CN110127712A - The method that the preparation of ordinary-pressure hydrolysis method has the mesoporous lithium metasilicate hollow sphere of micro-nano structure - Google Patents
The method that the preparation of ordinary-pressure hydrolysis method has the mesoporous lithium metasilicate hollow sphere of micro-nano structure Download PDFInfo
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- CN110127712A CN110127712A CN201910401077.2A CN201910401077A CN110127712A CN 110127712 A CN110127712 A CN 110127712A CN 201910401077 A CN201910401077 A CN 201910401077A CN 110127712 A CN110127712 A CN 110127712A
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- C01B33/00—Silicon; Compounds thereof
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Abstract
A kind of method of mesoporous lithium metasilicate hollow sphere of the ordinary-pressure hydrolysis method preparation with micro-nano structure, the method are as follows: mix na-montmorillonite with 1~5mol/L lithium hydroxide aqueous solution, 12~32h is stirred to react at 100~180 DEG C, it is cooled to room temperature later, it filters, filter cake is washed with deionized to pH=7~8, it is dry to get；Product purity prepared by the present invention is high, preparation process is without adding template, safe and efficient, equipment requirement is low, environmentally protective, the lithium metasilicate hollow ball structure of preparation is formed by 30-50 nanometers of lithium metasilicate little particle ordered fabrication, it is typical micro-nano structure, and form meso-hole structure, hollow sphere homogeneous grain size between little particle assembling, possess biggish specific surface area, reaches as high as 40m2/ g, the dispersibility with height, preparation process is relatively simple, and easily operated, raw materials used nontoxic, sodium-based montmorillonite is huge in China's reserves, and the method fits entirely into industrialized production.
Description
(1) technical field
The present invention relates to the methods that a kind of preparation of ordinary-pressure hydrolysis method has the mesoporous lithium metasilicate hollow sphere of micro-nano structure.
(2) background technique
In recent years, lithium metasilicate (Li2SiO3And Li2SiO4) due to its nontoxic characteristic and be widely applied to obtain
More concerns.Due to its preferable dissolubility to tritium, it is widely used in nuclear industry.In lithium ion battery, often
Lithium ion battery negative material as high capacity.In terms of alleviating greenhouse effects, lithium metasilicate can be used as stable high temperature CO2
Adsorbent and vehicle exhaust filtering agent.It, can anticorrosion, radiation protection, moisture proof etc. in addition, lithium metasilicate is also used for inorganic coating.
The preparation method of document report lithium metasilicate is mainly solid phase method calcination method, hydro-thermal method and sol method.However it is above-mentioned
For method there are the synthesis temperature height of distinct disadvantage, such as solid phase calcination method, the partial size of preparation is big, and it is serious to reunite, and energy consumption is serious.
Hydro-thermal method needs high temperature and pressure, high to water heating kettle equipment requirement, explosion danger easily occurs, is not suitable for industrialized production.It is molten
It is excessively high that glue method prepares lithium metasilicate cost.
The present invention is then directly using nonmetallic mineral na-montmorillonite (Na-MMT) original soil as raw material, abundance, China
Storage level is huge, low in cost, and prepares the mesoporous lithium metasilicate hollow sphere with micro-nano structure, purity is high, especially suitable
For nuclear industry, lithium ion battery and high temperature CO2The fields such as adsorbent.
(3) summary of the invention
It is simple and environmentally-friendly, low in cost that the purpose of the present invention is to provide a kind of processes, the preparation suitable for industrialized production
The method of mesoporous lithium metasilicate hollow sphere with micro-nano structure.
Technical scheme is as follows:
A kind of method of mesoporous lithium metasilicate hollow sphere of the ordinary-pressure hydrolysis method preparation with micro-nano structure, the method are as follows:
Na-montmorillonite (Na-MMT, dried powder) and 1~5mol/L (preferably 3mol/L) lithium hydroxide aqueous solution is mixed
It closes, stirring (recommending stirring rate 1200r/min) reacts 12~32h (preferably under 100~180 DEG C (preferably 100~150 DEG C)
For 24 hours), it is cooled to room temperature (20~30 DEG C), filters later, filter cake is washed with deionized to pH=7~8, dry (to recommend 85
DEG C) to get the mesoporous lithium metasilicate hollow sphere with micro-nano structure；
The volumetric usage of the lithium hydroxide aqueous solution is calculated as 10~100mL/g with the quality of na-montmorillonite, preferably
66.7mL/g。
The main body of technical effect of the preparation method of mesoporous lithium metasilicate hollow sphere of the present invention with micro-nano structure
It is present:
(1) present invention provides a kind of side of mesoporous lithium metasilicate hollow sphere of large scale preparation micro-nano structure at constant temperature and normal pressure
Method.
(2) the mesoporous lithium metasilicate hollow sphere object phase composition of the micro-nano structure prepared is mainly Li2SiO3, purity is higher, with hydrogen
Lithia aqueous solution is solvent without adding template, and simple to heat, safe and efficient, equipment requirement is low, environmentally protective.
(3) the lithium metasilicate hollow ball structure prepared is formed by 30-50 nanometers of lithium metasilicate little particle ordered fabrication, is typical
Micro-nano structure, and little particle assembling between form meso-hole structure.
(4) the mesoporous lithium metasilicate hollow sphere homogeneous grain size of the micro-nano structure prepared, possesses biggish specific surface area, most
High reachable 40m2/ g, the dispersibility with height.
(5) preparation process is relatively simple, easily operated, and raw materials used nontoxic, sodium-based montmorillonite is huge in China's reserves, this
Method fits entirely into industrialized production.
(4) Detailed description of the invention
Fig. 1 is 1 sample XRD spectrum of embodiment.
Fig. 2 is 1 sample surfaces scanning electron microscope diagram of embodiment.
Fig. 3 is 2 sample surfaces scanning electron microscope diagram of embodiment.
Fig. 4 is 3 sample surfaces scanning electron microscope diagram of embodiment.
(5) specific embodiment
Below by specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited in
This.
The na-montmorillonite used in following embodiment is purchased from Sanding Sci. & Tech. Co., Ltd., Zhejiang, model: SD0107B, pure
Degree: 95%.
Embodiment 1
(1) 45.0g na-montmorillonite (Na-MMT) powder (after dry) is accurately weighed, configuration 3000ml concentration is
Lithium hydroxide (LiOH) aqueous solution of 3.0mol/L；
(2) above-mentioned powder, solution being added in 5000mL three-necked flask, setting mechanical stirring speed is 1200r/min,
Being sufficiently stirred is dispersed in montmorillonite powder in solution.Then oil bath temperature is warming up to 150 DEG C, lasting to stir, isothermal reaction
24h；
(3) to the end of reacting, sample is cooled to room temperature, carries out filtering and washing with 10L deionized water after sediment is filtered out,
Diafiltration 5~6 times are repeated to pH until 7~8.Micro-nano structure is obtained after solid sample is dry at 85 DEG C after washing, separation
Mesoporous lithium metasilicate hollow sphere.
Using X ' the Pert PRO type X-ray diffractometer of Dutch PANalytical company to the crystal phase of each stage sample
Composition is characterized, and for result as shown in Figure 1, by matching with XRD standard card, the main object of this sample is mutually Li2SiO3, sample
The microstructure analysis of product is observed using II type field emission scanning electron microscope of HitachiS-4700, as shown in Figure 2.It can from figure
Know, sample is hollow ball-shape, size in 500nm or so, hollow sphere be by the smaller orderly self assembly of lithium metasilicate particle and
At.
Embodiment 2
(1) 45.0g na-montmorillonite (Na-MMT) powder (after dry) is accurately weighed, configuration 3000ml concentration is
Lithium hydroxide (LiOH) aqueous solution of 3.0mol/L；
(2) above-mentioned powder, solution being added in 5000mL three-necked flask, setting mechanical stirring speed is 1200r/min,
Being sufficiently stirred is dispersed in montmorillonite powder in solution.Then oil bath temperature is warming up to 130 DEG C, lasting to stir, isothermal reaction
24h；
(3) to the end of reacting, sample is cooled to room temperature, carries out filtering and washing with 10L deionized water after sediment is filtered out,
Diafiltration 5~6 times are repeated to pH until 7~8.Micro-nano structure is obtained after solid sample is dry at 85 DEG C after washing, separation
Mesoporous lithium metasilicate hollow sphere.
The microstructure analysis of sample is observed using II type field emission scanning electron microscope of HitachiS-4700, such as Fig. 3 institute
Show.It can be seen that sample is hollow ball-shape, for size in 500nm or so, hollow sphere is that had by smaller lithium metasilicate particle
Sequence self assembly forms.
Embodiment 3
(1) 45.0g na-montmorillonite (Na-MMT) powder (after dry) is accurately weighed, configuration 3000ml concentration is
Lithium hydroxide (LiOH) aqueous solution of 3.0mol/L；
(2) above-mentioned powder, solution being added in 5000mL three-necked flask, setting mechanical stirring speed is 1200r/min,
Being sufficiently stirred is dispersed in montmorillonite powder in solution.Then oil bath temperature is warming up to 170 DEG C, lasting to stir, isothermal reaction
24h；
(3) to the end of reacting, sample is cooled to room temperature, carries out filtering and washing with 10L deionized water after sediment is filtered out,
Diafiltration 5~6 times are repeated to pH until 7~8.Micro-nano structure is obtained after solid sample is dry at 85 DEG C after washing, separation
Mesoporous lithium metasilicate hollow sphere.
The microstructure analysis of sample is observed using II type field emission scanning electron microscope of HitachiS-4700, such as Fig. 4 institute
Show.It can be seen that sample is hollow ball-shape, for size in 500nm or so, hollow sphere is that had by smaller lithium metasilicate particle
Sequence self assembly forms.
Comparative example
Document " preparation of kaolin-lithium metasilicate and its CO absorption2Dynamics " propose one kind with kaolin-SiO2Or SiO2
And Li2CO3Dehydrated alcohol, 750 DEG C of calcining 6h are added in grinding.Dipper precipitation method, by LiNO3It is dissolved in dehydrated alcohol, heats, add
Enter kaolin-SiO2Or SiO2, impregnate, ammonium hydroxide be added, stand, unformed bulk is prepared in 750 DEG C or 650-800 DEG C calcinings
Lithium metasilicate sample.
It is needed in method disclosed in comparative example added with dehydrated alcohol as solvent, it is also necessary to add ammonium hydroxide, it is important to need
Calcining could complete.Technology is without reference to being directly obtained with lithium metasilicate for kaolin and lithium source hybrid reaction in comparative example
The technology contents and method of aspect, and the product obtained is not hollow structure.High-temperature calcination energy consumption is very big simultaneously, is calcining
Polluted gas can be also generated in the process, the sample for causing the environmental issues such as secondary pollution, and preparing is random block structure,
Do not have the feature and correlation function of intermediary hole hollow ball-shape structure of the present invention.
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of method that ordinary-pressure hydrolysis method preparation has the mesoporous lithium metasilicate hollow sphere of micro-nano structure, which is characterized in that described
Method are as follows:
Na-montmorillonite is mixed with 1~5mol/L lithium hydroxide aqueous solution, is stirred to react 12~32h at 100~180 DEG C,
Be cooled to room temperature, filter later, filter cake is washed with deionized to pH=7~8, it is dry to get described with micro-nano structure
Mesoporous lithium metasilicate hollow sphere；
The volumetric usage of the lithium hydroxide aqueous solution is calculated as 10~100mL/g with the quality of na-montmorillonite.
2. the method that ordinary-pressure hydrolysis method preparation as described in claim 1 has the mesoporous lithium metasilicate hollow sphere of micro-nano structure,
It is characterized in that, the concentration of the lithium hydroxide aqueous solution is 3mol/L.
3. the method that ordinary-pressure hydrolysis method preparation as described in claim 1 has the mesoporous lithium metasilicate hollow sphere of micro-nano structure,
It is characterized in that, the temperature of the reaction is 100~150 DEG C.
4. the method that ordinary-pressure hydrolysis method preparation as described in claim 1 has the mesoporous lithium metasilicate hollow sphere of micro-nano structure,
It is characterized in that, the rate of the stirring is 1200r/min.
5. the method that ordinary-pressure hydrolysis method preparation as described in claim 1 has the mesoporous lithium metasilicate hollow sphere of micro-nano structure,
It is characterized in that, the time of the reaction is for 24 hours.
6. the method that ordinary-pressure hydrolysis method preparation as described in claim 1 has the mesoporous lithium metasilicate hollow sphere of micro-nano structure,
It is characterized in that, the temperature of the drying is 85 DEG C.
7. the method that ordinary-pressure hydrolysis method preparation as described in claim 1 has the mesoporous lithium metasilicate hollow sphere of micro-nano structure,
It is characterized in that, the volumetric usage of the lithium hydroxide aqueous solution is calculated as 66.7mL/g with the quality of na-montmorillonite.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101652321A (en) * | 2007-02-09 | 2010-02-17 | 国立科学研究中心 | The blended lithium silicates |
| CN105645421A (en) * | 2015-12-30 | 2016-06-08 | 浙江工业大学 | Mesoporous hollow lithium silicate microspheres as well as preparation and application of mesoporous hollow lithium silicate microspheres |
-
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- 2019-05-15 CN CN201910401077.2A patent/CN110127712A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101652321A (en) * | 2007-02-09 | 2010-02-17 | 国立科学研究中心 | The blended lithium silicates |
| CN105645421A (en) * | 2015-12-30 | 2016-06-08 | 浙江工业大学 | Mesoporous hollow lithium silicate microspheres as well as preparation and application of mesoporous hollow lithium silicate microspheres |
Non-Patent Citations (3)
| Title |
|---|
| GEORGINA MONDRAGÓN-GUTIÉRREZ ET AL.: "Low Temperature Synthesis of Li2SiO3: Effect on Its Morphological and Textural Properties", 《RESEARCH LETTERS IN MATERIALS SCIENCE》 * |
| HERIBERTO PFEIER ET AL.: "Synthesis of lithium silicates", 《JOURNAL OF NUCLEAR MATERIALS》 * |
| 张良均 等: "硅酸锂的合成与应用研究", 《现代涂料与涂装》 * |
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Application publication date: 20190816 |