CN107815550A - Method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries - Google Patents

Method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries Download PDF

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CN107815550A
CN107815550A CN201711292337.4A CN201711292337A CN107815550A CN 107815550 A CN107815550 A CN 107815550A CN 201711292337 A CN201711292337 A CN 201711292337A CN 107815550 A CN107815550 A CN 107815550A
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manganese
zinc
sulfate
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filtrate
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CN107815550B (en
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蒋央芳
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/10—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/06—Sulfates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries, and belongs to the technical field of waste battery utilization. The method comprises the steps of crushing the waste zinc-manganese battery, namely putting the zinc-manganese battery into a crusher to be crushed into powder with the particle size of below 200 um; dissolving zinc-manganese battery powder materials, and adding acid and a reducing agent for dissolving; adjusting the pH value to remove iron and aluminum; separating zinc and manganese and preparing zinc sulfate, namely extracting and separating zinc by adopting a P204 extractant; removing impurities, adding a heavy metal catching agent and fluoride, and removing heavy metals, calcium and magnesium; and (3) preparing a manganese sulfate solution, namely extracting and separating manganese by adopting P507, and concentrating and crystallizing the obtained pure manganese solution to obtain the battery-grade manganese sulfate. According to the method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries, the battery-grade manganese sulfate and high-purity zinc sulfate crystals can be obtained, the obtained manganese sulfate crystals are granular, the caking phenomenon is avoided, the process is simple, and the recovery of all components is realized.

Description

Method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries
Technical Field
The invention relates to a method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries, and belongs to the technical field of waste batteries.
Background
The zinc-manganese battery is a primary battery which takes manganese dioxide as a positive electrode, zinc as a negative electrode and ammonium chloride aqueous solution as main electrolyte. The zinc-manganese battery is also called an alkaline dry battery, an alkaline zinc-manganese battery and an alkaline manganese battery, and is a variety with the best performance in a zinc-manganese battery series. Is suitable for long-time use with large discharge capacity. The internal resistance of the battery is lower, so the generated current is larger than that of the common manganese battery, and the environment-friendly mercury content is only 0.025%, and the recycling is not needed. Alkaline batteries are the most successful high capacity dry cells and are one of the most cost-effective batteries at present.
The zinc-manganese battery is a primary battery which takes manganese dioxide as a positive electrode, zinc as a negative electrode and ammonium chloride aqueous solution as main electrolyte. Commonly called dry cell. Also known in academia as the lux cell.
Manganese dioxide is used as a positive electrode, zinc is used as a negative electrode, and an ammonium chloride aqueous solution is used as a main electrolyte. Also known in academia as the lux cell. The electrolyte is gelled with flour, starch, etc., and does not flow to form a barrier layer, or is separated with cotton, paper, etc. MnO for zinc-manganese cell with start voltage 2 The type of the electrolyte, the composition of the electrolyte, the pH value and the like are different, and the voltage is generally 1.55 to 1.75V, and the nominal voltage is 1.5V. The most suitable use temperature is 15-30 ℃. Under the low temperature condition below-20 ℃, the common zinc-manganese battery can not work.
The zinc-manganese battery is portable, convenient to use, complete in variety, stable in process, rich in raw materials and low in price, so that the main status of chemical power products can be kept for a long time and the chemical power products can be continuously developed. But it has low specific energy and poor stability of working voltage, especially when discharging with large current density.
The zinc-manganese cell has wide application, and can be used as a direct current power supply required by telephones, signal devices, instruments and meters and the like, and a power supply of daily electric appliances such as illumination, radios, recorders, electric toys, calculators, hearing aids, cameras and the like.
The zinc-manganese battery has low price, convenient use and wide application, and is a battery with large output and sales volume. The waste zinc-manganese batteries contain heavy metals such as cadmium, zinc, copper, manganese and the like, and are discarded at will after use, so that the environment is polluted, the ecological environment and the human health are harmed, and metal resources are wasted. If the waste zinc-manganese battery can be recycled, resources can be saved, and the pollution of the waste battery to the environment can be eliminated. If 50 million waste zinc-manganese batteries are scrapped every year in China and can be completely recycled, 11 million manganese, 7 million zinc and 1.4 million copper can be regenerated, and t is a considerable resource. Therefore, the waste zinc-manganese battery is recycled, and the metal resources such as zinc, manganese and the like can be recycled.
However, in the existing process, the purity of the obtained manganese crystals is not high, and with the development of ternary battery materials, the demand of battery-grade manganese sulfate crystals is larger and larger, but at present, no process can directly extract battery-grade manganese sulfate from zinc-manganese batteries, and other metals in waste zinc-manganese batteries can be completely utilized.
Disclosure of Invention
In view of the above, the invention provides a method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries, which can obtain battery-grade manganese sulfate and high-purity zinc sulfate crystals, wherein the obtained manganese sulfate crystals are granular and have no caking phenomenon, the recovery rates of manganese and zinc are as high as more than 99%, and nickel, cobalt, copper and cadmium solutions with the purity of more than 95% can be obtained, the recovery rates of nickel, cobalt, copper and cadmium are more than 97%, the recovery rates of lead, calcium and magnesium are more than 96%, the purity of lead chloride is more than 97%, the purity of calcium sulfate is more than 98%, the purity of magnesium chloride is more than 97%, the process is simple, and the recovery of all components is realized.
The invention solves the technical problems by the following technical means:
the invention relates to a method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries, which comprises the following steps:
(1) Crushing the waste zinc-manganese battery, namely putting the zinc-manganese battery into a crusher to be crushed into powder with the particle size of below 200 um;
(2) Dissolving zinc-manganese battery powder materials, namely dissolving the zinc-manganese battery powder materials according to the solid-liquid ratio of 3-6:1, adding bottom water, simultaneously adding acid to maintain the pH value of 1-1.2 in the reaction process, maintaining the reaction temperature of 75-90 ℃, stirring at the rotating speed of 50-500r/min, taking a filter residue sample after reacting for 3-4 hours, detecting the manganese content of the filter residue, adding a reducing agent according to 1-3 times of the mass of manganese in the filter residue, and reacting for 1-4 hours under the conditions of pH value of 1-3, temperature of 30-90 ℃ and stirring at the rotating speed of 300-500r/min, so that the zinc-manganese content in the leached residue is reduced to be below 0.5 percent;
(3) Removing iron and aluminum, adding the crushed powder material obtained in the step (1) according to 2-3 times of the mass of iron in the leaching solution, reacting at the temperature of 70-90 ℃ until the pH value of the solution is 4.8-5.5, and then reacting for 2-4 hours at the pH value;
(4) Separating zinc and manganese and preparing zinc sulfate, namely separating solid and liquid of materials after iron and aluminum removal to obtain first filtrate and first filter residue, extracting and separating zinc and manganese from the first filtrate by using a P204 organic extracting agent, firstly saponifying the P204 extracting agent by using alkali, wherein the saponification rate is 50-70%, the P204 organic extracting agent comprises 10-30% of P204 extracting agent and 70-90% of diluent sulfonated kerosene by volume fraction, carrying out 6-10 level countercurrent extraction on the saponified P204 organic extracting agent and the first filtrate, washing at 6-12 level, carrying out 4-8 level back extraction, and carrying out back extraction to obtain pure zinc sulfate solution, wherein the feed liquid comprises: acid washing: acid reaction: the volume flow ratio of the saponified P204 organic extractant is 3-5:0.5-1:0.1-0.3:1, recycling a P204 organic extractant after back extraction to obtain a pure zinc sulfate solution, and concentrating, evaporating and crystallizing to obtain a zinc sulfate crystal;
(5) Removing impurities, adjusting pH of raffinate after zinc extraction to 1.5-2.5 with acid, adding heavy metal capture agent according to 1.1-1.5 times of total mole number of copper metal such as cobalt, nickel, cadmium, lead and copper, reacting at 40-60 deg.C for 1-3 hr, adjusting pH of solution to 3-5.5, adding fluoride according to 2.3-2.5 times of mole number of calcium and magnesium at pH3-5.5, reacting at 80-95 deg.C for 1-3 hr, and filtering to obtain second filtrate and second filter residue;
(6) Preparing a manganese sulfate solution, namely extracting and purifying the manganese solution by feeding the second filtrate into a P507 extraction line, saponifying a P507 organic extracting agent with alkali, wherein the saponification rate is 50-70%, the P507 organic extracting agent comprises 10-30% of a P507 extracting agent and 70-90% of sulfonated kerosene which are used as diluents in volume fraction, the saponification is performed by level 1, the countercurrent extraction is performed by level 4-8, the washing is performed by level 6-10, and the back extraction is performed by level 4-8 to obtain a pure manganese sulfate solution, wherein the feed liquid comprises: acid washing: acid reaction: the volume flow ratio of the saponified P507 organic extracting agent is 2-4:0.5-1:0.1-0.3:1, washing a sulfuric acid solution with the acid concentration of 0.5-1mol/L, back-extracting a sulfuric acid solution with the back-acid concentration of 2-5mol/L, and recycling the back-extracted P507 organic extractant;
(7) Adding sulfuric acid into the manganese sulfate solution obtained in the step (6) to adjust the pH value of the solution to 1-1.5, then concentrating and crystallizing to 50-52 Baume degree, the concentration temperature is 100-110 ℃, then cooling to 80 ℃, the cooling rate is 3-4.5 ℃/h, then cooling to 55 ℃, the cooling rate is 2-2.5 ℃/h, the temperature of 55 ℃ is maintained for 0.5-1 hour, meanwhile, 25-35kg of manganese sulfate seed crystal is added to each cubic meter of solution, then, the temperature is continuously cooled to 40 ℃, the cooling rate is 1-1.5 ℃/h, then, the temperature is continuously cooled to 10-20 ℃, the cooling rate is 2.5-3 ℃/h, then, a horizontal screw centrifuge is used for separation, then, fluidized bed drying is carried out, a grading sieve is adopted for screening to obtain manganese sulfate crystals, the mesh number of an upper layer sieve is 15-20 meshes, the mesh number of a lower layer is 40-50 meshes, and oversize and undersize materials are used as crystals.
The reducing agent in the step (2) is sulfurous acid, salt, metal simple substance powder and ferrous salt.
And (5) concentrating and crystallizing the raffinate obtained by extraction in the step (6) to obtain ammonium chloride crystals.
Roasting the second filter residue obtained in the step (5) at the temperature of 200-230 ℃ for 2-3 hours, introducing pure oxygen during roasting, roasting in an oxidizing atmosphere, continuously turning over the second filter residue during roasting, washing with hot water at the temperature of 80-95 ℃, washing away nickel sulfate, cobalt sulfate, cadmium sulfate and copper sulfate to obtain a third filtrate and a third filter residue, adding 3-4mol/L of sodium hydroxide solution into the third filter residue, reacting at the temperature of 70-80 ℃, filtering to obtain a fourth filtrate and a fourth filter residue, concentrating and crystallizing the fourth filtrate to obtain sodium fluoride, returning to remove calcium and magnesium, adding hydrochloric acid solution into the obtained fourth filter residue to adjust the pH value of the solution to 1-1.5, reacting at the temperature of 70-80 ℃ for 2-3 hours, then cooling to the temperature of 10-15 ℃, filtering to obtain a fifth filtrate and a fifth filter residue, wherein the fifth filter residue is lead chloride crystals, sulfate is added into the fifth filtrate for precipitation to obtain calcium sulfate, the filtrate for filtering the calcium sulfate precipitation residue is concentrated and crystallized to obtain magnesium chloride crystals, the third filtrate adopts a P507 organic extractant to completely extract metal ions onto the P507 organic extractant, the content of nickel ions, cobalt ions, copper ions and cadmium ions in the P507 organic extractant is measured, then 0.5mol/L hydrochloric acid solution is adopted for four-stage back extraction, the first stage of back extraction is used for obtaining nickel chloride solution, the number of the first stage of back extraction is 4-5, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of nickel ions in the P507 organic extractant, cadmium ions are back-extracted at a second stage to obtain a cadmium chloride solution, the number of the back-extraction stages at the second stage is 4-5, and the volume flow ratio of 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of cadmium ions in the P507 organic extracting agent is determined by performing back extraction on cobalt ions to obtain a cobalt chloride solution in a third stage, the number of the back extraction stages in the third stage is 4-5, and the volume flow ratio of 0.5mol/L hydrochloric acid solution to the P507 organic extracting agent is 0.25: the mole number of cobalt ions in the P507 organic extractant, copper ions are stripped in the fourth stage to obtain a copper chloride solution, the stripping stage number of the fourth stage is 4-5, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: moles of copper ions in the P507 organic extractant.
The manganese sulfate seed crystal obtained in the step (7) is subjected to dry ball milling for 1-2 hours, and the mass ratio of the grinding ball to the manganese sulfate crystal is (4-5): 1, grinding the manganese sulfate seed crystal into particles with the particle size of 0.02-0.05mm, wherein the particle size of the grinding balls is 0.5-2mm, and grinding and screening the particles.
Taking sulfuric acid as a leaching agent and sodium sulfite as a reducing agent as an example, the reaction equation is as follows:
Zn+H 2 SO 4 ——ZnSO 4 +H 2
Zn+MnO 2 +2H 2 SO 4 ——MnSO 4 +ZnSO 4 +2H 2 O
MnO 2 +Na 2 SO 3 +H 2 SO 4 ——MnSO 4 +Na 2 SO 4 +H 2 O
removing iron and aluminum. Because the battery powder material contains zinc powder and manganese dioxide powder, the zinc powder and manganese dioxide powder are used for increasing the pH of the leachate and oxidizing ferrous iron into ferric iron. Thereby achieving the purpose of removing iron and aluminum, and the solution after removing iron and aluminum comprises the following components:
components Mn Zn Co Ni Pb
Content (c) of 40-60g/L 40-70g/L 0.1-0.5g/L 0.1-0.3g/L 1-10mg/L
Components Cd Ca Mg Fe AL
Content (c) of 0.1-1g/L 0.1-0.5g/L 0.1-1g/L 1-10mg/L 1-20mg/L
The reaction chemical equation is as follows:
MnO 2 +2FeSO 4 +4H 2 O——MnSO 4 +2Fe(OH) 3 +H 2 SO 4
Al 2 (SO 4 ) 3 +6H 2 O——2Al(OH) 3 +3H 2 SO 4
separating zinc and manganese and preparing zinc sulfate, wherein the finally obtained zinc sulfate comprises the following components:
components Zn Mn Co Ni Pb
Content (wt.) 60-120g/L 0.5-2mg/L 0.2-1mg/L 0.1-0.3mg/L 0.1-0.5mg/L
Components Cd Ca Mg Fe Cu
Content (wt.) 0.1-1mg/L 0.1-1.5mg/L 0.1-1mg/L 0.2-1mg/L 0.3-1mg/L
The solution after zinc extraction comprises the following components:
components Mn Zn Co Ni Pb
Content (wt.) 35-55g/L 5-20mg/L 0.1-0.4g/L 0.1-0.3g/L 1-10mg/L
Components Cd Ca Mg Fe Cu
Content (c) of 0.1-0.9g/L 0.1-0.5g/L 0.1-1g/L 0.5-3mg/L 0.5-1mg/L
Removing impurities by using a heavy metal catching agent and fluoride. The chemical components of the final impurity-removed solution are as follows:
components Mn Zn Co Ni Pb
Content (wt.) 35-50g/L 0.5-1.5mg/L 0.1-1mg/L 0.1-1.5mg/L 0.1-1mg/L
Components Cd Ca Mg Fe Cu
Content (c) of 0.1-0.9mg/L 0.1-2.5mg/L 0.1-3mg/L 0.5-1mg/L 0.1-0.5mg/L
The obtained filter residue is a material rich in cobalt, nickel and copper, wherein the content of cobalt, nickel and copper is higher than 10%.
The components of the manganese sulfate finally obtained after purification are as follows:
components Mn Zn Co Ni Pb
Content (wt.) 60-120g/L 0.5-2mg/L 0.2-1mg/L 0.1-0.3mg/L 0.1-0.5mg/L
Components Cd Ca Mg Fe Cu
Content (wt.) 0.1-1mg/L 0.1-1.5mg/L 0.1-1mg/L 0.2-1mg/L 0.3-1mg/L
And concentrating, evaporating and crystallizing to obtain the battery-grade manganese sulfate.
The invention has the beneficial effects that:
(1) The recovery of all components of the zinc-manganese battery is realized, including the complete recovery of zinc-manganese-cobalt-nickel-copper-cadmium-calcium-magnesium-lead and ammonium chloride, and the recovery rate of manganese and zinc is up to more than 99%, the recovery rate of nickel, cobalt, copper and cadmium is more than 97%, and the recovery rate of lead, calcium and magnesium is more than 96%.
(2) The obtained components have high purity, manganese sulfate is battery grade, the purity can reach 99.85%, zinc sulfate is electroplating grade, the purity is 99.7%, nickel, cobalt, copper and cadmium solutions with the purity of more than 95% are obtained, the purity of lead chloride is more than 97%, the purity of calcium sulfate is more than 98%, and the purity of magnesium chloride is more than 97%.
(3) The method has the advantages that the process is simple, two-time extraction is skillfully adopted, and the extractants in different extraction sequences are selected, so that the zinc and manganese are recovered and purified, the battery-grade manganese sulfate and the electroplating-grade zinc sulfate are obtained, the obtained manganese sulfate crystals are granular, the agglomeration phenomenon is avoided, the separation and purification of nickel, cobalt, copper and cadmium are realized by adopting sulfating roasting and sectional extraction, and the process flow is short.
Drawings
The invention is further described below with reference to the figures and examples.
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention will be described in detail below with reference to the accompanying drawings, as shown in fig. 1: the method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries in the embodiment comprises the following steps:
(1) Crushing the waste zinc-manganese battery, namely putting the zinc-manganese battery into a crusher to be crushed into powder with the particle size of below 200 um;
(2) Dissolving zinc-manganese battery powder materials, namely dissolving the zinc-manganese battery powder materials according to the solid-liquid ratio of 3-6:1, adding bottom water, simultaneously adding acid to maintain the pH value of 1-1.2 in the reaction process, maintaining the reaction temperature of 75-90 ℃, stirring at the rotating speed of 50-500r/min, taking a filter residue sample after reacting for 3-4 hours, detecting the manganese content of the filter residue, adding a reducing agent according to 1-3 times of the mass of manganese in the filter residue, and reacting for 1-4 hours under the conditions of pH value of 1-3, temperature of 30-90 ℃ and stirring at the rotating speed of 300-500r/min to reduce the zinc-manganese content in the leached residue to below 0.5%;
(3) Removing iron and aluminum, adding the crushed powder material obtained in the step (1) according to 2-3 times of the mass of iron in the leachate, reacting at 70-90 ℃ until the pH value of the solution is 4.8-5.5, and then reacting at the pH value for 2-4 hours;
(4) Separating zinc and manganese and preparing zinc sulfate, namely performing solid-liquid separation on materials after iron and aluminum removal to obtain a first filtrate and a first filter residue, extracting and separating zinc and manganese from the first filtrate by using a P204 organic extracting agent, firstly saponifying the P204 extracting agent by using alkali, wherein the saponification rate is 50-70%, the P204 organic extracting agent consists of 10-30% of P204 extracting agent and 70-90% of diluent sulfonated kerosene by volume fraction, performing 6-10-level countercurrent extraction on the saponified P204 organic extracting agent and the first filtrate, washing at 6-12 levels, performing 4-8-level back extraction, and performing back extraction to obtain a pure zinc sulfate solution, wherein the feed liquid comprises: acid washing: acid reaction: the volume flow ratio of the saponified P204 organic extractant is 3-5:0.5-1:0.1-0.3:1, recycling a P204 organic extractant after back extraction to obtain a pure zinc sulfate solution, and concentrating, evaporating and crystallizing to obtain a zinc sulfate crystal;
(5) Removing impurities, adjusting pH of raffinate after zinc extraction to 1.5-2.5 with acid, adding heavy metal capture agent according to 1.1-1.5 times of total mole number of copper metal such as cobalt, nickel, cadmium, lead and copper, reacting at 40-60 deg.C for 1-3 hr, adjusting pH of solution to 3-5.5, adding fluoride according to 2.3-2.5 times of mole number of calcium and magnesium at pH3-5.5, reacting at 80-95 deg.C for 1-3 hr, and filtering to obtain second filtrate and second filter residue;
(6) Preparing a manganese sulfate solution, namely extracting and purifying the manganese solution by feeding the second filtrate into a P507 extraction line, saponifying a P507 organic extracting agent with alkali, wherein the saponification rate is 50-70%, the P507 organic extracting agent comprises 10-30% of a P507 extracting agent and 70-90% of sulfonated kerosene which are used as diluents in volume fraction, the saponification is performed by level 1, the countercurrent extraction is performed by level 4-8, the washing is performed by level 6-10, and the back extraction is performed by level 4-8 to obtain a pure manganese sulfate solution, wherein the feed liquid comprises: acid washing: acid reaction: the volume flow ratio of the saponified P507 organic extracting agent is 2-4:0.5-1:0.1-0.3:1, sulfuric acid solution with washing acid concentration of 0.5-1mol/L and sulfuric acid solution with back acid concentration of 2-5mol/L, and recycling the back extracted P507 organic extractant;
(7) Adding sulfuric acid into the manganese sulfate solution obtained in the step (6) to adjust the pH value of the solution to be 1-1.5, then concentrating and crystallizing to a Baume degree of 50-52, concentrating at a temperature of 100-110 ℃, then cooling to 80 ℃, wherein the cooling rate in the process is 3-4.5 ℃/h, then cooling to 55 ℃, the cooling rate in the process is 2-2.5 ℃/h, maintaining the temperature of 55 ℃ for 0.5-1 hour, simultaneously adding 25-35kg of manganese sulfate seed crystals per cubic meter of the solution, then continuously cooling to 40 ℃, the cooling rate in the process is 1-1.5 ℃/h, then continuously cooling to 10-20 ℃, the cooling rate in the process is 2.5-3 ℃/h, then performing solid-liquid separation by using a horizontal screw centrifuge, then feeding into a fluidized bed for drying, and screening by using a grading screen to obtain manganese sulfate crystals, wherein the mesh number of an upper screen is 15-20 meshes, the mesh number of a lower screen is 40-50 meshes, and oversize and undersize materials are used as the crystals.
The reducing agent in the step (2) is sulfurous acid, salt, metal simple substance powder and ferrous salt.
And (4) concentrating and crystallizing raffinate obtained by extraction in the step (6) to obtain ammonium chloride crystals.
Roasting the second filter residue obtained in the step (5) at the temperature of 200-230 ℃ for 2-3 hours, introducing pure oxygen during roasting, roasting in an oxidizing atmosphere, continuously turning over the second filter residue during roasting, washing with hot water at the temperature of 80-95 ℃, washing away nickel sulfate, cobalt sulfate, cadmium sulfate and copper sulfate to obtain a third filtrate and a third filter residue, adding 3-4mol/L sodium hydroxide solution into the third filter residue, reacting at the temperature of 70-80 ℃, filtering to obtain a fourth filtrate and a fourth filter residue, concentrating and crystallizing the fourth filtrate to obtain sodium fluoride, returning to remove calcium and magnesium, adding hydrochloric acid solution into the obtained fourth filter residue to adjust the pH value of the solution to 1-1.5, reacting at the temperature of 70-80 ℃ for 2-3 hours, then cooling to the temperature of 10-15 ℃, filtering to obtain a fifth filtrate and a fifth filter residue, wherein the fifth filter residue is a lead chloride crystal, sulfate is added into the fifth filtrate for precipitation to obtain calcium sulfate, the filtrate for filtering the calcium sulfate precipitation residue is concentrated and crystallized to obtain a magnesium chloride crystal, the third filtrate adopts a P507 organic extractant to completely extract metal ions onto the P507 organic extractant, the content of nickel ions, cobalt ions, copper ions and cadmium ions in the P507 organic extractant is measured, then 0.5mol/L hydrochloric acid solution is adopted for four-stage back extraction, the first stage of back extraction is used for nickel ions to obtain a nickel chloride solution, the first stage of back extraction is 4-5 stages, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of nickel ions in the P507 organic extractant, cadmium ions are back-extracted at a second stage to obtain a cadmium chloride solution, the number of the back-extraction stages at the second stage is 4-5, and the volume flow ratio of 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of cadmium ions in the P507 organic extractant is determined, cobalt ions are reversely extracted in the third section to obtain a cobalt chloride solution, the number of the reverse extraction stages in the third section is 4-5, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of cobalt ions in the P507 organic extractant, copper ions are stripped in the fourth stage to obtain a copper chloride solution, the stripping stage number of the fourth stage is 4-5, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: moles of copper ions in the P507 organic extractant.
The manganese sulfate crystal seeds in the step (7) are subjected to dry ball milling for 1-2 hours, and the mass ratio of the grinding balls to the manganese sulfate crystals is 4-5:1, grinding the grinding balls to be 0.5-2mm in particle size, and screening the grinded particles to obtain the manganese sulfate seed crystal with the particle size of 0.02-0.05mm.
Example 1
A method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries comprises the following steps:
(1) Crushing the waste zinc-manganese battery, namely putting the zinc-manganese battery into a crusher to be crushed into powder with the particle size of below 200 um;
(2) Dissolving a zinc-manganese battery powder material, namely dissolving the zinc-manganese battery powder material according to a solid-to-liquid ratio of 4:1 adding bottom water, simultaneously adding acid to maintain the pH value of 1.1 in the reaction process, maintaining the reaction temperature of 85 ℃, stirring at a rotating speed of 400r/min, taking a filter residue sample after reacting for 3.5 hours, detecting the manganese content of the filter residue sample, adding a reducing agent according to 2 times of the mass of manganese in the filter residue, and reacting for 2 hours under the conditions of pH value of 1.5, temperature of 60 ℃ and stirring at a rotating speed of 400r/min to reduce the zinc-manganese content in the leached residue to be below 0.5 percent;
(3) Removing iron and aluminum, adding the crushed powder material obtained in the step (1) according to 2.2 times of the mass of iron in the leachate, reacting at the temperature of 81 ℃ until the pH value of the solution is 4.95, and then reacting at the pH value for 3.1 hours;
(4) Separating zinc and manganese and preparing zinc sulfate, separating solid and liquid of materials after iron and aluminum removal to obtain first filtrate and first filter residue, extracting and separating zinc and manganese from the first filtrate by using a P204 organic extracting agent, firstly saponifying the P204 extracting agent by using alkali, wherein the saponification rate is 62%, the P204 organic extracting agent consists of 25-percent P204 extracting agent and 75% diluent sulfonated kerosene in volume fraction, the saponified P204 organic extracting agent and the first filtrate undergo 8-level countercurrent extraction, 10-level washing, 7-level back extraction and back extraction to obtain pure zinc sulfate solution, and the feed liquid comprises: acid washing: acid reaction: the volume flow ratio of the saponified P204 organic extractant is 4.2:0.8:0.18:1, washing a sulfuric acid solution with the acid concentration of 0.8mol/L, performing reverse extraction on a sulfuric acid solution with the reverse acid concentration of 3.5mol/L, recycling the P204 organic extractant after the reverse extraction to obtain a pure zinc sulfate solution, and concentrating, evaporating and crystallizing to obtain a zinc sulfate crystal;
(5) Removing impurities, adjusting pH of raffinate after zinc extraction back to 1.95 by using acid, then adding a heavy metal capture agent according to 1.25 times of the total mole number of cobalt, nickel, cadmium, lead and copper metal, reacting for 2.1 hours at 55 ℃, adjusting pH of the solution to 3.5, adding fluoride according to 2.4 times of the mole number of calcium and magnesium at pH3.5, reacting for 1.5 hours at 89 ℃, and filtering to obtain a second filtrate and a second filter residue;
(6) Preparing a manganese sulfate solution, namely, introducing a second filtrate into a P507 extraction line for extraction and purification of the manganese solution, firstly saponifying a P507 organic extracting agent with alkali, wherein the saponification rate is 65%, the P507 organic extracting agent comprises 30% volume fraction P507 extracting agent and 70% volume fraction sulfonated kerosene, carrying out 1-level saponification, carrying out 5-level countercurrent extraction, carrying out 9-level washing, and carrying out 7-level back extraction to obtain a pure manganese sulfate solution, namely a feed liquid: acid washing: acid reaction: the volume flow ratio of the saponified P507 organic extracting agent is 3:0.9:0.25:1, sulfuric acid solution with washing acid concentration of 0.8mol/L and sulfuric acid solution with back acid concentration of 3mol/L, and recycling the back extracted P507 organic extracting agent;
(7) Adding sulfuric acid into the manganese sulfate solution obtained in the step (6) to adjust the pH value of the solution to be 1.35, then concentrating and crystallizing until the Baume degree is 50.5, the concentration temperature is 103 ℃, then cooling, when the temperature is reduced to 80 ℃, the temperature reduction rate in the process is 3.5 ℃/h, then cooling to 55 ℃, the temperature reduction rate in the process is 2.3 ℃/h, the temperature of 55 ℃ is maintained for 0.6 hour, meanwhile, 29kg of manganese sulfate seed crystal is added into the solution according to each cubic meter, then the temperature is continuously reduced to 40 ℃, the temperature reduction rate in the process is 1.5 ℃/h, then the temperature is continuously reduced to 14 ℃, the temperature reduction rate in the process is 2.8 ℃/h, then carrying out solid-liquid separation by using a horizontal screw centrifuge, then carrying out fluidized bed drying, and carrying out screening by using a classifying screen to obtain manganese sulfate crystals, wherein the mesh number of an upper screen is 15 meshes, the mesh number of a lower screen is 45 meshes, and oversize and undersize products are used as the crystals.
The reducing agent in the step (2) is sulfurous acid, salt, metal simple substance powder and ferrous salt.
And (4) concentrating and crystallizing raffinate obtained by extraction in the step (6) to obtain ammonium chloride crystals.
Roasting the second filter residue obtained in the step (5) at 220 ℃ for 2.5 hours, introducing pure oxygen during roasting, roasting in an oxidizing atmosphere, continuously turning over the second filter residue during roasting, washing with hot water at 85 ℃, washing away nickel sulfate, cobalt sulfate, cadmium sulfate and copper sulfate to obtain a third filtrate and a third filter residue, adding 3.5mol/L sodium hydroxide solution into the third filter residue, reacting at 78 ℃, filtering to obtain a fourth filtrate and a fourth filter residue, concentrating and crystallizing the fourth filtrate to obtain sodium fluoride, returning to remove calcium and magnesium, adding hydrochloric acid solution into the obtained fourth filter residue to adjust the pH value of the solution to be 1.3, reacting at 78 ℃ for 2.3 hours, cooling to 13 ℃, filtering to obtain a fifth filtrate and a fifth filter residue, wherein the fifth filter residue is lead chloride crystal, adding sulfate precipitate into the fifth filtrate to obtain calcium sulfate precipitate, concentrating and crystallizing the filtrate to obtain magnesium chloride crystal, extracting the third filtrate by adopting P507 organic extracting agent to completely extract metal ions onto P507, extracting the P507 organic extracting agent to obtain a cobalt ion extracting solution, measuring the content of the P ion extracting agent, extracting the P extracting agent, extracting the content of the P ion extracting agent, wherein the P extracting solution is 0.5mol/L, the content of the P ion extracting agent is 0.507, and the content of the P extracting solution of the first stage, and the first stage of the P ion extracting agent, and the second stage extracting stage is 0.5/L, and the second stage extracting stage, wherein the third stage comprises the third stage: the mole number of nickel ions in the P507 organic extracting agent is determined by the second stage of stripping cadmium ions to obtain cadmium chloride solution, the second stage of stripping stage number is 5, and the volume flow ratio of 0.5mol/L hydrochloric acid solution to the P507 organic extracting agent is 0.25: the mole number of cadmium ions in the P507 organic extractant is determined, cobalt ions are reversely extracted in the third section to obtain a cobalt chloride solution, the number of the reverse extraction stages in the third section is 5, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of cobalt ions in the P507 organic extractant is calculated, copper ions are stripped in the fourth stage to obtain a copper chloride solution, the stripping stage number of the fourth stage is 5 stages, and the volume flow ratio of 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: moles of copper ions in the P507 organic extractant.
The manganese sulfate seed crystal obtained in the step (7) is subjected to dry ball milling for 1-2 hours, and the mass ratio of the grinding ball to the manganese sulfate crystal is 4.3:1, grinding the grinding balls to be 0.8mm in particle size, and screening the grinded materials to obtain the manganese sulfate seed crystal with the particle size of 0.04mm.
Analytical structure of manganese sulfate crystal
Item Mn Zn Cu Co Ni Pb
Numerical value 99.86％ 12ppm 0.5ppm 2.1ppm 3.2ppm 6.5ppm
Ca Mg Cd Na Cr Al Fe
2.5ppm 5.4ppm 0.2ppm 2.5ppm 1.5ppm 2.1ppm 0.5ppm
Analysis structure of zinc sulfate crystal
Item Zn Mn Cu Co Ni Pb
Numerical value 99.75％ 10.2ppm 0.5ppm 2.4ppm 3.2ppm 6.5ppm
Ca Mg Cd Na Cr Al Fe
2.5ppm 5.4ppm 0.2ppm 2.5ppm 2.5ppm 2.1ppm 0.1ppm
Example 2
A method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries comprises the following steps:
(1) Crushing the waste zinc-manganese battery, namely putting the zinc-manganese battery into a crusher to be crushed into powder with the particle size of below 200 um;
(2) Dissolving zinc-manganese battery powder materials, namely dissolving a zinc-manganese battery powder material according to a solid-liquid ratio of 4:1 adding bottom water, simultaneously adding acid to maintain the pH value of 1.1 in the reaction process, maintaining the reaction temperature of 85 ℃, stirring at a rotating speed of 400r/min, taking a filter residue sample after reacting for 3.5 hours, detecting the manganese content of the filter residue sample, adding a reducing agent according to 2 times of the mass of manganese in the filter residue, and reacting for 2 hours under the conditions of pH value of 1.5, temperature of 60 ℃ and stirring at a rotating speed of 400r/min to reduce the zinc-manganese content in the leached residue to be below 0.5 percent;
(3) Removing iron and aluminum, adding the crushed powder material obtained in the step (1) according to 2.2 times of the mass of iron in the leaching solution, reacting at the temperature of 81 ℃ until the pH value of the solution is 4.95, and then reacting at the pH value for 3.1 hours;
(4) Separating zinc and manganese and preparing zinc sulfate, namely performing solid-liquid separation on materials after iron and aluminum removal to obtain first filtrate and first filter residue, extracting and separating zinc and manganese from the first filtrate by using a P204 organic extracting agent, firstly saponifying the P204 extracting agent by using alkali, wherein the saponification rate is 62%, the P204 organic extracting agent consists of 25 percent of P204 extracting agent and 75 percent of diluent sulfonated kerosene in volume fraction, and the saponified P204 organic extracting agent and the first filtrate are subjected to 8-stage countercurrent extraction, 10-stage washing, 7-stage back extraction and back extraction to obtain pure zinc sulfate solution, wherein the feed liquid comprises: acid washing: acid reaction: the volume flow ratio of the saponified P204 organic extractant is 4.2:0.8:0.18:1, washing a sulfuric acid solution with the acid concentration of 0.8mol/L, performing reverse extraction on a sulfuric acid solution with the reverse acid concentration of 3.5mol/L, recycling the P204 organic extractant after the reverse extraction to obtain a pure zinc sulfate solution, and concentrating, evaporating and crystallizing to obtain a zinc sulfate crystal;
(5) Removing impurities, namely adjusting pH of raffinate after zinc extraction back to 1.95 by using acid, then adding a heavy metal capture agent according to 1.25 times of the total mole number of cobalt, nickel, cadmium, lead and copper metal, reacting at 55 ℃ for 2.1 hours, adjusting pH of the solution to 3.5, adding fluoride according to 2.4 times of the mole number of calcium and magnesium at pH3.5, reacting at 89 ℃ for 1.5 hours, and filtering to obtain second filtrate and second filter residue;
(6) Preparing a manganese sulfate solution, namely, introducing a second filtrate into a P507 extraction line for extraction and purification of the manganese solution, firstly saponifying a P507 organic extracting agent with alkali, wherein the saponification rate is 55%, the P507 organic extracting agent comprises 20% of the P507 extracting agent and 80% of diluent sulfonated kerosene by volume fraction, and the pure manganese sulfate solution and the feed liquid are obtained through 1-level saponification, 7-level countercurrent extraction, 10-level washing and 8-level back extraction: acid washing: acid reaction: the volume flow ratio of the saponified P507 organic extracting agent is 3.5:0.8:0.17:1, sulfuric acid solution with washing acid concentration of 0.8mol/L and sulfuric acid solution with back acid concentration of 3.2mol/L, and recycling the back extracted P507 organic extractant;
(7) Adding sulfuric acid into the manganese sulfate solution obtained in the step (6) to adjust the pH value of the solution to be 1.35, then concentrating and crystallizing until the Baume degree is 50.5, the concentration temperature is 103 ℃, then cooling, when the temperature is reduced to 80 ℃, the temperature reduction rate in the process is 3.5 ℃/h, then cooling to 55 ℃, the temperature reduction rate in the process is 2.3 ℃/h, the temperature of 55 ℃ is maintained for 0.6 hour, meanwhile, 29kg of manganese sulfate seed crystal is added into the solution according to each cubic meter, then the temperature is continuously reduced to 40 ℃, the temperature reduction rate in the process is 1.5 ℃/h, then the temperature is continuously reduced to 14 ℃, the temperature reduction rate in the process is 2.8 ℃/h, then carrying out solid-liquid separation by using a horizontal screw centrifuge, then carrying out fluidized bed drying, and carrying out screening by using a classifying screen to obtain manganese sulfate crystals, wherein the mesh number of an upper screen is 15 meshes, the mesh number of a lower screen is 45 meshes, and oversize and undersize products are used as the crystals.
The reducing agent in the step (2) is sulfurous acid, salt, metal simple substance powder and ferrous salt.
And (4) concentrating and crystallizing raffinate obtained by extraction in the step (6) to obtain ammonium chloride crystals.
Roasting the second filter residue obtained in the step (5) at 220 ℃ for 2.5 hours, introducing pure oxygen during roasting, roasting in an oxidizing atmosphere, continuously turning over the second filter residue during roasting, washing with hot water at 85 ℃, washing away nickel sulfate, cobalt sulfate, cadmium sulfate and copper sulfate to obtain a third filtrate and a third filter residue, adding 3.5mol/L sodium hydroxide solution into the third filter residue, reacting at 78 ℃, filtering to obtain a fourth filtrate and a fourth filter residue, concentrating and crystallizing the fourth filtrate to obtain sodium fluoride, returning to remove calcium and magnesium, adding hydrochloric acid solution into the obtained fourth filter residue to adjust the pH value of the solution to 1.3, reacting at 78 ℃ for 2.3 hours, cooling to 13 ℃ and filtering, obtaining a fifth filtrate and a fifth filter residue, wherein the fifth filter residue is lead chloride crystals, sulfate is added into the fifth filtrate for precipitation to obtain calcium sulfate, the filtrate for filtering the calcium sulfate precipitation residue is concentrated and crystallized to obtain magnesium chloride crystals, the third filtrate adopts a P507 organic extractant to completely extract metal ions onto the P507 organic extractant, the content of nickel ions, cobalt ions, copper ions and cadmium ions in the P507 organic extractant is measured, then 0.5mol/L hydrochloric acid solution is adopted for four-stage back extraction, the first stage of back extraction of the nickel ions obtains a nickel chloride solution, the number of the first stage of back extraction is 4, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of nickel ions in the P507 organic extractant is determined by performing back extraction on cadmium ions at a second stage to obtain a cadmium chloride solution, the number of the back extraction stages at the second stage is 5, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of cadmium ions in the P507 organic extracting agent is determined by performing back extraction on cobalt ions to obtain a cobalt chloride solution in a third stage, the number of the back extraction stages in the third stage is 5, and the volume flow ratio of 0.5mol/L hydrochloric acid solution to the P507 organic extracting agent is 0.25: the mole number of cobalt ions in the P507 organic extractant, copper ions are stripped in the fourth stage to obtain a copper chloride solution, the stripping stage number of the fourth stage is 5, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: moles of copper ions in the P507 organic extractant.
The manganese sulfate crystal seeds in the step (7) are subjected to dry ball milling for 1-2 hours, and the mass ratio of the grinding balls to the manganese sulfate crystals is 4.3:1, grinding the manganese sulfate seed crystal to obtain a manganese sulfate seed crystal with the particle size of 0.04mm, wherein the particle size of the grinding ball is 0.8mm, and the manganese sulfate seed crystal is ground and sieved.
Analytical structure of manganese sulfate crystal
Item Mn Zn Cu Co Ni Pb
Numerical value 99.85％ 11ppm 0.5ppm 2.2ppm 3.2ppm 6.5ppm
Ca Mg Cd Na Cr Al Fe
2.5ppm 5.3ppm 0.2ppm 2.5ppm 1.5ppm 2.1ppm 0.4ppm
Analysis structure of zinc sulfate crystal
Item Zn Mn Cu Co Ni Pb
Numerical value 99.73％ 10.5ppm 0.5ppm 2.4ppm 3.2ppm 7.5ppm
Ca Mg Cd Na Cr Al Fe
2.7ppm 5.4ppm 0.1ppm 2.5ppm 2.5ppm 2.1ppm 0.1ppm
Example 3
A method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries comprises the following steps:
(1) Crushing the waste zinc-manganese battery, namely putting the zinc-manganese battery into a crusher to be crushed into powder with the particle size of below 200 um;
(2) Dissolving zinc-manganese battery powder materials, namely dissolving a zinc-manganese battery powder material according to a solid-liquid ratio of 4:1, adding bottom water, adding acid at the same time to maintain the pH value of 1.1 in the reaction process, maintaining the reaction temperature at 85 ℃, stirring at a rotating speed of 400r/min, taking a filter residue sample after reacting for 3.5 hours, detecting the manganese content of the filter residue, adding a reducing agent according to 2 times of the manganese mass in the filter residue, and reacting for 2 hours under the conditions of pH value of 1.5, temperature of 60 ℃ and stirring at a rotating speed of 400r/min to reduce the zinc-manganese content in the leached residue to below 0.5%;
(3) Removing iron and aluminum, adding the crushed powder material obtained in the step (1) according to 2.2 times of the mass of iron in the leachate, reacting at the temperature of 81 ℃ until the pH value of the solution is 4.95, and then reacting at the pH value for 3.1 hours;
(4) Separating zinc and manganese and preparing zinc sulfate, namely performing solid-liquid separation on materials after iron and aluminum removal to obtain first filtrate and first filter residue, extracting and separating zinc and manganese from the first filtrate by using a P204 organic extracting agent, firstly saponifying the P204 extracting agent by using alkali, wherein the saponification rate is 55 percent, the P204 organic extracting agent consists of 18 percent of the P204 extracting agent and 82 percent of diluent sulfonated kerosene in volume fraction, and the saponified P204 organic extracting agent and the first filtrate are subjected to 9-stage countercurrent extraction, 12-stage washing, 8-stage back extraction and back extraction to obtain pure zinc sulfate solution, wherein the feed solution comprises: acid washing: acid reaction: the volume flow ratio of the saponified P204 organic extractant is 3.5:0.7:0.15:1, recycling a P204 organic extractant after back extraction to obtain a pure zinc sulfate solution, and concentrating, evaporating and crystallizing to obtain a zinc sulfate crystal;
(5) Removing impurities, adjusting pH of raffinate after zinc extraction back to 1.95 by using acid, then adding a heavy metal capture agent according to 1.25 times of the total mole number of cobalt, nickel, cadmium, lead and copper metal, reacting for 2.1 hours at 55 ℃, adjusting pH of the solution to 3.5, adding fluoride according to 2.4 times of the mole number of calcium and magnesium at pH3.5, reacting for 1.5 hours at 89 ℃, and filtering to obtain a second filtrate and a second filter residue;
(6) Preparing a manganese sulfate solution, namely, introducing a second filtrate into a P507 extraction line for extraction and purification of the manganese solution, firstly saponifying a P507 organic extracting agent with alkali, wherein the saponification rate is 55%, the P507 organic extracting agent comprises 20% of the P507 extracting agent and 80% of diluent sulfonated kerosene by volume fraction, and the pure manganese sulfate solution and the feed liquid are obtained through 1-level saponification, 7-level countercurrent extraction, 10-level washing and 8-level back extraction: acid washing: acid reaction: the volume flow ratio of the saponified P507 organic extracting agent is 3.5:0.8:0.17:1, sulfuric acid solution with washing acid concentration of 0.8mol/L and sulfuric acid solution with back acid concentration of 3.2mol/L, and recycling the back extracted P507 organic extractant;
(7) Adding sulfuric acid into the manganese sulfate solution obtained in the step (6) to adjust the pH value of the solution to be 1.35, then concentrating and crystallizing until the Baume degree is 50.5, the concentration temperature is 103 ℃, then cooling to 80 ℃, wherein the cooling rate in the process is 3.5 ℃/h, then cooling to 55 ℃, the cooling rate in the process is 2.3 ℃/h, the temperature of 55 ℃ is maintained for 0.6 hour, meanwhile, 29kg of manganese sulfate seed crystal is added into the solution per cubic meter, then the temperature is continuously cooled to 40 ℃, the cooling rate in the process is 1.5 ℃/h, then the temperature is continuously cooled to 14 ℃, the cooling rate in the process is 2.8 ℃/h, then solid-liquid separation is carried out by a horizontal screw centrifuge, then fluidized bed drying is carried out, a classifying screen is adopted for screening to obtain manganese sulfate crystals, the mesh number of an upper screen is 15 meshes, the mesh number of a lower screen is 45 meshes, and oversize and undersize products are used as the crystals.
The reducing agent in the step (2) is sulfurous acid, salt, metal simple substance powder and ferrous salt.
And (4) concentrating and crystallizing raffinate obtained by extraction in the step (6) to obtain ammonium chloride crystals.
Roasting the second filter residue obtained in the step (5) at 220 ℃ for 2.5 hours, introducing pure oxygen during roasting, roasting in an oxidizing atmosphere, continuously turning over the second filter residue during roasting, washing with hot water at 85 ℃, washing away nickel sulfate, cobalt sulfate, cadmium sulfate and copper sulfate to obtain a third filtrate and a third filter residue, adding 3.5mol/L sodium hydroxide solution into the third filter residue, reacting at 78 ℃, filtering to obtain a fourth filtrate and a fourth filter residue, concentrating and crystallizing the fourth filtrate to obtain sodium fluoride, returning to remove calcium and magnesium, adding hydrochloric acid solution into the obtained fourth filter residue to adjust the pH value of the solution to 1.3, reacting at 78 ℃ for 2.3 hours, cooling to 13 ℃ and filtering, obtaining a fifth filtrate and a fifth filter residue, wherein the fifth filter residue is lead chloride crystals, sulfate is added into the fifth filtrate for precipitation to obtain calcium sulfate, the filtrate for filtering the calcium sulfate precipitation residue is concentrated and crystallized to obtain magnesium chloride crystals, the third filtrate adopts a P507 organic extractant to completely extract metal ions onto the P507 organic extractant, the content of nickel ions, cobalt ions, copper ions and cadmium ions in the P507 organic extractant is measured, then 0.5mol/L hydrochloric acid solution is adopted for four-stage back extraction, the first stage of back extraction of the nickel ions obtains a nickel chloride solution, the number of the first stage of back extraction is 4, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of nickel ions in the P507 organic extractant is determined by performing back extraction on cadmium ions at a second stage to obtain a cadmium chloride solution, the number of the back extraction stages at the second stage is 5, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of cadmium ions in the P507 organic extractant is determined, cobalt ions are reversely extracted in the third section to obtain a cobalt chloride solution, the number of the reverse extraction stages in the third section is 5, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of cobalt ions in the P507 organic extractant, copper ions are stripped in the fourth stage to obtain a copper chloride solution, the stripping stage number of the fourth stage is 5, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: moles of copper ions in the P507 organic extractant.
The manganese sulfate crystal seeds in the step (7) are subjected to dry ball milling for 1-2 hours, and the mass ratio of the grinding balls to the manganese sulfate crystals is 4.3:1, grinding the grinding balls to be 0.8mm in particle size, and screening the grinded materials to obtain the manganese sulfate seed crystal with the particle size of 0.04mm.
Analytical structure of manganese sulfate crystal
Item Mn Zn Cu Co Ni Pb
Numerical value 99.87％ 11ppm 0.5ppm 2.1ppm 3.3ppm 6.5ppm
Ca Mg Cd Na Cr Al Fe
2.5ppm 5.5ppm 0.4ppm 2.7ppm 1.5ppm 2.1ppm 0.7ppm
Analysis structure of zinc sulfate crystal
Item Zn Mn Cu Co Ni Pb
Numerical value 99.77％ 10.2ppm 0.8ppm 2.4ppm 3.8ppm 6.5ppm
Ca Mg Cd Na Cr Al Fe
2.5ppm 5.8ppm 0.2ppm 2.5ppm 2.5ppm 2.8ppm 0.3ppm
Example 4
A method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries comprises the following steps:
(1) Crushing the waste zinc-manganese battery, namely putting the zinc-manganese battery into a crusher to be crushed into powder with the particle size of below 200 um;
(2) Dissolving zinc-manganese battery powder materials, namely dissolving a zinc-manganese battery powder material according to a solid-liquid ratio of 4:1, adding bottom water, adding acid at the same time to maintain the pH value of 1.1 in the reaction process, maintaining the reaction temperature at 85 ℃, stirring at a rotating speed of 400r/min, taking a filter residue sample after reacting for 3.5 hours, detecting the manganese content of the filter residue, adding a reducing agent according to 2 times of the manganese mass in the filter residue, and reacting for 2 hours under the conditions of pH value of 1.5, temperature of 60 ℃ and stirring at a rotating speed of 400r/min to reduce the zinc-manganese content in the leached residue to below 0.5%;
(3) Removing iron and aluminum, adding the crushed powder material obtained in the step (1) according to 2.2 times of the mass of iron in the leaching solution, reacting at the temperature of 81 ℃ until the pH value of the solution is 4.95, and then reacting at the pH value for 3.1 hours;
(4) Separating zinc and manganese and preparing zinc sulfate, namely performing solid-liquid separation on materials after iron and aluminum removal to obtain first filtrate and first filter residue, extracting and separating zinc and manganese from the first filtrate by using a P204 organic extracting agent, firstly saponifying the P204 extracting agent by using alkali, wherein the saponification rate is 55 percent, the P204 organic extracting agent consists of 18 percent of the P204 extracting agent and 82 percent of diluent sulfonated kerosene in volume fraction, and the saponified P204 organic extracting agent and the first filtrate are subjected to 9-stage countercurrent extraction, 12-stage washing, 8-stage back extraction and back extraction to obtain pure zinc sulfate solution, wherein the feed solution comprises: acid washing: acid reaction: the volume flow ratio of the saponified P204 organic extractant is 3.5:0.7:0.15:1, washing a sulfuric acid solution with the acid concentration of 0.75mol/L, performing reverse acid concentration of 3mol/L, recycling the back-extracted P204 organic extractant to obtain a pure zinc sulfate solution, and performing concentration, evaporation and crystallization to obtain a zinc sulfate crystal;
(5) Removing impurities, adjusting pH of raffinate after zinc extraction back to 1.95 by using acid, then adding a heavy metal capture agent according to 1.25 times of the total mole number of cobalt, nickel, cadmium, lead and copper metal, reacting for 2.1 hours at 55 ℃, adjusting pH of the solution to 3.5, adding fluoride according to 2.4 times of the mole number of calcium and magnesium at pH3.5, reacting for 1.5 hours at 89 ℃, and filtering to obtain a second filtrate and a second filter residue;
(6) Preparing a manganese sulfate solution, namely extracting and purifying the manganese solution by feeding the second filtrate into a P507 extraction line, saponifying a P507 organic extracting agent with alkali, wherein the saponification rate is 55 percent, the P507 organic extracting agent comprises a P507 extracting agent with the volume fraction of 20 percent and sulfonated kerosene with the volume fraction of 80 percent, saponifying the P507 organic extracting agent by level 1, performing 7-level countercurrent extraction, washing the P507 organic extracting agent by level 10, and performing 8-level back extraction to obtain a pure manganese sulfate solution, wherein the feed liquid comprises: acid washing: acid reaction: the volume flow ratio of the saponified P507 organic extracting agent is 3.5:0.8:0.17:1, washing a sulfuric acid solution with the acid concentration of 0.8mol/L, back-extracting a sulfuric acid solution with the back-acid concentration of 3.2mol/L, and recycling the back-extracted P507 organic extractant;
(7) Adding sulfuric acid into the manganese sulfate solution obtained in the step (6) to adjust the pH value of the solution to be 1.35, then concentrating and crystallizing until the Baume degree is 50.5, the concentration temperature is 103 ℃, then cooling, when the temperature is reduced to 80 ℃, the temperature reduction rate in the process is 3.5 ℃/h, then cooling to 55 ℃, the temperature reduction rate in the process is 2.3 ℃/h, the temperature of 55 ℃ is maintained for 0.6 hour, meanwhile, 29kg of manganese sulfate seed crystal is added into the solution according to each cubic meter, then the temperature is continuously reduced to 40 ℃, the temperature reduction rate in the process is 1.5 ℃/h, then the temperature is continuously reduced to 14 ℃, the temperature reduction rate in the process is 2.8 ℃/h, then carrying out solid-liquid separation by using a horizontal screw centrifuge, then carrying out fluidized bed drying, and carrying out screening by using a classifying screen to obtain manganese sulfate crystals, wherein the mesh number of an upper screen is 15 meshes, the mesh number of a lower screen is 45 meshes, and oversize and undersize products are used as the crystals.
The reducing agent in the step (2) is sulfurous acid, salt, metal simple substance powder and ferrous salt.
And (5) concentrating and crystallizing the raffinate obtained by extraction in the step (6) to obtain ammonium chloride crystals.
Roasting the second filter residue obtained in the step (5) at 208 ℃ for 2.5 hours, introducing pure oxygen during roasting, roasting in an oxidizing atmosphere, continuously turning over the second filter residue during roasting, washing with 89 ℃ hot water to wash away nickel sulfate, cobalt sulfate, cadmium sulfate and copper sulfate to obtain a third filtrate and a third filter residue, adding 3.5mol/L sodium hydroxide solution into the third filter residue, reacting at 78 ℃, filtering to obtain a fourth filtrate and a fourth filter residue, concentrating and crystallizing the fourth filtrate to obtain sodium fluoride, returning to remove calcium and magnesium, adding hydrochloric acid solution into the obtained fourth filter residue to adjust the pH value of the solution to be 1.35, reacting at 73 ℃ for 2.5 hours, cooling to 13 ℃ and filtering, obtaining a fifth filtrate and a fifth filter residue, wherein the fifth filter residue is lead chloride crystals, adding sulfate into the fifth filtrate for precipitation to obtain calcium sulfate, concentrating and crystallizing the filtrate for filtering calcium sulfate precipitation residues to obtain magnesium chloride crystals, completely extracting metal ions onto a P507 organic extractant by using the P507 organic extractant, measuring the contents of nickel ions, cobalt ions, copper ions and cadmium ions in the P507 organic extractant, then performing four-stage back extraction by using 0.5mol/L hydrochloric acid solution, performing first-stage back extraction on the nickel ions to obtain a nickel chloride solution, wherein the first-stage back extraction stage number is 4.3, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of nickel ions in the P507 organic extractant is determined by performing back extraction on cadmium ions at a second stage to obtain a cadmium chloride solution, the number of the back extraction stages at the second stage is 5, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of cadmium ions in the P507 organic extracting agent is determined by performing back extraction on cobalt ions to obtain a cobalt chloride solution in a third stage, the number of the back extraction stages in the third stage is 5, and the volume flow ratio of 0.5mol/L hydrochloric acid solution to the P507 organic extracting agent is 0.25: the mole number of cobalt ions in the P507 organic extractant is determined, copper ions are stripped in the fourth stage to obtain a copper chloride solution, the stripping stage number of the fourth stage is 4, and the volume flow ratio of 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: moles of copper ions in the P507 organic extractant.
The manganese sulfate crystal seeds in the step (7) are subjected to dry ball milling for 1-2 hours, and the mass ratio of the grinding balls to the manganese sulfate crystals is 4.3:1, grinding the grinding balls to be 0.8mm in particle size, and screening the grinded materials to obtain the manganese sulfate seed crystal with the particle size of 0.04mm.
Analytical structure of manganese sulfate crystal
Item Mn Zn Cu Co Ni Pb
Numerical value 99.86％ 11ppm 0.7ppm 2.1ppm 3.4ppm 6.5ppm
Ca Mg Cd Na Cr Al Fe
2.5ppm 5.3ppm 0.2ppm 2.5ppm 1.5ppm 2.7ppm 0.5ppm
Analysis structure of zinc sulfate crystal
Item Zn Mn Cu Co Ni Pb
Numerical value 99.75％ 10.3ppm 0.5ppm 4.4ppm 2.2ppm 6.5ppm
Ca Mg Cd Na Cr Al Fe
2.5ppm 5.4ppm 1.2ppm 2.5ppm 2.7ppm 2.1ppm 0.1ppm
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (5)

1. A method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries is characterized by comprising the following steps:
(1) Crushing the waste zinc-manganese battery, namely putting the zinc-manganese battery into a crusher to be crushed into powder with the particle size of below 200 um;
(2) Dissolving a zinc-manganese battery powder material, namely dissolving the zinc-manganese battery powder material according to a solid-to-liquid ratio of 3-6:1, adding bottom water, simultaneously adding acid to maintain the pH value of 1-1.2 in the reaction process, maintaining the reaction temperature of 75-90 ℃, stirring at the rotating speed of 50-500r/min, taking a filter residue sample after reacting for 3-4 hours, detecting the manganese content of the filter residue, adding a reducing agent according to 1-3 times of the mass of manganese in the filter residue, and reacting for 1-4 hours under the conditions of pH value of 1-3, temperature of 30-90 ℃ and stirring at the rotating speed of 300-500r/min, so that the zinc-manganese content in the leached residue is reduced to be below 0.5 percent;
(3) Removing iron and aluminum, adding the crushed powder material obtained in the step (1) according to 2-3 times of the mass of iron in the leaching solution, reacting at the temperature of 70-90 ℃ until the pH value of the solution is 4.8-5.5, and then reacting for 2-4 hours at the pH value;
(4) Separating zinc and manganese and preparing zinc sulfate, namely separating solid and liquid of materials after iron and aluminum removal to obtain first filtrate and first filter residue, extracting and separating zinc and manganese from the first filtrate by using a P204 organic extracting agent, firstly saponifying the P204 extracting agent by using alkali, wherein the saponification rate is 50-70%, the P204 organic extracting agent comprises 10-30% of P204 extracting agent and 70-90% of diluent sulfonated kerosene by volume fraction, carrying out 6-10 level countercurrent extraction on the saponified P204 organic extracting agent and the first filtrate, washing at 6-12 level, carrying out 4-8 level back extraction, and carrying out back extraction to obtain pure zinc sulfate solution, wherein the feed liquid comprises: acid washing: acid reaction: the volume flow ratio of the saponified P204 organic extractant is 3-5:0.5-1:0.1-0.3:1, sulfuric acid solution with washing acid concentration of 0.5-1mol/L, sulfuric acid solution with counter acid concentration of 2-4mol/L and P204 organic extractant after back extraction are recycled to obtain pure zinc sulfate solution, and zinc sulfate crystals are obtained through concentration, evaporation and crystallization;
(5) Removing impurities, namely adjusting the pH of raffinate after zinc extraction back to 1.5-2.5 by using acid, then adding a heavy metal catching agent according to 1.1-1.5 times of the total molar number of cobalt, nickel, cadmium, lead and copper metal, reacting for 1-3 hours at 40-60 ℃, adjusting the pH of the solution to 3-5.5, adding fluoride according to 2.3-2.5 times of the molar number of calcium and magnesium at the pH of 3-5.5, reacting for 1-3 hours at 80-95 ℃, and filtering to obtain a second filtrate and a second filter residue;
(6) Preparing a manganese sulfate solution, namely extracting and purifying the manganese solution by feeding the second filtrate into a P507 extraction line, saponifying a P507 organic extracting agent with alkali, wherein the saponification rate is 50-70%, the P507 organic extracting agent comprises 10-30% of a P507 extracting agent and 70-90% of sulfonated kerosene which are used as diluents in volume fraction, the saponification is performed by level 1, the countercurrent extraction is performed by level 4-8, the washing is performed by level 6-10, and the back extraction is performed by level 4-8 to obtain a pure manganese sulfate solution, wherein the feed liquid comprises: acid washing: acid reaction: the volume flow ratio of the saponified P507 organic extracting agent is 2-4:0.5-1:0.1-0.3:1, washing a sulfuric acid solution with the acid concentration of 0.5-1mol/L, back-extracting a sulfuric acid solution with the back-acid concentration of 2-5mol/L, and recycling the back-extracted P507 organic extractant;
(7) Adding sulfuric acid into the manganese sulfate solution obtained in the step (6) to adjust the pH value of the solution to be 1-1.5, then concentrating and crystallizing to a Baume degree of 50-52, concentrating at a temperature of 100-110 ℃, then cooling to 80 ℃, wherein the cooling rate in the process is 3-4.5 ℃/h, then cooling to 55 ℃, the cooling rate in the process is 2-2.5 ℃/h, maintaining the temperature of 55 ℃ for 0.5-1 hour, simultaneously adding 25-35kg of manganese sulfate seed crystals per cubic meter of the solution, then continuously cooling to 40 ℃, the cooling rate in the process is 1-1.5 ℃/h, then continuously cooling to 10-20 ℃, the cooling rate in the process is 2.5-3 ℃/h, then performing solid-liquid separation by using a horizontal screw centrifuge, then feeding into a fluidized bed for drying, and screening by using a grading screen to obtain manganese sulfate crystals, wherein the mesh number of an upper screen is 15-20 meshes, the mesh number of a lower screen is 40-50 meshes, and oversize and undersize materials are used as the crystals.
2. The method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries according to claim 1, characterized in that: the reducing agent in the step (2) is sulfurous acid, salt, metal simple substance powder and ferrous salt.
3. The method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries according to claim 1, characterized in that: and (4) concentrating and crystallizing raffinate obtained by extraction in the step (6) to obtain ammonium chloride crystals.
4. The method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries according to claim 1, characterized in that: roasting the second filter residue obtained in the step (5) at the temperature of 200-230 ℃ for 2-3 hours, introducing pure oxygen during roasting, roasting in an oxidizing atmosphere, continuously turning over the second filter residue during roasting, washing with hot water at the temperature of 80-95 ℃, washing away nickel sulfate, cobalt sulfate, cadmium sulfate and copper sulfate to obtain a third filtrate and a third filter residue, adding 3-4mol/L of sodium hydroxide solution into the third filter residue, reacting at the temperature of 70-80 ℃, filtering to obtain a fourth filtrate and a fourth filter residue, concentrating and crystallizing the fourth filtrate to obtain sodium fluoride, returning to remove calcium and magnesium, adding hydrochloric acid solution into the obtained fourth filter residue to adjust the pH value of the solution to 1-1.5, reacting at the temperature of 70-80 ℃ for 2-3 hours, then cooling to the temperature of 10-15 ℃, filtering to obtain a fifth filtrate and a fifth filter residue, wherein the fifth filter residue is lead chloride crystals, sulfate is added into the fifth filtrate for precipitation to obtain calcium sulfate, the filtrate for filtering the calcium sulfate precipitation residue is concentrated and crystallized to obtain magnesium chloride crystals, the third filtrate adopts a P507 organic extractant to completely extract metal ions onto the P507 organic extractant, the content of nickel ions, cobalt ions, copper ions and cadmium ions in the P507 organic extractant is measured, then 0.5mol/L hydrochloric acid solution is adopted for four-stage back extraction, the first stage of back extraction is used for obtaining nickel chloride solution, the number of the first stage of back extraction is 4-5, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of nickel ions in the P507 organic extractant, cadmium ions are back-extracted at a second stage to obtain a cadmium chloride solution, the number of the back-extraction stages at the second stage is 4-5, and the volume flow ratio of 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of cadmium ions in the P507 organic extractant is determined, cobalt ions are reversely extracted in the third section to obtain a cobalt chloride solution, the number of the reverse extraction stages in the third section is 4-5, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: the mole number of cobalt ions in the P507 organic extractant, copper ions are stripped in the fourth stage to obtain a copper chloride solution, the stripping stage number of the fourth stage is 4-5, and the volume flow ratio of the 0.5mol/L hydrochloric acid solution to the P507 organic extractant is 0.25: moles of copper ions in the P507 organic extractant.
5. The method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries according to claim 1, characterized in that: the manganese sulfate crystal seeds in the step (7) are subjected to dry ball milling for 1-2 hours, and the mass ratio of the grinding balls to the manganese sulfate crystals is 4-5:1, grinding the grinding balls to be 0.5-2mm in particle size, and screening the grinded particles to obtain the manganese sulfate seed crystal with the particle size of 0.02-0.05mm.
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CN109761289B (en) * 2018-12-29 2021-08-03 南通北新新能源科技有限公司 Gas storage type wet recovery process for lithium cobaltate battery
CN109761289A (en) * 2018-12-29 2019-05-17 启东市北新无机化工有限公司 A kind of gas storage type cobalt acid lithium battery wet recycling process
CN110372038A (en) * 2019-08-15 2019-10-25 衢州华友资源再生科技有限公司 A kind of method of raw material containing manganese preparation LITHIUM BATTERY manganese sulfate and its LITHIUM BATTERY manganese sulfate of preparation
CN110482613A (en) * 2019-08-23 2019-11-22 安庆市长虹化工有限公司 A kind of technique preparing manganese sulfate using Waste Sulfuric Acid in DYE PRODUCTION
CN114555839A (en) * 2019-10-18 2022-05-27 杰富意钢铁株式会社 Method and apparatus for recovering manganese from waste dry battery
CN114466941A (en) * 2019-10-18 2022-05-10 杰富意钢铁株式会社 Method and apparatus for recovering manganese from waste dry battery
CN111170368A (en) * 2020-02-27 2020-05-19 中国恩菲工程技术有限公司 Treatment system and treatment method for reducing content of impurities in soluble manganese sulfate solution
EP3904546A1 (en) * 2020-04-30 2021-11-03 Fortum OYJ Process for recovering components from alkaline batteries
CN111763828B (en) * 2020-05-26 2022-04-01 常州大学 Green comprehensive recovery method for valuable metal of nickel-metal hydride battery
CN111763828A (en) * 2020-05-26 2020-10-13 常州大学 Green comprehensive recovery method for valuable metal of nickel-metal hydride battery
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CN112079391A (en) * 2020-07-31 2020-12-15 浙江天能新材料有限公司 Method for preparing battery-grade manganese sulfate
CN112281001A (en) * 2020-10-22 2021-01-29 北京博萃循环科技有限公司 Method for preparing manganese salt by using manganese-containing waste liquid
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