CN100457677C - Method for synthesizing sphene - Google Patents
Method for synthesizing sphene Download PDFInfo
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- CN100457677C CN100457677C CNB2007100493259A CN200710049325A CN100457677C CN 100457677 C CN100457677 C CN 100457677C CN B2007100493259 A CNB2007100493259 A CN B2007100493259A CN 200710049325 A CN200710049325 A CN 200710049325A CN 100457677 C CN100457677 C CN 100457677C
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- aspidelite
- raw material
- synthetic method
- dioxide
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Abstract
This invention relates to synthetic method of a kind of sphene. According to weight, the raw material includes: calcium carbonate 35 to 45%, titanium dioxide 27 to 37%, silica 22 to 29% or metasillicio acid 27 to 34%. The process includes: blend the ingredient, then enclose to ball mill to take wet method fine grinding for 180 to 300 minutes, drying the material, calcinate the material at 1100 to 1350deg for 30 to 60 minutes, then gain high-purity sphene.
Description
Technical field
The invention belongs to the preparation of artificial rock, relate to a kind of aspidelite (CaTiSiO
5) synthetic method, be applicable to that high level waste is disposed, artificial rock solidification treatment.
Background technology
The radwaste that is produced by devices such as all kinds of nuclear reactors, Nuclear power plants has suitable hazardness, can not be directly to environmental emission, must be cured with suitable method and by the proper device compartmentalized storage, up to wherein radioelement decay to environment do not produced harm till.The solidification treatment of cool waste and disposal technology comparative maturity, widespread use.The solidification treatment of high level waste and disposal technology still are in conceptual phase, and the large-scale through engineering approaches that is unrealized is used.How safety, solidification treatment high level waste effectively, the protection existent environment of people guarantees nuclear industry, the health of nuclear science, Sustainable development, is the current important topic that faces.
The solidification treatment of high level waste mainly contains vitrification method and artificial rock solidification method.The vitrification Technology is comparative maturity, existing through engineering approaches is used in states such as the U.S., France, Canada, but because its curing medium material is a glassy phase, glassy phase belongs to the steady phase of unsettled Jie, therefore, the vitrification body will solidify the geological disposal that the transformation period reaches the actinium series nucleic in several ten thousand years to 10000000 year and realizes safety, and its long-term safety is alarming.In addition, vitrification uses equipment complexity, cost height, and material and energy-output ratio in the treating processes are big, thereby also have the high shortcoming of solidification treatment cost.
Because geology stability, chemical stability, thermostability and the anti-radiation performance of artificial rock cured body, all much better than vitrification body, therefore, artificial rock is widely regarded as s-generation high-level waste cured body, is the especially optimal dielectric material of actinium series high-level waste of present solidification treatment high-level waste.Since people such as Rinwood in 1978 invent Synroc (synroc), comprised that state countries in the world such as U.S., Australia, Russia, English, moral have all carried out the research work of this respect.Wherein, the U.S. and Australian scientist have done research and evaluation comparatively extensively and profoundly to aspects such as its curing mechanism, preparation technology, prescription composition, microstructure, physicals, leaching performance and irradiation behaviours.
Aspidelite (CaTiSiO
5) be one of ore deposit phase the most stable on the earth, have excellent chemical stability, mechanical stability, thermostability, anti-radiation performance, can be good at satisfying the requirement of high-level waste to curing substrate.Aspidelite has good containing ability to actinide elements, lanthanon, nucleic such as U, Pu, Sr can be fixed in its lattice as a crystalline part, the artificial rock cured body that obtains has fine long-term safety, therefore, aspidelite is one of cured high-level waste ideal curing medium material.
Aspidelite is as a kind of new artificial rock curing medium material, and countries in the world are less in the research work of carrying out aspect the preparation of the synthetic and cured body of aspidelite.There is following problem in the achievement in research of prior art:
(1) in the process of synthetic aspidelite, introduce Si, Ti with raw material forms such as hexafluoro epoxy silicic acid, tetraethyl-orthosilicic acid, oxychlorination titanium, n-butyl titanate, boric acid titanyls, prices of raw and semifnished materials costliness is former, is unfavorable for the through engineering approaches application.
(2) adopt the synthetic aspidelite of liquid phase method, operation is many, complex technical process, and technology controlling and process requires high, occurs secondary pollution easily in the solidification of radwaste of reality is handled.
Summary of the invention
Purpose of the present invention is intended to overcome above-mentioned deficiency of the prior art, by adopting solid-phase synthesis, provides the synthetic method of a kind of abundant raw material cheapness, cost is low, operation is few, simple to operate aspidelite.
Advantage such as aspidelite has that chemical stability is good, good mechanical stability, anti-irradiation ability are strong can have very strong containing ability to actinium series nucleic, Sr in the high-level waste.In existing problems aspect the preparation of the synthetic and cured body of aspidelite, the present invention adopts lime carbonate (CaCO at present both at home and abroad
3), titanium dioxide (TiO
2), silicon-dioxide (SiO
2) or metasilicic acid (H
2SiO
3) wait cheap raw material, by formulating of recipe, adopt simple high temperature solid state reaction under lower temperature synthesis of high purity aspidelite (CaTiSiO
5), its reaction equation is:
CaCO
3+SiO
2+TiO
2＝CaTiSiO
5+CO
2↑
CaCO
3+H
2SiO
3+TiO
2＝CaTiSiO
5+CO
2↑+H
2O↑
Content of the present invention is: a kind of synthetic method of aspidelite is characterized in that comprising the following steps:
(1) raw material and composition: get raw material lime carbonate (CaCO
3), titanium dioxide (TiO
2), and silicon-dioxide (SiO
2) or metasilicic acid (H
2SiO
3); The weight percent of raw material consists of:
Lime carbonate 35%-45%,
Titanium dioxide 27%-37% and
Silicon-dioxide 22%-29% or metasilicic acid 27%-34%;
(2) ball milling and drying: raw material is prepared burden by described weight percent, and the wet method fine grinding is 180 minutes-300 minutes in the ball mill of packing into then, makes powder enough thin, mixes enough even; With the drying materials after the fine grinding;
(3) calcining: will be thin and the material of mill oven dry 1100 ℃～1350 ℃ temperature lower calcination 30-60 minute, promptly make and obtain highly purified aspidelite (CaTiSiO
5).
In the content of the present invention: the composition of the weight percent of raw material described in the step (1) is preferably: lime carbonate 35.79-41.79%, titanium dioxide 27.95-33.95%, metasilicic acid 27.26-33.26%; When adopting this raw material and composition, incinerating temperature described in the step (3) is 1100 ℃～1300 ℃ preferably.
In the content of the present invention: the composition of the weight percent of raw material described in the step (1) is preferably: lime carbonate 38.70-44.70%, titanium dioxide 30.27-36.27%, silicon-dioxide 22.03-28.03%; During with this raw material and composition, incinerating temperature described in the step (3) is 1150 ℃～1350 ℃ preferably.
In the content of the present invention: the temperature of oven dry is 50 ℃～90 ℃ preferably described in the step (2).
In the content of the present invention: described in the step (2) in the ball mill weight ratio of raw material and abrading-ball be 1: 2 preferably.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) the present invention is with cheap, abundant silicon-dioxide (SiO
2) or metasilicic acid (H
2SiO
3), titanium dioxide (TiO
2) replace raw materials such as expensive hexafluoro epoxy silicic acid, tetraethyl-orthosilicic acid, oxychlorination titanium, n-butyl titanate, boric acid titanyl to introduce Si, Ti, adopting the synthetic aspidelite of solid state reaction, technology is simple, and cost is low, helps through engineering approaches and uses;
(2) the present invention as one of main raw material, utilizes the decomposition of silicon-dioxide metasilicic acid under the effect of grinding or under lower temperature with the silicon-dioxide of cheapness, metasilicic acid etc., generates active well SiO
2Effect by grinding makes the reactant uniform mixing, and obtains to answer active well SiO
2And TiO
2Thereby the high purity aspidelite (CaTiSiO of synthesizing stable at a lower temperature
5);
(3) utilization of the present invention aspidelite (CaTiSiO under lower temperature
5) generation, help aspidelite (CaTiSiO
5) basic artificial rock cured body realizes good sintering under lower temperature, the sintering of synthetic and cured body that makes the target mineral is finished in same operation, under the same temperature, can simplify the curing process of radwaste greatly, reduce the secondary pollution that produces in the solidification treatment process.
In sum, adopt the synthetic aspidelite of present method, raw materials cost is low, operation is few, simple to operate, easy control (can reduce or avoid the secondary pollution in the solidification treatment process in the high-level waste solidification treatment), synthesis temperature is lower, purity is high, helps aspidelite (CaTiSiO
5) basic artificial rock cured high-level waste (for example: actinium series nucleic high-level waste) use by through engineering approaches.
Further illustrate content of the present invention below by embodiment, but these embodiment do not limit protection scope of the present invention.
Embodiment 1:
A kind of synthetic method of aspidelite comprises the following steps:
(1) raw material and composition: get raw material lime carbonate (CaCO
3), titanium dioxide (TiO
2) and silicon-dioxide (SiO
2); The weight percent of raw material consists of: silicon-dioxide (SiO
2) 25.02wt.%, lime carbonate (CaCO
3) 41.7wt.%, titanium dioxide (TiO
2) 33.28wt.%.
(2) ball milling and drying: raw material is prepared burden by described weight percent, and the wet method fine grinding is 240 minutes in the ball mill of packing into then (for example planetary mills), makes powder enough thin, mixes enough even; Material after the fine grinding is dried down at 70 ℃;
(3) calcining: will be thin and the material of mill oven dry 1320 ℃ temperature lower calcination 30 minutes, promptly make and obtain highly purified aspidelite (CaTiSiO
5).
Embodiment 2:
A kind of synthetic method of aspidelite is with metasilicic acid (H
2SiO
3), lime carbonate (CaCO
3), titanium dioxide (TiO
2) be raw material, the weight percent of raw material consists of: metasilicic acid 30.27wt.%, CaCO
338.78wt.%, TiO
230.95wt.%.Press good above-mentioned each material of weight percent difference weighing of raw material, fine grinding is 210 minutes in fine grinding equipment ball mill (such as planetary mills), obtains fine size, forms uniform powder.Powder after the fine grinding 50 ℃ of down oven dry, and 1280 ℃ of calcinings and be incubated 30 minutes, is obtained highly purified aspidelite (CaTiSiO
5).
Embodiment 3:
A kind of synthetic method of aspidelite is with lime carbonate (CaCO
3), titanium dioxide (TiO
2) and silicon-dioxide (SiO
2) be raw material; The weight percent of raw material consists of: silicon-dioxide 25.52wt.% (weight percentage), CaCO
340.7wt.%, TiO
233.78wt.%.Press good above-mentioned each material of weight percent difference weighing of raw material, fine grinding is 240 minutes in fine grinding equipment ball mill (such as planetary mills), obtains fine size, forms uniform powder.70 ℃ of down oven dry, and 1290 ℃ of calcinings and be incubated 60 minutes obtain highly purified aspidelite (CaTiSiO with the powder after the fine grinding
5).
Embodiment 4:
A kind of synthetic method of aspidelite is with metasilicic acid (H
2SiO
3), lime carbonate (CaCO
3), titanium dioxide (TiO
2) be raw material, the weight percent of raw material consists of: metasilicic acid 30.77wt.% (weight percentage), CaCO
337.78wt.%, TiO
231.45wt.%.Press good above-mentioned each material of weight percent difference weighing of raw material, fine grinding is 210 minutes in fine grinding equipment ball mill (such as planetary mills), obtains fine size, forms uniform powder.Powder after the fine grinding 50 ℃ of down oven dry, and 1250 ℃ of calcinings and be incubated 60 minutes, is obtained highly purified aspidelite (CaTiSiO
5).
Embodiment 5-10:
A kind of synthetic method of aspidelite, raw material and weight percent consist of:
The synthesis preparation method of each embodiment is with embodiment 1 or 2 or identical with the processing method step described in the content of the present invention and condition, parameter, slightly in the table.
The invention is not restricted to the foregoing description, content of the present invention is described all can implement and have described good result.
Claims (7)
1, a kind of synthetic method of aspidelite is characterized in that comprising the following steps:
(1) raw material and composition: get raw material lime carbonate, titanium dioxide and silicon-dioxide or metasilicic acid; The weight percent of raw material consists of:
Lime carbonate 35%-45%,
Titanium dioxide 27%-37% and
Silicon-dioxide 22%-29% or metasilicic acid 27%-34%;
(2) ball milling and drying: raw material is prepared burden by described weight percent, and the wet method fine grinding is 180 minutes-300 minutes in the ball mill of packing into then; With the drying materials after the fine grinding;
(3) calcining: the material of fine grinding and oven dry 1100 ℃～1350 ℃ temperature lower calcination 30-60 minute, is promptly made and obtains highly purified aspidelite.
2, by the synthetic method of the described aspidelite of claim 1, it is characterized in that: the weight percent of raw material consists of described in the step (1): lime carbonate 35.79-41.79%, titanium dioxide 27.95-33.95%, metasilicic acid 27.26-33.26%.
3, by the synthetic method of the described aspidelite of claim 1, it is characterized in that: the weight percent of raw material consists of described in the step (1): lime carbonate 38.70-44.70%, titanium dioxide 30.27-36.27%, silicon-dioxide 22.03-28.03%.
4, by the synthetic method of claim 1,2 or 3 described aspidelites, it is characterized in that: the temperature of oven dry is 50 ℃～90 ℃ described in the step (2).
5, by the synthetic method of the described aspidelite of claim 2, it is characterized in that: incinerating temperature described in the step (3) is 1100 ℃～1300 ℃.
6, press the synthetic method of the described aspidelite of claim 3.It is characterized in that: incinerating temperature described in the step (3) is 1150 ℃～1350 ℃.
7, by the synthetic method of the described aspidelite of claim 1, it is characterized in that: described in the step (2) in the ball mill weight ratio of raw material and abrading-ball be 1: 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100493259A CN100457677C (en) | 2007-06-15 | 2007-06-15 | Method for synthesizing sphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100493259A CN100457677C (en) | 2007-06-15 | 2007-06-15 | Method for synthesizing sphene |
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|---|---|
| CN101070243A CN101070243A (en) | 2007-11-14 |
| CN100457677C true CN100457677C (en) | 2009-02-04 |
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ID=38897682
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|---|---|---|---|
| CNB2007100493259A Expired - Fee Related CN100457677C (en) | 2007-06-15 | 2007-06-15 | Method for synthesizing sphene |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102930915B (en) * | 2012-10-24 | 2015-08-19 | 西南科技大学 | A kind of preparation method of solidification of radwaste body |
| CN105400054A (en) * | 2015-12-29 | 2016-03-16 | 卓达新材料科技集团有限公司 | Anti-radiation plate and preparation method thereof |
| CN106448792B (en) * | 2016-10-11 | 2018-08-31 | 西南科技大学 | A kind of preparation method of aspidelite type prosthetic graft |
| CN106977104A (en) * | 2017-03-10 | 2017-07-25 | 华南理工大学 | A kind of preparation method of reflective insulation ceramics using titanium sphene as principal crystalline phase |
| CN107777694B (en) * | 2017-11-20 | 2020-09-15 | 吉林大学 | Method for preparing sphene from xonotlite |
| CN109231977B (en) * | 2018-11-02 | 2021-01-12 | 中国科学院上海硅酸盐研究所 | High-temperature stable dielectric ceramic material and preparation method thereof |
| CN114804829B (en) * | 2022-05-11 | 2023-07-14 | 中国地质大学（北京） | Modified sphene and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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2007
- 2007-06-15 CN CNB2007100493259A patent/CN100457677C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1767077A (en) * | 2005-08-06 | 2006-05-03 | 西南科技大学 | Method for preparing high radioactive waste curing treatment base material |
Non-Patent Citations (2)
| Title |
|---|
| 钙钛锆石和榍石人造岩石固化模拟放射性焚烧灰的研究. 车春霞等.辐射防护，第26卷第3期. 2006 |
| 钙钛锆石和榍石人造岩石固化模拟放射性焚烧灰的研究. 车春霞等.辐射防护，第26卷第3期. 2006 * |
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|---|---|
| CN101070243A (en) | 2007-11-14 |
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Granted publication date: 20090204 Termination date: 20120615 |