CN110648777A - Efficient cement solidification treatment method for low-pH radioactive waste liquid - Google Patents

Efficient cement solidification treatment method for low-pH radioactive waste liquid Download PDF

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Publication number
CN110648777A
CN110648777A CN201910536572.4A CN201910536572A CN110648777A CN 110648777 A CN110648777 A CN 110648777A CN 201910536572 A CN201910536572 A CN 201910536572A CN 110648777 A CN110648777 A CN 110648777A
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waste liquid
radioactive waste
stirring
cement
low
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CN110648777B (en
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闫晓俊
郭喜良
郭霄斌
柳兆峰
刘建琴
冯文东
高超
安鸿翔
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China Institute for Radiation Protection
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China Institute for Radiation Protection
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    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04Treating liquids
    • G21F9/06Processing
    • G21F9/16Processing by fixation in stable solid media
    • G21F9/162Processing by fixation in stable solid media in an inorganic matrix, e.g. clays, zeolites
    • G21F9/165Cement or cement-like matrix

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention belongs to the technical field of radioactive waste treatment, and relates to a high-efficiency cement solidification treatment method for low-pH radioactive waste liquid. The method sequentially comprises the following steps: (1) adding cement, lime and an additive into a stirring container in advance, starting stirring, lowering a stirring paddle, adding the radioactive waste liquid into the stirring container, finishing adding the radioactive waste liquid when the stirring paddle is lowered to the lowest position, and continuing stirring for a period of time after finishing adding the radioactive waste liquid; (2) and transferring the stirred cement paste for curing. By using the efficient cement solidification treatment method for the low-pH radioactive waste liquid, the high-volume-ratio solidification of the waste liquid can be realized on the premise that the solidified performance of the waste liquid meets various performance requirements of GB 14569.1-2011.

Description

Efficient cement solidification treatment method for low-pH radioactive waste liquid
Technical Field
The invention belongs to the technical field of radioactive waste treatment, and relates to a high-efficiency cement solidification treatment method for low-pH radioactive waste liquid.
Background
The radioactive waste liquid generated during the operation and maintenance of the high-temperature gas cooled reactor mainly comprises leakage waste water collected in a water collecting pit, waste water in a decontamination room, waste water in a laboratory, equipment decontamination and ground washing waste water and laundry waste water. Radioactive waste liquid from different sources needs to be measured for radioactivity, and waste liquid which can not be discharged up to standard is discharged into a low-level waste liquid storage tank, and is subjected to evaporation concentration and cement solidification treatment.
The cement solidification of radioactive waste liquid is a traditional low-level radioactive waste liquid treatment technology. The technology has the advantages of simple process, mature technology, good stability of waste solidified bodies, low cost and the like. The basic principle of cement curing is as follows: the cement is used as an inorganic gel curing base material, the cement, the radioactive waste and other materials are uniformly mixed according to a certain proportion, and a cured body is formed under proper curing conditions, so that the waste is stabilized.
From the viewpoint of the safety of radioactive waste disposal for a long time, the main factors to be considered in the research of radioactive waste liquid solidification technology are:
(1) aiming at the physical, chemical and radioactive characteristics of radioactive waste liquid, the development of a solidification method is carried out;
(2) from the perspective of practical engineering application, the curing method should meet the relevant technical requirements of the curing process and the curing equipment;
(3) from the viewpoint of waste minimization, the volume containing rate of the waste liquid is increased as much as possible;
(4) the performance of the waste liquid cement solidified body should meet various requirements of the cement solidified body (GB14569.1-2011) for the performance requirements of low and medium-level radioactive waste solidified bodies, including compressive strength, impact resistance, leaching resistance, soaking resistance, freezing and thawing resistance and irradiation resistance.
Disclosure of Invention
The invention aims to provide an efficient cement solidification treatment method for low-pH radioactive waste liquid, which can realize high-volume-ratio solidification of the waste liquid on the premise that the solidified performance of the waste liquid meets various performance requirements of GB 14569.1-2011.
To achieve this object, in a basic embodiment, the present invention provides a method for the efficient cement setting treatment of low pH radioactive waste liquid, said method comprising the following steps in sequence:
(1) adding cement, lime and an additive into a stirring container in advance, starting stirring, lowering a stirring paddle, adding the radioactive waste liquid into the stirring container, finishing adding the radioactive waste liquid when the stirring paddle is lowered to the lowest position, and continuing stirring for a period of time after finishing adding the radioactive waste liquid;
(2) and transferring the stirred cement paste for curing.
In a preferred embodiment, the invention provides a high-efficiency cement solidification treatment method for low-pH radioactive waste liquid, wherein the low-pH radioactive waste liquid is waste liquid generated during the operation and maintenance of a high-temperature gas-cooled reactor nuclear power plant, and the pH is 0.5-2.
In a more preferred embodiment, the present invention provides a method for the efficient cement solidification treatment of low pH radioactive waste liquid selected from one or more of the group consisting of leakage waste water collected in a sump, waste water from a decontamination room, waste water from a laboratory, waste water from equipment decontamination and ground washing, and waste water from a laundry.
In a preferred embodiment, the invention provides a high-efficiency cement solidification treatment method for low-pH radioactive waste liquid, wherein in the step (1), the additive is one or more selected from zeolite powder, bentonite and molecular sieve.
In a preferred embodiment, the invention provides a high-efficiency cement solidification treatment method for low-pH radioactive waste liquid, wherein in the step (1), the mass ratio of cement, radioactive waste liquid, lime and additives is 1: (0529-0.575): 0.02: (0.05-0.15).
In a preferred embodiment, the invention provides a high-efficiency cement solidification treatment method for low-pH radioactive waste liquid, wherein in the step (1), the stirring speed is 135-145 r/min.
In a preferred embodiment, the invention provides a high-efficiency cement solidification treatment method of low-pH radioactive waste liquid, wherein in the step (1), the stirring is continued for 10-15 min.
In a preferred embodiment, the invention provides a method for treating the low-pH radioactive waste liquid by curing cement, wherein in the step (2), the curing time is 28 days to 90 days.
In a preferred embodiment, the invention provides a high-efficiency cement solidification treatment method of low-pH radioactive waste liquid, wherein in the step (2), the temperature for curing is 20-30 ℃.
In a preferred embodiment, the invention provides a high-efficiency cement solidification treatment method for low-pH radioactive waste liquid, wherein in the step (2), the relative humidity of maintenance is more than or equal to 90%.
The method has the beneficial effects that the high-efficiency cement solidification treatment method of the low-pH radioactive waste liquid can realize high-volume-ratio solidification of the waste liquid on the premise that the solidification performance of the waste liquid meets various performance requirements of GB 14569.1-2011.
The method can be directly applied to the treatment of the radioactive waste liquid generated during the operation and maintenance of the high-temperature gas cooled reactor, and can also be popularized and applied to the cement stabilization treatment of the low-pH value radioactive waste liquid generated in the operation and decommissioning processes of other various nuclear facilities.
The beneficial effects of the invention are embodied in that:
(1) at present, the traditional cement solidification treatment process at home and abroad is to add radioactive waste liquid into a steel barrel, add a water reducing agent, start a mixer and continuously add lime, stir for a period of time to complete wet waste pretreatment, and continuously add cement until the mixture is uniformly stirred. The invention aims at a specific treatment process and equipment for high-temperature gas cooled reactor, and develops a cement solidification process which comprises the steps of firstly adding cement and an additive into a waste barrel at a cement adding station, then descending a stirring paddle at the stirring station and adding waste liquid at the same time. In the current traditional process at home and abroad, the metering error risk of dry materials is larger than that of wet wastes, and the solidified products are unqualified due to overlarge deviation of the dry materials. Compared with the traditional process, the process of metering the dry materials and then adding the waste liquid for curing reduces the probability of unqualified cured products.
(2) The pH value of the waste liquid treated by the traditional cement curing process at home and abroad is 6-7, and the volume containing rate of the waste liquid is 30-50%. Taking the westinghouse introduction process as an example, in order to realize the process with higher containment rate, the organic additive is adopted, the organic additive has high price, unique purchasing channel and difficult purchasing, and the risk of process re-verification caused by updating exists. The pH value of the waste liquid of the high-efficiency cement curing method provided by the invention is 0.5-2, and inorganic additives with low price, such as zeolite powder, bentonite, molecular sieve and the like, are used as additives for cement curing. The adoption of the inorganic additive improves the long-term disposal safety of the waste and reduces the waste treatment cost. When the curing mixture ratio is cement: waste liquid: lime: additive 1: (0529-0.575): 0.02: (0.05-0.15) (mass ratio), it increases the volume inclusion rate of the waste liquid to 60.0-62.5%, and reduces the amount of waste to be finally disposed.
(3) The solidified body meets various requirements of GB 14569.1-2011. On the basis of the traditional curing technology, the prepared curing body meets various requirements of GB14569.1-2011 including compressive strength, soaking resistance, gamma irradiation resistance, freeze-thaw resistance and impact resistance on the premise that the high packing capacity of wastes is realized and the process meets the related technical requirements of the nuclear facility curing process and equipment.
Detailed Description
The following examples further illustrate embodiments of the present invention.
Example 1: high efficiency cement solidification treatment of low pH radioactive waste liquid
The simulated low-pH value radioactive waste liquid comprises the following components in percentage by weight: 92.0g/L of sodium nitrate, 3.0g/L of sodium sulfate, 1.71 of pH, 95.0g/L of salt content and 1.058kg/L-1.06 of density4kg/L,137The activity concentration of Cs is 2.0E +05Bq/L,90the activity concentration of Sr is 6.0E +02Bq/L,110mthe activity concentration of Ag is 2.0E +03Bq/L,60the concentration of Co activity was 2.0E +05 Bq/L.
The simulated low pH radioactive waste liquid is subjected to cement solidification treatment by the following method steps.
(1) Adding cement, lime and an additive (zeolite powder) into a stirring container in advance, starting stirring (the stirring speed is 135r/min), lowering a stirring paddle while adding the simulated low-pH radioactive waste liquid into the stirring container, finishing adding the simulated low-pH radioactive waste liquid when the stirring paddle is lowered to the lowest position, and continuing stirring for 10min after finishing adding the simulated low-pH radioactive waste liquid. The mass ratio of the cement to the radioactive waste liquid to the lime to the additive is 1: 0529: 0.02: 0.05.
(2) collecting the stirred cement paste into a curing test mold, compacting and strickling the cement paste, and then placing the cement paste into a curing box for curing, wherein the curing temperature is 20 ℃, the curing relative humidity is 90%, and the curing time is 28 d. The prepared cured samples were used for curability performance testing.
Example 2: high-efficiency cement solidification treatment of low-pH radioactive waste liquid
The simulated low-pH value radioactive waste liquid comprises the following components in percentage by weight: 92.0g/L of sodium nitrate, 3.0g/L of sodium sulfate, 1.71 of pH, 95g/L of salt content and 1.058kg/L-1.064kg/L of density,137the activity concentration of Cs is 2.0E +05Bq/L,90the activity concentration of Sr is 6.0E +02Bq/L,110mthe activity concentration of Ag is 2.0E +03Bq/L,60the concentration of Co activity was 2.0E +05 Bq/L.
The simulated low pH radioactive waste liquid is subjected to cement solidification treatment by the following method steps.
(1) Adding cement, lime and an additive (bentonite) into a stirring container in advance, starting stirring (the stirring speed is 140r/min), lowering a stirring paddle, adding the simulated low-pH radioactive waste liquid into the stirring container, finishing adding the simulated low-pH radioactive waste liquid when the stirring paddle is lowered to the lowest position, and continuing stirring for 15min after finishing adding the simulated low-pH radioactive waste liquid. The mass ratio of the cement to the radioactive waste liquid to the lime to the additive is 1: 0.575: 0.02: 0.15.
(2) collecting the stirred cement paste into a curing test mold, compacting and strickling the cement paste, and then placing the cement paste into a curing box for curing, wherein the curing temperature is 30 ℃, the curing relative humidity is 95%, and the curing time is 60 d. The prepared cured samples were used for curability performance testing.
Example 3: high-efficiency cement solidification treatment of low-pH radioactive waste liquid
The simulated low-pH value radioactive waste liquid comprises the following components in percentage by weight: 92.0g/L of sodium nitrate, 3.0g/L of sodium sulfate, 1.71 of pH, 95g/L of salt content and 1.058kg/L-1.064kg/L of density,137the activity concentration of Cs is 2.0E +05Bq/L,90the activity concentration of Sr is 6.0E +02Bq/L,110mthe activity concentration of Ag is 2.0E +03Bq/L,60the concentration of Co activity was 2.0E +05 Bq/L.
The simulated low pH radioactive waste liquid is subjected to cement solidification treatment by the following method steps.
(1) Adding cement, lime and an additive (a molecular sieve) into a stirring container in advance, starting stirring (the stirring speed is 145r/min), lowering a stirring paddle, adding the simulated low-pH radioactive waste liquid into the stirring container, finishing adding the simulated low-pH radioactive waste liquid when the stirring paddle is lowered to the lowest position, and continuing stirring for 15min after finishing adding the simulated low-pH radioactive waste liquid. The mass ratio of cement, radioactive waste liquid, lime and additive is 1: 0.550: 0.02: 0.10.
(2) collecting the stirred cement paste into a curing test mold, compacting and strickling the cement paste, and then placing the cement paste into a curing box for curing, wherein the curing temperature is 25 ℃, the curing relative humidity is 93 percent, and the curing time is 90 days. The prepared cured samples were used for curability performance testing.
Example 4: EXAMPLES 1-3 cured body sample testing
The cured body samples of examples 1 to 3 were subjected to performance tests, and the test items, test methods, and results were as follows.
(1) Compressive Strength measurements according to the regulations of GB14569.1-2011, the samples of examples 1-3 did not deviate relatively more than. + -. 20% of the mean value, and the mean compressive strength was calculated to be 30.4 MPa.
(2) The anti-soaking property test is carried out according to the regulations of GB14569.1-2011, the compressive strength of the samples of examples 1-3 after the anti-soaking test is more than 7MPa, the relative deviation of 3 measured values does not exceed +/-20% of the average value, and the average compressive strength value of 3 samples is 35.2 MPa. Compared with the compressive strength before the anti-soaking test, the average compressive strength of the cement solidified body after the anti-soaking test is increased by 15.8 percent, and the compressive loss is avoided.
(3) The gamma radiation resistance test is according to the regulation of GB14569.1-2011, the compressive strength of the samples of examples 1-3 after the radiation test is larger than 7MPa, the relative deviation of 3 measured values does not exceed +/-20% of the average value, and the average compressive strength value of 3 samples is 33.7 MPa. Compared with the compressive strength before the irradiation test, the average compressive strength of the cement solidified body after the gamma irradiation resistance test is increased by 10.9 percent, and the compressive loss is avoided.
(4) The freeze-thaw resistance test is carried out according to the regulations of GB14569.1-2011, the compressive strength of the samples of examples 1-3 after the cycle of the freeze-thaw resistance test is more than 7MPa, the relative deviation of 3 measured values does not exceed +/-20% of the average value, and the average compressive strength value of 3 samples is 28.7 MPa. Compared with the compressive strength before the freeze-thaw resistance test, the average compressive strength after the freeze-thaw resistance test is reduced by 5.6% and is not more than 25%.
(5) Impact resistance test according to the regulations of GB14569.1-2011, after the samples of examples 1-3 are subjected to an impact resistance test, 1 sample has small angular fragments, 1 sample has large angular fragments, and 1 sample is broken into two pieces.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations. The foregoing examples or embodiments are merely illustrative of the present invention, which may be embodied in other specific forms or in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims should be construed to be included therein.

Claims (10)

1. The efficient cement solidification treatment method for the low-pH radioactive waste liquid is characterized by sequentially comprising the following steps of:
(1) adding cement, lime and an additive into a stirring container in advance, starting stirring, lowering a stirring paddle, adding the radioactive waste liquid into the stirring container, finishing adding the radioactive waste liquid when the stirring paddle is lowered to the lowest position, and continuing stirring for a period of time after finishing adding the radioactive waste liquid;
(2) and transferring the stirred cement paste for curing.
2. The method of claim 1, wherein: the radioactive waste liquid with the low pH value is waste liquid generated during the operation and maintenance of the high-temperature gas cooled reactor nuclear power station, and the pH value is 0.5-2.
3. The method of claim 2, wherein: the radioactive waste liquid with low pH value is one or more of leakage waste water collected in a water collecting pit, waste water in a decontamination room, waste water in a laboratory, equipment decontamination and ground washing waste water and waste water in a laundry.
4. The method of claim 1, wherein: in the step (1), the additive is selected from one or more of zeolite powder, bentonite and a molecular sieve.
5. The method of claim 1, wherein: in the step (1), the mass ratio of cement, radioactive waste liquid, lime and additive is 1: (0529-0.575): 0.02: (0.05-0.15).
6. The method of claim 1, wherein: in the step (1), the stirring speed is 135-145 r/min.
7. The method of claim 1, wherein: in the step (1), the stirring is continued for 10-15 min.
8. The method of claim 1, wherein: in the step (2), the curing time is 28 days to 90 days.
9. The method of claim 1, wherein: in the step (2), the curing temperature is 20-30 ℃.
10. The method of claim 1, wherein: in the step (2), the relative humidity of the maintenance is more than or equal to 90 percent.
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Cited By (3)

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CN113061006A (en) * 2021-03-12 2021-07-02 中核核电运行管理有限公司 Boron-containing concentrated waste liquid cement curing formula and curing method thereof
CN113658737A (en) * 2021-08-12 2021-11-16 上海市建筑科学研究院有限公司 Method for controlling condensation time of waste liquid cement solidified body of nuclear power station
CN116986858A (en) * 2023-07-04 2023-11-03 中广核工程有限公司 Cement solidified body for radioactive waste treatment of nuclear power plant, solidifying method and solidifying system

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CN116986858A (en) * 2023-07-04 2023-11-03 中广核工程有限公司 Cement solidified body for radioactive waste treatment of nuclear power plant, solidifying method and solidifying system

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