CN103366847A - Application of waste glass to curing radioactive nuclide and method for curing Sr2+ waste - Google Patents
Application of waste glass to curing radioactive nuclide and method for curing Sr2+ waste Download PDFInfo
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- CN103366847A CN103366847A CN2013103098153A CN201310309815A CN103366847A CN 103366847 A CN103366847 A CN 103366847A CN 2013103098153 A CN2013103098153 A CN 2013103098153A CN 201310309815 A CN201310309815 A CN 201310309815A CN 103366847 A CN103366847 A CN 103366847A
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- cullet
- refuse
- radioactive nuclide
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Abstract
The inventiondiscloses application of waste glass to curinga radioactive nuclide and a method for curing Sr2+ waste. The method comprises the following steps of mixing and stirring an alkaline exciting agent and waste glass powder into slurry; adding inorganic salt containing the radioactive Sr2+ waste into a slurry reaction system, stirring, and vibrating in a mould; and sealing, maintaining, demolding and drying to obtain a waste glass-based polymer solidified body containing the radioactive nuclide Sr2+. After the waste glass-based polymer solidified body is compared with the traditional silicate cement material, a result shows that the solidified body prepared from a glass-based polymer material has high mechanical property and leaching resistance.
Description
Technical field
The invention belongs to radioactive waste environmental protection treatment technical field, take cullet as curing material, develop a kind of application of new and effective curing radioactive nuclide, and provide curing to contain Sr
2+The normal temperature preparation method of refuse.
Background technology
Nuclear energy and nuclear technology have obtained increasingly extensive application in fields such as industry, national defence, scientific researches.But when the application nuclear technology is brought tremendous economic and social benefit to the mankind, also produced a large amount of radioactive wastes.These radioactive wastes have specific radiobiology toxicity, if be leaked to biosphere, can cause serious radioactive contamination, will cause huge harm to human and environment.
Cement is the curing technology of matrix because equipment is simple, investment and operating cost are low, has now become present topmost Solidification Measures of Radioactive Waste.But the characteristic that the poriness of cement solidification material and chemical stability are relatively poor causes the leaching rate of radioactive nuclide higher, has increased the difficulty of solidifying radioactive waste, has improved potential environmental risk.Therefore, the novel solidification of radwaste material of research and development has become whole world question of common concern.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of with the new purposes of cullet as curing material curing radioactive nuclide, particularly provides a kind of employing cullet to solidify and contains radioactive nuclide Sr
2+The normal temperature preparation method of refuse, the method can effectively reduce the leaching rate of radioactive nuclide, and with low cost, has very high practicality, the feature of environmental protection and using value.
The present invention asks for protection the new application of cullet in solidifying radioactive nuclide.
In addition, also provide the normal temperature cure of a kind of application cullet to contain radioactivity Sr
2+The method of refuse, it may further comprise the steps:
1) cullet is before use through cleaning-drying, and in bowl mill the ball milling powdered;
2) alkali-activator and cullet powder are mixed into slurry, what then will need to solidify contains radioactivity Sr
2+The inorganic salt solution of refuse or inorganic salts waste residue add in the slurry reaction system, and make radioactive nuclide Sr
2+With the mass ratio of cullet be 0.5 ~ 1.5:50, the liquid-solid ratio of alkaline excitation agent solution and cullet is 0.3 ~ 0.5;
3) put into mould after reaction system is fully stirred and vibrate, to get rid of contained bubble in the reaction system;
4) with the mould after vibration processing sealing, make after maintenance, the demoulding, the oven dry and contain radioactive nuclide Sr
2+Cullet based geopolymer firming body.
Above-mentioned steps 1) cullet in is the cullet that produces in the municipal cullet that reclaims or the commercial production.
Above-mentioned steps 2) the described alkaline excitation agent solution potpourri that is sodium hydroxide solution, potassium hydroxide solution, sodium silicate solution, potassium silicate solution or mentioned solution.
Above-mentioned steps 2) the described radioactivity Sr that contains
2+The inorganic salts form of refuse is strontium nitrate (Sr (NO
3)
2), strontium sulfate (SrSO
4), strontium chloride (SrCl
2) in one or more.
Beneficial effect of the present invention:
After measured, contain radioactive nuclide Sr
2+Cullet normal temperature cure body at 25 ℃ of deionized water solutions, 42 days Dynamic Leaching rates in 70 ℃ of deionized water solutions are respectively 0.46 * 10
-4Cm/d, 0.51 * 10
-4Cm/d., the 42 day leaching rates of solidified cement body in these two kinds of solution then are respectively 1.67 * 10
-4Cm/d, 1.4 * 10
-3Cm/d.Thereby glass-based normal temperature cure body can Effective Raise to radioactive nuclide Sr
2+Solidification effect, reduce its leaching rate.
In sum, use cullet normal temperature cure body and solidify radioactive nuclide Sr
2+Compare with traditional cement solidification, following advantage arranged:
1, uses cullet base normal temperature cure body and solidify radioactive nuclide Sr
2+, can effectively reduce radioactive nuclide Sr
2+Leaching rate, improve solidification effect.
2, use cullet base normal temperature cure body and solidify radioactive nuclide Sr
2+, fund input is lower, can effectively utilize the solid waste of banking up---cullet simultaneously, thereby have very high practicality, the feature of environmental protection and using value.
Description of drawings
Fig. 1: wherein Fig. 1 a is the solidified cement body scanning electron microscope (SEM) photograph, and Fig. 1 b is cullet based geopolymer firming body scanning electron microscope (SEM) photograph;
Fig. 2: cullet based geopolymer firming body and solidified cement body compressive strength figure;
Fig. 3: cullet based geopolymer firming body anti-leaching design sketch;
Fig. 4: solidified cement body anti-leaching design sketch.
Embodiment
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail:
Embodiment 1
1) with after cullet cleaning-drying and the ball-milling treatment, in 90 ℃ of baking ovens, dries by the fire 2h;
2) 1.5 moles of sodium silicate solutions and cullet powder are mixed into slurry, what then will need to solidify contains radioactivity Sr
2+Inorganic salt solution (the Sr(NO of refuse
3)
2Potpourri with SrCl2) adds in the slurry reaction system, make radioactive nuclide Sr
2+With the mass ratio of cullet be 1:50;
3) pour in steel three gang moulds after reaction system is fully stirred, mould was placed on the electric vibration table vibration 5 minutes, to get rid of contained bubble in the reaction system;
4) with the sealing of the mould after the vibration processing, place curing box in 60 ℃ of lower maintenance demouldings after 24 hours; Sample after the demoulding continues 60 ℃ of lower maintenances 28 days, makes after the drying to contain radioactive nuclide Sr
2+Cullet base normal temperature cure body.
Embodiment 2
1) with after cullet cleaning-drying and the ball-milling treatment, in 90 ℃ of baking ovens, dries by the fire 2h;
2) 1.0 moles of potassium silicate solutions and cullet powder are mixed into slurry, what then will need to solidify contains radioactivity Sr
2+Inorganic salts waste residue (the SrCl of refuse
2) add in the slurry reaction system, make radioactive nuclide Sr
2+With the mass ratio of cullet be 1.5:50;
3) pour in steel three gang moulds after reaction system is fully stirred, mould was placed on the electric vibration table vibration 5 minutes, to get rid of contained bubble in the reaction system;
4) with the sealing of the mould after the vibration processing, place curing box in 60 ℃ of lower maintenance demouldings after 24 hours; Sample after the demoulding continues 60 ℃ of lower maintenances 28 days, makes after the drying to contain radioactive nuclide Sr
2+Cullet base normal temperature cure body.
Embodiment 3
1) with after cullet cleaning-drying and the ball-milling treatment, in 90 ℃ of baking ovens, dries by the fire 2h;
2) mixed solution and the cullet powder with 10 molar sodium hydroxides and potassium hydroxide is mixed into slurry, and what then will need to solidify contains radioactivity Sr
2+Inorganic salt solution (the SrSO of refuse
4Solution) add in the slurry reaction system, make radioactive nuclide Sr
2+With the mass ratio of cullet be 0.5:50;
3) pour in steel three gang moulds after reaction system is fully stirred, mould was placed on the electric vibration table vibration 5 minutes, to get rid of contained bubble in the reaction system;
4) with the sealing of the mould after the vibration processing, place curing box in 60 ℃ of lower maintenance demouldings after 24 hours; Sample after the demoulding continues 60 ℃ of lower maintenances 28 days, makes after the drying to contain radioactive nuclide Sr
2+Cullet base normal temperature cure body.
Test effect:
1, the mensuration of firming body compressive property
Radioactive nuclide Sr to be contained
2+The normal temperature cure of cullet base recuperate and protect to the predetermined length of time, get 3 samples, measure its compressive strength, get three's mean value as the resistance to compression value of firming body, the results are shown in Figure 2;
2, firming body anti-leaching performance measurement
(1) maintenance is contained radioactive nuclide Sr to the predetermined length of time
2+Cullet base normal temperature cure body place respectively the plastic bottle with cover that 25 ℃ of deionized waters of 300ml, 70 ℃ of deionized waters are housed, and the plastic bottle that 25 ℃ of deionized water solutions, 70 ℃ of deionized water solutions will be housed places respectively 25 ℃, 70 ℃ baking oven to keep constant temperature;
(2) change leaching agent in leaching test the 1st, 3,7,10,14,21,28.34.42 days from beginning, and measure the concentration of radioactive nuclide in the leaching agent, the results are shown in Figure 3.Radioactive nuclide Sr in the leachate
2+Leaching rate
Pass with extraction time is:
In the formula:
Be the leaching rate of i component in the n leaching cycle, cmd
-1 
Be the quality of the i component that leaches in the n leaching cycle, g;
Be the initial mass of i component in the leaching test sample, g; F is the geometric area that sample contacts with leaching agent, cm
2V is the volume of sample, cm
3t
nBe the continuous days of n leaching cycle, d;
3, contrast experiment
Portland cement and suitable quantity of water are mixed into slurry, and what then will need to solidify contains radioactivity Sr
2+The inorganic salts of refuse (solution or waste residue) add in the cement slurry, make radioactive nuclide Sr
2+With the mass ratio of cement be 0.5 ~ 1.5:50; Pour in steel three gang moulds after reaction system fully stirred, mould was placed on the electric vibration table vibration 5 minutes, to get rid of contained bubble in the reaction system; With the sealing of the mould after the vibration processing, place curing box in 60 ℃ of lower maintenance demouldings after 24 hours; Sample after the demoulding continues 60 ℃ of lower maintenances 28 days, makes after the drying to contain radioactive nuclide Sr
2+The Portland cement firming body; Radioactive nuclide Sr to be contained
2+The maintenance of Portland cement firming body to the predetermined length of time, get 3 samples, measure its compressive strength, get three's mean value as the resistance to compression value of firming body, the results are shown in Figure 2; Maintenance is contained radioactive nuclide Sr to the predetermined length of time
2+The Portland cement firming body place respectively the plastic bottle with cover that 25 ℃ of deionized waters of 300ml, 70 ℃ of deionized waters are housed, and the plastic bottle that 25 ℃ of deionized water solutions, 70 ℃ of deionized water solutions will be housed places respectively 25 ℃, 70 ℃ baking oven to keep constant temperature; From beginning leaching test the 1st, changed leaching agent in 3,7,10,14,21,28,35,42 days, and measure the concentration of radioactive nuclide in the leaching agent, the results are shown in Figure 4.
Comparison diagram 1a, b can find that the microscopic appearance of cullet base normal temperature cure body is more smooth, fine and close; Fig. 2 shows that the compressive strength of cullet base normal temperature cure body is apparently higher than solidified cement body; Comprehensive Correlation Fig. 3 and Fig. 4 can draw, and the anti-leaching performance of cullet base normal temperature cure body in four kinds of solution all obviously is better than solidified cement body.
Claims (5)
1. the application of cullet in solidifying radioactive nuclide.
2. application cullet normal temperature cure contains radioactivity Sr
2+The method of refuse is characterized in that may further comprise the steps:
1) cullet is before use through cleaning-drying, and in bowl mill the ball milling powdered;
2) alkali-activator and cullet powder are mixed into slurry, what then will need to solidify contains radioactivity Sr
2+The inorganic salt solution of refuse or inorganic salts waste residue add in the slurry reaction system, and make radioactive nuclide Sr
2+With the mass ratio of cullet be 0.5 ~ 1.5:50, the liquid-solid ratio of alkaline excitation agent solution and cullet is 0.3 ~ 0.5;
3) put into mould after reaction system is fully stirred and vibrate, to get rid of contained bubble in the reaction system;
4) with the mould after vibration processing sealing, make after maintenance, the demoulding, the oven dry and contain radioactive nuclide Sr
2+Cullet based geopolymer firming body.
3. the normal temperature cure of described application cullet contains radioactivity Sr according to claim 1
2+The method of refuse is characterized in that, the cullet in the step 1) is the cullet that produces in the municipal cullet that reclaims or the commercial production.
4. application cullet according to claim 1 and 2 normal temperature cure contains radioactivity Sr
2+The method of refuse is characterized in that step 2) described alkaline excitation agent solution is the potpourri of sodium hydroxide solution, potassium hydroxide solution, sodium silicate solution, potassium silicate solution or mentioned solution.
5. application cullet according to claim 1 and 2 normal temperature cure contains radioactivity Sr
2+The method of refuse is characterized in that step 2) the described radioactivity Sr that contains
2+The inorganic salts form of refuse is strontium nitrate (Sr (NO
3)
2), strontium sulfate (SrSO
4), strontium chloride (SrCl
2) in one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103098153A CN103366847A (en) | 2013-07-23 | 2013-07-23 | Application of waste glass to curing radioactive nuclide and method for curing Sr2+ waste |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103098153A CN103366847A (en) | 2013-07-23 | 2013-07-23 | Application of waste glass to curing radioactive nuclide and method for curing Sr2+ waste |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103680660A (en) * | 2013-12-03 | 2014-03-26 | 南京大学 | Application of cullet in solidifying radionuclide and normal temperature solidifying method for waste comprising radioactive Cs+ |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4383944A (en) * | 1978-12-28 | 1983-05-17 | Kernforschungszentrum Karlsruhe Gesellschaft Mit Beschrankter Haftung | Method for producing molded bodies containing highly active radioactive wastes from glass granules embedded in a metallic matrix |
| JPS6040997A (en) * | 1983-08-15 | 1985-03-04 | 日本原子力研究所 | Back-filling material of high-level waste glass solidified body |
| US20100285945A1 (en) * | 2007-09-20 | 2010-11-11 | Energy Solutions, Llc | Mitigation of secondary phase formation during waste vitrification |
| CN102881346A (en) * | 2012-09-11 | 2013-01-16 | 南京大学 | Application of coal ash in solidification of radionuclide and method thereof for solidifying radionuclide I- |
-
2013
- 2013-07-23 CN CN2013103098153A patent/CN103366847A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4383944A (en) * | 1978-12-28 | 1983-05-17 | Kernforschungszentrum Karlsruhe Gesellschaft Mit Beschrankter Haftung | Method for producing molded bodies containing highly active radioactive wastes from glass granules embedded in a metallic matrix |
| JPS6040997A (en) * | 1983-08-15 | 1985-03-04 | 日本原子力研究所 | Back-filling material of high-level waste glass solidified body |
| US20100285945A1 (en) * | 2007-09-20 | 2010-11-11 | Energy Solutions, Llc | Mitigation of secondary phase formation during waste vitrification |
| CN102881346A (en) * | 2012-09-11 | 2013-01-16 | 南京大学 | Application of coal ash in solidification of radionuclide and method thereof for solidifying radionuclide I- |
Non-Patent Citations (1)
| Title |
|---|
| 谭宏斌 等: "放射性废物固化方法综述", 《云南环境科学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103680660A (en) * | 2013-12-03 | 2014-03-26 | 南京大学 | Application of cullet in solidifying radionuclide and normal temperature solidifying method for waste comprising radioactive Cs+ |
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Application publication date: 20131023 |