CN105776243B - A kind of preparation method of molecular sieve - Google Patents
A kind of preparation method of molecular sieve Download PDFInfo
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- CN105776243B CN105776243B CN201610147419.9A CN201610147419A CN105776243B CN 105776243 B CN105776243 B CN 105776243B CN 201610147419 A CN201610147419 A CN 201610147419A CN 105776243 B CN105776243 B CN 105776243B
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- C01—INORGANIC CHEMISTRY
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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Abstract
A kind of preparation method of molecular sieve, it is characterised in that use structure for
Description
Technical field
The present invention relates to a kind of preparation method of micro--mesopore molecular sieve, that is, one kind is used to have cation and nonionic concurrently
The compound of structure is the method that template prepares micro--mesopore molecular sieve.
Background technology
Since mesopore molecular sieve MAS series is developed successfully, because it has big homogeneous pore passage structure, act on big
Molecule reacts field, shows preferable application prospect.But the hole wall of such mesopore molecular sieve be amorphous state, hole wall easily because
Local hydrolysis or heat effect and penetrate, or even whole molecular sieve lattice room temperature is caved in, and is caused its hydrothermal stability poor, is constrained it
Commercial Application.In order to improve the hydrothermal stability of mesopore molecular sieve, scientists have carried out substantial amounts of research work.Wherein, it is situated between
Porous molecular sieve hole wall " crystallization " technology is especially prominent, and the method synthesizes micro- mesoporous composite molecular sieve by designing, and makes mesopore molecular sieve
Hole wall skeleton be changed into the crystalline state hole wall structure of micro porous molecular sieve so that improve its hydrothermal stability (CN1393403,
J.Phys.Chem.B,2001,105,7963-7966).At present, through under different condition more than the mesopore molecular sieve with crystalline state hole wall
Water (solvent) hot method (CN1208718, J.Phys.Chem.B, 2000,104,2817-2823) prepare.But the water (solvent)
Hot system easily causes resulting materials skeleton structure loosely in building-up process, and crystallinity declines, so as to influence the hydro-thermal of molecular sieve
Stability.Thus, the application uses a kind of compound to have cation and nonionic structure concurrently to prepare high hydro-thermal as template
The method of stable micro--mesopore molecular sieve.
The content of the invention
The problems such as present invention aim to address existing mesoporous molecular sieve framework for amorphous state and poor hydrothermal stability, adopt
It is micro--mesopore molecular sieve that template prepares high hydrothermal stability with a kind of compound for having cation and nonionic structure concurrently.
The present invention relates to a kind of preparation method of molecular sieve, i.e., it is a kind of using have concurrently the compound of cation and nonionic structure as
The method that template prepares micro--mesopore molecular sieve, it is characterised in that use structure for
Compound be template, by mol ratio Al2O3:SiO2:Na2O:Tetraethyl ammonium hydroxide:H2O is 1.0:5-30:1-5:20-
60:500-800 sodium metaaluminate, the aqueous silica solution of 30% mass percent, the tetraethyl hydrogen of 25% mass percent
Oxidation aqueous ammonium, sodium hydroxide and water are added sequentially in reactor, are uniformly mixed at room temperature, and homogeneous mixture is made
After gone in Hydrothermal Synthesiss kettle in crystallization 3-6 hours at 100-150 DEG C, be cooled to room temperature, directed agents be made, then gained are oriented to
Agent is added in the mixture of hydrochloric acid and template, in being stirred 16-24 hours at 30-60 DEG C, obtains homogeneous phase gel mixture, its
The consumption of middle hydrochloric acid is Al2O310-500 times of molal quantity, the consumption of template is Al2O30.1-0.5 times of molal quantity, water
Consumption is Al2O31000-5000 times of molal quantity, Hydrothermal Synthesiss kettle is transferred to by homogeneous phase gel, is sealed in crystallization at 100-130 DEG C
After 24-72 hours, room temperature is cooled to, filtering, washing are to neutrality, after 60 DEG C of filter cake is dry 12-24 hours, at 500-650 DEG C
Roasting 5-8 hours, that is, be made micro--mesopore molecular sieve product.
Reaction condition of the present invention is using mol ratio as Al2O3:SiO2:Na2O:Tetraethyl ammonium hydroxide:H2O is equal to
1.0:10-20:2-4:40-60:600-800 sodium metaaluminate, the aqueous silica solution of 30% mass percent, 25% mass
The tetraethyl ammonium hydroxide aqueous solution, sodium hydroxide, the water of percentage are added sequentially in Hydrothermal Synthesiss kettle in brilliant at 120-140 DEG C
Change 4-5 hours, be cooled to room temperature, directed agents are made, then gained directed agents are added in the mixture of hydrochloric acid and template, in
Stirred 20-22 hours at 40-50 DEG C, wherein wherein the consumption of hydrochloric acid is Al2O3100-300 times of molal quantity, the consumption of template
For Al2O30.3-0.4 times of molal quantity, the consumption of water is Al2O32000-3000 times of molal quantity, by obtained gel mixture
Hydrothermal Synthesiss kettle is transferred to, is sealed at 110-120 DEG C after crystallization 30-40 hours, room temperature, filtering, washing to neutrality, filter is cooled to
After 60 DEG C of cake is dry 15-20 hours, it is preferred within 6-7 hours in roasting at 550-600 DEG C.
The present invention solves this technical problem by the following technical programs：
1. templatePreparation process is as follows：Average molecular weight of fetching is 12600
PEO-PPOX-PEO triblock copolymer F12743.45g and ethyl acetate 50mL are in reaction
Stirred in bottle to being completely dissolved and in N255 DEG C are warming up under protection.Thionyl chloride 0.49g is slowly added in reaction bulb and stirred
Mix and 60 DEG C of insulation reaction 8h are warming up to after 2h.After reaction terminates, reactant mixture distills 0.5h in vacuum 1KPa room temperatures, removes
Unreacted thionyl chloride, obtains F127One end chlorizate.0.34g N- methylimidazoles are added to one end halogenation of gained
F127In product, in after 80 DEG C and insulation reaction 24h, mixture vacuum distillation is removed to the N- methylimidazoles of net excess, template is both obtained
Agent.
2. by mol ratio Al2O3:SiO2:Na2O:Tetraethyl ammonium hydroxide:H2O is 1.0:5-30:1-5:20-60:500-
800 sodium metaaluminates, the aqueous silica solution of 30% mass percent, 25% mass percent tetraethyl ammonium hydroxide it is water-soluble
Liquid, sodium hydroxide, water, are added sequentially in reactor, are well mixed in a kettle. at room temperature, and homogeneous mixture is made,
Homogeneous mixture is transferred in Hydrothermal Synthesiss kettle, sealing, crystallization 4-6 hours at 100-140 DEG C, and directed agents are made, and crystallization terminates
Afterwards, room temperature is cooled to, then gained directed agents are added to hydrochloric acid and template
Mixture in, in being stirred 16-24 hour at 30-60 DEG C, obtain homogeneous phase gel mixture, wherein the consumption of hydrochloric acid is Al2O3Rub
10-500 times of that number, the consumption of template is Al2O30.1-0.5 times of molal quantity, the consumption of water is Al2O3Molal quantity
1000-5000 times, homogeneous phase gel is transferred to Hydrothermal Synthesiss kettle, is sealed at 100-130 DEG C after crystallization 24-72 hours, is cooled to
Room temperature, filtering, is washed to neutrality, after 60 DEG C of filter cake is drys 12-24 hour, in roasting 5-8 hours at 500-650 DEG C, it is obtained it is micro--
Mesopore molecular sieve product.
3. the template that the method for the present invention is used is has the compound of cation and nonionic structure concurrently, obtained
Micro--mesopore molecular sieve has micro porous molecular sieve and mesopore molecular sieve each structural advantages concurrently, compared with obtained molecular sieve under hydrothermal system
Good hydrothermal stability.
The present invention is characterized in compared with conventional hydrothermal method：
1. obtained by micro--mesopore molecular sieve have under crystalline state hole wall and good meso-hole structure, more conventional hydrothermal system
Obtained mesopore molecular sieve good hydrothermal stability.
2. the template used has the property of cation and nonionic structure concurrently, Stability Analysis of Structures, function admirable can be synthesized
Microporous mesoporous micro--the mesopore molecular sieve coexisted.
It is that high-temperature high-voltage reaction is carried 3. the synthesis of the Gao Wenwei-mesopore molecular sieve, extends the scope of application of mesoporous material
Potential catalysis material or carrier are supplied.
Specific implementation method
The method of the present invention is described further with reference to embodiment, is not limitation of the invention.
Embodiment 1：0.3g sodium metaaluminates, the aqueous silica solution of the mass percents of 6.69g 30%, 23.71g 25%
The tetraethyl ammonium hydroxide aqueous solution, 0.22g sodium hydroxides, the 3.40g water of mass percent, are added sequentially in reactor, room
It is well mixed in a kettle. under temperature, goes in Hydrothermal Synthesiss kettle in crystallization 4 hours at 140 DEG C, be cooled to room temperature, then added
Enter into hydrochloric acid and template, in stirring 20h at 40 DEG C, obtain homogeneous phase gel mixture, the wherein consumption of hydrochloric acid is Al2O3Rub
130 times of that number, the consumption of template is Al2O30.3 times of molal quantity, the consumption of water is Al2O32600 times of molal quantity, will
This gel mixture is transferred to Hydrothermal Synthesiss kettle, is sealed at 110 DEG C after crystallization 30h, is cooled to room temperature, filters, washs to neutrality,
After the dry 20h of 60 DEG C of filter cake, micro--mesopore molecular sieve is produced in being calcined 6h at 550 DEG C.
Comparative example 1：Aqueous silica solution, the 23.71g of 0.3g sodium metaaluminates, the mass percents of 6.69g 30%
The tetraethyl ammonium hydroxide aqueous solution, 0.22g sodium hydroxides, the 3.40g water of 25% mass percent, are added sequentially to reactor and mix
Close uniform, go in Hydrothermal Synthesiss kettle in crystallization 4 hours at 140 DEG C, be cooled to room temperature, then add it to hydrochloric acid and as mould
PEO-PPOX of plate agent-PEO triblock copolymer F127In, wherein F127Number-average molecular weight be
12600, in stirring 20h at 40 DEG C, the wherein consumption of hydrochloric acid is Al2O3130 times of molal quantity, the consumption of template is Al2O3Rub
0.3 times of that number, the consumption of water is Al2O32600 times of molal quantity, are transferred to Hydrothermal Synthesiss kettle by this gel mixture, are sealed in
At 110 DEG C after crystallization 30h, room temperature is cooled to, filtering, washed to neutrality, after the dry 20h of 60 DEG C of filter cake, in being calcined 6h at 550 DEG C
Produce mesopore molecular sieve.
Comparative example 2：Aqueous silica solution, the 23.71g of 0.3g sodium metaaluminates, the mass percents of 6.69g 30%
The tetraethyl ammonium hydroxide aqueous solution, 0.22g sodium hydroxides, the 3.40g water of 25% mass percent, are added sequentially to reactor and mix
Close uniform, go in Hydrothermal Synthesiss kettle in crystallization 4 hours at 140 DEG C, be cooled to room temperature, then add it to hydrochloric acid and as mould
In the cetyl trimethylammonium bromide of plate agent, in stirring 20h at 40 DEG C, the wherein consumption of hydrochloric acid is Al2O3The 130 of molal quantity
Times, the consumption of template is Al2O30.3 times of molal quantity, the consumption of water is Al2O32600 times of molal quantity, this gel is mixed
Thing is transferred to Hydrothermal Synthesiss kettle, is sealed at 110 DEG C after crystallization 30h, is cooled to room temperature, and filtering, washing to neutrality, 60 DEG C of filter cake are done
After dry 20h, mesopore molecular sieve is produced in being calcined 6h at 550 DEG C.
What the mesopore molecular sieve that comparative example 1 and the method for comparative example 2 are synthesized was synthesized with by the method for embodiment 1
Micro--mesopore molecular sieve carries out heat endurance and hydrothermal stability test respectively.For heat endurance, different templates agent condition
The molecular screen material of lower synthesis all has preferable stability, is calcined at 1000 DEG C after 10h, using X-ray powder diffraction skills
Art is detected to material, as a result shows that the molecular sieve synthesized under the conditions of different templates agent all keeps good meso-hole structure, but
Micro--mesopore molecular sieve micropore diffraction maximum the peak intensity synthesized under the conditions of template described in this patent is higher.For hydrothermally stable
Property for, the porous molecular sieve synthesized under the conditions of template described in this patent is handled under 180 DEG C of vapor after 96h, remain to protect
Good meso-hole structure and crystallinity are held, and the porous molecular sieve synthesized according to comparative example 1 and the method for comparative example 2 exists
Handled under 180 DEG C of vapor after 12h, meso-hole structure is destroyed and derives peak without any crystal face substantially, shows its hydrothermally stable
Property is poor.It can be seen that, the micro--mesopore molecular sieve synthesized under the conditions of template described in this patent has more preferable hydrothermal stability.
Embodiment 2：0.3g sodium metaaluminates, the aqueous silica solution of the mass percents of 5.48g 30%, 26.94g 25%
The tetraethyl ammonium hydroxide aqueous solution, 0.26g sodium hydroxides, the 2.98g water of mass percent, are added sequentially to reactor mixing equal
It is even, go in Hydrothermal Synthesiss kettle in crystallization 4.5h at 130 DEG C, be cooled to room temperature, then add it in hydrochloric acid and template, in
21h is stirred at 45 DEG C, the wherein consumption of hydrochloric acid is Al2O3150 times of molal quantity, the consumption of template is Al2O3Molal quantity
0.4 times, the consumption of water is Al2O32500 times of molal quantity, Hydrothermal Synthesiss kettle is transferred to by this gel mixture, is sealed at 115 DEG C
After crystallization 35h, it is cooled to after room temperature, filtering, washing to neutrality, the dry 17h of 60 DEG C of filter cake, is produced in being calcined 6.5h at 600 DEG C
Micro--mesopore molecular sieve product.
Embodiment 3：0.3g sodium metaaluminates, the aqueous silica solution of the mass percents of 3.65g 30%, 21.55g 25%
The tetraethyl ammonium hydroxide aqueous solution, 0.18g sodium hydroxides, the 2.55g water of mass percent, are added sequentially to reactor mixing equal
It is even, go in Hydrothermal Synthesiss kettle in crystallization 4h at 120 DEG C, be cooled to room temperature, then add it in hydrochloric acid and template, in 40
20h is stirred at DEG C, the wherein consumption of hydrochloric acid is Al2O3100 times of molal quantity, the consumption of template is Al2O3The 0.3 of molal quantity
Times, the consumption of water is Al2O32000 times of molal quantity, Hydrothermal Synthesiss kettle is transferred to by this gel mixture, is sealed at 110 DEG C brilliant
Change after 30h, be cooled to after room temperature, filtering, washing to neutrality, the dry 15h of 60 DEG C of filter cake, micro--Jie is produced in being calcined 6h at 550 DEG C
Porous molecular sieve product.
Embodiment 4：0.3g sodium metaaluminates, the aqueous silica solution of the mass percents of 7.28g 30%, 32.33g 25%
The tetraethyl ammonium hydroxide aqueous solution, 0.35g sodium hydroxides, the 3.40g water of mass percent, are added sequentially to reactor mixing equal
It is even, go in Hydrothermal Synthesiss kettle in crystallization 5h at 140 DEG C, be cooled to room temperature, then add it in hydrochloric acid and template, in 50
22h is stirred at DEG C, the wherein consumption of hydrochloric acid is Al2O3300 times of molal quantity, the consumption of template is Al2O3The 0.4 of molal quantity
Times, the consumption of water is Al2O33000 times of molal quantity, Hydrothermal Synthesiss kettle is transferred to by this gel mixture, is sealed at 120 DEG C brilliant
Change after 40h, be cooled to room temperature, filtering, wash to neutrality, after the drys 20h of 60 DEG C of filter cake, in roasting 7h at 6000 DEG C produce it is micro--
Mesopore molecular sieve product.
Embodiment 5：0.3g sodium metaaluminates, the aqueous silica solution of the mass percents of 1.83g 30%, 10.78g 25%
The tetraethyl ammonium hydroxide aqueous solution, 0.09g sodium hydroxides, the 2.13g water of mass percent, are added sequentially to reactor mixing equal
It is even, go in Hydrothermal Synthesiss kettle in crystallization 3h at 100 DEG C, be cooled to room temperature, then add it in hydrochloric acid and template, in 30
16h is stirred at DEG C, the wherein consumption of hydrochloric acid is Al2O310 times of molal quantity, the consumption of template is Al2O3The 0.1 of molal quantity
Times, the consumption of water is Al2O31000 times of molal quantity, Hydrothermal Synthesiss kettle is transferred to by this gel mixture, is sealed at 100 DEG C brilliant
Change after 24h, be cooled to after room temperature, filtering, washing to neutrality, the dry 12h of 60 DEG C of filter cake, micro--Jie is produced in being calcined 5h at 500 DEG C
Porous molecular sieve product.
Embodiment 6：Aqueous silica solution, the 32.33g of 0.3g sodium metaaluminates, the mass percents of 10.95g 30%
The tetraethyl ammonium hydroxide aqueous solution, 0.44g sodium hydroxides, the 3.40g water of 25% mass percent, are added sequentially to reactor and mix
Close uniform, go in Hydrothermal Synthesiss kettle in crystallization 6h at 150 DEG C, be cooled to room temperature, then add it in hydrochloric acid and template,
In stirring 24h at 60 DEG C, the wherein consumption of hydrochloric acid is Al2O3500 times of molal quantity, the consumption of template is Al2O3Molal quantity
0.5 times, the consumption of water is Al2O35000 times of molal quantity, Hydrothermal Synthesiss kettle is transferred to by this gel mixture, is sealed at 130 DEG C
After crystallization 72h, be cooled to room temperature, filtering, wash to neutrality, after the drys 24h of 60 DEG C of filter cake, in roasting 8h at 650 DEG C produce it is micro--
Mesopore molecular sieve product.
Micro--mesopore molecular sieve synthesized by embodiment 2 to embodiment 6 is subjected to heat endurance and hydrothermal stability examination
Test.The result of heat stabilization test shows that the meso-hole structure of synthesized molecular sieve keeps good, micropore diffraction peak intensity；Hydro-thermal is steady
Qualitative results show that synthesized molecular sieve meso-hole structure and crystallinity keep good.
Claims (1)
1. a kind of preparation method of molecular sieve, i.e., a kind of to be prepared using the compound for having cation and nonionic structure concurrently as template
The method of micro--mesopore molecular sieve, it is characterised in that use structure forChange
Compound is template, by mol ratio Al2O3:SiO2:Na2O:Tetraethyl ammonium hydroxide:H2O is 1.0:5-30:1-5:20-60:
500-800 sodium metaaluminate, the aqueous silica solution of 30% mass percent, the tetraethyl hydroxide of 25% mass percent
Aqueous ammonium, sodium hydroxide and water are added sequentially in reactor, are uniformly mixed at room temperature, are made after homogeneous mixture and are turned
Into Hydrothermal Synthesiss kettle in crystallization 3-6 hours at 100-150 DEG C, room temperature is cooled to, directed agents are made, then gained directed agents are added
Enter into the mixture of hydrochloric acid and template, in being stirred 16-24 hours at 30-60 DEG C, obtain homogeneous phase gel mixture, wherein salt
The consumption of acid is Al2O310-500 times of molal quantity, the consumption of template is Al2O30.1-0.5 times of molal quantity, the consumption of water
For Al2O31000-5000 times of molal quantity, Hydrothermal Synthesiss kettle is transferred to by homogeneous phase gel, is sealed in crystallization 24-72 at 100-130 DEG C
After hour, room temperature is cooled to, filtering, washed to neutrality, after 60 DEG C of filter cake is dry 12-24 hours, in being calcined 5- at 500-650 DEG C
8 hours, that is, micro--mesopore molecular sieve product is made.
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|---|---|---|---|---|
| CN1769174A (en) * | 2004-11-01 | 2006-05-10 | 中国科学院生态环境研究中心 | Synthesis method for nano mesoporous molecular screen stable in intense heat |
| WO2008022531A1 (en) * | 2006-08-08 | 2008-02-28 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Sapo-34 molecular sieves having both micropores and mesopores and synthesis process thereof |
| CN101186311A (en) * | 2007-11-22 | 2008-05-28 | 复旦大学 | Y/MCM-48 composite molecular screen and preparation method thereof |
| CN102039198A (en) * | 2009-10-23 | 2011-05-04 | 中国科学院过程工程研究所 | Synthesis of spherical Fe-MCM-48 mesoporous material and preparation of catalytic combustion catalyst loaded with Ag of spherical Fe-MCM-48 mesoporous material |
| CN102390843A (en) * | 2011-08-02 | 2012-03-28 | 复旦大学 | Three-dimensional interconnected hierarchical-structured zeolite molecular sieve material and preparation method thereof |
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2016
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1769174A (en) * | 2004-11-01 | 2006-05-10 | 中国科学院生态环境研究中心 | Synthesis method for nano mesoporous molecular screen stable in intense heat |
| WO2008022531A1 (en) * | 2006-08-08 | 2008-02-28 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Sapo-34 molecular sieves having both micropores and mesopores and synthesis process thereof |
| CN101186311A (en) * | 2007-11-22 | 2008-05-28 | 复旦大学 | Y/MCM-48 composite molecular screen and preparation method thereof |
| CN102039198A (en) * | 2009-10-23 | 2011-05-04 | 中国科学院过程工程研究所 | Synthesis of spherical Fe-MCM-48 mesoporous material and preparation of catalytic combustion catalyst loaded with Ag of spherical Fe-MCM-48 mesoporous material |
| CN102390843A (en) * | 2011-08-02 | 2012-03-28 | 复旦大学 | Three-dimensional interconnected hierarchical-structured zeolite molecular sieve material and preparation method thereof |
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