CN109036612B - TiO with anatase structure2Method for treating technetium-containing waste liquid - Google Patents
TiO with anatase structure2Method for treating technetium-containing waste liquid Download PDFInfo
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Abstract
TiO with anatase structure2A method for treating technetium-containing waste liquid, which belongs to the field of nuclear waste treatment; the method comprises the following steps: 1) diluting the technetium-containing waste liquid; 2) mixing titanium powder and ammonium fluoride uniformly; 3) adding the mixed powder into a technetium-containing solution, and heating to boil; 4) centrifuging the obtained solid-liquid mixture to obtain a Tc-doped anatase structure and a colorless liquid; the scheme of the invention makes full use of anatase phase TiO in the titanium powder oxidation process2Formation of structures during which a large number of T's can be madeCThe components enter the structure, so that the curing effect is greatly improved, the fixing rate is up to more than 99.99 percent, the temperature of the process is low, only the technetium-containing solution is heated to boiling, the technetium-containing solution is not required to be heated to high temperature, and the volatilization of the technetium components in the high-temperature process is effectively avoided.
Description
Technical Field
The invention belongs to the field of nuclear waste treatment, and particularly relates to a method for treating nuclear waste by utilizing TiO with an anatase structure2A method for treating technetium-containing waste liquid.
Background
Technetium-99 (Tc) is a common nuclear fission product due to its long half-life (2.1X 10)5Year), high cracking rate (6%), high environmental mobility, and complicated long-term disposal of nuclear waste. At present, it is widely believed that "separation-solidification-deep geological" disposal is a viable high-emissivity waste liquid treatment disposal scheme. The method separates radionuclides with long half-life period, high radioactivity level and high biotoxicity from the high-level radioactive liquid waste, classifies the radionuclides according to nuclide types and radioactivity levels, performs cement curing on the large-volume low-level radioactive waste obtained after separation, and can perform glass curing or artificial rock curing on the small-volume high-level radioactive waste, so that the treatment burden is greatly reduced, and the treatment safety is improved. According to the "separation-solidification-deep geological disposal" protocol described above, technetium-containing waste is usually fixed in the form of borosilicate glass, but some of the volatile technetium-containing material is lost during vitrification, thereby greatly reducing the effectiveness of the protocol.
Disclosure of Invention
TiO with anatase structure2The method for treating the technetium-containing waste liquid comprises the following steps in sequence:
(1) diluting the technetium-containing waste liquid into a technetium-containing solution with the concentration of 1.8-2.3 mu g/mL by using deionized water;
(2) uniformly mixing titanium powder and ammonium fluoride to obtain mixed powder;
(3) adding the mixed powder into the technetium-containing solution according to the liquid-solid ratio (15-20) to 1 of the technetium-containing solution to the mixed powder, and heating the mixed powder to boiling from room temperature to obtain a solid-liquid mixture;
(4) centrifuging the solid-liquid mixture to obtain Tc-doped anatase structure TiO2And a colorless liquid.
The method for treating the technetium-containing waste liquid by using the anatase structure comprises the following steps:
in the step 2, the mass percentage of the metal titanium in the titanium powder is not less than 99.8%, and the granularity is 300-325 meshes; the ammonium fluoride is powdery, the purity is more than 99.5 percent (mass percentage content), and the granularity is 200-300 meshes.
In the step 2, the mass ratio of the titanium powder to the ammonium fluoride is (1-1.2) to 1.
In the step 2, mixing materials in a glass container provided with a reflux device.
In the step 3, the liquid-solid ratio refers to the ratio of the volume (unit: ml) of the solution to the mass (unit: g) of the mixture.
In the step 3, the technetium-containing solution and the mixed powder are heated to boiling (100 ℃) for 10-16 hours.
In the step 4, Tc is doped with Ti0 with anatase structure2As a brown-grey powder.
The prepared Tc-doped anatase-structure TiO2Leaching with water, and testing the Tc concentration in the leachate to be less than or equal to 0.0028% after 30-210 days.
TiO with anatase structure2The method for treating the technetium-containing waste liquid has the main design idea of the technical scheme that:
in the invention, the base is based on TCO2And anatase phase TiO2High similarity of structure, preparing technetium doped anatase phase TiO by direct oxidation of titanium powder2The structure of the anatase structure is such that technetium in the waste is permanently fixed to the anatase structure, thereby eliminating the risk of technetium-containing waste.
TiO with anatase structure2Compared with the prior art, the method for treating the technetium-containing waste liquid has the beneficial effects that:
(1) the temperature of the process is low, only the technetium-containing solution is required to be heated to boiling, and the technetium-containing solution is not required to be heated to high temperature (the existing process usually needs more than 600 ℃), so that the volatilization of technetium components in the high-temperature process is effectively avoided.
(2) The process is simple and efficient, and the technetium has a fixing rate of over 99.99 percent through the steps.
(3) The scheme of the invention makes full use of anatase phase TiO in the titanium powder oxidation process2Formation of structures during which a large number of T's can be madeCThe components enter the structure of the curing agent, thereby greatly improving the curing effect.
Drawings
FIG. 1 Tc-doped anatase TiO obtained according to example 1 of the invention2X-ray diffraction pattern of the powder.
FIG. 2 Tc-doped anatase TiO obtained in example 4 of the invention2Time-dependent curve of Tc extraction from the powder.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Example 1
TiO with anatase structure2The method for treating the technetium-containing waste liquid comprises the following steps in sequence:
(1) diluting the technetium-containing waste liquid into a technetium-containing solution with the concentration of 1.8 mu g/mL by using deionized water;
(2) uniformly mixing 24g of titanium powder with the purity of 99.9 percent and the granularity of 300 meshes with 24g of ammonium fluoride with the purity of 99.6 percent and the granularity of 200 meshes according to the mass ratio of the titanium powder to the ammonium fluoride of 1: 1 to obtain mixed powder;
(3) adding the mixed powder into the technetium-containing solution according to the liquid-solid ratio of the technetium-containing solution to the mixed powder of 15: 1, and heating to boil for 10 hours at room temperature to obtain a solid-liquid mixture;
(4) centrifuging the solid-liquid mixture to obtain TiO with brown-gray Tc doped anatase structure2Powder and colorless liquid.
The supernatant colorless liquid was taken to assay for the concentration of Tc, and the presence of Tc in the supernatant was not detected, indicating that Tc was successfully doped into the anatase powder. Taking dried Tc doped TiO2For powdersAnd (3) leaching with water, wherein the Tc concentration in the test leaching solution is 0.001% after 30 days, which shows that the fixation effect is good.
Tc-doped anatase TiO prepared in this example2The X-ray diffraction pattern of the powder is shown in FIG. 1.
Example 2
TiO with anatase structure2The method for treating the technetium-containing waste liquid comprises the following steps in sequence:
(1) diluting the technetium-containing waste liquid into a technetium-containing solution with the concentration of 2.0 mu g/mL by using deionized water;
(2) uniformly mixing 24g of titanium powder with the purity of 99.9 percent and the granularity of 300 meshes with 20g of ammonium fluoride with the purity of 99.6 percent and the granularity of 200 meshes according to the mass ratio of the titanium powder to the ammonium fluoride of 1.2: 1 to obtain mixed powder;
(3) adding the mixed powder into the technetium-containing solution according to the liquid-solid ratio of the technetium-containing solution to the mixed powder of 15: 1, and heating to boil for 12 hours at room temperature to obtain a solid-liquid mixture;
(4) centrifuging the solid-liquid mixture to obtain TiO with brown-gray Tc doped anatase structure2Powder and colorless liquid.
The supernatant was taken as a colorless liquid and assayed for Tc concentration and the presence of Tc in the supernatant was not detected, indicating that Tc was successfully incorporated into the anatase powder. Taking dried Tc doped TiO2The powder was leached with water and after 60 days the Tc concentration in the leachate was assayed to be 0.002%, indicating a good fixing effect.
Example 3
TiO with anatase structure2The method for treating the technetium-containing waste liquid comprises the following steps in sequence:
(1) diluting the technetium-containing waste liquid into a technetium-containing solution with the concentration of 2.3 mu g/mL by using deionized water;
(2) uniformly mixing 24g of titanium powder with the purity of 99.9 percent and the granularity of 325 meshes with 20g of ammonium fluoride with the purity of 99.7 percent and the granularity of 200 meshes according to the mass ratio of the titanium powder to the ammonium fluoride of 1.2: 1 to obtain mixed powder;
(3) adding the mixed powder into the technetium-containing solution according to the liquid-solid ratio of the technetium-containing solution to the mixed powder of 20: 1, and heating to boil for 15h at room temperature to obtain a solid-liquid mixture;
(4) centrifuging the solid-liquid mixture to obtain TiO with brown-gray Tc doped anatase structure2Powder and colorless liquid.
The supernatant was taken as a colorless liquid and assayed for Tc concentration and the presence of Tc in the supernatant was not detected, indicating that Tc was successfully incorporated into the anatase powder. Taking dried Tc doped TiO2The powder was leached with water and after 90 days the Tc concentration in the leachate was assayed to 0.0025%, indicating good fixing.
Example 4
TiO with anatase structure2The method for treating the technetium-containing waste liquid comprises the following steps in sequence:
(1) diluting the technetium-containing waste liquid into a technetium-containing solution with the concentration of 2.3 mu g/mL by using deionized water;
(2) uniformly mixing 24g of titanium powder with the purity of 99.8 percent and the granularity of 325 meshes with 24g of ammonium fluoride with the purity of 99.7 percent and the granularity of 300 meshes according to the mass ratio of the titanium powder to the ammonium fluoride of 1: 1 to obtain mixed powder;
(3) adding the mixed powder into the technetium-containing solution according to the liquid-solid ratio of the technetium-containing solution to the mixed powder of 20: 1, and heating to boil for 16h at room temperature to obtain a solid-liquid mixture;
(4) centrifuging the solid-liquid mixture to obtain TiO with brown-gray Tc doped anatase structure2Powder and colorless liquid.
The supernatant was taken as a colorless liquid and assayed for Tc concentration and the presence of Tc in the supernatant was not detected, indicating that Tc was successfully incorporated into the anatase powder. Taking dried Tc doped TiO2The powder was leached with water, and after 210 days, the Tc concentration in the test leachate was 0.0023%, and the Tc leaching rate was shown as a time-dependent curve in fig. 2, indicating that the fixation effect was good.
Tc-doped anatase TiO prepared in this example2The time-dependent curve of the Tc extraction rate of the powder is shown in FIG. 2.
Example 5
Use ofAnatase structure TiO2The method for treating the technetium-containing waste liquid comprises the following steps in sequence:
(1) diluting the technetium-containing waste liquid into a technetium-containing solution with the concentration of 2.3 mu g/mL by using deionized water;
(2) uniformly mixing 22g of titanium powder with the purity of 99.9 percent and the granularity of 325 meshes with 20g of ammonium fluoride with the purity of 99.7 percent and the granularity of 300 meshes according to the mass ratio of the titanium powder to the ammonium fluoride of 1.1: 1 to obtain mixed powder;
(3) adding the mixed powder into the technetium-containing solution according to the liquid-solid ratio of the technetium-containing solution to the mixed powder of 18: 1, and heating to boil for 16h at room temperature to obtain a solid-liquid mixture;
(4) centrifuging the solid-liquid mixture to obtain TiO with brown-gray Tc doped anatase structure2Powder and colorless liquid.
The supernatant was taken as a colorless liquid and assayed for Tc concentration and the presence of Tc in the supernatant was not detected, indicating that Tc was successfully incorporated into the anatase powder. Taking the dried TiO2The powder was leached with water and the Tc concentration in the leachate was assayed at 210 days to 0.0028%, indicating good fixation.
Claims (4)
1. TiO with anatase structure2The method for treating the technetium-containing waste liquid is characterized by comprising the following steps in sequence:
(1) diluting the technetium-containing waste liquid into a technetium-containing solution with the concentration of 1.8-2.3 mu g/mL by using deionized water;
(2) titanium powder and ammonium fluoride are mixed according to the mass ratio of (1-1.2): 1, uniformly mixing to obtain mixed powder;
(3) adding the mixed powder into the technetium-containing solution according to the liquid-solid ratio (15-20) of the technetium-containing solution to the mixed powder to 1, and heating the mixed powder to boiling from room temperature to obtain a solid-liquid mixture;
(4) centrifuging the solid-liquid mixture to obtain Tc-doped anatase structure TiO2And a colorless liquid.
2. The method of claim 1, wherein the TiO with anatase structure2Treatment of technetium-containing waste streamsThe method is characterized in that in the step 2, the mass percentage of metal titanium in the titanium powder is not less than 99.8%, and the granularity is 300-325 meshes; the ammonium fluoride is powdery, the purity is more than 99.5 percent (mass percentage content), and the granularity is 200-300 meshes.
3. The method of claim 1, wherein the TiO with anatase structure2The method for treating the technetium-containing waste liquid is characterized in that in the step 3, the technetium-containing solution and the mixed powder are heated to be boiled for 10-16 hours.
4. The method of claim 1, wherein the TiO with anatase structure2A method for treating technetium-containing waste liquid, characterized in that Tc-doped anatase-structured TiO produced by said method2Leaching with water, and testing the Tc concentration in the leachate to be less than or equal to 0.0028% after 30-210 days.
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Effective date of registration: 20230810 Address after: 230000 B-2704, wo Yuan Garden, 81 Ganquan Road, Shushan District, Hefei, Anhui. Patentee after: HEFEI LONGZHI ELECTROMECHANICAL TECHNOLOGY Co.,Ltd. Address before: 110159 No. 6 Nanping Road, Hunnan New District, Shenyang, Liaoning Patentee before: SHENYANG LIGONG University |