Composite purification material as well as preparation method and application thereof

Abstract

The invention relates to a composite purification material, a preparation method and application thereof. The composite purification material can deeply and synchronously remove fluorine, silicon, phosphorus and organic matters in a solution or extract wastewater, the reaction efficiency is high, the adaptability is strong, the developed synchronous impurity removal technology has the advantages of short process flow, high impurity removal efficiency, simplicity in operation, greenness, environmental protection and the like, and large-scale industrial application is easy to realize.

Description

Technical Field

[0001] The present invention relates to the technical field of battery recycling, and specifically refers to a composite purification material, a preparation method thereof, and an application thereof in the synchronous removal of fluorine, silicon, phosphorus, and organic matter in the leaching solution of ternary battery black powder or extraction wastewater. Background Art

[0002] With the rapid development of the lithium-ion battery industry, the demand for raw materials such as nickel sulfate, cobalt sulfate, and manganese sulfate for battery materials has increased sharply. These materials come from ore materials and battery recycling materials. The ore materials mainly include MHP, cobalt hydroxide, etc., and the battery recycling materials are mainly the products after the scrapping of ternary lithium batteries and lithium iron phosphate batteries. There are some impurity elements in these raw materials, such as fluorine, silicon and other elements. To a certain extent, these elements always exist in nickel sulfate and cobalt salts, which have a great impact on the performance of battery materials. The extraction process of nickel-cobalt sulfate salts generally adopts the extraction process. A large amount of raffinate wastewater is generated during the extraction process. The main impurities in the wastewater are oil, phosphorus, fluorine, etc. It needs to be treated to meet the discharge or evaporation crystallization index. Therefore, the problem of treating impurities such as fluorine, phosphorus, silicon, and oil has become a technical problem in the production process of battery materials. Studying methods for removing impurities such as fluorine, phosphorus, silicon, and oil is of great significance to the entire industry.

[0003] Currently, relatively mature methods for removing fluorine include coagulation precipitation method, adsorption method, ion exchange method, etc. Calcium salts are widely used defluorinating agents, which use the formation of insoluble CaF2 precipitation to remove fluorine, but there are problems such as insufficient defluorination depth and large amount of slag production; the resin method for removing fluorine is to use resin to adsorb fluorine and regenerate by backwashing, but there are problems such as small resin adsorption capacity and a large amount of acid-base-containing wastewater generated during backwashing regeneration that cannot be treated; the adsorption method generally uses liquid or solid defluorinating agents to adsorb fluorine in solutions or wastewater. Liquid defluorinating agents generally use aluminum sulfate salt adsorbents, which can treat fluorine with a content below 20 ppm. For high-fluorine solutions, the calcium method needs to be assisted for defluorination, which has defects such as large input, high defluorination cost, and difficult pressure filtration. Solid defluorinating agents generally use rare earth-based defluorinating agents, which can be used to treat fluorine below 20 - 50 ppm, but there are problems such as insufficient treatment depth, large usage amount, and high cost.

[0004] The existing methods for removing silicon mainly include alkali elution for desiliconization, precipitation desiliconization with acidic solutions, colloid adsorption, colloid adsorption after oxidation, or extraction separation for desiliconization. There are few reports on the direct deep desiliconization technology in the nickel-cobalt hydrometallurgy industry. Chinese Patent CN112143888 A introduces a method for removing silicon by resin adsorption. The saturated resin for adsorption is eluted with alkali, but there are problems such as difficult elution and a large amount of wastewater generated during actual use.

[0005] The problems of oil removal / phosphorus removal mainly exist in nickel-cobalt solutions and wastewater. In particular, oil removal / phosphorus removal in wastewater is a difficult problem that plagues the industry. Currently, the common oil removal methods include activated carbon adsorption, resin adsorption, coalescence oil removal, ultrasonic air flotation, etc. In the latter two oil removal methods, methods such as activated carbon oil removal and resin adsorption need to be combined and used together to achieve the treatment depth. The activated carbon oil removal method is one of the methods with the best treatment effect among the current oil removal methods. However, it has problems such as a large usage amount, a large amount of waste residue generated, the waste residue being hazardous waste, and a high treatment cost. Therefore, there are very few enterprises in the industry that use activated carbon oil removal alone; the oil removal treatment depth of the resin method can meet the standards. The resin can be backwashed and regenerated, and the operating cost is low. Therefore, more enterprises adopt it. However, there is a problem of difficult desorption. The eluent is generally liquid alkali or methanol, ethanol, etc. There are relatively large safety risks when operating in a high-temperature and high-pressure environment, and a large amount of eluent is generated, making the treatment difficult.

[0006] In addition, when treating impurities such as fluorine, phosphorus, silicon, and oil in nickel-cobalt solutions or wastewater, there is a problem that the reaction conditions are different for each step and need to be switched. For example, the pH values are different. After oil removal is completed, the pH value needs to be adjusted before removing fluorine, which requires a large amount of auxiliary materials and labor costs.

[0007] Therefore, finding a method that can remove fluorine, silicon, oil, and phosphorus simultaneously, and is fast, efficient, can deeply remove impurities, and has low costs is of great significance for solving the current situation of the industry. Summary of the Invention

[0008] The present invention aims to solve the above problems and provides a method that can remove fluorine, silicon, oil, and phosphorus simultaneously, with advantages such as a short process flow, high impurity removal efficiency, simple operation, and environmental friendliness, and can achieve large-scale industrial production.

[0009] On the one hand, the present invention provides a composite purification material, which comprises an activated carbon matrix and active components loaded on the activated carbon.

[0010] The active components are composed of two components, A and B. Component A contains zirconium and titanium ions, and component B contains aluminum, lanthanum, and cerium ions.

[0011] The activated carbon is powdered wood-based activated carbon, with a specific surface area of 1000 - 2000m 2 / g and a particle size of 10 - 15μm.

[0012] The loading amount of the active components is 50 - 100mg / g, based on the activated carbon.

[0013] On the other hand, the present invention provides a method for preparing a composite purification material, the method comprising the following steps: using activated carbon as a matrix, loading active materials onto the activated carbon by impregnation, and obtaining the composite purification material through processes such as filtration, washing, and drying.

[0014] In the present invention, the active material is a hydrochloride salt of an active ingredient, specifically preferably one or more of several substances such as zirconium oxychloride, titanium tetrachloride, aluminum chloride, lanthanum chloride, cerium chloride, etc.

[0015] In the present invention, it is preferred to first dissolve the active material in 10-15% dilute hydrochloric acid to obtain an active solution.

[0016] In the present invention, the mass-volume ratio of activated carbon to the active solution during the impregnation process is 1:3-6 kg / cm 3 .

[0017] In the present invention, the temperature of the impregnation is 70-95 °C and the time is 60-90 min.

[0018] In the present invention, the washing is carried out with pure water, and the amount used is 4-6 times the mass of the solid.

[0019] In the present invention, the drying temperature is 50-80 °C and the drying time is 1-3 h.

[0020] In the third aspect, the present invention provides a method for removing fluorine, silicon, phosphorus, and oil from the wastewater of ternary battery materials using the composite purification material, the method comprising the following steps:

[0021] (1) Impurity adsorption: Using the obtained composite purification material as an adsorbent, adsorbing and removing fluorine, silicon, phosphorus, and organic substances;

[0022] (2) Alkaline washing and desorption: Using an alkaline solution as a desorbent, stirring and washing the composite purification material adsorbed with impurities, and performing a hydrochloric acid activation step on the eluted composite purification material.

[0023] (3) Hydrochloric acid activation: Using dilute hydrochloric acid as an activator, performing activation treatment on the composite purification material after alkaline washing, and returning the activated composite purification material to the impurity removal process for recycling.

[0024] In the present invention, the addition amount of the composite purification material is 1-2 kg / m 3 wastewater, the adsorption and removal time is 20-60 min, the temperature is 20-60 °C; the pH for adsorption and removal is 2.5-6.

[0025] In the present invention, in the desorption and regeneration step, the alkali solution is selected from NaOH, the concentration of the alkali solution is preferably 1-2 wt%, and the mass-volume ratio of the impurity-loaded purification agent (i.e., the composite purification material after adsorbing impurities) to the alkali solution is 1:3-5 kg / cm 3 , the reaction temperature is 20-40 °C, and the reaction time is 30-60 min.

[0026] In the present invention, in the hydrochloric acid activation step, the concentration of hydrochloric acid used is 1-3 wt%, and the mass-volume ratio of the regenerated purification agent to the alkali solution is 1:3-5 kg / cm 3 , the activation temperature is 20-40 °C, and the activation time is 30-60 min.

[0027] The beneficial effects of the present invention are as follows:

[0028] (1) During the synthesis process, the rich pore structure of activated carbon is utilized to provide a larger reaction interface for the active components. At the same time, by grafting the active components, the active sites on the surface of activated carbon are enriched, enhancing the adsorption effect; the microstructure determines the properties of the material, and the grafting of different active components determines that this composite purification material has multiple functions such as silicon removal, fluorine removal, phosphorus removal, and oil removal. Compared with single materials for fluorine removal, silicon removal, phosphorus removal, etc., it has obvious advantages: avoiding the problems of different usage conditions for removing different impurities, the need to switch between various processes, use different auxiliary agent treatment methods, high consumption of auxiliary materials, and cumbersome operation procedures;

[0029] (2) The composite purification material has good adsorption effect. In the solution after fluorine and silicon removal, the concentration of F is lower than 0.001 g / L, the concentration of silicon (calculated as SiO2) is lower than 0.01 g / L, the concentration of TOC is lower than 0.015 g / L, and the concentration of TP is lower than 0.005 g / L; it meets the requirements for fluorine, silicon, TOC, and TP in the ternary precursor synthesis solution and the wastewater discharge into the sea index;

[0030] (3) No impurity ions are introduced, and it has no impact on the indicators of subsequent solutions or wastewater;

[0031] (4) It does not adsorb the main metal ions and has no impact on the direct recovery rate of the main metal;

[0032] (5) It has a small usage amount, low cost, a short process flow, mild reaction conditions, and is environmentally friendly. Description of the Drawings

[0033] Figure 1 It is a schematic process diagram of the present invention. Detailed Embodiments

[0034] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0035] Raw material sources and testing methods: The activated carbon powder is wood-based activated carbon, purchased from HanYan Company, with the brand number: HY-616(D); the liquid defluorinating agent, with the brand number: CL-1, purchased from Kleifu Company; PAM (polyacrylamide) is purchased from Zibo Lan'erqing High Polymer Materials Company; the solid defluorinating agent (CL-1000) is purchased from Changsha Huasheng New Materials Company; the ion exchange resin (A815) is purchased from Jiangsu Suqing Water Treatment Company; zirconium oxychloride, titanium tetrachloride, aluminum chloride, lanthanum chloride, and cerium chloride are purchased from Zibo Guanhai Industry and Trade Co., Ltd.; The main components of the wastewater are: nickel: 10 - 200 ppm, fluorine: 10 - 20 ppm, TOC: 100 - 300 ppm, TP: 10 - 100 ppm, Si: 20 - 60 ppm, pH value: 2.5; the nickel sulfate solution is generated from the extraction process, with the nickel sulfate concentration being: 23 - 27%, fluorine: 10 - 20 ppm, TOC: 100 - 300 ppm, TP: 10 - 100 ppm, Si: 20 - 60 ppm, and the pH value being 4 - 5.

[0036] The testing instrument for the metal ions and TP is ICP-OES, and the model of the equipment is Agilent5900SVDV; the detection instrument for the fluoride ions is a fluoride ion selective electrode, and the equipment model is: Leici PF-2-01 type, and the TOC detection instrument is a TOC analyzer, and the equipment model is: Shimadzu-TOC-1000e.

[0037] Example 1:

[0038] Synthesis process: Take the activated carbon powder (purchased from HanYan Company, with the brand number: HY-616(D))

[0039] 100 g, with a particle size of 0.10 - 0.15 microns, is added to the solution containing the active components in a ratio of 1:4. The active components are mainly composed of two components, A and B. Component A is zirconium oxychloride and titanium tetrachloride (zirconium oxychloride: 11.61 g, titanium tetrachloride: 0.76 g), and component B is aluminum chloride, lanthanum chloride, and cerium chloride (aluminum chloride: 22.4 g, lanthanum chloride: 5.9 g, cerium chloride: 5.9 g). The metal ion concentration of component A solution is 0.1 mol / L, and the metal ion concentration of component B solution is 0.6 mol / L. An impregnation reaction occurs at a reaction temperature of 85 °C for 60 min to obtain the active material, which is filtered by a vacuum filtration system at a pressure of 0.1 MPA, then washed with 500 mL of pure water, and dried at 50 °C for 1 h to obtain the composite purification material product.

[0040] Adsorption - elution process: Take 10 L of the raffinate wastewater from the extraction workshop. The main components of the wastewater are: nickel: 10 - 200 ppm, fluorine: 10 - 20 ppm, TOC: 100 - 300 ppm, TP: 10 - 100 ppm, Si: 20 - 60 ppm, pH value: 2.5. Add 10 g of the composite purification material, stir and react at 20 °C for 30 min, separate the solid and liquid to obtain the liquid after impurity removal and the impurity removal residue. The impurity removal residue is backwashed with 30 mL of 2% NaOH solution at 20 °C for 30 min and then filtered; then activated with 30 ml of 2% hydrochloric acid at 20 °C for 30 min and then filtered to complete regeneration. The removal effect is shown in Table 1.

[0041] Table 1 Composition and impurity removal rate of wastewater before and after impurity removal

[0042]

[0043] Example 2:

[0044] Synthesis process: Take 100 g of activated carbon powder with a particle size of 0.10 - 0.15 microns, and add it to the solution containing the active components in a ratio of 1:3. The active components are mainly composed of two components, A and B. Component A is zirconium oxychloride and titanium tetrachloride (zirconium oxychloride: 17.40 g, titanium tetrachloride: 1.14 g), and component B is aluminum chloride, lanthanum chloride, and cerium chloride (aluminum chloride: 19.22 g, lanthanum chloride: 4.42 g, cerium chloride: 4.42 g). The metal ion concentration of component A solution is 0.2 mol / L, and the metal ion concentration of component B solution is 0.7 mol / L. An impregnation reaction occurs at a reaction temperature of 90 °C for 70 min to obtain the active material, which is filtered by a vacuum filtration system at a pressure of 0.1 MPA, then washed with 1000 mL of pure water, and dried at 80 °C for 1 h to obtain the composite purification material product.

[0045] Adsorption - elution process: Take 10 L of raffinate wastewater from the extraction workshop, add 20 g of the composite purification material, stir and react at 60 °C for 60 min, then perform solid - liquid separation to obtain the impurity - removed liquid and impurity - removed residue. Wash the impurity - removed residue with 60 mL of 2% NaOH solution, back - wash at 60 °C for 20 min and then filter under pressure; then activate with 60 ml of 2% hydrochloric acid at 60 °C for 20 min and filter under pressure to complete regeneration. The removal effect is shown in Table 2.

[0046] Table 2 Composition and impurity removal rate of wastewater before and after impurity removal

[0047]

[0048] Example 3:

[0049] Synthesis process: Take 100 g of activated carbon powder with a particle size of 0.10 - 0.15 microns, add the solution containing the active components in a ratio of 1:6. The active components are mainly composed of two components, A and B. Component A is zirconium oxychloride and titanium tetrachloride (zirconium oxychloride: 52.2 g, titanium tetrachloride: 3.42 g), and component B is aluminum chloride, lanthanum chloride, and cerium chloride (aluminum chloride: 64.08 g, lanthanum chloride: 14.71 g, cerium chloride: 14.71 g). The metal ion concentration of component A solution is 0.3 mol / L, and the metal ion concentration of component B solution is 1.0 mol / L; carry out an impregnation reaction at a reaction temperature of 95 °C for 90 min to obtain the active material. Filter it through a vacuum filtration system with a pressure of 0.1 MPA, then wash it with 700 mL of pure water, and dry it at 60 °C for 3 h to obtain the composite purification material product.

[0050] Adsorption - elution process: Take 10 L of raffinate wastewater from the extraction workshop, add 10 g of the composite purification material, stir and react at 30 °C for 50 min, then perform solid - liquid separation to obtain the impurity - removed liquid and impurity - removed residue. Wash the impurity - removed residue with 50 mL of 2% NaOH solution, back - wash at 40 °C for 60 min and then filter under pressure; then activate with 50 ml of 2% hydrochloric acid at 40 °C for 60 min and filter under pressure to complete regeneration. The removal effect is shown in Table 3.

[0051] Table 3 Composition and impurity removal rate of wastewater before and after impurity removal

[0052]

[0053] Example 4

[0054] Synthesis process: Take 100 g of activated carbon powder with a particle size of 0.10 - 0.15 microns, and add it to the solution containing the active components in a ratio of 1:6. The active components are mainly composed of two components, A and B. Component A consists of zirconium oxychloride and titanium tetrachloride (zirconium oxychloride: 52.2 g, titanium tetrachloride: 3.42 g), and component B consists of aluminum chloride, lanthanum chloride, and cerium chloride (aluminum chloride: 64.08 g, lanthanum chloride: 14.71 g, cerium chloride: 14.71 g). The metal ion concentration of component A solution is 0.3 mol / L, and the metal ion concentration of component B solution is 1.0 mol / L. An impregnation reaction occurs at a reaction temperature of 95°C for 90 min to obtain the active material. After filtration through a vacuum filtration system at a pressure of 0.1 MPA, it is then washed with 500 mL of pure water and dried at 50°C for 2 h to obtain the composite purification material product.

[0055] Adsorption - elution process: Take 10 L of nickel sulfate solution from the finished product workshop, add 15 g of the composite purification material, and stir and react at 20°C for 60 min. After solid - liquid separation, the purified solution and the purification residue are obtained. The purified solution is returned to the ternary workshop for synthesizing ternary precursors. The purification residue is washed with 0.1 L of pure water, and the filtrate is merged into the purified solution. The filter residue is back - washed with 60 mL of 2% NaOH solution at 40°C for 60 min and then filtered; then it is activated with 60 mL of 2% hydrochloric acid at 40°C for 60 min and then filtered to complete regeneration. The impurity removal effect is shown in Table 4.

[0056] Table 4 Composition of the solution before and after impurity removal and impurity removal rate

[0057]

[0058]

[0059] Example 5

[0060] Synthesis process: Take 100 g of activated carbon powder with a particle size of 0.10 - 0.15 microns, and add it to the solution containing the active components in a ratio of 1:3. The active components are mainly composed of two components, A and B. Component A consists of zirconium oxychloride and titanium tetrachloride (zirconium oxychloride: 17.40 g, titanium tetrachloride: 1.14 g), and component B consists of aluminum chloride, lanthanum chloride, and cerium chloride (aluminum chloride: 19.22 g, lanthanum chloride: 4.42 g, cerium chloride: 4.42 g). The metal ion concentration of component A solution is 0.2 mol / L, and the metal ion concentration of component B solution is 0.7 mol / L. An impregnation reaction occurs at a reaction temperature of 70°C for 90 min to obtain the active material. After filtration through a vacuum filtration system at a pressure of 0.1 MPA, it is then washed with 500 mL of pure water and dried at 80°C for 1 h to obtain the composite purification material product.

[0061] Adsorption-elution process: Take 10L of nickel sulfate solution from the finished product workshop, add 15g of composite purification material, stir and react at 20℃ for 30min, separate solid and liquid, obtain impurity-free liquid and impurity-free residue, and return the impurity-free liquid to the ternary workshop for the synthesis of ternary precursor; wash the impurity-free residue with 0.1L pure water, combine the filtrate with the impurity-free liquid, backwash the residue with 60mL of 2% NaOH solution at 40℃ for 60min and filter press; then activate with 60ml of 2% hydrochloric acid at 40℃ for 60min and filter press to complete regeneration. The removal effect is shown in Table 5.

[0062] Table 5 Solution composition and impurity removal rate before and after impurity removal

[0063]

[0064]

[0065] Comparative Example 1: Take 10L of the residual wastewater from the extraction workshop, first add activated carbon to remove oil, the amount of activated carbon added is 50g, stir and react at 40℃ for 60min, separate the solid and liquid, and obtain the impurity-removed liquid and impurity-removed residue. The impurity-removed residue is a hazardous waste and is outsourced for treatment; the impurity-removed wastewater is subjected to a defluorination process, and a liquid defluorinating agent is used for defluorination. First, hydrochloric acid is added to adjust the pH of the wastewater to 5-6, stir, add 20g of liquid defluorinating agent, and then add 0.1g of PAM (polyacrylamide), the temperature is 40-50℃, and stirring is continued for 30min, filter press, produce defluorination residue, and outsource treatment; the wastewater is discharged to the park sewage treatment plant, and the removal effect of fluorine, TOC, and TP and the consumption of auxiliary materials are shown in Table 6.

[0066] Table 6 Wastewater composition, impurity removal rate and auxiliary material content before and after impurity removal

[0067]

[0068] Comparative Example 2

[0069] Take 10L of nickel sulfate solution from the finished product workshop, add activated carbon to remove oil first, the amount of activated carbon added is 40g, stir and react at 40℃ for 1h, separate the solid and liquid, and obtain the impurity-removed liquid and impurity-removed residue. The impurity-removed residue is a hazardous waste and is outsourced for treatment;

[0070] After impurities are removed, the nickel sulfate solution is subjected to a defluorination process, using a solid defluorinating agent (ZrO2) for defluorination. 20 g of the defluorinating agent is added, stirred at 20°C for 60 min, and filtered to produce defluorinated residue. The defluorinated residue is first washed with 1 L of water, then backwashed with 60 mL of 2% NaOH solution at 40°C for 60 min, and then filtered; then activated with 60 ml of 2% hydrochloric acid at 40°C for 60 min, and then filtered to complete regeneration.

[0071] Silicon in the nickel sulfate solution is removed by using ion exchange resin. The ion exchange resin used is strong base anion resin A815. The flow rate of the solution is 4 BV / h. After the resin is saturated with adsorption, it is regenerated with clarified lime water at a flow rate of 4 BV for 1 h, and then washed with pure water at a flow rate of 2.5 BV for 1 h to complete the regeneration. The removal effects of fluorine, TOC, TP, and silicon in the nickel sulfate solution and the consumption of auxiliary materials are shown in Table 7.

[0072] Table 7 Composition, impurity removal rate, and consumption of auxiliary materials of nickel sulfate solution before and after impurity removal

[0073]

[0074] Comparative Example 3

[0075] Synthesis process: Take 100 g of activated carbon powder with a particle size of 0.10 - 0.15 microns, and add it to the solution containing the active components according to a ratio of 1:4. The active components are mainly component B, and component B is aluminum chloride, lanthanum chloride, and cerium chloride (aluminum chloride: 22.4 g, lanthanum chloride: 5.9 g, cerium chloride: 5.9 g). The metal ion concentration of the component B solution is 0.6 mol / L; an impregnation reaction occurs at a reaction temperature of 85 °C for 60 min to obtain the active material, which is filtered by a vacuum filtration system with a pressure of 0.1 MPA, then washed with 500 mL of pure water, and dried at 50 °C for 1 h to obtain the composite purification material product.

[0076] Adsorption - elution process: Take 10 L of the raffinate wastewater from the extraction workshop, add 10 g of the composite purification material, stir and react at 20 °C for 60 min, perform solid - liquid separation to obtain the liquid after impurity removal and the impurity removal residue. The impurity removal residue is back - washed with 30 mL of 2% NaOH solution at 20 °C for 30 min and then pressure - filtered; then activated with 30 ml of 2% hydrochloric acid at 20 °C for 30 min and then pressure - filtered to complete the regeneration. The removal effects are shown in Table 8.

[0077] Table 8 Composition of wastewater before and after impurity removal and impurity removal rate

[0078]

[0079] Comparative Example 4

[0080] Synthesis process: Take 100 g of activated carbon powder with a particle size of 0.10 - 0.15 microns, and add it to the solution containing the active components according to a ratio of 1:6. The active components are mainly composed of component A, where component A is zirconium oxychloride and titanium tetrachloride (zirconium oxychloride: 52.2 g, titanium tetrachloride: 3.42 g). The metal ion concentration of the component A solution is 0.3 mol / L. An impregnation reaction occurs at a reaction temperature of 95 °C for 90 min to obtain the active material, which is filtered by a vacuum filtration system with a pressure of 0.1 MPA, then washed with 700 mL of pure water, and dried at 60 °C for 3 h to obtain the composite purification material product.

[0081] Adsorption - elution process: Take 10 L of the raffinate wastewater from the extraction workshop, add 10 g of the composite purification material, stir and react at 30 °C for 50 min, perform solid - liquid separation to obtain the impurity - removed liquid and impurity - removed residue. Use 50 mL of 2% NaOH solution to back - wash the impurity - removed residue at 40 °C for 60 min and then filter it under pressure; then activate it with 50 ml of 2% hydrochloric acid at 40 °C for 60 min and filter it under pressure to complete the regeneration. The removal effect is shown in Table 9.

[0082] Table 9 Composition of the solution before and after impurity removal and impurity removal rate

[0083]

[0084]

[0085] The above description is a detailed description of the preferred and feasible embodiments of the present invention. However, the embodiments are not used to limit the scope of the patent application of the present invention. Any equivalent changes or modified changes completed under the technical spirit disclosed by the present invention shall fall within the scope of the patent covered by the present invention.

Claims

1. A composite purification material, the composite purification material comprising an activated carbon matrix and active components supported on the activated carbon; the active components are composed of two components A and B, wherein component A contains zirconium and titanium ions, and component B contains aluminum, lanthanum, and cerium ions.

2. The composite purification material according to claim 1, wherein The activated carbon is powdered wood-based activated carbon with a specific surface area of 1,000 to 2,000 m 2 / g and a particle size of 10 to 15 μm; and / or, the loading amount of the active ingredient is 50 to 100 mg / g based on the activated carbon.

3. A method for preparing the composite purification material according to claim 1 or 2, the method comprising the following steps: using activated carbon as a matrix, loading active materials onto the activated carbon by an impregnation method, and obtaining the composite purification material through processes such as filtration, washing, and drying of the obtained substance.

4. The preparation method according to claim 3, wherein The active material is the hydrochloride salt of the active ingredient, and is preferably one or more of several substances such as zirconium oxychloride, titanium tetrachloride, aluminum chloride, lanthanum chloride, cerium chloride, etc.

5. The preparation method according to claim 3 or 4, wherein The mass-volume ratio of the activated carbon to the active solution during the impregnation process is 1:3 to 6 kg / cm 3 ; and / or, the temperature of the impregnation is 70 to 95 °C and the time is 60 to 90 min; and / or, the drying temperature is 50 to 80 °C and the drying time is 1 to 3 h.

6. A method for removing fluorine, silicon, phosphorus, and oil from the wastewater of a ternary battery material, the method comprising the following steps: (1) Impurity adsorption: using the composite purification material as an adsorbent to adsorb and remove fluorine, silicon, phosphorus, and organic substances; (2) Alkaline washing and desorption: using an alkaline solution as a desorbent, stirring and washing the composite purification material adsorbed with impurities, and performing a hydrochloric acid activation step on the eluted composite purification material. (3) Hydrochloric acid activation: using dilute hydrochloric acid as an activator to perform activation treatment on the composite purification material after alkaline washing, and returning the activated composite purification material to the impurity removal process for recycling. The composite purification material is selected from the composite purification material according to claim 1 or 2 or the composite purification material prepared by the preparation method according to any one of claims 3 - 5.

7. The method according to claim 6, wherein The addition amount of the composite purification material is 1 to 2 kg / m 3 For the wastewater, the adsorption and removal time is 20 to 60 min, the temperature is 20 to 60 °C; the pH for adsorption and removal is 2.5 to 6.

8. The method according to claim 6 or 7, wherein In the desorption step, the lye is selected from NaOH, the concentration of the lye is preferably 1-2 wt%, and the mass-volume ratio of the impurity-carrying purification agent (i.e., the composite purification material after adsorbing impurities) to the lye is 1:3-5 kg / cm 3 , the reaction temperature is 20-40 °C, and the reaction time is 30-60 min.

9. The method according to any one of claims 6 - 8, wherein In the hydrochloric acid activation step described above, the hydrochloric acid concentration used is 1-3 wt%, and the mass-volume ratio of the regenerated purifying agent to the alkali solution is 1:3 to 5 kg / cm 3 , the activation temperature is 20 to 40 °C, and the activation time is 30 to 60 min.

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