CN106507789B - A kind of preparation method of Li4SiO4 multiplication agents ball - Google Patents
A kind of preparation method of Li4SiO4 multiplication agents ballInfo
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- CN106507789B CN106507789B CN200910123914.6A CN200910123914A CN106507789B CN 106507789 B CN106507789 B CN 106507789B CN 200910123914 A CN200910123914 A CN 200910123914A CN 106507789 B CN106507789 B CN 106507789B
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Abstract
The present invention relates to a kind of Li4SiO4The preparation method of multiplication agent ball, belongs to energy and material nuclear material field.The present invention is successfully prepared Li using soft chemical method (i.e. water-based sol-gel method)4SiO4Ceramic Balls.The present invention with solubility lithium-containing compound and aerosil as raw material, with citric acid as chelating agent and solution pH adjusting agent, with deionized water as reaction medium, with acetone or dehydrated alcohol as coagulation bath, prepare gel ball；Gel ball finally gives Li through steps such as ageing, drying, low temperature presintering, high temperature sinterings4SiO4Ceramic Balls.Li prepared by the present invention4SiO4Ceramic Balls phase purity is high, and good sphericity is uniform in size, and consistency is higher, disclosure satisfy that the demand of application.
Description
Technical field
The present invention relates to a class Li is prepared with soft chemical method4SiO4The new method of Ceramic Balls, belongs to energy and material core
Material Field.
Technical background
In thermonuclear fusion reactor, in order to maintain the lasting progress of fusion reaction, it is necessary to constantly supplement raw material
Deuterium (D) and tritium (T).Wherein, deuterium (D) can be extracted from seawater, and rich reserves, and nature
In there's almost no tritium (T), current effective method is to breed tritium with neutron irradiation ceramics containing lithium.
Positive lithium metasilicate (Li4SiO4) there is higher lithium atom density, its tritium release performance is excellent and through neutron spoke
The radioactive pollutant of long half time will not be produced according to during, thus is considered as to have to increase using the tritium of future very much
Grow agent material.China is in the design that tritium breeds module (TBM), also by Li4SiO4Increase as preferred tritium
Grow agent material.
The shape that multiplication agent is used mainly has column, ring-type and spherical.Due to spherical multiplication agent have handling easily,
Permeability is good, is conducive to diffusion, the release of produced tritium.Reduction thermal stress is also helped using spherical, because
And when carrying tritium online, the shape that multiplication agent is used is mainly spherical.Li is prepared at present4SiO4The method of Ceramic Balls
Mainly molten atomizing method.The method needs to use complex device, is mainly made up of four parts：Calandria,
Dispenser, air gun and collector.Basic technology is as follows：First by raw materials used (Li4SiO4+SiO2Or
Li2CO3+SiO2Or LiOH+SiO2) uniform mixing according to a certain percentage, it is placed in platinum crucible；Then
The platinum crucible that will be equipped with raw material is put into heating in electric furnace until raw material is completely melt (1450 DEG C) and is incubated；It is logical
Cross a vertical dispenser slowly to ooze the raw material being completely melt, and lead on the direction vertical with dispenser
Air nozzle is crossed to spray 400 DEG C or so of stream of hot air to purge the fused raw material dripped, the original of such molten state
Feed liquid drop will be dispelled into droplet of different sizes, and the droplet of the molten state temperature during purging is anxious
Play declines and is frozen into bead；The Li of solidification is collected finally by collector4SiO4Or Li4SiO4+SiO2
Bead.
Molten atomizing method needs the temperature to reach more than 1450 DEG C of high temperature furnace, 400 DEG C of hot-air, resistance to height
The dispenser of temperature, the expensive device such as collector, thus the production cost of this method is of a relatively high, limits it
Extensive use and large-scale production.
Goal of the invention
The purpose of the present invention explores a kind of can prepare with enough consistency and good sphericity
Li4SiO4The method of Ceramic Balls, and the method explored is simple to operate, it is with low cost, it is easy to promote and advise
Modelling is produced.
The Li of the present invention4SiO4The preparation method of multiplication agent ball, it is characterised in that comprise the steps：
(1) soluble lithium-containing compound is dissolved in deionized water, and adds citric acid (C6H8O7·H2O)
To adjust the pH value of solution；
(2) it is 3.4-4.6 according to Li/Si atomic ratios, SiO is added into above-mentioned settled solution2Aeroge,
And continuous agitating solution；
(3) evaporation solvent is until generate transparent colloidal sol；
(4) colloidal sol is added dropwise in coagulation bath, colloidal sol drop dehydration is solidified to form gel ball, coagulation bath
For acetone or absolute ethyl alcohol；
(5) gel ball obtains the present invention's after ageing, drying, low temperature presintering, high temperature sintering
Li4SiO4Ceramic Balls.
Li is prepared present invention employs sol-gel technique4SiO4Ceramic Balls, respectively with soluble lithium-containing compound
(such as LiOH or CH3COOLi or LiNO3) and aerosil (SiO2) it is raw material, with C6H8O7Make
For complexing agent, using deionized water as reaction medium, coagulation bath is used as using acetone or absolute ethyl alcohol.Technical process
It is as follows：1. by LiOH (or CH3COOLi or LiNO3) be dissolved in deionized water, and add citric acid
(C6H8O7·H2O) come adjust solution pH be 6~10.5；2. SiO is added into above-mentioned settled solution2Gas
Gel (Li/Si atomic ratios are 3.4~4.6) is simultaneously stirred continuously, and now obtains showing slightly milky colloidal solution；
3. at 50~90 DEG C evaporation solvent until generating transparent colloidal sol；4. the colloidal sol is added dropwise to acetone (or anhydrous second
Alcohol) in, under surface tension and the dehydration of acetone (or absolute ethyl alcohol), the dehydration of colloidal sol drop solidification and
Form gel ball；5. gel ball ageing 5~12 hours in the acetone (or absolute ethyl alcohol) is certain to obtain
Intensity；6. gel ball is placed in 100~180 DEG C of baking oven and dried；7. dried gel ball is existed
Pre-burning 1.5~4 hours at 320~400 DEG C, so as to remove organic matter；8. the gel ball after pre-burning is at 700~1000 DEG C
Lower sintering just obtains Li in 2~8 hours4SiO4Ceramic Balls.Lithium salts used in the present invention can also be extended to other
Soluble lithium salt.This method has advantages below：Used low in raw material price, is easy to get；Easily operation,
Preparation process is simple；Expensive device is not needed, is adapted to promote and large-scale production.
Brief description of the drawings
Fig. 1 for the present invention in sol-gal process prepare Li4SiO4The process chart of Ceramic Balls.
Fig. 2 is the gel ball that is prepared with the sol-gal process dried shape appearance figure at 150 DEG C in the present invention.
Fig. 3 sintered for the gel ball for preparing in the present invention at 900 DEG C after 4h obtained by Li4SiO4Ceramic Balls
Shape appearance figure.
Fig. 4 is sinters 4 hours with the gel ball obtained by sol-gal process at 700 DEG C in the present invention after
XRD spectrum.
Fig. 5 is sinters 4 hours with the gel ball obtained by sol-gal process at 1000 DEG C in the present invention after
XRD spectrum.
Fig. 6 is the Li for preparing in the present invention4SiO4The scanning on Ceramic Balls surface after being sintered 4 hours at 850 DEG C
Electromicroscopic photograph.Ceramic ball surface has more stomata and fractue spacing, and this is conducive to material to produce tritium (T) tritium afterwards
(T) and helium (He) release.The presence of these stomatas is also the conduction of generation heat during neutron irradiation
There is provided passage, so as to be conducive to reducing the thermal stress in Ceramic Balls.
Embodiment
For the content of the invention, substantive features and the marked improvement of the present invention can be expanded on further, following comparison is hereby enumerated
Example and embodiment describe in detail as follows：
It is used as the comparative example 1 of the present invention：Li is prepared using molten atomizing method reported in the literature4SiO4Ceramic Balls.
By LiOH (analysis is pure) and SiO2(analysis is pure) is well mixed according to certain proportioning；Will be mixed uniformly
Presoma, which is put into high temperature furnace, to be heated to 1450 DEG C and is incubated 1 hour, and now raw material is melted completely；Pass through one
Individual vertical dispenser slowly oozes the raw material being completely melt, and in the side vertical with dispenser upwardly through sky
Gas jets spray 400 DEG C of stream of hot air to purge the fused raw material dripped；Collected finally by collector scattered
Fall the droplet solidified in atmosphere and rapidly.
It is used as embodiments of the invention 1：Li is prepared according to Fig. 1 (a) technological process4SiO4Ceramic Balls.First
LiOH is dissolved in deionized water, and is 8.5 with the pH of citric acid regulating solution；Add stoichiometric proportion
SiO2Aeroge (i.e. atomic ratio：Li/Si=4) and it is stirred continuously；Evaporation solvent at 70 DEG C is until generate transparent
Colloidal sol；The colloidal sol is added dropwise in acetone soln, cured formation gel ball；Gel ball is aged in acetone
It is dried after 6 hours at 150 DEG C；Desiccant gel ball pre-burning 2 hours at 380 DEG C, then at 900 DEG C
Lower sintering just obtains Li in 4 hours4SiO4Ceramic Balls.A diameter of 1.2mm of Ceramic Balls or so, relative density
For 75%.Fig. 2 and Fig. 3 sets forth the exterior appearance of desiccant gel ball and sintering Ceramic Balls.Sent out with this
Li prepared by the sol-gal process in bright4SiO4The sphericity of Ceramic Balls is preferable, and uniform in size.
Comparative examples 1 and embodiment 1, it is found that the present invention has advantages below：1. 1450 DEG C are not needed
High temperature, it is not required that 400 DEG C of stream of hot air, greatly save the energy；2. need not such as molten atomizing
Special device as method；3. raw material is easy to get, simple to operate, with low cost, is easy to promote.
It is used as embodiments of the invention 2：LiOH is dissolved in deionized water, adjusts above-mentioned with citric acid solution
The pH value of solution is 6.5, remaining preparation process be the same as Example 1.Prepared Li4SiO4Ceramic Balls it is relative
Consistency is 40%.
It is used as embodiments of the invention 3：LiOH is dissolved in deionized water, adjusts above-mentioned with citric acid solution
The pH value of solution is 8.5, adds SiO2Aeroge makes Li and Si atomic ratio be 3.6, other technological parameters
Be the same as Example 1.After Ceramic Balls are sintered 4 hours at 900 DEG C, its principal crystalline phase is Li4SiO4Phase, is only existed
A small amount of Li2SiO3Phase.
It is used as embodiments of the invention 4：LiOH is dissolved in deionized water, adjusts above-mentioned with citric acid solution
The pH value of solution is 8.5, adds SiO2Aeroge makes Li and Si atomic ratio be 4.4, other technological parameters
Be the same as Example 1.It was found that, after Ceramic Balls are sintered 4 hours at 900 DEG C, its principal crystalline phase is Li4SiO4
Phase, only exists a small amount of Li2O phases.
It is used as embodiments of the invention 5：LiOH is dissolved in deionized water, adjusts above-mentioned with citric acid solution
The pH value of solution is 8.5, adds SiO2Aeroge makes Li and Si atomic ratio be 4 (stoichiometric proportions).
The preparation process of gel ball and pre-sintered process be the same as Example 1.It is small that bead after pre-burning sinters 4 at 700 DEG C
When, its phase composition is detected with X-ray diffraction method.Gained diffracting spectrum is as shown in Figure 4.It can be seen that, Ceramic Balls
After being sintered at 700 DEG C, obtain for single-phase Li4SiO4。
It is used as embodiments of the invention 6：LiOH is dissolved in deionized water, adjusts above-mentioned with citric acid solution
The pH value of solution is 8.5, adds SiO2Aeroge makes Li and Si atomic ratio be 4 (stoichiometric proportions).
The preparation process of gel ball and pre-sintered process be the same as Example 1.Bead after pre-burning sinters 6 at 1000 DEG C
Hour, its phase composition is detected with X-ray diffraction method.Gained diffracting spectrum is as shown in Figure 5.As can be seen that
When sintering temperature brings up to 1000 DEG C, the second a small amount of phase Li is only existed in Ceramic Balls2SiO3。
It is used as embodiments of the invention 7：LiOH is dissolved in deionized water, adjusts above-mentioned with citric acid solution
The pH value of solution is 8.5, adds SiO2Aeroge makes Li and Si atomic ratio be 4 (stoichiometric proportions).
The preparation process of gel ball and pre-sintered process be the same as Example 1.It is small that bead after pre-burning sinters 4 at 950 DEG C
When.Resulting Li4SiO4The relative density of Ceramic Balls has reached 78%.
It is used as embodiments of the invention 8：Use CH3COOLi substitutions LiOH is used as lithium source.Use CH3COOLi
When making lithium source, because acetate has complexing power, and CH in itself3COOLi solution is in alkalescent, thus
Complexing agent and regulation pH value need not be made with citric acid.The technological process of ball processed is similar to Example 1.As a result
Show, use CH instead3COOLi makees also can successfully prepare Li after lithium source4SiO4Ceramic Balls.
Claims (8)
1. a kind of Li4SiO4The preparation method of multiplication agent ball, it is characterised in that comprise the steps：
(1) soluble lithium-containing compound is dissolved in deionized water, and adds citric acid (C6H8O7·H2O)
To adjust the pH value of solution；
(2) it is 3.4-4.6 according to Li/Si atomic ratios, SiO is added into above-mentioned settled solution2Aeroge, not
Disconnected agitating solution；
(3) evaporation solvent is until generate transparent colloidal sol；
(4) colloidal sol is added dropwise in coagulation bath, colloidal sol drop dehydration is solidified to form gel ball, coagulation bath is third
Ketone or absolute ethyl alcohol；
(5) gel ball obtains the present invention's after ageing, drying, low temperature presintering, high temperature sintering
Li4SiO4Ceramic Balls.
2. a kind of Li as described in claim 14SiO4The preparation method of multiplication agent ball, it is characterised in that described can
Dissolubility lithium-containing compound is LiOH or CH3COOLi or LiNO3。
3. a kind of Li as described in claim 1 or 24SiO4The preparation method of multiplication agent ball, it is characterised in that described
Solution pH value be 6-10.5.
4. a kind of Li as described in claim 1 or 24SiO4The preparation method of multiplication agent ball, it is characterised in that described
Evaporation solvent when temperature be 50-90 DEG C.
5. a kind of Li as described in claim 1 or 24SiO4The preparation method of multiplication agent ball, it is characterised in that described
Gel ball aging condition be -60 DEG C of room temperature at be aged 5-12 hours.
6. a kind of Li as described in claim 1 or 24SiO4The preparation method of multiplication agent ball, it is characterised in that described
Gel ball drying condition be 100-180 DEG C at dry 10-48 hours.
7. a kind of Li as described in claim 1 or 24SiO4The preparation method of multiplication agent ball, it is characterised in that described
Gel ball low temperature presintering condition be 320-400 DEG C at sinter 1.5-4 hours.
8. a kind of Li as described in claim 1 or 24SiO4The preparation method of multiplication agent ball, it is characterised in that described
Ceramic Balls high temperature sintering condition be 700-1000 DEG C at sinter 2-8 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910123914.6A CN106507789B (en) | 2009-11-30 | 2009-11-30 | A kind of preparation method of Li4SiO4 multiplication agents ball |
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| CN200910123914.6A CN106507789B (en) | 2009-11-30 | 2009-11-30 | A kind of preparation method of Li4SiO4 multiplication agents ball |
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| CN106507789B true CN106507789B (en) | 2012-10-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437871A (en) * | 2018-12-13 | 2019-03-08 | 西北有色金属研究院 | A kind of preparation method of porous positive silicic acid lithium material |
-
2009
- 2009-11-30 CN CN200910123914.6A patent/CN106507789B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437871A (en) * | 2018-12-13 | 2019-03-08 | 西北有色金属研究院 | A kind of preparation method of porous positive silicic acid lithium material |
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