CN1792795A - Process for synthesizing nano EMF molecular sieve material using polyquaternary ammonium salt-6 as fomework agent - Google Patents
Process for synthesizing nano EMF molecular sieve material using polyquaternary ammonium salt-6 as fomework agent Download PDFInfo
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- CN1792795A CN1792795A CN 200510119131 CN200510119131A CN1792795A CN 1792795 A CN1792795 A CN 1792795A CN 200510119131 CN200510119131 CN 200510119131 CN 200510119131 A CN200510119131 A CN 200510119131A CN 1792795 A CN1792795 A CN 1792795A
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Abstract
A process for preparing nano-class EMT molecular sieve by using poly-quaternary ammonium salt-6 as template agent, water glass as Si source, aluminum sulfate and/or aluminate as Al source includes such steps as preparing pilot agent, preparing Si-Al gel, and hydrothermal crystallizing at 95-110 deg.C for 4-15 days.
Description
Technical field
The invention belongs to inorganic chemistry and technical field of catalysis chemistry, particularly a kind of is the method for the hydro-thermal synthesis of nano EMT molecular screen material of template with polyquaternium-6.
Background technology
The faujusite molecular sieve analog has two kinds of forms: a kind of is the FAU type zeolite of cubic structure; Another kind is the EMT type zeolite of hexagonal structure.Utilize the six side EMT type zeolites that synthesized of crown ether (18-hat-6) success since Delprato in 1989, people have produced great interest to synthetic this 12 Yuans ring large pore molecular sieves, because EMT produces in the cracking reaction of the reaction of butane and normal heptane in the iso-butylene alkylation, reactivity ratio's cubical FAU type zeolite height.
Up to the present synthetic EMT type zeolite must use poisonous and expensive crown ether 18-crown-6 as template.In order to reduce production costs, reduce the pollution of building-up process to environment, the method that adopts is to reduce the usage quantity of crown ether 18-crown-6 in the reaction usually.The method that reduces template (18-crown-6) consumption in the synthetic EMT type zeolite process at present mainly contains: the method that adds tensio-active agent, inorganic or organic auxiliary and use the concussion crystallization in synthetic system.Employed 18-crown-6 and Al when utilizing the method for shaking crystallization to synthesize EMT type zeolite
2O
3Mol ratio be reduced to 0.14, use the crown ether amount minimum when being synthetic at present EMT, but its sample degree of crystallinity that synthesizes is not high.
Study group of Fudan University adds sodium phosphate in the system of synthetic EMT, work as 18-crown-6/Al
2O
3Molar ratio be to synthesize the higher EMT molecular sieve of degree of crystallinity at 0.33 o'clock, this technology is disclosed in Yunfei luo, Jianwei Sun, Wei Zhao, Jiandong Yao, Quanzhi li, Chem.Mater.2002,14,1906-1908.In addition, the synthetic at present employed silicon of EMT type zeolite source generally all is a silicon sol, because the technology of preparation silicon sol is complicated, makes that the silicon sol price is higher, thereby the production cost of EMT zeolite is improved.Use the granularity of crown ether 18-crown-6 synthetic EMT type zeolite crystal all bigger, all more than 2～3 μ m.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, do not re-use poisonous and expensive crown ether 18-crown-6 and makes template, synthesizes the EMT type zeolite crystal material of nano-scale particle size cheaply.
The preparation method of nanometer EMT molecular screen material of the present invention adopts directing agent method, and each component is in molar ratio in the directed agents: 16Na
2O: 1.0Al
2O
3: 15～19SiO
2: 350～370H
2O; With water glass is the silicon source, and Tai-Ace S 150 is or/and sodium aluminate is the aluminium source, and polyquaternium-6 is a template, and the mol ratio that feeds intake is: 2.9～3.5Na
2O: 1.0Al
2O
3: 8.4～10.0SiO
2: 200～300H
2O; The amount of used polyquaternium-6 is with the middle SiO that feeds intake
2Represent 3.0＜m＜18.0 with the mass ratio m of polyquaternium-6; The add-on of directed agents accounts for the middle Al that feeds intake
2O
33%～10% of total amount; Process through preparation directed agents, preparation silica-alumina gel, hydrothermal crystallizing makes nanometer EMT molecular screen material;
Said preparation silica-alumina gel process is, the silicon source added template, water, directed agents stir, and adds aluminium source solution again;
Said hydrothermal crystallization process is, silica-alumina gel at room temperature stirred 0.5～3 hour, 95～110 ℃ of crystallization 4～15 days.
Sample behind the hydrothermal crystallizing is through filtering and washing, the available crystal product of room temperature airing.
In the preparation silica-alumina gel process, the template agent scope is 5.0＜m＜15.0 preferably.
In the hydrothermal crystallization process, preferably 100 ℃ of crystallization temperatures; Crystallization time preferably 6～14 days.
Usual method is adopted in the preparation of directed agents of the present invention: sodium aluminate and sodium hydroxide are added the deionized water heating for dissolving, be added to after the cooling and obtain settled solution in the water glass, stir the back room temperature and placed 24 hours; Each component is in molar ratio: 16Na
2O: 1.0Al
2O
3: 15～19SiO
2: 350～370H
2O.Now enumerate the example of the preparation of a directed agents: take by weighing 0.283g sodium aluminate and 1.006g sodium hydroxide, add the 2.7mL deionized water, heating for dissolving, slowly join in the 4.3mL water glass after the cooling, obtain settled solution, stirred 15 minutes, room temperature is placed 24h, promptly obtains active higher structure directing agent.
The synthetic EMT type zeolite of the present invention uses cheap nontoxic polyquaternium-6 to replace employed costliness and deleterious crown ether (18-crown-6) in the method for traditional synthetic EMT as template; Employed silicon sol when using water glass to replace traditional synthetic EMT as the silicon source has reduced the synthetic cost greatly, has reduced the pollution to environment; The bright institute of this law synthetic product granularity is less, and diagonal is of a size of 250～500nm, is 50～100nm highly, in nano-scale range, belongs to nano material.Therefore the present invention has higher utility and economic worth.
Description of drawings
Fig. 1 is the XRD spectra of the nanometer EMT molecular screen material product 1 that makes of the present invention.
Fig. 2 is scanning electron microscope (SEM) photo of product 1.
Fig. 3 is scanning electron microscope (SEM) photo of the demonstration crystal size of product 1.
Fig. 4 is the XRD spectra of the nanometer EMT molecular screen material product 2 that makes of the present invention.
Fig. 5 is the XRD spectra of the nanometer EMT molecular screen material product 3 that makes of the present invention.
Fig. 6 is the XRD spectra of the nanometer EMT molecular screen material product 4 that makes of the present invention.
Fig. 7 is the XRD spectra of the nanometer EMT molecular screen material product 5 that makes of the present invention.
Fig. 8 is the XRD spectra of the nanometer EMT molecular screen material product 6 that makes of the present invention.
Fig. 9 is the XRD spectra of the nanometer EMT molecular screen material product 7 that makes of the present invention.
Figure 10 is the XRD spectra of the nanometer EMT molecular screen material product 8 that makes of the present invention.
Embodiment
Following illustrative example illustrates the preparation of nanometer EMT molecular screen material.
Embodiment 1
Take by weighing 0.278g polyquaternium-6, add 5.00mL water glass, 2.7g deionized water, the back that stirs adds the 0.69mL directed agents, and the back that stirs adds 1.15mL 0.88molL
-1Alum liquor and 1.19mL sodium aluminate solution (2.18molL
-1Na
2O, 1.02molL
-1Al
2O
3), make that the mol ratio of each component is 3.3Na in the silica-alumina gel
2O: 1.0Al
2O
3: 10.0SiO
2: 250H
2O, SiO
2With the mass ratio m of polyquaternium-6 be 12.40, gel stirred more than 0.5 hour, in the reactor of packing into, 100 ℃ of crystallization 7 days are taken out reactor, filtering and washing, sample room temperature airing obtains product 1.The XRD figure of product 1 such as Fig. 1, scanning electron microscope (SEM) photo such as Fig. 2, Fig. 3.By the SEM photo as can be known sample diagonal angle line length be 100～500nm, thickness is 50～100nm.
Embodiment 2
Take by weighing 0.373g polyquaternium-6, make SiO
2With the mass ratio of polyquaternium-6 be 9.25, other step that feeds intake, treatment process are identical with embodiment 1, the product that obtains is designated as product 2.The XRD figure of product 2 such as Fig. 4.
Embodiment 3
Take by weighing 0.638g polyquaternium-6, make SiO
2With the mass ratio of polyquaternium-6 be 5.41, other step that feeds intake, treatment process are identical with embodiment 1, the product that obtains is designated as product 3.The XRD figure of product 3 such as Fig. 5.
Embodiment 4
Take by weighing 0.278g polyquaternium-6, make SiO
2With the mass ratio of polyquaternium-6 be 12.40,100 ℃ of crystallization 5 days, other step that feeds intake, treatment process are identical with embodiment 1, the product that obtains is designated as product 4.The XRD figure of product 4 such as Fig. 6.
Embodiment 5
Take by weighing 0.278g polyquaternium-6, make SiO
2With the mass ratio of polyquaternium-6 be 12.40,95 ℃ of crystallization 15 days, other step that feeds intake, treatment process are identical with embodiment 1, the product that obtains is designated as product 5.The XRD figure of product 5 such as Fig. 7.
Embodiment 6
Take by weighing 0.431g polyquaternium-6, make SiO
2With the mass ratio of polyquaternium-6 be 8.00,100 ℃ of crystallization 14 days, other step that feeds intake, treatment process are identical with embodiment 1, the product that obtains is designated as product 6.The XRD figure of product 6 such as Fig. 8.
Embodiment 7
Take by weighing 0.228g polyquaternium-6, add 4.41mL water glass, 1.6g deionized water, the back that stirs adds the 0.72mL directed agents, and the back that stirs adds 1.30mL 0.88molL
-1Alum liquor and 1.30mL sodium aluminate solution (2.18molL
-1Na
2O, 1.02molL
-1Al
2O
3), make that the mol ratio of each component is 2.9Na in the silica-alumina gel
2O: 1.0Al
2O
3: 8.4SiO
2: 209H
2O, SiO
2With the mass ratio m of polyquaternium-6 be 13.26, gel stirred more than 0.5 hour, in the reactor of packing into, 100 ℃ of crystallization 6 days are taken out reactor, filtering and washing, sample room temperature airing obtains product 7.The XRD figure of product 7 such as Fig. 9.
Embodiment 8
Take by weighing 0.230g polyquaternium-6, make SiO
2With the mass ratio of polyquaternium-6 be 15.0,110 ℃ of crystallization 5d, other step that feeds intake, treatment process are identical with embodiment 1, the product that obtains is designated as product 8.The XRD figure of product 8 such as Figure 10.
From the XRD spectra of each given product of the present invention as can be known, all samples all is an EMT type zeolite, and contrasting each spectrogram is the degree of crystallinity difference of product.In addition because the granularity of product is less, in nano-scale range, so the relative intensity at each peak in the given XRD spectra is slightly different with the relative intensity at each peak in the XRD spectra of using crown ether 18-crown-6 synthetic product.From scanning electron microscope Fig. 2, Fig. 3 crystalline form of product as can be known is the hexahedron shape, but hexahedron is not very regular, and the granularity of product is: diagonal is of a size of 100～500nm, is 50～100nm highly, and in nano-scale range, crystal has agglomeration.
Claims (3)
1, a kind of polyquaternium-6 is the method for template synthesis of nano EMT molecular screen material, adopts directing agent method, and each component is in molar ratio in the directed agents: 16Na
2O: 1.0Al
2O
3: 15～19SiO
2: 350～370H
2O; It is characterized in that, be the silicon source with water glass, and Tai-Ace S 150 is or/and sodium aluminate is the aluminium source, and polyquaternium-6 is a template, and the mol ratio that feeds intake is: 2.9～3.5Na
2O: 1.0Al
2O
3: 8.4～10.0SiO
2: 200～300H
2O; The amount of used polyquaternium-6 is with the middle SiO that feeds intake
2Represent 3.0＜m＜18.0 with the mass ratio m of polyquaternium-6; The add-on of directed agents accounts for the middle Al that feeds intake
2O
33%～10% of total amount; Process through preparation directed agents, preparation silica-alumina gel, hydrothermal crystallizing makes nanometer EMT molecular screen material; Said preparation silica-alumina gel process is, the silicon source added template, water, directed agents stir, and adds aluminium source solution again; Said hydrothermal crystallization process is, silica-alumina gel at room temperature stirred 0.5～3 hour, 95～110 ℃ of crystallization 4～15 days.
2, be the method for template synthesis of nano EMT molecular screen material according to claim 1 described polyquaternium-6, it is characterized in that said template agent scope is 5.0＜m＜15.0.
3, be the method for template synthesis of nano EMT molecular screen material according to claim 1 or 2 described polyquaterniums-6, it is characterized in that in the said hydrothermal crystallization process, crystallization temperature is 100 ℃, crystallization time is 6～14 days.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015024378A1 (en) * | 2013-08-20 | 2015-02-26 | 中国科学院大连化学物理研究所 | Method for synthesizing beta molecular sieve |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5133953A (en) * | 1991-04-17 | 1992-07-28 | Exxon Research And Engineering Company | Method of preparing crystalline ZSM-20 zeolites (C-2517) |
| US5567407A (en) * | 1994-05-12 | 1996-10-22 | Coe; Charles G. | Li-exchanged low silica EMT-containing metallosilicates |
| CN1093086C (en) * | 1999-09-08 | 2002-10-23 | 复旦大学 | Process for synthesizing surfactant of EMT zeolite |
| CN1161274C (en) * | 2001-08-16 | 2004-08-11 | 复旦大学 | Process for preparing EMT zeolite with inorganic emulsifier as assistant |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015024378A1 (en) * | 2013-08-20 | 2015-02-26 | 中国科学院大连化学物理研究所 | Method for synthesizing beta molecular sieve |
| WO2015024379A1 (en) * | 2013-08-20 | 2015-02-26 | 中国科学院大连化学物理研究所 | Method for preparing beta molecular sieve having mesoporous/microporous combined channel |
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