CN101775497B - Method for recovering metal by using waste common zinc-manganese battery to purify flue gas - Google Patents
Method for recovering metal by using waste common zinc-manganese battery to purify flue gas Download PDFInfo
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Abstract
The method for recovering metal by using waste common zinc-manganese cell to purify flue gas includes the steps of firstly scrappingDisassembling the common zinc-manganese battery to obtain a positive electrode, a carbon rod, a battery shell and a sealing material, and mashing the positive electrode block into powder; adding the anode powder into the ammonia water solution, and introducing SO 2 Continuously adding the anode powder into the flue gas with the concentration of 50-7500 mg/l, and adjusting the pH value of the solution to 12-14 by using strong ammonia water in the purification process; when the solid-liquid ratio in the solution reaches 1: 6-1: 5, the SO-containing gas is stopped from being introduced into the solution 2 Continuously adding the anode powder into the solution, and detecting SO in the solution 3 2- When the concentration is lower than 10mg/l, stopping adding the anode powder into the solution, and stopping stirring the solution; will have stopped inputting SO-containing 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining at 300-370 ℃ for 1-3 h to prepare manganese dioxide; adjusting the pH value of the filtrate to 7-8 by using 0.5-3.0 mol/l sulfuric acid solution at the temperature of 20-95 ℃, and filtering to obtain the zinc hydroxide.
Description
Technical Field
The invention relates to a method for recovering metals by using waste batteries to purify flue gas, belonging to the technical field of environmental protection.
Background
The emission of sulfur dioxide-containing flue gas generated in industrial production is one of the important causes of atmospheric environmental pollution. SO in the atmosphere 2 The harm is great, the health of human bodies is greatly influenced, respiratory diseases can be caused, and emphysema and the like can be caused seriously; the normal growth of crops is influenced, so that the yield of the crops is reduced; corrosion of metal, especially steel structure, thereby threatening the safety of industrial facilities, living facilities and traffic facilities; SO 2 The formation of "acid mist" with the water vapor in the air and "acid rain" in rainy weather causes corrosion of lakes, groundwater, buildings, forests, antiques, and human clothing, and the long-term effects of acid rain cause immeasurable losses in soil and water. SO in the atmosphere 2 Mainly from combustion processes of sulfur-containing raw materials and fuels, e.g. thermal power, smelting of steel and non-ferrous metals, production of sulphuric acid and cement 2 And (4) discharging flue gas. China pays great attention to the environmental pollution caused by sulfur dioxide, and has put forward a definite target of energy conservation and emission reduction.
For eliminating or reducing SO 2 The pollution of the atmospheric environment by the flue gas emissions, developed from the flue gas emissions from the combustion of fuels or from industrial processesMore than 80 methods for removing sulfur dioxide. Wherein for high concentration SO 2 And low concentration of SO 2 The methods of flue gas remediation are different. High concentration of SO 2 The flue gas is flue gas with the sulfur dioxide concentration of more than 3.5 percent and can meet the technical requirements of the process for producing the sulfuric acid by using the contact method, so the high-concentration sulfur dioxide flue gas is used for producing the sulfuric acid by using the contact method. Low concentration of SO 2 The flue gas refers to SO 2 The flue gas with the concentration of less than 3.5 percent has been developed at home and abroad by ammonia method, calcium method, sodium method, lemon absorption method, aluminum method, oxidation method, adsorption method, catalysis method, electron beam method and the like. However, the current mature and widely applied methods mainly include ammonia method, calcium method and sodium method due to the limitations of technical reliability, economic rationality, industrial production characteristics and the like. The ammonia method is a traditional process in the flue gas desulfurization method, adopts liquid ammonia or ammonia water as an absorbent, has high absorption efficiency and thorough desulfurization, but has volatile ammonia, large consumption of the absorbent and large limitation of the source of the ammonia by regions. The calcium method is to wash the flue gas containing sulfur dioxide by using lime water or lime milk, and has mature technology, low production cost, slow absorption rate, small absorption capacity and generated CaSO 3 And CaSO 4 It is easy to block pipelines and equipment, and in addition, the method generates a large amount of waste residues which cause serious secondary pollution to the environment. The sodium method is to use sodium carbonate or sodium hydroxide and other common substances to absorb the flue gas containing sulfur dioxide, and has the advantages of large absorption capacity, high absorption rate and high desulfurization efficiency, but the biggest problem is that the raw material sodium alkali is expensive and the desulfurization production cost is high. The three processes also have the following common problems: (1) the investment of desulfurization equipment is large; (2) the byproducts in the desulfurization process are difficult to utilize; and (3) the environmental protection operation cost is higher.
Compared with alkaline zinc-manganese batteries, ordinary zinc-manganese batteries (also called carbon batteries) have low capacity and low price, and currently occupy a considerable share in the dry battery consumption field. The scrapped common zinc-manganese battery contains heavy metals such as mercury, cadmium, zinc, copper, manganese and the like, and if the discarded common zinc-manganese battery is discarded at will, serious harm is caused to the environmental ecology. At present, the recovery method of the waste common zinc-manganese battery mainly comprises a dry method, a wet method, a dry-wet combined method and the likeProvided is a technique. Zhang Ling Song et al in environmental engineering Vol.26No.4, 2008, 21-23 adopts mixed acid composed of nitric acid and hydrochloric acid with volume ratio of 1: 3 to dissolve waste carbon battery so as to make manganese, zinc, iron, nickel, mercury and other elements dissolve into solution, but there is Cl in the course of said treatment 2 、NO X And the generation of acid-containing waste gas causes pollution to the environment. Chinese patent 200410051920.2 reports that waste carbon batteries are dissolved by sulfuric acid, and then ferrite precursors are prepared and baked at high temperature to obtain ferrite products. The treatment method has the advantages of large acid consumption in the acid dissolution process and generation of acid waste gas in the treatment process. The Chinese patent 200910025818.8 reports the method for directly preparing the industrial desulfurizer from the waste common zinc-manganese battery.
The recovery of the waste conventional zinc-manganese battery reported at present mainly takes products of Mn and Zn obtained from the waste conventional zinc-manganese battery, but a large amount of MnO still contained in the waste conventional zinc-manganese battery 2 Are not fully utilized.
Disclosure of Invention
The invention aims to provide a method for purifying flue gas and recycling manganese and zinc in waste common zinc-manganese batteries by using the waste common zinc-manganese batteries.
The invention relates to a method for recovering metals by using purified flue gas of a waste common zinc-manganese battery, which comprises the following steps:
(1) Pretreatment of waste common zinc-manganese battery
Manually or mechanically disassembling a scrapped common zinc-manganese battery to obtain a positive electrode, a carbon rod, a battery shell and a sealing material, and mashing the positive electrode block into powder;
(2) SO in flue gas 2 Purification of
Adding the anode powder obtained in the last step into 0.1-4.0 mol/L ammonia water solution according to the solid-to-liquid ratio of 1: 1000-1: 10, controlling the temperature of the ammonia water solution at 20-95 ℃, controlling the stirring rate at 200-400 r/min, and then introducing SO at the air flow rate of 0.25-30.0L/min 2 The concentration of the flue gas is 50mg/L-7500mg/L, and SO contained in the flue gas is introduced into the flue gas per minute 2 At a rate of 5 to 50 times the mass ofContinuously adding anode powder into the solution, and adjusting the pH value of the solution to be within the range of 12-14 by using concentrated ammonia water in the purification process; when the solid-liquid ratio in the solution reaches 1: 6-1: 5, stopping introducing SO into the solution 2 The introduction of SO into the purifying liquid is continuously stopped 2 Before the flue gas, the flue gas introduced every minute contains SO 2 Adding the anode powder into the purified solution at a rate of 5-50 times of the mass of the anode powder, and detecting SO in the solution 3 2- When the concentration is lower than 10mg/L, stopping adding the anode powder into the solution, and stopping stirring the solution;
(3) Recovery of metal values
The input of SO in the step (2) is stopped 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining the filter residue in a muffle furnace at 300-370 ℃ for 1-3 h to prepare manganese dioxide; adjusting the pH value of the filtrate to 7-8 by using 0.5-3.0 mol/l sulfuric acid solution at the temperature of 20-95 ℃, and filtering to obtain the zinc hydroxide.
Compared with the prior art, the invention has the advantages that SO in the flue gas 2 The method has the advantages of high purification efficiency, high speed, simple process, easy operation, no pollution in the purification and recovery process, low cost, and the manganese dioxide and the zinc hydroxide obtained in the recovery process can be sold as products.
Detailed Description
The invention relates to a method for recovering metals by using purified flue gas of a waste common zinc-manganese battery, which comprises the following steps:
(1) Pretreatment of waste common zinc-manganese battery
Manually or mechanically disassembling a scrapped common zinc-manganese battery to obtain a positive electrode, a carbon rod, a battery shell and a sealing material, and mashing the positive electrode block into powder;
(2) SO in flue gas 2 Purification of
Adding the anode powder obtained in the last step into 0.1-4.0 mol/L ammonia water solution according to the solid-to-liquid ratio of 1: 1000-1: 10, controlling the temperature of the ammonia water solution at 20-95 ℃, controlling the stirring rate at 200-400 r/min, and then controlling the gas flow at 0.25-30.0L/minFlow rate of SO 2 The concentration of the flue gas is 50mg/L-7500mg/L, and SO contained in the flue gas is introduced into the flue gas per minute 2 Adding the anode powder into the solution uninterruptedly at a rate of 5-50 times of the mass of the anode powder, and adjusting the pH value of the solution to be within the range of 12-14 by using concentrated ammonia water in the purification process; when the solid-liquid ratio in the solution reaches 1: 6-1: 5, the SO-containing gas is stopped from being introduced into the solution 2 The introduction of SO into the purifying liquid is continuously stopped 2 Before the flue gas, the flue gas introduced every minute contains SO 2 Adding the anode powder into the purified solution at a rate of 5-50 times of the mass of the anode powder, and detecting SO in the solution 3 2- When the concentration is lower than 10mg/L, stopping adding the anode powder into the solution, and stopping stirring the solution;
(3) Recovery of valuable metals
The input of SO in the step (2) is stopped 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining the filter residue in a muffle furnace at 300-370 ℃ for 1-3 h to prepare manganese dioxide; adjusting the pH value of the filtrate to 7-8 by using 0.5-3.0 mol/L sulfuric acid solution at the temperature of 20-95 ℃, and filtering to obtain the zinc hydroxide.
The invention is developed below by means of a more specific example.
Example 1:
taking 20g of waste common zinc-manganese battery anode powder, putting the waste common zinc-manganese battery anode powder into 1000ml of ammonia water solution with the concentration of 1.0mol/L, heating the solution, keeping the temperature to 50 ℃, stirring the solution at the stirring speed of 300r/min, and then stirring SO at the speed of 0.25L/min 2 Introducing flue gas with a content of 50mg/L into the solution, and introducing SO contained in the flue gas per minute 2 30 times of the mass of the anode powder is added into the solution uninterruptedly to purify the SO 2 In the process, concentrated ammonia water is used for adjusting the pH value of the solution to be within the range of 12-13, after the reaction is carried out for 1h, the SO-containing solution is stopped from being introduced into the solution 2 While continuing to add the positive electrode powder to the solution at the same rate, while detecting SO in the solution 3 2- When the concentration is lower than 10mg/L, the addition of the positive electrode powder to the solution is stopped and the stirring of the solution is stopped. Will stop inputting SO-containing gas 2 Filtering the solution of flue gas, washing the filter residue with waterThen putting the mixture into a muffle furnace to calcine for 2 hours at 350 ℃ to prepare manganese dioxide; and (3) at room temperature, adjusting the pH value of the filtrate to 7 by using 1.0mol/L sulfuric acid solution, and filtering to obtain the zinc hydroxide.
Example 2:
taking 20g of waste common zinc-manganese battery anode powder, putting the waste common zinc-manganese battery anode powder into 1000ml of ammonia water solution with the concentration of 1.5mol/L, heating the solution, keeping the temperature to 50 ℃, stirring the solution at the stirring speed of 300r/min, and then stirring SO at the speed of 0.25L/min 2 Introducing flue gas with a content of 250mg/L into the solution, and introducing SO contained in the flue gas per minute 2 30 times of the mass of the anode powder is added into the solution uninterruptedly to purify the SO 2 In the process, concentrated ammonia water is used for adjusting the pH value of the solution to be within the range of 12-13, after the reaction is carried out for 1h, the SO-containing solution is stopped from being introduced into the solution 2 While continuing to add the positive electrode powder to the solution at the same rate, while detecting SO in the solution 3 2- When the concentration is lower than 10mg/L, the addition of the positive electrode powder to the solution is stopped and the stirring of the solution is stopped. Will stop inputting SO 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining the filter residue in a muffle furnace at 350 ℃ for 2h to obtain manganese dioxide. And (3) at room temperature, adjusting the pH value of the filtrate to 7 by using 1.0mol/L sulfuric acid solution, and filtering to obtain the zinc hydroxide.
Example 3:
taking 20g of waste common zinc-manganese battery anode powder, putting the waste common zinc-manganese battery anode powder into 1000ml of ammonia water solution with the concentration of 1.5mol/L, heating the solution, keeping the temperature to 50 ℃, stirring the solution at the stirring speed of 300r/min, and then stirring SO at the speed of 0.25L/min 2 Introducing flue gas with the content of 500mg/L into the solution, and introducing SO contained in the flue gas per minute 2 Is added into the solution at a rate of 30 times the mass of the solution, and the SO is purified 2 In the process, concentrated ammonia water is used for adjusting the pH value of the solution to be within the range of 12-13, and when the solid-to-liquid ratio in the solution reaches 1: 6, the SO-containing solution is stopped from being introduced into the solution 2 While continuing to add the positive electrode powder to the solution at the same rate, while detecting SO in the solution 3 2- When the concentration is lower than 10mg/L, the addition of the positive electrode powder to the solution is stopped and the stirring of the solution is stopped. Will be provided withStopping inputting SO 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining the filter residue in a muffle furnace at 350 ℃ for 2h to obtain manganese dioxide. And (3) at room temperature, adjusting the pH value of the filtrate to 7 by using 1.0mol/L sulfuric acid solution, and filtering to obtain the zinc hydroxide.
Example 4:
taking 50g of waste common zinc-manganese battery anode powder, putting the waste common zinc-manganese battery anode powder into 1000ml of ammonia water solution with the concentration of 1.5mol/L, heating the solution, keeping the temperature of the solution at 50 ℃, stirring the solution at the stirring speed of 300r/min, and then stirring SO at the speed of 0.25L/min 2 Introducing flue gas with content of 1500mg/L into the solution, and introducing SO contained in the flue gas per minute 2 Is added into the solution at a rate of 30 times the mass of the solution, and the SO is purified 2 In the process, concentrated ammonia water is used for adjusting the pH value of the solution to be within the range of 12-13, and when the solid-to-liquid ratio in the solution reaches 1: 6, the SO-containing solution is stopped from being introduced into the solution 2 While continuing to add the positive electrode powder to the solution at the same rate, while detecting SO in the solution 3 2- When the concentration is lower than 10mg/L, the addition of the positive electrode powder to the solution is stopped and the stirring of the solution is stopped. Will stop inputting SO-containing gas 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining the filter residue in a muffle furnace at 350 ℃ for 2h to obtain manganese dioxide. And (3) at room temperature, adjusting the pH value of the filtrate to 7 by using 1.0mol/L sulfuric acid solution, and filtering to obtain the zinc hydroxide.
Example 5:
taking 100g of waste common zinc-manganese battery anode powder, putting the waste common zinc-manganese battery anode powder into 1000ml of ammonia water solution with the concentration of 2.5mol/L, heating the solution, keeping the temperature to 50 ℃, stirring the solution at the stirring speed of 300r/min, and then stirring SO at the speed of 0.25L/min 2 Introducing flue gas with the content of 3500mg/L into the solution, and introducing SO contained in the flue gas per minute 2 30 times of the mass of the anode powder is added into the solution uninterruptedly to purify the SO 2 In the process, concentrated ammonia water is used for adjusting the pH value of the solution to be within the range of 12-13, and when the solid-to-liquid ratio in the solution reaches 1: 6, the SO-containing solution is stopped to be introduced into the solution 2 While continuing to add the positive electrode powder to the solution at the same rate, while detecting SO in the solution 3 2- When the concentration is lower than 10mg/L, the addition of the positive electrode powder to the solution is stopped and the stirring of the solution is stopped. Will stop inputting SO 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining the filter residue in a muffle furnace at 350 ℃ for 2h to obtain manganese dioxide. And (3) at room temperature, adjusting the pH value of the filtrate to 7 by using 1.0mol/L sulfuric acid solution, and filtering to obtain the zinc hydroxide.
Example 6:
taking 100g of waste common zinc-manganese battery anode powder, putting the waste common zinc-manganese battery anode powder into 1000ml of ammonia water solution with the concentration of 3.0mol/L, heating the solution, keeping the temperature to 50 ℃, stirring the solution at the stirring speed of 300r/min, and then stirring SO at the speed of 0.25L/min 2 Introducing flue gas with the content of 5000mg/L into the solution, and introducing SO contained in the flue gas per minute 2 30 times of the mass of the anode powder is added into the solution uninterruptedly to purify the SO 2 In the process, concentrated ammonia water is used for adjusting the pH value of the solution to be within the range of 12-13, and when the solid-to-liquid ratio in the solution reaches 1: 6, the SO-containing solution is stopped from being introduced into the solution 2 While continuing to add the positive electrode powder to the solution at the same rate, while detecting SO in the solution 3 2- When the concentration is lower than 10mg/L, the addition of the positive electrode powder into the solution is stopped, and the stirring of the solution is stopped. Will stop inputting SO-containing gas 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining the filter residue in a muffle furnace at 350 ℃ for 2h to obtain manganese dioxide. And (3) at room temperature, adjusting the pH value of the filtrate to 7 by using 1.0mol/L sulfuric acid solution, and filtering to obtain the zinc hydroxide.
Example 7:
taking 20g of waste common zinc-manganese battery anode powder, putting the waste common zinc-manganese battery anode powder into 1000ml of ammonia water solution with the concentration of 1.0mol/L, heating the solution, keeping the temperature to be 30 ℃, stirring the solution at the stirring speed of 300r/min, and then stirring SO at the speed of 0.25L/min 2 Introducing flue gas with a content of 50mg/L into the solution, and introducing SO contained in the flue gas per minute 2 30 times of the mass of the anode powder is added into the solution uninterruptedly to purify the SO 2 In the process, concentrated ammonia water is used for adjusting the pH value of the solution to be within the range of 12-13, after the reaction is carried out for 1h, the introduction of SO-containing solution into the solution is stopped 2 But continues at the same rate into the solutionAdding anode powder, and detecting SO in the solution 3 2- When the concentration is lower than 10mg/L, the addition of the positive electrode powder to the solution is stopped and the stirring of the solution is stopped. Will stop inputting SO 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining the filter residue in a muffle furnace at 350 ℃ for 2 hours to obtain manganese dioxide. And (3) at room temperature, adjusting the pH value of the filtrate to 7 by using 1.0mol/L sulfuric acid solution, and filtering to obtain the zinc hydroxide.
Example 8:
taking 20g of waste common zinc-manganese battery anode powder, putting the waste common zinc-manganese battery anode powder into 1000ml of ammonia water solution with the concentration of 1.0mol/L, heating the solution, keeping the temperature to be 40 ℃, stirring the solution at the stirring speed of 300r/min, and then stirring SO at the speed of 0.25L/min 2 Introducing flue gas with a content of 50mg/L into the solution, and introducing SO contained in the flue gas per minute 2 30 times of the mass of the anode powder is added into the solution uninterruptedly to purify the SO 2 In the process, concentrated ammonia water is used for adjusting the pH value of the solution to be within the range of 12-13, after the reaction is carried out for 1h, the SO-containing solution is stopped from being introduced into the solution 2 While continuing to add the positive electrode powder to the solution at the same rate, while detecting SO in the solution 3 2- When the concentration is lower than 10mg/L, the addition of the positive electrode powder to the solution is stopped and the stirring of the solution is stopped. Will stop inputting SO-containing gas 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining the filter residue in a muffle furnace at 350 ℃ for 2h to obtain manganese dioxide. And (3) at room temperature, adjusting the pH value of the filtrate to 7 by using 1.0mol/L sulfuric acid solution, and filtering to obtain the zinc hydroxide.
Example 9:
taking 20g of waste common zinc-manganese battery anode powder, putting the waste common zinc-manganese battery anode powder into 1000ml of ammonia water solution with the concentration of 1.0mol/L, heating the solution, keeping the temperature to 60 ℃, stirring the solution at the stirring speed of 300r/min, and then stirring SO at the speed of 0.25L/min 2 Introducing flue gas with a content of 50mg/L into the solution, and introducing SO contained in the flue gas per minute 2 30 times of the mass of the anode powder is added into the solution uninterruptedly to purify the SO 2 In the process, concentrated ammonia water is used for adjusting the pH value of the solution to be within the range of 12-13, after the reaction is carried out for 1h, the SO-containing solution is stopped from being introduced into the solution 2 While continuing to add the positive electrode powder to the solution at the same rate, while detecting SO in the solution 3 2- When the concentration is lower than 10mg/L, the addition of the positive electrode powder to the solution is stopped and the stirring of the solution is stopped. Will stop inputting SO-containing gas 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining the filter residue in a muffle furnace at 350 ℃ for 2h to obtain manganese dioxide. And (3) at room temperature, adjusting the pH value of the filtrate to 7 by using 1.0mol/L sulfuric acid solution, and filtering to obtain the zinc hydroxide.
Example 10:
taking 20g of waste common zinc-manganese battery anode powder, putting the waste common zinc-manganese battery anode powder into 1000ml of ammonia water solution with the concentration of 1.0mol/L, heating the solution, keeping the temperature of the solution at 70 ℃, stirring the solution at the stirring speed of 300r/min, and then stirring SO at the speed of 0.25L/min 2 Introducing flue gas with a content of 50mg/L into the solution, and introducing SO contained in the flue gas per minute 2 30 times of the mass of the anode powder is added into the solution uninterruptedly to purify the SO 2 In the process, concentrated ammonia water is used for adjusting the pH value of the solution to be within the range of 12-13, after the reaction is carried out for 1h, the SO-containing solution is stopped from being introduced into the solution 2 While continuing to add the positive electrode powder to the solution at the same rate, while detecting SO in the solution 3 2- When the concentration is lower than 10mg/L, the addition of the positive electrode powder to the solution is stopped and the stirring of the solution is stopped. Will stop inputting SO 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining the filter residue in a muffle furnace at 350 ℃ for 2h to obtain manganese dioxide. And (3) at room temperature, adjusting the pH value of the filtrate to 7 by using 1.0mol/L sulfuric acid solution, and filtering to obtain the zinc hydroxide.
Example 11:
taking 20g of waste common zinc-manganese battery anode powder, putting the waste common zinc-manganese battery anode powder into 1000ml of ammonia water solution with the concentration of 1.0mol/L, heating the solution, keeping the temperature of the solution at 80 ℃, stirring the solution at the stirring speed of 300r/min, and then stirring SO at the speed of 0.25L/min 2 Introducing flue gas with a content of 50mg/L into the solution, and introducing SO contained in the flue gas per minute 2 30 times of the mass of the anode powder is added into the solution uninterruptedly to purify the SO 2 In the process, concentrated ammonia water is used for adjusting the pH value of the solution to be within the range of 12-13, and the reaction is carried outAfter 1h, the introduction of SO into the solution was stopped 2 While continuing to add the positive electrode powder to the solution at the same rate, when SO in the solution is detected 3 2- When the concentration is lower than 10mg/L, the addition of the positive electrode powder to the solution is stopped and the stirring of the solution is stopped. Will stop inputting SO-containing gas 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining the filter residue in a muffle furnace at 350 ℃ for 2h to obtain manganese dioxide. And (3) at room temperature, adjusting the pH value of the filtrate to 7 by using 1.0mol/L sulfuric acid solution, and filtering to obtain the zinc hydroxide.
Example 12:
taking 20g of waste common zinc-manganese battery anode powder, putting the waste common zinc-manganese battery anode powder into 1000ml of ammonia water solution with the concentration of 1.0mol/L, heating the solution, keeping the temperature to 90 ℃, stirring the solution at the stirring speed of 300r/min, and then stirring SO at the speed of 0.25L/min 2 Introducing flue gas with a content of 50mg/L into the solution, and introducing SO contained in the flue gas per minute 2 Is added into the solution at a rate of 30 times the mass of the solution, and the SO is purified 2 In the process, concentrated ammonia water is used for adjusting the pH value of the solution to be within the range of 12-13, after the reaction is carried out for 1h, the SO-containing solution is stopped from being introduced into the solution 2 While continuing to add the positive electrode powder to the solution at the same rate, when SO in the solution is detected 3 2- When the concentration is lower than 10mg/L, the addition of the positive electrode powder to the solution is stopped and the stirring of the solution is stopped. Will stop inputting SO-containing gas 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining the filter residue in a muffle furnace at 350 ℃ for 2h to obtain manganese dioxide. At room temperature, the pH value of the filtrate is adjusted to 7 by using 1.0mol/L sulfuric acid solution, and the filtrate is filtered to obtain the zinc hydroxide.
Claims (1)
1. The method for recovering metals by using the purified flue gas of the waste common zinc-manganese battery comprises the following steps:
(1) Pretreatment of waste common zinc-manganese battery
Disassembling a scrapped common zinc-manganese battery to obtain a positive electrode, a carbon rod, a battery shell and a sealing material, and mashing the positive electrode block into powder;
(2) SO in flue gas 2 Purification of
Adding the anode powder obtained in the last step into 0.1-4.0 mol/L ammonia water solution according to the solid-to-liquid ratio g/ml of 1: 1000-1: 10, controlling the temperature of the ammonia water solution at 20-95 ℃, controlling the stirring rate at 200-400 r/min, and then introducing SO at the airflow rate of 0.25-30.0L/min 2 The concentration of the flue gas is 50mg/L-7500mg/L, and SO contained in the flue gas is introduced into the flue gas per minute 2 Adding the anode powder into the solution at a speed of 5-50 times of the mass of the anode powder, and adjusting the pH value of the solution to be within the range of 12-14 by using strong ammonia water in the purification process; when the solid-to-liquid ratio g/ml in the solution reaches 1: 6-1: 5, stopping introducing SO into the solution 2 The flue gas is continuously introduced into the purifying liquid according to the stopping state 2 Before the flue gas, the flue gas introduced every minute contains SO 2 Adding the anode powder into the purified solution at a rate of 5-50 times of the mass of the anode powder, and detecting SO in the solution 3 2- When the concentration is lower than 10mg/L, stopping adding the anode powder into the solution, and stopping stirring the solution;
(3) Recovery of metal values
The input of SO in the step (2) is stopped 2 Filtering the solution of the flue gas, washing the filter residue with water, and calcining the filter residue in a muffle furnace at 300-370 ℃ for 1-3 h to obtain manganese dioxide; adjusting the pH value of the filtrate to 7-8 by using 0.5-3.0 mol/L sulfuric acid solution at the temperature of 20-95 ℃, and filtering to obtain the zinc hydroxide.
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| CN101775497B true CN101775497B (en) | 2012-07-25 |
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| CN102030373B (en) * | 2010-11-10 | 2012-01-04 | 兰州理工大学 | Method for preparing potassium permanganate and recovering cobalt and lithium by using waste battery |
| CN106006750B (en) * | 2016-05-16 | 2017-05-10 | 兰州理工大学 | Method of purifyingtailgas from acid production with waste lithium manganate and recovering manganese and lithium |
| CN106006749B (en) * | 2016-05-16 | 2017-05-31 | 兰州理工大学 | Useless LiMn2O4 cooperates with the method for administering and reclaiming manganese lithium with relieving haperacidity tail gas |
| CN115591555A (en) * | 2022-10-09 | 2023-01-13 | 浙江浙能技术研究院有限公司（Cn） | Preparation method of cheap low-temperature denitration catalyst for recycling waste neutral zinc-manganese battery |
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| CN1211465A (en) * | 1997-07-19 | 1999-03-24 | 莱也茨·比肖夫有限公司 | Process for removing sulphur dioxide from flue gases |
| CN1772345A (en) * | 2005-10-25 | 2006-05-17 | 四川大学 | Waste gas desulfurizing method with composite absorbant comprising pyrolusite and pH buffering agent |
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| JPH0760122A (en) * | 1993-08-20 | 1995-03-07 | Nippon Steel Corp | Method for regenerating stack gas purifying catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1211465A (en) * | 1997-07-19 | 1999-03-24 | 莱也茨·比肖夫有限公司 | Process for removing sulphur dioxide from flue gases |
| CN1772345A (en) * | 2005-10-25 | 2006-05-17 | 四川大学 | Waste gas desulfurizing method with composite absorbant comprising pyrolusite and pH buffering agent |
Non-Patent Citations (2)
| Title |
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| JP特开平7-60122A 1995.03.07 |
| 陈枝.烟气脱硫产物亚硫酸铵氧化动力学研究.《重庆大学硕士学位论文》.2008,全文. * |
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