CN101857442B - Preparation method of lithium-based ceramic microsphere - Google Patents

Preparation method of lithium-based ceramic microsphere Download PDF

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Publication number
CN101857442B
CN101857442B CN2010101948605A CN201010194860A CN101857442B CN 101857442 B CN101857442 B CN 101857442B CN 2010101948605 A CN2010101948605 A CN 2010101948605A CN 201010194860 A CN201010194860 A CN 201010194860A CN 101857442 B CN101857442 B CN 101857442B
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preparation
water
microsphere
lithium
based ceramic
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CN101857442A (en
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张迎春
吴泽双
廖璐
林芳弘
万秀娟
葛昌纯
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/10—Nuclear fusion reactors

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Abstract

The invention provides a preparation method of a lithium-based ceramic microsphere, which is mainly used for preparing a tritium breeder in a fusion reactor blanket. The preparation method comprises the following steps: mixing a binder, water and ceramic powder to obtain uniform slurry by ball milling; adding a defoamer, heating in water bath and then forming sol; dripping into a medium mutually exclusive with water by a dispersing device; after the slurry is dispersed in the medium, forming micro-spherical gel; and washing, drying and sintering the microsphere so as to obtain the lithium-based ceramic microsphere. The preparation method of the invention has simple raw material, convenient forming and low cost, and the prepared ceramic microsphere has good sphericity and internal pore structure.

Description

A kind of preparation method of lithium-based ceramic microsphere
Technical field
The invention belongs to the nucleosynthesis field, relate in particular to a kind of preparation method of lithium-based ceramic microsphere, be mainly used in the preparation of tritium multiplication agent in the fusion reactor blanket.
Background technology
The society energy is day by day in short supply, and environment goes from bad to worse, and cleaning, efficient fusion energy receive much concern.The fuel that fusion reactor uses is the deuterium tritium gas, and wherein tritium is few at occurring in nature content.For production and the supplementary question that solves tritium, best bet is to realize that by tritium propagation covering the tritium of fusion reactor itself is self-holding.Tritium propagation is based upon in the nuclear reaction of neutron with lithium:
6Li+n＝ 3H+ 4He+4.5MeV
7Li+n＝ 3H+ 4He+n’-2.9MeV
The tritium multiplication agent that is rich in Li can be divided into liquid tritium multiplication agent and solid-state tritium multiplication agent by form, and wherein solid-state tritium multiplication agent extracts easily and widely used because of at high temperature having satisfactory stability and tritium.In order to guarantee effective release of tritium, solid tritium multiplication agent should be prepared into the grade microballoon, also should satisfy the characteristics such as density is high, intensity is large, open-celled structure is abundant simultaneously.
The preparation methods such as at present existing gel injection, wet method (adding PVA or alginate), molten atomizing, additive is complicated, sphericity is poor, high in cost of production is not enough, is difficult to reach requirement but have.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of lithium-based ceramic microsphere.Good sphericity, intensity is high, cost is low lithium-based ceramic microsphere can be prepared by present method, are used for fusion reactor blanket, and can be mass.
A kind of preparation method of lithium-based ceramic microsphere specifically may further comprise the steps:
(1) preparation slip: composition and the shared total mass per-cent of the raw material of preparation slip are: binding agent 0.5%～3%, water 50%～80%, ceramic powder 20%～50%.After described binding agent, water and ceramic powder mixing, carry out ball milling, obtain distributed slurry.
(2) preparation colloidal sol: after adding defoamer in the distributed slurry that is made by step (1), with the slurry water-bath, and constantly stir, obtain colloidal sol.
(3) microsphere gel: the colloidal sol that will be made by step (2) splashes in cold and the medium water mutual exclusion with diverting device, and sol solutions drops in the medium because surface tension is microspheroidal, solidifies rapidly, forms microsphere gel.
(4) with described microsphere gel with organic solvent washing and drying after, in high temperature sintering furnace, carry out sintering, make lithium-based ceramic microsphere.
Binding agent in the described step (1) is agar powder; Described ceramic powder is Li 2TiO 3, L 4SiO 4, LiAlO 2Or Li 2ZrO 3
In the described step (1), be with mixed slip on planetary ball mill with 350 rev/mins of ball millings 30 minutes.
In the described step (2), defoamer is 0.01～2% of slip total mass, and the bath temperature of slurry is 80 ℃～90 ℃, and the water-bath time is 25～50 minutes.
In the described step (3), medium temperature is-20 ℃～30 ℃.
In the described step (2), the add-on of defoamer is 0.01%, and the bath temperature of slurry is 85 ℃, and the water-bath time is 30 minutes.
Principle of the present invention is: contain a kind of gelifying agent agarose in the agar powder, it is dissolved in hot water, and solvent temperature is 80 ℃～90 ℃, and dissolving just can form colloidal sol after for some time, when being cooled to 37 ℃ or just can form rapidly gel when following.Therefore use agar powder as binding agent, same ceramic powder, solvent are uniformly mixed to form slip, formed colloidal sol in 30 minutes 85 ℃ of water-baths, in order to form the microspheroidal gel, also need colloidal sol is distributed in the medium with the solvent mutual exclusion, the colloidal sol drop is because surface tension forms the microspheroidal gel, and this gel ball has possessed some strength.Just can prepare lithium-based ceramic microsphere by further washing, drying and sintering process.
The invention has the advantages that:
(1) raw material required for the present invention is simple, only needs binding agent, defoamer, water, ceramic powder just can finally make microballoon; The quality reduction is little in the sintering process, only is 5%.
(2) the colloidal sol ball solidifies rapidly, be distributed in the medium after 5-10 just can form the gel ball with some strength in second, greatly dwindled the volume of microballoon collection device.
(3) the sphere diameter size is decided according to nozzle, thereby can prepare the microballoon of all size, and technique is flexible.
Embodiment
Embodiment 1
Li 2TiO 3The preparation of microballoon
(1) selecting agar powder is binding agent, and water is solvent.With both and Li 2TiO 3Powder mixes, and wherein agar powder accounts for the 1wt% of oeverall quality, and water accounts for the 66wt% of oeverall quality, Li 2TiO 3Powder accounts for the 33wt% of oeverall quality.With mixed solution on planetary ball mill with 350 rev/mins rotating speed ball milling 30 minutes, make distributed slurry.
(2) add 0.08% the defoamer isooctyl alcohol that accounts for oeverall quality in the distributed slurry, again in 85 ℃ of water-baths 30 minutes, and constantly stir, make colloidal sol.
(3) colloidal sol is splashed into by diverting device in 20 ℃ the methyl-silicone oil.
(4) leave standstill 30 minutes after, with microballoon washing, dry, sintering, make the Li of 0.5-1.5mm 2TiO 3Microballoon.
Embodiment 2
Li 4SiO 4The preparation of microballoon
(1) selecting agar powder is binding agent, and water is solvent.With both and Li 4SiO 4Powder mixes, and wherein agar powder accounts for the 1wt% of oeverall quality, and water accounts for the 64wt% of oeverall quality, Li 4SiO 4Powder accounts for the 35wt% of oeverall quality.With mixed solution on planetary ball mill with 350 rev/mins rotating speed ball milling 30 minutes, make distributed slurry.
(2) add 0.09% the defoamer isooctyl alcohol that accounts for oeverall quality in the distributed slurry, again in 85 ℃ of water-baths 30 minutes, and constantly stir, make colloidal sol.
(3) colloidal sol is splashed into by diverting device in-20 ℃ the methyl-silicone oil.
(4) leave standstill 30 minutes after, with microballoon washing, dry, sintering, make the Li of 0.5-1.5mm 4SiO 4Microballoon.
Embodiment 3
LiAlO 2The preparation of microballoon
(1) selecting agar powder is binding agent, and water is solvent.With both and LiAlO 2Powder mixes, and wherein agar powder accounts for the 1.2wt% of oeverall quality, and water accounts for the 75.8wt% of oeverall quality, LiAlO 2Powder accounts for the 23.0wt% of oeverall quality.With mixed solution on planetary ball mill with 350 rev/mins rotating speed ball milling 30 minutes, make distributed slurry.
(2) add 0.01% the defoamer isooctyl alcohol that accounts for oeverall quality in the distributed slurry, again in 85 ℃ of water-baths 30 minutes, and constantly stir, make colloidal sol.
(3) colloidal sol is splashed into by diverting device in 0 ℃ the methyl-silicone oil.
(4) leave standstill 30 minutes after, with microballoon washing, dry, sintering, make the LiAlO of 0.5-1.5mm 2Microballoon.
Embodiment 4
Li 2ZrO 3The preparation of microballoon
(1) selecting agar powder is binding agent, and water is solvent.With both and Li 2ZrO 3Powder mixes, and wherein agar powder accounts for the 0.9wt% of oeverall quality, and water accounts for the 58.5wt% of oeverall quality, Li 2ZrO 3Powder accounts for the 40.6wt% of oeverall quality.With mixed solution on planetary ball mill with 350 rev/mins rotating speed ball milling 30 minutes, make distributed slurry.
(2) add 0.12% the defoamer isooctyl alcohol that accounts for oeverall quality in the distributed slurry, again in 85 ℃ of water-baths 30 minutes, and constantly stir, make colloidal sol.
(3) colloidal sol is splashed into by diverting device in 10 ℃ the methyl-silicone oil.
(4) leave standstill 30 minutes after, with microballoon washing, dry, sintering, make the Li of 0.5-1.5mm 2ZrO 3Microballoon.

Claims (4)

1. the preparation method of a lithium-based ceramic microsphere is characterized in that, may further comprise the steps:
(1) preparation slip: composition and the shared total mass per-cent of the raw material of preparation slip are: binding agent 0.5～3%, water 50～75.8%, ceramic powder 20～50%, and each percentage composition sum is 100%; Described binding agent is agar powder; Described ceramic powder is Li 2TiO 3, Li 4SiO 4, LiAlO 2Or Li 2ZrO 3, after described binding agent, water and ceramic powder mixing, carry out ball milling, obtain distributed slurry;
(2) preparation colloidal sol: after adding the defoamer isooctyl alcohol in the distributed slurry that is made by step (1), with the slurry water-bath, and constantly stir, obtain colloidal sol; Described bath temperature is 80 ℃～90 ℃, and the water-bath time is 25～50 minutes;
(3) microsphere gel: the colloidal sol that will be made by step (2) splashes in cold and the medium methyl-silicone oil water mutual exclusion with diverting device, the temperature of described medium is-20 ℃～30 ℃, sol solutions drops in the medium and is microspheroidal owing to surface tension, solidifies rapidly, forms microsphere gel;
(4) with described microsphere gel with organic solvent washing and drying after, in high temperature sintering furnace, carry out sintering, make lithium-based ceramic microsphere.
2. the preparation method of a kind of lithium-based ceramic microsphere as claimed in claim 1 is characterized in that: in the described step (1), be with mixed slip on planetary ball mill with 350 rev/mins, ball milling 30 minutes.
3. the preparation method of a kind of lithium-based ceramic microsphere as claimed in claim 1, it is characterized in that: in the described step (2), defoamer is 0.01%～2% of slip total mass.
4. such as the preparation method of each described a kind of lithium-based ceramic microsphere in the claims 1 to 3, it is characterized in that: in the described step (2), the bath temperature of slurry is 85 ℃, and the water-bath time is 30 minutes.
CN2010101948605A 2010-05-28 2010-05-28 Preparation method of lithium-based ceramic microsphere Expired - Fee Related CN101857442B (en)

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Publication number Priority date Publication date Assignee Title
CN102731111B (en) * 2012-07-05 2014-01-15 北京科技大学 Novel preparation method of ceramic microspheres
CN103708419B (en) * 2013-12-27 2015-03-11 北京科技大学 Method for preparing of high-activity LiH microspheres through wet process
CN104387043B (en) * 2014-10-27 2016-04-27 北京科技大学 A kind of preparation method of the graded ceramics microballoon based on lithium silicate
CN107140953B (en) * 2017-04-18 2019-11-22 华中科技大学 A kind of method that quick extrusion prepares ceramic microsphere
CN107010955B (en) * 2017-05-08 2019-08-06 中国科学院上海应用物理研究所 A kind of preparation method of the ceramic microsphere of thorium oxide

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5676919A (en) * 1994-11-30 1997-10-14 Japan Atomic Energy Research Institute Method for producing sintered lithium oxide granules
FR2761057A1 (en) * 1997-03-21 1998-09-25 Genshi Nenryo Kogyo Lithium titanate chips preparation by gel precipitation method
FR2845080A1 (en) * 2002-08-27 2004-04-02 Ngk Insulators Ltd Tritium-generating fertile material useful in breeder blankets in nuclear fusion reactors comprises lithium titanate doped with an oxide
JP2004143036A (en) * 2002-08-30 2004-05-20 Ngk Insulators Ltd Method for manufacturing lithium titanate minute sphere
CN101062865A (en) * 2007-06-20 2007-10-31 中国原子能科学研究院 Li4SiO4Preparation process of ceramic ball

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Publication number Priority date Publication date Assignee Title
JP4017229B2 (en) * 1998-01-20 2007-12-05 独立行政法人 日本原子力研究開発機構 Method for producing fine sintered particles of lithium zirconate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5676919A (en) * 1994-11-30 1997-10-14 Japan Atomic Energy Research Institute Method for producing sintered lithium oxide granules
FR2761057A1 (en) * 1997-03-21 1998-09-25 Genshi Nenryo Kogyo Lithium titanate chips preparation by gel precipitation method
FR2845080A1 (en) * 2002-08-27 2004-04-02 Ngk Insulators Ltd Tritium-generating fertile material useful in breeder blankets in nuclear fusion reactors comprises lithium titanate doped with an oxide
JP2004143036A (en) * 2002-08-30 2004-05-20 Ngk Insulators Ltd Method for manufacturing lithium titanate minute sphere
CN101062865A (en) * 2007-06-20 2007-10-31 中国原子能科学研究院 Li4SiO4Preparation process of ceramic ball

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