CN102584018B - A kind of method of preparing high-radioactivity effluent glass-ceramic solidified body in microwave process - Google Patents
A kind of method of preparing high-radioactivity effluent glass-ceramic solidified body in microwave process Download PDFInfo
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Abstract
The invention discloses a kind of method of preparing high-radioactivity effluent glass-ceramic solidified body in microwave process, belong to field of new.It is for raw material with one or more in calcium titanate, zirconium silicate, calcium carbonate, titanium oxide, zirconium white and silicon oxide, take microwave as heating source, using Graphite Powder 99 or silicon carbide powder as sintering agent, first low-temperature microwave volume reduction treatment is carried out to high activity liquid waste, then at high temperature calcine, prepare associated mineral cured body, finally carry out vitrifying process, cured body volume is reduced further.The inventive method energy consumption is few, and technique is simple, and production cost is low.
Description
Technical field
The present invention relates to a kind of method of preparing high-radioactivity effluent glass-ceramic solidified body in microwave process.Be specifically related to a kind of method taking microwave as heating source and prepare high activity liquid waste associated mineral glass-ceramic cured body.
Background technology
Along with nuclear industry develops rapidly, a large amount of level radioactive nuclear waste will be produced, how process the bottleneck that these nuke rubbish have become the development of restriction nuclear industry safely and effectively.More feasible method is that the mode adopting lattice to replace radionuclide is solidificated in ceramic body, prove after deliberation under geological disposal is no more than 400 DEG C of conditions, zirconolite is comparatively excellent of ceramic solidification body, but real high activity liquid waste nucleic kind is many, and single curing substrate cannot meet.Therefore, whole components that the form adopting many substrate combination mineral of stable performance to solidify can be solidifying much waster liquid based, and relative to glass-based cured body, there is the advantages such as solidification content is high, stable chemical performance, mechanical property are strong, radiation resistance is good.
The routine method of preparing cured body such as isostatic pressing method, cold sintering and discharge plasma sintering process etc. also exist that synthesis temperature is high, the time is long, energy consumption is high and the shortcoming such as technical sophistication, and microwave heating technique because its rate of heating is fast, homogeneous heating, synthesis temperature are low, efficient energy-saving, the advantage such as safe and harmless, developed rapidly in ceramic preparation industry in nearly 30 years.
2 are had as the domestic patent in high-level waste curing substrate aspect at present using glass.Chinese patent CN101857355A discloses a kind of production method of the granulated glass sphere for solidifying high radioactive nucleus waste, the method is by heating raw materials, clarification, put into granulated glass sphere electric heating rotary furnace rolling balling shape after adding wood charcoal powder, carbon black mixing, more finally prepare nuke rubbish curing glass pearl through annealing and cooling; Chinese patent CN101826376A discloses a kind of preparation method for active nucleus waste matter vitrification base material, and this patent adopts (NH
4) H
2pO
4, Fe
2o
3, H
3bO
3for raw material, through preparing burden, mixing, at the temperature of 1100 DEG C ~ 1250 DEG C, melting is after 2 ~ 3.5 hours, then obtains through shaping and annealing the glass solidified body being base material with iron boron phosphorus system glass.But glass baseplate cured body is lower relative to its mechanical stability of ceramic base material cured body, radiation-resistant property, chemical stability and thermostability, be unfavorable for long-term geological disposal.
2 are had with the domestic patent of ceramic base material cured high-level waste.Chinese patent CN1767077 discloses a kind of preparation method of high radioactive waste curing treatment base material, and this patent is with natural zircon, CaCO
3and TiO
2for raw material, at the temperature lower calcination 20 ~ 60 minutes of 1150 DEG C ~ 1350 DEG C after fine grinding, vibration, prepare the prosthetic graft cured body of zirconolite and aspidelite; Chinese patent CN101070243 discloses a kind of synthetic method of aspidelite, this patent with calcium carbonate, titanium dioxide, be raw material with silicon-dioxide or metasilicic acid, after batching, fine grinding, oven dry, at the temperature lower calcination 30-60 minute of 1100 DEG C ~ 1350 DEG C, obtain highly purified aspidelite.But adopt common Electric Cooker high for cured body power consumption, heat, cool length consuming time, the high needs that can not meet society of production cost.
Summary of the invention
The object of this invention is to provide a kind of energy consumption few, technique is simple, and production cost is low, has the method preparing highly active waste glass-ceramic cured body of excellent physical, chemistry and mechanical property.
The present invention adopts microwave method process highly active waste, make high activity liquid waste subtract appearance and ceramic solidification combine, the pollution caused when decreasing more exchange device and waste, and can complete in same equipment, only temperature condition need be regulated to reach and subtract the effect held with solidification.The microwave treatment of high activity liquid waste is divided into two stages: the first stage is the volume reduction treatment of high activity liquid waste, namely change the water in high activity liquid waste and most of acid ion into gas form under cryogenic to discharge, small part acid ion changes small molecules form into; Subordinate phase is solidification treatment, namely makes radionuclide ion enter the intracell of curing substrate in the mode replaced under the high temperature conditions, finally carries out vitrifying process, the volume of cured body is reduced further.
A method for preparing high-radioactivity effluent glass-ceramic solidified body in microwave process, comprises the following steps successively:
A, raw material mix: by several sintering agent powder adding high activity liquid waste and massfraction 1 ~ 2% in calcium titanate, zirconium silicate, calcium carbonate, titanium oxide, zirconium white and silicon oxide, put into after Ball-stirring mill mixes and be positioned over corundum crucible;
B, raw material depickling: the crucible holding raw material is placed in microwave agglomerating furnace, temperature is risen to 600 ~ 800 DEG C, insulation 30 ~ 60min, the acid ion in removing high activity liquid waste;
C, high-level waste solidification sintering: the temperature of microwave agglomerating furnace is risen to 1300 ~ 1500 DEG C, insulation 1 ~ 3h;
D, the vitrifying of high-level waste cured body: the temperature of microwave agglomerating furnace is dropped to 600 ~ 800 DEG C, after insulation 1 ~ 2h, microwave power is reduced to 0W, makes sample naturally cool to room temperature.
beneficial effectcompared with prior art, tool of the present invention has the following advantages:
the microwave heating adopted has that rate of heating is fast, power consumption less, cleanliness without any pollution and the advantage such as production cost is low, relative to circuit common type of heating, rapidly and efficiently can solidify active nucleus waste matter at short notice;
high activity liquid waste volume reduction treatment and nucleic are solidified and unite two into one, technique is simple, decreases artifact pollution in the pollution of environment and operating process;
adopt polycomponent curing substrate, the multiple radionuclide of concurrently curable;
curing substrate adopts vitrifying process, reduces cured body volume, cost-saving for storing.
Embodiment
Adopt in calcium titanate, zirconium silicate, calcium carbonate, titanium oxide, zirconium white and silicon oxide two or more be combined as raw material, take microwave as heating source, add sintering agent, highly active waste associated mineral cured body is prepared at 3 ~ 6 hours, solidification content 20 ~ 40%, comprise the following steps successively: A, raw material mix: by several sintering agent powder adding high activity liquid waste and massfraction 1 ~ 2% in calcium titanate, zirconium silicate, calcium carbonate, titanium oxide, zirconium white and silicon oxide, put into after Ball-stirring mill mixes and be positioned over corundum crucible; B, raw material depickling: the crucible holding raw material is placed in microwave agglomerating furnace, temperature is risen to 600 ~ 800 DEG C, insulation 30 ~ 60min, the acid ion in removing high activity liquid waste; C, high-level waste solidification sintering: the temperature of microwave agglomerating furnace is risen to 1300 ~ 1500 DEG C, insulation 1 ~ 3h; D, the vitrifying of high-level waste cured body: the temperature of microwave agglomerating furnace is dropped to 600 ~ 800 DEG C, after insulation 1 ~ 2h, microwave power is reduced to 0W, makes sample naturally cool to room temperature.
Below in conjunction with concrete embodiment, the invention will be further described.
embodiment 1.zirconolite-calcium titanate associated mineral preparation:
Raw material: CaCO
320.6%, ZrO
225.1%, TiO
233.3%; High activity liquid waste type: Zr ion, Mo ion, Ru ion, Pd ion, Np ion, Pu ion, nitrate ion, oxalate denominationby; Sintering agent: Graphite Powder 99 1%.
Pour raw material, sintering agent powder into corundum crucible after fully mixing with high activity liquid waste, regulate microwave power, make temperature-stable at 800 DEG C, be incubated 30 minutes.Raise microwave power, make temperature rise to 1400 DEG C, be incubated 3 hours.Reduce microwave power at 600 DEG C, be incubated 2 hours.Microwave power is down to 0W, until temperature drops to room temperature.The cured body prepared is zirconolite-calcium titanate associated mineral cured body.
embodiment 2.zirconolite-calcium titanate associated mineral preparation:
Raw material: CaCO
320.6%, ZrO
225.1%, TiO
233.3%; High activity liquid waste type: Y ion, Mo ion, Ru ion, Pd ion, La ion, Ce ion, Pr ion, Nd ion, Sm ion, Eu ion, Gd ion, Am ion, Cm ion, nitrate ion; Sintering agent: silicon carbide powder 1%.
Pour raw material, sintering agent powder into corundum crucible after fully mixing with high activity liquid waste, regulate microwave power, make temperature-stable at 800 DEG C, be incubated 30 minutes.Raise microwave power, make temperature rise to 1400 DEG C, be incubated 3 hours.Reduce microwave power at 600 DEG C, be incubated 2 hours.Microwave power is down to 0W, until temperature drops to room temperature.The cured body prepared is zirconolite-calcium titanate associated mineral cured body.
embodiment 3.aspidelite-zircon associated mineral preparation:
Raw material: CaCO
333.3%, SiO
219.6%, TiO
226.1%; High activity liquid waste type: Zr ion, Mo ion, Ru ion, Pd ion, Np ion, Pu ion, nitrate ion, oxalate denominationby; Sintering agent: Graphite Powder 99 1%.
Pour raw material, sintering agent powder into corundum crucible after fully mixing with high activity liquid waste, regulate microwave power, make temperature-stable at 800 DEG C, be incubated 30 minutes.Raise microwave power, make temperature rise to 1300 DEG C, be incubated 3 hours.Reduce microwave power at 800 DEG C, be incubated 2 hours.Microwave power is down to 0W, until temperature drops to room temperature.The cured body prepared is zirconolite-calcium titanate associated mineral cured body.
embodiment 4.aspidelite-zircon associated mineral preparation:
Raw material: CaCO
333.3%, SiO
219.6%, TiO
226.1%; High activity liquid waste type: Y ion, Mo ion, Ru ion, Pd ion, La ion, Ce ion, Pr ion, Nd ion, Sm ion, Eu ion, Gd ion, Am ion, Cm ion, nitrate ion; Sintering agent: silicon carbide powder 1%.
Pour raw material, sintering agent powder into corundum crucible after fully mixing with high activity liquid waste, regulate microwave power, make temperature-stable at 800 DEG C, be incubated 30 minutes.Raise microwave power, make temperature rise to 1300 DEG C, be incubated 3 hours.Reduce microwave power at 800 DEG C, be incubated 2 hours.Microwave power is down to 0W, until temperature drops to room temperature.The cured body prepared is zirconolite-calcium titanate associated mineral cured body.
embodiment 5.zirconolite-aspidelite-calcium titanate-zirconium silicate associated mineral preparation:
Raw material: CaCO
325.4%, SiO
28.8%, TiO
229.6%, ZrO
215.2%; High activity liquid waste type: Zr ion, Mo ion, Ru ion, Pd ion, Np ion, Pu ion, nitrate ion, oxalate denominationby; Sintering agent: graphite 1%.
Pour raw material, sintering agent powder into corundum crucible after fully mixing with high activity liquid waste, regulate microwave power, make temperature-stable at 800 DEG C, be incubated 30 minutes.Raise microwave power, make temperature rise to 1400 DEG C, be incubated 3 hours.Reduce microwave power at 800 DEG C, be incubated 2 hours.Microwave power is down to 0W, until temperature drops to room temperature.The cured body prepared is zirconolite-calcium titanate associated mineral cured body.
embodiment 6.zirconolite-aspidelite-calcium titanate-zirconium silicate associated mineral preparation:
Raw material: CaCO
325.4%, SiO
28.8%, TiO
229.6%, ZrO
215.2%; High activity liquid waste type: Y ion, Mo ion, Ru ion, Pd ion, La ion, Ce ion, Pr ion, Nd ion, Sm ion, Eu ion, Gd ion, Am ion, Cm ion, nitrate ion; Sintering agent: silicon carbide powder 1%.
Pour raw material, sintering agent powder into corundum crucible after fully mixing with high activity liquid waste, regulate microwave power, make temperature-stable at 800 DEG C, be incubated 30 minutes.Raise microwave power, make temperature rise to 1400 DEG C, be incubated 3 hours.Reduce microwave power at 800 DEG C, be incubated 2 hours.Microwave power is down to 0W, until temperature drops to room temperature.The cured body prepared is zirconolite-calcium titanate associated mineral cured body.
embodiment 7.zirconolite-aspidelite-calcium titanate associated mineral preparation:
Raw material: CaTiO
340.7%, ZrSiO
227.4%, TiO
211.9%; High activity liquid waste type: Zr ion, Mo ion, Ru ion, Pd ion, Np ion, Pu ion, nitrate ion, oxalate denominationby; Sintering agent: Graphite Powder 99 2%.
Pour raw material, sintering agent powder into corundum crucible after fully mixing with high activity liquid waste, regulate microwave power, make temperature-stable at 600 DEG C, be incubated 30 minutes.Raise microwave power, make temperature rise to 1300 DEG C, be incubated 3 hours.Reduce microwave power at 600 DEG C, be incubated 2 hours.Microwave power is down to 0W, until temperature drops to room temperature.The cured body prepared is zirconolite-calcium titanate associated mineral cured body.
embodiment 8.zirconolite-aspidelite-calcium titanate associated mineral preparation:
Raw material: CaTiO
340.7%, ZrSiO
227.4%, TiO
211.9%; High activity liquid waste type: Y ion, Mo ion, Ru ion, Pd ion, La ion, Ce ion, Pr ion, Nd ion, Sm ion, Eu ion, Gd ion, Am ion, Cm ion, nitrate ion; Sintering agent: silicon carbide powder 2%.
Pour raw material, sintering agent powder into corundum crucible after fully mixing with high activity liquid waste, regulate microwave power, make temperature-stable at 800 DEG C, be incubated 30 minutes.Raise microwave power, make temperature rise to 1300 DEG C, be incubated 3 hours.Reduce microwave power at 800 DEG C, be incubated 2 hours.Microwave power is down to 0W, until temperature drops to room temperature.The cured body prepared is zirconolite-calcium titanate associated mineral cured body.
Calcium carbonate described in example of the present invention, titanium oxide, zirconium white, silicon oxide, Graphite Powder 99, silicon carbide powder purity should be greater than 99%, and granularity should be 1 ~ 50 micron.Solidification content, for effectively to solidify content, namely removes the virtual mass after moisture and volatilization gas.
The product reaching the object of the invention can be prepared according to aforementioned manufacturing method by the various embodiments described above.Embodiments of the invention all can be implemented, and the invention is not restricted to these embodiments.
Claims (1)
1. a method for preparing high-radioactivity effluent glass-ceramic solidified body in microwave process, is characterized in that, comprises the following steps successively:
A, raw material mix: two or more in calcium titanate, zirconium silicate, calcium carbonate, titanium oxide, zirconium white and silicon oxide be combined as raw material, add the microwave sintering agent powder of high activity liquid waste and massfraction 1 ~ 2%, put into after Ball-stirring mill mixes and be positioned over corundum crucible; Silicon oxide granularity is 1 ~ 50 micron, and high activity liquid waste virtual mass is 20 ~ 40%; Described high activity liquid waste is by the combination of two or more in heavy metal ion, rare earth ion, radionuclide ion; Microwave sintering agent is graphite or silicon carbide powder; Adding content is 1 ~ 2%;
B, raw material depickling: the crucible holding raw material is placed in microwave agglomerating furnace, temperature is risen to 600 ~ 800 DEG C, insulation 30 ~ 60min, the acid ion in removing high activity liquid waste;
C, high-level waste solidification sintering: the temperature of microwave agglomerating furnace is risen to 1300 ~ 1500 DEG C, insulation 1 ~ 3h;
D, the vitrifying of high-level waste cured body: the temperature of microwave agglomerating furnace is dropped to 600 ~ 800 DEG C, after insulation 1 ~ 2h, microwave power is reduced to 0W, makes sample naturally cool to room temperature.
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| CN104844190B (en) * | 2015-04-08 | 2017-03-01 | 西南科技大学 | A kind of preparation method of fluor-apatite ceramic solidification body |
| CN105810279A (en) * | 2016-03-30 | 2016-07-27 | 中国科学院上海应用物理研究所 | Fluorine-containing and/or fluorine radioactive waste glass ceramic solidified body and preparation method thereof |
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| CN106531277B (en) * | 2016-12-26 | 2018-10-23 | 西南科技大学 | A kind of processing method of live graphite |
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| CN108046737A (en) * | 2018-02-24 | 2018-05-18 | 航天慧能（江苏）环境工程有限公司 | A kind of processing method containing heavy metal hazardous waste |
| CN109859877B (en) * | 2018-11-16 | 2020-11-24 | 清华大学 | Experimental method for solidifying radioactive graphite powder at normal temperature |
| CN110345753A (en) * | 2019-07-18 | 2019-10-18 | 中国原子能科学研究院 | Rotary calcining furnace |
| CN111138190A (en) * | 2020-01-10 | 2020-05-12 | 广东工业大学 | Perovskite type ceramic solidified body and preparation method and application thereof |
| CN111584114B (en) * | 2020-04-07 | 2022-08-19 | 西南科技大学 | Method for solidifying high-level waste |
| CN114315134A (en) * | 2021-12-31 | 2022-04-12 | 西南科技大学 | Method for directly vitrifying high-level waste by using discharge plasma |
| CN114276013A (en) * | 2021-12-31 | 2022-04-05 | 西南科技大学 | Method for directly vitrifying high-level waste by utilizing microwave |
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| CN1287364A (en) * | 2000-09-08 | 2001-03-14 | 清华大学 | Microwave heating process to solidify high radioactive waste liquid |
| CN1767077A (en) * | 2005-08-06 | 2006-05-03 | 西南科技大学 | Method for preparing high radioactive waste curing treatment base material |
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| JP3369780B2 (en) * | 1995-04-06 | 2003-01-20 | 日立金属株式会社 | Manufacturing method of glass ceramic composite substrate |
| US20110224474A1 (en) * | 2010-03-09 | 2011-09-15 | Kurion, Inc. | Advanced Microwave System for Treating Radioactive Waste |
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| CN1287364A (en) * | 2000-09-08 | 2001-03-14 | 清华大学 | Microwave heating process to solidify high radioactive waste liquid |
| CN1767077A (en) * | 2005-08-06 | 2006-05-03 | 西南科技大学 | Method for preparing high radioactive waste curing treatment base material |
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