CN108520790B - Method for solidifying fluorine-containing radioactive waste liquid - Google Patents

Method for solidifying fluorine-containing radioactive waste liquid Download PDF

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CN108520790B
CN108520790B CN201810294474.XA CN201810294474A CN108520790B CN 108520790 B CN108520790 B CN 108520790B CN 201810294474 A CN201810294474 A CN 201810294474A CN 108520790 B CN108520790 B CN 108520790B
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cement
fluorine
waste liquid
radioactive waste
containing radioactive
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CN108520790A (en
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钱正华
刘学阳
乔延波
夏晓彬
马洪军
王帅
秦强
施柳青
彭红花
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Shanghai Institute of Applied Physics of CAS
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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/16—Processing by fixation in stable solid media
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/20—Disposal of liquid waste

Abstract

The invention provides a method for solidifying fluorine-containing radioactive waste liquid, which comprises the following steps: s1, providing fluorine-containing radioactive waste liquid, wherein the fluorine-containing radioactive waste liquid comprises fluorine and radioactive waste liquid; s2, mixing cement ash with the fluorine-containing radioactive waste liquid to form cement paste, wherein the cement ash comprises: KH (Perkin Elmer)2PO4Reburning MgO, additive and borax; s3, forming a first cement solidified body by curing, initial setting and final setting of the cement paste; and S4, curing the first cement cured body to form a second cement cured body. The second cement solidified body has higher compressive strength and can form effective package on radioactive elements and fluorine ions, and the requirement of final disposal is met.

Description

Method for solidifying fluorine-containing radioactive waste liquid
Technical Field
The invention relates to a radioactive waste liquid curing method, in particular to a method for curing fluorine-containing radioactive waste liquid.
Background
Molten salt reactor adopts molten fluoride salt as main coolant, and fuel of liquid molten salt reactor is dissolved in fluoride high-temperature molten salt. The development and operation processes of the molten salt reactor can generate radioactive wastes with fluorine salt as a main component, and the processes of dry-method post-treatment, fuel salt analysis and test, separation and recovery of fuel added salt and the like of the spent fuel can also generate various types of radioactive wastes, wherein the radioactive wastes necessarily comprise fluorine-containing radioactive waste liquid. In order to ensure the safety of peripheral public and reduce the pollution of waste liquid to the environment, the fluorine-containing radioactive waste liquid needs to be subjected to volume reduction and solidification treatment so as to meet the requirement of safe temporary storage.
When the silicate cement solidifies the fluorine-containing radioactive waste liquid with higher fluorine ion concentration, the initial setting time of the cement paste is greatly reduced, and the initial setting time is only 2-3min when the fluorine ion concentration is 8 wt%; after the retarder (borax) is added, the compressive strength of the cement solidified body is greatly reduced, and the national standard requirement cannot be met.
Therefore, a new cement formula and a new method are needed for curing the fluorine-containing radioactive waste liquid so as to solve the problem of short initial setting time of cement paste. Meanwhile, the cement solidified body has higher compressive strength and can form effective package on radioactive elements and fluorine ions, and the requirement of final disposal is met.
Disclosure of Invention
In order to solve the problems of short initial setting time and the like of the solidification of the fluorine-containing radioactive waste liquid cement, the invention provides a solidification method of fluorine-containing radioactive waste liquid.
The invention provides a method for solidifying fluorine-containing radioactive waste liquid, which comprises the following steps: s1, providing fluorine-containing radioactive waste liquid, wherein the fluorine-containing radioactive waste liquid comprises fluorine and radioactive waste liquid; s2, mixing cement ash with the fluorine-containing radioactive waste liquid to form cement paste, wherein the cement ash comprises KH2PO4Reburning MgO, additive and borax; s3, forming a first cement solidified body by curing, initial setting and final setting of the cement paste; and S4, curing the first cement cured body to form a second cement cured body.
Specifically, in step S3, the first cement cured product is cured in air to form a second cement cured product.
Preferably, in step S3, the first cement cured product is cured in air for 28 days to form a second cement cured product. Wherein, step S2 includes: s21, providing a mixture of cement ash and fluorine-containing radioactive waste liquid; s22, slowly stirring for 20-40S, and then quickly stirring for 80-100S to obtain uniform cement slurry.
Preferably, in step S21, the weight ratio of the cement ash to the fluorine-containing radioactive waste liquid is 1: 0.18-0.19.
Preferably, the initial setting time of the cement is 20-30min, and the final setting time is 1-2 min.
Preferably, KH2PO4The weight ratio of the dead burned MgO, the additive and the borax is 0.25: 1: 0-0.1: 0.1-0.15. The adoption of the phosphate to replace silicate prolongs the initial setting time of the cement paste, enhances the compressive strength of the second cement solidified body and has better wrapping property on fluorine ions. The reactivity of the cement ash is increased by reburning MgO. The initial setting time of the cement paste is prolonged by adopting borax. The compressive strength of the second cement solidified body is improved by using the additive.
Preferably, the additive comprises at least one of quartz sand, zeolite, silica fume and fly ash.
Preferably, the weight percentage of fluorine in the fluorine-containing radioactive waste liquid is 0.01-12%.
Preferably, the weight percentage of fluorine in the fluorine-containing radioactive waste liquid is 2%.
Preferably, the fluorine content in the fluorine-containing radioactive waste liquid is 12% by weight.
Preferably, the fluorine-containing radioactive waste liquid contains Cs+、Sr2+And Co2+At least one of (1).
Preferably, the radioactive waste liquid contains 0-4.412g/L of radioactive element Cs.
Preferably, the radioactive waste liquid contains 0-4.601g/L of radioactive element Sr.
Preferably, the radioactive waste liquid contains 0-4.305g/L of radioactive element Co.
The invention provides a method for curing fluorine-containing radioactive waste liquid, which solves the problem of short initial setting time of cement paste. Meanwhile, the cement solidified body has higher compressive strength and can form effective package on radioactive elements and fluorine ions, and the requirement of final disposal is met.
Drawings
FIG. 1 is a graph showing the change in leaching rates of radioactive elements 0 to 42d in a second cement solidification product according to example 1;
FIG. 2 is a graph showing the change in the cumulative leaching rates of radioactive elements 0 to 42d in a second cement solidification body according to example 1;
FIG. 3 shows F in a second cement cured body according to example 1-0-42d average leaching concentration variation graph;
FIG. 4 shows F in a second cement cured body according to example 1-The leaching rate and the accumulated leaching proportion change chart of 0-42 d.
Detailed Description
The technical solutions of the present invention will be described in detail below with reference to specific embodiments thereof, but the following examples are only for understanding the present invention and do not limit the present invention, the examples of the present invention and features thereof may be combined with each other, and the present invention may be implemented in various different ways as defined and covered by the claims.
Example 1
The method for solidifying the fluorine-containing radioactive waste liquid provided by the invention comprises the step S1 of providing the fluorine-containing radioactive waste liquid, wherein the fluorine-containing radioactive waste liquid comprises fluorine and radioactive waste liquid.
The radioactive waste liquid adopts CsNO3、Sr(NO3)2And Co (NO)3)2Solution mix preparation, the fluorine is provided by NaF added to the radioactive spent solution. Thus, CsNO is adopted as the fluorine-containing radioactive waste liquid3、Sr(NO3)2、Co(NO3)2And NaF solution is prepared to form simulated radioactive waste liquid, wherein the contents of radioactive elements Sr, Cs and Co are 4.412g/L, 4.601g/L and 4.305g/L respectively.
The solidification method of the fluorine-containing radioactive waste liquid provided by the invention comprises the step S2 of adding cement ash and 44.4mL of fluorine-containing radioactive waste liquid into a cement paste mixer, wherein the weight ratio of the cement ash to the fluorine-containing radioactive waste liquid is 1: 0.185, slowly stirring for 30s, and then rapidly stirring for 90s to obtain uniform cement slurry.
The method for curing the fluorine-containing radioactive waste liquid comprises the step S3 of injecting the obtained cement paste into a diameter of 50 x 50mm3Curing in the plastic mould, performing initial setting and final setting to obtain a first cement cured body, and curing for 28 days to obtain a second cementAnd (5) curing the body.
The cement ash comprises KH2PO4The additive comprises quartz sand, zeolite, silica fume and fly ash. In this example, the cement ash component described above and 2.12g of NaF solids were mixed uniformly using a cement paste mixer according to the formulation in Table 1. In the embodiment, the reburning MgO is 200 meshes, so that the reactivity of the cement ash is increased; the silica sand size is 800 mesh, thereby reducing the porosity of the formed first and second cement cured bodies.
The cement slurry, the first cement cured body, and the second cement cured body were characterized by the following methods.
(1) Characterization of cement paste: and (5) observing the fluidity and the existence of the layering phenomenon of the cement paste. And recording the initial setting time and the final setting time of the cement.
Specifically, in the embodiment, the cement slurry has moderate fluidity and no layering phenomenon. The initial setting time of the cement paste is about 30min, the initial setting time is longer, and the final setting is 1-2min after the initial setting.
(2) First cement cured body characterization: the appearance of the first cement cured body was observed.
Specifically, in this example, the first cement cured body was intact in appearance, had no cracks, and had no free liquid on the surface.
(3) Second cement solidification body leaching test: the leaching performance test is carried out according to the requirements of GBT 7023-.
Specifically, in this embodiment, the compressive strength of the second cement solidified body is greater than 50MPa, which is much greater than the requirement of 7MPa in the national standard. After the second cement solidified body is soaked in deionized water for 42 days, no obvious crack or crazing exists in the appearance of the second cement solidified body, the loss of the compressive strength is 12.8 percent, the requirement that the loss of the compressive strength of the second cement solidified body after being soaked in the national standard is not more than 25 percent is met, and the compressive strength is higher.
Referring to FIGS. 1 and 2, in the present embodiment, Sr is contained in the second cement solidification body2+The extraction rate of (d) 42 was 1.96X 10-5cm/d, cumulative leaching rate of 6.10 multiplied by 10-4cm；Cs+The extraction rate of (d) 42 was 6.46X 10-4cm/d, cumulative extraction rate of 5.80X 10-2cm；Co2+The extraction rate of (d) 42 was 8.29X 10-8cm/d, cumulative extraction rate of 5.57X 10-5cm, which results meet the limits of GB14569.1-2011, forming an effective package for radioactive elements.
Referring to fig. 3, the maximum average leaching concentration of fluoride ions of the second cement cured body in the present embodiment is 35mg/L which is much lower than the limit of 100mg/L of GB 5085.3-2007.
Referring to FIG. 4, the 42d leaching rate of fluoride ions of the second cement cured body in this example was 1.74X 10-3cm/d, the result is lower than that of the prior art portland cement with the leaching rate of 4.59 multiplied by 10 in 42d-3cm/d. The 42d leaching amount of the fluoride ions accounts for 10.68 percent of the total amount of the fluoride ions in the cement solidified body sample, and the rest 89.32 percent of the fluoride ions are wrapped in a second cement solidified body which effectively wraps the fluoride ions.
Example 2-example 12
Essentially identical to the experimental procedure of example 1, except that the amounts of the components used in each example were different, as shown in table 1 below.
Figure BDA0001618399750000051
In examples 2 to 12, the cement slurries were moderately fluid and free from delamination. The initial setting time of each cement paste is 20min-30min, the final setting is carried out within 1-2min after the initial setting, and the initial setting time is longer.
Each of the first cement cured bodies was intact in appearance and free from cracks.
The compressive strength of each second cement solidified body is more than 50MPa, which accords with the limit value of national standard GB14569.1-2011 and has higher compressive strength. Co of each second cement cured body2+The extraction rate of 42d is lower than 1.54 multiplied by 10-7cm/d，Sr2+The extraction rate of 42d is lower than 2.63 multiplied by 10-5cm/d，Cs+The extraction rate of 42d is lower than 6.92 multiplied by 10-4cm/d, meets the limit value of GB14569.1-2011, and improves the packaging capacity of radioactive elements. The leaching concentration of the fluoride ions of each second cement solidified body is lower than 100mg/L, and the second cement solidified body conforms to GB5085.3-2007, effective encapsulation of fluoride ions.
The above embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and various changes may be made in the above embodiments of the present invention. Even if not in accordance with the method provided by the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.

Claims (2)

1. A method for solidifying fluorine-containing radioactive waste liquid, which is characterized by comprising the following steps:
s1, providing a fluorine-containing radioactive waste liquid, wherein the fluorine-containing radioactive waste liquid comprises fluorine and radioactive waste liquid, the weight percentage of the fluorine in the fluorine-containing radioactive waste liquid is 0.01-12%, and the radioactive waste liquid contains Cs+、Sr2+And Co2+(ii) a Said Sr2+、Cs+And Co2+The content of the compounds is 4.412g/L, 4.601g/L and 4.305g/L respectively;
s2, mixing the components in a weight ratio of 1: mixing 0.18-0.19 cement ash with the fluorine-containing radioactive waste liquid, slowly stirring for 20-40 s, and then quickly stirring for 80-100s to form uniform cement paste, wherein the cement ash comprises KH2PO4Re-burning MgO and borax, KH2PO4The weight ratio of the dead burned MgO to the borax is 0.25: 1: 0.1-0.15;
s3, curing the cement paste, initially setting and finally setting to form a first cement cured body, wherein the initial setting time is 20-30min, and the final setting time is 1-5 min;
and S4, curing the first cement solidified body to form a second cement solidified body.
2. The solidification method according to claim 1, wherein the fluorine-containing radioactive waste liquid is a simulated radioactive waste liquid.
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CN109748567B (en) * 2019-01-11 2021-09-07 济南大学 Medium-low radioactivity waste resin phosphoaluminate cement-based cured base material
CN109903875A (en) * 2019-02-28 2019-06-18 西南科技大学 A kind of method that phosphate polymer solidifies boracic nuclear waste
CN110491538A (en) * 2019-09-27 2019-11-22 中国科学院上海应用物理研究所 A kind of curing method of radioactive liquid waste with high salt
CN114751666B (en) * 2022-04-27 2023-03-10 中国科学院青海盐湖研究所 Method for preparing magnesium material by using waste aluminum electrolysis waste cathode carbon block as raw material

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