KR101118116B1 - Fiter type trapping agent for volatile compounds from nuclear fuel fabrication process or incineration process and method for trapping volatile compounds - Google Patents

Abstract

The present invention relates to a filter-type trapping material for collecting volatile compounds generated in a nuclear fuel manufacturing process or an industrial waste incineration process, and a method for collecting volatile compounds using the same. 15% by weight, 20-35% by weight calcium oxide, 10-30% by weight magnesium oxide, 1-3% by weight chromium oxide and 0.5-5% by weight vanadium oxide and using the filter-type collector Volatile rhenium, technetium, ruthenium, tellurium, antimony, mol generated from nuclear fuel manufacturing process including industrial fuel, high temperature heat treatment process, vitrification process, fluoride manufacturing process, chloride manufacturing process, and nitride manufacturing process or industrial waste incineration process The present invention relates to a method for collecting compounds such as ribdenium.

Nuclear Fuel Manufacturing Process, Industrial Waste Incineration Process, Volatile Compounds, Collectors

Description

Filter type trapping agent for volatile compounds from the nuclear fuel manufacturing process or industrial waste incineration process and the method for capturing volatile compounds using the same {nuclear fuel fabrication process or incineration process and method for trapping volatile compounds}

The present invention relates to a filter type trapping material for collecting volatile compounds generated in a nuclear fuel manufacturing process or an industrial waste incineration process, and a method for collecting volatile compounds using the same.

Radioactive gaseous wastes such as technetium, ruthenium, tellurium, antimony and molybdenum are treated at high temperature spent fuel materials such as nuclear or spent fuel high temperature oxidation process, electrolytic process, fluorination process, chlorination process, and reprocessing. Occurs during roasting of high-level radioactive waste and vitrification of radioactive waste. There is an urgent need to develop a technology that can safely capture radioactive gaseous waste so that fission gas generated in the above processes is not released. The spent fuel is one of the subsequent dry processes because only tritium is removed in the volatile voloxidation process at low temperature (approximately 500 ℃), and almost no nucleus of I, Kr, Xe, C-14 as well as Cs is removed. There is a problem to be removed in the electrowinning process. In order to overcome the above problems, the spent fuel highly volatile oxidation process is carried out using Kr, Xe, C-14, H-3, Cs, I, Tc, Ru, Nuclides such as Te, Sb and Mo can be removed. Among the generated exhausts, Kr, Xe, C-14, H-3, Cs, and I have problems due to the development of various existing treatment technologies, but related technologies such as Tc, Ru, Te, Sb, and Mo are poorly developed. Therefore, there is an urgent need to develop a technology for safely capturing these nuclides.

Meanwhile, in order to effectively remove volatile Re, Tc, Ru, Te, Sb, and Mo, physical methods such as a condensation method of generating these gaseous fission gases as fine aerosol particles and then removing them using a high performance filter. Was mainly used. However, there is a problem with high radiation risk and high chemical reactivity, and because it is not a technique for collecting in a chemically stable form, there is a problem in disposal . In addition, the Republic of Korea Patent No. 10-0655586 relates to a volatile rhenium or technetium compound collecting agent and a collecting method using the same, 10 to 70% by weight of yttria, 10 to 70% by weight of oyster shell and 5 to 20% by weight of lithium A method of capturing technetium using a composition comprising an oxide is described. However, the present invention is a trapping material that collects only volatile technetium and rhenium, so that the treatment operation must be performed independently in an independent exhaust gas treatment unit process, and thus, when Ru, Tc, Te, Sb, Mo, etc. coexist, The number of exhaust gas treatment unit processes increases, the volume of the apparatus increases, and the amount of waste generated increases. Therefore, there is a demand for an exhaust gas treatment technology for simultaneously collecting Tc, Ru, Te, Sb, and Mo contained in the exhaust gas. In addition, US Patent No. 4,092,265 relates to radioactive ruthenium, molybdenum, technetium prevention method, calcium oxide, strontium oxide, barium oxide, lanthanide element oxides, lead and mixtures thereof, calcium carbonate, strontium carbonate, carbonate Barium, lanthanide element oxides, lead and mixtures thereof are in contact with ruthenium, molybdenum and technetium to prevent their leakage. Since the invention is an invention for trapping gaseous ruthenium, molybdenum and technetium in powder form, the exhaust gas treatment is performed due to clogging and pressure drop of the pipe wall due to non-oxidation and low gas / solid contact efficiency due to channeling phenomenon. There is a problem in driving.

Thus, the inventors of the present invention while studying a method for capturing compounds such as rhenium, technetium, ruthenium, tellurium, antimony, molybdenum, silica 40-40% by weight, alumina 5-15% by weight, calcium oxide 20-35 Volatile rhenium, technetium, ruthenium, tellurium, antimony, molybdenum, etc., using a trapping material comprising a weight%, 10-30% by weight of magnesium oxide, 1-3% by weight of chromium oxide and 0.5-5% by weight of vanadium oxide The method of collecting the compound of was developed, and this invention was completed.

An object of the present invention is to provide a filter-type trapping material for trapping volatile compounds generated in the nuclear fuel production process or industrial waste incineration process.

Another object of the present invention is to provide a method for collecting volatile compounds using the filter-type trapping material.

In order to achieve the above object, the present invention provides 20-40% by weight of silica, 5-15% by weight of alumina, 20-35% by weight of calcium oxide, 10-30% by weight of magnesium oxide, 1-3% by weight of chromium oxide and vanadium oxide. Provided is a filter type trapping material that collects volatile compounds from nuclear fuel manufacturing or industrial waste incineration processes containing 0.5 to 5% by weight.

In addition, the present invention is a volatile generated in the nuclear fuel manufacturing process or industrial waste incineration process including the spent nuclear fuel, high temperature heat treatment process, vitrification process, fluoride manufacturing process, chloride manufacturing process, nitride manufacturing process using the filter type trapping material Provided are methods for capturing compounds such as rhenium, technetium, ruthenium, tellurium, antimony, molybdenum and the like.

Filter-type trapping material for collecting compounds such as volatile rhenium, technetium, ruthenium, tellurium, antimony, molybdenum, etc. according to the present invention is manufactured in the form of a solid filter, the components of the trapping material is not scattered to improve the working environment, gas Increasing the contact efficiency between the solid and the solid increase the exhaust gas collection efficiency, and the method of capturing compounds such as volatile rhenium, technetium, ruthenium, tellurium, antimony and molybdenum simultaneously captures the volatile compounds, It is simple and can reduce the disposal cost by reducing the amount of waste filter. Therefore, it is useful for capturing compounds such as rhenium, technetium, ruthenium, tellurium, antimony, molybdenum, etc. generated in fuel manufacturing process or industrial waste incineration process. Can be.

The present invention provides a filter type trapping material for trapping volatile compounds generated in the nuclear fuel production process or industrial waste incineration process.

Hereinafter, the present invention will be described in detail.

The filter type trapping material for trapping volatile compounds generated in a nuclear fuel manufacturing process or an industrial waste incineration process including spent nuclear fuel high temperature heat treatment process, vitrification process, fluoride process, chloride process, nitride process, and dry process is made of silica 20 40% by weight, 5-15% by weight of alumina, 20-35% by weight of calcium oxide, 10-30% by weight of magnesium oxide, 1-3% by weight of chromium oxide and 0.5-5% by weight of vanadium oxide.

The trapping material for capturing a compound such as volatile rhenium, technetium, ruthenium, tellurium, antimony, molybdenum or the like according to the present invention may be provided in the form of a solid filter. The shape of the filter may be provided in various forms such as ceramic foam, porous spherical and cylindrical. In order to be provided in the form of a solid filter, the components of the collecting material must not be scattered and it is required to be excellent in workability. The workability is required to contain a predetermined amount or more of components of silica, alumina, calcium oxide, magnesium oxide, chromium oxide and vanadium oxide among the constituents of the collecting material. The trapping material of the present invention provided in the form of a filter has the advantage of improving the working environment by solving problems such as clogging and pressure drop of the pipe wall due to non-oxidation as compared to the conventional powder type trapping material, and other fine porous By using the filter type trapping material, as well as solving the channeling (Channeling) problem of the powder type trapping material, there is an advantage that can increase the exhaust gas collection efficiency by increasing the contact efficiency of the gas and solid.

Furthermore, the filter-type trapping material according to the present invention can be prepared by sintering the composition consisting of the member elements in the range of 1300-1500 ℃. If the sintering temperature of the collecting material is less than 1300 ℃, there is a problem that the sintering temperature in the sintering process, which is a thermal activation process, after the collecting raw material powder particles are molded into a filter and thus cannot be maintained in the form of a porous filter, 1500 ℃ In the case of exceeding, the raw powder particles are melted into the glass due to the high temperature, and thus the shape of the filter is destroyed.

In addition, the present invention using the filter-type trapping material described above occurs in the nuclear fuel manufacturing process or industrial waste incineration process, including spent nuclear fuel, high temperature heat treatment process, vitrification process, fluoride manufacturing process, chloride manufacturing process, nitride manufacturing process Provided are methods for capturing volatile rhenium, technetium, ruthenium, tellurium, antimony, molybdenum and the like.

Specifically, the method of capturing volatile compounds according to the present invention is a gaseous rhenium, technetium, ruthenium, tellurium, antimony which is volatilized after supplying the above-described filter type trapping material to a workplace in which these gaseous compounds are required to be removed. Can be removed by contacting with a compound such as molybdenum and collecting. At this time, the temperature of the working environment for collecting is preferably 400-1000 ℃. If the capture temperature is less than 400 ℃, the trapping material does not meet the energy to react with compounds such as gaseous rhenium, technetium, ruthenium, tellurium, antimony, molybdenum, there is a problem that the collection reaction does not occur, 1000 If the temperature exceeds ℃, there is a problem that various problems such as corrosion, stability and operating cost of the device occurs due to the high temperature collection temperature.

Meanwhile, the collection reaction captures compounds such as rhenium, technetium, ruthenium, tellurium, antimony, and molybdenum in the above temperature range, wherein the collected rhenium is in the form of Ca (ReO ₄ ) ₂ (calcium rhenium oxide) compound. , Technetium in the form of Ca (TcO ₄ ) ₂ (calcium technetium oxide) compound, ruthenium in the form of CaRuO ₃ (calcium ruthenium oxide) compound, tellurium in the form of CaTeO ₃ and CaTeO ₆ (calcium tellerium oxide) compounds Antimony can be captured by immobilization of MgSb ₂ O ₆ (bystromite), MgSb ₂ O ₇ (romeite), CaSbO ₆ (calcium antimony oxide) compounds, and molybdenum in the form of Ca (MoO ₄ ) compounds. .

In addition, the collection may collect compounds such as volatile rhenium, technetium, ruthenium, tellurium, antimony and molybdenum, respectively or simultaneously.

The filter-type trapping material to collect the volatile compounds according to the present invention is manufactured in the shape of a solid filter, the components of the trapping material is not scattered to improve the working environment, increase the contact efficiency of the gas and solid to increase the exhaust gas collection efficiency, Compound capture methods such as volatile rhenium, technetium, ruthenium, tellurium, antimony, and molybdenum simultaneously collect the volatile compounds, thereby simplifying the exhaust gas treatment process and reducing the amount of waste filters, thereby reducing disposal costs. It may be useful for capturing compounds such as rhenium, technetium, ruthenium, tellurium, antimony, and molybdenum generated in the fuel manufacturing process or the industrial waste incineration process.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are merely to illustrate the invention, the content of the present invention is not limited by the following examples.

Example 1 Preparation of Filter Type Collecting Material Collecting Volatile Compounds

A slurry solution was prepared by uniformly mixing silica, alumina, calcium oxide, magnesium oxide, chromium oxide, and vanadium oxide, and then homogeneously mixing 60% to 40% by weight with a 1.0% polyvinyl alcohol solution as a binder. The slurry solution was impregnated 7 times into a 25 ppi (pores per inch) polyurethane sponge and then air was blown to remove excess slurry. After the slurry impregnation and air spraying were repeated five times, the filter was molded by drying at 110 ° C. for 6 hours. The filter was sintered at 1370 ° C. for 3 hours so that each particle aggregate in the molding was formed into a dense, high-strength polycrystal, 28 wt% silica, 15 wt% alumina, 35 wt% calcium oxide, 20 wt% magnesium oxide. And volatile rhenium (Re), technetium (Tc), ruthenium (Ru), tellurium (Te), antimony (Sb), and molybdenum (Mo) including 1.5 wt% of chromium oxide and 0.5 wt% of vanadium oxide. A porous ceramic bubble-type collector for collecting the compound was prepared (see FIG. 1).

Example 2 Collection of Volatile Rhenium Compounds

A gaseous rhenium was supplied from 1 g of rhenium (Re) using an exhaust gas experiment. The volatile rhenium compounds were collected at 600 ° C. for 1 hour at a flow rate of 10 cm / sec under an air atmosphere using 10 collectors of Example 1.

Example 3 Collection of Volatile Ruthenium Compounds

A gaseous ruthenium was supplied from 3 g of ruthenium oxide (RuO ₂ ) using an exhaust gas experiment. The volatile ruthenium compound was collected at 600 ° C. for 5 hours at a flow rate of 10 cm / sec under an air atmosphere.

Example 4 Collection of Volatile Tellurium Compounds 1

A gaseous tellurium was supplied from 0.2 g of tellurium oxide (TeO ₂ ) using an exhaust gas experiment. A volatile tellurium compound was collected in the same manner as in Example 2 except that the collection temperature was performed at 800 ° C.

Example 5 Collection 2 of Volatile Tellurium Compounds

A gaseous tellurium was supplied from 0.2 g of tellurium oxide (TeO ₂ ) using an exhaust gas experiment. A volatile tellurium compound was collected in the same manner as in Example 4, except that the vacuum was carried out at a pressure of 100 torr.

Example 6 Collection of Volatile Tellurium Compounds 3

A gaseous tellurium was supplied from 0.2 g of tellurium oxide (TeO ₂ ) using an exhaust gas experiment. A volatile tellurium compound was collected in the same manner as in Example 4, except that the reaction was carried out under a pressure of 10 torr under vacuum.

Example 7 Collection of Volatile Antimony Compounds

A gaseous antimony was fed from 1 g of antimony oxide (Sb ₂ O ₃ ) using an exhaust gas experiment. A volatile antimony compound was collected in the same manner as in Example 2 except that the collection temperature was performed at 700 ° C.

Example 8 Collection of Volatile Molybdenum Compounds

Gas phase molybdenum was supplied from 1.5 g of molybdenum oxide (MoO ₃ ) using an exhaust gas experiment. A volatile molybdenum compound was collected in the same manner as in Example 2 except that the collection temperature was performed at 700 ° C.

Example 9 Collection of Volatile Rhenium, Ruthenium, Tellurium, Antimony, and Molybdenum Compounds

Using the exhaust gas experiment, rhenium, ruthenium, tellurium, antimony, and molybdenum compounds were mixed in 0.5 g each, and then supplied as gaseous rhenium, ruthenium, tellurium, antimony, and molybdenum. Except that the collection time was carried out for 3 hours, volatile rhenium, technetium, ruthenium, tellurium, antimony and molybdenum compounds were simultaneously collected in the same manner as in Example 2.

Collection conditions of Examples 2 to 9 are summarized in Table 1 below.

Yes Capture exhaust Collection temperature (℃) pressure Capture time (hours) Example 2 Re 600 Atmospheric pressure One Example 3 Ru 600 Atmospheric pressure 5 Example 4 Te 800 Atmospheric pressure 2.5 Example 5 Te 800 100 Torr 2.5 Example 6 Te 800 10 Torr 2.5 Example 7 Sb 700 Atmospheric pressure One Example 8 Mo 700 Atmospheric pressure One Example 9 Re + Ru + Te + Sb + Mo 800 Atmospheric pressure 3

Experimental Example 1 Analysis of Removal Rate and Shape of Collection Filter after Rhenium Compounds were Collected

After collecting the rhenium compound was photographed to determine the weight change of the collecting material and the shape of the collecting filter, the results are shown in FIG.

After generating a volatile rhenium compound in rhenium using an exhaust gas experiment apparatus, the rhenium compound was collected for 1 hour at 600 ° C. at a flow rate of 10 cm / sec in an air atmosphere using the trapping material of Example 1 (Example 2). As a result of analyzing the amount of reagent after the collection reaction and the weight change amount of the filter before and after collection, the rhenium removal rate was 99.9%. Technetium is an artificial element and it is judged that technetium has similar results from the collection result of the rhenium compound having similar chemical properties and behavior.

As shown in Figure 2, it can be seen that the rhenium compound is collected in the porous sphere.

Experimental Example 2 Analysis of Removal Rate and Shape of Capture Filter after Capture of Volatile Antimony Compound

After collecting the volatile antimony compound was photographed to determine the appearance of the collecting filter, the results are shown in FIG.

After the volatile antimony compound was generated from the antimony oxide using an exhaust gas experiment apparatus, the volatile antimony compound was collected at 700 ° C. for 1 hour at a flow rate of 10 cm / sec under an air atmosphere using the trapping material of Example 1 ( Example 7). As a result of analyzing the amount of reagent after the collection reaction and the weight change amount of the filter before and after collection, the antimony removal rate was 99.9%.

As shown in Figure 3, it can be seen that the antimony compound is collected in the porous sphere.

<Experiment 3> Removal rate and shape analysis of the collection filter after collecting volatile rhenium, ruthenium, tellurium, antimony, molybdenum compounds

Volatile rhenium, ruthenium, tellurium, antimony, and molybdenum compounds were simultaneously captured and photographed to determine the appearance of the collecting pen, and the results are shown in FIG. 4.

After generating multi-component volatile gases from rhenium, ruthenium, tellurium, antimony and molybdenum using an exhaust gas experiment apparatus, the trapping material of Example 1 was used at 800 ° C. at a flow rate of 10 cm / sec under an air atmosphere. Captured over time (Example 9). As a result of analyzing the amount of reagent generated after the collection reaction and the weight change amount of the filter before and after collection, the removal rate of the multicomponent gas was 99.9%.

As shown in Figure 4, it can be seen that the multi-component compound is collected in the porous sphere.

<Experiment 4> Analysis of the collecting filter after collecting the volatile ruthenium compound

After collecting the volatile ruthenium compound X-ray diffraction analysis (XRD, Simens, D-5000) to analyze the phase of the collection filter, the results are shown in FIG.

After the gaseous ruthenium was generated from ruthenium oxide (RuO ₂ ) using an exhaust gas experiment apparatus, the collecting material of Example 1 was collected at 600 ° C. for 3 hours at a flow rate of 10 cm / sec under an air atmosphere (Example 3), the image of the collecting filter was analyzed.

As shown in FIG. 5, X-ray diffraction analysis showed that CaRuO ₃ (calcium ruthenium oxide) was formed.

<Experiment 5> Analysis on the collecting filter after collecting the volatile antimony compound

After collecting the volatile antimony compound, an X-ray diffraction analysis (XRD, Simens, D-5000) was performed to analyze the phase of the collecting filter, and the results are shown in FIG. 6.

After the gas phase antimony was generated from the antimony oxide (Sb ₂ O ₃ ) by the capture filter of Example 1 by using the exhaust gas experiment apparatus, the capture material of Example 1 was 700 at a flow rate of 10 cm / sec under an air atmosphere. It was collected for 3 hours at ℃ (Example 7), and the phase of the collecting filter was analyzed.

As shown in FIG. 6, MgSb ₂ O ₆ (bystromite), MgSb ₂ O ₇ (romeite), and CaSb ₂ O ₆ (calcium antimony oxide) were formed by X-ray diffraction analysis.

Experimental Example 6 Phase Analysis of the Filter after Capture of Volatile Molybdenum Compounds

After collecting the volatile molybdenum compound X-ray diffraction analysis (XRD, Simens, D-5000) to analyze the phase of the collection filter, the results are shown in FIG.

After the gaseous molybdenum was generated from molybdenum oxide (MoO ₃ ) using an exhaust gas experiment apparatus, the collector of Example 1 was collected at 700 ° C. at a flow rate of 10 cm / sec under an air atmosphere for 3 hours. (Example 8) and the image of the collection filter was analyzed.

As shown in FIG. 7, Ca (MoO ₄ ) (powellite) was formed by X-ray diffraction analysis.

Experimental Example 7 Measurement of the Amount of Collection of Volatile Tellurium Compounds According to Vacuum Degree

The collection amount of the volatile tellurium compound according to the degree of vacuum was measured, and the result is shown in FIG. 8.

The gaseous tellurium was generated from 1.6 g of tellurium oxide (TeO ₂ ) by heating to 1200 ° C. in a volatilization zone using an exhaust gas experimental apparatus for 1.5 hours, and then subjected to atmospheric pressure with the trapping material of Example 1 located in the collecting zone. (Example 4), 100 torr (Example 5) and 10 torr (Example 6) were collected for 2.5 hours at 800 ℃.

As shown in FIG. 8, the lower the vacuum degree, the higher the collection amount of the tellurium compound at the lower filter depth, and excellent removal efficiency of 99.9% even under the vacuum condition of 10 torr.

1 is a photograph showing an embodiment of a filter-type trapping material for collecting a volatile compound according to the present invention;

2 is a photograph showing a collecting material after collecting the volatile rhenium compound at 600 ° C. for 1 hour at a flow rate of 10 cm / sec using an air collecting material according to the present invention (Example 2);

3 is a photograph showing a collecting material after collecting the volatile antimony compound at 700 ° C. for 1 hour at a flow rate of 10 cm / sec using an air collecting material according to the present invention (Example 7);

Figure 4 after using the trapping material according to the invention to collect volatile rhenium, ruthenium, tellurium, antimony and molybdenum at 800 ℃ for 3 hours at a flow rate of 10 cm / sec under an air atmosphere (Example 9) It is a photograph showing the collecting material of;

FIG. 5 shows the results of X-ray diffraction (XRD) analysis of a filter (Example 3) which collected volatile ruthenium compounds at 600 ° C. for 3 hours at a flow rate of 10 cm / sec using an air collector according to the present invention. Is a graph showing;

FIG. 6 shows the results of X-ray diffraction (XRD) analysis of a filter (Example 7) in which a volatile antimony compound was collected at 700 ° C. for 3 hours at a flow rate of 10 cm / sec using an air collector according to the present invention. Is a graph showing;

7 is an X-ray diffraction (XRD) of a filter (Example 8) in which a volatile molybdenum compound was collected at 700 ° C. for 3 hours at a flow rate of 10 cm / sec using an air collector according to the present invention. A graph showing the results of the analysis; And

8 is a graph showing the results of measuring the collection amount (Examples 4, 5 and 6) of the volatile tellurium compound according to the degree of vacuum for 2.5 hours at 800 ℃ using the collecting material according to the present invention.

Claims (6)

A composition comprising 20-40 wt% silica, 5-15 wt% alumina, 20-35 wt% calcium oxide, 10-30 wt% magnesium oxide, 1-3 wt% chromium oxide and 0.5-5 wt% vanadium oxide A filter type trapping material for trapping volatile compounds generated in a nuclear fuel manufacturing process or an industrial waste incineration process, which is produced by sintering at 1300-1500 ° C. The method of claim 1, wherein the trapping material is a filter type trapping material for trapping volatile compounds generated in the nuclear fuel manufacturing process or industrial waste incineration process, characterized in that the ceramic bubble type, porous spherical or cylindrical. delete A composition comprising 20-40 wt% silica, 5-15 wt% alumina, 20-35 wt% calcium oxide, 10-30 wt% magnesium oxide, 1-3 wt% chromium oxide and 0.5-5 wt% vanadium oxide Using the trapping material manufactured by sintering at 1300-1500 ℃, it is produced in the nuclear fuel manufacturing process or industrial waste incineration process including spent fuel, high temperature heat treatment process, vitrification process, fluoride manufacturing process, chloride manufacturing process and nitride manufacturing process Method of collecting volatile compounds. The method of claim 4, wherein the capture is any one or more compounds selected from the group consisting of volatile rhenium, technetium, ruthenium, tellurium, antimony and molybdenum compounds at a temperature of 400-1000 ℃ using the collecting material A method for capturing volatile compounds generated in a nuclear fuel manufacturing process or an industrial waste incineration process, characterized in that carried out by collecting. The method of claim 5, wherein the rhenium is in the form of a Ca (ReO ₄ ) ₂ compound, the technetium is in the form of a Ca (TcO ₄ ) ₂ compound, the ruthenium is in the form of a CaRuO ₃ compound, and the tellurium is CaTeO ₃ or Ca _3. In the form of TeO ₆ compounds, the antimony is MgSb ₂ O ₆ , MgSb ₂ O ₇ Or in the form of a CaSbO ₆ compound, molybdenum is trapped in the form of a Ca (MoO ₄ ) compound to capture volatile compounds generated in a nuclear fuel manufacturing process or an industrial waste incineration process.

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