CN103058664B - Preparation method of pyrochlore type man-made rock solidified body - Google Patents
Preparation method of pyrochlore type man-made rock solidified body Download PDFInfo
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- CN103058664B CN103058664B CN201110316069.1A CN201110316069A CN103058664B CN 103058664 B CN103058664 B CN 103058664B CN 201110316069 A CN201110316069 A CN 201110316069A CN 103058664 B CN103058664 B CN 103058664B
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Abstract
The invention discloses a preparation method of a pyrochlore type man-made rock solidified body. The method comprises the steps of: preparing evenly mixed compositional powder of a pyrochlore type man-made rock base material; adding the mixed powder into a highly radioactive waste liquid, and simultaneously adding an organic monomer and a crosslinking agent, and mixing them evenly; adding an initiator, conducting standing to perform gelatination; after complete gelatination, carrying out dehydration drying; putting a dried gel into an air furnace to perform sintering; and finally implementing furnace cooling. The preparation method disclosed in the invention can make the solidified body directly dried and molded, and the process can be finished in one air furnace. The sintering temperature is low, and the sintering time is short, so that energy is substantially saved. Particularly, the risk of environmental pollution caused by heating volatilization of highly radioactive substances is reduced, and the security of solidified body preparation is greatly improved. In addition, the preparation method provided in the invention has the advantages of simple operation, no need of special equipment and strict requirements, thus being in line with the requirements of industrialized production.
Description
Technical field
The present invention relates to the preparation method of artificial rock cured body, specifically, relate to the preparation method of the artificial rock cured body of a kind of pyrochlore-type.
Background technology
Vitrification highly active waste is realized industrialization in some countries, and China is the built cold stand of highly active waste vitrification also, starts to carry out cold experiment.But because construction and the working cost in the dark geological disposal of highly active waste storehouse increase day by day, be totally uneconomic with vitrification by highly active waste.Therefore, think that at present more feasible way is by the fission element (90Sr of long-life actinide elements and high heat release in highly active waste, 137Cs) separate, after solidifying, carry out dark geological disposal, using remaining large volume waste liquid as middle low-level waste, after cement solidification, carry out near surface disposal, to reduce the refuse amount that needs dark geological disposal.This just needs a kind of cured body better with hot leaching performance than large, the anti-irradiation of glass solidified body containing amount to solidify the highly active waste after separating.Artificial rock, as the heterogeneous titanate ceramics body of one, by the ore deposit phase composite of some geochemistry stable performances, can be fixed rejected ions in its lattice, is the cured body getting a good chance of that meets this requirement.
Pyrrhite (Pyrochlore) and zirconolite (Zirconolite, CaZrTi2O7) are all ore deposit phases of occurring in nature stable existence.Zirconolite is ore deposit phase the most stable in artificial rock, is also the main mine phase that contains actinide elements.Pyrrhite can, in the artificial rock process of preparation, form in the time that the replacement of the zirconium position of metal ion to zirconolite exceedes certain solid solubility.Because it and zirconolite have close structure, therefore they have identical performance, but research shows that the artificial rock of pyrochlore-type can reach higher containing amount, anti leaching performance preferably, is the desirable cured body that solidifies Actinides and carry out final geological disposal.
The preparation method of the artificial rock cured body of pyrochlore-type of report mainly contains following 2 kinds at present: 1) nitrate solution that contains radionuclide is mixed mutually with titanium tetrachloride solution, mixing solutions and the aqueous solution of citric acid and ethylidene glycol are hydrolyzed to react and form gel, after dry, obtain base-material through 700 DEG C of calcining 15min, finally by after the powder moulding obtaining after calcining at 1400 DEG C of sintering 10～30h.Because this method need to be calcined in two steps, and must be through compression molding, strengthen the radionuclide risk level polluting of volatilizing, industrial applications is extremely restricted.2) use hot constant-voltage method, need be under the nitrogen atmosphere that contains 5% hydrogen, 750 DEG C of pre-burnings, and then calcine under 200Mpa constant voltage.The whole operating process complexity of this method, and fission products easily volatilization under high pressure-temperature, easily cause the risk of environmental pollution.Therefore, this area is general needs research a kind of simple to operate, is applicable to the preparation method of the artificial rock cured body of industrialized pyrochlore-type.
Summary of the invention
For the existing the problems referred to above of prior art and defect, the invention provides a kind of preparation method of simple to operate, the applicable artificial rock cured body of industrialized pyrochlore-type, to meet the requirement of industrial treatment high level waste.
For achieving the above object, the technical solution used in the present invention is as follows:
A preparation method for the artificial rock cured body of pyrochlore-type, comprises the steps:
A) take each constitutive material according to the compositing formula of the artificial rock base material of pyrochlore-type, the powder that ball milling becomes to mix;
B) mixed powder step a) being made adds in highly active waste, adds organic monomer and linking agent simultaneously, and limit edged stirs, and makes to mix; Described organic monomer is acrylamide or Methacrylamide; Described linking agent is N, N '-methylene-bisacrylamide;
C) under agitation add initiator, leave standstill and make its gelation;
D) after the complete gelation of slurry, dehydrate;
E) dried gelinite is inserted and in air furnace, carry out sintering: be first warmed up to 500～900 DEG C, insulation 0.5～3h, then be warmed up to 1000～1500 DEG C, and insulation 1～8h, temperature rise rate is controlled at 2～20 DEG C/min; Then furnace cooling, obtains the described artificial rock cured body of pyrochlore-type.
The compositing formula of the artificial rock base material of described pyrochlore-type is as follows:
Above-mentioned compositing formula is that the artificial rock cured body of pyrochlore-type taking 100 weight parts of oxide form tabular form is as benchmark.
The ball milling of step in a) can be that wet ball grinding technique can be also dry ball milling technique, preferably wet ball grinding technique.
The particle diameter of the mixed powder that step a) makes is recommended < 0.125mm, preferably < 10 μ m.
The pyrochlore-type artificial rock cured body of step described in b) is 20%～60% to the containing amount of high level waste, is preferably 30%～50%.
Step b) in mixed powder to add the solid volume fraction of the suspension liquid forming in highly active waste be 30～60%, be preferably 30～50%.
The add-on of the organic monomer of step described in b) recommends to add 1%～4% by material powder quality criteria, is preferably 1.5%～3.5%.
The mass ratio of the linking agent of step described in b) and organic monomer is recommended as 1: 10～and 1: 25.
The initiator of step in c) is recommended as ammonium persulphate.
Described ammonium persulphate is recommended to add with aqueous solution form, and the mass concentration of the aqueous solution is preferably 10%.
The add-on of described ammonium persulfate initiator is preferably 3%～8% of organic monomer quality, is preferably 4%～7%.
Steps d) in dehydrate and can be seasoning, drying with water bath or heat drying.
Compared with prior art, adopt the artificial rock cured body of pyrochlore-type prepared of the inventive method can convection drying moulding, can in air furnace, complete by a stove, and sintering temperature is low, sintering time is short, greatly save the energy, especially the risk that has reduced the environmental pollution that high level waste causes because of heating volatilization, has improved security prepared by cured body greatly; In addition, preparation method of the present invention has simple to operate, without specific installation and harsh requirement, is applicable to the requirement of suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail and completely.In view of pollution and the toxic of high level waste, below in embodiment all with cerous nitrate simulation high level waste, the cerous nitrate aqueous solution simulation highly active waste of preparation.
Embodiment 1
Take the raw material of the artificial rock base material of composition pyrochlore-type by following formula: titanium oxide is that 44.4g, zirconium white are that 2.8g, barium oxide are 1.1g, and aluminum oxide is that 0.7g and calcium oxide are 9.9g; Above-mentioned raw materials is carried out to wet ball grinding 28h, dry to obtain the powder that mixes, its grain diameter is less than 0.5 μ m;
The cerous nitrate crystal (its oxide form shared massfraction in formula is 41.1%) that takes the stand-in of 98.6g high level waste-with 6 xln water, adds 52mL water to be mixed with solution, as the highly active waste of simulation;
The mixed powder of artificial pyrochlore-type of above-mentioned preparation rock base material is added in the highly active waste of simulation of above-mentioned preparation, the slurry that formation solid volume fraction is 35%, add while stirring 1.47g organic monomer acrylamide and 0.07g linking agent N, N '-methylene-bisacrylamide, stir 30min, slurry is mixed;
Drip while stirring the 10% ammonium persulfate aqueous solution 0.09g preparing in advance, after stirring, leave standstill and treat the whole gelations of slurry;
Take out gelinite, insert 80 DEG C of oven dryings 48 hours;
Dried gelinite is inserted and in air furnace, carried out sintering: be first warmed up to 800 DEG C, insulation 2h; Be warmed up to again 1300 DEG C, insulation 4h, temperature rise rate is controlled at 10 DEG C/min; Then furnace cooling, obtains the described artificial rock cured body of pyrochlore-type.
Prepared artificial rock cured body is carried out to performance test after section, polishing, polishing.Measure its volume density and apparent porosity by drainage and method to boil water, measure its Vickers' hardness with Wilson-Wolpert Tukon2100B Vickers hardness tester, test result is shown in Table 1.
Embodiment 2
Take the raw material of the artificial rock base material of composition pyrochlore-type by following formula: titanium oxide is that 33.3g, zirconium white are that 2.1g, barium oxide are 0.8g, and aluminum oxide is that 0.6g and calcium oxide are 7.4g; Above-mentioned raw materials is carried out to wet ball grinding 20h, dry to obtain the powder that mixes, its grain diameter is less than 3 μ m;
The cerous nitrate crystal (its oxide form shared massfraction in formula is 55.8%) that takes the stand-in of 140.8g high level waste-with 6 xln water, adds 73.8mL water to be mixed with solution, as the highly active waste of simulation;
The mixed powder of artificial pyrochlore-type of above-mentioned preparation rock base material is added in the highly active waste of simulation of above-mentioned preparation, the slurry that formation solid volume fraction is 30%, add while stirring 1.32g organic monomer acrylamide and 0.05g linking agent N, N '-methylene-bisacrylamide, stir 30min, slurry is mixed;
Drip while stirring the 10% ammonium persulfate aqueous solution 0.05g preparing in advance, after stirring, leave standstill and treat the whole gelations of slurry;
Take out gelinite, insert 80 DEG C of oven dryings 60 hours;
Dried gelinite is inserted and in air furnace, carried out sintering: be first warmed up to 900 DEG C, insulation 0.5h; Be warmed up to again 1500 DEG C, insulation 1h, temperature rise rate is controlled at 2 DEG C/min; Then furnace cooling, obtains the described artificial rock cured body of pyrochlore-type.
Prepared artificial rock cured body is carried out to performance test after section, polishing, polishing.Measure its density and apparent porosity by drainage and method to boil water, measure its Vickers' hardness with Wilson-Wolpert Tukon2100B Vickers hardness tester, test result is shown in Table 1.
Embodiment 3
Take the raw material of the artificial rock base material of composition pyrochlore-type by following formula: titanium oxide is that 59.0g, zirconium white are that 3.8g, barium oxide are 1.4g, and aluminum oxide is that 1.0g and calcium oxide are 13.1g; Above-mentioned raw materials is carried out to wet ball grinding 20h, dry to obtain the powder that mixes, its grain diameter is less than 0.6 μ m;
The cerous nitrate crystal (its oxide form shared massfraction in formula is 21.7%) that takes the stand-in of 54.8g high level waste-with 6 xln water, adds 56.3mL water to be mixed with solution, as the highly active waste of simulation;
The mixed powder of artificial pyrochlore-type of above-mentioned preparation rock base material is added in the highly active waste of simulation of above-mentioned preparation, the slurry that formation solid volume fraction is 40%, add while stirring 0.78g organic monomer acrylamide and 0.08g linking agent N, N '-methylene-bisacrylamide, stir 30min, slurry is mixed;
Drip while stirring the 10% ammonium persulfate aqueous solution 0.05g preparing in advance, after stirring, leave standstill and treat the whole gelations of slurry;
Take out gelinite, insert 80 DEG C of oven dryings 40 hours;
Dried gelinite is inserted and in air furnace, carried out sintering: be first warmed up to 500 DEG C, insulation 3h; Be warmed up to again 1000 DEG C, insulation 8h, temperature rise rate is controlled at 20 DEG C/min; Then furnace cooling, obtains the described artificial rock cured body of pyrochlore-type.
Prepared artificial rock cured body is carried out to performance test after section, polishing, polishing.Measure its density and apparent porosity by drainage and method to boil water, measure its Vickers' hardness with Wilson-Wolpert Tukon2100B Vickers hardness tester, test result is shown in Table 1.
The performance test data of the prepared artificial rock cured body of table 1 embodiment 1～3
| Embodiment | Volume density (g/cm 3) | Apparent porosity (%) | Vickers' hardness (kg/mm 2) |
| 1 | 4.7 | 0.56 | 890 |
| 2 | 4.5 | 0.47 | 719 |
| 3 | 4.5 | 0.29 | 709 |
From table 1: the prepared artificial rock cured body of pyrochlore-type of the present invention all has good physicals, and density is large, and apparent porosity is little, and hardness is high, can meet the performance requriements that solidifies high level waste.
Finally should be noted that: above embodiment is only for the invention will be further described; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (13)
1. a preparation method for the artificial rock cured body of pyrochlore-type, is characterized in that, comprises the steps:
A) take each constitutive material according to the compositing formula of the artificial rock base material of pyrochlore-type, the powder that ball milling becomes to mix;
B) mixed powder step a) being made adds in highly active waste, adds organic monomer and linking agent simultaneously, and limit edged stirs, and makes to mix; Described organic monomer is acrylamide or Methacrylamide; Described linking agent is N, N '-methylene-bisacrylamide;
C) under agitation add initiator, leave standstill and make its gelation;
D) after the complete gelation of slurry, dehydrate;
E) dried gelinite is inserted and in air furnace, carry out sintering: be first warmed up to 500～900 DEG C, insulation 0.5～3h, then be warmed up to 1000～1500 DEG C, and insulation 1～8h, temperature rise rate is controlled at 2～20 DEG C/min; Then furnace cooling, obtains the described artificial rock cured body of pyrochlore-type.
2. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 1, is characterized in that, the compositing formula of the artificial rock base material of described pyrochlore-type is as follows:
Above-mentioned compositing formula is that the artificial rock cured body of pyrochlore-type taking 100 weight parts of oxide form tabular form is as benchmark.
3. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 1, is characterized in that: the ball milling of step in a) adopts wet ball grinding technique or dry ball milling technique.
4. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 1, is characterized in that: the particle diameter <0.125mm of the mixed powder that step a) makes.
5. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 4, is characterized in that: the particle diameter <10 μ m of the mixed powder that step a) makes.
6. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 1, is characterized in that: the pyrochlore-type artificial rock cured body of step described in b) is 20%～60% to the containing amount of high level waste.
7. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 1, is characterized in that: step b) in mixed powder to add the solid volume fraction of the suspension liquid forming in highly active waste be 30%～60%.
8. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 1, is characterized in that: the add-on of the organic monomer of step described in b) adds 1%～4% by material powder quality criteria.
9. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 1, is characterized in that: the linking agent of step described in b) and the mass ratio of organic monomer are 1:10～1:25.
10. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 1, is characterized in that: the initiator of step in c) is ammonium persulphate.
The preparation method of the artificial rock cured body of 11. pyrochlore-type according to claim 10, is characterized in that: described ammonium persulphate adds taking mass concentration as 10% aqueous solution form.
The preparation method of the artificial rock cured body of 12. pyrochlore-type according to claim 10, is characterized in that: the add-on of the initiator ammonium persulfate solution of step in c) is 3%～8% of organic monomer quality.
The preparation method of the artificial rock cured body of 13. pyrochlore-type according to claim 1, is characterized in that: steps d) in dehydrate as seasoning or heat drying.
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| CN102097147A (en) * | 2010-11-02 | 2011-06-15 | 清华大学 | Method for solidifying cement with radioactive organic waste liquid |
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| CN102097147A (en) * | 2010-11-02 | 2011-06-15 | 清华大学 | Method for solidifying cement with radioactive organic waste liquid |
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| Title |
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| 周冠南等.烧绿石固化高放废物的研究进展.《材料导报》.2006,第20卷(第9期), |
| 烧绿石固化高放废物的研究进展;周冠南等;《材料导报》;20060930;第20卷(第9期);第38-42页 * |
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