CN103058664A - Preparation method of pyrochlore type man-made rock solidified body - Google Patents
Preparation method of pyrochlore type man-made rock solidified body Download PDFInfo
- Publication number
- CN103058664A CN103058664A CN2011103160691A CN201110316069A CN103058664A CN 103058664 A CN103058664 A CN 103058664A CN 2011103160691 A CN2011103160691 A CN 2011103160691A CN 201110316069 A CN201110316069 A CN 201110316069A CN 103058664 A CN103058664 A CN 103058664A
- Authority
- CN
- China
- Prior art keywords
- pyrochlore
- preparation
- artificial rock
- cured body
- type according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
The vitrification highly active waste is realized industrialization in some countries, and China is the built cold stand of highly active waste vitrification also, begins 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 uneconomic with vitrification totally with highly active waste.Therefore, think that at present more feasible way is the fission element (90Sr with long-life actinide elements and high heat release in the highly active waste, 137Cs) separate, carry out dark geological disposal after the curing, with remaining large volume waste liquid as in low-level waste, carry out near surface disposal after the cement solidification, to reduce the refuse amount that needs dark geological disposal.This just needs a kind ofly to solidify highly active waste after separating than large, the anti-irradiation of glass solidified body containing amount and the cured body that it is good that hot dipping goes out performance.Artificial rock, can be fixed rejected ions in its lattice by the ore deposit phase composite of some geochemistry stable performances as a kind of heterogeneous titanate ceramics body, is the cured body that gets a good chance of that satisfies this requirement.
Pyrrhite (Pyrochlore) and zirconolite (Zirconolite, CaZrTi2O7) all are ore deposit phases of occurring in nature stable existence.Zirconolite is ore deposit phase the most stable in the artificial rock, also is the main mine phase that contains actinide elements.Pyrrhite can in the artificial rock process of preparation, form when metal ion surpasses certain solid solubility to the replacement of the zirconium position of zirconolite.Because it and zirconolite have close structure, therefore they have identical performance, but studies show that the artificial rock of pyrochlore-type can reach higher containing amount, the anti leaching performance is the desirable cured body that solidifies Actinides and carry out final geological disposal preferably.
The preparation method of the artificial rock cured body of pyrochlore-type of report mainly contains following 2 kinds at present: the nitrate solution that 1) will contain radionuclide mixes mutually with titanium tetrachloride solution, the reaction that is hydrolyzed of the aqueous solution of mixing solutions and citric acid and ethylidene glycol is formed gel, dry obtain base-material by 700 ℃ of calcining 15min, after the powder moulding that will obtain after will calcining at last at 1400 ℃ of sintering 10～30h.Because this method needs in two steps calcining, and must strengthen the risk level that the radionuclide volatilization pollutes through compression molding, industrial applications is extremely restricted.2) use hot constant-voltage method, need under the nitrogen atmosphere that contains 5% hydrogen, 750 ℃ of pre-burnings, and then under the 200Mpa constant voltage, calcine.The whole operating process of this method is complicated, and fission products easily volatilization under high pressure-temperature, easily causes the risk of environmental pollution.Therefore, this area is general to need research a kind of simple to operate, is fit 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 defective, the invention provides a kind of preparation method of simple to operate, the suitable artificial rock cured body of industrialized pyrochlore-type, to satisfy the requirement of industrial treatment high level waste.
For achieving the above object, the technical solution used in the present invention is as follows:
The preparation method of the artificial rock cured body of a kind of pyrochlore-type comprises the steps:
A) compositing formula according to the artificial rock base material of pyrochlore-type takes by weighing each constitutive material, the powder that ball milling becomes to mix;
B) mixed powder that step a) is made adds in the highly active waste, adds simultaneously organic monomer and linking agent, and the 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 carry out sintering in the air furnace: be warmed up to first 500～900 ℃, insulation 0.5～3h is warmed up to 1000～1500 ℃ again, insulation 1～8h, and temperature rise rate is controlled at 2～20 ℃/min; Then furnace cooling namely gets the artificial rock cured body of described pyrochlore-type.
The compositing formula of the artificial rock base material of described pyrochlore-type is as follows:
Above-mentioned compositing formula is as benchmark take the artificial rock cured body of the pyrochlore-type of 100 weight parts of oxide form tabular form.
The ball milling of step in a) can also can be dry ball milling technique for wet ball grinding technique, preferred wet ball grinding technique.
Particle diameter recommendation＜the 0.125mm of the mixed powder that step a) makes, preferred＜10 μ m.
Step b) the artificial rock cured body of the pyrochlore-type described in is 20%～60% to the containing amount of high level waste, is preferably 30%～50%.
The solid volume fraction of the suspension liquid that forms in the mixed powder adding highly active waste step b) is 30～60%, is preferably 30～50%.
The add-on of the organic monomer step b) is recommended to press the material powder quality criteria and is added 1%～4%, is preferably 1.5%～3.5%.
The mass ratio of the linking agent step b) and organic monomer is recommended as 1: 10～and 1: 25.
Step c) initiator in 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%.
Dehydrating steps d) can be seasoning, drying with water bath or heat drying.
Compared with prior art, but adopt the artificial rock cured body of the pyrochlore-type convection drying moulding of the inventive method preparation, can in air furnace, finish by a stove, and sintering temperature is low, sintering time is short, greatly saved the energy, especially reduce the risk of the environmental pollution that high level waste causes because of heated volatile, greatly improved the security of cured body preparation; In addition, preparation method of the present invention has simple to operate, need not specific installation and harsh requirement, is fit to the requirement of suitability for industrialized production.
Embodiment
The present invention is described in further detail and completely below in conjunction with embodiment.In view of pollution and the toxic of high level waste, below among the embodiment all with cerous nitrate simulation high level waste, the cerous nitrate aqueous solution simulation highly active waste of preparation.
Embodiment 1
Take by weighing the raw material that forms the artificial rock base material of pyrochlore-type by following prescription: 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 wet ball grinding 28h, dry to get the powder that mixes, its grain diameter is less than 0.5 μ m;
Take by weighing the stand-in of 98.6g high level waste-with the cerous nitrate crystal (its oxide form shared massfraction in prescription is 41.1%) of 6 xln water, add 52mL water and be mixed with solution, as the highly active waste of simulation;
The mixed powder of the artificial rock base material of the pyrochlore-type of above-mentioned preparation is added in the highly active waste of simulation of above-mentioned preparation, the formation solid volume fraction is 35% slurry, 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 for preparing in advance, after stirring, leave standstill and treat the whole gelations of slurry;
Take out gelinite, inserted 80 ℃ of oven dryings 48 hours;
Dried gelinite inserted carry out sintering in the air furnace: be warmed up to first 800 ℃, insulation 2h; Be warmed up to again 1300 ℃, insulation 4h, temperature rise rate is controlled at 10 ℃/min; Then furnace cooling namely gets the artificial rock cured body of described pyrochlore-type.
Prepared artificial rock cured body is carried out performance test after section, polishing, polishing.Measure its volume density and apparent porosity with 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 by weighing the raw material that forms the artificial rock base material of pyrochlore-type by following prescription: 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 wet ball grinding 20h, dry to get the powder that mixes, its grain diameter is less than 3 μ m;
Take by weighing the stand-in of 140.8g high level waste-with the cerous nitrate crystal (its oxide form shared massfraction in prescription is 55.8%) of 6 xln water, add 73.8mL water and be mixed with solution, as the highly active waste of simulation;
The mixed powder of the artificial rock base material of the pyrochlore-type of above-mentioned preparation is added in the highly active waste of simulation of above-mentioned preparation, the formation solid volume fraction is 30% slurry, 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 for preparing in advance, after stirring, leave standstill and treat the whole gelations of slurry;
Take out gelinite, inserted 80 ℃ of oven dryings 60 hours;
Dried gelinite inserted carry out sintering in the air furnace: be warmed up to first 900 ℃, insulation 0.5h; Be warmed up to again 1500 ℃, insulation 1h, temperature rise rate is controlled at 2 ℃/min; Then furnace cooling namely gets the artificial rock cured body of described pyrochlore-type.
Prepared artificial rock cured body is carried out performance test after section, polishing, polishing.Measure its density and apparent porosity with 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 by weighing the raw material that forms the artificial rock base material of pyrochlore-type by following prescription: 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 wet ball grinding 20h, dry to get the powder that mixes, its grain diameter is less than 0.6 μ m;
Take by weighing the stand-in of 54.8g high level waste-with the cerous nitrate crystal (its oxide form shared massfraction in prescription is 21.7%) of 6 xln water, add 56.3mL water and be mixed with solution, as the highly active waste of simulation;
The mixed powder of the artificial rock base material of the pyrochlore-type of above-mentioned preparation is added in the highly active waste of simulation of above-mentioned preparation, the formation solid volume fraction is 40% slurry, 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 for preparing in advance, after stirring, leave standstill and treat the whole gelations of slurry;
Take out gelinite, inserted 80 ℃ of oven dryings 40 hours;
Dried gelinite inserted carry out sintering in the air furnace: be warmed up to first 500 ℃, insulation 3h; Be warmed up to again 1000 ℃, insulation 8h, temperature rise rate is controlled at 20 ℃/min; Then furnace cooling namely gets the artificial rock cured body of described pyrochlore-type.
Prepared artificial rock cured body is carried out performance test after section, polishing, polishing.Measure its density and apparent porosity with 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 artificial rock cured body that table 1 embodiment 1～3 is prepared
| 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 |
By as seen from Table 1: the prepared artificial rock cured body of pyrochlore-type of the present invention all has preferably physicals, and density is large, and apparent porosity is little, and hardness is high, can meet the performance requriements that solidifies high level waste.
Should be noted that at last: 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. the preparation method of the artificial rock cured body of pyrochlore-type is characterized in that, comprises the steps:
A) compositing formula according to the artificial rock base material of pyrochlore-type takes by weighing each constitutive material, the powder that ball milling becomes to mix;
B) mixed powder that step a) is made adds in the highly active waste, adds simultaneously organic monomer and linking agent, and the 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 carry out sintering in the air furnace: be warmed up to first 500～900 ℃, insulation 0.5～3h is warmed up to 1000～1500 ℃ again, insulation 1～8h, and temperature rise rate is controlled at 2～20 ℃/min; Then furnace cooling namely gets the artificial rock cured body of described 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 as benchmark take the artificial rock cured body of the pyrochlore-type of 100 weight parts of oxide form tabular form.
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 of the mixed powder that step a) makes＜10 μ m.
6. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 1, it is characterized in that: the artificial rock cured body of the pyrochlore-type step 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: to add the solid volume fraction of the suspension liquid that forms in the highly active waste be 30%～60% to mixed powder step b).
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 step b) is pressed the material powder quality criteria and is added 1%～4%.
9. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 1, it is characterized in that: the mass ratio of the linking agent step b) and organic monomer is 1: 10～1: 25.
10. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 1, it is characterized in that: the initiator step c) is ammonium persulphate.
11. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 10 is characterized in that: described ammonium persulphate adds take the aqueous solution form of mass concentration as 10%.
12. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 10 is characterized in that: the add-on of the initiator ammonium persulfate solution step c) is 3%～8% of organic monomer quality.
13. the preparation method of the artificial rock cured body of pyrochlore-type according to claim 1 is characterized in that: dehydrating steps d) is seasoning, drying with water bath or heat drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110316069.1A CN103058664B (en) | 2011-10-18 | 2011-10-18 | Preparation method of pyrochlore type man-made rock solidified body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110316069.1A CN103058664B (en) | 2011-10-18 | 2011-10-18 | Preparation method of pyrochlore type man-made rock solidified body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103058664A true CN103058664A (en) | 2013-04-24 |
| CN103058664B CN103058664B (en) | 2014-07-16 |
Family
ID=48101599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110316069.1A Active CN103058664B (en) | 2011-10-18 | 2011-10-18 | Preparation method of pyrochlore type man-made rock solidified body |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103058664B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761500A (en) * | 2019-03-06 | 2019-05-17 | 西南科技大学 | A kind of preparation method of the borosilicate glass ceramic solidification body containing uranpyrochlore |
| CN110590014A (en) * | 2019-09-17 | 2019-12-20 | 济南大学 | Method for purifying electroplating wastewater and application of obtained xerogel in glass |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102097147A (en) * | 2010-11-02 | 2011-06-15 | 清华大学 | Method for solidifying cement with radioactive organic waste liquid |
-
2011
- 2011-10-18 CN CN201110316069.1A patent/CN103058664B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102097147A (en) * | 2010-11-02 | 2011-06-15 | 清华大学 | Method for solidifying cement with radioactive organic waste liquid |
Non-Patent Citations (1)
| Title |
|---|
| 周冠南等: "烧绿石固化高放废物的研究进展", 《材料导报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761500A (en) * | 2019-03-06 | 2019-05-17 | 西南科技大学 | A kind of preparation method of the borosilicate glass ceramic solidification body containing uranpyrochlore |
| CN110590014A (en) * | 2019-09-17 | 2019-12-20 | 济南大学 | Method for purifying electroplating wastewater and application of obtained xerogel in glass |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103058664B (en) | 2014-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103030382B (en) | Method for molding fused quartz ceramic by gel casting of low-toxicity gel system | |
| CN103086699A (en) | Regenerative ceramic tile and producing method thereof | |
| CN104844190B (en) | A kind of preparation method of fluor-apatite ceramic solidification body | |
| CN107399988A (en) | A kind of method for preparing alumina carbon SiClx composite porous ceramic using aluminium silicon systems industrial residue | |
| JP6268583B2 (en) | Method for producing fired product | |
| CN103641503B (en) | Anti-erosion mullite brick for blast furnace and preparation method thereof | |
| CN105948711B (en) | A kind of fired brick and preparation method thereof | |
| CN103058664B (en) | Preparation method of pyrochlore type man-made rock solidified body | |
| CN103408304B (en) | Preparation method of kularite ceramic solidifying body | |
| CN103265171B (en) | Arsenious waste curing method as well as generated solid arsenic crystal product and application thereof | |
| CN102786304A (en) | Preparation method for hot-pressed boron carbide ceramic | |
| CN104961444A (en) | Method for manufacturing high-strength durable ganged bricks with waste aluminum ash | |
| CN105801108B (en) | A kind of preparation method of three-dimensional open-framework lithium matrix body tritium increment agent material | |
| CN108794052B (en) | Sludge shale heat-preservation microporous brick and preparation method thereof | |
| CN110357582A (en) | A method of blending incineration of refuse flyash prepares road surface fired brick | |
| CN104326734A (en) | Ultra-thin renewable ceramic brick and making method thereof | |
| CN103521696A (en) | Molding sand for pressure plate casting and preparation method of molding sand | |
| CN103468240B (en) | Ultralow-density ceramsite proppant with flint clay tailings as raw materials and preparation method of ultralow-density ceramsite proppant | |
| CN107056288A (en) | A kind of preparation method of zirconium oxide electronics load bearing board | |
| CN106673681A (en) | High-strength clay refractory bricks produced by recycling clay bricks | |
| CN103724003A (en) | Method for producing ceramsite sand | |
| CN104628382A (en) | Treatment method for recovering zirconia ceramic injection feedstock | |
| CN105152629A (en) | Basalt ceramsite | |
| CN108975877A (en) | The method of one heavy metal species slag manufacture building materials brick | |
| CN102659100A (en) | Preparation method of high-density fine-grain graphite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |