Efficient in-situ curing treatment method for copper-based iodine waste

Abstract

The invention discloses an efficient in-situ curing treatment method for copper-based iodine waste, which comprises the following steps: grinding and mixing Bi2O3, B2O3 and ZnO powder according to a certain proportion, drying, sintering, water quenching, drying, grinding and sieving to obtain xBi2O3-B2O3-ZnO glass powder, x being 100 times of the molar percentage content of Bi2O3 in the xBi2O3-B2O3-ZnO glass powder, and the value range of x being 0-100; the xBi2O3-B2O3-ZnO glass powder and the copper-based iodine waste are fully ground and mixed, sintering is performed after tabletting, a solidified body is obtained, and in-situ solidification treatment of the copper-based iodine waste is completed. According to the method, Bi2O3-B2O3-ZnO glass is used as a curing base material, in-situ curing treatment of the copper-based iodine waste is carried out under the inert atmosphere, efficient curing treatment of the iodine waste is achieved, and a new material and a new strategy are provided for radioactive iodine waste treatment.

Description

Technical Field

[0001] The present invention belongs to the technical field of radioactive waste treatment, and more particularly, relates to a high-efficiency in-situ solidification treatment method for copper-based iodine waste. Background Art

[0002] Radioactive iodine waste (such as 129 I) Due to its long half-life and high activity, it poses a serious threat to the environment and human health. Traditional iodine waste treatment methods usually involve multiple steps such as adsorption, separation and solidification. The process is complex, the cost is high, and it may lead to secondary release of iodine. In addition, copper-based materials are a highly promising iodine adsorbent developed in recent years. After use, the adsorbent becomes copper-based iodine waste, and there is currently a lack of effective solidification treatment methods for it. Therefore, the development of a treatment method that can achieve efficient adsorption and in-situ solidification has important scientific significance and practical application value. Summary of the Invention

[0003] An object of the present invention is to solve at least the above problems and / or disadvantages and to provide at least the advantages which will be described hereinafter.

[0004] In order to achieve these purposes and other advantages according to the present invention, there is provided a method for efficiently solidifying copper-based iodine waste in situ, comprising the following steps: Step 1: Grind and mix Bi2O3, B2O3 and ZnO powders in a certain proportion, dry and sinter, quench with water, dry, grind and sieve to obtain x Bi2O3-B2O3-ZnO glass powder, x For Bi2O3 x 100 times the molar percentage of Bi2O3-B2O3-ZnO in glass powder, x The value range is 0~100; Step 2: x The Bi2O3-B2O3-ZnO glass powder and the copper-based iodine waste are fully ground and mixed, pressed into tablets, and then sintered to obtain a solidified body, thereby completing the in-situ solidification treatment of the copper-based iodine waste.

[0005] Preferably, in step 1, anhydrous ethanol is used as the medium, and the molar ratio of B2O3 to ZnO powder is 1:1.

[0006] Preferably, in the step 1, the drying temperature is 50-70°C.

[0007] Preferably, in the step 1, the sintering temperature is 1000-1400° C., and the sintering time is 3-8 hours.

[0008] Preferably, in step 2, the copper-based iodine waste is a copper-based silica material after iodine adsorption, and the iodine content thereof is 40-60 wt%.

[0009] Preferably, in the step 2, the specific method of tableting is to press the tablets at a pressure of 14 to 16 MPa on a tablet press. x A mixture of Bi2O3-B2O3-ZnO glass powder and copper-based iodine waste was pressed into discs with a diameter of 10~15mm.

[0010] Preferably, in the step 2, the sintering temperature is 400-600° C., and the sintering time is 3-8 hours.

[0011] Preferably, in the step 2, the sintering atmosphere is air or nitrogen.

[0012] Preferably, in the step 2, the solidified body is named x Bi2O3-B2O3-ZnO- y I, where y is 100 times the amount of iodine solid solution, and the value of y is 2~8.

[0013] Preferably, in the step 2, x The mass ratio of Bi2O3-B2O3-ZnO glass powder to copper-based iodine waste is 5:0.2~1.5.

[0014] Preferably, in the step 2, x Bi2O3-B2O3-ZnO glass powder and copper-based iodine waste are fully ground and mixed to obtain a mixed powder, and the mixed powder is doped with phosphogypsum and silicon: S1. Add the mixture powder, SiO2 powder, and CaSO4·2H2O powder into water and stir evenly to obtain a suspension; add polyethylene glycol-200 as a dispersant to the suspension, and stir magnetically at 300-500 rpm for 20-60 min to obtain a dispersion system; wherein the amount ratio of the mixed powder, SiO2 powder, CaSO4·2H2O powder, polyethylene glycol-200, and water is 5-10 g:1-3 g:1-3 g:0.5-1 g:400-600 mL; S2. Add γ-glycidyloxypropyltrimethoxysilane in an amount of 1 to 10 wt% by weight of the mixed powder to the dispersion system, and add oxalic acid to adjust the pH of the dispersion system to 2 to 4. Stir at 300 to 500 rpm and raise the temperature to 60 to 80°C. Keep warm for 1 to 12 hours. After standing for 12 to 24 hours, filter and wash the powder to neutrality, dry to obtain a mixed powder of phosphogypsum and silicon-doped powder, and then press and sinter to obtain a solidified body.

[0015] The present invention has at least the following beneficial effects: The present invention uses Bi2O3-B2O3-ZnO glass as the solidification substrate and carries out in-situ solidification treatment of copper-based iodine waste under an inert atmosphere (N2), achieving efficient solidification treatment of iodine waste and providing new materials and new strategies for the treatment of radioactive iodine waste.

[0016] The present invention will x Bi2O3-B2O3-ZnO glass powder and copper-based iodine waste are fully ground and mixed to obtain a mixed powder, the mixed powder is doped with phosphogypsum and silicon, polyethylene glycol-200 is used as a dispersant, and a dispersion system is obtained after being fully dispersed. γ-glycidyloxypropyltrimethoxysilane is used for coupling modification to enhance the bonding between SiO2 powder, CaSO4·2H2O powder and x The compatibility of Bi2O3-B2O3-ZnO glass powder and copper-based iodine waste, and the hydrolysis and condensation of γ-glycidyloxypropyltrimethoxysilane under acidic conditions enhance the binding force between the inorganic phases, forming a dense three-dimensional network structure, thereby inhibiting the leaching of iodine and reducing the iodine leaching rate after in-situ solidification of copper-based iodine waste.

[0017] Other advantages, objectives and features of the present invention will be reflected in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The contents of Bi2O3 in Example 1, Example 2 and Comparative Example 1 are different. x XRD pattern of Bi2O3-B2O3-ZnO glass; Figure 2 XRD patterns of 10Bi2O3-B2O3-ZnO-8I solids sintered at 550°C under different atmospheres (N2, Air) in Example 3 and Example 10; Figure 3 XRD patterns of 10Bi2O3-B2O3-ZnO-8I solid bodies sintered at different temperatures in Example 6, Example 8, Example 9 and Example 10; Figure 4 The XRD patterns of the solidified bodies with different Bi2O3 contents in Example 7 and Example 10; Figure 5 XRD patterns of 10Bi2O3-B2O3-ZnO-yI solidified bodies with different I contents in Example 2, Example 4, Example 5 and Example 10; Figure 6 The solidified bodies with different Bi2O3 contents in Example 7, Example 10 and Comparative Example 1 are shown in FIG. LR I Curves changing over time; Figure 7The 10Bi2O3-B2O3-ZnO-yI solidified bodies with different I contents in Example 2, Example 4, Example 5 and Example 10 are shown in FIG. LR I Curves changing over time. DETAILED DESCRIPTION

[0019] The present invention will be described in further detail below in conjunction with the accompanying drawings so that those skilled in the art can implement the invention with reference to the description.

[0020] It should be understood that terms such as “having”, “including” and “comprising” used herein do not preclude the existence or addition of one or more other elements or combinations thereof.

[0021] Example 1 A highly efficient in-situ solidification treatment method for copper-based iodine waste comprises the following steps: Step 1: Grind and mix 0.1 mol Bi2O3, 0.95 mol B2O3, and 0.95 mol ZnO powders, and transfer the mixed sample to a 60°C oven for drying; then sinter in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry, grind, and pass through a 200-mesh sieve to obtain 5Bi2O3-B2O3-ZnO glass powder; Step 2: Grind and mix 5g of 5Bi2O3-B2O3-ZnO glass powder and 0.23g of copper-based iodine waste thoroughly, press them into discs with a diameter of 12 mm at a pressure of 16 MPa on a tablet press, and sinter them at 550°C for 6h in a nitrogen atmosphere to obtain a solidified body 5Bi2O3-B2O3-ZnO-2I. The in-situ solidification treatment of copper-based iodine waste is completed.

[0022] Example 2 A highly efficient in-situ solidification treatment method for copper-based iodine waste comprises the following steps: Step 1: Grind and mix 0.2 mol Bi2O3, 0.90 mol B2O3, and 0.90 mol ZnO powders. Transfer the mixed sample to a 60°C oven for drying. Then, sinter it in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry it, grind it, and pass it through a 200-mesh sieve to obtain 10Bi2O3-B2O3-ZnO glass powder. Step 2: 5 g of 10Bi2O3-B2O3-ZnO glass powder and 0.23 g of copper-based iodine waste were thoroughly ground and mixed, and pressed into a disc with a diameter of 12 mm at a pressure of 16 MPa on a tablet press. The disc was sintered at 550°C for 6 h under a nitrogen atmosphere to obtain a solidified body 10Bi2O3-B2O3-ZnO-2I, and the in-situ solidification treatment of the copper-based iodine waste was completed.

[0023] Example 3 A highly efficient in-situ solidification treatment method for copper-based iodine waste comprises the following steps: Step 1: Grind and mix 0.2 mol Bi2O3, 0.90 mol B2O3, and 0.90 mol ZnO powders. Transfer the mixed sample to a 60°C oven for drying. Then, sinter it in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry it, grind it, and pass it through a 200-mesh sieve to obtain 10Bi2O3-B2O3-ZnO glass powder. Step 2: 5 g of 10Bi2O3-B2O3-ZnO glass powder and 1.03 g of copper-based iodine waste were thoroughly ground and mixed, and pressed into a disc with a diameter of 12 mm at a pressure of 16 MPa on a tablet press. The disc was sintered at 550°C for 6 h in an air atmosphere to obtain a solidified body 10Bi2O3-B2O3-ZnO-8I, and the in-situ solidification treatment of the copper-based iodine waste was completed.

[0024] Example 4 A highly efficient in-situ solidification treatment method for copper-based iodine waste comprises the following steps: Step 1: Grind and mix 0.2 mol Bi2O3, 0.90 mol B2O3, and 0.90 mol ZnO powders. Transfer the mixed sample to a 60°C oven for drying. Then, sinter it in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry it, grind it, and pass it through a 200-mesh sieve to obtain 10Bi2O3-B2O3-ZnO glass powder. Step 2: 5 g of 10Bi2O3-B2O3-ZnO glass powder and 0.46 g of copper-based iodine waste were thoroughly ground and mixed, and pressed into a disc with a diameter of 12 mm at a pressure of 16 MPa on a tablet press. The disc was sintered at 550°C for 6 h under a nitrogen atmosphere to obtain a solidified body 10Bi2O3-B2O3-ZnO-4I, and the in-situ solidification treatment of the copper-based iodine waste was completed.

[0025] Example 5 A highly efficient in-situ solidification treatment method for copper-based iodine waste comprises the following steps: Step 1: Grind and mix 0.2 mol Bi2O3, 0.90 mol B2O3, and 0.90 mol ZnO powders. Transfer the mixed sample to a 60°C oven for drying. Then, sinter it in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry it, grind it, and pass it through a 200-mesh sieve to obtain 10Bi2O3-B2O3-ZnO glass powder. Step 2: 5 g of 10Bi2O3-B2O3-ZnO glass powder and 0.74 g of copper-based iodine waste were thoroughly ground and mixed, and pressed into a disc with a diameter of 12 mm at a pressure of 16 MPa on a tablet press. The disc was sintered at 550°C for 6 h under a nitrogen atmosphere to obtain a solidified body 10Bi2O3-B2O3-ZnO-6I, and the in-situ solidification treatment of the copper-based iodine waste was completed.

[0026] Example 6 A highly efficient in-situ solidification treatment method for copper-based iodine waste comprises the following steps: Step 1: Grind and mix 0.2 mol Bi2O3, 0.90 mol B2O3, and 0.90 mol ZnO powders. Transfer the mixed sample to a 60°C oven for drying. Then, sinter it in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry it, grind it, and pass it through a 200-mesh sieve to obtain 10Bi2O3-B2O3-ZnO glass powder. Step 2: 5 g of 10Bi2O3-B2O3-ZnO glass powder and 1.03 g of copper-based iodine waste were thoroughly ground and mixed, and pressed into a disc with a diameter of 12 mm at a pressure of 16 MPa on a tablet press. The disc was sintered at 400°C for 6 h in a nitrogen atmosphere to obtain a solidified body 10Bi2O3-B2O3-ZnO-8I, and the in-situ solidification treatment of the copper-based iodine waste was completed.

[0027] Example 7 A highly efficient in-situ solidification treatment method for copper-based iodine waste comprises the following steps: Step 1: Grind and mix 0.1 mol Bi2O3, 0.95 mol B2O3, and 0.95 mol ZnO powders, and transfer the mixed sample to a 60°C oven for drying; then sinter in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry, grind, and pass through a 200-mesh sieve to obtain 5Bi2O3-B2O3-ZnO glass powder; Step 2: 5g of 5Bi2O3-B2O3-ZnO glass powder and 1.03g of copper-based iodine waste were thoroughly ground and mixed, and pressed into a disc with a diameter of 12 mm at a pressure of 16 MPa on a tablet press. The disc was sintered at 550°C for 6h under a nitrogen atmosphere to obtain a solidified body 5Bi2O3-B2O3-ZnO-8I, and the in-situ solidification treatment of the copper-based iodine waste was completed.

[0028] Example 8 A highly efficient in-situ solidification treatment method for copper-based iodine waste comprises the following steps: Step 1: Grind and mix 0.2 mol Bi2O3, 0.90 mol B2O3, and 0.90 mol ZnO powders. Transfer the mixed sample to a 60°C oven for drying. Then, sinter it in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry it, grind it, and pass it through a 200-mesh sieve to obtain 10Bi2O3-B2O3-ZnO glass powder. Step 2: 5 g of 10Bi2O3-B2O3-ZnO glass powder and 1.03 g of copper-based iodine waste were thoroughly ground and mixed, and pressed into a disc with a diameter of 12 mm at a pressure of 16 MPa on a tablet press. The disc was sintered at 450°C for 6 h in a nitrogen atmosphere to obtain a solidified body 10Bi2O3-B2O3-ZnO-8I, and the in-situ solidification treatment of the copper-based iodine waste was completed.

[0029] Example 9 A highly efficient in-situ solidification treatment method for copper-based iodine waste comprises the following steps: Step 1: Grind and mix 0.2 mol Bi2O3, 0.90 mol B2O3, and 0.90 mol ZnO powders. Transfer the mixed sample to a 60°C oven for drying. Then, sinter it in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry it, grind it, and pass it through a 200-mesh sieve to obtain 10Bi2O3-B2O3-ZnO glass powder. Step 2: 5 g of 10Bi2O3-B2O3-ZnO glass powder and 1.03 g of copper-based iodine waste were thoroughly ground and mixed, and pressed into a disc with a diameter of 12 mm at a pressure of 16 MPa on a tablet press. The disc was sintered at 500°C for 6 h in a nitrogen atmosphere to obtain a solidified body 10Bi2O3-B2O3-ZnO-8I, and the in-situ solidification treatment of the copper-based iodine waste was completed.

[0030] Example 10 A highly efficient in-situ solidification treatment method for copper-based iodine waste comprises the following steps: Step 1: Grind and mix 0.2 mol Bi2O3, 0.90 mol B2O3, and 0.90 mol ZnO powders. Transfer the mixed sample to a 60°C oven for drying. Then, sinter it in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry it, grind it, and pass it through a 200-mesh sieve to obtain 10Bi2O3-B2O3-ZnO glass powder. Step 2: 5 g of 10Bi2O3-B2O3-ZnO glass powder and 1.03 g of copper-based iodine waste were thoroughly ground and mixed, and pressed into a disc with a diameter of 12 mm at a pressure of 16 MPa on a tablet press. The disc was sintered at 550°C for 6 h under a nitrogen atmosphere to obtain a solidified body 10Bi2O3-B2O3-ZnO-8I, and the in-situ solidification treatment of the copper-based iodine waste was completed.

[0031] Example 11 A highly efficient in-situ solidification treatment method for copper-based iodine waste comprises the following steps: Step 1: Grind and mix 0.1 mol Bi2O3, 0.95 mol B2O3, and 0.95 mol ZnO powders, and transfer the mixed sample to a 60°C oven for drying; then sinter in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry, grind, and pass through a 200-mesh sieve to obtain 5Bi2O3-B2O3-ZnO glass powder; Step 2: 5g of 5Bi2O3-B2O3-ZnO glass powder and 1.03g of copper-based iodine waste are fully ground and mixed to obtain a mixed powder, and the mixed powder is subjected to phosphogypsum and silicon doping treatment, specifically comprising: S1. Add 6.03 g of the mixture powder, 1 g of SiO2 powder, and 1 g of CaSO4·2H2O powder into 400 mL of water and stir to obtain a suspension. Add 0.5 g of polyethylene glycol-200 as a dispersant to the suspension and stir magnetically at 500 rpm for 30 min to obtain a dispersion system. S2. 0.4 g of γ-glycidyloxypropyltrimethoxysilane was added to the dispersion system, and oxalic acid was added to adjust the pH of the dispersion system to 2. The mixture was stirred at 500 rpm and heated to 80° C., kept warm for 3 h, and allowed to stand for 12 h. The powder was filtered and washed to neutrality, and dried to obtain a mixed powder of phospho-gypsum and silicon-doped treatment. The mixed powder was pressed into discs with a diameter of 12 mm at a pressure of 16 MPa on a tablet press. The pellets were sintered at 550° C. for 6 h in a nitrogen atmosphere to obtain a solidified body of phospho-gypsum and silicon-doped 5Bi2O3-B2O3-ZnO-8I. The in-situ solidification treatment of copper-based iodine waste was completed.

[0032] Example 12 A highly efficient in-situ solidification treatment method for copper-based iodine waste comprises the following steps: Step 1: Grind and mix 0.2 mol Bi2O3, 0.90 mol B2O3, and 0.90 mol ZnO powders. Transfer the mixed sample to a 60°C oven for drying. Then, sinter it in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry it, grind it, and pass it through a 200-mesh sieve to obtain 10Bi2O3-B2O3-ZnO glass powder. Step 2: 5g of 10Bi2O3-B2O3-ZnO glass powder and 1.03g of copper-based iodine waste are fully ground and mixed to obtain a mixed powder, and the mixed powder is subjected to phosphogypsum and silicon doping treatment, specifically comprising: S1. Add 6.03 g of the mixture powder, 1 g of SiO2 powder, and 1 g of CaSO4·2H2O powder into 400 mL of water and stir to obtain a suspension. Add 0.5 g of polyethylene glycol-200 as a dispersant to the suspension and stir magnetically at 500 rpm for 30 min to obtain a dispersion system. S2. 0.4 g of γ-glycidyloxypropyltrimethoxysilane was added to the dispersed system, and oxalic acid was added to adjust the pH of the dispersed system to 2. The mixture was stirred at 500 rpm and heated to 80°C. The mixture was kept warm for 3 h. After standing for 12 h, the powder was filtered and washed to neutrality. The mixture was dried to obtain a mixed powder of phospho-gypsum and silicon-doped gypsum. The mixed powder was pressed into a disc with a diameter of 12 mm at a pressure of 16 MPa on a tablet press. The disc was sintered at 550°C for 6 h in a nitrogen atmosphere to obtain a solidified body of phospho-gypsum and silicon-doped 10Bi2O3-B2O3-ZnO-8I. The in-situ solidification treatment of copper-based iodine waste was completed.

[0033] Comparative Example 1 Step 1: Grind and mix 1 mol of B2O3 and 1 mol of ZnO powder, transfer the mixed sample to a 60°C oven for drying, then sinter in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry, grind, and pass through a 200-mesh sieve to obtain 5Bi2O3-B2O3-ZnO glass powder. Step 2: 5 g of B2O3-ZnO glass powder and 1.03 g of copper-based iodine waste were thoroughly ground and mixed, and pressed into a disc with a diameter of 12 mm at a pressure of 16 MPa on a tablet press. The disc was sintered at 400°C for 6 h in a nitrogen atmosphere to obtain a solidified body B2O3-ZnO-8I, and the in-situ solidification treatment of the copper-based iodine waste was completed.

[0034] Comparative Example 2 A highly efficient in-situ solidification treatment method for copper-based iodine waste comprises the following steps: Step 1: Grind and mix 0.1 mol Bi2O3, 0.95 mol B2O3, and 0.95 mol ZnO powders, and transfer the mixed sample to a 60°C oven for drying; then sinter in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry, grind, and pass through a 200-mesh sieve to obtain 5Bi2O3-B2O3-ZnO glass powder; Step 2: 5g of 5Bi2O3-B2O3-ZnO glass powder and 1.03g of copper-based iodine waste are fully ground and mixed to obtain a mixed powder, and the mixed powder is subjected to phosphogypsum and silicon doping treatment, specifically comprising: S1. Add 6.03 g of the mixture powder, 1 g of SiO2 powder, and 1 g of CaSO4·2H2O powder into 400 mL of water and stir to obtain a suspension. Add 0.5 g of polyethylene glycol-200 as a dispersant to the suspension and stir magnetically at 500 rpm for 30 min to obtain a dispersion system. S2. After filtering the dispersed system, the powder was washed to neutrality and dried to obtain a mixed powder of phospho-gypsum and silicon-doped treatment. The mixed powder was pressed into a disc with a diameter of 12 mm at a pressure of 16 MPa on a tablet press. The disc was sintered at 550°C for 6 h under a nitrogen atmosphere to obtain a solidified body 5Bi2O3-B2O3-ZnO-8I of phospho-gypsum and silicon-doped treatment. The in-situ solidification treatment of copper-based iodine waste was completed.

[0035] Comparative Example 3 A highly efficient in-situ solidification treatment method for copper-based iodine waste comprises the following steps: Step 1: Grind and mix 0.2 mol Bi2O3, 0.90 mol B2O3, and 0.90 mol ZnO powders. Transfer the mixed sample to a 60°C oven for drying. Then, sinter it in a muffle furnace at 1200°C for 6 hours. Immediately quench the molten glass with water, dry it, grind it, and pass it through a 200-mesh sieve to obtain 10Bi2O3-B2O3-ZnO glass powder. Step 2: 5g of 10Bi2O3-B2O3-ZnO glass powder and 1.03g of copper-based iodine waste are fully ground and mixed to obtain a mixed powder, and the mixed powder is subjected to phosphogypsum and silicon doping treatment, specifically comprising: S1. Add 6.03 g of the mixture powder, 1 g of SiO2 powder, and 1 g of CaSO4·2H2O powder into 400 mL of water and stir to obtain a suspension. Add 0.5 g of polyethylene glycol-200 as a dispersant to the suspension and stir magnetically at 500 rpm for 30 min to obtain a dispersion system. S2. After filtering the dispersed system, the powder was washed to neutrality and dried to obtain a mixed powder of phospho-gypsum and silicon-doped treatment. The mixed powder was pressed into a disc with a diameter of 12 mm at a pressure of 16 MPa on a tablet press. The disc was sintered at 550°C for 6 h in a nitrogen atmosphere to obtain a solidified body 10Bi2O3-B2O3-ZnO-8I of phospho-gypsum and silicon-doped. The in-situ solidification treatment of copper-based iodine waste was completed.

[0036] Figure 1 for xXRD patterns of Bi2O3-B2O3-ZnO glass substrate. As can be seen from the figure, the XRD patterns of the three glasses B2O3-ZnO, 5Bi2O3-B2O3-ZnO, and 10Bi2O3-B2O3-ZnO all show typical amorphous peaks, indicating that after sintering at 1200 ° C for 6 hours and water quenching, the x Bi2O3-B2O3-ZnO glass substrate.

[0037] Figure 2 The following are XRD patterns of 10Bi2O3-B2O3-ZnO-8I solid bodies before and after sintering in N2 and air atmospheres. It can be observed from the figure that the main phase of copper-based iodine waste before sintering is CuI. After sintering in an air atmosphere, the characteristic peak of CuI in the sample disappeared, and the characteristic peak of CuO appeared. This indicates that CuI underwent oxidative decomposition, resulting in the loss of I. However, after sintering and solidification treatment in a N2 atmosphere, the characteristic peak of CuI was still retained in the solid body. This shows that I was successfully solidified in the glass solid body without causing any loss of I. The results of this study show that the sintering atmosphere has a greater influence on the solidification effect of copper-based iodine waste, and sintering in a N2 atmosphere is more conducive to the effective solidification of iodine waste.

[0038] Figure 3 The following are XRD patterns of 10Bi2O3-B2O3-ZnO-8I solids sintered at different temperatures. As can be seen from the figure, the main phase in the solids after sintering is CuI. Furthermore, the intensity of the characteristic diffraction peak of CuI decreases with increasing temperature, which can be attributed to the decomposition of CuI at high temperatures. Furthermore, the characteristic diffraction peak of elemental Bi appears when the sintering temperature is increased above 500°C. This is likely because the Cu generated by the decomposition of CuI reduces Bi2O3 to form elemental Bi.

[0039] Figure 4 The XRD patterns of xBi2O3-B2O3-ZnO-8I solids with different Bi2O3 contents (550°C, 6h, N2) are shown. As can be seen from the figure, the characteristic peaks of elemental Bi increase with increasing Bi2O3 content, while the CuI phase is still retained in the solid.

[0040] Figure 5 Figure 2 shows the XRD patterns of 10Bi2O3-B2O3-ZnO-yI solids with different I contents. It can be seen that with the increase of I content, the CuI phase is retained in the solid, and its characteristic diffraction peak gradually strengthens.

[0041] As the sintering temperature increases from 400 to 550 °C, the density of the solidified body increases from 3.66 to 3.70 g / cm 3, the open porosity decreased from 5.76% to 5.06%.The results show that the increase of sintering temperature is conducive to the densification of the solid body.

[0042] Effect of Bi2O3 content on the density of solidified body As the Bi2O3 content increases from 0 to 10 mol%, the density of the solidified body increases from 2.76 g / cm 3 Increased to 3.70 g / cm 3 , the open porosity decreased from 11.8% to 5.06%. This result shows that the incorporation of Bi2O3 is beneficial to the densification of the solidified body.

[0043] As the I content in the solidified body increases from 2 to 8 wt%, the density of the solidified body decreases slightly from 3.88 g / cm 3 Down to 3.70 g / cm 3 , the open porosity increased from 1.81% to 5.06%, which may be due to the higher iodine volatilization caused by the high I content.

[0044] Figure 6 Solidification of different Bi2O3 contents LR I Time-dependent curve. It can be clearly observed from the figure that the normalized leaching rate of I in the solidified body decreases with the increase of leaching time and tends to be stable after 21 days. When the leaching time reaches 42 days, the normalized leaching rates of I in B2O3-ZnO-8I, 5Bi2O3-B2O3-ZnO-8I and 10Bi2O3-B2O3-ZnO-8I samples are 3.26×10 -3 gm -2 d -1 , 1.35×10 -3 gm -2 d -1 and 7.06×10 -4 gm -2 d -1 This indicates that the Bi2O3 content has a significant impact on the chemical stability of the solidified body. As the Bi2O3 content increases, the chemical stability of the solidified body increases. This result indicates that increasing the Bi2O3 content is beneficial to improving the chemical stability of the solidified body.

[0045] Figure 7 Different I content solid LR ICurve of change with time. As can be seen from the figure, the leaching rate of I decreases with the increase of leaching time, and the normalized leaching rate tends to be stable after 21 days. The normalized leaching rate of I in the solidified body increases slightly with the increase of I content. The normalized leaching rate of I in the solidified bodies of 10Bi2O3-B2O3-ZnO-2I, 10Bi2O3-B2O3-ZnO-4I, 10Bi2O3-B2O3-ZnO-6I and 10Bi2O3-B2O3-ZnO-8I is as low as 2.95×10 -4 gm -2 d -1 , 3.42×10 -4 gm -2 d -1 , 5.16×10 -4 gm -2 d -1 and 7.06×10 -4 gm -2 d -1 The results show that the copper-based iodine waste solidified body obtained by the method of the present invention has good chemical stability.

[0046] Among them, when the leaching time reaches 42 days, the normalized leaching rates of the solid bodies I of Example 1, Example 10-Example 12, and Comparative Example 2-Comparative Example 3 are shown in the following table: It can be seen from the above table that after Examples 11-12 and Comparative Examples 2-3 were treated with phospho-gypsum and silicon, the normalized leaching rate of the solidified body I was significantly reduced. Among them, the normalized leaching rate of the solidified body I of Examples 11 and 12 was reduced most significantly.

[0047] The number of devices and processing scales described herein are intended to simplify the description of the present invention. Applications, modifications, and variations of the present invention will be readily apparent to those skilled in the art.

[0048] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the description and implementation methods. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and illustrations shown and described herein.

Claims

1. An efficient in-situ solidification treatment method for copper-based iodine waste, characterized in that: The following steps are involved: Step 1: Grind and mix Bi2O3, B2O3 and ZnO powders in a certain proportion, dry and sinter, water quench, dry, grind and sieve to obtain x Bi2O3-B2O3-ZnO glass powder, x For Bi2O3 x 100 times the molar percentage of Bi2O3-B2O3-ZnO in glass powder, x The value range is 0~100; Step 2: x The Bi2O3-B2O3-ZnO glass powder and the copper-based iodine waste are fully ground and mixed, pressed into tablets, and then sintered to obtain a solidified body, thereby completing the in-situ solidification treatment of the copper-based iodine waste.

2. The efficient in-situ solidification treatment method for copper-based iodine waste according to claim 1, wherein In the step 1, anhydrous ethanol is used as the medium, and the molar ratio of B2O3 to ZnO powder is 1:

1.

3. The efficient in-situ solidification treatment method for copper-based iodine waste according to claim 1, wherein In the step 1, the drying temperature is 50-70°C.

4. The efficient in-situ solidification treatment method for copper-based iodine waste according to claim 1, wherein In the step 1, the sintering temperature is 1000-1400° C., and the sintering time is 3-8 hours.

5. The efficient in-situ solidification treatment method for copper-based iodine waste according to claim 1, wherein In the step 2, the copper-based iodine waste is a copper-based silica material after iodine adsorption, and its iodine content is 40-60wt%.

6. The efficient in-situ solidification treatment method for copper-based iodine waste according to claim 1, wherein In the step 2, the specific method of tableting is to press the tablets at a pressure of 14-16 MPa on a tablet press. x A mixture of Bi2O3-B2O3-ZnO glass powder and copper-based iodine waste was pressed into discs with a diameter of 10~15mm.

7. The efficient in-situ solidification treatment method for copper-based iodine waste according to claim 1, wherein In the step 2, the sintering temperature is 400-600° C., the sintering time is 3-8 hours, and the sintering atmosphere is air or nitrogen.

8. The efficient in-situ solidification treatment method for copper-based iodine waste according to claim 1, wherein In the step 2, the solidified body is named x Bi2O3-B2O3-ZnO- y I, where y is 100 times the amount of iodine solid solution, and the value of y is 2~8.

9. The efficient in-situ solidification treatment method for copper-based iodine waste according to claim 1, wherein In the step 2, x The mass ratio of Bi2O3-B2O3-ZnO glass powder to copper-based iodine waste is 5:0.2~1.

5.

10. The efficient in-situ solidification treatment method for copper-based iodine waste according to claim 1, wherein In the step 2, x Bi2O3-B2O3-ZnO glass powder and copper-based iodine waste are fully ground and mixed to obtain a mixed powder, and the mixed powder is doped with phosphogypsum and silicon: S1. Add the mixture powder, SiO2 powder, and CaSO4·2H2O powder into water and stir evenly to obtain a suspension; add polyethylene glycol-200 as a dispersant to the suspension, and stir magnetically at 300-500 rpm for 20-60 min to obtain a dispersion system; wherein the amount ratio of the mixed powder, SiO2 powder, CaSO4·2H2O powder, polyethylene glycol-200, and water is 5-10 g:1-3 g:1-3 g:0.5-1 g:400-600 mL; S2. Add γ-glycidyloxypropyltrimethoxysilane in an amount of 1 to 10 wt% by weight of the mixed powder to the dispersion system, and add oxalic acid to adjust the pH of the dispersion system to 2 to 4. Stir at 300 to 500 rpm and raise the temperature to 60 to 80°C. Keep warm for 1 to 12 hours. After standing for 12 to 24 hours, filter and wash the powder to neutrality, dry to obtain a mixed powder of phosphogypsum and silicon-doped powder, and then press and sinter to obtain a solidified body.

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