CN113979444A - Preparation method of molecular sieve with FER structure and molecular sieve with FER structure - Google Patents
Preparation method of molecular sieve with FER structure and molecular sieve with FER structure Download PDFInfo
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- CN113979444A CN113979444A CN202010733011.6A CN202010733011A CN113979444A CN 113979444 A CN113979444 A CN 113979444A CN 202010733011 A CN202010733011 A CN 202010733011A CN 113979444 A CN113979444 A CN 113979444A
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- 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 141
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 145
- 239000013078 crystal Substances 0.000 claims abstract description 63
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003513 alkali Substances 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 229910001868 water Inorganic materials 0.000 claims abstract description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 50
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 50
- 239000000377 silicon dioxide Substances 0.000 claims description 37
- 230000032683 aging Effects 0.000 claims description 30
- 229910052681 coesite Inorganic materials 0.000 claims description 29
- 229910052906 cristobalite Inorganic materials 0.000 claims description 29
- 229910052682 stishovite Inorganic materials 0.000 claims description 29
- 229910052905 tridymite Inorganic materials 0.000 claims description 29
- 238000002425 crystallisation Methods 0.000 claims description 27
- 230000008025 crystallization Effects 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 22
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 21
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 21
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 9
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 4
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 claims description 4
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 claims description 4
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical compound CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 4
- 239000012265 solid product Substances 0.000 description 34
- 238000003756 stirring Methods 0.000 description 32
- -1 amine compound Chemical class 0.000 description 21
- 239000000376 reactant Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 238000001514 detection method Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- 238000001914 filtration Methods 0.000 description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 17
- 239000004810 polytetrafluoroethylene Substances 0.000 description 17
- 229910001220 stainless steel Inorganic materials 0.000 description 17
- 239000010935 stainless steel Substances 0.000 description 17
- 238000005406 washing Methods 0.000 description 17
- 229910001657 ferrierite group Inorganic materials 0.000 description 14
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 10
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 10
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical group NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical group NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000005700 Putrescine Chemical group 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 229910052908 analcime Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000000123 silicon containing inorganic group Chemical group 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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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
-
- 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
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
-
- 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
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- C01B39/44—Ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a molecular sieve with FER structure and a preparation method thereof, comprising the following steps: crystallizing a mixture formed by raw materials containing a silicon source, an aluminum source, an alkali source, an imidazole structure directing agent and water. The molecular sieve is a flaky molecular sieve with FER structure, the crystal thickness is 15-90nm, the molecular diffusion is facilitated, and carbon deposition is not easy to occur when the molecular sieve is used as a catalyst; the silicon-aluminum ratio is more than 25 and less than 60, the limitation that only the flaky ZSM-35 molecular sieve with low silicon-aluminum ratio (less than 25) can be synthesized in the prior art is broken through, and the application range of the flaky ZSM-35 molecular sieve is favorably expanded.
Description
Technical Field
The invention relates to a preparation method of a molecular sieve with FER structure and the molecular sieve with FER structure.
Background
Molecular sieves having the structure FER are a class of molecular sieves defined by the international association of molecular sieves, the basic structural units of which are five-membered rings ingeniously connected by ten-and six-membered rings, and ZSM-35 molecular sieves and ferrierite are representative of such molecular sieves.
Ferrierite is a natural mineral, and the ZSM-35 molecular sieve was first synthesized in 1977 by the Mobil company, bank et al, using hexamethylenediamine as an organic template, using a hydrothermal method [ bank C J, rosski E J, Rubin M k. crystal zeolite and method of preparing same, US 4016245.1977 ]. The channel structure of ZSM-35 molecular sieve is a two-dimensional cross channel system composed of five-membered ring, eight-membered ring and ten-membered ring, wherein the diameter of ten-membered ring channel parallel to [001] direction is 0.42nm × 0.54nm, and the diameter of eight-membered ring channel parallel to [010] direction is 0.35nm × 0.48nm [ Zeolite.1994, 14(6):458-461 ].
Due to the unique pore channel structure, the ferrierite molecular sieve is mainly applied to the reactions of isobutene preparation by n-butene skeletal isomerization, hexene skeletal isomerization, butene polymerization and the like in the field of catalysis. However, the ferrierite is easy to produce side reaction in the catalytic reaction and cause carbon deposition, thereby causing the reduction of the catalytic performance. Generally, during the catalytic reaction, the mass transfer rate of reactant molecules inside the pores of the molecular sieve is much lower than that of reactant molecules on the surface of the molecular sieve, and aggregation of molecules and carbon deposition easily occur inside the pores, shortening the catalyst life [ Holm M S, Taarning E, Egeblad K and Christensen C h.catalysis Today, 2011, 168: 3-16]. Therefore, attempts have been made to reduce the diffusion limitation by increasing the pore diameter of the catalyst or shortening the diffusion distance in order to improve the diffusion properties of the reactants and products and to prevent the deactivation of carbon deposits.
The early artificial synthesis of ferrierite molecular sieve was carried out in an inorganic system without organic template agent, and Na was required in the synthesis system+And K+Exist to balance the charge in the framework and have higher crystallization temperature. The molecular sieve synthesized by the system has lower silicon-aluminum ratio (Si/Al) and purity, and is easy to generate heterocrystal phases such as mordenite, analcime and the like.
At present, when a ferrierite or ZSM-35 molecular sieve is synthesized by adopting a hydrothermal crystallization method, an organic template agent is generally used. Commonly used templating agents are n-butylamine [ chinese petrochemical company, ltd., ZL200710304472.6, 2011.06.15], cyclohexylamine [ chinese petrochemical company, ltd., ZL201310370348.5, 2017.03.01], [ continuos heterogeneous catalyst company, ltd., ZL 201210120962.1, 2014.07.16], ethylenediamine [ chinese petroleum and gas company, northeast petroleum university, ZL201410784583.1, 2016.07.13], tetrahydrofuran, piperidine, pyridine [ Kamimura Y, Kowenje C, Yamanaka K, et al. 154, 159 ℃ or pyrrolidine [ US 5516959], etc. Ferrierite obtained by conventional methods tends to have larger grains [ Szosta K r.hand book of Molecular Sieves; van NostrandReinhold, New York,1992 ]. At present, no report exists for synthesizing ferrierite or ZSM-35 molecular sieve by using imidazole and similar compounds thereof as template agents.
201410784583.1[ China oil and gas resources Co., Ltd., northeast university of Petroleum, 2016.07.13]Discloses a preparation method of a small-grain ZSM-35 molecular sieve, which comprises the following steps: uniformly mixing a silicon source, an aluminum source, an alkali source, a template agent and water to obtain a colloidal solution, wherein the molar ratio of each component is as follows: SiO 22/Al2O318.5-28.6, template agent/SiO2＝0.81-1.25、OH-/SiO2＝0.03-0.18、H2O/SiO210-26; crystallizing the colloidal solution at 15-80 deg.C for 5-30 hr, and crystallizing at 150-200 deg.C for 10-30 hr; after being filtered, washed and dried,and preparing the small-grain ZSM-35 molecular sieve. The obtained ZSM-35 molecular sieve is spherical, and the minimum grain size can reach about 0.5 mu m.
201510446231.X [ university of east China, 2017.07.04] discloses a method for synthesizing nano flaky ferrierite, which is characterized in that inorganic silicon source, aluminum source, alkali source and piperidine, piperazine, tetrahydrofuran or hexanediamine are mixed, then cetyl trimethyl ammonium bromide (CTABr) is introduced and stirred at room temperature, and then crystallization is carried out, wherein the obtained molecular sieve has a thin flaky composition, but the flakes are tightly combined.
CN108793189A (Beijing, China university of Petroleum, 2018.11.13) discloses a layered nano-flake ferrierite molecular sieve, a preparation method and application thereof, wherein the flake thickness is 30-80nm, two templates are needed for synthesis, and a first template R1 is pyridine, pyrrole, furan, piperidine, pyrrolidine, tetrahydrofuran or cyclohexylamine; the second template R2 is n-butylamine, ethylenediamine, trimethylamine, 1, 3-diaminopropane, 1, 4-diaminobutane, tetramethylammonium hydroxide or tetraethylammonium hydroxide.
CN108946764A (China university of Petroleum (Beijing), 2018.12.07) discloses a hierarchical pore nano ferrierite aggregate and a preparation method thereof, wherein the silica-alumina ratio is 10-1500, preferably 25-1000, more preferably 100-600; the ferrierite aggregate is formed by aggregating smaller grains, the grain diameter is 10-100nm, but the ferrierite aggregate is not in a flaky shape. The templating agent used is an organic amine compound such as pyridine, piperidine, pyrrole, pyrrolidine, trimethylamine, 1, 3-diaminopropane, 1, 4-diaminobutane, cyclohexylamine, n-butylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, or a mixture thereof. The auxiliary agent is NaF, NH4F, ethanol, glycol or the mixture thereof.
CN109110779A (2019.01.01, China petrochemical Co., Ltd.) discloses a preparation method of a ZSM-35 molecular sieve, which comprises mixing a silicon source, an aluminum source, alkali, water, an I organic template and an II organic template into a gel, performing hydrothermal crystallization, filtering, washing, drying and roasting to obtain the ZSM-35 molecular sieve, wherein the ZSM-35 molecular sieve has a sheet structure along the c-axis direction, but the silicon-aluminum ratio is not specified. The I organic template is an amine compound, preferably ethylenediamine, cyclohexylamine or butanediamine; and/or the II organic template is a six-membered heterocyclic compound, preferably a nitrogen-containing six-membered heterocyclic compound, more preferably pyridine or piperidine.
CN109502606A [ Shandong Qilu Xingaokao Co., Ltd., 2019.03.22] discloses a preparation method of a ZSM-35 molecular sieve, which comprises the following steps: a) preparing an aluminum source, a complexing agent and water into a solution a, and aging to obtain an aging solution; b) uniformly mixing a silicon source, an aluminum source, an alkali source, a template agent, water and ZSM-35 molecular sieve seed crystal to obtain gel b; c) crystallizing at 50-150 ℃ for 1-36 h; d) and (c) adding the aging liquid obtained in the step a) into the crystallization kettle obtained in the step c), and crystallizing at 150-180 ℃ for 12-72 hours. The template agent is one or a mixture of more of cyclohexylamine, n-butylamine and ethylenediamine. The product is similar to an ellipsoid, and the particle size is 100-500 nm.
As can be seen from the above review, although the method for synthesizing the ZSM-35 molecular sieve is mature, it is difficult to synthesize ZSM-35 molecular sieve nanosheets with high silica-alumina ratio, thereby resulting in a great limitation in the application of the ZSM-35 molecular sieve.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a synthesis method for obtaining a molecular sieve with FER structure, which has a flaky shape, a small thickness and a silicon-aluminum ratio greater than that of a conventional low-silicon-aluminum ratio molecular sieve and can meet different requirements of catalysts in chemical production, aiming at the defects of the prior art.
According to a first aspect of the present invention, there is provided a process for the preparation of a molecular sieve according to the present invention, which process comprises: crystallizing a mixture formed by raw materials containing a silicon source, an aluminum source, an alkali source, an imidazole structure directing agent and water.
Preferably, the imidazole structure directing agent is at least one of imidazole, N-ethylimidazole, N-propylimidazole, 1-N-butylimidazole, 2-methylimidazole, 4-methylimidazole, 1, 2-dimethylimidazole and 2, 4-dimethylimidazole.
Preferably, the molar composition of the mixture comprises: SiO 22/Al2O35 to 500; SDA/SiO20.01 to 1.5; OH group-/SiO20.01 to 0.50; h2O/SiO29 to 35; wherein the silicon source is SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by OH-And (6) counting.
Preferably, the molar composition of the mixture comprises: SiO 22/Al2O310 to 400; SDA/SiO20.05 to 1.2; OH group-/SiO20.05 to 0.40; h2O/SiO212 to 30; wherein the silicon source is SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by OH-And (6) counting.
Preferably, the silicon source includes at least one of silica gel, silica sol, and tetraalkyl silicate.
Preferably, the aluminum source comprises at least one of sodium aluminate, aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum hydroxide, and aluminum isopropoxide.
Preferably, the alkali source is one or more of sodium hydroxide, potassium hydroxide and ammonia water.
Preferably, the crystallization temperature is 140-190 ℃, preferably 150-175 ℃.
Preferably, the crystallization time is 20-400 h, preferably 30-80 h.
Preferably, the feedstock contains seeds, calculated as oxides, preferably seed/SiO2The weight ratio of (A) to (B) is 1-20: 100, preferably 3-15: 100; more preferably, the seed crystal is a ZSM-35 molecular sieve.
Preferably, the feedstock contains seed crystals, the process comprising:
(1) aging a solution containing an aluminum source and seed crystals at 40-99 ℃ to obtain a mixture A;
(2) mixing a silicon source and an imidazole structure directing agent to obtain a mixture B;
(3) mixing the mixture B with the mixture A to obtain a mixture C, and controlling the pH value of the mixture C to be more than 9;
(4) crystallizing the obtained mixture C, and then carrying out solid-liquid separation and heat treatment;
wherein step (1) and/or step (2) and/or step (3) is/are carried out in the presence of an alkali source.
Preferably, the feedstock contains seed crystals, the process comprising:
(1) aging a mixed solution of an aluminum source, an imidazole structure directing agent and seed crystals at 40-99 ℃ to obtain a mixture A;
(2) mixing a silicon source with the mixture A to obtain a mixture B, and controlling the pH value of the mixture B to be more than 9;
(3) crystallizing the obtained mixture B, and then carrying out solid-liquid separation and heat treatment, wherein the step (1) and/or the step (2) are carried out in the presence of an alkali source.
Preferably, the temperature of aging is from 50 to 70 ℃.
Preferably, the aging time is from 1 to 10 hours, preferably from 2 to 6 hours.
According to a second aspect of the present invention, the present invention provides a molecular sieve having FER structure, the molecular sieve having a crystal structure with a plate-like morphology, the crystal thickness being 15-90 nm; the silicon-aluminum ratio is between 25 and 60.
Preferably, the molecular sieve has a crystal thickness of 20 to 80 nm.
Preferably, the molecular sieve has a silica to alumina ratio of 27 to 55.
Compared with the prior art, the invention has the following advantages: the molecular sieve is a flaky molecular sieve with FER structure, the crystal thickness is 15-90nm, the molecular diffusion is facilitated, and carbon deposition is not easy to occur when the molecular sieve is used as a catalyst; the silicon-aluminum ratio is more than 25 and less than 60, the limitation that only the flaky ZSM-35 molecular sieve with low silicon-aluminum ratio (less than 25) can be synthesized in the prior art is broken through, and the application range of the flaky ZSM-35 molecular sieve is favorably expanded.
Drawings
FIG. 1 is an SEM photograph of the molecular sieve prepared in example 1;
FIG. 2 is an XRD spectrum of the molecular sieve prepared in comparative example 1;
FIG. 3 is an SEM photograph of the molecular sieve prepared in example 2;
fig. 4 is an SEM photograph of the molecular sieve prepared in example 3.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a molecular sieve, which comprises the following steps: crystallizing a mixture formed by raw materials containing a silicon source, an aluminum source, an alkali source, an imidazole structure directing agent and water.
The imidazole structure directing agent is found to be capable of improving the silicon-aluminum ratio of the molecular sieve with the flaky crystal structure and improving the crystal thickness for the first time.
According to the method of the invention, the imidazole structure directing agent has a wide selection range of types, for example, C1-C4 alkyl substituted imidazole can be used in the invention, for example, one or more of methyl imidazole, ethyl imidazole, propyl imidazole and butyl imidazole. For the present invention, preferably, the imidazole structure directing agent is at least one of imidazole, N-ethylimidazole, N-propylimidazole, 1-N-butylimidazole, 2-methylimidazole, 4-methylimidazole, 1, 2-dimethylimidazole and 2, 4-dimethylimidazole, and according to a preferred embodiment of the present invention, imidazole is preferred.
According to the invention, the composition of the mixture is not particularly critical, the object of the invention being achieved by the mixture composition of the customary synthetic molecular sieves, for which purpose the molar composition of the mixture preferably comprises: SiO 22/Al2O35 to 500; SDA/SiO20.01 to 1.5; OH group-/SiO20.01 to 0.50; h2O/SiO29 to 35; wherein the silicon source is SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by OH-And (6) counting.
According to a more preferred embodiment of the invention, it is preferred that the molar composition of the mixture comprises: SiO 22/Al2O310 to 400; SDA/SiO20.05 to 1.2; OH group-/SiO20.05 to 0.40; h2O/SiO212 to 30; wherein the silicon source is SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by OH-And (6) counting.
In the invention, the optional range of the types of the silicon source, the aluminum source and the alkali source is wide, and the commonly used silicon source, aluminum source and alkali source can be used in the invention. The following list is not intended to limit the scope of the present invention.
In the present invention, an inorganic silicon source such as silicon dioxide, silica sol, silica gel and other silicon-containing inorganic substances and/or an organic silicon source such as organosilicate can be used, and according to a preferred embodiment of the present invention, the silicon source includes at least one of silica gel, silica sol and tetraalkyl silicate.
In the present invention, the kind of the aluminum source is widely selected, and an inorganic aluminum source and/or an organic aluminum source can be used in the present invention, and the aluminum source is, for example, an aluminum-containing salt, alumina, aluminum hydroxide, etc., such as sodium aluminate, aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum hydroxide, and the organic aluminum source can be an organic aluminum alkoxide, and the organic aluminum alkoxides commonly used in the art can be used in the present invention.
In the present invention, the kind of the alkali source can be selected from a wide range, and any of common alkali sources can be used in the present invention, for example, sodium hydroxide, potassium hydroxide, and ammonia water.
According to a preferred embodiment of the present invention, preferably, the raw material contains a seed, preferably seed/SiO, calculated as oxide2The weight ratio of (A) to (B) is 1 to 20:100, preferably 3 to 15: 100.
According to a preferred embodiment of the invention, the invention is an isomorphous seed, preferably a ZSM-35 molecular sieve.
According to a preferred embodiment of the present invention, the raw material contains seed crystals, and the step of preparing the molecular sieve comprises:
(1) aging a solution containing an aluminum source and seed crystals at 40-99 ℃ to obtain a mixture A;
(2) mixing a silicon source and an imidazole structure directing agent to obtain a mixture B;
(3) mixing the mixture B with the mixture A to obtain a mixture C, and controlling the pH value of the mixture C to be more than 9, preferably more than 11, and more preferably 11-13.5;
(4) crystallizing the obtained mixture C, and then carrying out solid-liquid separation and heat treatment;
wherein, the step (1) and/or the step (2) and/or the step (3) are/is carried out in the presence of an alkali source, and the step (1) and/or the step (2) and/or the step (3) are/is carried out in the presence of the alkali source for the purpose of adjusting to the target pH value.
According to the present invention, it is preferable that both of the step (1) and the step (2) are carried out in the presence of an alkali source to adjust the pH of both the mixture A and the mixture B to 9 or more, preferably 11 or more, more preferably 11 to 13.5.
According to a preferred embodiment of the present invention, the step of preparing the molecular sieve comprises:
(1) aging a mixed solution of an aluminum source, an imidazole structure directing agent and seed crystals at 40-99 ℃ to obtain a mixture A;
(2) mixing a silicon source with the mixture A to obtain a mixture B, and controlling the pH value of the mixture B to be more than 9, preferably more than 11, and more preferably 11-13.5;
(3) crystallizing the obtained mixture B, and then carrying out solid-liquid separation and heat treatment, wherein the step (1) and/or the step (2) are carried out in the presence of an alkali source, and the step (1) and/or the step (2) are carried out in the presence of an alkali source for the purpose of adjusting the pH value to a target pH value.
According to the present invention, it is preferable that both of the step (1) and the step (2) are carried out in the presence of an alkali source to adjust the pH of both the mixture A and the mixture B to 9 or more, preferably 11 or more, more preferably 11 to 13.5.
According to a preferred embodiment of the invention, the temperature of ageing is between 50 and 70 ℃.
According to the invention, the aging time is preferably from 1 to 10 hours, more preferably from 2 to 6 hours.
According to a preferred embodiment of the present invention, the crystallization temperature is 140 to 190 ℃, preferably 150 to 175 ℃.
According to a preferred embodiment of the present invention, the crystallization time is 20 to 400 hours, preferably 30 to 80 hours.
The operations and treatments involved in the present invention are conventional in the art unless otherwise specified.
The molecular sieve of the invention can be synthesized by the method of the invention.
The invention provides a molecular sieve with FER structure, which has a flaky crystal structure, wherein the crystal thickness is 15-90 nm; the silicon-aluminum ratio is between 25 and 60.
According to a preferred embodiment of the invention, the molecular sieve has a crystal thickness of 20 to 80 nm.
According to a preferred embodiment of the invention, the molecular sieve has a silica to alumina ratio of from 27 to 55.
The apparatus used in the present invention is an apparatus conventional in the art unless otherwise specified.
The raw materials involved in the specific embodiment of the invention are as follows:
(A) silica sol: containing SiO 240 wt%, industrial product;
(B) sodium aluminate: containing Al2O341% by weight, commercial product;
(C) imidazole: content 99 wt%, commercial product;
(D) sodium hydroxide: content 96 wt%, commercial product;
(E) and potassium hydroxide: content 85% by weight, commercially available product.
The detection method related in the specific embodiment of the invention is as follows:
(1) determination of the thickness of the molecular sieve:
and (3) importing the SEM picture of the prepared molecular sieve into Nano Measurer software, calibrating a ruler, and then carrying out software measurement on the thickness of the molecular sieve sheet, so as to obtain the thickness distribution of the sheet-shaped molecular sieve after ensuring that the statistics of the molecular sieve samples is more than or equal to 100, and measuring the average thickness of the molecular sieve.
(2) And (3) determining the silicon-aluminum ratio of the molecular sieve:
the composition of the molecular sieve is measured by adopting an ICP-AES internal standard method (analytical test technology and instrument, 2004,10(1), 30-33), and the silicon-aluminum ratio of the molecular sieve is obtained by calculating according to the measurement result of the content of Si and Al elements.
(3) Determination of molecular sieve crystallinity: and (3) measuring by using a conventional X-ray diffractometer, wherein the tube voltage is 40kV, the tube current is 40mA, the scanning speed is 10 degrees/min, and the diffraction pattern of the sample is recorded in the range of 5-50 degrees 2 theta. Assuming that the sample obtained in comparative example 1 is a reference sample, the relative crystallinity thereof is set to 100, the peak intensities of characteristic diffraction peaks 2 θ of 9.302 °, 13.405 °, 22.319 °, 22.549 °, 23.083 °, 23.580 °, 24.299 °, 25.208 °, 25.577 ° and 28.401 ° of each sample are summed, and the relative crystallinity of each sample is calculated as compared with the sum of the peak intensities of the reference sample (Verbiest J., Vansant E.Dehydration, Dearmmoniation and Thermal Stability of Ferrierite [ J ]. Bulletin des Soci nices gels, 1986,95(2): 75-81).
Example 1
(1) Dissolving 1.233 g of sodium aluminate, 0.08 g of sodium hydroxide, 0.72 g of potassium hydroxide and 2.83 g of imidazole in 39 g of deionized water, adding 0.6 g of ZSM-35 molecular sieve seed crystal, and aging at 50 ℃ for 4 hours to obtain a mixture A;
(2) slowly adding 23.2 g of silica sol under the stirring condition, then continuing stirring for one hour to obtain a mixture B, and measuring the pH value of the mixture B to be 12;
(3) and (3) putting the obtained mixture B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 40 hours at 175 ℃. And after crystallization is finished, filtering, washing and drying to obtain 11.2 g of a solid product, wherein XRD detection results show that the solid product is a molecular sieve nanosheet with an FER structure, and the relative crystallinity is 173. The silica to alumina ratio of the molecular sieve was 35.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝31；SDA/SiO2＝0.4；OH-/SiO2＝0.08；H2O/SiO2＝19。
the XRD diffraction results of the molecular sieve having FER structure prepared in example 1 are shown in table 1.
TABLE 1
An SEM photograph of the molecular sieve having FER structure prepared in example 1 is shown in fig. 1, and it was measured that the molecular sieve had an average thickness of 50nm and the plate-shaped crystals were randomly staggered rather than regularly stacked.
Comparative example 1
1.233 g of sodium aluminate, 0.08 g of sodium hydroxide and 0.8 g of potassium hydroxide are dissolved in 39 g of deionized water, 13.9g of silica sol is slowly added under the condition of stirring, then 1.04 g of ZSM-35 molecular sieve seed crystal is added, the mixture is continuously stirred for one hour and then is put into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and the crystallization is carried out for 40 hours at the temperature of 175 ℃. After the crystallization, the solid product was filtered, washed and dried to obtain 6.4 g, and XRD detection results (as shown in fig. 2) showed that the solid product contained a large amount of amorphous material in addition to the ZSM-35 molecular sieve, and the relative crystallinity was set to 100. The silica to alumina ratio of the molecular sieve was 19.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝19；OH-/SiO2＝0.15；H2O/SiO2＝28。
the molecular sieve having FER structure prepared in comparative example 1 had an average thickness of 200 nm.
Example 2
(1) Dissolving 1.648 g of sodium aluminate, 0.27 g of sodium hydroxide and 1.72 g of potassium hydroxide in 25 g of deionized water to obtain a clear solution, adding 1.04 g of ZSM-35 molecular sieve seed crystal, and aging at 50 ℃ for 4 hours to obtain a mixture A;
(2) adding 15 g of deionized water into 13.9g of silica sol under stirring, adding 7.03 g of imidazole, and continuing stirring for 1 hour to obtain a mixture B;
(3) mixing the mixture B with the mixture A under stirring to obtain a mixture C, and measuring the pH value of the mixture C to be 13;
(4) and (3) putting the obtained mixture C into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 40 hours at 175 ℃. After crystallization is finished, filtering, washing and drying are carried out to obtain 8.2 g of a solid product, and XRD detection results show that the solid product is a ZSM-35 molecular sieve pure phase and has a relative crystallinity of 178. The silica to alumina ratio of the molecular sieve was 28.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝14；SDA/SiO2＝1.1；OH-/SiO2＝0.35；H2O/SiO2＝29。
an SEM photograph of the molecular sieve having the FER structure obtained in example 2 is shown in FIG. 3, and the average thickness is 35nm, and the plate-shaped crystals are randomly staggered rather than regularly stacked.
Example 3
(1) Dissolving 0.066 g of sodium aluminate, 0.04 g of sodium hydroxide, 0.72 g of potassium hydroxide and 0.96 g of imidazole in 15 g of deionized water, adding 0.6 g of ZSM-35 molecular sieve seed crystal, and aging at 70 ℃ for 2 hours to obtain a mixture A;
(2) slowly adding 13.9g of silica sol into the mixture A under the stirring condition, and continuously stirring for 1 hour to obtain a mixture B, wherein the pH value of the mixture B is 11;
(3) and (3) putting the obtained mixture B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 40 hours at 175 ℃. And after crystallization is finished, filtering, washing and drying to obtain 5.8 g of a solid product, wherein XRD detection results show that the solid product is a molecular sieve nanosheet with an FER structure, and the relative crystallinity is 170. The silica to alumina ratio of the molecular sieve was 53.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝350；SDA/SiO2＝0.15；OH-/SiO2＝0.14；H2O/SiO2＝14。
an SEM photograph of the molecular sieve having the FER structure obtained in example 3 is shown in FIG. 4, in which the average thickness is 25nm and the plate-shaped crystals are randomly staggered rather than regularly stacked.
Example 4
(1) Dissolving 1.233 g of sodium aluminate, 0.08 g of sodium hydroxide, 0.8 g of potassium hydroxide and 2.83 g of imidazole in 39 g of deionized water to obtain a clear solution, adding 1.04 g of ZSM-35 molecular sieve seed crystal, and aging at 60 ℃ for 3 hours to obtain a mixture A;
(2) slowly adding 13.9g of silica sol into the mixture A under the stirring condition, continuously stirring for 1 hour to obtain a mixture B, and measuring the pH value of the mixture B to be 12;
(3) and (3) putting the obtained mixture B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 72 hours at 150 ℃. After crystallization is finished, filtering, washing and drying are carried out to obtain 7.2 g of a solid product, and XRD detection results show that the solid product is a ZSM-35 molecular sieve pure phase and has a relative crystallinity of 178. The molecular sieve has a silicon-aluminum ratio of 28, an average thickness of 75nm, and flaky crystals which are randomly staggered but not regularly stacked.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝19；SDA/SiO2＝0.4；OH-/SiO2＝0.15；H2O/SiO2＝28。
example 5
(1) Dissolving 1.233 g of sodium aluminate, 0.08 g of sodium hydroxide, 0.8 g of potassium hydroxide and 4.08 g of N-propylimidazole in 39 g of deionized water to obtain a clear solution, adding 1.04 g of ZSM-35 molecular sieve seed crystal, and aging at 50 ℃ for 4 hours to obtain a mixture A;
(2) slowly adding 13.9g of silica sol into the mixture A under the stirring condition, continuously stirring for 1 hour to obtain a mixture B, and measuring the pH value of the mixture B to be 12;
(3) and (3) putting the obtained mixture B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 72 hours at 150 ℃. After crystallization is finished, filtering, washing and drying are carried out to obtain 8.1 g of a solid product, and XRD detection results show that the solid product is a ZSM-35 molecular sieve pure phase and has the relative crystallinity of 166. The molecular sieve has a silicon-aluminum ratio of 27 and an average thickness of 60nm, and flaky crystals are randomly staggered and are not regularly stacked together.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝19；SDA/SiO2＝0.4；OH-/SiO2＝0.15；H2O/SiO2＝28。
example 6
(1) Dissolving 1.233 g of sodium aluminate, 0.08 g of sodium hydroxide, 0.8 g of potassium hydroxide and 3.56 g of 1, 2-dimethylimidazole in 39 g of deionized water to obtain a clear solution, adding 1.04 g of ZSM-35 molecular sieve seed crystal, and aging at 50 ℃ for 4 hours to obtain a mixture A;
(2) slowly adding 13.9g of silica sol into the mixture A under the stirring condition, continuously stirring for 1 hour to obtain a mixture B, and measuring the pH value of the mixture B to be 12;
(3) and (3) putting the obtained mixture B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 72 hours at 150 ℃. After crystallization, filtering, washing and drying are carried out to obtain 7.4 g of a solid product, and XRD detection results show that the solid product is a ZSM-35 molecular sieve pure phase and has a relative crystallinity of 159. The molecular sieve has a silicon-aluminum ratio of 28, an average thickness of 50nm, and flaky crystals which are randomly staggered but not regularly stacked. The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝19；SDA/SiO2＝0.4；OH-/SiO2＝0.15；H2O/SiO2＝28。
example 7
(1) Dissolving 1.233 g of sodium aluminate, 0.08 g of sodium hydroxide, 0.8 g of potassium hydroxide and 4.60 g of 1-n-butylimidazole in 39 g of deionized water to obtain a clear solution, adding 1.04 g of ZSM-35 molecular sieve seed crystal, and aging at 50 ℃ for 4 hours to obtain a mixture A;
(2) slowly adding 13.9g of silica sol into the mixture A under the stirring condition, continuously stirring for 1 hour to obtain a mixture B, and measuring the pH value of the mixture B to be 12;
(3) and (3) putting the obtained mixture B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 72 hours at 150 ℃. After crystallization is finished, filtering, washing and drying are carried out to obtain 7.0 g of solid product, XRD detection results show that the solid product is ZSM-35 molecular sieve pure phase, and the relative crystallinity is 161. The molecular sieve has a silicon-aluminum ratio of 25, an average thickness of 50nm, and flaky crystals which are randomly staggered but not regularly stacked.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝19；SDA/SiO2＝0.4；OH-/SiO2＝0.15；H2O/SiO2＝28。
example 8
(1) Dissolving 1.233 g of sodium aluminate, 0.08 g of sodium hydroxide, 0.8 g of potassium hydroxide and 4.0 g of N-ethylimidazole in 39 g of deionized water to obtain a clear solution, adding 1.04 g of ZSM-35 molecular sieve seed crystal, and aging at 50 ℃ for 4 hours to obtain a mixture A;
(2) slowly adding 13.9g of silica sol into the mixture A under the stirring condition, continuously stirring for 1 hour to obtain a mixture B, and measuring the pH value of the mixture B to be 12;
(3) and (3) putting the obtained mixture B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 72 hours at 150 ℃. After crystallization is finished, filtering, washing and drying are carried out to obtain 7.2 g of a solid product, and XRD detection results show that the solid product is a ZSM-35 molecular sieve pure phase and has a relative crystallinity of 162. The molecular sieve has a silicon-aluminum ratio of 29 and an average thickness of 70nm, and flaky crystals are randomly staggered and are not regularly stacked together.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝19；SDA/SiO2＝0.4；OH-/SiO2＝0.15；H2O/SiO2＝28。
example 9
(1) Dissolving 1.233 g of sodium aluminate, 0.08 g of sodium hydroxide, 0.8 g of potassium hydroxide and 3.41 g of 2-methylimidazole in 39 g of deionized water to obtain a clear solution, adding 1.04 g of ZSM-35 molecular sieve seed crystal, and aging at 50 ℃ for 4 hours to obtain a mixture A;
(2) slowly adding 13.9g of silica sol into the mixture A under the stirring condition, continuously stirring for 1 hour to obtain a mixture B, and measuring the pH value of the mixture B to be 12;
(3) and (3) putting the obtained mixture B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 72 hours at 150 ℃. After crystallization is finished, filtering, washing and drying are carried out to obtain 7.2 g of a solid product, and XRD detection results show that the solid product is a ZSM-35 molecular sieve pure phase and has a relative crystallinity of 168. The molecular sieve has a silicon-aluminum ratio of 28 and an average thickness of 70nm, and flaky crystals are randomly staggered and are not regularly stacked together.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝19；SDA/SiO2＝0.4；OH-/SiO2＝0.15；H2O/SiO2＝28。
example 10
(1) Dissolving 1.233 g of sodium aluminate, 0.08 g of sodium hydroxide, 0.8 g of potassium hydroxide and 3.41 g of 4-methylimidazole in 39 g of deionized water to obtain a clear solution, adding 1.04 g of ZSM-35 molecular sieve seed crystal, and aging at 50 ℃ for 4 hours to obtain a mixture A;
(2) slowly adding 13.9g of silica sol into the mixture A under the stirring condition, continuously stirring for 1 hour to obtain a mixture B, and measuring the pH value of the mixture B to be 12;
(3) and (3) putting the obtained mixture B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 72 hours at 150 ℃. After crystallization is finished, filtering, washing and drying are carried out to obtain 7.2 g of a solid product, and XRD detection results show that the solid product is a ZSM-35 molecular sieve pure phase and has the relative crystallinity of 166. The molecular sieve has a silicon-aluminum ratio of 28 and an average thickness of 70nm, and flaky crystals are randomly staggered and are not regularly stacked together.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝19；SDA/SiO2＝0.4；OH-/SiO2＝0.15；H2O/SiO2＝28。
example 11
(1) Dissolving 1.233 g of sodium aluminate, 0.08 g of sodium hydroxide, 0.8 g of potassium hydroxide and 3.56 g of 2, 4-dimethylimidazole in 39 g of deionized water to obtain a clear solution, adding 1.04 g of ZSM-35 molecular sieve seed crystal, and aging at 50 ℃ for 4 hours to obtain a mixture A;
(2) slowly adding 13.9g of silica sol into the mixture A under the stirring condition, continuously stirring for 1 hour to obtain a mixture B, and measuring the pH value of the mixture B to be 12;
(3) and (3) putting the obtained mixture B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 72 hours at 150 ℃. After crystallization is finished, filtering, washing and drying are carried out to obtain 7.4 g of a solid product, and XRD detection results show that the solid product is a ZSM-35 molecular sieve pure phase and has a relative crystallinity of 158. The molecular sieve has a silicon-aluminum ratio of 28, an average thickness of 50nm, and flaky crystals which are randomly staggered but not regularly stacked. The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝19；SDA/SiO2＝0.4；OH-/SiO2＝0.15；H2O/SiO2＝28。
example 12
(1) Dissolving 2.6 g of sodium aluminate, 0.04 g of sodium hydroxide, 0.20 g of potassium hydroxide and 8.9 g of imidazole in 48 g of deionized water to obtain a clear solution, adding 1.04 g of ZSM-35 molecular sieve seed crystal, and aging at 50 ℃ for 6 hours to obtain a mixture A;
(2) slowly adding 13.9g of silica sol into the mixture A under the stirring condition, continuously stirring for 1 hour to obtain a mixture B, and measuring the pH value of the mixture B to be 13;
(3) and (3) putting the obtained mixture B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 72 hours at 150 ℃. After crystallization is finished, filtering, washing and drying are carried out, and 9.4 g of a solid product is obtained, wherein XRD detection results show that the solid product is a ZSM-35 molecular sieve pure phase, and the relative crystallinity is 143. The molecular sieve has a silicon-aluminum ratio of 26, an average thickness of 85nm, and flaky crystals which are randomly staggered but not regularly stacked.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝9；SDA/SiO2＝1.4；OH-/SiO2＝0.04；H2O/SiO2＝34。
example 13
(1) Dissolving 0.05 g of sodium aluminate, 0.04 g of sodium hydroxide, 0.36 g of potassium hydroxide and 0.255 g of imidazole in 10 g of deionized water to obtain a clear solution, adding 1.04 g of ZSM-35 molecular sieve seed crystal, and aging at 50 ℃ for 6 hours to obtain a mixture A;
(2) slowly adding 13.9g of silica sol into the mixture A under the stirring condition, and continuously stirring for 1 hour to obtain a mixture B, wherein the pH value of the mixture B is 11;
(3) and (3) putting the obtained mixture B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 96 hours at the temperature of 140 ℃. After crystallization is finished, filtering, washing and drying are carried out, and 5.4 g of solid product is obtained, wherein XRD detection results show that the solid product is a ZSM-35 molecular sieve pure phase, and the relative crystallinity is 124. The molecular sieve has a silicon-aluminum ratio of 59, an average thickness of 18nm, and randomly staggered flaky crystals which are not regularly stacked.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝450；SDA/SiO2＝0.04；OH-/SiO2＝0.07；H2O/SiO2＝11。
example 14
(1) Dissolving 1.233 g of sodium aluminate, 0.04 g of sodium hydroxide, 0.36 g of potassium hydroxide and 8.75 g of imidazole in 39 g of deionized water to obtain a clear solution, adding 0.6 g of ZSM-35 molecular sieve seed crystal, and aging at 50 ℃ for 4 hours to obtain a mixture A;
(2) slowly adding 48.23 g of silica sol into the mixture A under the stirring condition, and continuously stirring for 1 hour to obtain a mixture B, wherein the pH value of the mixture B is 11;
(3) and (3) putting the obtained mixture B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 40 hours at 175 ℃. After crystallization, filtering, washing and drying are carried out to obtain 14.5 g of a solid product, and XRD detection results show that the solid product is a ZSM-35 molecular sieve pure phase and has the relative crystallinity of 135. The molecular sieve has a silicon-aluminum ratio of 49 and an average thickness of 60nm, and flaky crystals are randomly staggered and are not regularly stacked together.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝65；SDA/SiO2＝0.4；OH-/SiO2＝0.02；H2O/SiO2＝12。
example 15
(1) Dissolving 1.233 g of sodium aluminate, 0.41 g of sodium hydroxide, 2.1 g of potassium hydroxide and 2.83 g of imidazole in 39 g of deionized water to obtain a clear solution, adding 1.04 g of ZSM-35 molecular sieve seed crystal, and aging at 50 ℃ for 4 hours to obtain a mixture A;
(2) slowly adding 13.9g of silica sol into the mixture A under the stirring condition, and continuously stirring for 1 hour to obtain a mixture B, wherein the pH value of the mixture B is measured to be 12;
(3) and (3) putting the obtained mixture B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 40 hours at 175 ℃. After crystallization, filtering, washing and drying are carried out to obtain 7.0 g of a solid product, and XRD detection results show that the solid product is a ZSM-35 molecular sieve pure phase and has a relative crystallinity of 142. The molecular sieve has a silicon-aluminum ratio of 26, an average thickness of 20nm, and flaky crystals which are randomly staggered but not regularly stacked.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝19；SDA/SiO2＝0.4；OH-/SiO2＝0.45；H2O/SiO2＝28。
example 16
Prepared according to the method of example 15, except that it is prepared as follows:
(1) dissolving ZSM-35 molecular sieve seed crystals of 1.04 g, silica sol of 13.9g, sodium aluminate of 1.233 g, sodium hydroxide of 0.41 g, potassium hydroxide of 2.1 g and imidazole of 2.83 g in deionized water to obtain a mixture, and measuring the pH value of the mixture to be 12;
(3) the obtained mixture was put into a stainless steel reaction vessel with a polytetrafluoroethylene inner liner and crystallized at 175 ℃ for 40 hours. After crystallization, filtering, washing and drying are carried out to obtain 7.0 g of a solid product, and XRD detection results show that the solid product is a ZSM-35 molecular sieve pure phase and has a relative crystallinity of 112. The molecular sieve has a silicon-aluminum ratio of 25 and an average thickness of 40nm, and flaky crystals are randomly staggered and are not regularly stacked together.
The material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝19；SDA/SiO2＝0.4；OH-/SiO2＝0.45；H2O/SiO2＝28。
the preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for preparing a molecular sieve with FER structure is characterized by comprising the following steps: crystallizing a mixture formed by raw materials containing a silicon source, an aluminum source, an alkali source, an imidazole structure directing agent SDA and water.
2. The production method according to claim 1,
the imidazole structure directing agent SDA is at least one of imidazole, N-ethylimidazole, N-propylimidazole, 1-N-butylimidazole, 2-methylimidazole, 4-methylimidazole, 1, 2-dimethylimidazole and 2, 4-dimethylimidazole, and is preferably imidazole; and/or
The silicon source comprises at least one of silica gel, silica sol and tetraalkyl silicate; and/or
The aluminum source comprises at least one of sodium aluminate, aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum hydroxide and aluminum isopropoxide; and/or
The alkali source is one or more of sodium hydroxide, potassium hydroxide and ammonia water.
3. The production method according to claim 1 or 2,
the molar composition of the mixture comprises: SiO 22/Al2O35 to 500; SDA/SiO20.01 to 1.5; OH group-/SiO20.01 to 0.50; h2O/SiO29 to 35; wherein the silicon source is SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by OH-Counting; preferably, the first and second electrodes are formed of a metal,
the molar composition of the mixture comprises: SiO 22/Al2O310 to 400; SDA/SiO20.05 to 1.2; OH group-/SiO20.05 to 0.40; h2O/SiO212 to 30; wherein the silicon source is SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by OH-Counting; and/or
The crystallization temperature is 140-190 ℃, and preferably 150-175 ℃; and/or
The crystallization time is 20-400 h, preferably 30-80 h.
4. The production method according to any one of claims 1 to 3, wherein the raw material contains a seed crystal in terms of oxide, seed crystal/SiO2The weight ratio of (A) to (B) is 1-20: 100, preferably 3-15: 100; preferably, the seed crystal is a ZSM-35 molecular sieve.
5. The production method according to any one of claims 1 to 4, wherein the raw material contains a seed crystal, and the method comprises:
(1) aging a solution containing an aluminum source and seed crystals at 40-99 ℃ to obtain a mixture A;
(2) mixing a silicon source and an imidazole structure directing agent to obtain a mixture B;
(3) mixing the mixture B with the mixture A to obtain a mixture C, and controlling the pH value of the mixture C to be more than 9;
(4) crystallizing the obtained mixture C, and then carrying out solid-liquid separation and heat treatment;
wherein step (1) and/or step (2) and/or step (3) is/are carried out in the presence of an alkali source.
6. The production method according to any one of claims 1 to 4, wherein the raw material contains a seed crystal, and the method comprises:
(1) aging a solution obtained by mixing an aluminum source, an imidazole structure directing agent and seed crystals at 40-99 ℃ to obtain a mixture A;
(2) mixing a silicon source with the mixture A to obtain a mixture B, and controlling the pH value of the mixture B to be more than 9;
(3) crystallizing the obtained mixture B, and then carrying out solid-liquid separation and heat treatment;
wherein step (1) and/or step (2) is carried out in the presence of an alkali source.
7. The production method according to claim 5 or 6,
the aging temperature is 50-70 ℃; and/or
The aging time is 1-10h, preferably 2-6 h.
8. The molecular sieve with the FER structure has a flaky crystal structure, and the thickness of the crystal is 15-90 nm; the mole ratio of silicon to aluminum is between 25 and 60.
9. The molecular sieve of claim 8, wherein the molecular sieve has a crystal thickness of 20-80 nm.
10. The molecular sieve of claim 8 or 9, wherein the molecular sieve has a silica to alumina ratio of 27 to 55.
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