A method for synergistic treatment of beryllium and thallium-containing waste residues
By mixing beryllium and thallium-containing waste residue with inorganic mineral materials such as fly ash, zeolite, and steel slag, and then allowing it to stand for curing, the simultaneous and efficient stabilization of beryllium and thallium in the waste residue is achieved. This solves the problems of high environmental pollution risk and high cost, and provides an economical and environmentally friendly treatment solution.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- INSTITUTE OF PROCESS ENGINEERING CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2025-06-19
- Publication Date
- 2026-05-29
AI Technical Summary
Existing technologies are difficult to effectively treat waste containing beryllium and thallium, resulting in high environmental pollution risks, and commercial passivation materials are expensive.
By mixing beryllium and thallium-containing waste residue with inorganic mineral materials such as fly ash, zeolite, and steel slag, and allowing it to stand for curing, beryllium and thallium are converted into a stable state through physicochemical processes, thereby reducing their bioavailability.
It achieves simultaneous and efficient treatment of beryllium and thallium, reduces environmental risks, and has mild reaction conditions, no secondary pollution, low cost, and is suitable for large-scale promotion.
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Figure CN120885532B_ABST
Abstract
Description
Technical Field
[0001] This application belongs to the field of solid waste treatment technology, specifically relating to a synergistic treatment method for waste residue containing beryllium and thallium. Background Technology
[0002] With the rapid development of high-end equipment manufacturing and the semiconductor industry, the industrial waste containing beryllium (Be) and thallium (Tl) generated by the metallurgical and electronics manufacturing industries is showing a significant upward trend. According to toxicological data from the International Union of Pure and Applied Chemistry (IUPAC), beryllium is a Group IIA carcinogen; its soluble fluorides and oxides can cause chronic beryllium disease (CBD) through inhalation exposure, with a median lethal concentration (LC50) as low as 0.5 mg / m³. 3 Thallium is listed as a priority pollutant by the WHO, and its I-valent cation (Tl) + Beryllium and thallium exhibit potassium-like interference effects, and their concentration is strictly limited to ≤0.002 mg / L according to EPA drinking water standards. Their occurrence in waste residue is complex, with high leaching rates of exchangeable beryllium and thallium, potentially leading to pollution of surrounding soil and groundwater, posing a significant environmental risk. Therefore, treating beryllium and thallium-containing waste residue at its source is of great importance. Summary of the Invention
[0003] In view of this, this application provides a synergistic treatment method for waste residue containing beryllium and thallium, which can achieve simultaneous and efficient treatment of beryllium and thallium in the waste residue, with mild reaction conditions and no secondary pollution.
[0004] The method described in this application includes the following steps:
[0005] S1: Pre-treat the waste residue containing beryllium and thallium to obtain homogenized slag;
[0006] S2: Mix homogenized slag with inorganic mineral materials, wherein the inorganic mineral materials include at least one of fly ash, zeolite, and steel slag;
[0007] S3: Add water to obtain a mixed system containing homogenized slag and inorganic mineral materials. Stir and let the mixed system stand to cure.
[0008] By adopting the above technical solution, beryllium and thallium in waste residue can be treated simultaneously and efficiently, and the reaction conditions are mild, with no secondary pollution, making it easy to promote and apply on a large scale.
[0009] In some embodiments, the inorganic mineral material content is 10% to 30% by mass of the homogenized slag. Inorganic mineral materials within this content range can better achieve their physicochemical interaction with the homogenized slag.
[0010] In some implementations, during the static curing process of the mixture, the moisture content of the mixture is controlled between 50% and 70%. Controlling the appropriate moisture content during static curing can improve the strength and stability of the entire mixture.
[0011] In some implementations, the static curing temperature of the mixed system is 20°C to 28°C.
[0012] In some implementations, the static curing period is 7 to 21 days. After 7 to 21 days of static curing, the entire mixture tends to stabilize and can effectively prevent beryllium and thallium from seeping out. During the static curing process, the mixture is weighed and water is added every 2 to 3 days to control the moisture content of the mixture at 50% to 70%.
[0013] In some embodiments, the pretreatment process in S1 includes removing large impurities from the beryllium- and thallium-containing waste residue and crushing and grinding it through a 20-mesh sieve. After pretreatment, the beryllium- and thallium-containing waste residue has smaller particles and a larger specific surface area, allowing for a more complete reaction with inorganic mineral materials, resulting in better treatment of beryllium and thallium.
[0014] In some embodiments, the inorganic mineral materials in S2 need to be crushed and ground before mixing. After crushing and grinding, the mesh size of the inorganic mineral materials is 10 to 20 mesh. The size of the inorganic mineral materials is similar to that of the homogenized waste residue, which allows for better reaction with the homogenized waste residue and improves the synergistic treatment effect of beryllium and thallium.
[0015] In some implementations, the waste residue containing beryllium and thallium is lithium smelting slag.
[0016] This application has at least the following beneficial effects:
[0017] This application provides a synergistic treatment method for beryllium and thallium-containing waste residue, enabling simultaneous and efficient treatment of beryllium and thallium in the waste residue. The inorganic mineral materials used in this application can, through physicochemical synergy, transform beryllium and thallium in the waste residue from an exchangeable state to a stable state. After static curing, simultaneous and efficient removal of beryllium and thallium can be achieved. The reaction conditions in this application are mild, with no secondary pollution, and the inorganic mineral materials used are industrial solid waste, realizing the resource utilization of industrial solid waste. The solution is simple, easy to implement, economical, environmentally friendly, and suitable for large-scale application. Attached Figure Description
[0018] Figure 1 This is a schematic flowchart of a synergistic treatment method for beryllium and thallium-containing waste residue in an embodiment of this application;
[0019] Figure 2 This is a schematic diagram illustrating the influence of different inorganic mineral materials on the effective content of Be and Tl metals in beryllium and thallium-containing waste residues;
[0020] Figure 3 This is a schematic diagram showing the effective metal content of Be and Tl after treating beryllium and thallium-containing waste residues with 10% fly ash, 10% zeolite and 10% steel slag respectively in the embodiments of this application;
[0021] Figure 4 This is a schematic diagram showing the effective metal content of Be and Tl after treating beryllium and thallium-containing waste residues with 20% fly ash, 20% zeolite and 20% steel slag respectively in the embodiments of this application;
[0022] Figure 5 This is a schematic diagram showing the effective metal content of Be and Tl after treating beryllium and thallium-containing waste residues with 30% fly ash, 30% zeolite and 30% steel slag respectively in the embodiments of this application; Detailed Implementation
[0023] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.
[0024] The solution of this application will be described below with reference to the following specific embodiments. Unless otherwise specified, the raw materials used in the following embodiments are all from commercially available products, and the devices or equipment used are all purchased from conventional market sales channels.
[0025] In the field of solid waste treatment, a widely discussed method is the addition of passivating materials to the soil or waste residue to be remediated. This method works by using the passivating material to interact with toxic metals in the solid waste, immobilizing the metals within them and thus reducing their mobility and bioavailability in the environment. Beryllium and thallium-containing waste residue is a common type of solid waste with a wide range of sources, including lithium smelting slag, particularly the residue generated after sulfate roasting and leaching of lithium from lepidolite ore. While commercially available passivating materials are effective in treating toxic metals in waste residue, their cost is relatively high.
[0026] In view of this, this application provides a method for the synergistic treatment of waste containing beryllium and thallium, comprising the following steps:
[0027] S1: Pre-treat the waste residue containing beryllium and thallium to obtain homogenized slag;
[0028] S2: Mix homogenized slag with inorganic mineral materials, wherein the inorganic mineral materials include at least one of fly ash, zeolite, and steel slag;
[0029] S3: Add water to obtain a mixed system containing homogenized slag and inorganic mineral materials. Stir and let the mixed system stand to cure.
[0030] The inventors discovered that mixing at least one of fly ash, zeolite, or steel slag with pretreated beryllium- and thallium-containing waste residue, and then allowing it to stand and cure with water for a period of time, can transform the highly active beryllium and thallium in the waste residue into a stable state, reducing the content of the effective state and achieving synergistic control of beryllium and thallium. Please see [link to product description]. Figure 2 Compared with other inorganic mineral materials, fly ash, zeolite, and steel slag were mixed with pretreated beryllium and thallium-containing waste residues, respectively. After being cured by adding water, the DTPA available content of beryllium and thallium decreased to below 1.0 μg / kg and 10 μg / kg, respectively. The bioavailability of beryllium and thallium in the waste residues was significantly reduced, indicating that fly ash, zeolite, and steel slag can achieve simultaneous and efficient treatment of beryllium and thallium in waste residues.
[0031] In this application, fly ash refers to solid waste generated during coal-fired power generation, coke oven manufacturing, and industrial boiler production. It is the fine particulate matter remaining after excessively large particles have been removed by electric or mechanical screening. Its main components include silicon dioxide, alumina, iron oxide, and calcium oxide, among which silicon dioxide and alumina are the main components of fly ash and are usually present in high concentrations. The inventors have discovered that fly ash generally has porous characteristics and a large specific surface area, resulting in good adsorption of beryllium and thallium. Furthermore, the active silica-alumina components abundant in fly ash can undergo specific hydroxyl complexation reactions with beryllium and thallium ions to form stable complexes Be(OH)2 and TlOH stable phases, transforming beryllium and thallium from an exchangeable state (metallic effective state) to a stable state.
[0032] Steel slag is a type of alkaline industrial solid waste generated during the steelmaking process in iron and steel production. It is mainly formed by a series of physicochemical reactions between impurities in pig iron and added slag-forming agents and fluxes at high temperatures. Calcium and iron are the most common and major components of steel slag. The inventors discovered that the iron and calcium components in steel slag exhibit specific adsorption of beryllium and thallium. Through surface adsorption and the formation of insoluble precipitates, steel slag can fix beryllium and thallium ions on its surface and inside, achieving efficient treatment of beryllium and thallium.
[0033] Zeolite is a porous aluminosilicate mineral with a naturally occurring pore structure. Its numerous channels and pores of varying sizes and shapes provide ample surface area and a certain degree of adsorption capacity. Simultaneously, the zeolite lattice contains a large number of exchangeable cations, such as Na+. + K + Ca 2+ These cations can undergo ion exchange reactions with beryllium ions, thallium ions, etc., thereby achieving the removal of these harmful ions.
[0034] In summary, this application provides a method for the synergistic stabilization of beryllium and thallium in beryllium- and thallium-containing waste residues. Through the interaction of fly ash (solid waste from coal-fired power plants), steel slag (byproduct of the metallurgical industry), zeolite (mining tailings resources) with the beryllium- and thallium-containing waste residues, highly reactive beryllium and thallium in the waste residues can be simultaneously converted into stable states, reducing the content of the effective forms and achieving synergistic control of these two toxic metals. See also... Figures 3-5 After treatment, the DTPA-available content of beryllium and thallium was reduced to below 1.0 μg / kg and 10 μg / kg, respectively. The bioavailability of beryllium and thallium in the waste residue was significantly reduced, thus lowering environmental risks. The technical solution presented in this application can be implemented under normal temperature and pressure conditions, is simple and easy to carry out, and does not generate secondary pollution, demonstrating significant environmental benefits. Furthermore, fly ash, steel slag, and zeolite are all bulk industrial solid wastes, with raw material costs significantly lower than commercial materials. The waste residue treatment cost is low, the solid waste resource utilization rate is high, and the economic benefits are good.
[0035] In some embodiments, the inorganic mineral material content is 10% to 30% by mass of the homogenized slag. Exemplarily, the inorganic mineral material content is 10%, 12%, 15%, 20%, 22%, 30%, or any combination of two of these values. Inorganic mineral materials within this content range can be utilized efficiently and their physicochemical interaction with the homogenized slag can be effectively achieved.
[0036] In some embodiments, during the static curing process of the mixed system, the moisture content of the mixed system is controlled between 50% and 70%. Exemplarily, the moisture content can be 50%, 55%, 58%, 60%, 64%, 70%, or any combination of two of these values. The active components in the inorganic mineral materials can react with water to generate hydrated silicates or gel-like substances, binding the waste particles together, thereby improving the strength and stability of the entire mixed system. Furthermore, water can also act as a filler and lubricant in the mixed system, making the particles more tightly packed, thus enhancing its impermeability and compressive strength. A suitable moisture content during static curing can maintain the stability of the mixed system, enhance its strength, and prevent cracking and shrinkage, thereby achieving a better stabilization effect.
[0037] In some embodiments, the static curing temperature is 20°C to 28°C. For example, the static curing temperature can be 20°C, 22°C, 23°C, 25°C, 26°C, 28°C, or any combination of two of the above values.
[0038] In some implementations, the static curing period is 7 to 21 days. After 7 to 21 days of static curing, the entire mixture tends to stabilize, effectively preventing the leakage of beryllium and thallium. During the static curing period, the mixture can be weighed and water added every 2 to 3 days to maintain the moisture content of the entire mixture at a stable level of 50% to 70%.
[0039] In some embodiments, the pretreatment process in S1 includes removing large impurities from the beryllium- and thallium-containing waste residue and crushing and grinding it through a 20-mesh sieve. After pretreatment, the beryllium- and thallium-containing waste residue has smaller particles and a larger specific surface area, allowing for a more complete reaction with inorganic mineral materials, resulting in better treatment of beryllium and thallium.
[0040] In some embodiments, the inorganic mineral materials in S2 need to be crushed and ground before mixing. After crushing and grinding, the mesh size of the inorganic mineral materials is 10 to 20 mesh. Inorganic mineral materials of this size can react better with homogenized waste residue, thereby improving the synergistic treatment effect of beryllium and thallium.
[0041] In some implementations, the waste residue containing beryllium and thallium is lithium smelting slag.
[0042] The solution of this application will be described below with reference to the following specific embodiments. Unless otherwise specified, the raw materials used in the following embodiments are all from commercially available products, and the devices or equipment used are all purchased from conventional market sales channels.
[0043] Test methods
[0044] This scheme refers to the relevant methods in "Diethylenetriaminepentaacetic acid extraction-inductively coupled plasma atomic emission spectrometry" (GB HJ804-2016) to determine the effective state of beryllium (Be) and thallium (Tl), and uses the effective state content of beryllium (Be) and thallium (Tl) in DTPA leachate as the evaluation index.
[0045] Example 1
[0046] Smelting waste slag was collected from the spodumene leaching slag storage of Ganfeng Lithium Industry in Jiangxi Province. Gravel and plant debris larger than 5 mm were removed, and the slag was transferred to the laboratory and spread evenly on kraft paper. It was then air-dried naturally for 48 hours under ventilated conditions. The air-dried sample was ground in an agate mortar and passed through a 20-mesh nylon sieve. Subsequently, 200 g of the waste slag was accurately weighed and placed in a 500 mL beaker. 10-20 mesh fly ash was mixed with the waste slag at a mass ratio of 10%, and an appropriate amount of water was added to maintain a moisture content of approximately 50%. After standing at room temperature (20℃) for 7, 14, and 21 days, samples were taken for analysis to determine the effective leaching content of the metal.
[0047] Example 2
[0048] Smelting waste slag was collected from the spodumene leaching slag pool of Ganfeng Lithium Industry in Jiangxi Province. Gravel and plant debris larger than 5 mm were removed, and the slag was transferred to the laboratory and spread evenly on kraft paper. It was then air-dried naturally for 48 hours under ventilated conditions. The air-dried sample was ground in an agate mortar and passed through a 20-mesh nylon sieve. Subsequently, 200 g of the waste slag was accurately weighed and placed in a 500 mL beaker. Zeolite of 10-20 mesh was mixed with the waste slag at a mass ratio of 10%, and an appropriate amount of water was added to maintain a moisture content of approximately 50%. After standing at 20℃ for 7, 14, and 21 days, samples were taken for analysis to determine the effective leaching content of the metal.
[0049] Example 3
[0050] Smelting waste slag was collected from the spodumene leaching slag storage of Ganfeng Lithium Industry in Jiangxi Province. Gravel and plant debris larger than 5 mm were removed, and the slag was transferred to the laboratory and spread evenly on kraft paper. It was then air-dried naturally for 48 hours under ventilated conditions. The air-dried sample was ground in an agate mortar and passed through a 20-mesh nylon sieve. Subsequently, 200 g of the waste slag was accurately weighed and placed in a 500 mL beaker. Steel slag of 10-20 mesh was mixed with the waste slag at a mass ratio of 10%, and an appropriate amount of water was added to maintain a moisture content of approximately 50%. After standing at room temperature (20℃) for 7, 14, and 21 days, samples were taken for analysis to determine the effective leaching content of the metal.
[0051] Example 4
[0052] Smelting waste slag was collected from the spodumene leaching slag storage of Ganfeng Lithium Industry in Jiangxi Province. Gravel and plant debris larger than 5 mm were removed, and the slag was transferred to the laboratory and spread evenly on kraft paper. It was then air-dried naturally for 48 hours under ventilated conditions. The air-dried sample was ground in an agate mortar and passed through a 20-mesh nylon sieve. Subsequently, 200 g of the waste slag was accurately weighed and placed in a 500 mL beaker. 10-20 mesh fly ash was mixed with the waste slag at a mass ratio of 20%, and an appropriate amount of water was added to maintain a moisture content of approximately 50%. After standing at 20℃ for 7, 14, and 21 days, samples were taken for analysis to determine the effective leaching content of the metal.
[0053] Example 5
[0054] Smelting waste slag was collected from the spodumene leaching slag pool of Ganfeng Lithium Industry in Jiangxi Province. Gravel and plant debris larger than 5 mm were removed, and the slag was transferred to the laboratory and spread evenly on kraft paper. It was then air-dried naturally for 48 hours under ventilated conditions. The air-dried sample was ground in an agate mortar and passed through a 20-mesh nylon sieve. Subsequently, 200 g of the waste slag was accurately weighed and placed in a 500 mL beaker. Zeolite of 10-20 mesh was mixed with the waste slag at a mass ratio of 20%, and an appropriate amount of water was added to maintain a moisture content of approximately 50%. After standing at 20℃ for 7, 14, and 21 days, samples were taken for analysis to determine the effective leaching content of the metal.
[0055] Example 6
[0056] Smelting waste slag was collected from the spodumene leaching slag storage of Ganfeng Lithium Industry in Jiangxi Province. Gravel and plant debris larger than 5 mm were removed, and the slag was transferred to the laboratory and spread evenly on kraft paper. It was then air-dried naturally for 48 hours under ventilated conditions. The air-dried sample was ground in an agate mortar and passed through a 20-mesh nylon sieve. Subsequently, 200 g of the waste slag was accurately weighed and placed in a 500 mL beaker. Steel slag of 10-20 mesh was mixed with the waste slag at a mass ratio of 20%, and an appropriate amount of water was added to maintain a moisture content of approximately 50%. After standing at 20℃ for 7, 14, and 21 days, samples were taken for analysis to determine the effective leaching content of the metal.
[0057] Example 7
[0058] Smelting waste slag was collected from the spodumene leaching slag storage of Ganfeng Lithium Industry in Jiangxi Province. Gravel and plant debris larger than 5 mm were removed, and the slag was transferred to the laboratory and spread evenly on kraft paper. It was then air-dried naturally for 48 hours under ventilated conditions. The air-dried sample was ground in an agate mortar and passed through a 20-mesh nylon sieve. Subsequently, 200 g of the waste slag was accurately weighed and placed in a 500 mL beaker. 10-20 mesh fly ash was mixed with the waste slag at a mass ratio of 30%, and an appropriate amount of water was added to maintain a moisture content of approximately 60%. After standing at 20℃ for 7, 14, and 21 days, samples were taken for analysis to determine the effective leaching content of the metal.
[0059] Example 8
[0060] Smelting waste slag was collected from the spodumene leaching slag pool of Ganfeng Lithium Industry in Jiangxi Province. Gravel and plant debris larger than 5 mm were removed, and the slag was transferred to the laboratory and spread evenly on kraft paper. It was then air-dried naturally for 48 hours under ventilated conditions. The air-dried sample was ground in an agate mortar and passed through a 20-mesh nylon sieve. Subsequently, 200 g of the waste slag was accurately weighed and placed in a 500 mL beaker. Zeolite of 10-20 mesh was mixed with the waste slag at a mass ratio of 30%, and an appropriate amount of water was added to maintain a moisture content of approximately 60%. After standing at room temperature (20℃) for 7, 14, and 21 days, samples were taken for analysis to determine the effective leaching content of the metal.
[0061] Example 9
[0062] Smelting waste slag was collected from the spodumene leaching slag pool of Ganfeng Lithium Industry in Jiangxi Province. Gravel and plant debris larger than 5 mm were removed, and the slag was transferred to the laboratory and spread evenly on kraft paper. It was then air-dried naturally for 48 hours under ventilated conditions. The air-dried sample was ground in an agate mortar and passed through a 20-mesh nylon sieve. Subsequently, 200 g of the waste slag was accurately weighed and placed in a 500 mL beaker. Steel slag of 10-20 mesh was mixed with the waste slag at a mass ratio of 30%, and an appropriate amount of water was added to maintain a moisture content of approximately 60%. After standing at room temperature (20℃) for 7, 14, and 21 days, samples were taken for analysis to determine the effective leaching content of the metal.
[0063] The test results are shown in Table 1. Figures 3-5 As shown.
[0064] Table 1
[0065]
[0066] Comparative Examples 1 to 5
[0067] The types of inorganic mineral materials were adjusted according to the parameters in Table 2. The static curing time was 7 days. The mass content of all inorganic mineral materials was 10%. The test results are shown in Table 2. Figure 2 As shown.
[0068] Table 2
[0069] serial number Types of inorganic mineral materials Be (μg / kg) Tl(μg / kg) Example 1 fly ash 0.552 0.958 Example 2 zeolite 0.451 0.851 Example 3 steel slag 0.437 0.542 Comparative Example 1 Biochar 1.279 3.501 Comparative Example 2 Bentonite 0.625 14.255 Comparative Example 3 sepiolite 2.3623 0.854 Comparative Example 4 humic acid 10.521 43.833 Comparative Example 5 Comparison (waste residue) 12.68 46.29
[0070] As shown in Tables 1 and 2, by mixing fly ash, zeolite, and steel slag with steel containing 10%, 20%, and 30% by mass, respectively, and controlling the moisture content to be between 50% and 70%, and allowing the mixture to stand for a period of time, the effective states of beryllium and thallium decreased to below 1.0 μg / kg and 10 μg / kg, respectively, thus achieving efficient and simultaneous treatment of beryllium and thallium.
[0071] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the principles of this application should be included within the protection scope of this application.
Claims
1. A method for the synergistic treatment of waste containing beryllium and thallium, characterized in that, The method includes the following steps: S1: The beryllium- and thallium-containing waste residue is pretreated to obtain homogenized slag; S2: Mix the homogenized slag with inorganic mineral materials, wherein the inorganic mineral materials include at least one of fly ash, zeolite, and steel slag; S3: Add water to obtain a mixed system containing the homogenized slag and the inorganic mineral material, stir, and allow the mixed system to stand for curing; during the standing curing process, control the moisture content of the mixed system to be between 50% and 70%; the standing curing temperature is between 20°C and 28°C; the standing curing time is between 7 and 21 days; wherein, the mixed system is weighed and water is added every 2 to 3 days to control the moisture content of the mixed system to be between 50% and 70%.
2. The method according to claim 1, characterized in that, In step S2, the inorganic mineral material has a mass content of 10% to 30% based on the mass of the homogenized slag.
3. The method according to claim 1, characterized in that, In step S1, the pretreatment process includes removing large impurities and crushing and grinding them through a 20-mesh sieve.
4. The method according to claim 1 or 2, characterized in that, In step S2, the inorganic mineral material needs to be crushed and ground before mixing. After crushing and grinding, the mesh size of the inorganic mineral material is 10 to 20 mesh.
5. The method according to claim 1 or 2, characterized in that, The waste residue containing beryllium and thallium is lithium smelting slag.