AG10 battery.Introduction to waste zinc-manganese battery recycling and processing technology

　　Introduction to scrap zinc-manganese battery recycling technology Zinc-manganese batteries are mainly disposable batteries. The main components of various types of zinc-manganese batteries are: zinc skin, zinc powder, zinc chloride, carbon rods, acetylene black, ammonium chloride, lead , cadmium, mercury, electropaste, asphalt, manganese oxide, plastic, copper cap, iron shell and paper, etc. Whether it is an acid battery or an alkaline battery, its main valuable components are zinc and manganese.

　　There are three main methods for recycling waste zinc-manganese batteries: dry method, wet method and dry-wet method.

　　1. Dry method

　　Dry method, also known as smoke method or fire method, uses the different melting, boiling points and vapor pressures of various metals or metal oxides to separate, evaporate and condense them at different temperatures to achieve the purpose of resource recovery and reuse. . Dry treatment of waste zinc-manganese batteries generally does not require the addition of additional chemicals and has good mercury removal effects, but the disadvantage is that the cost is higher.

　　(1) Vacuum heat treatment technology

　　Li Suying and others from Harbin Institute of Technology evaporated zinc and mercury at different temperatures when the vacuum degree was 0.08Mpa (i.e. 150mmHg), and then condensed them separately for recovery. This technology needs to consider organic impurities and carbon rods in used batteries during the processing process. Pre-sorting will make batch processing difficult. Abroad, SaotomeY and others have also studied the use of vacuum devices to recover metals in scrap zinc-manganese batteries at different temperatures. The waste battery vacuum treatment furnace developed by Beijing Donghua Xinxin Waste Battery Recycling Center has completed pilot testing.

　　(2) Direct heat treatment technology

　　Zhao Lianchao conducted a roasting experiment at a temperature of 350°C and a time of 50 minutes. The residual amount of mercury in the zinc skin and black powder obtained can reach the secondary soil standard. The residual amount of ammonium in the black powder is low and can meet the requirements of manganese chloride, etc. General product grade requirements. Zhao Zhixing and others also conducted similar experiments. The higher the temperature and the longer the time, the better the mercury removal effect. Lin Huidong and others from South China Agricultural University conducted research using a tube furnace and found that the mercury removal effect is best when the roasting temperature is 550°C and the roasting time is 120 minutes.

　　2. Wet method

　　The wet method uses acid to leach waste batteries and react to generate soluble salts. Then electrolysis can be used to extract zinc, manganese dioxide and other heavy metals in the batteries.

　　(1) Full wet technology to recover zinc and manganese

　　Cui Peiying used waste zinc and manganese batteries to obtain manganese sulfate (MnSO4·nH20) and ZnSO4·H2O through acid leaching and other processes. After crushing, he added ammonium sulfate and the like to obtain zinc and manganese composite micro-fertilizers. This process is relatively simple, but requires additional addition of active zinc. Yan Xun studied the use of ammonia leaching process to recover zinc and manganese and remove harmful heavy metals. The effect is better in small-scale treatment, but there are still many problems that need to be solved for industrialization. Hong Kong S. T. Lau et al. studied the use of ore screens to recover zinc and manganese from spent zinc-manganese batteries.

　　Abroad, Brazilian Leonardo Roger Silva Veloso and others sorted and crushed waste zinc-manganese batteries. Remove the potassium oxide by washing with water to obtain a potassium hydroxide solution. Then carry out acid leaching treatment, divided into two routes: one is to use dilute sulfuric acid (0.2%V/V) at a higher temperature (70℃) and a higher solid-liquid ratio (1/10g·l-1 ) to leach zinc from waste battery powder; the second is to use a higher concentration of sulfuric acid (3%V/V) at a lower temperature (40°C) and a lower solid-liquid ratio (1/30g·l-1) And under the condition of adding hydrogen peroxide, all zinc and manganese are leached into the solution. After acid leaching, potassium hydroxide solution is used to adjust the pH value of the acid leaching solution to separate zinc and manganese. AfineL. Salgado et al. studied the extraction effect of Cyanex272 on zinc and manganese from waste zinc-manganese batteries at different temperatures and pH values. Cleusa Cristi, Na Bueno, Marthade Souza and others used sulfuric acid to leach waste zinc and manganese batteries. The process can leach 30% of manganese and nearly 100% of zinc.

　　(2) Acid leaching electrowinning technology to recover zinc and manganese

　　ItalyN. VaTIstas et al. separated the waste battery into three parts: anode material, cathode material and a mixture of metal materials, paper and plastic. Then they used sulfuric acid to leach the roasted anode material. 67% of the zinc entered the solution, and then the zinc in the solution was Ions are recovered using electrowinning methods. In 1975, Gamzinc Company in South Africa and Reston Factory in Australia used the same tank electrolysis process to treat manganese-zinc ore, but the resulting anode product MnO2 contained a large amount of impurities such as pb and K, which did not meet the quality standards of battery MnO2. In 1982, someone in India also reported that qualified Zn and MnO2 products were produced by electrolysis in the same tank, but there were no reports of industrialization. Since then, MEturo Bartolozzi of the Italian Academy of Industrial Chemistry and Materials Science has published research on the simultaneous electrolytic recovery of Zn and MnO2 from alkali-manganese waste batteries. However, the anode precipitate only contains 70% MnO2, and the anode current efficiency is low. The process of acid leaching followed by electrolysis in the same tank studied by Cleusa Cristina, BuenoMartha, deSouza and others in Brazil can recover 40% of the manganese and nearly 100% of the zinc in the waste zinc-manganese battery. In China, since 1973, Guizhou Institute of Technology, Central South University, etc. have also begun to study Zn-Mn co-tank electrolysis, but they have not successfully used it for the recycling of waste dry batteries. In 2005, Li Suizhong's electrolysis temperature was 85°C, the initial acidity pH value was 4 to 5, and the final acidity was no more than 0.6 mol/l; the cathode current density was 1016A/m2, and the anode current density was 64A/m2; the additives were a combination of bone glue and phenolic compounds. The experiment was carried out under the conditions. The obtained electrolytic zinc flakes meet the chemical composition requirements of GB1978-1988 battery zinc plates, and the obtained electrolytic manganese dioxide meets the second-level quality standard of GB13001-1986 electrolytic manganese dioxide, and the discharge performance reaches the first-level standard.

　　3. Dry and wet method

　　The dry and wet method combines the advantages of dry and wet methods and has better results, but it generally has the disadvantages of complicated processes and high costs.

　　(1) Dry and wet technology to recycle waste zinc and manganese batteries to produce compound micro-fertilizer

　　Bai Qingzi and others washed the waste batteries with water, added sulfuric acid and dilute nitric acid to the undissolved solid matter and reacted. Use boron magnesium mud to adjust the pH value of the solution to 5-6. The resulting solution is heated, evaporated, concentrated, crystallized, and dried together with the previously washed filtrate, and an appropriate amount of calcium, magnesium, and phosphate fertilizer is mixed in to obtain a compound microfertilizer. This process does not properly handle the harmful heavy metal mercury and its compounds in waste zinc-manganese batteries. Peng Guosheng and others have also conducted similar research. Their process can recover more than 90% of copper, zinc, manganese and other elements in waste zinc-manganese batteries.

　　(2) Dry and wet technology to recycle waste zinc and manganese batteries to produce manganese-zinc ferrite

　　Xi Guoxi and others reacted waste batteries with sulfuric acid and hydrogen peroxide. After filtering, they used ammonia to adjust the pH of the filtrate to 2~4. They added Fe and MnSO4·H2O and properly disposed of the precipitated mercury. Boil to remove the hydrogen peroxide, adjust the pH value to 7.0-10.5 with NH3·H2O, and then move it to an autoclave for hydrothermal reaction. After the reaction is completed, it is cooled, filtered, washed with deionized water and ethanol, and dried at about 105°C to obtain manganese-zinc ferrite.

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