CN106542541A - A kind of small size NaA zeolite molecular sieve and preparation method thereof - Google Patents
A kind of small size NaA zeolite molecular sieve and preparation method thereof Download PDFInfo
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- CN106542541A CN106542541A CN201610979218.5A CN201610979218A CN106542541A CN 106542541 A CN106542541 A CN 106542541A CN 201610979218 A CN201610979218 A CN 201610979218A CN 106542541 A CN106542541 A CN 106542541A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B39/14—Type A
- C01B39/16—Type A from aqueous solutions of an alkali metal aluminate and an alkali metal silicate excluding any other source of alumina or silica but seeds
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The invention discloses a kind of small size NaA zeolite molecular sieve and preparation method thereof, the hydrothermal crystallizing of the preparation of preparation, inhibitor solution, the addition of inhibitor solution and molecular sieve including NaA molecular sieve mother solution：Final gel is transferred in the stainless steel cauldron containing polypropylene liner, the hydro-thermal solid product of gained is repeatedly washed, dried by crystallization 4 ~ 6 hours at 90 ~ 110 DEG C, finally gives NaA type molecular sieves.The method is the approach by Hydrothermal Synthesiss, and the materials such as saccharide compound are added in the mother solution of NaA molecular sieve, and Inhibitory molecules sieve the growth of nucleus, so as to prepare undersized molecular screen material.Sieve particle size ratio prepared by the method reduces 10 times by the product that traditional method is obtained.The preparation method process is simple, it is with low cost, it is adapted to the efficient production of small size NaA molecular sieve.
Description
Technical field
The invention belongs to zeolitic material synthesis field, and in particular to a kind of small size NaA type zeolite molecular sieve and its preparation
Method.
Background technology
Zeolite molecular sieve is crystalline microporous inorganic compound, is the inorganic framework material for developing in recent decades.At it
Space networks rack-like structure in be filled with open cavity and duct and with huge internal surface area so as to adsorptivity,
The performances such as ion exchangeable, catalysis and acidproof heat-proof, can be used for the aspects such as gas drying, purification and environmental conservation, construction material,
Also the fields such as petrochemical industry, fine chemistry industry can be used for as important catalysis material.
It, by one of zeolite molecular sieve of synthetic, is the sial with cubic lattice that NaA type zeolite molecular sieves are earliest
Phosphate compounds, constitute three-dimensional network by silicon-oxy tetrahedron and aluminum-oxygen tetrahedron, with uniform sequential pore passage structure and huge
Specific surface area, be widely used as carrier of washing assisant, adsorbent and metal ion etc..NaA types zeolite molecular sieve synthesizes
Method have solvent（Water）Thermal synthesis method, xerogel transformation approach, microwave irradiation, etc..Wherein, solvent（Water）Full-boiled process is zeolite
Develop most ripe, most widely used synthetic method in synthesis, it is structure directing agent that it utilizes alkali metal or organic amine, is generally existed
Crystallization at a temperature of 100 DEG C, the granule of synthesized molecular sieve are larger, and size is typically in 3 ~ 5 μ ms.Small size NaA type
The crystallite dimension of zeolite molecular sieve is typically between 1 nm ~ 1 μm, more much smaller than the size of Conventional zeolites.Due to zeolite
Grain size is strongly reduced, external surface area is increased dramatically, and little particle NaA type zeolite molecular sieve shows obvious volume
Effect, skin effect and quantum size effect, are improving the utilization rate of catalyst, are strengthening macromole conversion capability, reduce depth
The aspects such as reaction, raising selectivity and reduction coking and deactivation are superior to common zeolite molecular sieve.
The synthetic method for effectively reducing NaA molecular sieve particle size is more, and main method is to change zeolite molecular sieve
Nucleation environment.Silicon source and silicon source presoma show different dissolving forms and existing forms under alkaline system, can be tight
Ghost image rings the nucleation and crystallization process of zeolite molecular sieve, so as to affect molecule sieve size and pattern.B. Bayati et al. once exists
《European Ceramic Society》Journal of the European Ceramic Society（2008, 28, 2653）It is reported in not
In the case of having using template, in the silicon source for having dissolved, Deca Ludox carries out hydrothermal crystallizing, by change chemical composition,
Response time and crystallization temperature prepare NaA type molecular sieve of the particle diameter within 50 nm.CN201510264500.0 discloses one
The method for preparing the NaA molecular sieve of submicron order using solid silicone as silicon source, methods described is by solid silicone and inclined aluminum
Sour sodium is mixed according to certain ratio, and gel is aged 30 hours, and at 80 ~ 120 DEG C, crystallization can obtain grain size and exist
The NaA crystal grains of 400 ~ 700 nm.Above-mentioned report is all to find effective silicon source presoma to be synthesized, what gel needed
Digestion time is longer, it is impossible to the effectively save energy, and silicon source is often confined in several predecessors such as silica gel, waterglass, is fed intake suitable
Certain change is made in sequence, Zeolite synthesis greenization now, the demand for development simplified is not met.
Hydrothermal synthesis method for effectively reducing NaA zeolite molecular sieve granule, patent of the present invention employ a kind of addition
The preparation method of inhibitor effectively reduces zeolitic molecular sieve particle size.Preparation process of the method in molecular sieve gel presoma
In, it is added directly into sucrose as the inhibitor of crystal growth in molecular sieve gel.Sucrose is used as a kind of free of contamination nucleus
Inhibitor, can effectively hinder the superficial growth of zeolite nucleus, make the size of NaA molecular sieve be reduced to 0.5 ~ 1 by 3 ~ 5 μm
Between μm.Silicon source and silicon source are fed intake by the present invention first according to certain molar ratio, prepare the mother solution of NaA molecular sieve.Then
Sucrose is added in mother solution according to different mass percents, is sufficiently mixed, form gel, last crystallization.As sucrose fills
When the effect of inhibitor, the superficial growth of nucleus is prevented during nucleus growth, cause the zeolite crystal of generation
Size submicron order is changed into from micron order.Finally by fully washing, drying, short grained NaA zeolite molecules are finally given
Sieve.
The content of the invention
To overcome the deficiencies in the prior art, the purpose of the present invention is to propose to one kind effectively reduces NaA zeolite molecular sieve size
Preparation method.The method has the advantages that process is simple, response time are short, is easy to regulation and control, the chi of prepared NaA molecular sieve
It is very little to be reduced between present 0.5 ~ 1 μm by be conventionally synthesized 3 ~ 5 μm.To achieve these goals, the present invention is using as follows
Technical scheme：
A kind of preparation method for effectively reducing NaA zeolite molecular sieve size, it is characterised in that comprise the steps of：
The preparation of a, NaA molecular sieve mother solution：Sodium metaaluminate, sodium silicate, sodium hydroxide and deionized water are proportionally mixed, is stirred
Mix uniform, form mother solution, wherein Na2O、Al2O3、SiO2And H2The mol ratio of O is (2 ~ 3):1:(2~7):(100~180)；
The preparation of b, inhibitor solution：Saccharide compound is weighed, is dissolved in a small amount of deionized water, configuration quality score content is
The sugar juice of 10 ~ 20 %；
The addition of c, inhibitor solution：The sugar juice of different quality is pipetted, is slowly added in mother solution, the addition of sugar juice is accounted for
Mass percent 1% ~ 10% in mother solution, continues stirring 4 ~ 6 hours, forms gel after completion of dropping；
The hydrothermal crystallizing of d, molecular sieve：Final gel is transferred in the stainless steel cauldron containing polypropylene liner, 90 ~
Crystallization 4 ~ 6 hours at 110 DEG C, the hydro-thermal solid product of gained are repeatedly washed, dried, finally give NaA type molecular sieves.
Na in described NaA molecular sieve mother solution2O、Al2O3、SiO2And H2O mol ratios are (2 ~ 3):1:(2~7):(100~
180)。
Described inhibitor is saccharide compound, including sucrose, glucose, Fructose, maltose.
The quality score specific concentration of the sugar juice of described configuration is 10 ~ 20%.
The mass percent 1% ~ 10% that the dosage of described inhibitor is accounted in mother solution for sugar juice.
In described step d, crystallization temperature is 90 ~ 110 DEG C.
In described step d, crystallization time is controlled to 4 ~ 6 hours.
A kind of small size NaA zeolite molecular sieve, it is characterised in that prepared according to any of the above-described methods described.
The method is the approach by Hydrothermal Synthesiss, and the materials such as saccharide compound are added in the mother solution of NaA molecular sieve,
Inhibitory molecules sieve the growth of nucleus, so as to prepare undersized molecular screen material.
The present invention proposes a kind of preparation method of the crystallite dimension that can be substantially reduced zeolite molecular sieve, the NaA for obtaining
Generally between 0.5 ~ 1 μm, compared to the prior art, the zeolite molecular sieve particle diameter of synthesis is reduced the size of zeolite molecular sieve
10 times；The addition of saccharide compound, changes the heat transfer in system crystallization process and mass transport process, can be in molecular sieve nucleus
Surface hinders the growth of nucleus, shortens crystallization time.The method of direct adding carbohydrate compound, process is simple are with low cost,
The production cycle is shortened, is adapted to the efficient production of small size NaA molecular sieve.
Description of the drawings
Fig. 1 is the SEM figures of the small particle NaA molecular sieve of the synthesis of the embodiment of the present invention 1.
Fig. 2 is the XRD figure of the small particle NaA molecular sieve of the synthesis of the embodiment of the present invention 1.
Fig. 3 be the embodiment of the present invention it is 2-in-1 into small particle NaA molecular sieve SEM figure.
Specific embodiment
The present invention is described in detail below by instantiation, but protection scope of the present invention is not only restricted to these realities
Apply example.
Embodiment 1：
（1）The preparation of NaA molecular sieve mother solution：First 0.373 g sodium hydroxide is dissolved in 80 mL deionized waters, magnetic force is used
The mixing that stirs is until complete molten；Then the sodium hydroxide solution for obtaining is divided equally in two beakers, adds in a beaker
8.258 g sodium aluminates, quickly stir into beaker solution clarification；15.48 g sodium metasilicates are added in No. two beakers, quickly
Stirring is mixed until clarification；Then solution of sodium metasilicate through is added rapidly in sodium aluminate solution, is stirred vigorously and fills until gel
Divide mixing.
（2）The preparation of sucrose solution：Weigh and be dissolved under the sucrose of 5.0 g, magnetic agitation in 50 ml deionized waters, make
It is standby go out 10 wt% sucrose solution.
（3）The addition of sucrose solution：The configured sucrose solution of 10 ml is measured, sucrose solution is slowly dropped to into NaA
In molecular sieve mother solution, continue stirring 4 hours, form gel.
（4）The crystallization of molecular sieve：Molecular sieve gel is transferred in the stainless steel cauldron containing polypropylene liner,
Crystallization 4 hours at 100 DEG C, open reactor after natural cooling, the solid matter with deionized water of gained is repeatedly washed, then
It is dried in 60 DEG C of constant temperature oven, finally gives NaA type molecular sieves.Fig. 1 is the scanning electron microscope of synthesized NaA molecular sieve
Figure, the particle diameter of NaA molecular sieve is generally between 0.5 ~ 1 μm as seen from the figure；Fig. 2 is that the powder of synthesized NaA molecular sieve spreads out
Penetrate spectrogram, it is seen that the crystallinity of NaA molecular sieve is good.
Embodiment 2：
（1）The preparation method of NaA molecular sieve mother solution is with the step in embodiment 1（1）；
（2）The preparation of sucrose solution is with the step in embodiment 1（2）；
（3）The addition of sucrose solution：Implementation is with the step in embodiment 1（3）, the difference with embodiment 3 is addition
The amount of sucrose solution is different, and the implementation case improves the addition of sucrose.The sucrose solution of the configured in advance of 20 ml is measured,
Sucrose solution is slowly dropped in NaA molecular sieve mother solution, continues stirring 4 hours, form gel.
（4）The crystallization of molecular sieve：Present implementation is with the step in embodiment 1（4）；Fig. 3 is synthesized NaA point of addition
The scanning electron microscope (SEM) photograph of son sieve, the particle diameter of NaA molecular sieve is generally between 0.5 ~ 1 μm as seen from the figure, still with less grain
Footpath.
Embodiment 3：
（1）The preparation method of NaA molecular sieve mother solution is with the step in embodiment 1（1）；
（2）The preparation of sugar juice is with the step in embodiment 1（2）；It is Fructus Vitis viniferae that difference with embodiment 1 is the sugar juice of configuration
Sugar juice, prepares content for glucose solution that mass percent concentration is 10 wt%.
（3）The addition of glucose solution：Implementation is with the step in embodiment 1（3）；Measure the configured in advance of 10 ml
Glucose solution, glucose solution is slowly dropped in NaA molecular sieve mother solution, continue stirring 4 hours, formed gel.
（4）The crystallization of molecular sieve：Present implementation is with the step in embodiment 1（4）；Prepared NaA molecular sieve is still
With less particle diameter.
Claims (8)
1. a kind of preparation method for effectively reducing NaA zeolite molecular sieve size, it is characterised in that comprise the steps of：
The preparation of a, NaA molecular sieve mother solution：Sodium metaaluminate, sodium silicate, sodium hydroxide and deionized water are proportionally mixed, is stirred
Mix uniform, form mother solution, wherein Na2O、Al2O3、SiO2And H2The mol ratio of O is (2 ~ 3):1:(2~7):(100~180)；
The preparation of b, inhibitor solution：Saccharide compound is weighed, is dissolved in a small amount of deionized water, configuration quality score content is
The sugar juice of 10 ~ 20 %；
The addition of c, inhibitor solution：The sugar juice of different quality is pipetted, is slowly added in mother solution, the addition of sugar juice is accounted for
Mass percent 1% ~ 10% in mother solution, continues stirring 4 ~ 6 hours, forms gel after completion of dropping；
The hydrothermal crystallizing of d, molecular sieve：Final gel is transferred in the stainless steel cauldron containing polypropylene liner, 90 ~
Crystallization 4 ~ 6 hours at 110 DEG C, the hydro-thermal solid product of gained are repeatedly washed, dried, finally give NaA type molecular sieves.
2. a kind of preparation method for effectively reducing NaA zeolite molecular sieve size according to claim 1, it is characterised in that institute
Na in the NaA molecular sieve mother solution stated2O、Al2O3、SiO2And H2O mol ratios are (2 ~ 3):1:(2~7):(100~180).
3. a kind of preparation method for effectively reducing NaA zeolite molecular sieve size according to claim 1, it is characterised in that institute
The inhibitor stated is saccharide compound, including sucrose, glucose, Fructose, maltose.
4. a kind of preparation method for effectively reducing NaA zeolite molecular sieve size according to claim 1, it is characterised in that institute
The quality score specific concentration of the sugar juice of the configuration stated is 10 ~ 20%.
5. a kind of preparation method for effectively reducing NaA zeolite molecular sieve size according to claim 1, it is characterised in that institute
The mass percent 1% ~ 10% that the dosage of the inhibitor stated is accounted in mother solution for sugar juice.
6. a kind of preparation method for effectively reducing NaA zeolite molecular sieve size according to claim 1, it is characterised in that institute
In the step of stating d, crystallization temperature is 90 ~ 110 DEG C.
7. a kind of preparation method for effectively reducing NaA zeolite molecular sieve size according to claim 1, it is characterised in that institute
In the step of stating d, crystallization time is controlled to 4 ~ 6 hours.
8. a kind of small size NaA zeolite molecular sieve, it is characterised in that prepared according to the arbitrary methods described of claim 1-7.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721072A (en) * | 2019-02-22 | 2019-05-07 | 中海油天津化工研究设计院有限公司 | A method of KA type molecular sieve is prepared by solvent-thermal method |
| CN116143137A (en) * | 2023-02-27 | 2023-05-23 | 中化学科学技术研究有限公司 | Molecular sieve and preparation method and application thereof |
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| US4372931A (en) * | 1980-05-30 | 1983-02-08 | Air Products And Chemicals, Inc. | Microcrystalline synthetic faujasite |
| CN101468803A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for synthesizing fine grain NaY molecular sieve |
| CN102583426A (en) * | 2012-02-29 | 2012-07-18 | 华东师范大学 | Method for adjusting pH value with oligosaccharide during synthesizing titanium silicalite molecular sieve (TS-1) |
| CN104828837A (en) * | 2015-05-22 | 2015-08-12 | 山东理工大学 | Method for synthesizing submicron order NaA molecular sieve |
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| US3639099A (en) * | 1970-08-13 | 1972-02-01 | Grace W R & Co | Preparation of high-silica faujasite |
| US4372931A (en) * | 1980-05-30 | 1983-02-08 | Air Products And Chemicals, Inc. | Microcrystalline synthetic faujasite |
| CN101468803A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for synthesizing fine grain NaY molecular sieve |
| CN102583426A (en) * | 2012-02-29 | 2012-07-18 | 华东师范大学 | Method for adjusting pH value with oligosaccharide during synthesizing titanium silicalite molecular sieve (TS-1) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721072A (en) * | 2019-02-22 | 2019-05-07 | 中海油天津化工研究设计院有限公司 | A method of KA type molecular sieve is prepared by solvent-thermal method |
| CN109721072B (en) * | 2019-02-22 | 2022-05-17 | 中海油天津化工研究设计院有限公司 | Method for preparing KA type molecular sieve by solvothermal method |
| CN116143137A (en) * | 2023-02-27 | 2023-05-23 | 中化学科学技术研究有限公司 | Molecular sieve and preparation method and application thereof |
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Application publication date: 20170329 |