CN109903875A - A kind of method that phosphate polymer solidifies boracic nuclear waste - Google Patents
A kind of method that phosphate polymer solidifies boracic nuclear waste Download PDFInfo
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- CN109903875A CN109903875A CN201910148097.3A CN201910148097A CN109903875A CN 109903875 A CN109903875 A CN 109903875A CN 201910148097 A CN201910148097 A CN 201910148097A CN 109903875 A CN109903875 A CN 109903875A
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Abstract
The invention discloses a kind of polymer solidify in low-activity nuclear waste method, its essence is a kind of phosphate polymers to solidify the method for boracic nuclear waste.Mainly comprise the following steps: (1) concentrated phosphoric acid is mixed in a certain ratio with the boracic nuclear waste after concentration and prepares mixed solution；(2) using waterglass and aluminium polychloride as raw material, hydrochloric acid is that additive prepares polymer precursor；(3) mixed solution in step (1) is mixed in a certain ratio with the polymer precursor in step (2), stirs evenly, prepares boracic nuclear waste solidified body.This method boracic nuclear waste inclusion quantity is big, does not need to add alkali neutralization, overcomes the strong defect of cement solidification method deferred action, and final solidified body stability is good, and preparation process is simple, at low cost, without secondary pollution, is easy to be engineered application.
Description
Technical field
The present invention relates to a kind of methods that phosphate polymer solidifies boracic nuclear waste, and it is useless to belong to a kind of middle low-activity nuclear
Liquid solidification technology and Material Field.
Background technique
Global energy crisis has pushed the fast development of nuclear energy uses.While nuclear power industry high speed development, Spent Radioactive
Object safe disposal problem is further prominent.Boracic nuclear waste is useless as the radioactive nucleus generated in pressurized-water reactor nuclear power plant operational process
Liquid is mainly made of borate, a small amount of sodium nitrate and sodium phosphate, and acid stronger, salt content is high, and processing difficulty is big.Currently, nuclear power
It stands and disposes the main thought of boracic nuclear waste are as follows: nuclear waste is concentrated-adds alkali neutralization-cement solidification-final disposal.
Cement solidification technique is that nuclear waste blending is formed to the process of solidified cement body in base-material.But conventional cement solidifies
For technique when solidifying boracic nuclear waste, that there are quantity of alkali consumptions is big, at high cost, inclusion quantity is low, borate deferred action is strong, secondary
The defects of pollution, it would be highly desirable to develop a kind of safe and efficient novel boracic nuclear waste curing process.
A.M. the scholars' studies have shown that carrying out cured process to radioactive waste using cement such as El-Kamash
In, zeolite is added into ordinary portland cement, the compression strength of solidified cement body can be effectively improved and reduce radionuclide ion leaching
Extracting rate, but the problems such as this method needs plus alkali neutralization, and quantity of alkali consumption is big, and there are slow settings.Chinese patent CN 101456715A is public
Cloth is a kind of, and that leaching rate of the radionuclide in solidified cement body and addition lime are reduced by addition zeolite is solid to adjust
Change the curing method of the setting time of body, but this method complex treatment process, needs to mix the addition such as water-reducing agent in disposal process
Agent, it is at high cost.Chinese patent CN 105741899A disclose a kind of new radioactivity borate waste solution curing process additive,
Curing formula and technique are accelerated hardening of cement using sodium metaaluminate and are condensed, added again by the way that borate is prepared into condensed borate
The solidified body boric acid containing rate for adding the cured method of curing agent that can make preparation reaches 49.5%, can preferably make up conventional cement
Solidify that containing rate is low and the strong defect of deferred action.But it is big, secondary that the technology still remains complex technical process, quantity of alkali consumption
The disadvantages of pollution and high cost.
Above method is all made of alkaline cementitious material solidification boracic nuclear waste, but can not overcome simultaneously quantity of alkali consumption it is big,
At high cost, the defects of inclusion quantity is low, borate deferred action is strong, secondary pollution.In order to make up the deficiency of cement solidification technology,
The present invention proposes that using concentrated phosphoric acid as exciting agent, boracic nuclear waste is solvent, mixes, preparation contains with polymer precursor material
Boron nuclear waste solidified body.Inventive polymers solidification process handles nuclear waste by curing agent of sour excited cementing material, solidifies
Without adding alkali neutralization in journey, the cured deficiency of conventional cement can be made up.
Summary of the invention
The present invention provides a kind of method that phosphate polymer solidifies boracic nuclear waste, specific summary of the invention is as follows:
Boracic nuclear waste, concentrated phosphoric acid and polymer precursor after concentration is mixed with boracic nuclear waste solidified body by the present invention.
Concentrated phosphoric acid and boracic nuclear waste provide strong acid and hypersaline environment for polymerization reaction, not only increase polymerization rate, also effective
Shorten curing time.
Beneficial effects of the present invention:
(1) for curing process of the present invention without adding alkali neutralization, the acid medium for including using acid solution and boracic nuclear waste itself is molten
Silane agent is solved, low energy consumption, and simple process is easy to engineer application；
(2) solidified body of the present invention does not need to be press-formed, and can voluntarily pour hardening；
(3) solidified body mechanical performance of the present invention and corrosion resistance are strong, and long-term safety stability is good, and containing rate is high, are conducive to contain
The solidification of boron nuclear waste；
(4) whole preparation process and use process involved in the present invention are generated without any toxic pollutant, safety and environmental protection.
Specific embodiment
Case study on implementation 1:
A kind of method that phosphate polymer solidifies boracic nuclear waste, with Si/Al molar ratio be 0.5 by waterglass (m=3.17) and
Aluminium polychloride mixing, is slowly added to hydrochloric acid (plural gel pH=3 ~ 4) while stirring, through suction filtration, washing, drying after 2 h of stirring
And grinding process, 2 h are calcined under the conditions of 800 oC, 2 h of ball milling, obtains polymer precursor after cooled to room temperature, with
Boracic nuclear waste, polybenzazole precursor body mass ratio 2:3:4 mixing after concentrated phosphoric acid (85 wt.%), concentration, stir moulding by casting system
Standby solidified body, after conserving 28 d, compression strength is up to 32 MPa.According to PCT method in ASTM standard to solidified body anti-leaching performance
It is analyzed, the Sr measured2+、Cs+Normalized leaching rate 10-5Below.
Case study on implementation 2:
A kind of method that phosphate polymer solidifies boracic nuclear waste, with Si/Al molar ratio be 0.5 by waterglass (m=3.17) and
Aluminium polychloride mixing, is slowly added to hydrochloric acid (plural gel pH=3 ~ 4) while stirring, through suction filtration, washing, drying after 2 h of stirring
And grinding process, 2 h are calcined under the conditions of 800 oC, 2 h of ball milling, obtains polymer precursor after cooled to room temperature, with
Boracic nuclear waste, polybenzazole precursor body mass ratio 1:1:1 mixing after concentrated phosphoric acid (85 wt.%), concentration, stir moulding by casting system
Standby solidified body, after conserving 28 d, compression strength is up to 29 MPa.According to PCT method in ASTM standard to solidified body anti-leaching
It can be carried out analysis, the Sr measured2+、Cs+Normalized leaching rate 10-5Below.
Finally, it is stated that the above preferred implementation case is only used to illustrate the technical scheme of the present invention and not to limit it, although
The present invention is described in detail by above-mentioned preferred implementation case, however, those skilled in the art should understand that, can
To make various change to it in the form and details, without departing from claims of the present invention limited range.
Claims (5)
1. the invention discloses a kind of polymer solidify in low-activity nuclear waste method, its essence is a kind of phosphate polymerize
The method that object solidifies boracic nuclear waste.Mainly comprise the following steps:
(1) the boracic nuclear waste after concentrated phosphoric acid and concentration is mixed in a certain ratio and prepares mixed solution；
(2) using waterglass and aluminium polychloride as raw material, hydrochloric acid is additive, and it is compound solidifying to prepare waterglass-aluminium polychloride
Glue prepares polymer precursor through suction filtration, washing, drying, grinding, calcining and ball milling process；
(3) mixed solution in step (1) is mixed in a certain ratio with the polymer precursor in step (2), is stirred evenly,
Pour maintenance.
2. concentrated phosphoric acid according to claim 1, main feature are as follows: concentrated phosphoric acid mass percent concentration
Range is 85 ~ 95%.
3. waterglass according to claim 1, main feature are as follows: modulus of water glass range is 2.5 ~ 3.5.
4. the preparation of polymer precursor according to claim 1, main feature are as follows: waterglass and polyaluminium
Aluminum solutions uniformly mix, and Si/Al molar ratio is=0.5 ~ 1；It is slowly added to hydrochloric acid while stirring, its pH value is made to be maintained at 3 ~ 4 ranges
It is interior, prepare waterglass-aluminium polychloride plural gel；It is separated by solid-liquid separation after 2 ~ 5 h of stirring, and is washed with deionized 2 ~ 3
It is secondary；Filter cake after washing is ground to powder after dry 24 h of 105 oC in drying box；It is right under the conditions of 800 ~ 1000 oC
2 ~ 5 h of xerogel powder calcination, cooled to room temperature；Using ball mill to calcined 2 ~ 5 h of xerogel powder ball milling, obtain
To polymer precursor.
5. the preparation of mixed solution according to claim 1 and boracic nuclear waste solidified body, main feature are as follows:
mConcentrated phosphoric acid: mBoracic nuclear waste=0.65~1.5；mPresoma: mMixed solution=0.7~1。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482853A (en) * | 2019-09-17 | 2019-11-22 | 济南大学 | It is a kind of that toxic metal ions in electroplating wastewater are solidified to method and gained glass in sodium calcium aluminium silicate glass |
| CN111403072A (en) * | 2020-03-21 | 2020-07-10 | 哈尔滨工程大学 | Method for curing iodine-containing zeolite by using phosphate adhesive |
| CN113620638A (en) * | 2021-09-22 | 2021-11-09 | 中国核动力研究设计院 | Radioactive waste curing treatment additive, preparation method and curing agent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482853A (en) * | 2019-09-17 | 2019-11-22 | 济南大学 | It is a kind of that toxic metal ions in electroplating wastewater are solidified to method and gained glass in sodium calcium aluminium silicate glass |
| CN111403072A (en) * | 2020-03-21 | 2020-07-10 | 哈尔滨工程大学 | Method for curing iodine-containing zeolite by using phosphate adhesive |
| CN111403072B (en) * | 2020-03-21 | 2022-12-13 | 哈尔滨工程大学 | Method for curing iodine-containing zeolite by using phosphate adhesive |
| CN113620638A (en) * | 2021-09-22 | 2021-11-09 | 中国核动力研究设计院 | Radioactive waste curing treatment additive, preparation method and curing agent |
| CN113620638B (en) * | 2021-09-22 | 2022-07-01 | 中国核动力研究设计院 | Radioactive waste curing treatment additive, preparation method and curing agent |
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