CN1240193A - Ultrafine granule five-element circular type zeolite - Google Patents
Ultrafine granule five-element circular type zeolite Download PDFInfo
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- CN1240193A CN1240193A CN 99102700 CN99102700A CN1240193A CN 1240193 A CN1240193 A CN 1240193A CN 99102700 CN99102700 CN 99102700 CN 99102700 A CN99102700 A CN 99102700A CN 1240193 A CN1240193 A CN 1240193A
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- 239000010457 zeolite Substances 0.000 title claims abstract description 102
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 98
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 98
- 239000008187 granular material Substances 0.000 title description 2
- 239000013078 crystal Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 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 abstract description 12
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract 4
- 150000003839 salts Chemical class 0.000 claims abstract 2
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 10
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 7
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 3
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 8
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007323 disproportionation reaction Methods 0.000 abstract description 3
- 230000029936 alkylation Effects 0.000 abstract description 2
- 238000005804 alkylation reaction Methods 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010555 transalkylation reaction Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 abstract 1
- 235000011128 aluminium sulphate Nutrition 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 238000006477 desulfuration reaction Methods 0.000 abstract 1
- 230000023556 desulfurization Effects 0.000 abstract 1
- 230000002779 inactivation Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 8
- 230000000274 adsorptive effect Effects 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- ZISSAWUMDACLOM-UHFFFAOYSA-N triptane Chemical compound CC(C)C(C)(C)C ZISSAWUMDACLOM-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- BELFSAVWJLQIBB-UHFFFAOYSA-N 2,8-dimethylquinoline Chemical compound C1=CC=C(C)C2=NC(C)=CC=C21 BELFSAVWJLQIBB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- 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 1
- -1 Pyridine 2,8-dimethyl quinoline Chemical compound 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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Abstract
The present invention uses water glass, silica sol and aluminium sulfate as raw materials. In the presence of organic amine or quaternary ammonium salt or alkali, the above-mentioned raw materials are mixed with alkali, salt, water and seed crystal according to a certain mole ratio, and after going through the processes of changing temp., crystallizing, separating, washing with water and drying, the 10-500nm superfine particles of Pentasil type ZSM-5 and ZSM-11 zeolites are obtained. They possess high reactive activity, stability and resistance to carbon deposition inactivation, can be used for preparing catalysts for alkylation, dismutation and transalkylation of benzene, methylbenzene and ethylbenzene, the reaction of removing thiofuran from benzene and desulfurization of gasoline.
Description
The invention belongs to zeolite molecular sieve and preparation method thereof.
Zeolite molecular sieve is a kind of microporous crystalline material, is used widely in fields such as refining of petroleum, petrochemical complex, fine chemistry industries as catalyzer with it.As be used for the y-type zeolite of catalytic cracking, mercerising M type zeolite, benzene or the ethylbenzene of toluene disproportionation is selected ethylating ZSM-5 type zeolite, assisted catalyst for catalyzing cracking HZSM-5 type zeolite etc., the zeolite molecular sieve grain-size that these catalyzer use is micron (μ m) level, their ubiquitous problems are that temperature of reaction is higher, and catalyzer is very fast because of coking deactivation.In order to improve material molecule, the micron order zeolite molecular sieve is improved always, but do not have the qualitative leap progress in intracrystalline surface reaction situation.The production of little crystal grain zeolite, existing many patent reports, as: EP173,901 adopt ethylene glycol and a small amount of TPAOH positive ion (TPA
+) or by adding TPA
+The method of synthetic crystal seed prepares the ZSM-5 zeolite of crystal grain less than 0.3 μ m, and what in fact obtain is the aggregate of 0.1～0.3 μ m.U.S. Pat 4,205,053 has reported the technological process of producing ZSM-5 and ZSM-35 zeolite, and minimum crystal grain is the stratiform twin of 0.2～0.5 μ m or 0.1 μ m.US 3,78l, 226 and US 3,926,782 patents have been reported the production method of KL and ZSM-5 type zeolite, and it is to adopt TPAOH (TPAOH) to be template, synthesizing grain size is the ZSM-5 zeolite of 0.005～0.1 μ m, expectation obtains stable soliquid, and what in fact obtain is the aggregate of 0.1～1.0 μ m, can not form steady suspension.U.S. Pat 4,526,879 have reported the synthetic method of low sodium ZSM-5, synthetic system is the mixture of alkalimetal oxide, aluminum oxide, silicon oxide, amine, halogenide and solubility promoter, crystal grain is 0.05～20 μ m, in fact be still aggregate, the method for control grain size and uniformity coefficient is not reported.European patent EP l30,809 to adopt tripropyl amines be template, made the ZSM-5 type zeolite of 0.02～0.05 μ m 102 ℃ of crystallization, will add tensio-active agent in the synthetic system, the silicon source is sedimentary silicon-dioxide.
Along with the development of ultra-fine grain nanometer (nm) level Materials science, granularity refine to nano level from micron order, and the variation by amount has caused qualitative leap.The ultra-fine grain zeolite is meant the ultramicron of grain-size less than 500nm (nanometer), the former subgroup that it is made up of number atom seldom, and its principal feature is that the ratio of surface atom is big, specific surface area is big, shows as high surface energy and surfactivity.Surface effects and Body Effect that ultrafine particle produces are to being that the catalyzed reaction of feature has been brought revolutionary opportunity to develop with the surface action.
For a long time, the shape selective catalysis of high contraposition alkylbenzene, the catalyzer that has been to use the modified ZSM-5 type zeolite of big crystal grain to make needs high-temperature operation, and the catalyzer rapid deactivation, and this problem has become the industrialized biggest obstacle of shape selective catalysis reaction technology.
The objective of the invention is to prepare have high reaction activity, the ultra-fine grain Pentasil type zeolite of stability and strong anti-coking deactivation ability.Make it further to make various catalyzer, the alkylation, disproportionation, transalkylation, the benzene that are used for aromatic hydrocarbons such as benzene, toluene, ethylbenzene remove reactions such as removing sulphur in thiophene, the gasoline.
The present invention uses different template in the method for preparing ultra-fine grain Pentasil type zeolite, can obtain the ZSM-5 or the ZSM-11 type zeolite of different structure.The silicon source of adopting can be silicon sol, water glass, silicic acid, water glass; The aluminium source of being adopted can be Al
2(SO
4)
318H
2O, Na
2AlO
2, AlCl
3Deng; The template that is adopted can be n-Butyl Amine 99, ethamine, propylamine, under certain conditions synthesizing superfine particle ZSM-5 type zeolite; And when preparation ultra-fine grain ZSM-11 type zeolite, template can adopt the mixture of TBAH (TBAOH), Tetrabutyl amonium bromide (TBABr), tetrabutylammonium chloride (TBACl), Tributylamine and n-butyl bromide.
Ultra-fine grain ZSM-5 type zeolite synthetic is to be raw material with water glass, Tai-Ace S 150, organic amine (n-Butyl Amine 99, ethamine or propylamine) be template in the presence of, by following chemical constitution (mol ratio) batching:
Al
2O
3???????????????????????????????1
SiO
2?????????????????????????????????20～100
Na
2O?????????????????????????????????2～4
NaCl??????????????????????????????????15～60
H
2O??????????????????????????????????800～4000
Tai-Ace S 150, sulfuric acid, sodium-chlor and water are made into A solution; Water glass, crystal seed and water are made into B solution; Organic amine is a C solution, be respectively charged in the reactor, under violent stirring, in about 100 ℃, kept 24 hours, 150～170 ℃ of crystallization 2～8 days, lower the temperature then, separate, wash, dry, the ultra-fine grain ZSM-5 type zeolite that makes white 10～500nm (nanometer).
Ultra-fine grain ZSM-11 type zeolite synthetic is to be raw material with silicon sol, Tai-Ace S 150, TBAH (TBAOH) or Tetrabutyl amonium bromide (TBABr) be template in the presence of, by following chemical constitution (mol ratio) batching:
Al
2O
3??????????????????????????????1
SiO
2????????????????????????????????20～100
Na
2O????????????????????????????????2～10
NaCl?????????????????????????????????5～15
H
2O?????????????????????????????????400～1200
Tai-Ace S 150, sulfuric acid, sodium-chlor and water are made into A solution; Silicon sol, crystal seed and water are made into B solution; Organic amine and sodium hydroxide are made into C solution; Be respectively charged in the reactor, under violent stirring, kept 1～8 day in 60～90 ℃, lower the temperature then, separation, washing, drying, make 100～500nm (nanometer) ultra-fine grain ZSM-11 type zeolite of white.
If do not add the aluminium source, can directly prepare B and C solution, obtain 100～500nm ultra-fine high-silicon ZSM-5-11 type zeolite by above-mentioned steps, its forming step is referring to ultra-fine grain ZSM-5 type zeolite.
The grain size or the aggregate size of ultra-fine grain Pentasil type zeolite obtain changing by the modulation crystallization temperature.In general, crystallization temperature is low more, and crystal grain is more little.In addition, crystal seed and electrolytical amount also have influence significantly to grain size.
The ultra-fine grain zeolite that employing the present invention makes and the physical and chemical performance of micron zeolite have difference significantly, as follows face table 1:
The performance of ultra-fine ZSM-5 zeolite of table 1 and micron order zeolite
| Granular size | Pore volume (cm 3/g) | Specific surface area (m 2/g) | Adsorptive capacity (wt%) | ??????Si/Al | |||
| ?????nC 6 | ????cC 6 | ?2，2，3TMB | The body phase | The surface | |||
| ??20nm ??10μm | ??0.728 ??0.610 | ????436 ????366 | ????12.70 ????11.80 | ????7.70 ????6.05 | ????64 ????0 | ?12.16 ?12.10 | ?11.96 ??9.05 |
Ultra-fine ZSM-5 zeolite has than large pore volume, specific surface area and high adsorption capacity, and especially 2,2,3TMB (2,2,3 triptane) adsorptive capacity is big, proves that secondary pore exists, and body phase silica alumina ratio and surface silicon aluminum ratio are approaching.
Other physical and chemical performance also shows:
1. in different organic amine systems, the grain size of synthetic nano level ZSM-5 type zeolite is also inequality, sees Table 2
The brilliant looks of ZSM-5 type zeolite in the different organic amine systems of table 2
| Sample | Silica alumina ratio SiO in the glue 2/Al 2O 3 | Synthetic system | The brilliant looks of zeolite | |
| Grain shape | Grain size (nm) | |||
| ?NZE-1 ?NZB-1 ?NZT-1 * | ????93.5 ????31.2 ????104.2 | Ethamine n-Butyl Amine 99 triethylamine+monobromethane+acetone | Aggregate aggregate aggregate | ????50 ????22 ????30 |
*TEA∶EBr∶Ac＝1∶1∶3.2
2. the size-grade distribution of different system synthetic nano level ZSM-5 type zeolites.See that Fig. 1-a is the ethamine system, ordinate is a crystal grain percentage ratio, and abscissa is grain size (nm); Fig. 1-b is the n-Butyl Amine 99 system, and ordinate is a crystal grain percentage ratio, and abscissa is grain size (nm); Fig. 1-c is the triethylamine system, and ordinate is a crystal grain percentage ratio, and abscissa is grain size (nm).The granularity of ethamine system synthetic ZSM-5 type zeolite is mainly at 50nm, and the granularity of n-Butyl Amine 99 system synthetic ZSM-5 type zeolite is mainly at 20nm, and the granularity of triethylamine system synthetic ZSM-5 type zeolite is mainly at 30nm.
3. the phasor of synthesis nano ZSM-5 type zeolite
Can batching is formed be the important factor that synthesize nano level (nm) zeolite, sees Fig. 2 phasor, 1-μ mZSM-5 as seen from the figure, and 2-nmZSM-5,3-is amorphous, 4-α-SiO
2, the synthetic phase region of nano level ZSM-5 type zeolite is very little, and the key that really obtains the nano level zeolite is to be into glue and ageing technology, controls nucleation stage well.
4. the pore texture of nano level zeolite
Synthetic in table 3 ethamine system and the n-Butyl Amine 99 system
NaZSM-5 zeolite adsorption alkane ability
| Sample | System | Grain size/μ m | Adsorptive capacity/% | ||
| Triptane | The 3-methylpentane | Normal hexane | |||
| ????4-2-3 ????4-2-5 ????NZE-1 | Ethamine | ????2×4 ????1×1 ????0.05 | ?????????0 ?????????1 ?????????25 | ????100 ????100 ????100 | ??100 ??100 ??100 |
| ????ZB-5 ????ZB-3 ????NZB-1 | N-Butyl Amine 99 | ????18.8 ????3.4 ????0.022 | ?????????0 ?????????5.5 ?????????64.0 | ????100 ????100 ????100 | ??100 ??100 ??100 |
Table 3 data declaration, with ethamine or n-Butyl Amine 99 system synthetic nano level ZSM-5 type zeolite and micron order zeolite the alkane adsorptive capacity of differing molecular size and configuration is compared discovery, 3-methylpentane and normal hexane molecule can enter the zeolite framework duct and be adsorbed in the hole, and molecular dimension is greater than 2 of ZSM-5 type zeolite aperture, 2,3-triptane molecule can not be adsorbed in the skeleton duct (being the one-level duct) of zeolite by the aperture.And the micron order zeolite does not almost have adsorptive power to triptane, nano level zeolite coacervate is piled up and is formed intergranular space (being the secondary duct), makes 2,2,3-triptane molecule can enter the intergranular space and be adsorbed in the secondary duct, has high macromole adsorptive power.
5. the surface-area of zeolite
The surface-area that flowing chromatography records zeolite reduces and increases with zeolite grain.See Table 4:
The surface-area of the different grain size zeolites of table 4
| Sample | ??NZB-1 | ??ZB-2 | ???ZB-3 | ???ZB-4 | ????ZB-5 |
| Grain size/μ m S Total surface area(BET) ????S Outer surface area | ??0.022 ???436 ???76 | ??0.24 ??418 ??48 | ????3.4 ????392 ????10.17 | ???10.2 ???366 ???4.17 | ????18.8 ????348 ????0.17 |
6. the silica alumina ratio of zeolite
Different grain size zeolites, basic identical by the overall budget Si/Al that atomic absorption method records, the outer surface of zeolite Si/Al that XPS records reduces with the increase of grain-size, illustrates that the Al distribution of zeolite body phase is inhomogenous.Increase this result from zeolite body phase center gradually to outer shell Al content and support the Silicon-rich mechanism of nucleation.Fig. 3 is the outer surface of zeolite silica alumina ratio (Si/Al) of different grain sizes.Ordinate is a silica alumina ratio, and abscissa is a grain size.
7. the acid matter of zeolite
Use NH
3-TPD studies the acid matter of Hydrogen nano zeolite, and compares with micron order ZSM-5 zeolite, the results are shown in Table 5:
Table 5 Hydrogen nano level zeolite and micron order zeolitic acid character are relatively
| Grain-size | Peak 1 | Peak 2 | ||
| ??Tmax/K | ?n(×10 -4/mol/g | ??Tmax/K | ?n(×10 -4)/mol/g | |
| ??20nm ??10μm | ???544 ???551 | ?????3.49 ?????3.36 | ????744 ????755 | ?????2.48 ?????2.01 |
Hydrogen nano level zeolitic acid center is many, and a little less than the strength of acid, promptly ammonia desorption summit temperature is lower than Hydrogen micron order zeolite desorption summit temperature.
Pyridine alkalescence molecule can be diffused into the duct internal adsorption on the acid site by HZSM-5 zeolite aperture; And 2,8-dimethyl quinoline alkalescence molecule can not enter in the HZSM-5 zeolite pore, can only be adsorbed on the acid site, outside surface and aperture place.
Synthetic HZSM-5 zeolite adsorption alkalescence molecule ability in the table 6 ethamine system
| Sample | Grain size/μ m | Adsorptive capacity/mmol/ | 2,8 | |
| Pyridine | ||||
| 2,8-dimethyl quinoline * 10 2 | Pyridine * 10 2 | |||
| ??4-2-13 ??4-2-15 ??NZE-1 | ???4×2 ???1×1 ???0.05 | ??0.265 ??0.301 ??0.362 | ?????0.109 ?????0.262 ?????0.498 | ????4.11 ????8.70 ????10.99 |
The result reduces with crystal grain as can be seen by table 6, and increase in zeolite surfaces externally and internally acid site, and the ratio that outside surface and acid site, aperture account for total acid content increases.
8. the thermostability of zeolite
The thermostability of nano level zeolite is lower than the micron order zeolite, sees Table 7:
The thermostability of the ZSM-5 type zeolite of the different crystal grain of table 7
The TG-DTA of the ZSM-5 type zeolite of different grain sizes the results are shown in Figure 4-a, ordinate is a weight loss percentage ratio, abscissa is a temperature, TG-DTA (18.8 μ m), Fig. 4-b TG-DTA (0.5 μ m) and Fig. 4-c TG-DTA (22nm), along with reducing of grain-size, the skeleton fail temperature of ZSM-5 zeolite reduces.
| Sample | ???????????ZSM-5 | |
| ????NZB-1 | ????ZB-5 | |
| Grain-size/μ m Na 2O/wt％ ????RE 2O 3760 ℃ 816 ℃ 843 ℃ of/wt% relative crystallinity % | ????0.22 ????98 ????88 | ????18.8 ????100 ????97 |
9. the hydrothermal stability of zeolite
The hydrothermal stability of the ZSM-5 type zeolite of the different grain sizes of table 8
| Sample | ??????????HZSM-5 | |
| ????NZB-1 | ????ZB-5 | |
| Grain-size/μ m Si/Al relative crystallinity/% (before handling) 100% water vapor, 750 ℃, 5 hours | ????0.022 ????12.2 ????100 ????87 | ????18.8 ????12.1 ????100 ????100 |
As can be seen from Table 8, after superheated vapor was handled, the micron order zeolite was before and after handling, and relative crystallinity does not have considerable change, and the nano level zeolite drops to 87%, and the hydrothermal stability that the nano level zeolite is described is not as the micron order zeolite.
The unique texture of ultra-fine grain zeolite makes it have high reaction activity and stability and strong anti-carbon deposit performance; The good reproducibility of preparation.
Characteristics of the present invention are to have adopted pyritous variable temperature crystallization behind the first low temperature, thereby have shortened crystallization time.In addition, also can adopt low temperature crystallized always preparation method, it is simple to have synthetic method, is suitable for suitability for industrialized production.
Embodiment 1
By chemical constitution (mol ratio) Al
2O
3: SiO
2: Na
2O: n-C
4H
9NH
2: NaCl: H
2O=1.0: 31.2: 2.0: 12.2: 18: 833.3 preparation B solution (water glass+water+crystal seed), A solution (Tai-Ace S 150+water+sulfuric acid+sodium-chlor) and C solution n-Butyl Amine 99.
At first B solution is packed in the reactor of 100 liters, C solution under violent stirring, slowly is added in the B solution, after stirring evenly, A solution is added in the still at last, stir down and be warming up to 100 ℃ gradually, kept 5～24 hours, and in 2 hours, be warming up to 170 ℃ again, kept 30～40 hours, reduce to normal temperature then, filter, tell mother liquor, reaction product is through washing, drying, obtain the white powdery ZSM-5 type zeolite of 20～30nm, silica alumina ratio is 30.
By chemical constitution Al
2O
3: SiO
2: Na
2O: TBAOH: NaCl: H
2O=1.0: 31.2: 9.9: 5.3: 6.6: 1020 (mol ratio) preparation B solution (silicon sol+water+crystal seed), A solution (Tai-Ace S 150+water+sodium-chlor) and C solution (TBAOH+NaOH).
At first B solution is packed in 250 milliliters of reactors, C solution under violent stirring, slowly is added in the B solution, after stirring evenly, add A solution in the still at last, be warming up to 90 ℃ under continuously stirring, crystallization 3 days is reduced to room temperature then, high speed centrifugation separates, reaction product obtains the white powdery ZSM-11 type zeolite that 300nm is even spheroid through washing, drying, and silica alumina ratio is 30.
By chemical constitution SiO
2: Na
2O: TBAOH: H
2O: NaCl=1: 0.11: 0.16: 30: 0.2 (mol ratio) preparation B solution (silicon sol+water+crystal seed), A solution (sodium-chlor+water) and C solution (TBAOH+NaOH).
At first B solution is packed in 250 milliliters of reactors, C solution under violent stirring, slowly is added in the B solution, after stirring evenly, be added to A solution in the still at last, under continuously stirring, be warming up to 90 ℃ gradually, kept 3 days, reduce to room temperature then, isolate mother liquor, reaction product obtains being about 300nm the white powdery high-silicon ZSM-5-11 type zeolite of even spheroid through washing, drying.(this system then can obtain the even ellipse garden shape of 300～500nm if change static crystallization into).
Accompanying drawing 5 is the electromicroscopic photograph (300～500nm) of ultra-fine grain ZSM-11.
Claims (4)
1. zeolite made from aluminium source, silicon source, template, it is characterized in that this zeolite is a ultra-fine grain Pentasil type, it is that water glass, silicon sol, Tai-Ace S 150 with cheapness is raw material, in the presence of organic amine, quaternary ammonium salt or alkali template, add alkali, salt, water and crystal seed, by the certain molar ratio batching,, make ultra-fine grain 10～500nm (nanometer) zeolite through variable temperature crystallization, separation, washing, drying.
2. according to the described ultra-fine grain zeolite of claim 1, it is characterized in that ultra-fine grain ZSM-5 type zeolite is is raw material with water glass, Tai-Ace S 150, be template with organic amine (ethamine, propylamine or n-Butyl Amine 99), prepare burden by following chemical constitution (mol ratio):
Al
2O
3??????????????????????????1
SiO
2????????????????????????????20～100
Na
2O????????????????????????????2～4
Organic amine 10～15
NaCl?????????????????????????????15～60
H
2O?????????????????????????????800～4000
Crystal seed 2～5% (in product)
Tai-Ace S 150, sulfuric acid, sodium-chlor and water are made into A solution, water glass, crystal seed and water are made into B solution, and organic amine is a C solution, are respectively charged in the reactor, under violent stirring, in about 100 ℃, kept 24 hours, and in 150～170 ℃ of crystallization 2～8 days or directly 90 ℃ of following crystallization, reduced to normal temperature again, isolate mother liquor, the product washing after the drying, makes 10～500nm ultra-fine grain ZSM-5 type zeolite.
3. according to the described ultra-fine grain zeolite of claim 1, it is characterized in that ultra-fine grain ZSM-11 type zeolite is is raw material with silicon sol, Tai-Ace S 150, be template with quaternary ammonium salt or alkali, by following chemical constitution (mol ratio) batching:
Al
2O
3????????????????????????????????1
SiO
2??????????????????????????????????20～100
Na
2O??????????????????????????????????2～10
Quaternary amine or alkali 5～10
NaCl??????????????????????????????5～15
H
2O??????????????????????????????400～1200
Crystal 2～5% (in product)
Tai-Ace S 150, sodium-chlor and water are made into A solution, silicon sol, crystal seed and water are made into B solution, quaternary ammonium salt or alkali and sodium hydroxide are made into C solution, are respectively charged in the reactor, under violent stirring, kept 1～8 day in 60～90 ℃, cooling then, centrifugation, washing product, drying makes 100～500nm ultra-fine grain ZSM-11 type zeolite.
4. according to the described ultra-fine grain zeolite of claim 3, it is characterized in that not adding the aluminium source, can make ultra-fine grain high-silicon ZSM-5-11 type zeolite.
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|---|---|---|---|
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| WO2001004051A1 (en) * | 1999-07-13 | 2001-01-18 | Mobil Oil Corporation | Synthesis of zsm-5 and zsm-11 |
| CN100364890C (en) * | 2005-06-14 | 2008-01-30 | 大连理工大学 | Synthesis method of fine grain ZSM-5 zeolite molecular sieve with high silicon aluminium ratio |
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| CN101837298A (en) * | 2010-05-14 | 2010-09-22 | 广西壮族自治区化工研究院 | Small-grain ZSM-5 molecular sieve catalyst used for preparing ethylene from bioethanol and preparation method thereof |
| CN1886197B (en) * | 2003-12-02 | 2010-10-13 | 巴斯福股份公司 | Pentasil-structuer zeolithic material, the production and use thereof |
| CN1972867B (en) * | 2004-04-23 | 2010-11-03 | 环球油品公司 | High silica zeolites UZM-5HS |
| CN102302945A (en) * | 2011-10-04 | 2012-01-04 | 大连理工大学 | Method for preparing propene by catalytic cracking |
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