CN102502696B - Synthetic method of ZSM-5 zeolites - Google Patents
Synthetic method of ZSM-5 zeolites Download PDFInfo
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- CN102502696B CN102502696B CN201110364516.0A CN201110364516A CN102502696B CN 102502696 B CN102502696 B CN 102502696B CN 201110364516 A CN201110364516 A CN 201110364516A CN 102502696 B CN102502696 B CN 102502696B
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- 239000010457 zeolite Substances 0.000 title claims abstract description 217
- 238000010189 synthetic method Methods 0.000 title claims abstract description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 209
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 207
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 107
- 239000010703 silicon Substances 0.000 claims abstract description 107
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 105
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 64
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 60
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 51
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002253 acid Substances 0.000 claims abstract description 32
- 239000003513 alkali Substances 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 106
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 89
- 238000002425 crystallisation Methods 0.000 claims description 84
- 230000008025 crystallization Effects 0.000 claims description 84
- 239000004411 aluminium Substances 0.000 claims description 48
- 239000013078 crystal Substances 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 38
- 239000011734 sodium Substances 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 29
- 239000011707 mineral Substances 0.000 claims description 29
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 238000013019 agitation Methods 0.000 claims description 15
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 15
- 238000009415 formwork Methods 0.000 claims description 15
- 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
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 8
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 27
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002808 molecular sieve Substances 0.000 abstract description 15
- 238000006555 catalytic reaction Methods 0.000 abstract description 14
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 2
- 238000004939 coking Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract 1
- 238000005504 petroleum refining Methods 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 238000000034 method Methods 0.000 description 156
- 239000000243 solution Substances 0.000 description 71
- 239000000499 gel Substances 0.000 description 51
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 32
- 239000000047 product Substances 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 239000007788 liquid Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 17
- 230000032683 aging Effects 0.000 description 16
- 238000010899 nucleation Methods 0.000 description 14
- -1 silicon aluminate Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 150000001412 amines Chemical group 0.000 description 12
- 230000007062 hydrolysis Effects 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- 230000006911 nucleation Effects 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229960001866 silicon dioxide Drugs 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000908 ammonium hydroxide Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000005287 template synthesis Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003973 alkyl amines Chemical group 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Chemical group 0.000 description 2
- 150000001342 alkaline earth metals Chemical group 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001640 fractional crystallisation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 229940057054 1,3-dimethylurea Drugs 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
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000013456 study Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to the synthesis field of aluminosilicate ZMS (Zeolite Molecular Sieve), and relates to a synthetic method of ZSM-5 zeolite molecular sieves. ZSM-5 zeolites are high-silicon micro-porous zeolites with unique three-dimensional ten-membered ring crossing aperture passages, the diameters of the aperture passages are close to the sizes of benzene rings, and the ZSM-5 zeolites can be widely applied to petroleum refining, petrochemical industry and fine chemicals synthesis. Particularly, nano-sized ZSM-5 zeolites achieve larger external surface area and higher intracrystalline diffusion rate, and have higher activity and selectivity as well as strong coking deactivation-resisting capability in hydrocarbons catalysis conversion reactions. The synthetic method regulates the polymerization degrees of silicon sources and aluminum sources respectively by adding acid and alkali so as to obtain highly reactive reactants, and can rapidly achieve nucleus formation in large quantities in a system so as to obtain nano-sized zeolites. The synthetic method is not limited by the types of the silicon sources and the aluminum sources, has strong applicability to raw materials, changes the activity of the raw materials through simple regulation, and can rapidly synthesize products of the nano-sized ZSM-5 zeolites with well crystallinity under the dosage conditions of no template and low-cost templates.
Description
Technical field
The invention belongs to the synthetic field of aluminosilicate zeolite, relate to a kind of synthetic method of ZSM-5 zeolite.
Background technology
The ZSM-5 zeolite (USP 3702886) of U.S. Mobil oil company invention becomes a kind of very important shape selective catalysis material with its unique pore passage structure 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, by the Cyclar technique (LPG BTX) of the synthetic aromatic hydrocarbons of light hydrocarbons, Mobil-Badger synthesizing ethyl benzene technique, toluene gasifying process (MTDP), xylene isomerization process (MVPI), preparing gasoline by methanol technique (MTG) and p-methyl-ethylbenzene synthesis technique (PET).
Following patent and document all relate to the application of ZSM-5 zeolite:
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Because ZSM-5 zeolite belongs to micro-pore zeolite, pore size is less, so limited to a certain extent its application in bulky molecular catalysis reaction.At present solution to this problem mainly contains two kinds, is a kind ofly in ZSM-5 zeolite microvoid structure, to introduce meso-hole structure or is micropore by the crystallization of pore wall of mesoporous material, is formed with the transmission path that is beneficial to macromolecular cpd diffusion; Another kind method is exactly the synthetic superfine molecular sieves with nanoscale.The material with ZSM-5 zeolite Jie micropore composite structure can improve the diffusion of product, made up the deficiency of micro porous molecular sieve, for macromolecular reaction provides favourable sterie configuration, but its acidity is weak and hydrothermal stability is relatively low etc., 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.Compared with micron order ZSM-5 zeolite, nano-ZSM-5 zeolite has the intracrystalline rate of diffusion of larger outer surface area and Geng Gao, duct is short, and there is a large amount of intracrystalline pores, improving the utilization ratio of catalyzer, strengthen macromole conversion capability, reduce deep reaction, improve the aspects such as selectivity and all show more superior performance, in some hydrocarbons catalytic conversions reactions, show better active, selectivity and strong anti-coking deactivation ability.At present, nano-ZSM-5 zeolite has been used as aromizing, the catalyzer of the processes such as benzene alkylation, preparing gasoline by methanol (MTG).
Following patent and document all relate to the application of small crystal grain ZSM-5 zeolite:
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Due to the huge applications potentiality that nano-ZSM-5 zeolite all shows in numerous reactions, make to produce nano-ZSM-5 becomes the focus of domestic and international research always.Existing a lot of about the synthetic report of this respect at present.
Following patent and open source literature all relate to synthesis of nano ZSM-5 zeolite in the system that quaternary ammonium hydroxide and quaternary ammonium salt are template:
U.S. Pat 3926782 (1975) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: on the basis of patent US3702886 with TPAOH, 4-propyl bromide or both mixtures are as structure directing agent, crystallization process adopts violent stirring to reach high mass transfer velocity, and at 75～205 ℃, crystallization obtains the ZSM-5 zeolite of 5～100nm for 1 hour～6 days.Molar ratio is SiO
2/ Al
2o
3=15～300, Na
2o/SiO
2=0.14～2, TPA
+/ (TPA
++ Na
+)=0.4～0.9, H
2o/OH
-=10～300.But the essence of the method is to rely on the object of doing template and two kinds of means of violent stirring and reach synthesis of nano ZSM-5 zeolite with expensive quaternary ammonium salt and quaternary ammonium hydroxide.
European patent EP 0173901 (1985) has disclosed the method for synthetic ZSM-5 a kind of.Its technical characterictic is: by raw mixture pre-treatment 6 hours at 80 ℃, then by pre-treatment thing with 15% ratio with newly join raw mixture crystallization 8 hours at 175 ℃, can obtain silica alumina ratio and be 60 ZSM-5 zeolite, grain-size is about 100～300nm, consumption (the mol ratio R:SiO of quaternary amines template (TPA, TEA)
2) can be decreased to 0.05.Molar ratio is SiO
2/ Al
2o
3=40～80, (Si+Al)/H
2o=0.06～0.09, R/SiO
2< 0.4, H
2o/OH
-=50～70.At 80 ℃ in the method, the pre-treatment of 6 hours is equivalent to prepare directed agents by aging method, and still needs to use expensive quaternary amines template to reach the object of synthesis of nano ZSM-5 zeolite.
U.S. Pat 4606900 (1986) has disclosed the method for synthetic ZSM-5 a kind of.Its technical characterictic is: on the basis of patent US3702886, in the reaction system that contains a large amount of template, add by tetrapropyl quaternary ammonium salt or the previously prepared amorphous silicon alumina gel of quaternary ammonium hydroxide directed agents, crystallization rate can be accelerated on the one hand, degree of crystallinity can be improved on the other hand.The method can obtain the ZSM-5 zeolite of 100nm～100um by controlling the amount of amorphous silicon alumina gel crystallization accelerator.The molar ratio of patent is SiO
2/ Al
2o
3> 5, Na
2o/SiO
2=2 × 10
-10～2, TPA/SiO
2=0.01～2.0, H
2o/OH
-=0.7～3000.The method is to rely on directed agents and expensive quaternary amines template to reach the object of synthesis of nano ZSM-5 zeolite.
World patent WO 9703019 (1997) has disclosed the method for synthetic ZSM-5 a kind of.Its technical characterictic is: take Tai-Ace S 150, silicon sol, ammoniacal liquor and TPAOH as raw material, adopt clear liquid synthesis method to synthesize nano-ZSM-5.A certain proportion of Tai-Ace S 150 and silicon sol are joined in 20% the TPAOH aqueous solution of boiling continuously, under reflux conditions, stir 10 minutes, obtain clear liquid, be cooled to room temperature.Clear liquid is placed in to the matrass that reflux cooler is housed, 80 ℃ of backflows.The molar ratio of patent is SiO
2/ Al
2o
3=8～10, K
2o/Al
2o
3=0.25～0.5, (TMA)
2o/SiO
2=0.05, H
2o/Al
2o
3=80～100.The feature of the method is to adopt synthetic method under stillness of night normal pressure and low temperature, and needs to adopt expensive TPAOH to do template and reach the object of synthesis of nano ZSM-5 zeolite.
Open source literature Zeolites, 14 (1994) 643-649 have introduced the synthetic method of a kind of ZSM-5.The silicon that the method obtains take silicon sol or from GEOTHERMAL WATER as silicon source, 4-propyl bromide is aluminium source as template, sodium hydroxide as alkali source, aluminum nitrate, dynamic crystallization under 433K, obtains the ZSM-5 zeolite aggregate of 30～50nm.The method is that dependence is stirred and expensive 4-propyl bromide is the object that template reaches synthesis of nano ZSM-5 zeolite.
Open source literature Zeolites, 15 (1995) 611-619 have introduced a kind of method of clear liquid method synthetic ZSM-5 zeolite.The method has been synthesized nano-ZSM-5 take Tai-Ace S 150, tetraethyl silicate, ammoniacal liquor and TPAOH as raw material.First, with ammoniacal liquor and Tai-Ace S 150, TPAOH, prepare tetrapropyl aluminium under certain condition, then make tetraethyl silicate 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 ℃, and synthesizing grain-size is the nano-ZSM-5 zeolite of 130～230nm.The essence of the method is employing stillness of night method, stirring is synthetic and low temperature is synthetic, and expensive tetrapropyl hydrogen-oxygen ammonium is the object that template reaches synthesis of nano ZSM-5 zeolite.
Open source literature Micropor.Mesopor.Mater, 39 (2000) 135-147 have introduced the synthetic method of a kind of ZSM-5.The method is take TEOS and aluminum isopropylate as raw material, and TPAOH is that template adopts without sodium clear liquid method and synthesized the ZSM-5 zeolite that elementary crystal grain is 10～100nm under higher basicity.Feed molar proportioning is 1Al
2o
3: 60SiO
2: 21.4TPAOH: 650H
2o, crystallization 48h at 170 ℃, finds that the existence of sodium ion has reduced the crystallization velocity of ZSM-5 zeolite, causes crystal grain obviously to increase.What the method adopted is the object of high alkalinity, the stillness of night synthesizing and reach by methods such as expensive tetrapropyl hydrogen-oxygen ammonium are template synthesis of nano ZSM-5 zeolite.
Open source literature Micropor.Mesopor.Mater, 57 (2003) 83-92 have introduced a kind of method of preparing ZSM-5 zeolite based on two step synthesis program.The method is not adding under the condition in aluminium source, first synthetic total silicon zeolite (silicalile-1).Take total silicon zeolite as crystal seed, Tai-Ace S 150 as aluminium source, silicon oxide as silicon source, TPAOH is template, adopts the synthetic method of clear liquid, normal pressure, backflow, synthesize the ZSM-5 that grain-size is 100～300nm at 80 ℃.The advantage of the method is the concentration by adjusting crystal seed in mother liquor, can well control grain-size.Its essence is that the combined method that adopts stillness of night colloid, low temperature crystallized and expensive TPAOH to do template reaches the object of synthesis of nano ZSM-5 zeolite.
Open source literature Langmuir, 20 (2004) 8301～8306 have introduced the synthetic method of a kind of ZSM-5.The method adopts clear liquid method crystallization 120h at 165 ℃ to obtain the small crystal grain ZSM-5 zeolite aggregate of 100～600nm.Silica alumina ratio=40, TPAOH/Si=0.36, the use of organic formwork agent contributes to form rapidly a large amount of nucleus.But the method, owing to being synthetic without sodium, requires the content of sodium ion in raw material extremely low, this requires highly to raw material, and correspondingly cost is also high.Its essence is the object that adopts stillness of night method and expensive TPAOH to do template to reach synthesis of nano ZSM-5 zeolite.
Open source literature Micropor.Mesopor.Mater, 75 (2004) 41-49 have introduced the synthetic method of a kind of ZSM-5.It is template that the method adopts expensive TPAOH, TEOS is raw material, and sec.-propyl aluminium is that aluminium source crystallization under 70～90 ℃ of low temperature more than 12 days, obtains the glomerocryst being comprised of the ZSM-5 zeolite of 10～20nm, silica alumina ratio < 60, TPAOH/Si is about 0.36.Because the method low temperature has suppressed the growth of crystal, obtain nanocrystalline time causing yield very low.Its essence is and adopt low temperature crystallized and expensive TPAOH to do template and reach the object of synthesis of nano ZSM-5 zeolite.
Open source literature Catalysis Today, 116 (2006) 82～87 have introduced the method for synthetic ZSM-5 a kind of.The method in the gelling system of white carbon black and sodium metaaluminate, respectively with Tetramethylammonium hydroxide, tetraethyl-hydrogenation ammonium, TPAOH, TBAH is template, at 230 ℃, crystallization obtains 159.9nm for 45 hours, 76.3nm, the ZSM-5 zeolite of 55.8nm and 87.2nm.The method adopts is that the methods such as the tetrapropyl hydrogen-oxygen ammonium of high Gentle costliness is template reach the synthetic object of receiving ZSM-5 zeolite.
Chinese patent CN1715186 (application number 200410048354.X, 2004) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: be 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, then carry out hydrothermal crystallizing, and filtration, dry, roasting, finally obtain product.The method can make the ZSM-5 zeolite that silica alumina ratio is 15～200, elementary crystal grain particle is 100～500nm.Molar ratio is SiO
2/ Al
2o
3=20～600, Na
2o/SiO
2=0.25～1, R/SiO
2=0.01～0.2, H
2o/SiO
2=2～15, R is quaternary ammonium salt template.The feature of the method is requirement synthetic system reaches synthesis of nano ZSM-5 zeolite object without sodium and quaternary ammonium salt template.
Chinese invention patent CN1730391 (application number 200510016885.5,2005 years) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: synthesis of nano yardstick ZSM-5 zeolite under microwave action.First TPAOH and silicon source are added to the water, after mixing, under agitation add aluminium source prepare silicon aluminate solution; The direct microwave of reaction soln 3～180 minutes is synthetic, or after microwave heating in 3～30 minutes 150～190 ℃ of crystallization 1～3 day; Centrifugation or filtration after crystallization, washing is dry, obtains nano level ZSM-5 zeolite, and its grain size is adjustable within the scope of 50～300nm, and molar ratio is (0～10) Al
2o
3: (20～30) SiO
2: (100～1500) H
20: (4～45) TPAOH.The essence of the method is the object that relies on microwave and expensive TPAOH to do template to reach synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN1915819 (application number 200510028781.6,2005 years) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: before crystallization, to adding in crystallization mother liquor in advance take tetraethoxy, silicon sol or White Carbon black as silicon source, TPAOH or 4-propyl bromide are seeding director prepared by template.Directed agents is prepared in weathering process and has been produced a large amount of ZSM-5 primary structure and secondary structure unit at it, in synthetic crystallization process below, as the nucleus of ZSM-5 zeolite crystallization growth, obtains the ZSM-5 zeolite crystal of 100nm.The molar ratio of patent is XNa
2o: YAl
2o
3: 100SiO
2: ZH
2o, wherein, X=4～36, Y=0～3, Z=1400～6000, the seeding director amount preferable range adding is 1.0～10% of crystallization mother liquor weight.The essence of the method is the object that relies on seeding director and expensive TPAOH to do template to reach synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN1958453 (application number 200610097462.5,2006 years) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: adopting silicone grease or silane is raw material, and 4-propyl bromide is template, obtains the ZSM-5 zeolite of 100～400nm.Wherein silicon source is in advance in 6.0 times hydrolysis of acidic conditions PH <, and hydrolysis temperature is 20～40 ℃, and hydrolysis time is 6～24 hours.Molar ratio is SiO
2/ Al
2o
3=20～200, Na
2o/SiO
2=0.15～0.6, R/SiO
2=0.001～0.02, H
2o/SiO
2=0.1258～3.The essence of the method be rely on low water silicon than and expensive 4-propyl bromide do template and reach the object of synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN101733143 (application number 200810043970.4,2008 years) has disclosed a kind of method of fractional crystallization synthetic ZSM-5 zeolite.Its technical characterictic is: sial mixed gel, prior at 90～110 ℃ aging 4～10 hours, then is warming up to 120～150 ℃, crystallization 6～30 hours.Lower basicity and the water yield are selected in requirement, when guaranteeing solution alkali concn, make reaction mixture in crystallization process, keep hypersaturated state, thereby are conducive to a large amount of formation of low temperature crystallized stage molecular sieve nucleus.High temperature crystallization is conducive to the ZSM-5 nucleus Fast Growth forming, and obtains being less than the ZSM-5 zeolite of 300nm.Molar ratio is SiO
2/ Al
2o
3=400～1500, Na
2o/SiO
2=0.2～2, R/SiO
2=0.02～2, H
2o/SiO
2=10～35.The essence of the method is the object that the combined method that adopts low temperature aging, low wash water, fractional crystallization and expensive TPAOH to do template reaches synthesis of nano ZSM-5 zeolite.
Open source literature Chinese Journal of Inorganic Chemistry, 19 (2003) 396 have introduced the synthetic method of a kind of ZSM-5.The method is take 4-propyl bromide as template, and silicon sol is silicon source, and Tai-Ace S 150 is that aluminium source crystallization 1～9d under 100～150 ℃ of crystallization temperatures obtains nano-ZSM-5 zeolite.The method requires in synthetic system, to add appropriate an alkali metal salt, an alkali metal salt and Al
2o
3ratio in 40～120 scopes, can make the particle diameter of ZSM-5 zeolite drop to 60nm left and right.The essence of the method is to adopt low temperature aging, the combined method of adding an alkali metal salt and using expensive TPAOH to do template to reach the object of synthesis of nano ZSM-5 zeolite.
Open source literature petrochemical complex Journal of Chinese Universities, 18 (2005) 20～23 have introduced the synthetic method of a kind of ZSM-5.The method is take TPAOH as template, and aluminum isopropylate is aluminium source, and water glass is silicon source, adopts By Surface-wetting Method synthesis of nano ZSM-5 zeolite.Aluminum isopropylate and TPAOH solution are mixed according to certain ratio, stir with magnetic stirring apparatus, until solution is clarified completely.Above-mentioned settled solution is joined in a certain amount of silica gel, and limit edged stirs, until silica gel complete wetting.To soak silica gel completely and add in crystallizing kettle, at 170 ℃, crystallization 2～4d obtains the ZSM-5 zeolite of 100nm.The essence of the method is the object that adopts dampening and expensive TPAOH to do template to reach synthesis of nano ZSM-5 zeolite.
Quaternary ammonium hydroxide and quaternary ammonium salt are that a kind of cost is high, produce the Zeolite synthesis raw material of high pollution, highly toxic chemical exhaust while removing, and a large amount of uses can make the synthetic cost of molecular sieve significantly increase.In order to reduce the synthetic cost of molecular sieve, Many researchers attempts replacing TPAOH synthesis of nano ZSM-5 zeolite with other template, is aided with salt adding, low temperature aging, the means such as stirring simultaneously.
Following patent and open source literature have all related to the method with non-quaternary amines template synthesis of nano ZSM-5 zeolite:
U.S. Pat 4151189 (1979) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: on the basis of patent US3702886, use the primary amine that contains 2-9 carbon atom instead as template, at 75～300 ℃, crystallization synthesizes small crystal grain ZSM-5 zeolite for 24 hours～500 hours.The method is not used expensive quaternary ammonium salt or quaternary ammonium hydroxide, and only introduces a small amount of alkali metal cation.Molar ratio is SiO
2/ Al
2o
3=10～40, Na
2o/SiO
2=0.14～2, R/ (R+Na
+)=0.4～0.9, H
2o/OH
-=10～300, R is template.The feature of the method is that less salt, low silica-alumina ratio reach synthesis of nano ZSM-5 zeolite.
U.S. Pat 4526879 (1985) has disclosed the method for the synthetic ZSM-5 of a kind of low sodium.Its technical characterictic is: use composite mould plate agent to substitute quaternary ammonium hydroxide and quaternary ammonium salt, at 180～350 ℃, crystallization obtains the ZSM-5 zeolite that crystal grain is 50nm～20um for 3 hours～30 days.Composite mould plate agent is alkylamine and alkyl halide, by the ratio that changes both, controls crystal size size.Molar ratio is SiO
2/ Al
2o
3=20～200, M/SiO
2=0.01～2.0, R/SiO
2=0.1～1.0, H
2o/SiO
2=15～60.R is template, and M is basic metal or alkaline-earth metal.The feature of the method is the object that low sodium, high temperature and use alkylamine reach synthesis of nano ZSM-5 zeolite.
U.S. Pat 5268162 (1993) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: adopt the repeatedly method of the aging nucleation of alternating temperature, using 1,3 dimethyl urea is organic directed agents, and synthesizing Si-Al is than the ZSM-5 zeolite that is 25～40, and granularity is 100～500nm approximately.Molar ratio is SiO
2/ Al
2o
3=25～50, Na
2o/SiO
2=0.2～0.3, SO
4 2-/ SiO
2=0.15～0.25, R/SiO2=0.05, H
2o/SiO
2=20～300.The feature of the method is to rely on alternating temperature aging and use special template agent at low silica-alumina ratio, to be issued to the object of synthesis of nano ZSM-5 zeolite.
U.S. Pat 6180550 (calendar year 2001) has disclosed the method for synthetic ZSM-5 a kind of.Its technical characterictic is: raw material is a kind of amorphous silicon aluminum, adopts Tri N-Propyl Amine to make template, and adds crystal seed, and at 100～200 ℃, crystallization makes the ZSM-5 zeolite that is less than 500nm.Molar ratio is SiO
2/ Al
2o
3=15～20, M/SiO
2=0.15～0.2, R/SiO
2=0～0.4, H
2o/SiO
2=8～20.M is basic metal or alkaline-earth metal.The feature of the method is to rely on crystal seed, an alkali metal salt at low silica-alumina ratio, to be issued to the object of synthesis of nano ZSM-5 zeolite.
Open source literature Journal of the Indian chemical society, 83 (2006) 686-691 have introduced the method for synthetic ZSM-5 a kind of.The method, take quadrol as template, is used 1.85Na
2o: 0.25Al
2o
3: 15.2SiO
2: 19.7C
2dN: 592H
2fill a prescription at 177 ℃ crystallization 6～10 days of O, synthesizes the spherical ZSM-5 zeolite that crystal formation perfection, crystal grain are about 500nm.The feature of the method is that crystallization time is long.
Chinese invention patent CN1240193 (application number 99102700.0,1999 years) has disclosed the method for synthetic ZSM-5 a kind of.Its technical characterictic is: take n-Butyl Amine 99 as template, water glass, Tai-Ace S 150 and sodium hydroxide are raw material, carrys out the grain-size of Molecular regulator sieve by changing the amount of crystallization time, temperature and an alkali metal salt, obtains the ZSM-5 zeolite of 10～500nm.Molar ratio is SiO
2/ Al
2o
3=20～100, Na
2o/SiO
2=0.04～0.1, R/SiO
2=0.15～0.5, H
2o/SiO
2=40～200.The essence of the method is to rely on the measure of interpolation an alkali metal salt and low temperature aging to reach the object of synthesis of nano ZSM-5 zeolite.
Chinese patent CN1417121 (application number 02155482.X, 2004) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: adopt directing agent method synthesizing small crystal grain ZSM-5-5 zeolite.Concrete method is by a certain percentage directed agents to be 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 that accounts for cumulative volume 5～10%.Constant temperature 20～25 hours at 120 ℃, crystallization prepares the ZSM-5 zeolite of 100nm left and right for 20～25 hours at 155～165 ℃.The mol ratio of directed agents each component is SiO
2: Al
2o
3: Na
2o: organic amine: mineral acid: H
2o=40～80: 1: (7～15): (25～40): (3.0～7.5): (2000～4000).Molar ratio is SiO
2: Al
2o
3: Na
2o: organic amine: mineral acid: H
2o=20～100: 1: 7～15: 2～4: 0.5～8.5: 2000～4000.Organic amine is n-Butyl Amine 99, quadrol, ethamine or 1,6-hexanediamine.The essence of the method is to rely on directed agents and low temperature aging to reach the object of synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN101837298 (application number 201010171630.7,2010 years) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: the sial weight ratio of ZSM-5 zeolite is 10～200, and particle diameter is 60～100nm, and the preparation method of this molecular sieve is as follows: with alkyl alcohol, and alkylamine and aromatic amine composition ternary organic template agent; Silicon source is dissolved in to ternary organic template agent and water is made into A liquid; Aluminium source is dissolved in organic acid and water obtains B liquid; Under vigorous stirring state, B liquid is added in A liquid, be mixed with colloidal solution, pack synthesis reactor reaction crystallization into, be cooled to room temperature, water obtains small crystal grain ZSM-5 zeolite after synthetic product is washed, is dried.Molar ratio is Na
2o: SiO
2: Al
2o
3: H
2o: ternary organic template agent=5～18: 20～150: 1: 700～3500:: 0.05～100.The essence of the method is to rely on stirring and polynary template to reach the object of synthesis of nano ZSM-5 zeolite.
Open source literature chemistry journal, 12 (1978) 85-87 have introduced the synthetic method of a kind of ZSM-5.It is template that the method adopts n-Butyl Amine 99, ethamine or tripropyl amine, and water glass is silicon source, and Tai-Ace S 150 is aluminium source static crystallization 12 hours at 105 ℃, then 125 ℃ of crystallization, within 38 hours, obtains being less than the ZSM-5 zeolite of 100nm.But the method must add NaCl when synthetic, and makes NaCl/Al
2o
3mol ratio is in 30～60 scopes, the too high or too low small crystal grain ZSM-5 zeolite that all can not get.The essence of the method is to rely on interpolation an alkali metal salt and low temperature aging at low silica-alumina ratio, to be issued to the object of synthesis of nano ZSM-5 zeolite.
Open source literature refining of petroleum, 12 (1983) 744-748 have introduced the synthetic method of a kind of ZSM-5.The method is take n-Butyl Amine 99 as template, and water glass is silicon source, and Tai-Ace S 150 is aluminium source, and sodium hydroxide is the ZSM-5 zeolite that alkali source crystallization at 100～130 ℃ obtains 100nm and 700nm.By adding inorganic salt modulation zeolite particle diameter, find that the content that increases NaCl can make its crystal grain be decreased to 70 nanometer left and right.The essence of the method is to rely on interpolation NaCl and low temperature aging at low silica-alumina ratio, to be issued to the object of synthesis of nano ZSM-5 zeolite.
In addition, there is scholar to adopt confined space method synthesis of nano ZSM-5.Confined space method carrys out the growth of restriction molecule sieve crystal grain by means of the hole of gac nano-scale, but after synthetic, needs gac oxidation to remove the rear zeolite product that just can obtain pure phase, and complex manufacturing and cost are high.
Following discloses document has related to the method for confined space method synthesis of nano ZSM-5 zeolite:
Open source literature Chem.Commum, (1999) 673-674 has introduced a kind of method of confined space method synthetic ZSM-5 zeolite.The method is take TPAOH as template, take TEOS as silicon source, and the total silicon nano-ZSM-5 zeolite of growing in the pore structure of carbon black matrix.But it is larger that the synthetic nano zeolite of the method is affected by the pore size distribution of inert media, to having relatively high expectations of inertia mesoporous material; Also must guarantee that synthetic liquid enters the mesoporous inside of inert media completely, reduces the residual quantity outside hole; Inert media large usage quantity, and need take roasting method to remove, increased cost.
Open source literature Chem Mater, 15 (2003) 1664-1668 have introduced the synthetic method of a kind of ZSM-5.The method is impregnated in gluey charcoal template after the raw material such as aluminum isopropylate, tetraethyl silicate, water, TPAOH and ethanol is mixed, then crystallization 48h at 180 ℃.At 570 ℃, roasting 8h removes gluey charcoal, synthesizes the ZSM-5 that homogeneous grain-size is 13nm, 22nm, 42nm and 90nm.The grain-size homogeneous that the method is synthetic, but cost is higher.
Open source literature petrochemical complex Journal of Chinese Universities, 18 (2005) 17～19 have introduced the synthetic method of a kind of ZSM-5.The method adopts mesoporous carbon to receive material pipe for inertial base, take tetraethoxy, n-Butyl Amine 99, the vitriol oil, sodium hydroxide, dehydrated alcohol as raw material.By Confined space synthesis method, crystallization 4～5d at 170 ℃ obtains the nano-ZSM-5 molecular sieve that mean grain size is 27nm.The method is carried out on hydrothermal method basis, relates to crystallization in the hole of matrix, limits the size of grain-size with the hole dimension of carbon base body.But the Grain size distribution of still finding synthesized nano molecular sieve is wider, there is the crystal grain existence that a certain amount of grain-size is greater than matrix hole size.
Forefathers' research shows, although use organic formwork agent can synthesize purity and the very high zeolite of degree of crystallization, the price of template itself is but costliness very, and process exists the pollution problem to environment.And use the synthetic ZSM-5 zeolite of organic formwork agent to need high-temperature roasting, to remove organism contained in zeolite cavity, removed template method produces again atmospheric pollution.In view of using the many disadvantages of organic amine, it is in inorganic method that Many researchers are just transferred to non-organic amine template sight, and the process of synthetic ZSM-5 zeolite has been carried out to a large amount of systematic studyes.
Following patent and open source literature have all related to the method for inorganic method synthesis of nano ZSM-5 zeolite:
U.S. Pat 5240892 (1993) has disclosed a kind of method of inorganic method high-density synthetic ZSM-5 zeolite.Its technical characterictic is: do not use organic formwork agent, first water-soluble silicate (as water glass) is made to non-water-soluble precipitation silica gel by mineral acid precipitation agent precipitation, take this, precipitate silica gel and as silicon source, be prepared into the solid content that contains silicon source, aluminium source, alkali and water and be at least 35% heavy reaction mixture, then by this reaction mixture stir and lower than the condition of 250 ℃ under crystallization obtain the ZSM-5 zeolite of 5～20nm granularity.Molar ratio is SiO
2/ Al
2o
3=25～50, Na
2o/SiO
2=0.22, H
2o/SiO
2=5.The method is that employing precipitation silica gel is silicon source, relies on low wash water and stir crystallization the object that is issued to synthesis of nano ZSM-5 zeolite at low silica-alumina ratio.
Open source literature Materials Letters, 59 (2005) 3827-3430 have introduced the synthetic method of a kind of ZSM-5.The method is not using under the condition of organic formwork agent, and take silicon sol, sodium metaaluminate and sodium hydroxide as raw material, ratio of components is 12Na
2o: 100SiO
2: 2Al
2o
3: 2500H
2o.Feed liquid is aging 12h at normal temperatures, and crystallization 24h at 180 ℃, synthesizes the ZSM-5 that grain-size is about 15nm.The essence of the method is to rely on low temperature aging to reach the object of synthesis of nano ZSM-5 zeolite, but the zeolite crystal size obtaining is inhomogeneous and degree of crystallinity is not high, also exists stray crystal to equate.
Open source literature Journal of Materials Processing Technology, 206 (2005) 445 have introduced a kind of method without template synthesis of nano ZSM-5 zeolite, but the method can only synthesize specific silicon aluminum ratio (SiO
2/ Al
2o
3be 50) nano-ZSM-5 zeolite, work as SiO
2/ Al
2o
3mol ratio is greater than or less than at 50 o'clock, and the stray crystal phases such as mordenite all appear in the crystallization product obtaining, and cannot prepare the pure phase nanometer ZSM-5 zeolite of high-crystallinity.
Chinese invention patent CN1067226 (application number 92103601.9,1992 years) has disclosed the method for synthetic ZSM-5 a kind of.Its technical characterictic is: by one, containing specific surface, be 100～250m
2the nucleus that contains of/g partial crystallization forms slurries and raw material mixing post-heating, can obtain being greater than 250m containing specific surface area
2the product slurry of the particulate zeolite of/g.Be actually the grain fineness number by preparing a kind of pre-crystallization slurry mixture control molecular sieve, to reaching the object of producing particulate zeolite.Molar ratio is SiO
2/ Al
2o
3=20～50, Na
2o/SiO
2=0.2～0.4, SO
4 2-/ SiO
2=0.1～0.3, H
2o/SiO
2=40～200.The essence of the method is to rely on directed agents to reach the object of synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN1303816 (application number 00109593.5,2003 year) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: adopt directing agent method quickly synthesizing small crystal grain ZSM-5-5 zeolite, comprise directed agents preparation, Zeolite synthesis two steps.The preparation of the first step directed agents, first after silicon source and deionized water being made to A solution according to ratio of components, organic amine template is added, under agitation again aluminium source is splashed into homogeneous reaction, regulate potential of hydrogen to carry out temperature programming processing, then by connecing diaphanous part in synthetic fluid, isolate and be directed agents.The building-up process of molecular sieve is identical with directed agents, just the organic amine template in proportioning raw materials is replaced by directed agents, and crystallization process needs can complete for 65～75 hours, obtains the ZSM-5 zeolite of median size 100nm.Molar ratio is Na
2o: SiO
2: Al
2o
3: H
2o: organic amine=3～10: 20～100: 1: 2500～5000: 25～40.The essence of the method is to rely on directed agents to reach the object of synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN101041442 (application number 200710087075.8,2007 years) has disclosed a kind of method without template synthetic ZSM-5 zeolite.Its technical characterictic is: introduced ultrasonic technology and carried out crystallization pre-treatment.Take silicon source, aluminium source and mineral acid be as raw material, have or without crystal seed, exist under silica-alumina gel is carried out to ultrasonication 0.5～3 hour in 70 ℃, make feed composition be thoroughly mixed to form a large amount of nucleus, obtain the ZSM-5 zeolite of 100～500nm.The molar ratio of patent is SiO
2/ Al
2o
3=20～150, Na
2o/SiO
2=0.25～1, H
2o/SiO
2=40～200.The essence of the method is to rely on ultrasonic technology and low temperature aging to reach the object of synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN101643219 (application number 200910072747,2009 years) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: the crystal seed of pre-crystallization is joined in the gelling system without template synthesis of nano ZSM-5 zeolite, and crystallization 24 hours at 160～180 ℃, is cooled to room temperature by product centrifuging, washing, dry, roasting., obtain silica alumina ratio 60～160 nanoscale height assemble ZSM-5 zeolite.The molar ratio of patent: 7.2～19.2Na
2o: 1Al
2o
3: (60～160) SiO
2: (1500～4000) H
2o.The essence of the method is to rely on crystal seed to reach the object of synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN 101654259 (application number 200910172206.1,2009 years) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: adopt twin columns methods preparation gel, be about to silicon source, aluminium source and with identical speed, be added drop-wise to and in high speed agitator, prepare gel simultaneously.Take by weight silicon source solution 300-500 part, in the NaOH aqueous solution that the concentration that joins the parts by weight that measure and be 200-300 part is 10%, add parts by weight and be the pure water of 350 parts high-speed stirring 2 hours, form translucent milky white solution; Take by weight aluminium source solution 30-60 part, adding the parts by weight that measure is in 1200 parts of pure water, and stirring at room 2 hours forms clear solution; The interpolation speed of then He Lv source, silicon source being divided with 100-300ml/ is added dropwise in high speed agitator simultaneously, continues to stir 1 hour after dripping, and forms oyster white homogeneous gel.Gel crystallization 1～100 hour at 140 ℃～240 ℃, makes high-crystallinity, highly purified small crystal grain ZSM-5 zeolite.Its elementary crystal grain can reach 20～30nm, and the silica alumina ratio of each crystal grain is basically identical.The method does not need to introduce organic formwork agent, its essence is to rely on twin columns methods to prepare burden under the condition of high-speed stirring and crystallization reaches the object of synthesis of nano ZSM-5 zeolite, but operating process complexity.
Chinese invention patent CN 102001680 (application number 201010588177.X, 2010) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: adopt two-step approach to prepare presoma, without template agent method raw materials liquid and agitation and dropping legal system for mixed glue solution; In glue, add 1～10% crystal seed, at 100～200 ℃, crystallization obtains the zeolite of 50～100nm.Without template agent method, preparing mixing solutions is by the NaOH in reactor, NaAlO
2with the rotating speed of per minute 200-300, stir 2-4 hour with deionized water, bath temperature is 60-90 ℃, obtains the mixing solutions mixing; NaOH, NaAlO
2with the mass ratio of deionized water be 10: (3-6): (320-380).Agitation and dropping legal system is when mixing solutions is proceeded to stirring for mixed glue solution, by volumetric ratio, in solution, slowly drips silicon sol, acquisition mixed glue solution after silicon sol drips; The volumetric ratio of described mixing solutions and silicon sol is 200: (115-135).The essence of the method is to rely on crystal seed and low temperature aging to reach the object of synthesis of nano ZSM-5 zeolite.
Open source literature Industrial Catalysis, 16 (2008) 20～23 have introduced the synthetic method of a kind of ZSM-5.The method is take silicon sol and Tai-Ace S 150 as raw material, adds self-control seeding director and obtain being less than the ZSM-5 zeolite of 100nm in the Hydrothermal Synthesis system of not introducing organic formwork agent.Prepared seeding director is the SiO of the elementary or secondary structure unit of Silicalite-1 zeolite nano particle, the zeolite of total silicon
2and the mixed colloidal solution of template TPAOH.Preparation method is as raw material, according to n (TPA) take TPAOH (TPAOH) solution and tetraethyl orthosilicate (TEOS)
2o: n (SiO
2): n (EtOH): n (H
2o)=1: mix at 5.5: 22: 0, under room temperature, stir and spend the night, then at the aging certain hour of certain temperature, make.The essence of the method is to rely on nanosized seeds directed agents to reach the object of synthesis of nano ZSM-5 zeolite.
Inorganic method has successfully overcome the variety of issue that organic formwork agent exists above, but inorganic method synthetic ZSM-5 zeolite sial is lower, and in most cases degree of crystallinity is relatively poor, and product performance are not as synthetic by organic formwork agent method.
From patent documentation, synthesis of nano ZSM-5 zeolite is still a challenge at present.Although it is a lot of to relate to the report of this respect, but sum up, get up to need nothing more than to use directed agents, nanosized seeds, tensio-active agent, inorganic salt, or use inertia mesoporous material that hard template is provided, or when crystallization, adopt stirring, the method such as microwave, ultrasonic and two-part crystallization.Technique effect is subject to raw material type, and synthetic ratio and crystallization condition impact are very large.
Zeolite is in strong alkali solution, to be reacted with aluminate by silicate, and crystallization generates.As the He Lv source, silicon source that generates the main starting material of zeolite, multi-silicate radical ion and aluminate ion with different polymerization degree under different acid-base conditions exist, and panoramic zeolite molecular sieve is formed by these structural unit assemblings.We are through research discovery, and the polymerization state in He Lv source, silicon source has material impact to synthetic nano zeolite.
This is because the silicon source that zeolite synthesis is conventional can be divided into SiO
2micelle (silicon sol, solid silicone and amorphous Si O
2powder) and soluble silicate (water glass, water glass).SiO
2micelle is a kind of polymer being formed by connecting by silicon-oxy tetrahedron, and under the condition of soda acid, the following depolymerization behavior of meeting generation obtains the silicate of oligomeric state and monomer:
For soluble silicate, it exists with silicate hydrate root negatively charged ion in the aqueous solution, silicate ion and the large poly-state silicate ion of height of relative molecular mass that can generate oligomeric state also can there is depolymerization behavior as above in high poly-state silicate ion under the condition of soda acid.That is to say, the aggregation problem in silicon source is extensively present in the various raw materials of synthesis of molecular sieve, and the polymerization degree in adjusting silicon source is improved Zeolite synthesis universal significance.
On the other hand, pseudo-boehmite, sodium metaaluminate, homemade aluminium hydroxide, mineral acid aluminium salt and aluminum isopropylate are the conventional aluminium sources in zeolite synthesis.In basic solution, the main existence form of aluminate ion is Al (OH)
4 -.(Na in solution when alkaline concentration is increased to a certain degree
2the concentration of O is greater than 25%), Al (OH)
4 -just dewater and be transformed into AlO
2 -anionic form.Its dehydration has two kinds of modes:
The first
The second
In acidic solution, aluminium is with Al
3+the form of hydrated ion exists.Acidity is larger, and this hydrated ion is more stable.
So the He Lv source, silicon source of high poly-state can stepwise hydrolysis under the condition of soda acid obtains silicate and the aluminate of oligomeric state and monomer.
In general, hydrothermal crystallizing synthetic zeolite is via following three phases: the reaction of Yu Lv source, silicon source generates silica-alumina gel, gel nucleation and crystal growth.Nucleation is the key of whole crystallization process, no matter be homogeneous nucleation or heterogeneous nucleation, a large amount of nucleation is supplied with crystal growth by making to lack enough reactive behavior species in reaction system with " nutritive ingredient ", thus restriction crystalline size.In addition, the size of crystal grain and distribution are decided by nucleation rate and crystalline growth velocity, accelerate nucleation rate and also can cause synthesizing superfine particulate molecular sieve.The He Lv source, silicon source of oligomeric state, is conducive to generate uniform silica-alumina gel, reduces gel and resets the time, cause a large amount of nucleations, thereby it is synthetic to be conducive to nano zeolite.
Therefore, when synthetic ZSM-5 zeolite, in He Lv source, silicon source, adding a certain amount of acid or alkali to make its high reactivity silicate and aluminate of being depolymerized to oligomeric state or monomer, is an important channel that obtains nano zeolite and little crystal grain zeolite.
Summary of the invention
The invention provides a kind of soda acid that uses and regulate respectively polymerizable raw material degree, the method for quickly synthesizing nano ZSM-5 zeolite.The method and existing methods difference are, need in building-up process, not introduce expensive template, also do not need to prepare directed agents by loaded down with trivial details step, need not add inorganic salt, strong to adaptability to raw material.The key of controlling crystal size is the polymerization degree of raw material.Concrete technical scheme of the present invention is:
The first step: regulate respectively the polymerization degree in Ji Lv source, silicon source with acid, alkali, carry out in two kinds of situation;
(1), by the polymerization degree in mineral alkali adjusting silicon source, with mineral acid, regulate the polymerization degree in aluminium source.
A is scattered in silicon source in water, stirs and keeps 20 ℃～100 ℃ temperature, makes the depolymerization of silicon source with alkali, and the depolymerization time is 5min～100h, then adds organic formwork agent, obtains solution A;
Described silicon source is a kind of and any mixture in silicon sol, water glass, white carbon black, solid silicone; Described sodium hydroxide, potassium hydroxide for alkali, a kind of and any mixture in ammoniacal liquor provides; Described template is a kind of and any mixture in methylamine, ethamine, propylamine, n-Butyl Amine 99, quadrol, tripropyl amine, ethanol.
B is scattered in aluminium source in water, stirs and keeps 20 ℃～100 ℃ temperature, makes the depolymerization of aluminium source by acid solution, and the depolymerization time is 5min～100h, obtains solution B.
Described aluminium source is a kind of and any mixture in boehmite, Tai-Ace S 150, aluminum chloride, aluminum nitrate, sodium metaaluminate, aluminium hydroxide, aluminum isopropylate; A kind of and any mixture in the optional sulfuric acid of described acid solution, phosphoric acid, nitric acid, hydrochloric acid.
When above preparation solution A, do not add template and can also synthesize ZSM-5 zeolite, this does not affect the depolymerization in silicon source.Secondly for the alkali mole number of silicon source depolymerization, must equal the sour mole number for the depolymerization of aluminium source, to guarantee that acid-alkali cancels out each other, not affect the pH value of gel.
(2) by the polymerization degree in mineral acid adjusting silicon source, with mineral alkali, regulate the polymerization degree in aluminium source, pre-treatment is carried out in He Lv source, silicon source.
A is scattered in silicon source in water, stirs and keeps 20 ℃～100 ℃ temperature, makes the depolymerization of silicon source by acid solution, and the depolymerization time is 5min～100h, then adds organic formwork agent, obtain solution A ';
A kind of and any mixture in the described optional silicon sol in silicon source, water glass, white carbon black, solid silicone; A kind of and any mixture in the optional sulfuric acid of described acid solution, phosphoric acid, nitric acid, hydrochloric acid; Described template is a kind of and any mixture in methylamine, ethamine, propylamine, n-Butyl Amine 99, quadrol, tripropyl amine, ethanol.
B is scattered in aluminium source in water, stirs and keeps 20 ℃～100 ℃ temperature, makes the depolymerization of aluminium source with alkali, and the depolymerization time is 5min～100h, obtain solution B '.
A kind of and any mixture in the described optional pseudo-boehmite in aluminium source, Tai-Ace S 150, aluminum chloride, aluminum nitrate, sodium metaaluminate, aluminium hydroxide, aluminum isopropylate; The described a kind of and any mixture in sodium hydroxide, potassium hydroxide, ammoniacal liquor for alkali lye provides.
Equally, do not add template and can also synthesize ZSM-5 zeolite when above preparation solution A, this does not affect the depolymerization in silicon source.Secondly for the sour mole number of silicon source depolymerization, must equal to cancel out each other to guarantee acid-alkali for the alkali mole number of aluminium source depolymerization, not affect the pH value of gel.
Second step: with He Lv source, the silicon source synthetic ZSM-5 zeolite of depolymerization
(1) prepare gel
The B solution that depolymerization is obtained is under agitation added drop-wise to lentamente the B ' solution obtaining in A solution or by depolymerization and is under agitation added drop-wise to lentamente in A ' solution, makes even gel.Gel mixture has following mole of composition: SiO
2/ Al
2o
3=10～1000, Na
2o/SiO
2=0.05～0.3, R/SiO
2=0～1.0, H
2o/SiO
2=10～50, crystal seed/SiO
2=0～20wt%, R is template.
(2) gel crystallization
By the gel preparing hydrothermal crystallizing under optimum conditions, the solid that crystallization goes out after filtration, washing, dry, roasting, obtain nano-ZSM-5 zeolite.
Described crystallization condition is 80～200 ℃ of crystallization temperatures; Crystallization time 1～400 hour.Crystallization can be carried out under static state, but in order to make crystallization product homogeneous grain diameter, recommend adoption stirs.Stirring is advisable to reach to mix, can continuously stirring, and also can intermittent stirring.
The invention has the beneficial effects as follows: by adding soda acid to reduce respectively the polymerization degree in He Lv source, silicon source, obtain highly active reactant, can, by a large amount of nucleus that produce in system, obtain nano zeolite.Need in building-up process, not introduce expensive template, not need to prepare directed agents by loaded down with trivial details step yet, need not add inorganic salt etc.The present invention is not limited to the kind in He Lv source, silicon source, strong to adaptability to raw material, by simple adjustment feed change activity, can be under without template and low cheap template consumption condition the good nano-ZSM-5 zeolite product of synthetic crystallization degree fast.
Embodiment
The invention will be further described by the following examples, but content not thereby limiting the invention.
Comparative example 1: use not He Lv source, the silicon source synthetic ZSM-5 zeolite of depolymerization
By 104g silicon sol (technical grade, SiO
2>=30wt%) be scattered in 40g deionized water, then add 14.86g n-Butyl Amine 99 solution (technical grade), under room temperature, fully stir 1 hour, make A liquid; By 2.3gAl
2o
3powder (pseudo-boehmite) is scattered in 100g deionized water, under room temperature, fully stirs 1 hour, makes B liquid.Then, B solution is under agitation added drop-wise in A solution lentamente, makes even gel, and add 2.78g NaOH solid to regulate the pH value of gel, continue stir about 1h.The molar ratio of each material is: SiO
2/ Al
2o
3=30, NaOH/SiO
2=0.12, NBA/SiO
2=0.39, H
2o/SiO
2=26, the even gel making is transferred in synthesis reactor, at 170 ℃, crystallization approximately 20 hours, is cooled to room temperature, filters, washs.After filter cake is dry at 110 ℃, with x-ray powder diffraction, recording the wherein relative crystallinity of ZSM-5 zeolite is 97%, and granularity is 25um.
Comparative example 2
Repeat comparative example 1, but add 1g crystal seed, crystal seed/SiO in gel
2=3.2wt%.At 170 ℃, crystallization obtains ZSM-5 zeolite product for approximately 6 hours, and granularity is 4um.Its relative crystallinity is 95.2%.
Comparative example 3
Repeat comparative example 1, but add 18.5g Na in gel
2sO
4.At 170 ℃, crystallization obtains ZSM-5 zeolite product for 16 hours, and granularity is 25um.Its relative crystallinity is 96.4%.
Embodiment 1
(1), by the polymerization degree in mineral alkali adjusting silicon source, with mineral acid, regulate the polymerization degree in aluminium source.
By 104g silicon sol (technical grade, SiO
2>=30wt%) be scattered in 40g deionized water, then add under 6.95g NaOH solid room temperature and stir fully and be hydrolyzed 1 hour, then add 14.86g n-Butyl Amine 99 solution (technical grade), make A solution; By 2.3gAl
2o
3powder (pseudo-boehmite) is scattered in 100g deionized water, then drips under the vitriol oil room temperature of 5g 98% and stirs fully hydrolysis 1 hour, makes B solution.
(2) He Lv source, the silicon source synthetic ZSM-5 zeolite of use depolymerization.
The B solution that depolymerization is obtained is under agitation added drop-wise in A solution lentamente, makes even gel.Gel mixture has following mole of composition: SiO
2/ Al
2o
3=30, NaOH/SiO
2=0.12, NBA/SiO
2=0.39, H
2o/SiO
2=26.The gel making is transferred in synthesis reactor, and at 170 ℃, crystallization approximately 20 hours, is cooled to room temperature, filters, washs.After filter cake is dry at 110 ℃, with x-ray powder diffraction, recording the wherein relative crystallinity of ZSM-5 zeolite is 78.2%, and granularity is the nano zeolite of highly assembling.
Embodiment 2
Repeat embodiment 1, but will in (1) silicon sol, add 9.035g NaOH solid, Al
2o
3in add the vitriol oil of 7.819g 98%, obtain ZSM-5 zeolite product, its relative crystallinity is 75.2%, granularity is the nano zeolite of highly assembling.
Embodiment 3
Repeat embodiment 1, but will in (1) silicon sol, add 13.205g NaOH solid, Al
2o
3in add the vitriol oil of 13.031g98%, obtain ZSM-5 zeolite product, its relative crystallinity is 77.7%, granularity is the nano zeolite of highly assembling.
Embodiment 4
Repeat embodiment 1, but will in (1) silicon sol, add 23.63g NaOH solid, Al
2o
3in add the vitriol oil of 26.062g 98%, obtain ZSM-5 zeolite product, its relative crystallinity is 75.6%, granularity is the nano zeolite of highly assembling.
Embodiment 5
Repeat embodiment 4, but do not add organic formwork agent.Corresponding gel preparation process is as follows:
(1), by the polymerization degree in mineral alkali adjusting silicon source, with mineral acid, regulate the polymerization degree in aluminium source.
By 104g silicon sol (technical grade, SiO
2>=30wt%) be scattered in 40g deionized water, then add under 23.63g NaOH solid room temperature and stir fully hydrolysis 1 hour, make A solution; By 2.3gAl
2o
3powder (pseudo-boehmite) is scattered in 100g deionized water, then drips under the vitriol oil room temperature of 26.062g 98% and stirs fully hydrolysis 1 hour, makes B solution.
(2) He Lv source, the silicon source synthetic ZSM-5 zeolite of use depolymerization.
The B solution that depolymerization is obtained is under agitation added drop-wise in A solution lentamente, makes even gel.Gel mixture has following mole of composition: SiO
2/ Al
2o
3=30, NaOH/SiO
2=0.12, H
2o/SiO
2=26.The gel making is transferred in synthesis reactor, and at 170 ℃, crystallization approximately 84 hours, is cooled to room temperature, filters, washs.After filter cake is dry at 110 ℃, with x-ray powder diffraction, recording the wherein relative crystallinity of ZSM-5 zeolite is 60.2%, and granularity is the nano zeolite of highly assembling.
Embodiment 6
Repeat embodiment 5, but will in (2) gel, add 1g crystal seed, crystal seed/SiO
2=3.2wt%, the product crystalline phase that crystallization obtains for approximately 18 hours at 170 ℃ is ZSM-5 zeolite, and its relative crystallinity is 80.2%, and granularity is the nano zeolite of highly assembling.
Embodiment 7
Repeat embodiment 1, but with mineral acid regulate silicon source and with alkali regulate aluminium source.Corresponding gel preparation process is as follows:
(1), by the polymerization degree in mineral acid adjusting silicon source, with mineral alkali, regulate the polymerization degree in aluminium source.
By 104g silicon sol (technical grade, SiO
2>=30wt%) be scattered in 40g deionized water, then drip and under the vitriol oil room temperature of 5g 98%, stir fully hydrolysis 1 hour, then add 14.86g n-Butyl Amine 99 solution (technical grade), make A ' solution; By 2.3gAl
2o
3powder (pseudo-boehmite) is scattered in 100g deionized water, then adds under 6.95g NaOH room temperature and stirs fully hydrolysis 1 hour, makes B ' solution.
(2) He Lv source, the silicon source synthetic ZSM-5 zeolite of use depolymerization.
B ' solution that depolymerization is obtained is under agitation added drop-wise in A ' solution lentamente, makes even gel.Gel mixture has following mole of composition: SiO
2/ Al
2o
3=30, NaOH/SiO
2=0.12, NBA/SiO
2=0.39, H
2o/SiO
2=26.The gel making is transferred in synthesis reactor, and at 170 ℃, crystallization approximately 20 hours, is cooled to room temperature, filters, washs.After filter cake is dry at 110 ℃, with x-ray powder diffraction, recording the wherein relative crystallinity of ZSM-5 zeolite is 78.4%, and granularity is the nano zeolite of highly assembling.
Embodiment 8
Repeat embodiment 7, but will in (1) silicon sol, drip the vitriol oil of 13.031g98%, Al
2o
3in add 13.205g NaOH solid, obtain ZSM-5 zeolite product, its relative crystallinity is 76.5%, granularity be highly assemble nano zeolite.
Embodiment 9
Repeat embodiment 7, but by dripping the vitriol oil of 26.062g 98% in (1) silicon sol, to Al
2o
3in add 23.63gNaOH solid, obtain ZSM-5 zeolite product, its relative crystallinity is 75.6%, granularity be highly assemble nano zeolite.
Embodiment 10
Repeat embodiment 1, but will in (2) gel, add 1g crystal seed, crystal seed/SiO
2=3.2wt%, the product crystalline phase that crystallization obtains for approximately 6 hours at 170 ℃ is ZSM-5 zeolite, and its relative crystallinity is 78.2%, and granularity is the nano zeolite of highly assembling.
Embodiment 11
Repeat embodiment 1, but change respectively the depolymerization temperature in He Lv source, (1) silicon source into 20 ℃ and 100 ℃, the product crystalline phase obtaining is ZSM-5 zeolite, and its relative crystallinity is respectively 77.2%, 76.8%.
Embodiment 12
Repeat embodiment 1, but change respectively the depolymerization time in He Lv source, (1) silicon source into 20min, 48h and 100h, the product crystalline phase obtaining is ZSM-5 zeolite, and its relative crystallinity is respectively 79.3%, 76.7%, and 77.8%.
Embodiment 13
Repeat embodiment 3, but change (1) silicon source into white carbon black silicon-dioxide, corresponding gel preparation process is as follows:
(1), by the polymerization degree in mineral alkali adjusting silicon source, with mineral acid, regulate the polymerization degree in aluminium source.
31.2g white carbon black is scattered in 40g deionized water, then adds under 13.205g NaOH solid room temperature and stir fully and be hydrolyzed 1 hour, then add 14.86g n-Butyl Amine 99 solution (technical grade), make A solution; By 2.3gAl
2o
3powder (pseudo-boehmite) is scattered in 100g deionized water, then drips under the vitriol oil room temperature of 13.031g98% and stirs fully hydrolysis 1 hour, makes B solution.
(2) He Lv source, the silicon source synthetic ZSM-5 zeolite of use depolymerization.
The B solution that depolymerization is obtained is under agitation added drop-wise in A solution lentamente, makes even gel.Gel mixture has following mole of composition: SiO
2/ Al
2o
3=30, NaOH/SiO
2=0.12, NBA/SiO
2=0.39, H
2o/SiO
2=26.The gel making is transferred in synthesis reactor, and at 170 ℃, crystallization approximately 20 hours, is cooled to room temperature, filters, washs.After filter cake is dry at 110 ℃, with x-ray powder diffraction, recording the wherein relative crystallinity of ZSM-5 zeolite is 80%, and granularity is the nano zeolite of highly assembling.
Embodiment 14
Repeat embodiment 1, but change (1) silicon source into water glass, corresponding gel preparation process is as follows:
(1), by the polymerization degree in mineral alkali adjusting silicon source, with mineral acid, regulate the polymerization degree in aluminium source.
By 120.5g water glass (SiO
225.88%, NaO
28.21%, technical grade) be scattered in 40g deionized water, then add under 6.95g NaOH solid room temperature and stir fully and be hydrolyzed 1 hour, then add 14.86g n-Butyl Amine 99 solution (technical grade), make A solution; By 2.3gAl
2o
3powder (pseudo-boehmite) is scattered in 100g deionized water, then drips under the vitriol oil room temperature of 20.8g 98% and stirs fully hydrolysis 1 hour, makes B solution.
(2) He Lv source, the silicon source synthetic ZSM-5 zeolite of use depolymerization.
The B solution that depolymerization is obtained is under agitation added drop-wise in A solution lentamente, makes even gel.Gel mixture has following mole of composition: SiO
2/ Al
2o
3=30, NaOH/SiO
2=0.12, NBA/SiO
2=0.39, H
2o/SiO
2=26.The gel making is transferred in synthesis reactor, and at 170 ℃, crystallization approximately 20 hours, is cooled to room temperature, filters, washs.After filter cake is dry at 110 ℃, with x-ray powder diffraction, recording the wherein relative crystallinity of ZSM-5 zeolite is 85.6%, and granularity is the nano zeolite of highly assembling.
Embodiment 15
Repeat embodiment 14, difference aluminium source is Tai-Ace S 150 (Al
2o
315.8%, technical grade), corresponding gel preparation process is as follows:
(1), by the polymerization degree in mineral alkali adjusting silicon source, with mineral acid, regulate the polymerization degree in aluminium source.
By 120.5g water glass (SiO
225.88%, NaO
28.21%, technical grade) be scattered in 40g deionized water, then add under 6.95g NaOH solid room temperature and stir fully and be hydrolyzed 1 hour, then add 14.86g n-Butyl Amine 99 solution (technical grade), make A solution; By 10.9g Tai-Ace S 150 (Al
3o
215.8.%, technical grade) be scattered in 100g deionized water, then drip under the vitriol oil room temperature of 15g98% and stir fully hydrolysis 1 hour, make B solution.
(2) He Lv source, the silicon source synthetic ZSM-5 zeolite of use depolymerization.
The B solution that depolymerization is obtained is under agitation added drop-wise in A solution lentamente, makes even gel.Gel mixture has following mole of composition: SiO
2/ Al
2o
3=30, NaOH/SiO
2=0.12, NBA/SiO
2=0.39, H
2o/SiO
2=26.The gel making is transferred in synthesis reactor, and at 170 ℃, crystallization approximately 16 hours, is cooled to room temperature, filters, washs.After filter cake is dry at 110 ℃, with x-ray powder diffraction, recording the wherein relative crystallinity of ZSM-5 zeolite is 85.6%, and granularity is the nano zeolite of highly assembling.
Embodiment 16
Repeat embodiment 1, but change respectively (2) gel crystallization temperature into 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 180 ℃, 190 ℃, corresponding gel crystallization time 72 hours, 62 hours, 56 hours respectively, 42 hours, 36 hours, 16 hours and 12 hours, the product crystalline phase obtaining was ZSM-5 zeolite, its relative crystallinity is respectively 74.3%, 73.9%, 74.5%, 76.3%, 78.9%, 84.5%, 84.3%, and granularity is the nano zeolite of highly assembling.
Embodiment 17
Repeat embodiment 15, but change respectively (1) template n-Butyl Amine 99 into methylamine (31.05g) ethamine (13.47g), diethylamine (73.14g), Tri N-Propyl Amine (59.11g), Isopropylamine (59.11g), crystallization approximately 24 hours at 170 ℃, the product crystalline phase all obtaining is ZSM-5 zeolite, its relative crystallinity is respectively 75.2%, 74.3%, 73.9%, 74.5%, 76.5%, and granularity is the nano zeolite of highly assembling.
Claims (1)
1. a synthetic method for ZSM-5 zeolite, is characterized in that following steps:
The first step: pre-treatment is carried out in silicon source, aluminium source, carry out in two kinds of situation;
(1), by the polymerization degree in mineral alkali adjusting silicon source, with mineral acid, regulate the polymerization degree in aluminium source;
A is scattered in silicon source in water, stirs and keeps 20 ℃ ~ 100 ℃ temperature, makes the depolymerization of silicon source with alkali, and the depolymerization time is 5 min ~ 100 h, then adds organic formwork agent, obtains solution A;
B is scattered in aluminium source in water, stirs and keeps 20 ℃ ~ 100 ℃ temperature, makes the depolymerization of aluminium source by acid solution, and the depolymerization time is 5 min ~ 100 h, obtains solution B;
(2), by the polymerization degree in mineral acid adjusting silicon source, with mineral alkali, regulate the polymerization degree in aluminium source;
A is scattered in silicon source in water, stirs and keeps 20 ℃ ~ 100 ℃ temperature, makes the depolymerization of silicon source by acid solution, and the depolymerization time is 5 min ~ 100 h, then adds organic formwork agent, obtain solution A ';
B is scattered in aluminium source in water, stirs and keeps 20 ℃ ~ 100 ℃ temperature, makes the depolymerization of aluminium source with alkali, and the depolymerization time is 5 min ~ 100 h, obtain solution B ';
Second step: with He Lv source, the silicon source synthetic ZSM-5 zeolite of depolymerization;
The B solution that depolymerization is obtained is under agitation added drop-wise to lentamente the B' solution obtaining in A solution or by depolymerization and is under agitation added drop-wise to lentamente in A' solution, makes even gel; Then gel is transferred in synthesis reactor and carried out hydrothermal crystallizing, the solid that crystallization goes out, through filtration, washing, dry, roasting, obtains nano-ZSM-5 zeolite;
Described silicon source is a kind of and any mixture in silicon sol, water glass, white carbon black, solid silicone;
Described aluminium source is a kind of and any mixture in boehmite, Tai-Ace S 150, aluminum chloride, aluminum nitrate, sodium metaaluminate, aluminium hydroxide, aluminum isopropylate;
A kind of and any mixture in the optional sulfuric acid of described mineral acid, phosphoric acid, nitric acid, hydrochloric acid; The described a kind of and any mixture in sodium hydroxide, potassium hydroxide, ammoniacal liquor for alkali;
Described template is a kind of and any mixture in methylamine, ethamine, propylamine, n-Butyl Amine 99, quadrol, tripropyl amine, ethanol; Crystallization temperature scope is 80 ~ 200 ℃; Crystallization time is 1 ~ 400 hour; Silica-alumina gel mixture has following mole of composition: SiO
2/ Al
2o
3=10 ~ 1000, Na
2o/SiO
2=0.05 ~ 0.3, R/SiO
2=0 ~ 1.0, H
2o/SiO
2=10 ~ 50, crystal seed/SiO
2=0 ~ 20wt%, R is template.
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