ZSM-5 molecular sieve obtained in example 4;
FIG. 6: scanning Electron Microscope (SEM) image of the ZSM-5 molecular sieve containing zinc, nickel and lanthanum in the multistage structure obtained in example 4;
FIG. 7: scanning Electron Microscope (SEM) image of the metal-free ZSM-5 molecular sieve with the multilevel structure obtained in the comparative example 1.
Detailed Description
The invention provides a lanthanum-containing and nickel or/and zinc-containing ZSM-5 molecular sieve with a multilevel structure, which is ZSM-5 zeolite with a silicon-aluminum atomic ratio of 10-50 obtained by a hydrothermal synthesis method, wherein: the channels in the zeolite contain lanthanum and contain zinc or/and nickel, and the atomic ratio of said zinc to said silicon is 0-0.04, the atomic ratio of said nickel to said silicon is 0-0.03, and the atomic ratio of said lanthanum to said silicon is 0.001-0.02; 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 volume of the mesopores is not less than 0.09cm3Per g, specific surface area greater than 200cm2(ii)/g, wherein the primary particles of the molecular sieve have a size of about 300nm to 2 μm and the secondary packed particles of the molecular sieve have a size of 2 μm to 8 μm.
The invention also provides a preparation method of the lanthanum-containing and nickel or/and zinc-containing ZSM-5 molecular sieve with the multilevel structure, wherein the preparation method comprises the following steps: mixing a silicon-containing source solution and an aluminum-containing source solution by a hydrothermal synthesis method, and then carrying out hydrothermal crystallization, post-treatment and roasting to obtain the lanthanum-containing and nickel-or/and zinc-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)2O3): zinc source (in ZnO): nickel source (as NiO): lanthanum source (with La)2O3Meter): silicon source (with SiO)2In terms of) is 0.01 to 0.05: 0-0.04: 0-0.03: 0.01-0.15: 1.
in a preferred embodiment of the invention, 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.
In the preferred embodiment of the present inventionIn an embodiment, the aluminum source is aluminum (as Al)2O3): zinc source (in ZnO): nickel source (as NiO): lanthanum source (with La)2O3Meter): silicon source (with SiO)2In terms of) is 0.02 to 0.04: 0.01-0.02: 0.01-0.02: 0.05-0.1: 1.
in a preferred embodiment of the present invention, the silicon-containing source solution is obtained by adding the silicon source, or the silicon source and the nickel source to the template solution and stirring; the aluminum-containing source solution is obtained by mixing and stirring the aluminum source and the lanthanum source, or the aluminum source and the zinc source and the lanthanum source.
In a preferred embodiment of the present invention, an aging treatment is performed before or after the silicon-containing source solution and the aluminum-containing source solution are mixed; wherein, before mixing, the aging treatment conditions of the silicon source-containing solution are as follows: aging at 50-70 deg.C for 2-10 hr; before mixing, the aging treatment conditions of the aluminum source-containing solution are as follows: aging at 30-70 deg.C for 5-10 hr; after mixing, 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.
In a preferred embodiment of the present invention, 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.
In the invention, because transition metal elements such as zinc, nickel, lanthanum and the like are added, metal ions influence the crystallization and growth processes of silicon and aluminum gel in the zeolite synthesis process in a hydrothermal system, so that the crystallization of zeolite becomes more difficult. Therefore, a special treatment mode is needed to avoid the technical problem that the introduction of transition metal ions causes difficulty in zeolite synthesis.
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 (2) mixing and stirring an aluminum source and a lanthanum source or the aluminum source, a zinc source and the lanthanum source to form an aluminum-containing source solution, dripping the finally obtained aluminum-containing source solution into the finally obtained silicon-containing source solution, and aging to obtain a hydrothermal synthesis system.
In a preferred embodiment of the present invention, the hydrothermal synthesis system of the present invention is prepared by the steps of:
(1) and (3) treating the aluminum source-containing solution:
dissolving an aluminum source and a lanthanum source or an aluminum source, a zinc source and a lanthanum source in water at the temperature of 20-50 ℃, adjusting the pH value, uniformly stirring to be a clear state to obtain an aluminum source solution or an aluminum source and a zinc source or an aluminum source, a zinc source and a lanthanum source solution, and then aging for 5-10 hours at the temperature of 30-90 ℃ to obtain a uniform solution;
(2) 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 for a period of time 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;
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 present invention is not particularly limited to silicon sources, aluminum sources, zinc sources, nickel sources, and lanthanum sources, and may be applied to any sources commonly used in the art. In a preferred embodiment of the present invention, 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 acetate; the lanthanum source is lanthanum chloride or lanthanum nitrate; the template agent is tetrapropylammonium hydroxide or tetrapropylammonium bromide.
In a preferred embodiment of the present invention, the post-treatment and the firing comprise: performing 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 leacheate is 7-8, then drying the product leacheate for 8-12 hours at the temperature of 60-100 ℃, and then heating the product leacheate to 600 ℃ for roasting for 4-6 hours; the washing and the baking were repeated three times. In a preferred embodiment of the present invention, the rate of temperature rise is 1 to 4 ℃/min.
The multi-stage structure ZSM-5 molecular sieve 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 gasoline desulfurization-olefin reduction. 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 lanthanum source, particularly the zinc source and the nickel source, introduced into zeolite pore 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 treatment and adding sequence of the raw materials to prepare the ZSM-5 zeolite molecular sieve with the zinc, nickel and lanthanum 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 silicon source and the nickel source solution can be kept in a neutral condition of pH 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 the aluminum source, the zinc source and the lanthanum source, because the aluminum and the zinc are all bipolar metals, and the lanthanum source has higher solubility in an alkaline solution, a small amount of water and a certain amount of alkali metal can be added, so that the aluminum source, the zinc source and the lanthanum source can be kept at higher alkalinity, and the aluminum source, the zinc source and the lanthanum source can be fully dissolved and uniformly mixed in an ionic stateAnd (6) mixing.
In the invention, the silicon-containing source solution and the aluminum-containing source solution are mixed and aged for 2 to 5 hours. 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 invention prefers two-stage crystallization method, firstly limits the crystal growth at low temperature and promotes the crystal nucleus generation, when the crystal nucleus quantity is generated enough, the temperature is quickly raised, the crystal rapidly grows into small particles at high temperature in short time, and the small particles can spontaneously aggregate to form 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 hydro-thermal synthesis of the zinc, nickel and lanthanum containing low-silicon ZSM-5 molecular sieve with a multistage structure is finally realized, the uniform distribution of transition metal species is ensured, and the characteristic of the multistage structure can be utilized to improve the accessibility problem of reactants and the active center of the catalyst, thereby improving the performance of the catalyst.
The invention also provides application of the low-silicon ZSM-5 zeolite molecular sieve containing zinc, nickel and lanthanum in the aspects of gasoline desulfurization and olefin reduction.
The lanthanum-containing and nickel or/and zinc-containing ZSM-5 molecular sieve has higher acid content and L acid/B acid ratio, and more mesoporous structures improve the diffusion rate of macromolecular reactants or products, so that the carbon-containing capacity of the catalyst is enhanced, and the catalyst has higher desulfurization and olefin-octane number reduction recovery activity and long-period stability in the catalytic gasoline olefin reduction-modification reaction.
Compared with the prior art, the zinc, nickel and lanthanum-containing low-silicon ZSM-5 molecular sieve and the synthesis 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, nickel and lanthanum containing ZSM-5 molecular sieve prepared by the hydrothermal method 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 and lanthanum-containing low-silicon molecular sieve with the multilevel structure has the advantages of higher crystallinity, good test repeatability, larger secondary particle aggregate and low industrial separation cost.
4. The ZSM-5 molecular sieve with the zinc, nickel and lanthanum multi-stage structure prepared by the hydrothermal synthesis system can be used for catalyzing gasoline desulfurization-olefin reduction reaction.
Example 1: preparation of zinc and lanthanum 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, a zinc source and a lanthanum source:
adding 0.57g of sodium metaaluminate (0.0025mol, equivalent to 0.02 time of the coarse silica gel) into 8.75g of water (0.486mol, equivalent to 3.889 times of the coarse silica gel), stirring for 5min, adding 1.47g of zinc nitrate hexahydrate (0.0049mol, equivalent to 0.04 time of the coarse silica gel), adding 0.57g of lanthanum chloride (0.0014mol, equivalent to 0.011 time of the coarse silica gel), adding 1.0g of sodium hydroxide (0.02mol, equivalent to 0.16 time of the coarse silica gel), adjusting the pH value to about 13.1, continuously stirring for about 40min to a clear state to obtain an aluminum source and a zinc source solution, and aging for 10 hours at 30 ℃ to obtain a uniform solution;
and finally, adding the silicon source solution into the aluminum source, zinc source and lanthanum 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 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 with the zinc and lanthanum containing hierarchical structure.
SEM examination of the resulting sample (see FIG. 1) showed that the sample was a multi-stage structure formed by stacking of nano-rod-shaped ZSM-5 particles, the nano-rod-shaped particles having a length of about 500-800nm and the aggregated particles having a size of about 1-2 μm.
Example 2: preparation of ZSM-5 zeolite molecular sieve containing nickel and lanthanum 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 0.93g of nickel nitrate 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) Treating an aluminum source and a lanthanum source:
adding 1.02g of aluminum isopropoxide (0.0025mol, which is equivalent to 0.02 time of white carbon black) into 8.75g of water (0.486mol, which is equivalent to 3.889 times of white carbon black), adding 0.29g of lanthanum chloride (0.0007mol, which is equivalent to 0.006 time of white carbon black) and 0.9g of sodium hydroxide (0.0225mol, which is equivalent to 0.18 time of coarse pore silica gel) at 25 ℃, adjusting the pH value to be about 13.2, continuously stirring for about 40min to a clear state to obtain an aluminum source solution, and then aging for 5 hours at 90 ℃ to obtain a uniform solution;
and finally, adding the silicon source solution and the nickel source solution into the aluminum source solution and the lanthanum source solution, and aging for 5 hours at 90 ℃ 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 a 120 ℃ oven for pre-crystallization for 24 hours, and then the temperature is raised 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 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 ZSM-5 zeolite molecular sieve containing the nickel and lanthanum hierarchical structure.
SEM tests (see FIG. 2) of the obtained sample showed that the sample was a multistage structure ZSM-5 in which flaky particles of about 800nm were stacked to form large particles of about 2 to 3 μm.
Example 3: preparation of zinc, nickel and lanthanum containing low-silicon ZSM-5 zeolite molecular sieve with multi-stage structure
(1) Treating a silicon source and a nickel source:
3g of tetrapropylammonium bromide (0.0188mol, which is equivalent to 0.15 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 30 ℃ respectively, and after uniform stirring, 7.5g of coarse silica gel (0.125mol) and 0.41g of nickel nitrate hexahydrate (0.0014mol, which is equivalent to 0.011 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 2 hours at 90 ℃ to obtain a uniform solution.
(2) Treating an aluminum source, a zinc source and a lanthanum source:
1.02g of aluminum isopropoxide (0.0025mol, corresponding to 0.02 times of the coarse silica gel) was added to 8.75g of water (0.486mol, corresponding to 3.889 times of the coarse silica gel) at 30 ℃, stirred for 5min, then 0.26g of zinc nitrate hexahydrate (0.0016mol, corresponding to 0.013 times of the coarse silica gel) was added, stirred for 5min, then 0.82g of lanthanum nitrate (0.0014mol, corresponding to 0.011 times of the coarse silica gel) was added, and 1.2g of sodium hydroxide (0.03mol, corresponding to 0.24 times of the coarse silica gel) was added to adjust the pH to about 13.2, and stirred for about 40min to a clear state to obtain a source solution of aluminum, zinc and lanthanum, which was then aged at 50 ℃ for 4 hours to obtain a homogeneous solution.
And finally, adding the silicon source solution and the nickel source solution into the aluminum source solution, the zinc source solution and the lanthanum source solution, and aging for 4 hours at 50 ℃ 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 at 110 ℃ 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 finally obtain the ZSM-5 zeolite molecular sieve containing zinc, nickel and lanthanum and having a multilevel structure.
XRD testing of the obtained sample (see figure 3) can show that the sample has a characteristic peak of MFI topological structure of the typical ZSM-5 zeolite and has higher crystallinity. Thus successfully preparing the ZSM-5 molecular sieve with the zinc, nickel and lanthanum low-silicon multi-stage structure; SEM tests (see FIG. 4) of the obtained sample showed that the sample was a ZSM-5 molecular sieve of a multi-stage structure of 6 μm to 8 μm formed by stacking nano-strip-shaped plate-shaped particles with a width of about 2 μm.
Example 4: preparation of zinc, nickel and lanthanum 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 25 ℃ 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 aging is carried out for 4 hours at 70 ℃ to obtain a uniform solution.
(2) Treating an aluminum source, a zinc source and a lanthanum source:
adding 2.55g of aluminum isopropoxide (0.00625mol, equivalent to 0.05 times of coarse silica gel) into 8.75g of water (0.486mol, equivalent to 3.889 times of coarse silica gel) at 25 ℃, stirring for 5min, adding 0.47g of zinc nitrate hexahydrate (0.0016mol, equivalent to 0.0127 times of coarse silica gel), stirring for 5min, adding 0.57g of lanthanum nitrate (0.00098mol, equivalent to 0.0078 times of coarse silica gel) and 1.5g of sodium hydroxide (0.0375mol, equivalent to 0.3 times of coarse silica gel) to adjust the pH value to about 13.3, continuously stirring for about 40min to a clear state to obtain an aluminum source, a zinc source and a lanthanum source solution, and aging for 5 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, the zinc source solution and the lanthanum source solution, 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 at 110 ℃ 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 finally obtain the ultralow-silicon ZSM-5 zeolite molecular sieve containing zinc, nickel and lanthanum.
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 characteristic peak of ZSM-5 zeolite, and the successful preparation of the ZSM-5 molecular sieve with the ultralow silicon multilevel structure containing zinc, nickel and lanthanum is shown; SEM test (see figure 6) of the obtained sample shows that the sample is formed by stacking nano flaky particles to form a zinc, nickel and lanthanum containing multi-stage structure large-particle ZSM-5 molecular sieve with the particle size of about 6-8 mu m.
Comparative example 1: preparation of zinc, nickel and lanthanum 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 0.38g of pseudo-boehmite (0.0025mol, corresponding to 0.02 time of coarse silica gel) into 8.75g of water (0.486mol, corresponding to 3.889 times of coarse silica gel) at 25 ℃, adding 0.9g of sodium hydroxide (0.0225mol, corresponding to 0.18 time of coarse silica gel) to adjust the pH value to be about 13.2, and continuously stirring for about 40min to be in a clear state 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 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 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 FIG. 7) of the obtained sample shows that the sample has a multilevel structure formed by stacking of nano ZSM-5 particles, wherein the primary particles are about 50-150nm, and the secondary aggregates are about 0.5-1.5 μm;
(5) preparing a zinc, nickel and lanthanum loaded ZSM-5 zeolite molecular sieve catalyst: adopting an isometric impregnation method, taking 7.83g of the ZSM-5 zeolite molecular sieve synthesized by the method as a carrier, preparing a metal impregnation liquid according to the water absorption of the molecular sieve carrier, weighing a certain amount of deionized water, adding 0.82g of lanthanum nitrate, stirring for 30min until the lanthanum nitrate is dissolved, adding 0.95g of zinc nitrate, stirring for 10min until the zinc nitrate is dissolved, adding 0.41g of nickel nitrate hexahydrate, stirring for 10min until the nickel nitrate is dissolved, and finally performing constant volume by using the deionized water. The carrier is impregnated by an isometric impregnation method, and after the carrier is placed for 12 hours, the carrier is dried for 4 hours at 120 ℃ and roasted for 4 hours at 550 ℃. And preparing the zinc, nickel and lanthanum loaded multistage ZSM-5 molecular sieve catalyst.
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.
A hydrothermal system is prepared by adopting CN104556135B in example 3 and the published feeding molar ratio range, then a zinc source, a nickel source and a lanthanum source are added, and the steps 2 and 3 are adopted for crystallization, separation, drying and roasting, so that the prepared ZSM-5 molecular sieve is almost not synthesized due to extremely low crystallinity, is mostly of a block structure with a smooth surface and has no accumulation phenomenon. The method is greatly different from the zinc, nickel and lanthanum-containing ZSM-5 molecular sieve, and firstly, the zinc, nickel and lanthanum-containing low-silicon ZSM-5 molecular sieve prepared by the method has higher crystallinity and no mixed crystal; secondly, the zinc, nickel and lanthanum-containing ultralow-silicon ZSM-5 molecular sieve prepared by the invention is a large-particle multi-stage 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 the mixed solution, and adding the required sodium metaaluminate into the mixed solutionAnd (3) dripping 25% of 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: (>70cm3Per g) and pore volume>0.15cm3/g) and the mesoporous content of the molecular sieve is higher and accounts for more than 50 percent of the pore volume.
Experimental example 2: research on catalytic gasoline olefin reduction reaction performance of catalyst
ZSM-5 with zinc, nickel and lanthanum multi-stage structures prepared by the embodiment of the invention is used as a catalystIn the catalytic heavy gasoline olefin reduction reaction, a 20ml small fixed bed microreactor is used as a reaction evaluation device, 20ml of 20-40-mesh ZSM-5 molecular sieve catalyst with a multistage structure is filled in the reactor, catalytic gasoline is used as a reaction raw material, hydrogen is used as a carrier gas, and the reaction pressure is 2MPa, the temperature is 400 ℃, and the reaction temperature is H2The volume ratio of the catalytic heavy gasoline is 300:1 and the speed 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 2: olefin reduction performance test of zinc, nickel and lanthanum-containing low-silicon ZSM-5 molecular sieve for catalyzing gasoline
Table 2 shows that, compared with the conventional impregnation method for loading zinc, nickel and lanthanum catalysts, the hydrothermally synthesized ultra-low silicon multi-stage structure ZSM-5 molecular sieve containing zinc, nickel and lanthanum has high selectivity of high octane number products such as isoparaffin and aromatic hydrocarbon and lower octane number loss.
The result shows that the catalyst provided by the invention is a ZSM-5 molecular sieve containing lanthanum and nickel or/and zinc and having a multi-stage structure, has a rich mesoporous structure, higher metal loading capacity and lower silicon-aluminum ratio, and shows higher desulfurization and octane number recovery performance in the catalytic gasoline olefin reduction-upgrading 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 (11)
1. A multi-stage structure ZSM-5 molecular sieve containing lanthanum and nickel or/and zinc is ZSM-5 zeolite with a silicon-aluminum atomic ratio of 10-50 obtained by a hydrothermal synthesis method, and is characterized in that: the channels in the zeolite contain lanthanum, and contain zinc or/and nickel, and the zinc and the siliconAn atomic ratio of 0-0.04, an atomic ratio of said nickel to said silicon of 0-0.03, and an atomic ratio of said lanthanum to said silicon of 0.001-0.02; 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 volume of the mesopores is not less than 0.09cm3Per g, specific surface area greater than 200cm2(ii)/g, wherein the primary particles of the molecular sieve have a size of about 300nm to 2 μm and the secondary packed particles of the molecular sieve have a size of 2 μm to 8 μm.
2. A method for preparing the multi-stage structured ZSM-5 molecular sieve containing lanthanum and nickel or/and zinc 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 crystallization, post-treatment and roasting to obtain the lanthanum-containing and nickel-or/and zinc-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)2O3): zinc source (in ZnO): nickel source (as NiO): lanthanum source (with La)2O3Meter): silicon source (with SiO)2In terms of) is 0.01 to 0.05: 0-0.04: 0-0.03: 0.01-0.15: 1.
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)2O3): zinc source (in ZnO): nickel source (as NiO): lanthanum source (with La)2O3Meter): silicon source (with SiO)2In terms of) is 0.02 to 0.04: 0.01-0.02: 0.01-0.02: 0.05-0.1: 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 and the lanthanum source, or the aluminum source and the zinc source and the lanthanum source.
6. The production method according to claim 3, characterized in that:
performing an aging treatment before or after mixing the silicon-containing source solution and the aluminum-containing source solution;
wherein, before mixing, the aging treatment conditions of the silicon source-containing solution are as follows: aging at 50-70 deg.C for 2-10 hr;
before mixing, the aging treatment conditions of the aluminum source-containing solution are as follows: aging at 30-70 deg.C for 5-10 hr;
after mixing, 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.
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 and separation on the crystallized product, washing the crystallized product by using an ammonium chloride solution until the pH value of a product leacheate is 7-8, then drying the product leacheate for 8-12 hours at the temperature of 60-100 ℃, and then heating the product leacheate to 600 ℃ for roasting for 4-6 hours; the washing and the baking were repeated three times.
9. The method of claim 8, wherein: the rate of temperature rise is 1-4 ℃/min.
10. 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 acetate;
the lanthanum source is lanthanum chloride or lanthanum nitrate;
the template agent is tetrapropylammonium hydroxide or tetrapropylammonium bromide.
11. Use of the lanthanum-containing and nickel or/and zinc-containing multi-stage structure ZSM-5 molecular sieve of claim 1 or the lanthanum-containing and nickel or/and zinc-containing multi-stage structure ZSM-5 molecular sieve prepared by the preparation method of any one of claims 2 to 10 as a catalyst in gasoline desulfurization-olefin reduction, characterized in that: the lanthanum-containing and nickel or/and zinc-containing ZSM-5 molecular sieve with the multi-stage structure is used as a catalyst in a reaction for catalyzing heavy gasoline to reduce olefin, wherein 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-1The olefins in the heavy gasoline are converted into high octane components under the process conditions of (1).
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| CN1608990A (en) * | 2004-09-16 | 2005-04-27 | 华东师范大学 | Process of preparing ZSM-5 molecular sieve of nano size and containing hetero atom |
| CN102500409A (en) * | 2011-09-28 | 2012-06-20 | 大连理工大学 | Gasoline aromatization and isomerization reforming catalyst and preparation method and applications thereof |
| CN104030314A (en) * | 2013-03-06 | 2014-09-10 | 中国石油大学(华东) | ZSM-5-based hierarchical porous molecular sieve material and preparation method thereof |
| WO2018113004A1 (en) * | 2016-12-23 | 2018-06-28 | 中节能万润股份有限公司 | Method for preparing molecular sieve-multielement oxide composite integrally extruded denitration catalyst |
| CN108262060A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | Aromatization catalyst for catalyzing gasoline to reduce olefin and preparation method and application thereof |
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| CN113649064A (en) * | 2021-07-22 | 2021-11-16 | 中国石油大学(北京) | Zeolite molecular sieve loaded metal catalyst and synthesis method and application thereof |
| CN113649064B (en) * | 2021-07-22 | 2022-12-13 | 中国石油大学(北京) | Zeolite molecular sieve supported metal catalyst and synthesis method and application thereof |
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