CN107311193B - A kind of preparation method of pollucite tiny balloon - Google Patents
A kind of preparation method of pollucite tiny balloon Download PDFInfo
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- CN107311193B CN107311193B CN201710699879.7A CN201710699879A CN107311193B CN 107311193 B CN107311193 B CN 107311193B CN 201710699879 A CN201710699879 A CN 201710699879A CN 107311193 B CN107311193 B CN 107311193B
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- 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
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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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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- 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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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a kind of preparation methods of pollucite tiny balloon, it is characterized in that: taking metakaolin, silicon ash and a hydronium(ion) cesium oxide, it is added in the steam pressure reaction kettle for being built-in with blender, deionized water is added, it is stirred to react 12 at 160~200 DEG C of temperature, 0.6~1.2MPa of pressure~for 24 hours, it is cooling, filtering, solid product is washed, dry, obtains pollucite tiny balloon.The present invention removes removing template or surfactant without adding inorganic, organic template material, surfactant and zeolite seed crystal, without post-processing, and a step realizes the preparation of pollucite tiny balloon in a mild condition；Obtained pollucite tiny balloon can be used as microreactor, High-temperature-rescatalyst catalyst carrier, radioactive waste separation curing materials, be applied to the fields such as chemical industry, environment, defence and military.
Description
Technical field
The invention belongs to inorganic chemistry, are related to a kind of preparation method of pollucite tiny balloon.Caesium boiling prepared by the present invention
Stone tiny balloon can be used as microreactor, High-temperature-rescatalyst catalyst carrier, radioactive waste separation curing materials etc., be widely used in
The fields such as chemical industry, environment, defence and military.
Background technique
Pollucite is also referred to as pollucite, and theoretical chemistry structural formula is CsAlSi2O6, it is analcime (Na AlSi2O6) family
Race's a member.Since pollucite has high Cs content, excellent hydrothermal stability and high temperature resistance (1900 DEG C of fusing point >) etc., because
This area research person focuses on being used for Cs radioactive source source core material for a long time, contain137The solidification of Cs nuke rubbish and aerospace
Equal fields.The zeolite channels size of pollucite is aboutAnd the diameter of Cs is aboutOnce that is Cs into
Enter into pollucite crystal structure, absorption would not be swapped with other ions.And from this point analysis, as can pollucite is made
For microreactor or catalyst carrier, so that it may avoid influence of the Cs plasma diffusing W,Mo to reactant or catalyst in zeolite.And it boils
Stone tiny balloon is then the preferential selection as microreactor or catalyst carrier, but up to the present, there are no document reports
The preparation method of pollucite tiny balloon.
Currently, the preparation of zeolite hollow microsphere is still the difficult point in the field.In the prior art, limited document report its
The preparation of his type zeolite hollow structure, but mostly mixing dependent on inorganic, organic formwork, surfactant and zeolite seed crystal
Enter.Above method operating procedure is more, complex process, expensive starting materials, and needs to post-process (high temperature sintering, chemical attack etc.) to go
Except residual inorganic or organic formwork, surfactant.Pollucite has zeolite structured microchannel, and Cs therein is ion stabilized, difficult
In release, and pollucite high temperature resistance itself is excellent, as can it to be further made to hollow structure, then its application field will be into
One step is widened.Therefore, a kind of surfactant-free is badly in need of finding, without template, without zeolite seed crystal, low temperature, technique and set in this field
The standby method for simply preparing pollucite tiny balloon.
Summary of the invention
The purpose of the present invention is intended to overcome deficiency in the prior art, provides a kind of preparation side of pollucite tiny balloon
Method.The present invention is directed to overcome in existing traditional zeolite class tiny balloon technology of preparing to need additional soft or hard template, crystal seed, and cause
Product purity and the problem that low output, preparation process are complicated, difficulty is big, provide one kind and do not need to add any other template, table
Face activating agent and zeolite seed crystal, simple process, the pollucite of mild condition (160~200 DEG C, 0.6~1.2MPa thermal and hydric environment)
One one step preparation method of low temperature.
The contents of the present invention are: a kind of preparation method of pollucite tiny balloon, it is characterized in that step are as follows:
A, by 100 parts by weight metakaolins, 25~155 parts by weight silicon ashes, the weight of 145 parts by weight, one hydronium(ion) cesium oxide
Proportion takes solid material metakaolin, silicon ash and a hydronium(ion) cesium oxide, is added in the steam pressure reaction kettle for being built-in with blender；
B, by the total weight of solid material metakaolin and silicon ash and a hydronium(ion) cesium oxide: deionized water is 1:15~20
Weight ratio remove ionized water, be added in steam pressure reaction kettle become liquid-solid mixture, close steam pressure reaction kettle；
It c, will under conditions of 160~200 DEG C of temperature, 0.6~1.2MPa of pressure, 60~100 rev/min of mixing speed
Liquid-solid mixture (crystallization in thermal and hydric environment) reaction 12~for 24 hours, it is cooling, liquid-solid mixture is taken out, filtering, what is be obtained by filtration consolidates
Body product is after washing, dry, that is, pollucite tiny balloon is prepared；The pollucite tiny balloon is equal in microcosmic lower shape
Even hollow ball shape, hollow bulb diameter is about 300nm (can be 280~320nm), hollow sphere pore wall thickness is 10~20nm.
In the contents of the present invention: in solid material described in step a, it is preferable to Cs:Al for the dosage mole of each element:
Si=1:1:1.5~4.
In the contents of the present invention: dry described in step c to be preferably placed in temperature 60 C (can be 50~70 DEG C) very
In empty (vacuum degree >=0.085MPa) drying box dry 48h (can be 24~96h).
In the contents of the present invention: silicon ash described in step a be using ferroalloy smelting Antaciron or using quartz and
When coke smelting commercial silicon (metallic silicon), under the conditions of 1500 DEG C or more of temperature, generate that (a large amount of volatility are very out in electric furnace
SiO by force)2With Si gas, precipitated after gas discharge with (rapid) the oxidation condensation of air, it is microcosmic lower for diameter 300nm
The medicine ball of left and right, SiO2Mass percentage >=97%；The silicon ash can be the bright limited duty of day comprehensive utilization of resources in Sichuan
97 grades of 95 grades of silicon ashes of Ren company, 97 grades of silicon ashes of Chengdu Jin Xiang Science and Technology Ltd. or Ai Ken Elken company, Germany silicon ashes.
In the contents of the present invention: main chemical compositions and the weight percent composition of metakaolin described in step a
For SiO250~55%, Al2O340~45%, other microcomponent (microcomponent Fe2O3、Na2O、K2O, CaO etc.) 3%
~5%；The metakaolin can be the K1300 type metakaolin of Inner Mongolia Chaopai Kaolin Co., Ltd.'s production.
In the contents of the present invention: a hydronium(ion) cesium oxide described in step a is chemical pure or technical pure, primary chemical at
Divide and weight percent group becomes CsOH.H2O >=99.9%.
In the contents of the present invention: the steam pressure reaction kettle for being built-in with blender (or stirring blade) is that Weihai is global
The GSH type reaction kettle of chemical machinery Co., Ltd.The equipment of industrialized production is the global chemical machinery Co., Ltd in Weihai
The GSH type reaction kettle of 100L or more.
Compared with prior art, the present invention have following features and the utility model has the advantages that
(1) using the present invention, metakaolin and silicon ash are dissolved in cesium hydroxide solution, and single step reaction of going forward side by side generates caesium boiling
Stone crystal grain, pollucite crystal grain generated are covered in silicon ash spherome surface and form pollucite particles coat silicon ash microballoon
Core-shell type structure, as reaction carries out, kernel portion silicon ash sphere, which further dissolves, diffuses to surface crystallization is grown to caesium
Zeolite hollow microsphere；Chemical equation in present invention preparation are as follows: 4SiO2+Al2O3+ 2CsOH=2CsAlSi2O6+H2O；
(2) using the present invention, it is prepared for pollucite tiny balloon for the first time, there is no pertinent literature to report both at home and abroad；It overcomes
Surfactant, soft or hard casting formwork or the zeolite that must be added in existing traditional zeolite hollow ball material preparation process are brilliant
Kind, it is a kind of green synthesis method for meeting sustainable development；
(3) using the present invention, (160~200 DEG C, 0.6~1.2MPa thermal and hydric environment) realizes pollucite in a mild condition
The one-step synthesis of tiny balloon, without in addition adding inorganic, organic template material, surfactant and zeolite seed crystal, after being not necessarily to
Removing template or surfactant are removed in processing, avoid the harm of surfactant, last handling process to environment, low energy consumption, is conducive to
Environmental protection；
(4) pollucite tiny balloon prepared by the present invention can be used as microreactor, High-temperature-rescatalyst catalyst carrier, Spent Radioactive
Object separates curing materials etc., extensive using future in fields such as chemical industry, environment, defence and militaries；
(5) preparation process of the present invention is simple, and process is easy, easy to operate, and tiny balloon yield and product purity are high, is easy to
Size industrial enterprises metaplasia produces, practical.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum of 3 product of embodiment, and Fig. 1 shows in 3 product of embodiment and X ray diffracting data library
Pollucite data (Reference code:00-029-0407) are consistent, i.e., 3 product of embodiment is pollucite；
Fig. 2 is the scanning electron microscope map of 3 product of embodiment, and Fig. 2 shows that prepared pollucite tiny balloon is in empty substantially
Bulbus cordis shape, size are about 300nm；
Fig. 3 is the transmission electron microscope map of 3 product individual particle of embodiment, and Fig. 3 combination Fig. 2 further demonstrates that 3 product of embodiment
For pollucite tiny balloon, tiny balloon diameter is about 300nm, and hollow sphere pore wall thickness is about 10~20nm.
Specific embodiment
The embodiments given below are intended to further illustrate the invention, but is not to be construed as to the scope of the present invention
Limitation, some nonessential improvement and tune that person skilled in art makes the present invention according to the content of aforementioned present invention
It is whole, still fall within protection scope of the present invention.
Embodiment 1:
A kind of preparation method of pollucite tiny balloon, step are as follows: each raw material dosage is 100 parts by weight according to weight ratio
Metakaolin, 50 parts by weight silicon ashes, 145 parts by weight, one hydronium(ion) cesium oxide carry out ingredient, so that each element dosage molar ratio is
Cs:Al:Si=1:1:2 weighs metakaolin, silicon ash, a hydronium(ion) cesium oxide, and is added to built-in stirring blade and (stirs
It is device, rear same) steam pressure reaction kettle in；Deionized water, which is added, makes solid material and deionized water quality ratio raw material: deionized water
For 1:15-20, capping kettle, setting mixing speed is 60~100 rpms；160 DEG C of temperature, pressure 0.6~
It is cooling after crystallization 20h in the thermal and hydric environment of 1.2MPa to take out, it washed, be dried to obtain pollucite tiny balloon.
Embodiment 2:
A kind of preparation method of pollucite tiny balloon, step are as follows: each raw material dosage is 100 parts by weight according to weight ratio
Metakaolin, 50 parts by weight silicon ashes, 145 parts by weight, one hydronium(ion) cesium oxide carry out ingredient, so that each element dosage molar ratio is
Cs:Al:Si=1:1:2 weighs metakaolin, silicon ash, a hydronium(ion) cesium oxide, and the steam pressure for being added to built-in stirring blade is anti-
It answers in kettle；Deionized water, which is added, makes solid material and deionized water quality ratio raw material: deionized water 1:15-20, and closing is anti-
Kettle is answered, setting mixing speed is 60~100 rpms；180 DEG C of temperature, 0.6~1.2MPa of pressure thermal and hydric environment in it is brilliant
Cooling is taken out after changing 20h, is washed, is dried to obtain pollucite tiny balloon.
Embodiment 3:
A kind of preparation method of pollucite tiny balloon, step are as follows: each raw material dosage is 100 parts by weight according to weight ratio
Metakaolin, 50 parts by weight silicon ashes, 145 parts by weight, one hydronium(ion) cesium oxide carry out ingredient, so that each element dosage molar ratio is
Cs:Al:Si=1:1:2 weighs metakaolin, silicon ash, a hydronium(ion) cesium oxide, and the steam pressure for being added to built-in stirring blade is anti-
It answers in kettle；Deionized water, which is added, makes solid material and deionized water quality ratio raw material: deionized water 1:15-20, and closing is anti-
Kettle is answered, setting mixing speed is 60~100 rpms；200 DEG C of temperature, 0.6~1.2MPa of pressure thermal and hydric environment in it is brilliant
Cooling is taken out after changing 20h, is washed, is dried to obtain pollucite tiny balloon.
Embodiment 4:
A kind of preparation method of pollucite tiny balloon, step are as follows: each raw material dosage is 100 parts by weight according to weight ratio
Metakaolin, 25 parts by weight silicon ashes, 145 parts by weight, one hydronium(ion) cesium oxide carry out ingredient, so that each element dosage molar ratio is
Cs:Al:Si=1:1:1.5 weighs metakaolin, silicon ash, a hydronium(ion) cesium oxide, and is added to the steam pressure of built-in stirring blade
In reaction kettle；Deionized water, which is added, makes solid material and deionized water quality ratio raw material: deionized water 1:15-20, closing
Reaction kettle, setting mixing speed are 60~100 rpms；180 DEG C of temperature, 0.6~1.2MPa of pressure thermal and hydric environment in
It is cooling after crystallization 20h to take out, it washed, be dried to obtain pollucite tiny balloon.
Embodiment 5:
A kind of preparation method of pollucite tiny balloon, step are as follows: each raw material dosage is 100 parts by weight according to weight ratio
Metakaolin, 76 parts by weight silicon ashes, 145 parts by weight, one hydronium(ion) cesium oxide carry out ingredient, so that each element dosage molar ratio is
Cs:Al:Si=1:1:2.5 weighs metakaolin, silicon ash, a hydronium(ion) cesium oxide, and is added to the steam pressure of built-in stirring blade
In reaction kettle；Deionized water, which is added, makes solid material and deionized water quality ratio raw material: deionized water 1:15-20, closes
Reaction kettle, setting mixing speed are 60~100 rpms；180 DEG C of temperature, 0.6~1.2MPa of pressure thermal and hydric environment in
It is cooling after crystallization 20h to take out, it washed, be dried to obtain pollucite tiny balloon.
Embodiment 6:
A kind of preparation method of pollucite tiny balloon, step are as follows: each raw material dosage is 100 parts by weight according to weight ratio
Metakaolin, 102 parts by weight silicon ashes, 145 parts by weight, one hydronium(ion) cesium oxide carry out ingredient, so that each element dosage molar ratio is
Cs:Al:Si=1:1:3 weighs metakaolin, silicon ash, a hydronium(ion) cesium oxide, and the steam pressure for being added to built-in stirring blade is anti-
It answers in kettle；Deionized water, which is added, makes solid material and deionized water quality ratio raw material: deionized water 1:15-20, and closing is anti-
Kettle is answered, setting mixing speed is 60~100 rpms；180 DEG C of temperature, 0.6~1.2MPa of pressure thermal and hydric environment in it is brilliant
Cooling is taken out after changing 20h, is washed, is dried to obtain pollucite tiny balloon.
Embodiment 7:
A kind of preparation method of pollucite tiny balloon, step are as follows: each raw material dosage is 100 parts by weight according to weight ratio
Metakaolin, 128 parts by weight silicon ashes, 145 parts by weight, one hydronium(ion) cesium oxide carry out ingredient, so that each element dosage molar ratio is
Cs:Al:Si=1:1:3.5 weighs metakaolin, silicon ash, a hydronium(ion) cesium oxide, and is added to the steam pressure of built-in stirring blade
In reaction kettle；Deionized water, which is added, makes solid material and deionized water quality ratio raw material: deionized water 1:15-20, closes
Reaction kettle, setting mixing speed are 60~100 rpms；180 DEG C of temperature, 0.6~1.2MPa of pressure thermal and hydric environment in
It is cooling after crystallization 20h to take out, it washed, be dried to obtain pollucite tiny balloon.
Embodiment 8:
A kind of preparation method of pollucite tiny balloon, step are as follows: each raw material dosage is 100 parts by weight according to weight ratio
Metakaolin, 155 parts by weight silicon ashes, 145 parts by weight, one hydronium(ion) cesium oxide carry out ingredient, so that each element dosage molar ratio is
Cs:Al:Si=1:1:4 weighs metakaolin, silicon ash, a hydronium(ion) cesium oxide, and the steam pressure for being added to built-in stirring blade is anti-
It answers in kettle；Deionized water, which is added, makes solid material and deionized water quality ratio raw material: deionized water 1:15-20, and closing is anti-
Kettle is answered, setting mixing speed is 60~100 rpms；180 DEG C of temperature, 0.6~1.2MPa of pressure thermal and hydric environment in it is brilliant
Cooling is taken out after changing 20h, is washed, is dried to obtain pollucite tiny balloon.
9~embodiment of embodiment 11:
A kind of preparation method of pollucite tiny balloon, step are as follows: it is tested using method same as Example 3,
But change crystallization time, the crystallization through 12h, 16h, for 24 hours in thermal and hydric environment obtains pollucite tiny balloon.
Embodiment 12:
A kind of preparation method of pollucite tiny balloon, step are as follows:
A, by 100 parts by weight metakaolins, 25 parts by weight silicon ashes, 145 parts by weight, one hydronium(ion) cesium oxide weight proportion
Solid material metakaolin, silicon ash and a hydronium(ion) cesium oxide are taken, is added in the steam pressure reaction kettle for being built-in with blender；
B, by the total weight of solid material metakaolin and silicon ash and a hydronium(ion) cesium oxide: deionized water is the weight of 1:15
Amount ratio removes ionized water, and being added in steam pressure reaction kettle becomes liquid-solid mixture, closes steam pressure reaction kettle；
C, under conditions of 160 DEG C of temperature, pressure 0.6MPa, 60 rev/min of mixing speed by liquid-solid mixture (in water
Crystallization in thermal environment) it reacts for 24 hours, it is cooling, liquid-solid mixture, filtering are taken out, the solid product being obtained by filtration after washing, is done
It is dry, that is, pollucite tiny balloon is prepared.
Embodiment 13:
A kind of preparation method of pollucite tiny balloon, step are as follows:
A, by 100 parts by weight metakaolins, 155 parts by weight silicon ashes, 145 parts by weight, one hydronium(ion) cesium oxide weight proportion
Solid material metakaolin, silicon ash and a hydronium(ion) cesium oxide are taken, is added in the steam pressure reaction kettle for being built-in with blender；
B, by the total weight of solid material metakaolin and silicon ash and a hydronium(ion) cesium oxide: deionized water is the weight of 1:20
Amount ratio removes ionized water, and being added in steam pressure reaction kettle becomes liquid-solid mixture, closes steam pressure reaction kettle；
C, by liquid-solid mixture (In under conditions of 200 DEG C of temperature, pressure 1.2MPa, 100 rev/min of mixing speed
Crystallization in thermal and hydric environment) reaction 12h, cooling, taking-up liquid-solid mixture filters, and the solid product being obtained by filtration after washing, is done
It is dry, that is, pollucite tiny balloon is prepared.
Embodiment 14:
A kind of preparation method of pollucite tiny balloon, step are as follows:
A, by 100 parts by weight metakaolins, 90 parts by weight silicon ashes, 145 parts by weight, one hydronium(ion) cesium oxide weight proportion
Solid material metakaolin, silicon ash and a hydronium(ion) cesium oxide are taken, is added in the steam pressure reaction kettle for being built-in with blender；
B, by the total weight of solid material metakaolin and silicon ash and a hydronium(ion) cesium oxide: deionized water is the weight of 1:18
Amount ratio removes ionized water, and being added in steam pressure reaction kettle becomes liquid-solid mixture, closes steam pressure reaction kettle；
C, under conditions of 180 DEG C of temperature, pressure 0.9MPa, 80 rev/min of mixing speed by liquid-solid mixture (in water
Crystallization in thermal environment) reaction 18h, cooling, taking-up liquid-solid mixture filters, and the solid product being obtained by filtration after washing, is done
It is dry, that is, pollucite tiny balloon is prepared.
Embodiment 15~21:
A kind of preparation method of pollucite tiny balloon, step are as follows:
A, by 100 parts by weight metakaolins, 25~155 parts by weight silicon ashes, the weight of 145 parts by weight, one hydronium(ion) cesium oxide
Proportion takes solid material metakaolin, silicon ash and a hydronium(ion) cesium oxide, is added in the steam pressure reaction kettle for being built-in with blender；
The specific parts by weight dosage of each solid material see the table below in each embodiment:
B, by the total weight of solid material metakaolin and silicon ash and a hydronium(ion) cesium oxide: deionized water is 1:15~20
Weight ratio (embodiment 15~21 be respectively 1:15,1:16,1:17,1:18,1:19,1:19,1:20) remove ionized water, add
Entering into steam pressure reaction kettle becomes liquid-solid mixture, closes steam pressure reaction kettle；
It c, will under conditions of 160~200 DEG C of temperature, 0.6~1.2MPa of pressure, 60~100 rev/min of mixing speed
Liquid-solid mixture (crystallization in thermal and hydric environment) reaction 12~for 24 hours, it is cooling, liquid-solid mixture is taken out, filtering, what is be obtained by filtration consolidates
Body product is after washing, dry, that is, pollucite tiny balloon is prepared.
In above-described embodiment 12~21: in solid material described in step a, the dosage molar ratio of each element is in Cs:
In the range of Al:Si=1:1:1.5~4.
In above-described embodiment: drying described in step c is preferably placed in temperature 60 C (can be 50~70 DEG C) vacuum
In (vacuum degree >=0.085MPa) drying box dry 48h (can be 24~96h).
In above-described embodiment: silicon ash described in step a is using ferroalloy smelting Antaciron or to utilize quartz and coke
When charcoal smelting commercial silicon (metallic silicon), under the conditions of 1500 DEG C or more of temperature, (a large amount of volatility are very strong out) is generated in electric furnace
SiO2With Si gas, precipitated after gas discharge with (rapid) the oxidation condensation of air, it is microcosmic lower for diameter 300nm or so
Medicine ball, SiO2Mass percentage >=97%；It is public that the silicon ash can be the bright day comprehensive utilization of resources Limited Liability in Sichuan
Take charge of 97 grades of 95 grades of silicon ashes, 97 grades of silicon ashes of Chengdu Jin Xiang Science and Technology Ltd. or Ai Ken Elken company, Germany silicon ashes.
In above-described embodiment: the main chemical compositions and weight percent group of metakaolin described in step a become
SiO250~55%, Al2O340~45%, other (microcomponent such as Fe2O3、Na2O、K2O, CaO etc.) 3%~5%；It is described
Metakaolin is the K1300 type metakaolin of Inner Mongolia Chaopai Kaolin Co., Ltd.'s production.
In above-described embodiment: a hydronium(ion) cesium oxide described in step a is chemical pure or technical pure, main chemical compositions
Become CsOH.H with weight percent group2O >=99.9%.
In above-described embodiment: the steam pressure reaction kettle for being built-in with blender is the global chemical machinery Co., Ltd in Weihai
GSH type reaction kettle.The equipment of industrialized production is the GSH type reaction of the global chemical machinery Co., Ltd 100L or more in Weihai
Kettle.
Pollucite tiny balloon made from above-described embodiment is uniform hollow ball shape, hollow bulb diameter in microcosmic lower shape
About 300nm (can be 280~320nm), hollow sphere pore wall thickness are 10~20nm.
In above-described embodiment: used each raw material is commercial product.
In above-described embodiment: it is not specifically specified in used percentage, be weight (quality) percentage or
Well known to a person skilled in the art percentages；Described weight (quality) part can be gram or kilogram.
In above-described embodiment: technological parameter (temperature, time, pressure, revolving speed etc.) and dosage of each component number in each step
Value etc. is range, and any point is applicable.
The technology contents being not specifically delineated in the content of present invention and above-described embodiment are compared with technology.
Above-described embodiment has only selected different hydrothermal temperatures, crystallization time and different mol ratio Cs, Al, Si, carries out caesium boiling
The preparation of stone tiny balloon easily can make difference on the basis of these embodiments for those skilled in the art
Modification, and General Principle described herein is applied in other embodiments need not be by creative labor, therefore, this hair
It is bright to be not limited to the above embodiments；Those skilled in the art's announcement according to the present invention does not depart from the improvement that scope is done
It all should be within protection scope of the present invention with modification.
Claims (5)
1. a kind of preparation method of pollucite tiny balloon, it is characterized in that step are as follows:
A, by 100 parts by weight metakaolins, 25~155 parts by weight silicon ashes, 145 parts by weight, one hydronium(ion) cesium oxide weight proportion
Solid material metakaolin, silicon ash and a hydronium(ion) cesium oxide are taken, is added in the steam pressure reaction kettle for being built-in with blender；
B, by the total weight of solid material metakaolin and silicon ash and a hydronium(ion) cesium oxide: deionized water is the weight of 1:15~20
Amount ratio removes ionized water, and being added in steam pressure reaction kettle becomes liquid-solid mixture, closes steam pressure reaction kettle；
C, liquid is consolidated under conditions of 160~200 DEG C of temperature, 0.6~1.2MPa of pressure, 60~100 rev/min of mixing speed
Mixture reaction 12~for 24 hours, it is cooling, liquid-solid mixture is taken out, filtering, the solid product being obtained by filtration is after washing, dry, i.e.,
Pollucite tiny balloon is prepared.
2. by the preparation method of pollucite tiny balloon described in claim 1, it is characterized in that: in solid material described in step a,
The dosage molar ratio of each element is Cs:Al:Si=1:1:1.5~4.
3. the preparation method of pollucite tiny balloon as claimed in claim 1 or 2 is pressed, it is characterized in that: drying described in step c is to set
The dry 48h in temperature 60 C vacuum oven.
4. the preparation method of pollucite tiny balloon as claimed in claim 1 or 2 is pressed, it is characterized in that: silicon ash described in step a is
When using ferroalloy smelting Antaciron or using quartz and coke smelting commercial silicon, under the conditions of 1500 DEG C or more of temperature,
The SiO generated in electric furnace2With Si gas, precipitated after gas discharge with air oxidation condensation.
5. the preparation method of pollucite tiny balloon as claimed in claim 1 or 2 is pressed, it is characterized in that: higher ridge described in step a
The main chemical compositions and weight percent group of soil become SiO250~55 %, Al2O340~45%, other 3%~5%.
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