CN103204515B - Preparation method for high-dispersion zeolite molecular sieves - Google Patents
Preparation method for high-dispersion zeolite molecular sieves Download PDFInfo
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- CN103204515B CN103204515B CN201310081007.6A CN201310081007A CN103204515B CN 103204515 B CN103204515 B CN 103204515B CN 201310081007 A CN201310081007 A CN 201310081007A CN 103204515 B CN103204515 B CN 103204515B
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- Prior art keywords
- molecular sieve
- crystallization
- grams
- zeolite
- preparation
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 276
- 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 275
- 239000010457 zeolite Substances 0.000 title claims abstract description 185
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 182
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 239000006185 dispersion Substances 0.000 title abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 147
- 230000008025 crystallization Effects 0.000 claims abstract description 147
- 238000000034 method Methods 0.000 claims abstract description 132
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 150000001367 organochlorosilanes Chemical class 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 82
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 64
- 229910001868 water Inorganic materials 0.000 claims description 59
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 18
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- -1 stir Chemical class 0.000 claims description 14
- 238000010907 mechanical stirring Methods 0.000 claims description 13
- 235000019353 potassium silicate Nutrition 0.000 claims description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 11
- 230000005494 condensation Effects 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 7
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 6
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 5
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 67
- 239000000047 product Substances 0.000 description 62
- 229910052710 silicon Inorganic materials 0.000 description 55
- 239000010703 silicon Substances 0.000 description 54
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 35
- 230000015572 biosynthetic process Effects 0.000 description 35
- 238000003786 synthesis reaction Methods 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- 230000002194 synthesizing effect Effects 0.000 description 31
- 229910052782 aluminium Inorganic materials 0.000 description 28
- 235000013339 cereals Nutrition 0.000 description 28
- 239000003795 chemical substances by application Substances 0.000 description 28
- 238000010189 synthetic method Methods 0.000 description 27
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 24
- 239000004411 aluminium Substances 0.000 description 24
- 238000006555 catalytic reaction Methods 0.000 description 23
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 22
- 239000011148 porous material Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 239000003921 oil Substances 0.000 description 20
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 20
- 238000012546 transfer Methods 0.000 description 20
- 239000002994 raw material Substances 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000001179 sorption measurement Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 239000003513 alkali Substances 0.000 description 13
- 239000013543 active substance Substances 0.000 description 12
- 230000032683 aging Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 11
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 229960001866 silicon dioxide Drugs 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000006259 organic additive Substances 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- 239000012265 solid product Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 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 description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229960004756 ethanol Drugs 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000013335 mesoporous material Substances 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 8
- 238000011175 product filtration Methods 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000011799 hole material Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000009415 formwork Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- 239000004530 micro-emulsion Substances 0.000 description 4
- 229910052680 mordenite Inorganic materials 0.000 description 4
- 229920001542 oligosaccharide Polymers 0.000 description 4
- 150000002482 oligosaccharides Chemical class 0.000 description 4
- 150000001282 organosilanes Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920002101 Chitin Polymers 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 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 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000004064 cosurfactant Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical group CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 239000013504 Triton X-100 Substances 0.000 description 2
- 229920004890 Triton X-100 Polymers 0.000 description 2
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- 230000004913 activation Effects 0.000 description 2
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- 238000004220 aggregation Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
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- 238000002288 cocrystallisation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
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- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
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- 229910000077 silane Inorganic materials 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- 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 description 1
- HXGZXUVDQQOSAR-UHFFFAOYSA-M 1,3-di(propan-2-yl)imidazol-1-ium;hydroxide Chemical compound [OH-].CC(C)N1C=C[N+](C(C)C)=C1 HXGZXUVDQQOSAR-UHFFFAOYSA-M 0.000 description 1
- JRLPEMVDPFPYPJ-UHFFFAOYSA-N 1-ethyl-4-methylbenzene Chemical compound CCC1=CC=C(C)C=C1 JRLPEMVDPFPYPJ-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 235000011868 grain product Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a preparation method for high-dispersion zeolite molecular sieves. The preparation method includes preparing gel and performing hydrothermal crystallization on nanometer molecular sieves, pressing organochlorosilane in a crystallization kettle filled with crystallized matter through pressurization of nitrogen under the condition of stirring when the crystallization of the molecular sieves is finished so as to enable the organochlorosilane to fully contact and react with the surfaces of the molecular sieves, and collecting products after reaction of the organochlorosilane and the crystallized matter is finished. The mass ratio of the added organochlorosilane R is R/SIO2=0.01-2, the reaction time is no more than 100 hours, and the reaction temperature ranges from room temperature to 200 DEG C. The organochlorosilane is added when the crystallization of the molecular sieves is finished, and the condensation reaction of the organochlorosilane and the surface hydroxyl groups of the molecular sieves is utilized to block agglomeration among the molecular sieves, so that the defect that prior methods affect crystallization kinetics of the molecular sieves is overcome. Obtained molecular sieve products have good dispersibility and large specific surface areas, and are easy to filter.
Description
Technical field
The invention belongs to field of zeolite molecular sieve preparation, relate to a kind of method being conducive to preparing the little crystal grain zeolite molecular sieve of high dispersive.
Background technology
Zeolite molecular sieve is the most important integral part in inorganic microporous material, and be the crystalline material that can sieve material on a molecular scale, its skeleton is by TO
4share the multidimensional four syndeton composition that summit is formed between tetrahedron, wherein T refers to Si, Al or other heteroatoms.Zeolite molecular sieve is due to regular pore passage structure, unique ion exchangeable, select shape adsorptivity, composition and the easy modulation of character, the high reactivity of numerous small molecules catalyzed reaction and selectivity etc., make it be widely used in many fields such as commercial run and hitech materials, the catalysis especially in refining of petroleum, petrochemical complex and fine chemistry industry and daily-use chemical industry, to adsorb and the research field such as ion-exchange.Wherein with the MFI family zeolite molecular sieve that ZSM-5 and ZSM-11, ZSM-8, TS-1 are representative, the MWW family being representative with MCM-22 and MCM-49 and take Beta as the BEA family of representative, because the pore passage structure of uniqueness and good catalytic performance become the very important catalytic material of a few class.
(1) ZSM-5 zeolite (USP 3702886) of U.S. Mobil oil company invention becomes a kind of very important shape selective catalysis material with the pore passage structure of its uniqueness and good catalytic performance.Have by the famous technique of ZSM-5 zeolite exploitation: Mobil intermediate distillates takes off cured technique (MDDW), lubricating oil takes off cured technique (MLDW), catalytic reforming process, the selectoforming of gasoline and M-reforming process, the Cyclar technique (LPG BTX) of aromatic hydrocarbons is synthesized, Mobil-Badger synthesizing ethyl benzene technique, toluene gasifying process (MTDP) by light hydrocarbons, xylene isomerization process (MVPI), preparing gasoline by methanol technique (MTG) and p-methyl-ethylbenzene synthesis technique (PET).
(2) titanium-silicon molecular sieve TS-1 (GB2071071A, USP4410501) is substituted by the Al atom in ZSM-5 with Ti atom, thus have selective oxidation active centre, and have the new catalytic material of ZSM-5 shape selective catalysis performance.TS-1 has the katalysis do not replaced in a series of low-temp. selective oxidation reaction participated in by rare hydrogen peroxide such as epoxidation of propylene and phenol hydroxylation.What is particularly worth mentioning is that: the application of TS-1 in epoxidation of propylene, be expected to the contamination type production model thoroughly breaking away from existing technique, have huge industrial application potentiality.
(3) Beta zeolite (US 3308069) is a kind of supersiliceous zeolite with three-dimensional twelve-ring intersection pore passage structure, because of the structure of its uniqueness and good thermostability, hydrothermal stability and being used in the refining of petroleum such as hydrocracking, hysomer, dewaxing, alkylating aromatic hydrocarbon and olefin hydration and petrochemical process as catalyzer, it is a kind of important industrial zeolite molecular sieve.
(4) MCM-22 molecular sieve (US 4954325) is the lamellar zeolite with MWW topological framework, synthesized under hexamethylene imine template system first in nineteen ninety by Mobil company, it has two and overlaps independently pore canal system: the twelve-ring hole (0.71 × 0.71 × 1.82nm) of the ten-ring sinusoidal pore canal system of two dimension and crystal outside surface in the pore canal system that interlayer ten-ring (0.40 × 0.59nm) is connected, layer.Afterwards, people had synthesized again MCM-49, MCM-56, MCM-36, ITQ-1 and ITQ-2 equimolecular sieve under hexamethylene imine template system, and found that they are the lamellar zeolite with MWW structure equally.Therefore, these molecular sieves are referred to as MCM-22 family molecular sieves by people.MCM-22 family molecular sieves has broad application prospects because of the pore passage structure of its uniqueness in the reaction such as alkylation, aromizing, catalytic cracking and isomerization.
This few class Zeolite catalytic materials belongs to micro-pore zeolite, and pore size is less, and macromole exists larger diffusional resistance in zeolite pore, thus limit to a certain extent it bulky molecular catalysis reaction in application.At present, solution to this problem mainly contains two kinds: be a kind ofly in zeolitic microporous structure, introduce meso-hole structure or be micropore by the crystallization of pore wall of mesoporous material, is formed with the transmission path being beneficial to macromolecular cpd diffusion; Another kind method is exactly the superfine molecular sieves that synthesis has nanoscale.The material with zeolite Jie micro-pore composite structure can improve the diffusion of product, compensate for the deficiency of micro porous molecular sieve, and for macromolecular reaction provides favourable sterie configuration, but the more weak and hydrothermal stability of its acidity is relatively low etc., and problem exists always.And the crystal size of molecular sieve is reduced to nano level from micron order, the performances such as its mass transfer, absorption and catalysis all can change.With micron order zeolite facies ratio, nano zeolite has the micropore diffusion speed of larger outer surface area and Geng Gao, duct is short, and there is a large amount of intracrystalline pores, in the utilization ratio, enhancing macromole conversion capability, reduction deep reaction, raising selectivity etc. of raising catalyzer, all show more superior performance, in the reaction of some hydrocarbons catalytic conversions, show better activity, selectivity and strong anti-coking deactivation ability.
Following patent and document describe the application of little crystal grain (nanometer) molecular sieve.
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Applied Catalysis, A:General(1997), 153(1-2), 233-241, Journal of Molecular Catalysis (1999), 13(6), 457-460, J Catal, 187(1999) 167-176, Materials Chemistry and Physics(2003), 77(2), 406-410, Studiesin Surface Science and Catalysis(2004), 154C, 2754-2759, Catalysis Communications, 2004,5(4): 191-194, Appl catal A, 289(2005) 2-9, Applied Catalysis A:General, 2005,290(1-2): 191-199, Catalysis Today, 2005,106(1-4): 149-153, Energy Fuel, 20(2006) 1388-1391, catalysis journal, 2007,28(1): 34-38, Catal.Commun, 9(2008), chemical research, 2008,19(2): 25-27, Chem Mater, 21(2009) 641-654, Catal.Commun, 10(2009) 1582-1585, Journal of Chemical Engineering of Japan(2009), 42(10), 760-766, Journal of Chemical Engineering of Japan(2009), Pet.Sci.Technol, 28(2010) 219-224, Applied Catalysis A:General, 2011,397(1-2): 13-21, Journal of MolecularCatalysis A:Chemical, 2011,338(1-2): 24-32, Applied Catalysis A:General, 2011,394(1-2): 101-104.
Because nano zeolite all shows huge application potential in numerous reaction, make to produce the focus that nano zeolite becomes research both at home and abroad always.Report at present about this respect synthesis is existing a lot.
Following discloses patent describes the preparation method of ZSM-5 molecular sieve with small crystal grains.
Chinese Patent Application No.: 201210141312.5(2012-05-09) disclose a kind of synthetic method of high-dispersion submicron ZSM-5 zeolite molecular sieve.Its technical characteristic is, under the system of Template-free method, adds the method for alkali by adding segmentation in pre-crystallization liquid and Hydrothermal Synthesis process in crystallization mother liquor, and synthesis obtains the ZSM-5 zeolite molecular sieve that size distribution mainly concentrates on 400 ~ 500nm.The method is the method synthesizing small-grain zeolite molecular sieve utilizing pre-crystallization liquid and segmentation to add alkali.
Chinese Patent Application No.: 201010261877.8(2010-08-23) disclose a kind of preparation method of small crystal grain molecular sieve.Its technical characteristic is, makes synthetic larger crystal molecular sieve raw material enter disintegrating apparatus, carries out physics fragmentation, after grading, obtain small crystal grain molecular sieve.
Chinese Patent Application No.: 201010261597.7(2010-08-23) disclose a kind of preparation method of small crystal grain ZSM-5 zeolite.Its technical characteristic is, after the sial bead of 10 ~ 200 μm that are obtained by spray drying forming and template, mineral alkali, template and water are mixed to get raw mixture, at 100 ~ 200 DEG C of crystallization 10 ~ 360h after the directed agents adding raw mixture weight 0.5 ~ 20% mixes, obtain the ZSM-5 zeolite that grain-size is 200 ~ 1000nm.The method utilizes directed agents and prefabricated sial bead synthesizing small-grain zeolite molecular sieve.
Chinese Patent Application No.: 201010261929.1(2010-08-23) disclose a kind of synthetic method of small crystal grain ZSM-5 zeolite molecular sieve.Its technical characteristic is, the directed agents of slurry weight 0.5 ~ 20% is added in spray slurry, by solid content be 20 ~ 50% slurries spray-driedly shapingly obtain 10 ~ 200 μm of sial beads, again sial bead is mixed with template, mineral alkali and water and obtain raw mixture, through hydrothermal crystallizing, obtaining grain-size is 200 ~ 1000nm small crystal grain ZSM-5 zeolite molecular sieve.The method is also utilize directed agents and prefabricated sial bead synthesizing small-grain zeolite molecular sieve.
Chinese Patent Application No.: 200910248667.2(2009-12-23) disclose a kind of synthetic method of fine grain rare earth ZSM-5/ZSM-11 cocrystallization zeolite.Its technical characteristic is, with silicon source, aluminium source, mineral alkali (or mineral acid), 1, the salt of 6-hexanediamine, rare earth element, additive and deionized water are synthesis material, first through 60 ~ 98 DEG C of low temperature aging process 4 ~ 30h, again at 160 ~ 195 DEG C, through hydrothermal crystallizing 15 ~ 70h, obtain the fine grain rare earth ZSM-5/ZSM-11 cocrystallization zeolite that mean particle size is less than 500nm.The method mainly utilizes low temperature aging measure to reduce the grain fineness number of molecular sieve.
Chinese Patent Application No.: 200810043970.4(2008-11-21) disclose a kind of synthetic method of ZSM-5 molecular sieve with small crystal grains.Its technical characteristic is, is template with 4-propyl bromide, after aged at room temperature, then obtains SiO by two-stage method crystallization
2/ Al
2o
3be not less than 200, particle diameter is less than the ZSM-5 zeolite molecular sieve of 300nm.The method mainly utilizes low temperature aging measure to increase nucleus, reduces the grain fineness number of molecular sieve.
Chinese Patent Application No.: 200710087075.8(2007-03-19) disclose a kind of synthetic method of fine grain strong acid type ZSM-5 molecular sieve.Its technical characteristic is, does not use any organic formwork agent, and introduces ultrasonic wave pre-treatment, then through hydrothermal crystallizing, obtains ZSM-5 molecular sieve with small crystal grains.The method utilizes ultrasonication to control the grain fineness number of molecular sieve.
Chinese Patent Application No.: 200610118536.9(2006-11-21) disclose a kind of preparation method of small-grain ZSM-5/mordenite composite molecular sieve.Its technical characteristic is, adds the ZSM-5 containing suitable silicon aluminum ratio and mordenite crystal seed in sieve synthesis procedure, and the pH value regulating synthesized gel rubber is 9 ~ 14, through hydrothermal crystallizing, obtains ZSM-5/ mordenite composite molecular sieve.Wherein crystal seed used is silica alumina ratio is 20 ~ 100, and particle diameter is the amorphous article of 10 ~ 100nm, and the method is by reducing ZSM-5/ mordenite composite molecular sieve grain fineness number to the control of crystal seed and gel pH value.
Chinese Patent Application No.: 200610097462.5(2006-11-10) disclose a kind of method of synthetic ZSM-5 zeolite.Its technical characteristic is, adopt silicone grease or silane to be raw material, 4-propyl bromide is template, regulates the pH value of the mixed solution of silicon source and deionized water and stirs hydrolysis, add crystal seed, through hydrothermal crystallizing, obtain the product that grain fineness number is 100 ~ 400nm with acid solution.
Chinese Patent Application No.: 200510028781.6(2005-08-15) disclose a kind of method preparing small crystal grain ZSM-5 zeolite.Its technical characteristic is, with water glass, silicon sol or white carbon black for silicon source, aluminium salt or aluminate are aluminium source, in crystallization forward direction crystallization mother liquor, add a small amount of seeding director, then through hydrothermal crystallizing, obtain the ZSM-5 zeolite of little crystal grain.The method is also utilize directed agents method synthesizing small-grain zeolite molecular sieve.
Chinese Patent Application No.: 200510028782.0(2005-08-15) disclose the small crystal grain ZSM-5 zeolite synthetic method of the shaping rear crystallization of a kind of elder generation.Its technical characteristic is, to adopt with diatomite or white carbon black as main raw material, adds seeding director, and using silicon sol or water glass shaping as binding agent, then to process mutually with water vapor gas-solid with organic amine and be converted into integrated small-grain ZSM-5.
Chinese Patent Application No.: 200510200328.9(2005-06-14) disclose a kind of synthetic method of high silica alumina ratio small crystal grain ZSM-5 zeolite molecular sieve.Its technical characteristic is, Virahol, propyl carbinol, the trimethyl carbinol or isopropylcarbinol tensio-active agent are joined in the aluminum salt solution of acidifying, again the basic solution formed by water glass, template, crystal seed is added drop-wise in aluminum salt solution at leisure, again through hydrothermal crystallizing, obtain small crystal grain ZSM-5 zeolite molecular sieve.
Chinese Patent Application No.: 200410048354.X(2004-06-29) disclose a kind of preparation method of small crystal grain ZSM-5 zeolite.Its technical characteristic is, by SiO
2/ Al
2o
3mol ratio 20 ~ 600, granularity are the aqueous solution of 20 ~ 300 object alumino silica gel particles and organic formwork agent, through hydrothermal crystallizing, obtain the ZSM-5 zeolite that silica alumina ratio is 15 ~ 200, primary grains particle is 0.1 ~ 0.5 μm.
Chinese Patent Application No.: 02155482.X(2002-12-16) disclose a kind of method of Fast back-projection algorithm strong acid type ZSM-5 zeolite molecular sieve.Its technical characteristic is, by a certain percentage directed agents is made in silicon source and template, aluminium source, mineral acid, deionized water; By a certain percentage silicon source and template, aluminium source, mineral acid, deionized water are configured to crystallization mother liquor again, in mother liquor, add the directed agents accounting for cumulative volume 5 ~ 10%.Gained gel obtains the small crystal grain ZSM-5 zeolite that crystal grain is about 100nm after hydrothermal crystallizing.The method is also utilize directed agents method synthesizing small-grain zeolite molecular sieve.
Chinese Patent Application No.: 00109593.5(2000-06-28) disclose a kind of method of directing agent method quickly synthesizing small crystal grain ZSM-5-5 molecular sieve.Its technical characteristic replaces organic amine template by directed agents, through hydrothermal crystallizing 65-75h, obtains the ZSM5 molecular sieve that median size is 0.1 μm.The method is also utilize directed agents method synthesizing small-grain zeolite molecular sieve.
Chinese Patent Application No.: 99102700.0(1999-04-21) disclose a kind of method of synthesizing ZSM-5.Its technical characteristic is, take n-Butyl Amine 99 as template, and water glass, Tai-Ace S 150 and sodium hydroxide are raw material, by the grain-size using an alkali metal salt to regulate zeolite molecular sieve, obtains ZSM-5 and the ZSM-11 zeolite of 10 ~ 500nm.
US Patent No. 19980218191(1998-12-22) disclose a kind of method of synthetic ZSM-5 zeolite molecular sieve.Its technical characteristic is, with a kind of amorphous silicon aluminum for raw material, template adopts Tri N-Propyl Amine, adds crystal seed, at 100 ~ 200 DEG C, through hydrothermal crystallizing, obtains the ZSM-5 zeolite molecular sieve that crystal grain is less than 500nm.
Chinese Patent Application No.: 98123933.1(1998-11-07) disclose a kind of preparation method of small-grain FeZSMS zeolite molecular sieve.Its technical characteristic is, adopts silicon-containing material, inorganic molysite, inorganic sodium, organic amine, mineral acid and deionized water to be raw material, through low-temperature hydrothermal dynamic crystallization, obtains the hetero-atom molecular-sieve containing Fe that crystal grain is less than 1 μm.
US Patent No. 19920882015(1992-05-13) disclose a kind of method of synthesizing ZSM-5.Its technical characteristic is, prefabricated is carried out mixture containing nucleus slurries and raw material, through hydrothermal crystallizing, obtains the ZSM-5 molecular sieve of granularity about 100 ~ 500nm.
European patent EP 19850110256(1985-08-16) disclose a kind of method of synthesizing ZSM-5.Its technical characteristic is, by raw mixture pre-treatment 6h at 80 DEG C, then by pre-treatment thing with 15% ratio with newly join raw mixture at 175 DEG C, through hydrothermal crystallizing 8h, obtaining silica alumina ratio is 60, and grain-size is about the ZSM-5 zeolite molecular sieve of 100 ~ 300nm.The method is also utilize directed agents method synthesizing small-grain zeolite molecular sieve.
US Patent No. 19850694536(1985-01-24) disclose a kind of method of synthesizing ZSM-5.Its technical characteristic is, on the basis of patent US 3702886, in the reaction system containing a large amount of template, interpolation tetrapropyl quaternary ammonium salt or quaternary ammonium hydroxide previously prepared amorphous silicon alumina gel directed agents, through hydrothermal crystallizing, can obtain the ZSM-5 molecular sieve of more than 100nm.
US Patent No. 19830520746(1983-08-05) disclose the method for a kind of low sodium synthesis ZSM-5.Its technical characteristic is, adopts alkylamine and alkyl halide composite mould plate agent to substitute quaternary ammonium hydroxide and quaternary ammonium salt, after hydrothermal crystallizing, obtains the ZSM-5 molecular sieve that grain fineness number is 50nm ~ 20 μm.
US Patent No. 19730330925(1973-02-09) disclose a kind of method of synthetic ZSM-5 zeolite.Its technical characteristic is, with TPAOH on the basis of patent US D3702886,4-propyl bromide or both mixtures, as template, adopt violent stirring to reach high mass transfer velocity, through hydrothermal crystallizing, obtain the ZSM-5 zeolite molecular sieve of 5 ~ 100nm.
Following discloses patent describes the preparation method of little crystal grain TS-1 molecular sieve.
Chinese Patent Application No.: 201010552093.0(2010-11-17) disclose a kind of preparation method of little crystal grain MFI structure HTS.Its technical characteristic is, the little crystal grain MFI structure HTS synthesized is containing skeleton organic group, and this organosilicon is at 1213 ~ 1278cm of infrared spectra
-1there is corresponding absorption peak at place.
Chinese Patent Application No.: 201010235977.3(2010-07-20) disclose a kind of method of quickly synthesizing small-crystallite titanium-silicon molecular sieve in cheap system.Its technical characteristic is, take silicon sol as silicon source, and titanium tetrachloride or tetrabutyl titanate are titanium source, 4-propyl bromide is template, and organic amine is alkali source, and adopts nano level TS-1 mother liquor as crystal seed, through hydrothermal crystallizing, obtain the HTS that particle size is less than 1 μm.The method is also utilize crystal seed method synthesizing small-grain zeolite molecular sieve.
Chinese Patent Application No.: 200910217756.0(2009-10-26) disclose a kind of synthetic method of TS-1 molecular sieve.Its technical characteristic is, take tetraethoxy as silicon source, and tetrabutyl titanate is titanium source, and TPAOH is template, and water and Virahol are solvent, H
2o
2for inorganic additives, through hydrothermal crystallizing, obtain TS-1 molecular sieve.
Chinese Patent Application No.: 02132325.9(2003-03-12) disclose a kind of synthetic method of small-crystallite titanium-silicon molecular sieve.Its technical characteristic is, adopt self-control 4-propyl bromide to exchange through strongly basic anionic resin, concentrated to obtain TPAOH be template, tetraethoxy is silicon source, and tetrabutyl titanate does titanium source, obtains the HTS that crystal grain is 0.1 μm after hydrothermal crystallizing.
Chinese Patent Application No.: 01145256.0(2001-12-28) disclose a kind of preparation method of small-crystallite titanium-silicon molecular sieve catalyzer.Its technical characteristic is, adopt tetraalkyl brometo de amonio to be template, organic amine is alkali source, and silicon sol is silicon source, and the alcoholic solution of titanium tetrachloride does titanium source, through alternating temperature hydrothermal crystallizing, obtains the HTS that grain size is 0.85 μm × 0.4 μm × 0.15 μm.
Chinese Patent Application No.: 99122123.0(2001-05-09) disclose a kind of synthetic method of small-crystallite titanium-silicon molecular sieve.Its technical characteristic is, employing TPAOH is template, and tetraethyl orthosilicate is silicon source, and inorganic titanium salt or organic titanium ester do titanium source, to join after glue through repeatedly alternating temperature hydrothermal crystallizing, obtain the HTS that crystal grain is less than 0.3 μm at 0 DEG C.
Chinese Patent Application No.: 99107790.3(2000-12-06) disclose a kind of synthetic method of small-crystallite titanium-silicon molecular sieve.Its technical characteristic is, employing organic bases is template, and tetraalkyl silicon ester is silicon source, and the alcoholic solution of titanium tetrachloride does titanium source, crystallization in microwave radiation field, obtains the HTS that grain size is 0.10 ~ 0.25 μm.
US Patent No. 19950380724(1995-01-30) disclose a kind of method preparing TS-1 molecular sieve.Its technical characteristic is, loads in container, supplement positive silicon ester and the TPAOH aqueous solution a small amount of water, then mixture is warming up to 80 DEG C, carries out except after alcohol 2h, then after mixture is cooled to 35 DEG C, adds TiF
4, stir 5 minutes, through hydrothermal crystallizing, obtain little crystal grain TS-1 molecular sieve.
Following discloses patent describes the preparation method of little grain MCM-22 molecular sieve.
Chinese Patent Application No.: 201010221287.2(2010-07-07) disclose a kind of preparation method of little grain MCM-22 molecular sieve.Its technical characteristic is, adopts the mode left standstill to be separated in the little grain MCM-22 molecular sieve mixture after crystallization, gets the raw material of upper suspension as synthesizing small-grain MCM-22 molecular sieve.
Chinese Patent Application No.: 02132508.1(2002-06-28) disclose a kind of preparation method of nano level MCM-22 zeolite molecular sieve.Its technical characteristic is, the template adopting patent US 4954325 used and other raw material, by controlling the water yield, alkali number and the crystallization temperature in raw mixture, through hydrothermal crystallizing, obtain the nano-grade MCM-22 molecular sieve of crystal diameter lower than 900nm.This patent mainly utilizes under the condition of low wash water, makes gel keep hypersaturated state in crystallization process, is conducive to a large amount of formation of nucleus, and at a higher temperature, is conducive to the growth of crystal, obtains the MCM-22 zeolite molecular sieve of nanometer at short notice.
Following discloses patent describes the preparation method of small-crystallite beta molecular sieve.
Chinese Patent Application No.: 201110294304.X(2011-10-06) disclose a kind of synthetic method of Beta zeolite.Its technical characteristic is, first carries out high-temperature water thermal treatment to Beta zeolite seed crystal, the Beta zeolite seed crystal dip treating in acid solution then under agitation hydrothermal treatment consists crossed, and the crystal seed after acid treatment washes with water to neutrality; Finally, silicon source, aluminium source, sodium source, tetraethylammonium cation source and water are mixed with homogeneous gel, then add pretreated Beta zeolite seed crystal, the homogeneous gel obtained, through hydrothermal crystallizing, obtains Beta zeolite.
Chinese Patent Application No.: 201110008767.5(2011-01-17) disclose a kind of synthetic method of Beta zeolite.Its technical characteristic is, crystal seed is made by the Beta zeolite powder adding cryodrying, and when preparing gel, high speed shear emulsion dispersion is carried out to crystal seed, give full play to the structure-directing effect of Beta zeolite seed crystal, thus widened the crystal seed scope be suitable for, under low template consumption, within the scope of wider silica alumina ratio, through hydrothermal crystallizing, the Beta zeolite product that degree of crystallinity is good can be obtained.
Chinese Patent Application No.: 201010552179.3(2010-11-17) disclose a kind of synthetic method of nanometer Beta zeolite.Its technical characteristic is, by silicon source, aluminium source, alkali MOH, composite mould plate agent RN and the obtained reaction mixture of water mixing, through hydrothermal crystallizing, obtains crystallization liquid; Wherein said composite mould plate agent RN is R
1and R
2mixture, R
1be selected from least one in tetraethyl ammonium hydroxide and triethylamine or diethylamine, R
2be selected from tetraethyl-ammonium halide, R
1with R
2mol ratio be 0.05 ~ 2.0; In crystallization liquid, add acidic cpd again, regulate crystallization liquid pH value to be less than 11, after separation, washing, drying, obtain the Beta zeolite of 10 ~ 100nm, wherein said acidic cpd is selected from least one in mineral acid, organic acid or ammonium chloride.
Chinese Patent Application No.: 200910130913.4(2009-04-17) disclose a kind of synthetic method of full-silicon beta zeolite with small crystal grains molecular sieve.Its technical characteristic is, silicon source, fluoride sources, tetraethyl ammonium ion source and deionized water is mixed by specific composition, through hydrothermal crystallizing, obtains the full-silicon beta zeolite molecular sieve that crystal grain is less than 5 μm.
Chinese Patent Application No.: 200810228359.9(2008-10-28) disclose the method for a kind of polynite synthesis small-particle beta-zeolite molecular sieve.Its technical characteristic is, activation treatment is carried out in polynite, then with the polynite of activation treatment for raw material provides all or part of aluminium source, through hydrothermal crystallizing, obtains small-particle beta-zeolite molecular sieve.The method is the surface by being grown closely by the beta-molecular sieve of synthesis in polynite, form the structure of similar nucleocapsid, improve catalyzed reaction efficiency to shorten reactant and product molecule in the path of zeolite molecular sieve internal diffusion, but gained zeolite molecular sieve is coacervate.
Chinese Patent Application No.: 200810152303.X(2008-10-10) disclose a kind of preparation method of nanometer high specific surface Beta zeolite.Its technical characteristic is, tetraethyl-ammonium halide, tetraethyl ammonium hydroxide, and mixed templates mixes, silicon source, appropriate crystal seed, alkali metal halide, after organic solvent mixing, through hydrothermal crystallizing, obtains the nano level Beta zeolite compared with high-ratio surface.This patent introduces alkali metal chloride in synthetic mixture, the organic solvents such as methyl alcohol.
Chinese Patent Application No.: 200710064979.9(2007-03-30) disclose a kind of preparation method of nano aluminum-rich Beta zeolite.Its technical characteristic is, silicon source and the hydrolytic reagent mixing plastic of alcohols will be soluble in, aging drying obtains silica gel, mix with hydrated aluminum oxide, acid again and obtain sial and mix glue, with tetraethylammonium cation compound, mix containing F-ionic compound and water after aging, through hydrothermal crystallizing, obtain low silica-alumina ratio, particle diameter is less than the Beta zeolite of 100nm.
Following discloses document also relates to the preparation method of small crystal grain ZSM-5 zeolite molecular sieve.
Open source literature SCI, 33(2012) 453 ~ 457 describe a kind of method of synthesizing Mn-ZSM-5 nano molecular sieve.Be characterized in, synthesized in classical formalism particle diameter at about 80nm containing manganese hetero-atom molecular-sieve, but the method not providing dispersing molecule to sieve.
Open source literature Catalysis Today, 116(2006) 82 ~ 87 describe a kind of method of synthesizing ZSM-5.Be characterized in, in the gelling system of white carbon black and sodium metaaluminate, respectively with Tetramethylammonium hydroxide, tetraethyl-hydrogenation ammonium, TPAOH, TBAH is template, at 230 DEG C, through hydrothermal crystallizing, obtain 159.9nm, the ZSM-5 zeolite of 76.3nm, 55.8nm and 87.2nm, the method does not add other organism.
Open source literature petrochemical complex Journal of Chinese Universities, 18(2005) 20 ~ 23 describe a kind of method of synthesizing ZSM-5.Be characterized in, aluminum isopropylate and TPAOH solution mixed according to a certain percentage, clarifies completely to solution by magnetic stirrer.Above-mentioned settled solution is joined in a certain amount of silica gel, until silica gel complete wetting.Wetting silica gel is completely added in crystallizing kettle, through hydrothermal crystallizing, obtains the ZSM-5 zeolite of 100nm.
Open source literature Materials Letters, 59(2005) 3827-3430 describes a kind of method of synthesizing ZSM-5.Be characterized in, under the condition not using organic formwork agent, with silicon sol, sodium metaaluminate and sodium hydroxide for raw material, proportioning raw materials is 12Na
2o:100SiO
2: 2Al
2o
3: 2500H
2o.Aging 12h at normal temperatures, then at 180 DEG C, through hydrothermal crystallizing, obtaining take grain-size as the ZSM-5 zeolite coacervate that 15nm forms.
Open source literature petrochemical complex Journal of Chinese Universities, 18(2005) 17 ~ 19 describe a kind of method of synthesizing ZSM-5.Be characterized in, adopt mesoporous carbon to receive and expect that pipe is for inertial base, with tetraethoxy, n-Butyl Amine 99, the vitriol oil, sodium hydroxide, dehydrated alcohol for raw material.The nano-ZSM-5 molecular sieve that mean grain size is 27nm is prepared by Confined space synthesis method.
Open source literature Microporous Mesoporous Materials, 75(2004) 41-49 describes a kind of method of synthesizing ZSM-5.Be characterized in, employing TPAOH is template, and TEOS is raw material, sec.-propyl aluminium be aluminium source under 70 ~ 90 DEG C of low temperature, through hydrothermal crystallizing, obtain with 10 ~ 20nm composition ZSM-5 zeolite coacervate.
Open source literature Langmuir, 20(2004) 8301-8306 describes a kind of method of synthesizing ZSM-5.Be characterized in, adopt clear liquid method at 165 DEG C, through hydrothermal crystallizing 120h, obtain the small crystal grain ZSM-5 zeolite coacervate of 100 ~ 600nm.
Open source literature Microporous Mesoporous Materials, 57(2003) 83-92 describes a kind of method based on two step synthesis ZSM-5 zeolite molecular sieve.Be characterized in, under the condition not adding aluminium source, first synthesize total silicon zeolite (silicalile-1).With total silicon zeolite be crystal seed, Tai-Ace S 150 is aluminium source, silicon oxide is silicon source, TPAOH for template, adopt the method for clear liquid synthesis, normal pressure, backflow at 80 DEG C, synthesize the ZSM-5 zeolite molecular sieve that grain-size is 100 ~ 300nm.
Open source literature Chem Mater, 15(2003) 1664-1668 describes the synthetic method of a kind of ZSM-5.Be characterized in, after the raw material mixing such as aluminum isopropylate, tetraethyl silicate, water, TPAOH and ethanol, be impregnated in gluey charcoal template, then at 180 DEG C, through hydrothermal crystallizing 48h, obtain the ZSM-5 zeolite molecular sieve that homogeneous grain-size is 13nm, 22nm, 42nm and 90nm.
Open source literature Microporous Mesoporous Materials, 39(2000) 135-147 describes the synthetic method of a kind of ZSM-5.Be characterized in, with TEOS and aluminum isopropylate for raw material, TPAOH is that template adopts at higher basicities and synthesized without sodium clear liquid method the ZSM-5 zeolite molecular sieve that primary grains is 10 ~ 100nm.
Open source literature Zeolites, 15(1995) 611-619 describes a kind of method of clear liquid method synthetic ZSM-5 zeolite.Be characterized in, under certain condition, ammoniacal liquor and Tai-Ace S 150, TPAOH are prepared tetrapropyl aluminium, then tetraethyl silicate is made to be hydrolyzed 10 ~ 24h in the TPAOH aqueous solution, again by preparation tetrapropyl aluminium under strong stirring, join in the hydrolyzed solution of tetraethyl orthosilicate, mixed clear liquid refluxes at 98 DEG C, obtains the nano-sized ZSM-5 zeolite molecular sieve that grain-size is 130 ~ 230nm.
Open source literature Zeolites, 14(1994) 643-649 describes the synthetic method of a kind of ZSM-5.Be characterized in, with silicon sol or the silicon that obtains from GEOTHERMAL WATER be silicon source, 4-propyl bromide is template, sodium hydroxide is alkali source, aluminum nitrate for aluminium source, at 160 DEG C, through Dynamic Hydrothermal crystallization, obtain the ZSM-5 zeolite aggregate of 30 ~ 50nm.
Open source literature refining of petroleum, 12(1983) 744-748 describes the synthetic method of a kind of ZSM-5.Be characterized in, by adding inorganic salt modulation sized zeolite particles, research finds that the content increasing NaCl can make its crystal grain be decreased to about 70nm.
Open source literature chemistry journal, 12(1978) 85-87 describes the synthetic method of a kind of ZSM-5.Be characterized in, must NaCl be added during synthesis, and make NaCl/A1
2o
3in the scope of 30 ~ 60, too high or too lowly all can not get small crystal grain ZSM-5 zeolite, the ZSM-5 zeolite crystal grain utilizing the method to prepare is less than 100nm.
Open source literature Journal of the Indian chemical society, 83(2006) 686-691 describes a kind of method of synthetic ZSM-5 zeolite molecular sieve.Being characterized in, is template with quadrol, synthesizes the spherical ZSM-5 zeolite molecular sieve that crystal grain is about 500nm.
Following discloses document also relates to the preparation method of little crystal grain TS-1.
Open source literature Catalysis today, 158(2010) 510-514 describes a kind of method of synthesizing TS-1 molecular sieve.Be characterized in, use tetraethyl orthosilicate and tetrabutyl titanate respectively as silicon source and titanium source, TPAOH, as template, uses three kinds of methods to dissolve tetrabutyl titanate: 1. make solvent with ethanol, and retain in crystallization process always respectively; 2. make solvent with Virahol, retain in crystallization process always; 3. make solvent with Virahol, but carry out before crystallization except alcohol.The method can obtain the TS-1 zeolite molecular sieve of little crystal grain.
Following discloses document also relates to the preparation method of MCM-22 zeolite molecular sieve.
Open source literature chemical research, 2009,20(1): describe a kind of method utilizing sucrose to prepare meso-porous carbon molecular sieve in 24-28.Be characterized in, first adopt vitriol oil carbonization of being dewatered by sucrose to be prepared into carbon source, using SBA-15 as template, prepare specific surface area and the larger meso-porous carbon molecular sieve of pore volume.
Open source literature Microporous and Mesoporous Materials, describes a kind of synthetic method of MCM-22 molecular sieve in 2009,118:1-10.Be characterized in, take silicon-dioxide as silicon source, sodium aluminate is aluminium source, hexamethylene imine is template, through water-heat transfer crystallization, obtains the MCM-22 molecular sieve that silica alumina ratio is respectively 9,21,30,46.
Open source literature chemical engineer, 2009,163(4): the synthetic method describing a kind of MCM-22 molecular sieve in 18-19.Be characterized in, adopt silicon sol and sodium metaaluminate to be silicon source and aluminium source, with hexamethylene imine and piperazine diamine for template, through water-heat transfer crystallization, obtain MCM-22 molecular sieve.
Open source literature catalysis journal, 2006,27(7): the method describing a kind of different silica sources synthesis MCM-22 molecular sieve in 585-590.Be characterized in, using industrial columns layer silica gel, white carbon black or silicon sol as silicon source, intending pellicular water aluminium masonry is aluminium source, and hexamethylene imine, as template, through hydrothermal crystallizing, obtains MCM-22 molecular sieve.The method by aging to silica-alumina gel ultrasonic wave, facilitate the synthesis of MCM-22 molecular sieve, shortens the crystallization time of MCM-22 molecular sieve, expand can synthesizing Si-Al than scope, change the pattern of MCM-22 molecular sieve.
Open source literature catalysis journal, 2005,26(10): describe a kind of method of synthesizing MCM-22 molecular sieve in 851-854.Being characterized in, take solid silicone as silicon source, and sodium aluminate is aluminium source, and hexamethylene imine and hexahydroaniline diamine are template, through water-heat transfer crystallization, obtains MCM-22 molecular sieve.The method utilizes hexahydroaniline to the stabilization of skeleton, improves the degree of crystallinity of MCM-22 molecular sieve.
Wherein method therefor comprises: gel is aging, ultrasonic pretreatment, prefabricated directed agents, various each high dispersive silicon source, special attachments matrix, post-modification, multistage intensification crystallization, dampening and the special salt of introducing or fluorochemical etc., but do not relate to and add special organism.
Following discloses patent describes adds organic method in the preparation process of little grain MCM-22 molecular sieve.
Chinese Patent Application No.: 201010264235.3(2010-08-24) disclose a kind of method of synthesizing small-grain MCM-22 zeolite molecular sieve.Its technical characteristic is, silicon source, aluminium source, alkali source, water, lignin salt's compounds and template hexamethylene imine are mixed, through hydrothermal crystallizing, obtains the MCM-22 zeolite molecular sieve of little crystal grain, and prepared molecular sieve particle diameter is 100 ~ 500nm, thickness is 20 ~ 50nm.The lignin salt's compounds mainly sodium lignin sulphate adopted in the method, xylogen potassium sulfate, sodium lignosulfonate, lignosulfonic acid potassium etc.Lignin salt is a kind of anion surfactant, and xylogen is the complicated phenol polymer of one formed by alcohol monomer.
Chinese Patent Application No.: 200510025147.7(2005-04-18) disclose a kind of synthetic method of MCM-22 molecular sieve.Its technical characteristic is, adopts hexamethylene imine and piperidines to be the composition of mixed templates, adjusting template agent, through Hydrothermal Synthesis, and can the grain size of control MCM-22 molecular sieve.The zeolite crystal with hexamethylene imine being wherein template synthesis is comparatively large, and along with the increase of piperidines amount, the crystal grain of molecular sieve can reduce gradually.
Chinese Patent Application No.: 200410043273.0(2004-05-17) disclose a kind of preparation method of little crystal grain MCM-22 zeolite molecular sieve.Its technical characteristic is, adopt hexanolactam shortening product directly as template, and in reaction gel, add the organic additive such as Sodium dodecylbenzene sulfonate, polyethylene glycols tensio-active agent, through hydrothermal crystallizing, obtain the stratiform MCM-22 zeolite molecular sieve that particle diameter is less than 600nm, thickness is less than 100nm.
Following discloses patent describes adds organic method in the preparation process of β small crystal grain molecular sieve.
Chinese Patent Application No.: 200810204229.1(2008-12-09) disclose a kind of preparation method of beta zeolite in small crystal grain molecular sieve.Its technical characteristic is, joins in the mixing solutions containing alcohol, tensio-active agent using the aqueous precursor gel containing secondary structure unit of beta zeolite as synthesis material, through hydrothermal crystallizing, obtains little crystal grain zeolite molecules.In the method, alcohol used is the liquid alcohols such as propyl carbinol, isopropylcarbinol, hexanol, and tensio-active agent used is cetyl trimethylammonium bromide cationoid tensio-active agent.
Chinese Patent Application No.: 00107486.5(2000-05-19) disclose a kind of synthetic method of beta zeolite in small crystal grain molecular sieve.Its technical characteristic is, be made into working solution by soluble in water to aluminium source, tetraethylammonium cation and alkali source, then be that 20 ~ 300 object silica gel particles mix mutually with working solution by granularity, and add a kind of organic additive, through hydrothermal crystallizing, obtain beta zeolite in small crystal grain molecular sieve.Wherein organic additive is polyol-based non-ionic surfactant, polyether class lubricating oil or their mixture.The method is that the surface energy reducing raw material by adding organic additive makes template accelerate silica gel particle surface " nibbling ", and reduces the viscosity of gel, accelerates nucleus growth, reduces grain size.
Following discloses patent describes adds organic method in the preparation process of other small crystal grain molecular sieve.
Chinese Patent Application No.: 200710304470.7(2007-12-28) disclose a kind of synthetic method of small crystal grain NaY molecular sieve.Its technical characteristic is, introduces and Al in gel in synthesized gel rubber or crystallization process
2o
3weight ratio be 0.1-3: 1 chitin and or oligosaccharides.The method be by add chitin and or oligosaccharides make original large grain size (200 ~ 800nm), the system being 5 at silica alumina ratio synthesizes the small crystal grain NaY molecular sieve that silica alumina ratio is 5.5; Chitin and or joining day of oligosaccharides can be in synthesis or in crystallization process.And adding fashionable in crystallization process, the preferred joining day is 8-16 hour after crystallization, but after introducing additive, crystallization time must not be less than 10 hours.
Chinese Patent Application No.: 200480034919.7(2004-10-29) disclose the preparation method of a kind of little crystal grain SSZ-32.Its technical characteristic is, this patent is the method with reference to patents such as US 5252527, through hydrothermal crystallizing, obtains small crystal grain molecular sieve product.Wherein add N, N '-di-isopropyl imidazolium hydroxide or N-methyl-N '-isopropylimdazole oxyhydroxide and alkylamine play template and fill the effect of duct rock steady structure.
Chinese Patent Application No.: 200410077908.9(2004-09-17) disclose a kind of preparation method of ZSM-35 molecular sieve.Its technical characteristic is, silicon source, aluminium source, alkali source, hexahydroaniline, organic additive and deionized water are prepared into gel, at 140 ~ 190 DEG C, through hydrothermal crystallizing, obtains the ZSM-35 molecular sieve of little crystal grain.Wherein organic additive is Sodium dodecylbenzene sulfonate, polyethylene glycols tensio-active agent or their mixture, but adds the degree of crystallinity that organic object is to improve molecular sieve.
Chinese Patent Application No.: 01135686.3(2001-10-19) disclose a kind of method of synthesizing small-grain A-type molecular sieve.Its technical characteristic is, utilizes alumino silica gel, oil, tensio-active agent and cosurfactant to prepare stable W/O microemulsion, finally by microemulsion at 90-120 DEG C, through hydrothermal crystallizing, obtain the A type molecular sieve that average grain size is less than 400nm.The method mainly utilizes carries out in specific water-in-oil (W/O) microemulsion system, crystal growth by by oil phase the finite space in the small aqueous phase that wraps up limit, avoid excessively growing up of crystal.Oil used is hexanaphthene, sherwood oil; Tensio-active agent is Triton X-100, sodium laurylsulfonate; Cosurfactant is Pentyl alcohol, n-hexyl alcohol.The method utilizes surfactant-based material and oil phase to form water in oil Emulsions, and provide place for the crystallization of molecular sieve.
Chinese Patent Application No.: 01135684.7(2001-10-19) disclose a kind of method preparing small crystal grain Y-shaped molecular sieve.Its technical characteristic is, with optimal conditions, utilizes and carries out in specific water-in-oil (W/O) microemulsion system, crystal growth by by oil phase the finite space in the small aqueous phase that wraps up limit, avoid excessively growing up of crystal.Oil used is hexanaphthene, sherwood oil; Tensio-active agent is Triton X-100, sodium laurylsulfonate; Cosurfactant is Pentyl alcohol, n-hexyl alcohol.
Chinese Patent Application No.: 00111065.9(2000-06-02) disclose a kind of synthetic method of fine grain NaY type molecular sieve.Its technical characteristic is, first adopts special method to prepare directed agents, then joins in the building-up process of molecular sieve, through hydrothermal crystallizing, obtains the NaY type molecular sieve of small particle size.The method adds glycerol, ethylene glycol or Virahol as organic dispersing agent when preparing directed agents, and organic dispersing agent can also be methyl alcohol, ethanol, dimethyl sulfoxide (DMSO) and left-right rotary sugar etc.In this patent, dispersion agent plays reduction gel viscosity, the nucleus of directed agents is made to be disperseed fully and expose, increase grain density, reach the object reducing zeolite crystal size, and the best of organic dispersing agent introduces the time for after first time, silicon source added, and introduce the object all not reaching fully dispersion directed agents nucleus in aging and crystallization process.
U.S. Patent Application No.: US19810325457(1981-11-27) disclose a kind of method of synthesizing small-grain faujasite molecular sieve.Its technical characteristic is, plastic under zero point to 10 DEG C low temperature, and in synthetic system, adds monose or disaccharides, synthesizing small-grain faujasite molecular sieve.
Following patent also describes adds organic method in Zeolite synthesis.
Chinese Patent Application No.: 201010501473.1(2010-10-0) disclose the preparation method of a kind of multi-stage porous titanium-silicon zeolite TS-1.Its technical characteristic is, sugary TS-1 Zeolite synthesis colloidal sol is prepared dry glue through thermal treatment, in this process, sugar is heated and partially carbonized dehydration forms hard template, so the molecular sieve prepared has the mesoporous of 4-50nm and is greater than the macropore of 50nm and the TS-1 molecular screen material be interconnected between multistage pore canal simultaneously.The method synthesizes multilevel hole material as hard template after utilizing organic carbon.
Chinese Patent Application No.: 200910187933.5(2009-10-16) disclose a kind of synthetic method of MCM-22 molecular sieve.Its technical characteristic is, employing hexamethylene imine is template (mould silicon is than being 0.15-1.0), and add dimethylene imines, may also be dimethylene imines and hydro carbons, organic amine, alcohols, ketone etc. as auxiliary organic formwork agent, prepare the MCM-22 molecular sieve of pure phase.But the method just reaches shortening crystallization time by adding auxiliary organism, reduce the effect of crystallization temperature.
Chinese Patent Application No.: 200710062872.0(2007-01-19) disclose a kind of preparation method of MCM-22 molecular sieve.Its technical characteristic is, in conventional synthesized gel rubber, adds appropriate C
2-C
9alcohols, C
2-C
6branched paraffin substituted benzene organic additive, through hydrothermal crystallizing, obtain MCM-22 molecular sieve.The method mainly utilizes the selection of organic additive kind and consumption to carry out the pore structure of modulation molecular sieve, and most probable pore size is distributed can reach 0.65nm, and pore volume is maximum can by 0.346m
3/ g increases to 0.435m
3/ g.
Following discloses patent describes the method for adding organosilane in the preparation process of molecular sieve.
Chinese Patent Application No.: 200710011690.0(2007-06-11) disclose a kind of preparation method containing ordered mesopore structure zeolite molecular sieve.Its technical characteristic is, utilizes tensio-active agent and organosilane mixing solutions to be template, by the crystallization process of the ratio control zeolite molecular sieve of both adjustments, finally obtains the MFI zeolite molecular sieve of ordered mesopore structure.
Chinese Patent Application No.: 201010519498.4(2010-10-26) disclose a kind of preparation method of small crystal grain NaY molecular sieve.Its technical characteristic is, adopts chlorosilane to be silicon source, through hydrothermal crystallizing, obtains the NaY molecular sieve of granularity ~ about 100nm.
Chinese Patent Application No.: 201010546164.6(2010-11-16) disclose a kind of preparation method of ZSM-5 zeolite molecular sieve.Its technical characteristic is, employing 4-propyl bromide is template, take water glass as silicon source, Tai-Ace S 150 directly joins in the synthetic system of traditional Z SM-5 zeolite for aluminium source, commercialization silane coupling agent, obtains the zeolite product with hierarchical porous structure.
Chinese Patent Application No.: 201110182984.6(2011-06-30) disclose a kind of preparation method of Y-type zeolite molecular sieve.Its technical characteristic is, take water glass as silicon source, with Tai-Ace S 150 and sodium aluminate for aluminium source, with molecules surfactant N, N-diethyl-N-hexadecyl-N-(3-methoxy silane propane) ammonium iodide is template, has synthesized the Y zeolite containing meso-hole structure by traditional hydrothermal method.While the zeolite product that the method obtains has conventional molecular sieve microvoid structure, also there is a large amount of meso-hole structures.
Chinese Patent Application No.: 201210011147.1(2012-01-13) disclose a kind of preparation method of mesoporous MFI zeolite molecular sieve.Its technical characteristic is, utilizes the mixture of organosilane or organosilane and tensio-active agent for template, synthesizes hierarchical zeolite molecular sieve under Microwave-assisted firing condition.The material that the method synthesizes combines the advantage of micro-pore zeolite and mesoporous material, has both maintained the strongly-acid of micro-pore zeolite, highly selective and high hydrothermal stability, also possesses the advantage that mesoporous material aperture is conducive to greatly molecular diffusion simultaneously.
Chinese Patent Application No.: 201210073742.8(2012-03-20) disclose a kind of preparation method of ZSM-5 zeolite molecular sieve microsphere.Its technical characteristic is, utilize methylic organo-siloxane and tetraethoxy to make silicon source single stage method and prepare ZSM-5 zeolite molecular sieve microsphere, microballoon is made up of tiny ZSM-5 zeolite crystal grain, and change the addition containing methylsiloxane, the large I of microballoon is 3-8 μm of adjustment.The ZSM-5 zeolite molecular sieve microsphere size uniform that the method obtains, good dispersity, preparation process is simple, is easy to a large amount of preparation.
From patent, document, the method for current synthesizing small-grain (nanometer) zeolite is more.Such as: use directed agents, nanosized seeds, inorganic salt, or use inertia mesoporous material to provide hard template, or adopt stirring, microwave, ultrasonic and multi-stage type crystallization etc. when crystallization.But the less then plane of crystal of zeolite crystal size can be larger, inevitably there is the problem that molecular sieve product is reunited.All can reunite in the filtration of Crystallization of Zeolite process (especially crystallization later stage) and zeolite product, washing, drying, roasting, finally cause outer surface area effective rate of utilization low, molecular sieve nanometer advantage seriously reduces.And in existing method, reduction zeolite crystal size and certain dissemination can be reached by adding some organism of interpolation (as: oligosaccharides, polyoxyethylene glycol, tensio-active agent) at synthesized gel rubber or crystallization initial stage.But, add the amount of organic additive less time can not play the effect of dispersion; When add-on is slightly large, there is again serious inhibition to the crystallization of molecular sieve, cause crystallization time obviously to extend, add the production cost of molecular sieve.And add polyhydroxy substance at synthesized gel rubber or crystallization initial stage, the growth of molecular sieve crystal is hindered because organic hydroxyl is elementary with molecular sieve or secondary structure combines, the zeolite product inside obtained inevitably also exists defect, causes the degradation of molecular sieve.Therefore, directly prepare the little crystal grain zeolitic molecular sieve of high dispersive to be of great significance.
Summary of the invention
The invention provides the method for the little crystal grain zeolite molecular sieve of a kind of direct synthesis high dispersive.We study and find at MFI, Beta, MWW family molecular sieves synthesized gel rubber or crystallization initial stage, add organochlorosilane and can affect zeolite molecular sieve process of growth, (wherein T refers to Si to limiting structure hydroxyl T-OH, Al, P or other heteroatoms) between dehydration form T-O-T key, thus the polymerization of restriction zeolite molecular sieve, play the effect of dispersion zeolitic molecular sieve particle.Obvious dissemination can not be played when but the amount adding organochlorosilane is less, when add-on is large, then have serious inhibition to the crystallization process of molecular sieve.We find in the zeolite molecular sieve crystallization later stage through large quantifier elimination, at the end of crystallization just, especially introduce organochlorosilane can obtain the little crystal grain zeolite molecular sieve of high dispersive.This is because, after hydrolyzing organochlorosilanes hydroxyl can with molecular sieve surface hydroxyl generation condensation, hinder the T-OH dehydration between molecular sieve to combine and form T-O-T key, and then stop the polymerization of zeolite molecular sieve.Meanwhile, the combination between silane species and structural hydroxyl can also reduce the wetting ability of molecular sieve, makes molecular sieve be easy to filter, is conducive to product-collecting, and makes product keep good dispersiveness after baking.In the crystallization later stage, especially crystallization adds organochlorosilane just, not only can not change brilliant looks and the composition of molecular sieve, and can not disturbing molecule sieve normal crystallization, the product obtained not only has polymolecularity, also maintains the performance of little crystal grain product preferably.
Technical scheme of the present invention is as follows:
Scheme one: directly add organochlorosilane when gel crystallization is complete
The first step: preparation synthesized gel rubber
The slip-stick artist being familiar with this area all can adopt the technological method reported in existing open source literature and patent, prepares the gel for the synthesis of little crystal grain or nano molecular sieve.As gel ZL200510200328.9, ZL200510028781.6, ZL01145256.0, ZL00107486.5, ZL200710064979.9, ZL200810204229.1, ZL200510025147.7, Zeolites needed for the method preparation introduced in following patent, 15 (1995) 611-619, Micropor.Mesopor.Mater, 57 (2003) 83-92, Chinese Journal of Inorganic Chemistry, 19 (2003) 396, Catalysis today, 158(2010) 510-514, Nankai University's journal (natural science edition), 39 (2006) 4.Small-grain ZSM-5 is prepared as an example: take industrial aluminum sulphate 8.6 grams according to embodiment in patent ZL200510200328.9 1, adding deionized water 230 grams wherein makes it dissolve, then 28 grams, sulfuric acid is added, the basicity of regulator solution, add 10 grams, sodium-chlor again, after constantly stirring makes it dissolve completely, then add Virahol 1.5 grams, form solution A.Dilute 517 grams of water glass with 100 grams of deionized waters, then add homemade ZSM-5 crystal seed 2.5 grams, in reinforced process, constantly carry out mechanical stirring, after adding n-Butyl Amine 99 at leisure, form B solution.Under constantly stirring, B solution is joined in solution A at leisure, then uses mulser emulsification 15 minutes, then reaction mixture is installed in reactor, stir crystallization 24 hours at 100 DEG C, be then warming up to 170 DEG C, crystallization 24 hours.
Second step: add organochlorosilane when gel crystallization is complete in crystallization system
At the end of Crystallization of Zeolite, under agitation by nitrogen pressurization, organochlorosilane press-in is equipped with in the crystallizing kettle of crystallization thing, makes organochlorosilane and the abundant contact reacts of molecular sieve surface.Refer to the crystallization end time that the crystallization curve by investigating molecular sieve is determined at the end of said Crystallization of Zeolite, the slip-stick artist being familiar with this area all can complete this operation; Any one in the selected organochlorosilane such as the optional METHYL TRICHLORO SILANE of organochlorosilane, methyl hydrogen dichlorosilane, trimethylchlorosilane or its any mixture; The amount wherein adding organochlorosilane (R) is R/SiO
2=0.01 ~ 2(mass ratio).Reaction times is 0 ~ 100h, and the preferred reaction time is 2 ~ 10h.Temperature of reaction is room temperature ~ 200 DEG C, preferably 100 ~ 160 DEG C.Applicable molecular sieve comprises MFI, Beta, MWW family molecular sieves etc.
3rd step: collect product
After organochlorosilane and crystallization thing react and terminate, ordinary method is adopted to collect product.Such as adopt Plate Filtration to carry out solid-liquid separation, with deionized water, product is washed to pH=8 ~ 9, then dry 24h at 110 DEG C, and through 540 DEG C of roasting 6h, obtain the molecular sieve of Nano zeolite product of high dispersive.
Scheme two: gel crystallization reclaims mother liquor completely afterwards and adds organochlorosilane again
Iteration scheme one, but at the end of gel crystallization, open the reducing valve of crystallizing kettle, the part water in crystallization feed liquid and whole volatile organic components are fully vaporized, is recycled mother liquor through condensation, reclaiming mother liquor can recycle.Then, under agitation in post-decompression crystallizing kettle, be pressed into organochlorosilane, make organochlorosilane and the abundant contact reacts of molecular sieve surface.In this method, post-decompression crystallization feed liquid is long-pending to be reduced, and temperature and pressure reduces, and is conducive to the consumption reducing organochlorosilane, and is conducive to operation.
The invention has the beneficial effects as follows: by adding organochlorosilane in the Crystallization of Zeolite later stage, effectively can reduce condensation between molecular sieve and reuniting, zeolite product good dispersity, the external surface area of gained be large, be easy to filter.And hydrolyzing organochlorosilanes discharges hydrogenchloride can regulate synthetic system pH value, inhibition system turns brilliant.The molecular sieve utilizing present method to prepare has more catalytic active center to expose on the outer surface, is conducive to preparing high performance catalyst.
Embodiment
Below by embodiment, the present invention will be further described, but the present invention is not by the restriction of these embodiments.
Comparative example 1
According to the report of patent ZL200510200328.9, choose the synthesis that a representative formula carries out ZSM-5 molecular sieve.By water glass (SiO
2), water, sulfuric acid, Tai-Ace S 150 (Al
2o
3), Virahol (IPA) and n-Butyl Amine 99 (NBA) be SiO by mol ratio
2/ Al
2o
3=178, OH
-/ SiO
2=0.58, NBA/SiO
2=0.40, IPA/SiO
2=0.01, H
2o/SiO
2=15 are prepared into homogeneous gel, and add its SiO in gel
2the ZSM-5 molecular sieve crystal seed of gross weight 2%.By reaction gel with after mulser emulsification 15min, transfer in high pressure water heating kettle, stir aging 24h in 100 DEG C, then be warming up to 170 DEG C of crystallization 24h.After crystallization terminates, open reducing valve, make the part water in crystallization material liquid, vaporizable Virahol and n-Butyl Amine 99, be recycled through condensation, Ethylene recov can be used for synthesis next time ZSM-5 molecular sieve.Gained solid product through deionized water wash to pH=8 ~ 9, dry 24h at 110 DEG C, and at 540 DEG C roasting 6h, obtain pure ZSM-5 molecular sieve.The relative crystallinity of product is 100%.Characterize through SEM, product is the nano zeolite of high aggregation.Through N
2physical adsorption characterizes, and its BET outer surface area is 50m
2/ g, product filters slowly.
Comparative example 2
According to open source literature Catalysis today, 158(2010) report of 510-514, choose the synthesis that a representative formula carries out TS-1 molecular sieve.Be SiO by tetraethoxy (TEOS), water, tetrabutyl titanate (TBOT), ethanol (EtOH), Virahol (IPA) and TPAOH (TPAOH) by mol ratio
2/ TiO
2=30.0, H
2o/SiO
2=20.0, TPA
+/ SiO
2=0.20, IPA/TiO
2=1.5 are prepared into homogeneous gel.After reaction gel is removed alcohol 4h at 70 DEG C, then add equal-volume water, after stirring 1h, transfer in high pressure water heating kettle, in 165 DEG C of dynamic crystallization 30h.After crystallization terminates, open reducing valve, make the part water in crystallization material liquid, vaporizable ethanol and Virahol, be recycled through condensation, Ethylene recov can be used for synthesis next time TS-1 molecular sieve.Gained solid product through deionized water wash to pH=8 ~ 9, dry 24h at 110 DEG C, and at 540 DEG C roasting 6h, obtain pure TS-1 molecular sieve.The relative crystallinity of product is 100%.Characterize through SEM, product pattern is the coccoid of about 120nm.Through N
2physical adsorption characterizes, and its BET outer surface area is 70m
2/ g, product filters very difficult, adopts collected by centrifugation.
Comparative example 3
According to the report of publication ZL00107486.5, choose the synthesis that a representative formula carries out Beta molecular sieve.Be SiO by silochrom, water, sodium hydroxide, pseudo-boehmite, vacuum pump oil and tetraethyl ammonium hydroxide (TEAOH) by mol ratio
2/ Al
2o
3=30, Na
2o/SiO
2=0.075, TEAOH/SiO
2=0.09, H
2o/SiO
2=6.5, vacuum pump oil/SiO
2=0.5, be prepared into homogeneous gel.After reaction gel mechanical stirring 1h, transfer in high pressure water heating kettle, prior at 120 DEG C, crystallization 24h, then be warming up to 148 DEG C of crystallization 48h.After crystallization terminates, open reducing valve, make the part water vapor in crystallization material liquid, through condensate drainage.Gained solid product through deionized water wash to pH=8 ~ 9, dry 24h at 110 DEG C, and at 540 DEG C roasting 6h, obtain pure Beta molecular sieve.The relative crystallinity of product is 100%.Characterize through SEM, product is the nano zeolite of high aggregation.Through N
2physical adsorption characterizes, and its BET external surface area is 80m
2/ g, product filters slowly, adopts collected by centrifugation.
Comparative example 4
According to the report of publication ZL200510025147.7, choose the synthesis that a representative formula carries out MCM-22 molecular sieve.By NaAlO
2, NaOH, water, silicon sol and hexamethylene imine (HMI) be SiO by mol ratio
2/ A1
2o
3=30.0, OH
-/ SiO
2=0.15, H
2o/SiO
2=15.0, Na
+/ SiO
2=0.09, HMI/SiO
2=0.35 is prepared into homogeneous gel, adds the MCM-22 molecular sieve crystal seed of mixing butt gross weight 5% in gel.After reaction gel mechanical stirring 1h, transfer in high pressure water heating kettle, in 140 DEG C of crystallization 120h.After crystallization terminates, open reducing valve, make the part water in crystallization material liquid and vaporizable U-4527, be recycled through condensation, Ethylene recov can be used for synthesis next time MCM-22 molecular sieve.Gained solid product through deionized water wash to pH=8 ~ 9, dry 24h at 110 DEG C, and at 540 DEG C roasting 6h, obtain pure phase MCM-22 molecular sieve.The relative crystallinity of product is 100%.Characterize through SEM, product pattern is in serious flowers shape of reuniting.Through N
2physical adsorption characterizes, and its BET outer surface area is 100m
2/ g, product filters extremely slow.
Comparative example 5
According to the report of patent ZL200510200328.9, choose the synthesis that a representative formula carries out ZSM-5 molecular sieve.By water glass (SiO
2), water, sulfuric acid, Tai-Ace S 150 (Al
2o
3), Virahol (IPA), trimethylchlorosilane (R) and n-Butyl Amine 99 (NBA) they are SiO by mol ratio
2/ Al
2o
3=178, OH
-/ SiO
2=0.58, NBA/SiO
2=0.40, IPA/SiO
2=0.01, H
2o/SiO
2=15 and mass ratio R/SiO
2=0.3 is prepared into homogeneous gel, and adds its SiO in gel
2the ZSM-5 molecular sieve crystal seed of gross weight 2%.By reaction gel with after mulser emulsification 15min, transfer in high pressure water heating kettle, stir aging 24h in 100 DEG C, be warming up to 170 DEG C of crystallization 24h.After crystallization terminates, open reducing valve, make the part water in crystallization material liquid, vaporizable Virahol and n-Butyl Amine 99, be recycled through condensation, Ethylene recov can be used for synthesis next time ZSM-5 molecular sieve.Gained solid product through deionized water wash to pH=8 ~ 9, dry 24h at 110 DEG C, and at 540 DEG C roasting 6h, obtain pure ZSM-5 molecular sieve.The relative crystallinity of product is 45%.
Comparative example 6
According to open source literature Catalysis today, 158(2010) report of 510-514, choose the synthesis that a representative formula carries out TS-1 molecular sieve.Be SiO by tetraethoxy (TEOS), water, tetrabutyl titanate (TBOT), ethanol (EtOH), Virahol (IPA), trimethylchlorosilane (R) and TPAOH (TPAOH) by mol ratio
2/ TiO
2=30.0, TPA
+/ SiO
2=0.20, IPA/TiO
2=1.5, H
2o/SiO
2=20.0 and mass ratio R/SiO
2=0.3 is prepared into homogeneous gel.After reaction gel is removed alcohol 4h at 70 DEG C, then add equal-volume water, after stirring 1h, transfer in high pressure water heating kettle, in 165 DEG C of dynamic crystallization 30h.After crystallization terminates, open reducing valve, make the part water in crystallization material liquid, vaporizable ethanol and Virahol, be recycled through condensation, Ethylene recov can be used for synthesis next time TS-1 molecular sieve.Gained solid product through deionized water wash to pH=8 ~ 9, dry 24h at 110 DEG C, and at 540 DEG C roasting 6h, obtain pure TS-1 molecular sieve.The relative crystallinity of product is 50%.
Comparative example 7
According to the report of publication ZL00107486.5, choose the synthesis that a representative formula carries out Beta molecular sieve.Be SiO by silochrom, water, sodium hydroxide, pseudo-boehmite, vacuum pump oil, trimethylchlorosilane (R) and tetraethyl ammonium hydroxide (TEAOH) by mol ratio
2/ Al
2o
3=30, Na
2o/SiO
2=0.075, TEAOH/SiO
2=0.09, H
2o/SiO
2=6.5, vacuum pump oil/SiO
2=0.5 and mass ratio R/SiO
2=0.3, be prepared into homogeneous gel.After reaction gel mechanical stirring 1h, transfer in high pressure water heating kettle, prior at 120 DEG C, crystallization 24h, then be warming up to 148 DEG C of crystallization 48h.After crystallization terminates, open reducing valve, make the part water vapor in crystallization material liquid, and through condensate drainage.Gained solid product through deionized water wash to pH=8 ~ 9, dry 24h at 110 DEG C, and at 540 DEG C roasting 6h, obtain pure Beta molecular sieve.The relative crystallinity of product is 40%.
Comparative example 8
According to the report of publication ZL200510025147.7, choose the synthesis that a representative formula carries out MCM-22 molecular sieve.By NaAlO
2, NaOH, water, silicon sol, trimethylchlorosilane (R) and hexamethylene imine (HMI) be SiO by mol ratio
2/ A1
2o
3=30.0, OH
-/ SiO
2=0.15, Na
+/ SiO
2=0.09, HMI/SiO
2=0.35, H
2o/SiO
2=15.0 and mass ratio R/SiO
2=0.3, be prepared into homogeneous gel, in gel, add the MCM-22 molecular sieve crystal seed of mixing butt gross weight 5%.After reaction gel mechanical stirring 1h, transfer in high pressure water heating kettle, in 140 DEG C of crystallization 120h.After crystallization terminates, open reducing valve, make the part water in crystallization material liquid and vaporizable U-4527, be recycled through condensation, Ethylene recov can be used for synthesis next time MCM-22 molecular sieve.Gained solid product through deionized water wash to pH=8 ~ 9, dry 24h at 110 DEG C, and at 540 DEG C roasting 6h, obtain pure phase MCM-22 molecular sieve.The relative crystallinity of product is 43%.
Embodiment 1
Repeat comparative example 1, by water glass (SiO
2), water, sulfuric acid, Tai-Ace S 150 (Al
2o
3), Virahol (IPA) and n-Butyl Amine 99 (NBA) be SiO by mol ratio
2/ Al
2o
3=178, OH
-/ SiO
2=0.58, NBA/SiO
2=0.40, IPA/SiO
2=0.01, H
2o/SiO
2=15 are prepared into homogeneous gel, and add its SiO in gel
2the ZSM-5 molecular sieve crystal seed of gross weight 2%.By reaction gel with after mulser emulsification 15min, transfer in high pressure water heating kettle, stir aging 24h in 100 DEG C, then be warming up to 170 DEG C of crystallization 23h.Wherein 23h is the crystallization curve by investigating zeolite molecular sieve, the crystallization end time of the zeolite molecular sieve determined.When zeolite molecular sieve crystallization time reaches 23h, by nitrogen pressurization by trimethylchlorosilane (R/SiO in mass ratio
2=0.5) press-in is equipped with in the crystallizing kettle of crystallization thing, stirs, at 170 DEG C, reacts 2h again.Gained slurries are through Plate Filtration, and washing, dry, roasting, obtain pure ZSM-5 molecular sieve.The relative crystallinity of product is 90.0%, characterizes through SEM, and product is in the nano zeolite of dispersion.Through N
2physical adsorption characterizes, and its BET outer surface area is 75m
2/ g, and product filtration velocity is 10 times of comparative example 1.
Embodiment 2
Repeat enforcement 1, but substitute trimethylchlorosilane by the METHYL TRICHLORO SILANE of equal in quality, methyl hydrogen dichlorosilane respectively, then the product obtained proves to be pure ZSM-5 molecular sieve through X-ray diffraction analysis, and its relative crystallinity is respectively 86%, 90%.Characterize through SEM, product is in the nano zeolite of dispersion.Through N
2physical adsorption characterizes, and its BET outer surface area is respectively 70m
2/ g, 65m
2/ g, and product filtration velocity is 10 times of comparative example 1.
Embodiment 3
Repeat embodiment 1, when zeolite molecular sieve crystallization time reaches 23h, open reducing valve, make the part water in crystallization material liquid, vaporizable Virahol and n-Butyl Amine 99, be recycled through condensation, Ethylene recov can recycle.Be equipped with in the still of crystallization material liquid after decompression and be pressed into trimethylchlorosilane, stir, at 100 DEG C, react 5h.Gained solid product, through Plate Filtration, through washing, dry, roasting, obtains pure ZSM-5 molecular sieve.The relative crystallinity of product is 93.0%, characterizes through SEM, and product is in the nano zeolite of dispersion.Through N
2physical adsorption characterizes, and its BET outer surface area is 70m
2/ g, and product filtration velocity is 10 times of comparative example 1.
Embodiment 4
Repeating comparative example 2, is SiO by tetraethoxy (TEOS), water, tetrabutyl titanate (TBOT), ethanol (EtOH), Virahol (IPA) and TPAOH (TPAOH) by mol ratio
2/ TiO
2=30.0, H
2o/SiO
2=20.0, TPA
+/ SiO
2=0.20, IPA/TiO
2=1.5 are prepared into homogeneous gel.After reaction gel is removed alcohol 4h at 70 DEG C, then add equal-volume water, after stirring 1h, transfer in high pressure water heating kettle, in 165 DEG C of dynamic crystallization 29h.Wherein 29h is the crystallization curve by investigating zeolite molecular sieve, the crystallization end time of the zeolite molecular sieve determined.When zeolite molecular sieve crystallization time reaches 29h, by nitrogen pressurization by trimethylchlorosilane (R/SiO in mass ratio
2=0.5) press-in is equipped with in the crystallizing kettle of crystallization thing, stirs, at 165 DEG C, reacts 3h again.Gained slurries are through Plate Filtration, and washing, dry, roasting, obtain pure TS-1 molecular sieve.The relative crystallinity of product is 84%, and characterize through SEM, product pattern is the coccoid of about 120nm.Through N
2physical adsorption characterizes, and its BET outer surface area is 90.0m
2/ g, and product can adopt conventional Plate Filtration method to collect.
Embodiment 5
Repeat embodiment 4, but substitute trimethylchlorosilane by the METHYL TRICHLORO SILANE of equal in quality, methyl hydrogen dichlorosilane respectively, then the product obtained is pure TS-1 molecular sieve through X-ray diffraction analysis proof, and its relative crystallinity is respectively 82%, 84%.Characterize through SEM, product pattern is the coccoid of about 120nm.Through N
2physical adsorption characterizes, and its BET outer surface area is respectively 95m
2/ g, 90.0m
2/ g, and product can adopt conventional Plate Filtration method to collect.
Embodiment 6
Repeating comparative example 3, is SiO by silochrom, water, sodium hydroxide, pseudo-boehmite, vacuum pump oil and tetraethyl ammonium hydroxide (TEAOH) by mol ratio
2/ Al
2o
3=30, Na
2o/SiO
2=0.075, TEAOH/SiO
2=0.09, H
2o/SiO
2=6.5, vacuum pump oil/SiO
2=0.5, be prepared into homogeneous gel.After reaction gel mechanical stirring 1h, transfer in high pressure water heating kettle, prior at 120 DEG C, crystallization 24h, then be warming up to 148 DEG C of crystallization 47h.Wherein 47h is the crystallization curve by investigating zeolite molecular sieve, the crystallization end time of the zeolite molecular sieve determined.When zeolite molecular sieve crystallization time reaches 47h, by nitrogen pressurization by trimethylchlorosilane (R/SiO in mass ratio
2=0.5) press-in is equipped with in the crystallizing kettle of crystallization thing, stirs, at 148 DEG C, reacts 5h again.Gained slurries, through Plate Filtration, washing, drying, roasting, obtain pure Beta molecular sieve.The relative crystallinity of product is 90%, characterizes through SEM, and product is in the nano zeolite of dispersion.Through N
2physical adsorption characterizes, and its BET outer surface area is 100m
2/ g, and product can adopt conventional Plate Filtration method to collect.
Embodiment 7
Repeat embodiment 6, but substitute trimethylchlorosilane by the METHYL TRICHLORO SILANE of equal in quality, methyl hydrogen dichlorosilane respectively, then the product obtained is pure Beta molecular sieve through X-ray diffraction analysis proof, and its relative crystallinity is respectively 88%, 90%.Characterize through SEM, product is in the nano zeolite of dispersion.Through N
2physical adsorption characterizes, and its BET outer surface area is respectively 105m
2/ g, 100m
2/ g, and product can adopt conventional Plate Filtration method to collect.
Embodiment 8
Repeat comparative example 4, by NaAlO
2, NaOH, water, silicon sol and hexamethylene imine (HMI) be SiO by mol ratio
2/ A1
2o
3=30.0, OH
-/ SiO
2=0.15, H
2o/SiO
2=15.0, Na
+/ SiO
2=0.09, HMI/SiO
2=0.35 is prepared into homogeneous gel, adds the MCM-22 molecular sieve crystal seed of mixing butt gross weight 5% in gel.After reaction gel mechanical stirring 1h, transfer in high pressure water heating kettle, in 140 DEG C of crystallization 119h.Wherein 119h is the crystallization curve by investigating zeolite molecular sieve, the crystallization end time of the zeolite molecular sieve determined.When zeolite molecular sieve crystallization time reaches 119h, by nitrogen pressurization by trimethylchlorosilane (R/SiO in mass ratio
2=0.5) press-in is equipped with in the crystallizing kettle of crystallization thing, stirs, at 140 DEG C, reacts 5h again.Gained slurries, through Plate Filtration, washing, drying, roasting, obtain pure MCM-22 molecular sieve.The relative crystallinity of product is 88%, and characterize through SEM, product pattern is the flake that thickness is 20-50nm.Through N
2physical adsorption characterizes, and its BET outer surface area is 150m
2/ g, and product filtration velocity is 10 times of comparative example 4.
Embodiment 9
Repeat enforcement 8, but substitute trimethylchlorosilane by the METHYL TRICHLORO SILANE of equal in quality, methyl hydrogen dichlorosilane respectively, then the product obtained proves to be pure MCM-22 molecular sieve through X-ray diffraction analysis, and its relative crystallinity is respectively 86%, 89%.Characterize through SEM, product pattern is the flake that thickness is 20-50nm.Through N
2physical adsorption characterizes, and its BET outer surface area is respectively 155m
2/ g, 150m
2/ g, and product filtration velocity is 10 times of comparative example 4.
Embodiment 10
Repeat enforcement 8, by NaAlO
2, NaOH, water, silicon sol and hexamethylene imine (HMI) be SiO by mol ratio
2/ A1
2o
3=30.0, OH
-/ SiO
2=0.15, H
2o/SiO
2=15.0, Na
+/ SiO
2=0.09, HMI/SiO
2=0.35 is prepared into homogeneous gel, adds the MCM-22 molecular sieve crystal seed of mixing butt gross weight 5% in gel.After reaction gel mechanical stirring 1h, transfer in high pressure water heating kettle, in 140 DEG C of crystallization 119h.Wherein 119h is the crystallization curve by investigating zeolite molecular sieve, the crystallization end time of the zeolite molecular sieve determined.When zeolite molecular sieve crystallization time reaches 119h, by nitrogen pressurization by trimethylchlorosilane (difference R/SiO in mass ratio
2=0.1,0.3,0.8 and 1.0) press-in is equipped with in the crystallizing kettle of crystallization thing, stirs, at 140 DEG C, reacts 5h again.Gained slurries, through Plate Filtration, washing, drying, roasting, obtain pure MCM-22 molecular sieve.The relative crystallinity of product is respectively 95%, 92%, 86% and 86%, and characterize through SEM, product pattern is the flake that thickness is 20-70nm.Through N
2physical adsorption characterizes, and its BET outer surface area is respectively 130m
2/ g, 140m
2/ g, 155m
2/ g and 155m
2/ g, and product filtration velocity is 10 times of comparative example 4.
Embodiment 11
Repeat enforcement 8, by NaAlO
2, NaOH, water, silicon sol and hexamethylene imine (HMI) be SiO by mol ratio
2/ A1
2o
3=30.0, OH
-/ SiO
2=0.15, H
2o/SiO
2=15.0, Na
+/ SiO
2=0.09, HMI/SiO
2=0.35 is prepared into homogeneous gel, adds the MCM-22 molecular sieve crystal seed of mixing butt gross weight 5% in gel.After reaction gel mechanical stirring 1h, transfer in high pressure water heating kettle, in 140 DEG C of crystallization 119h.Wherein 119h is the crystallization curve by investigating zeolite molecular sieve, the crystallization end time of the zeolite molecular sieve determined.When zeolite molecular sieve crystallization time reaches 119h, by nitrogen pressurization by trimethylchlorosilane (R/SiO in mass ratio
2=0.5) press-in is equipped with in the crystallizing kettle of crystallization thing, stirs, at 140 DEG C, reacts 2h, 10h, 30h and 100h respectively again.Gained slurries, through Plate Filtration, washing, drying, roasting, obtain pure MCM-22 molecular sieve.The relative crystallinity of product is respectively 92%, 85%, 85% and 85%, and characterize through SEM, product pattern is the flake that thickness is 20-50nm.Through N
2physical adsorption characterizes, and its BET outer surface area is respectively 145m
2/ g, 150m
2/ g, 155m
2/ g and 155m
2/ g, and product filtration velocity is 10 times of comparative example 4.
Embodiment 12
Repeat enforcement 8, by NaAlO
2, NaOH, water, silicon sol and hexamethylene imine (HMI) be SiO by mol ratio
2/ A1
2o
3=30.0, OH
-/ SiO
2=0.15, H
2o/SiO
2=15.0, Na
+/ SiO
2=0.09, HMI/SiO
2=0.35 is prepared into homogeneous gel, adds the MCM-22 molecular sieve crystal seed of mixing butt gross weight 5% in gel.After reaction gel mechanical stirring 1h, transfer in high pressure water heating kettle, in 140 DEG C of crystallization 119h.Wherein 119h is the crystallization curve by investigating zeolite molecular sieve, the crystallization end time of the zeolite molecular sieve determined.When zeolite molecular sieve crystallization time reaches 119h, by nitrogen pressurization by trimethylchlorosilane (R/SiO in mass ratio
2=0.5) press-in is equipped with in the crystallizing kettle of crystallization thing, stirs, at 40 DEG C, 80 DEG C, 120 DEG C, 160 DEG C, 180 DEG C, reacts 5h respectively again.Gained slurries, through Plate Filtration, washing, drying, roasting, obtain pure MCM-22 molecular sieve.The relative crystallinity of product is respectively 90%, 90%, 90%, 90% and 90%, and characterize through SEM, product pattern is the flake that thickness is 20-50nm.Through N
2physical adsorption characterizes, and its BET outer surface area is respectively 140m
2/ g, 145m
2/ g, 150m
2/ g, 155m
2/ g and 155m
2/ g, and product filtration velocity is 10 times of comparative example 4.
Claims (9)
1. a preparation method for high dispersive zeolite molecular sieve, is characterized in that following steps:
The first step: preparation gel, the hydrothermal crystallizing of nano molecular sieve;
Second step: at the end of Crystallization of Zeolite, is under agitation equipped with organochlorosilane press-in in the crystallizing kettle of crystallization thing by nitrogen pressurization, makes organochlorosilane and the abundant contact reacts of molecular sieve surface; Or at the end of Crystallization of Zeolite, open reducing valve, part water in crystallization material liquid and whole volatile organic components are fully vaporized, be recycled through condensation, Ethylene recov recycles, then in post-decompression crystallizing kettle, be pressed into organochlorosilane, stir, organochlorosilane and molecular sieve surface are fully reacted; The mass ratio wherein adding organochlorosilane R is R/SiO
2=0.01 ~ 2, the reaction times, temperature of reaction was room temperature ~ 200 DEG C in order to be not more than 100h; After organochlorosilane and crystallization thing react and terminate, collect product.
2. preparation method according to claim 1, is characterized in that, described organochlorosilane is one in METHYL TRICHLORO SILANE, methyl hydrogen dichlorosilane, trimethylchlorosilane or its any mixture.
3. preparation method according to claim 1 and 2, is characterized in that, temperature of reaction is 100 ~ 160 DEG C.
4. preparation method according to claim 1 and 2, is characterized in that, described molecular sieve comprises MFI, Beta, MWW family molecular sieves.
5. preparation method according to claim 3, is characterized in that, described molecular sieve comprises MFI, Beta, MWW family molecular sieves.
6. the preparation method according to claim 1 or 2 or 5, is characterized in that, after reaction terminates, adopts Plate Filtration to collect product.
7. the preparation method according to claim 1 or 2 or 5, it is characterized in that the hydrothermal crystallization step of the preparation of gel and nano molecular sieve is as follows, industrial aluminum sulphate 8.6 grams, adding deionized water 230 grams wherein makes it dissolve, then 28 grams, sulfuric acid is added, the basicity of regulator solution, add 10 grams, sodium-chlor again, after constantly stirring makes it dissolve completely, add Virahol 1.5 grams again, form solution A, 517 grams of water glass are diluted with 100 grams of deionized waters, then ZSM-5 crystal seed 2.5 grams is added, constantly mechanical stirring is carried out in reinforced process, after adding n-Butyl Amine 99 at leisure, form B solution, under constantly stirring, B solution is joined in solution A at leisure, then uses mulser emulsification 15 minutes, then reaction mixture is installed in reactor, stir crystallization 24 hours at 100 DEG C, be then warming up to 170 DEG C, crystallization 24 hours.
8. preparation method according to claim 3, it is characterized in that the hydrothermal crystallization step of the preparation of gel and nano molecular sieve is as follows, industrial aluminum sulphate 8.6 grams, adding deionized water 230 grams wherein makes it dissolve, then 28 grams, sulfuric acid is added, the basicity of regulator solution, add 10 grams, sodium-chlor again, after constantly stirring makes it dissolve completely, add Virahol 1.5 grams again, form solution A, 517 grams of water glass are diluted with 100 grams of deionized waters, then ZSM-5 crystal seed 2.5 grams is added, constantly mechanical stirring is carried out in reinforced process, after adding n-Butyl Amine 99 at leisure, form B solution, under constantly stirring, B solution is joined in solution A at leisure, then uses mulser emulsification 15 minutes, then reaction mixture is installed in reactor, stir crystallization 24 hours at 100 DEG C, be then warming up to 170 DEG C, crystallization 24 hours.
9. preparation method according to claim 4, it is characterized in that the hydrothermal crystallization step of the preparation of gel and nano molecular sieve is as follows, industrial aluminum sulphate 8.6 grams, adding deionized water 230 grams wherein makes it dissolve, then 28 grams, sulfuric acid is added, the basicity of regulator solution, add 10 grams, sodium-chlor again, after constantly stirring makes it dissolve completely, add Virahol 1.5 grams again, form solution A, 517 grams of water glass are diluted with 100 grams of deionized waters, then ZSM-5 crystal seed 2.5 grams is added, constantly mechanical stirring is carried out in reinforced process, after adding n-Butyl Amine 99 at leisure, form B solution, under constantly stirring, B solution is joined in solution A at leisure, then uses mulser emulsification 15 minutes, then reaction mixture is installed in reactor, stir crystallization 24 hours at 100 DEG C, be then warming up to 170 DEG C, crystallization 24 hours.
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| CN106315611A (en) * | 2016-08-24 | 2017-01-11 | 山东齐鲁华信高科有限公司 | SSZ -13 molecular sieve preparing method |
| CN106430235B (en) * | 2016-08-31 | 2019-01-11 | 中国科学院上海高等研究院 | Nano-ZSM-5 molecular sieve and preparation method thereof |
| CN109485065B (en) * | 2017-09-09 | 2021-03-05 | 中国石油化工股份有限公司 | Hierarchical pore molecular sieve and preparation method thereof |
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| CN110627090A (en) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | Preparation method and application of sulfydryl functionalized SBA molecular sieve |
| CN109231236B (en) * | 2018-11-13 | 2022-02-22 | 南开大学 | Synthesis method of spherical SSZ-13 zeolite molecular sieve |
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