CN107437626A - Method for preparing carbon-coated manganese phosphate from waste zinc-manganese battery - Google Patents
Method for preparing carbon-coated manganese phosphate from waste zinc-manganese battery Download PDFInfo
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Abstract
The invention discloses a method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries. The method comprises the steps of pretreating, crushing and sorting the waste zinc-manganese batteries to obtain manganese dioxide, purifying to obtain a pure manganese solution, extracting a di (2,4,4-trimethylpentyl) phosphonic acid saponification solution to obtain di (2,4,4-trimethylpentyl) manganese phosphonate, and performing high-temperature oxidation catalytic decomposition to obtain the carbon-coated manganese phosphate. The method for preparing the carbon-coated manganese phosphate from the waste zinc-manganese battery realizes the cyclic utilization and high-end utilization of the waste zinc-manganese battery, recovers zinc in the waste zinc-manganese battery, has simple process and small waste water production amount, and the obtained manganese phosphate is the carbon-coated manganese phosphate, has low impurity content, is of a spherical structure, has high tap density and narrow particle size distribution, and can regulate and control the carbon content.
Description
Technical Field
The invention relates to a method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries, belonging to the field of new energy battery materials.
Background
The theoretical specific capacity of the lithium iron phosphate is 170mAh/g, the discharge platform is 3.4V, and the energy density of the material is 578Wh/kg; the theoretical specific capacity of the lithium manganese phosphate is 171mAh/g, the discharge platform is 4.1V, and the energy density of the material is 701Wh/kg, which is 21 percent higher than that of the material.
The lithium manganese iron phosphate has the same capacity as that of lithium iron phosphate theoretically, and is 170mAh/g, but the electrode potential of the lithium manganese iron phosphate relative to Li +/Li is 4.1V, which is much higher than 3.4V of the lithium iron phosphate, and the lithium manganese iron phosphate is positioned in a stable electrochemical window of an organic electrolyte system. The high potential of 4.1V provides the manganese lithium phosphate with the potential advantage of high energy density, which is the greatest advantage over lithium iron phosphate, and if the actual capacity of the manganese lithium phosphate is exerted to the same extent as that of the lithium iron phosphate, the energy density of the manganese lithium phosphate is increased by 35% as compared with that of the current lithium iron phosphate, and the energy density of the manganese lithium phosphate can be increased by more than 20% as compared with that of the lithium manganese phosphate with the same voltage. In addition, the lithium manganese phosphate has low raw material cost and is environment-friendly, so the battery and the material have wide market prospect.
On the other hand, as a precursor of lithium manganese iron phosphate or lithium manganese phosphate, manganese dioxide and the like are generally used conventionally, but manganese phosphate is receiving more and more attention as a precursor thereof. And the carbon-coated manganese phosphate has better conductivity, so that the prepared anode material has better performance.
Disclosure of Invention
In view of the above, the invention provides a method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries, which uses the waste zinc-manganese batteries as raw materials, realizes the cyclic utilization and high-end utilization of the waste zinc-manganese batteries, simultaneously recovers zinc therein, has simple process and less wastewater generation amount, obtains manganese phosphate as carbon-coated manganese phosphate, has low impurity content, spherical structure, high tap density and specific surface of 10-15m 2 The grain diameter distribution is narrow, and the carbon content can be adjusted and controlled.
The invention solves the technical problems by the following technical means:
the invention discloses a method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries, which comprises the following steps:
(1) Pretreating, namely crushing the waste zinc-manganese battery until the particle size of the material is 0.1-1mm, sorting the material in integrated equipment of air separation and electrostatic sorting, adding pure water into the obtained black powder material for slurrying, adding sodium hydroxide solution into the slurried material, reacting for 3-4 hours at 90-95 ℃ in a sealed reaction kettle, simultaneously arranging an exhaust pipe, inserting the exhaust pipe into the pure water to obtain ammonia solution, after the reaction is finished, filtering and washing to obtain first filtrate and first filter residue;
(2) Purifying, adding acid solution into the first filter residue,simultaneously adding rough manganese powder, maintaining the pH value of the solution at 0.5-1.5, reacting at 70-85 ℃ for 5-6 hours, then continuously adding the rough manganese powder, adjusting the pH value of the solution to 5.5-6, then introducing air, completely oxidizing ferrous ions into ferric iron and precipitating, then filtering to obtain a second filtrate and a second filter residue, adjusting the pH value of the second filtrate to 2-2.5, adding ammonium sulfide, reacting at 45-65 ℃ for 2-3 hours, and adding ammonium sulfide with the mol number of Cu in the second filtrate 2+ 、Co 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 1.1-1.25 times of the total mole number, then filtering to obtain a third filtrate and a third filter residue, mixing the third filtrate with a P507 extractant saponified by ammonia water, and performing 5-7 stages of countercurrent extraction, 5-7 stages of countercurrent washing, 5-7 stages of first countercurrent back extraction, 4-6 stages of second countercurrent back extraction and 1-2 stages of countercurrent water washing to obtain a raffinate, a first stage of strip liquor and a second stage of strip liquor, wherein the volume flow ratio of the third filtrate, the P507 extractant saponified by ammonia water, a washing solution, the first strip liquor, the second strip liquor and the washing water is 0.5-0.15: 0.2-0.25, washing with 0.5-1mol/L hydrochloric acid, 1-1.5mol/L hydrochloric acid as primary stripping solution, 1.5-2mol/L hydrochloric acid as secondary stripping solution, adding heavy metal scavenger into the primary stripping solution, reacting at pH2.5-3.5 for 2-3 hours, maintaining the temperature at 30-40 ℃, filtering, adding ammonium fluoride into the filtrate, reacting at 90-95 ℃ for 2-3 hours to make the calcium and magnesium ions in the filtrate lower than 5mg/L, and filtering to obtain pure manganese solution;
(3) Preparing a di (2,4,4-trimethylpentyl) phosphonic acid saponification solution, and performing 10-12-stage countercurrent extraction, 8-10-stage countercurrent acid solution washing and 4-5-stage countercurrent pure water washing on the di (2,4,4-trimethylpentyl) phosphonic acid saponification solution and a pure manganese solution to obtain a washed organic phase;
(4) Adding 1-bromo-2-methylpropane into the organic phase washed by water in the step (3), mixing and stirring for 0.5-1 hour at the temperature of 40-50 ℃, then standing while adding ultrasonic waves for layering, taking the upper organic phase, roasting for 2-3 hours at the temperature of 450-500 ℃, simultaneously adding a catalyst, and introducing CO in the roasting process 2 And O 2 Maintaining CO in the mixed gas 2 And O 2 The volume ratio of (1) to (2-2.5) is as follows, the material is completely mixed with liquidAnd after the black solid is changed, continuing to react for 0.5 to 3 hours, stopping the reaction, and cooling to obtain the high-purity carbon-coated manganese phosphate.
The integrated equipment for winnowing and electrostatic separation comprises a spiral blanking machine, wherein the spiral blanking machine is connected with a storage bin, at least one layer of magnetic net is arranged in the storage bin, the aperture of the magnetic net is 1-1.5mm, the magnetic net is connected with an electromagnet, an electrostatic generator is arranged on one side of the middle of the storage bin, a first discharge port is arranged below the electrostatic generator, an air outlet is formed in one side of the lower portion of the storage bin, a second discharge port is formed below the air outlet, and a third discharge port is formed in the bottom of the storage bin.
In the step (1), the concentration of the sodium hydroxide solution is 2-3mol/L, the mass ratio of the black powder material to the sodium hydroxide is 1.5-0.6, the first filtrate is added with sulfuric acid to adjust the pH value of the solution to 7.5-8, so as to obtain zinc hydroxide precipitate, the zinc hydroxide precipitate is filtered, dissolved by adding sulfuric acid, and concentrated and crystallized to obtain zinc sulfate crystals.
In the step (2), the second filter residue is returned to be mixed with the first filter residue for acid dissolution, the mass ratio of the crude manganese powder to the manganese dioxide in the first filter residue is 1:0.7-0.8, the third filter residue is passed through, and the preparation method of the P507 extracting agent after the ammonia water saponification comprises the steps of uniformly mixing the P507 extracting agent with No. 260 solvent oil, wherein the concentration of P507 is 0.5-0.6mol/L, then adding ammonia water for mixing reaction at normal temperature for 0.5-1 hour, standing for layering, wherein the organic phase is the P507 extracting agent after the ammonia water saponification, the molar ratio of P507 to ammonia is 1.6-1.8, the heavy metal catching agent is an organic sulfur compound, and the addition amount of the heavy metal catching agent is Cu in the primary back extraction liquid 2+ 、Co 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 2-3 times of the total mass to finally obtain the pure Mn solution]0.7-0.75mol/L, zn < 5Mg/L, ca/Mg < 5Mg/L, and other metal ion content less than 2Mg/L.
Sampling and measuring the raffinate in the extraction process in the step (2), and controlling Mn in the raffinate 2+ When the content of manganese ions is less than 5mg/L, the flow rate of the third filtrate is increased, and when the content of manganese ions is more than 10mg/L, the flow rate of the third filtrate is reduced.
The preparation method of the bis (2,4,4-trimethylpentyl) phosphonic acid saponification liquid in the step (3) comprises the steps of uniformly mixing bis (2,4,4-trimethylpentyl) phosphonic acid with 260# solvent oil, adding ammonia water for mixing reaction, mixing and reacting for 0.5-1 hour at normal temperature, standing for layering, wherein an organic phase is bis (4325 zxft 3963-trimethylpentyl) phosphonic acid saponification liquid, the molar ratio of bis (2,4,4-trimethylpentyl) phosphonic acid to ammonia is 1.
The volume ratio of the organic phase washed by water in the step (4) to the 1-bromo-2-methylpropane is 1:3-5, and the lower organic phase obtained after layering is distilled to separate the 1-bromo-2-methylpropane from the No. 260 solvent oil.
The catalyst in the step (4) is one of nitric acid, perchloric acid and hypochlorous acid, the molar ratio of the catalyst to the upper organic phase is 1:3-5, and the pressure is 1-3Mpa.
The invention adopts waste zinc-manganese batteries as raw materials, and the waste zinc-manganese batteries comprise the following components:
| index (I) | Mn | Zn | Plastic material | Ni |
| Numerical value | 20-25％ | 15-20％ | 5-10％ | 1-2％ |
| NH 4 Cl | Co | Ca | Si | Al |
| 3-8％ | 0.5-2％ | 0.5-1％ | 0.5-1％ | 0.1-0.2％ |
| Cr | Cu | Mg | Fe | Na |
| 0.5-0.8％ | 0.5-2％ | 1-2％ | 5-10％ | 0.5-1％ |
From data, the components of the waste zinc-manganese battery are complex, the separation of zinc and manganese and the separation and purification of other impurities are complex, the cost is high, the waste water generation amount is large, generally speaking, the recovery value or the recovery yield is basically zero, and the waste water can be realized only by realizing high-end recycling.
The invention adopts the integrated equipment of air separation and electrostatic separation to carry out separation, the integrated equipment of air separation and electrostatic separation comprises a spiral blanking machine, the spiral blanking machine is connected with a storage bin, at least one layer of magnetic conduction net is arranged in the storage bin, the aperture of the magnetic conduction net is 1-1.5mm, the magnetic conduction net is connected with an electromagnet, one side of the middle part of the storage bin is provided with an electrostatic generator, the lower part of the electrostatic generator is provided with a first discharge hole, one side of the lower part of the storage bin is provided with an air outlet, the lower part of the air outlet is provided with a second discharge hole, the bottom of the storage bin is provided with a third discharge hole, the feeding can be automatically realized by adopting the spiral blanking machine, meanwhile, the magnetic conduction net is adopted and is connected with the electromagnet, the magnetic conduction net can suck magnetic materials and simultaneously slow down the falling speed of the materials, the electrostatic separation of materials such as plastics can be realized, the separation of materials such as manganese dioxide and zinc metal or iron metal can be realized by adopting air separation, and the enrichment and purification of manganese dioxide can be preliminarily realized.
Adding an acid solution into the first filter residue, simultaneously adding rough manganese powder, maintaining the pH value of the solution to be 0.5-1.5, reacting for 5-6 hours at 70-85 ℃, taking the rough manganese powder as a reducing agent, avoiding the introduction of impurities, leaching and reducing manganese dioxide to obtain manganese ions with a divalent state, continuously adding the rough manganese powder, adjusting the pH value of the solution to be 5.5-6, introducing air, completely oxidizing ferrous ions into ferric iron and precipitating, simultaneously removing metal ions such as Cr/Al/Si/Sn/Ti and the like, filtering to obtain a second filtrate and a second filter residue, wherein the second filter residue contains the manganese powder and unreacted manganese dioxide, and returning to continuously dissolving.
Adjusting the pH of the second filtrate to 2-2.5, adding ammonium sulfide, reacting at 45-65 deg.C for 2-3 hr, wherein the molar number of the added ammonium sulfide is Cu in the second filtrate 2+ 、Co 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 1.1-1.25 times of the total mole number, filtering to obtain a third filtrate and a third filter residue, wherein sulfide can effectively remove Cu 2+ 、Co 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ The plasma is generated by the plasma of the metal ions,
mixing the third filtrate with a P507 extractant saponified by ammonia water, and performing 5-7-stage countercurrent extraction, 5-7-stage countercurrent washing, 5-7-stage primary countercurrent back extraction, 4-6-stage secondary countercurrent back extraction and 1-2-stage countercurrent water washing to obtain raffinate, primary strip liquor and secondary strip liquor, wherein the volume flow ratio of the third filtrate, the P507 extractant saponified by ammonia water, the washing solution, the primary strip liquor, the secondary strip liquor and the washing water is 0.1-0.15:0.2-0.25, washing with 0.5-1mol/L hydrochloric acid, 1-1.5mol/L hydrochloric acid as primary stripping solution, 1.5-2mol/L hydrochloric acid as secondary stripping solution, adding heavy metal scavenger into the primary stripping solution, reacting at pH2.5-3.5 for 2-3 hr, maintaining the temperature at 30-40 deg.C, filtering, adding ammonium fluoride into the filtrate, reacting at 90-95 deg.C for 2-3 hr to make the calcium and magnesium ions in the filtrate lower than 5mg/L, filtering to obtain pure manganese solution, and according to the extraction sequence of P507, preferentially selecting Fe 3+ /Zn 2+ Extracting and then extracting Ca 2+ /Mn 2+ /Cu 2+ Then extracting Mg again 2+ /Ni 2+ /Co 2+ The invention adopts an extracting agent to extract manganese ions into an organic phase, and because of the problem of the extraction sequence, ferric iron, zinc ions, calcium ions and part of copper ions can be extracted, thereby controlling Mn in the raffinate 2+ When the content of manganese ions is less than 5mg/L and the content of manganese ions is more than 10mg/L, the flow of the third filtrate is increased, when the content of manganese ions is more than 10mg/L, the flow of the third filtrate is reduced, the large amount of magnesium ions and cobalt nickel ions can be prevented from being extracted, the difficulty of subsequent purification is reduced, then two-stage back extraction is adopted, the manganese ions are back extracted by the first-stage back extraction, meanwhile, part of calcium ions and copper ions are back extracted, the zinc ions are back extracted and enriched by the second-stage back extraction, then the back extracted manganese solution is subjected to heavy metal precipitation by a heavy metal trapping agent, calcium and magnesium are removed by fluoride, and the manganese solution with high purity can be obtained.
Preparing a bis (2,4,4-trimethylpentyl) phosphonic acid saponification solution, carrying out 10-12-stage countercurrent extraction, 8-10-stage countercurrent acid solution washing and 4-5-stage countercurrent pure water washing on the bis (2,4,4-trimethylpentyl) phosphonic acid saponification solution and a pure manganese solution to obtain an organic phase after water washing, and extracting manganese ions by using bis (2,4,4-trimethylpentyl) phosphonic acid to obtain an organic phase of bis (2,4,4-trimethylpentyl) manganese phosphonate, and further separating from ions such as magnesium, sodium, cobalt, nickel and the like to further improve the purity of the organic phase.
Adding 1-bromo-2-methylpropane into the washed organic phase, mixing and stirring at 40-50 deg.C for 0.5-1 hr, standing while adding ultrasonic wave for layering, collecting the upper organic phase, calcining at 450-500 deg.C for 2-3 hr while adding catalyst, introducing CO during calcination 2 And O 2 Maintaining CO in the mixed gas 2 And O 2 The volume ratio of (2-2.5) is as follows, in the reaction process, after the material is completely changed into black solid from liquid, the reaction is continued for 0.5-3 hours, the reaction is stopped, and the high-purity carbon-coated manganese phosphate is obtained after cooling. 1-bromo-2-methylpropane is adopted and can be mutually soluble with 260# solvent oil, bis (2,4,4-trimethylpentyl) manganese phosphonate independently forms a phase to realize the separation with 260# solvent oil, the obtained 260# solvent oil can be returned for use after the 1-bromo-2-methylpropane and the 260# solvent oil are subjected to distillation separation, the obtained bis (2,4,4-trimethylpentyl) manganese phosphonate is subjected to catalytic decomposition at high temperature to decompose carbon chains in the manganese phosphonate into carbon dioxide and water, and meanwhile, a certain atmosphere is maintained to avoid the complete combustion of carbon, so that the carbon is coated on the manganese phosphate, the reaction time is controlled, and the coating amount of the carbon can be controlled.
Because the lithium manganese phosphate or the lithium manganese iron phosphate and the lithium iron phosphate anode material have certain problems, namely poor conductivity, the improvement of the conductivity is generally realized by two ways of reducing the granularity of the lithium iron phosphate and coating the conductive material, and the carbon-coated manganese phosphate prepared by the method has greatly improved conductivity.
Meanwhile, the waste water generated by liquid phase precipitation synthesis is avoided, the waste water amount is greatly reduced, and the process flow is short.
The 260# solvent oil is recycled, and simultaneously, the ammonium chloride and the like in the waste zinc-manganese battery can be effectively utilized to recover the zinc in the waste zinc-manganese battery, so that the cost can be reduced.
The indexes of the finally obtained manganese phosphate are as follows:
| index (I) | Manganese content | Phosphorus content | Tap density | Carbon content | Na |
| Numerical value | 39.5±0.3％ | 14.9±0.1％ | 1.2±0.1g/mL | 1.8-2.2％ | 1-2ppm |
| Cr | Ca | Mg | Na | Ni | Co |
| 0.1-0.5ppm | 5-7ppm | 3-4ppm | 1-5ppm | 1-2ppm | 0.1-0.5ppm |
| Fe | Zn | Cu | Ti | Al | Si |
| 4-6ppm | 5-10ppm | 0.1-0.5ppm | 0.1-0.5ppm | 1-2ppm | 1-2ppm |
| D10 | D50 | D90 | BET | Sulfate radical | Chloride ion |
| 0.7-0.8μm | 1-1.5μm | 1.9-2.1μm | 12.5±2.5m 2 /g | 3-5ppm | 1-3ppm |
The invention has the beneficial effects that:
1. the waste zinc-manganese battery is used for preparing the high-purity carbon-coated manganese phosphate, the cost is low, and the process is short.
2. The discharge amount of waste water is less, compared with liquid phase precipitation, the waste water amount is greatly reduced, about 80 tons of waste water is generated by each ton of manganese phosphate produced by liquid phase precipitation, and only 20-30 tons of waste water is generated by the method.
3. The method adopts catalytic oxidation decomposition to prepare the carbon-coated manganese phosphate, and the obtained carbon-coated manganese phosphate has high purity, narrow particle size distribution and high tap density.
Detailed Description
The invention will be described in detail with reference to specific embodiments, and the method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries of the embodiment comprises the following steps:
(1) Pretreating, namely crushing the waste zinc-manganese battery until the particle size of the material is 0.1-1mm, sorting the material in integrated equipment of air separation and electrostatic sorting, adding pure water into the obtained black powder material for slurrying, adding sodium hydroxide solution into the slurried material, reacting for 3-4 hours at 90-95 ℃ in a sealed reaction kettle, simultaneously arranging an exhaust pipe, inserting the exhaust pipe into the pure water to obtain ammonia solution, after the reaction is finished, filtering and washing to obtain first filtrate and first filter residue;
(2) Purifying, adding acid solution into the first filter residue, adding crude manganese powder, maintaining the pH of the solution at 0.5-1.5, reacting at 70-85 ℃ for 5-6 hours, continuously adding the crude manganese powder, adjusting the pH of the solution to 5.5-6, introducing air, completely oxidizing ferrous ions into ferric iron, precipitating, filtering to obtain second filtrate and second filter residue, adjusting the pH of the second filtrate to 2-2.5, adding ammonium sulfide, reacting at 45-65 ℃ for 2-3 hours, and adding ammonium sulfide with the molar number of the ammonium sulfide being Cu in the second filtrate 2+ 、Co 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 1.1 to 1.25 times of the total mole number, then filtering to obtain a third filtrate and a third filter residue, mixing the third filtrate with a P507 extractant saponified by ammonia water, and performing 5 to 7-stage countercurrent extraction, 5 to 7-stage countercurrent washing, 5 to 7-stage one-time countercurrent back extraction, 4 to 6-stage two-stage countercurrent back extraction and 1 to 2-stage countercurrent water washing to obtain raffinate, a first-stage back extraction solution and a second-stage back extraction solution, wherein the third filtrate, the third filter residue and the third filter residue are obtained by the steps of,The volume flow ratio of the P507 extracting agent, the washing liquid, the primary stripping liquid, the secondary stripping liquid and the washing water after the ammonia water saponification is 0.5-0.65: 0.2-0.25, washing with 0.5-1mol/L hydrochloric acid, 1-1.5mol/L hydrochloric acid as primary stripping solution, 1.5-2mol/L hydrochloric acid as secondary stripping solution, adding heavy metal scavenger into the primary stripping solution, reacting at pH2.5-3.5 for 2-3 hours, maintaining the temperature at 30-40 ℃, filtering, adding ammonium fluoride into the filtrate, reacting at 90-95 ℃ for 2-3 hours to make the calcium and magnesium ions in the filtrate lower than 5mg/L, and filtering to obtain pure manganese solution;
(3) Preparing a di (2,4,4-trimethylpentyl) phosphonic acid saponification solution, and performing 10-12-stage countercurrent extraction, 8-10-stage countercurrent acid solution washing and 4-5-stage countercurrent pure water washing on the di (2,4,4-trimethylpentyl) phosphonic acid saponification solution and a pure manganese solution to obtain an organic phase after water washing;
(4) Adding 1-bromo-2-methylpropane into the organic phase washed by water in the step (3), mixing and stirring for 0.5-1 hour at the temperature of 40-50 ℃, then standing while adding ultrasonic waves for layering, taking the upper organic phase, roasting for 2-3 hours at the temperature of 450-500 ℃, simultaneously adding a catalyst, and introducing CO in the roasting process 2 And O 2 Maintaining CO in the mixed gas 2 And O 2 The volume ratio of (2-2.5) is that after the materials are completely changed into black solids from liquid, the reaction is continued for 0.5-3 hours, the reaction is stopped, and the high-purity carbon-coated manganese phosphate is obtained after cooling.
The integrated equipment for winnowing and electrostatic separation comprises a spiral blanking machine, wherein the spiral blanking machine is connected with a storage bin, at least one layer of magnetic net is arranged in the storage bin, the aperture of the magnetic net is 1-1.5mm, the magnetic net is connected with an electromagnet, an electrostatic generator is arranged on one side of the middle of the storage bin, a first discharge port is arranged below the electrostatic generator, an air outlet is formed in one side of the lower portion of the storage bin, a second discharge port is formed below the air outlet, and a third discharge port is formed in the bottom of the storage bin.
In the step (1), the concentration of the sodium hydroxide solution is 2-3mol/L, the mass ratio of the black powder material to the sodium hydroxide is 1.5-0.6, the first filtrate is added with sulfuric acid to adjust the pH value of the solution to 7.5-8, so as to obtain zinc hydroxide precipitate, the zinc hydroxide precipitate is filtered, dissolved by adding sulfuric acid, and concentrated and crystallized to obtain zinc sulfate crystals.
In the step (2), the second filter residue is returned to be mixed with the first filter residue for acid dissolution, the mass ratio of the crude manganese powder to the manganese dioxide in the first filter residue is 1:0.7-0.8, the third filter residue is passed through, and the preparation method of the P507 extracting agent after the ammonia water saponification comprises the steps of uniformly mixing the P507 extracting agent with No. 260 solvent oil, wherein the concentration of P507 is 0.5-0.6mol/L, then adding ammonia water for mixing reaction at normal temperature for 0.5-1 hour, standing for layering, wherein the organic phase is the P507 extracting agent after the ammonia water saponification, the molar ratio of P507 to ammonia is 1.6-1.8, the heavy metal catching agent is an organic sulfur compound, and the addition amount of the heavy metal catching agent is Cu in the primary back extraction liquid 2+ 、Co 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 2-3 times of the total mass to finally obtain the pure Mn solution]0.7-0.75mol/L, zn < 5Mg/L, ca/Mg < 5Mg/L, and other metal ion content less than 2Mg/L.
Sampling and measuring the raffinate in the extraction process in the step (2), and controlling Mn in the raffinate 2+ When the content of manganese ions is less than 5mg/L, the flow rate of the third filtrate is increased, and when the content of manganese ions is more than 10mg/L, the flow rate of the third filtrate is reduced.
The preparation method of the bis (2,4,4-trimethylpentyl) phosphonic acid saponification liquid in the step (3) comprises the steps of uniformly mixing bis (2,4,4-trimethylpentyl) phosphonic acid with 260# solvent oil, adding ammonia water for mixing reaction, mixing and reacting for 0.5-1 hour at normal temperature, standing for layering, wherein an organic phase is bis (4325 zxft 3963-trimethylpentyl) phosphonic acid saponification liquid, the molar ratio of bis (2,4,4-trimethylpentyl) phosphonic acid to ammonia is 1.
The volume ratio of the organic phase washed by water in the step (4) to the 1-bromo-2-methylpropane is 1:3-5, and the lower organic phase obtained after layering is distilled to separate the 1-bromo-2-methylpropane from the No. 260 solvent oil.
The catalyst in the step (4) is one of nitric acid, perchloric acid and hypochlorous acid, the molar ratio of the catalyst to the upper organic phase is 1:3-5, and the pressure is 1-3Mpa.
Example 1
A method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries comprises the following steps:
(1) Pretreating, namely crushing the waste zinc-manganese battery until the particle size of the material is 0.6mm, sorting the material in integrated equipment of air separation and electrostatic sorting, adding the obtained black powder material into pure water for slurrying, adding the slurried material into a sodium hydroxide solution, reacting for 3.3 hours at 92.5 ℃ in a sealed reaction kettle, simultaneously arranging an exhaust pipe, inserting the exhaust pipe into the pure water to obtain an ammonia solution, after the reaction is finished, filtering and washing to obtain a first filtrate and a first filter residue;
(2) Purifying, adding acid solution into the first filter residue, adding crude manganese powder at the same time, maintaining the pH value of the solution at 1.2, reacting for 5.5 hours at 82 ℃, further adding the crude manganese powder, adjusting the pH value of the solution to 5.8, introducing air, completely oxidizing ferrous ions into ferric iron and precipitating, filtering to obtain a second filtrate and a second filter residue, adjusting the pH value of the second filtrate to 2.3, adding ammonium sulfide, reacting for 2.5 hours at 55 ℃, and adding ammonium sulfide with the mol number of Cu in the second filtrate 2+ 、Co 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 1.21 times of the total mole number, then filtering to obtain a third filtrate and a third filter residue, mixing the third filtrate with a P507 extractant after ammonia water saponification, performing 6-stage countercurrent extraction, 6-stage countercurrent washing, 5-stage primary countercurrent back extraction, 5-stage secondary countercurrent back extraction and 2-stage countercurrent water washing to obtain a raffinate, a primary strip liquid and a secondary strip liquid, wherein the volume flow ratio of the third filtrate, the P507 extractant after ammonia water saponification, the washing liquid, the primary strip liquid, the secondary strip liquid and the washing water is 0.13:0.23, washingAdding a heavy metal capture agent into the primary stripping solution by using 0.7mol/L hydrochloric acid, wherein the primary stripping solution is 1.35mol/L hydrochloric acid, and the secondary stripping solution is 1.8mol/L hydrochloric acid, reacting at the pH of 3.1 for 2.5 hours, maintaining the temperature at 35 ℃, filtering, adding ammonium fluoride into the filtrate, reacting at the temperature of 92.5 ℃ for 2.6 hours to ensure that calcium and magnesium ions in the filtrate are lower than 5mg/L, and filtering to obtain a pure manganese solution;
(3) Preparing a di (2,4,4-trimethylpentyl) phosphonic acid saponification solution, and performing 11-stage countercurrent extraction, 8-stage countercurrent acid solution washing and 4-stage countercurrent pure water washing on the di (2,4,4-trimethylpentyl) phosphonic acid saponification solution and a pure manganese solution to obtain an organic phase after water washing;
(4) Adding 1-bromo-2-methylpropane into the organic phase washed by water in the step (3), mixing and stirring for 0.8 hour at the temperature of 45 ℃, then standing while adding ultrasonic waves for layering, taking the upper organic phase, roasting for 2.5 hours at the temperature of 465 ℃, simultaneously adding a catalyst, introducing CO in the roasting process 2 And O 2 Maintaining CO in the mixed gas 2 And O 2 The volume ratio of (2.3) is as follows, after the material is completely changed into black solid from liquid, the reaction is stopped after 1 hour of continuous reaction, and high-purity carbon-coated manganese phosphate is obtained after cooling.
Selection by winnowing and electrostatic separation integration equipment includes spiral blanking machine, spiral blanking machine is connected with the feed bin, is provided with at least one deck in the feed bin and leads the magnetic net, and the aperture of leading the magnetic net is 1.4mm, it is connected with the electro-magnet to lead the magnetic net, and middle part one side of feed bin is provided with electrostatic generator, and electrostatic generator's below is provided with first discharge gate, lower part one side air outlet of feed bin, and the below of air outlet is provided with the second discharge gate, and the bottom of feed bin is provided with the third discharge gate.
In the step (1), the concentration of the sodium hydroxide solution is 2.3mol/L, the mass ratio of the black powder material to the sodium hydroxide is 1.
In the step (2), the second filter residue is returned to be mixed with the first filter residue for continuous acid dissolution, and the rough manganese powder and the first filter residue are mixedThe mass ratio of manganese dioxide to manganese dioxide is 1 2+ 、Co 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 2.5 times of the total mass, finally obtaining pure Mn solution]0.73mol/L, zn less than 5Mg/L, ca/Mg less than 5Mg/L, and the content of other metal ions is less than 2Mg/L.
Sampling and measuring the raffinate in the extraction process in the step (2), and controlling Mn in the raffinate 2+ At 7mg/L.
The preparation method of the bis (2,4,4-trimethylpentyl) phosphonic acid saponified solution in the step (3) comprises the steps of uniformly mixing bis (2,4,4-trimethylpentyl) phosphonic acid with 260# solvent oil, wherein the concentration of bis (2,4,4-trimethylpentyl) phosphonic acid is 0.55mol/L, then adding ammonia water for mixing reaction, mixing and reacting for 0.8 hour at normal temperature, standing for layering, wherein an organic phase is the bis (2,4,4-trimethylpentyl) phosphonic acid saponified solution, the molar ratio of bis (2,4,4-trimethylpentyl) phosphonic acid to ammonia is 1.7, in the extraction process, the volume flow ratio of an organic phase, an aqueous phase, an acid solution and pure water is 0.25.
The volume ratio of the washed organic phase to the 1-bromo-2-methylpropane in the step (4) is 1.5, and the lower organic phase obtained after layering is distilled to separate the 1-bromo-2-methylpropane from the No. 260 solvent oil.
The catalyst in the step (4) is one of nitric acid, perchloric acid and hypochlorous acid, the molar ratio of the catalyst to the upper organic phase is 1:4, and the pressure is 1.5Mpa.
The final product index is as follows:
| index (I) | Manganese content | Phosphorus content | Tap density | Carbon content | Na |
| Numerical value | 39.6％ | 14.95％ | 1.28g/mL | 1.99％ | 1.2ppm |
| Cr | Ca | Mg | Na | Ni | Co |
| 0.18ppm | 6ppm | 3.5ppm | 2.8ppm | 1.95ppm | 0.43ppm |
| Fe | Zn | Cu | Ti | Al | Si |
| 4.9ppm | 8ppm | 0.25ppm | 0.35ppm | 1.2ppm | 1.2ppm |
| D10 | D50 | D90 | BET | Sulfate radical | Chloride ion |
| 0.77μm | 1.35μm | 2.0μm | 13.8m 2 /g | 4.2ppm | 2.5ppm |
Meanwhile, the final recovery rate of manganese is 97.8%, and the waste water produced by each ton of manganese phosphate is 25 tons.
Example 2
A method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries comprises the following steps:
(1) Pretreating, namely crushing the waste zinc-manganese battery until the particle size of the material is 0.6mm, sorting the material in integrated equipment of air separation and electrostatic sorting, adding the obtained black powder material into pure water for slurrying, adding the slurried material into a sodium hydroxide solution, reacting for 3.3 hours at 92.5 ℃ in a sealed reaction kettle, simultaneously arranging an exhaust pipe, inserting the exhaust pipe into the pure water to obtain an ammonia solution, after the reaction is finished, filtering and washing to obtain a first filtrate and a first filter residue;
(2) Purifying, adding acid solution into the first filter residue, adding crude manganese powder at the same time, maintaining the pH value of the solution at 1.2, reacting for 5.5 hours at 83 ℃, then continuously adding the crude manganese powder, adjusting the pH value of the solution to 5.8, then introducing air, completely oxidizing ferrous ions into ferric iron and precipitating, then filtering to obtain a second filtrate and a second filter residue, adjusting the pH value of the second filtrate to 2.3, adding ammonium sulfide, reacting for 2.5 hours at 55 ℃, and adding ammonium sulfide with the mol number of Cu in the second filtrate 2+ 、Co 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 1.21 times of the total mole number, then filtering to obtain a third filtrate and a third filter residue, mixing the third filtrate with a P507 extractant saponified with ammonia water, and performing 6-stage countercurrent extraction, 6-stage countercurrent washing, 5-stage primary countercurrent back extraction, 5-stage secondary countercurrent back extraction and 2-stage countercurrent water washing to obtain a raffinate, a primary strip liquor and a secondary strip liquor, wherein the volume flow ratio of the third filtrate, the P507 extractant saponified with ammonia water, the washing solution, the primary strip liquor, the secondary strip liquor and the washing water is 0.62: 0.24, washing by using 0.7mol/L hydrochloric acid, adding a heavy metal capture agent into the primary stripping solution which is 1.33mol/L hydrochloric acid, and adding a heavy metal capture agent into the secondary stripping solution which is 1.8mol/L hydrochloric acid, reacting at the pH value of 3.1 for 2.5 hours, maintaining the temperature at 35 ℃, filtering, adding ammonium fluoride into the filtrate, reacting at the temperature of 92.5 ℃ for 2.6 hours to ensure that calcium and magnesium ions in the filtrate are lower than 5mg/L, and filtering to obtain a pure manganese solution;
(3) Preparing a di (2,4,4-trimethylpentyl) phosphonic acid saponification solution, and performing 10-stage countercurrent extraction, 8-stage countercurrent acid solution washing and 4-stage countercurrent pure water washing on the di (2,4,4-trimethylpentyl) phosphonic acid saponification solution and a pure manganese solution to obtain a washed organic phase;
(4) Adding 1-bromo-2-methylpropane into the organic phase washed by water in the step (3), mixing and stirring for 0.8 hour at the temperature of 45 ℃, then standing while adding ultrasonic waves for layering, taking the upper organic phase, roasting for 2.9 hours at the temperature of 475 ℃, simultaneously adding a catalyst, introducing CO in the roasting process 2 And O 2 Maintaining CO in the mixed gas 2 And O 2 The volume ratio of (2.5) to (1), after the materials are completely changed into black solids from liquid, continuing to react for 1.5 hours, stopping the reaction, and cooling to obtain the high-purity carbon-coated manganese phosphate.
Selection by winnowing and electrostatic separation integration equipment includes the spiral blanking machine, the spiral blanking machine is connected with the feed bin, is provided with at least one deck in the feed bin and leads the magnetic net, and the aperture of leading the magnetic net is 1.4mm, it is connected with the electro-magnet to lead the magnetic net, and middle part one side of feed bin is provided with electrostatic generator, and electrostatic generator's below is provided with first discharge gate, lower part one side air outlet of feed bin, the below of air outlet are provided with the second discharge gate, and the bottom of feed bin is provided with the third discharge gate.
In the step (1), the concentration of the sodium hydroxide solution is 2.3mol/L, the mass ratio of the black powder material to the sodium hydroxide is 1.
In the step (2), the second filter residue is returned to be mixed with the first filter residue for acid dissolution, the mass ratio of the crude manganese powder to the manganese dioxide in the first filter residue is 1 2+ 、Co 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 2.5 times of the total mass, finally obtaining pure Mn solution]0.72mol/L, zn less than 5Mg/L, ca/Mg less than 5Mg/L, and the content of other metal ions less than 2Mg/L.
Sampling and measuring the raffinate in the extraction process in the step (2), and controlling Mn in the raffinate 2+ At 6mg/L.
The preparation method of the bis (2,4,4-trimethylpentyl) phosphonic acid saponified solution in the step (3) comprises the steps of uniformly mixing bis (2,4,4-trimethylpentyl) phosphonic acid with 260# solvent oil, wherein the concentration of bis (2,4,4-trimethylpentyl) phosphonic acid is 0.55mol/L, then adding ammonia water for mixing reaction, mixing and reacting for 0.8 hour at normal temperature, standing for layering, wherein an organic phase is the bis (2,4,4-trimethylpentyl) phosphonic acid saponified solution, the molar ratio of bis (2,4,4-trimethylpentyl) phosphonic acid to ammonia is 1.7, in the extraction process, the volume flow ratio of an organic phase, an aqueous phase, an acid solution and pure water is 0.55.
The volume ratio of the washed organic phase to the 1-bromo-2-methylpropane in the step (4) is 1.5, and the lower organic phase obtained after layering is distilled to separate the 1-bromo-2-methylpropane from the No. 260 solvent oil.
The catalyst in the step (4) is one of nitric acid, perchloric acid and hypochlorous acid, the molar ratio of the catalyst to the upper organic phase is 1.
The final product index is as follows:
| index (I) | Manganese content | Phosphorus content | Tap density | Carbon content | Na |
| Numerical value | 39.7％ | 14.99％ | 1.30g/mL | 1.85％ | 1.2ppm |
| Cr | Ca | Mg | Na | Ni | Co |
| 0.18ppm | 5.8ppm | 3.5ppm | 2.8ppm | 1.95ppm | 0.43ppm |
| Fe | Zn | Cu | Ti | Al | Si |
| 4.6ppm | 7.2ppm | 0.25ppm | 0.33ppm | 1.2ppm | 1.2ppm |
| D10 | D50 | D90 | BET | Sulfate radical | Chloride ion |
| 0.78μm | 1.42μm | 2.05μm | 13.2m 2 /g | 4.1ppm | 2.1ppm |
Meanwhile, the final recovery rate of manganese is 98.1%, and the amount of wastewater generated by each ton of manganese phosphate is 24 tons.
Example 3
A method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries comprises the following steps:
(1) Pretreating, crushing the waste zinc-manganese battery until the particle size of the material is 0.6mm, sorting the material in integrated equipment of air separation and electrostatic sorting, adding the obtained black powder material into pure water for slurrying, adding the slurried material into a sodium hydroxide solution, reacting for 3.3 hours at 92.5 ℃ in a sealed reaction kettle, simultaneously arranging an exhaust pipe, inserting the exhaust pipe into the pure water to obtain an ammonia solution, filtering and washing after the reaction is finished to obtain a first filtrate and a first filter residue;
(2) Purifying, adding acid solution into the first filter residue, adding crude manganese powder at the same time, maintaining the pH value of the solution at 1.1, reacting at 85 ℃ for 5.5 hours, then continuously adding the crude manganese powder, adjusting the pH value of the solution to 5.8, then introducing air, completely oxidizing ferrous ions into ferric iron and precipitating, then filtering to obtain a second filtrate and a second filter residue, adjusting the pH value of the second filtrate to 2.3, adding ammonium sulfide, reacting at 55 ℃ for 2.5 hours, and adding ammonium sulfide with the mol number of Cu in the second filtrate 2+ 、Co 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 1.23 times of the total mole number, then filtering to obtain a third filtrate and a third filter residue, mixing the third filtrate with a P507 extractant saponified with ammonia water, performing 6-stage countercurrent extraction, 6-stage countercurrent washing, 5-stage primary countercurrent back extraction, 5-stage secondary countercurrent back extraction and 1-stage countercurrent water washing to obtain a raffinate, a primary strip liquor and a secondary strip liquor, wherein the volume flow ratio of the third filtrate, the P507 extractant saponified with ammonia water, the washing solution, the primary strip liquor, the secondary strip liquor and the washing water is 0.13:0.25, washing with 0.7mol/L hydrochloric acid, adding a heavy metal capture agent into the primary stripping solution, reacting at pH3.1 for 2.5 hours, maintaining the temperature at 35 ℃, filtering, adding ammonium fluoride into the filtrate, reacting at 92.5 ℃ for 2.8 hours to ensure that calcium and magnesium ions in the filtrate are lower than 5mg/L, and filtering to obtain a pure manganese solution;
(3) Preparing a di (2,4,4-trimethylpentyl) phosphonic acid saponification solution, and performing 12-stage countercurrent extraction, 8-stage countercurrent acid solution washing and 4-stage countercurrent pure water washing on the di (2,4,4-trimethylpentyl) phosphonic acid saponification solution and a pure manganese solution to obtain an organic phase after water washing;
(4) Adding 1-bromo-2-methylpropane into the organic phase washed by water in the step (3), mixing and stirring for 0.8 hour at the temperature of 45 ℃, then standing while adding ultrasonic waves for layering, taking the upper organic phase, roasting for 2.8 hours at the temperature of 480 ℃, simultaneously adding a catalyst, introducing CO in the roasting process 2 And O 2 Maintaining CO in the mixed gas 2 And O 2 The volume ratio of (1) is 23.
Selection by winnowing and electrostatic separation integration equipment includes the spiral blanking machine, the spiral blanking machine is connected with the feed bin, is provided with at least one deck in the feed bin and leads the magnetic net, and the aperture of leading the magnetic net is 1.4mm, it is connected with the electro-magnet to lead the magnetic net, and middle part one side of feed bin is provided with electrostatic generator, and electrostatic generator's below is provided with first discharge gate, lower part one side air outlet of feed bin, the below of air outlet are provided with the second discharge gate, and the bottom of feed bin is provided with the third discharge gate.
In the step (1), the concentration of the sodium hydroxide solution is 2.3mol/L, the mass ratio of the black powder material to the sodium hydroxide is 1.
In the step (2), the second filter residue is returned to be mixed with the first filter residue for acid dissolution, the mass ratio of the crude manganese powder to the manganese dioxide in the first filter residue is 1 2+ 、Co 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 2.5 times of the total mass, finally obtaining pure Mn solution]0.71mol/L, zn less than 5Mg/L, ca/Mg less than 5Mg/L, and the content of other metal ions is less than 2Mg/L.
Sampling and measuring the raffinate in the extraction process in the step (2), and controlling Mn in the raffinate 2+ At 9mg/L.
The preparation method of the bis (2,4,4-trimethylpentyl) phosphonic acid saponified solution in the step (3) comprises the steps of uniformly mixing bis (2,4,4-trimethylpentyl) phosphonic acid and 260# solvent oil, wherein the concentration of bis (2,4,4-trimethylpentyl) phosphonic acid is 0.55mol/L, then adding ammonia water for mixing reaction, mixing and reacting for 0.8 hour at normal temperature, standing and layering, wherein the organic phase is the bis (2,4,4-trimethylpentyl) phosphonic acid saponified solution, the molar ratio of bis (2,4,4-trimethylpentyl) phosphonic acid to ammonia is 1.7, in the extraction process, the volume flow ratio of an organic phase, an aqueous phase, an acid solution and pure water is 0.3.
The volume ratio of the washed organic phase to the 1-bromo-2-methylpropane in the step (4) is 1.5, and the lower organic phase obtained after layering is distilled to separate the 1-bromo-2-methylpropane from the No. 260 solvent oil.
The catalyst in the step (4) is one of nitric acid, perchloric acid and hypochlorous acid, the molar ratio of the catalyst to the upper organic phase is 1.
The final product index is as follows:
| index (I) | Manganese content | Phosphorus content | Tap density | Carbon content | Na |
| Numerical value | 39.9％ | 14.94％ | 1.35g/mL | 1.85％ | 1.2ppm |
| Cr | Ca | Mg | Na | Ni | Co |
| 0.11ppm | 5ppm | 3.5ppm | 2.8ppm | 1.90ppm | 0.4ppm |
| Fe | Zn | Cu | Ti | Al | Si |
| 4.9ppm | 9ppm | 0.25ppm | 0.35ppm | 1.1ppm | 1.1ppm |
| D10 | D50 | D90 | BET | Sulfate radical | Chloride ion |
| 0.80μm | 1.39μm | 2.0μm | 13.58m 2 /g | 4.0ppm | 2.0ppm |
Meanwhile, the final recovery rate of manganese is 97.5%, and the waste water produced by each ton of manganese phosphate is 28 tons.
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 (8)
1. A method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries is characterized by comprising the following steps:
(1) Pretreating, namely crushing the waste zinc-manganese battery until the particle size of the material is 0.1-1mm, sorting the material in integrated equipment of air separation and electrostatic sorting, adding pure water into the obtained black powder material for slurrying, adding sodium hydroxide solution into the slurried material, reacting for 3-4 hours at 90-95 ℃ in a sealed reaction kettle, simultaneously arranging an exhaust pipe, inserting the exhaust pipe into the pure water to obtain ammonia solution, after the reaction is finished, filtering and washing to obtain first filtrate and first filter residue;
(2) Purifying, adding acid solution into the first filter residue, adding crude manganese powder, maintaining the pH of the solution at 0.5-1.5, reacting at 70-85 ℃ for 5-6 hours, continuously adding the crude manganese powder, adjusting the pH of the solution to 5.5-6, introducing air, completely oxidizing ferrous ions into ferric iron, precipitating, filtering to obtain second filtrate and second filter residue, adjusting the pH of the second filtrate to 2-2.5, adding ammonium sulfide, reacting at 45-65 ℃ for 2-3 hours, and adding ammonium sulfide with the molar number of the ammonium sulfide being Cu in the second filtrate 2+ 、Co 2+ 、Ni 2 + 、Pb 2+ 、Cd 2+ 、Zn 2+ 1.1-1.25 times of the total mole number, then filtering to obtain a third filtrate and a third filter residue, mixing the third filtrate with a P507 extractant saponified by ammonia water, and performing 5-7 stages of countercurrent extraction, 5-7 stages of countercurrent washing, 5-7 stages of first countercurrent back extraction, 4-6 stages of second countercurrent back extraction and 1-2 stages of countercurrent water washing to obtain a raffinate, a first stage of strip liquor and a second stage of strip liquor, wherein the volume flow ratio of the third filtrate, the P507 extractant saponified by ammonia water, a washing solution, the first strip liquor, the second strip liquor and the washing water is 0.5-0.15: 0.2-0.25, washing with 0.5-1mol/L hydrochloric acid, 1-1.5mol/L hydrochloric acid as primary stripping solution, 1.5-2mol/L hydrochloric acid as secondary stripping solution, adding heavy metal scavenger into the primary stripping solution, reacting at pH2.5-3.5 for 2-3 hours, maintaining the temperature at 30-40 ℃, filtering, adding ammonium fluoride into the filtrate, reacting at 90-95 ℃ for 2-3 hours to make the calcium and magnesium ions in the filtrate lower than 5mg/L, and filtering to obtain pure manganese solution;
(3) Preparing a di (2,4,4-trimethylpentyl) phosphonic acid saponification solution, and performing 10-12-stage countercurrent extraction, 8-10-stage countercurrent acid solution washing and 4-5-stage countercurrent pure water washing on the di (2,4,4-trimethylpentyl) phosphonic acid saponification solution and a pure manganese solution to obtain an organic phase after water washing;
(4) Adding 1-bromo-2-methylpropane into the organic phase washed by water in the step (3), mixing and stirring for 0.5-1 hour at the temperature of 40-50 ℃, then standing while adding ultrasonic waves for layering, taking the upper organic phase, roasting for 2-3 hours at the temperature of 450-500 ℃, simultaneously adding a catalyst, and introducing CO in the roasting process 2 And O 2 Maintaining CO in the mixed gas 2 And O 2 The volume ratio of (2-2.5) is that after the materials are completely changed into black solids from liquid, the reaction is continued for 0.5-3 hours, the reaction is stopped, and the high-purity carbon-coated manganese phosphate is obtained after cooling.
2. The method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries according to claim 1, characterized by comprising the following steps: the integrated equipment for winnowing and electrostatic separation comprises a spiral blanking machine, wherein the spiral blanking machine is connected with a storage bin, at least one layer of magnetic net is arranged in the storage bin, the aperture of the magnetic net is 1-1.5mm, the magnetic net is connected with an electromagnet, an electrostatic generator is arranged on one side of the middle of the storage bin, a first discharge port is arranged below the electrostatic generator, an air outlet is formed in one side of the lower portion of the storage bin, a second discharge port is formed below the air outlet, and a third discharge port is formed in the bottom of the storage bin.
3. The method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries according to claim 1, characterized by comprising the following steps: in the step (1), the concentration of the sodium hydroxide solution is 2-3mol/L, the mass ratio of the black powder material to the sodium hydroxide is 1.5-0.6, the first filtrate is added with sulfuric acid to adjust the pH value of the solution to 7.5-8, so as to obtain zinc hydroxide precipitate, the zinc hydroxide precipitate is filtered, dissolved by adding sulfuric acid, and concentrated and crystallized to obtain zinc sulfate crystals.
4. The method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries according to claim 1, characterized by comprising the following steps: in the step (2), the second filter residue is returned to be mixed with the first filter residue for continuous acid dissolution, the mass ratio of the rough manganese powder to the manganese dioxide in the first filter residue is 1.7-0.8, the third filter residue is subjected to ammonia saponification, and the preparation method of the P507 extracting agent comprises the steps of uniformly mixing the P507 extracting agent with No. 260 solvent oil, the concentration of P507 is 0.5-0.6mol/L, then ammonia water is added for mixing reaction, the mixing reaction is carried out for 0.5-1 hour at normal temperature, standing and layering are carried out, the organic phase is P507 extracting agent obtained after the ammonia water is saponified, the molar ratio of P507 to ammonia is 1.6-1.8, the heavy metal catching agent is organic sulfur compound, and the heavy metal is heavy metalThe addition amount of the trapping agent is Cu in the primary stripping solution 2+ 、Co 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 2-3 times of the total mass to finally obtain the pure Mn solution]0.7-0.75mol/L, zn < 5Mg/L, ca/Mg < 5Mg/L, and other metal ion content less than 2Mg/L.
5. The method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries according to claim 1, characterized by comprising the following steps: sampling and measuring the raffinate in the extraction process in the step (2), and controlling Mn in the raffinate 2+ When the content of manganese ions is less than 5mg/L, the flow rate of the third filtrate is increased, and when the content of manganese ions is more than 10mg/L, the flow rate of the third filtrate is reduced.
6. The method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries according to claim 1, characterized by comprising the following steps: the preparation method of the bis (2,4,4-trimethylpentyl) phosphonic acid saponification liquid in the step (3) comprises the steps of uniformly mixing bis (2,4,4-trimethylpentyl) phosphonic acid with 260# solvent oil, adding ammonia water for mixing reaction, mixing and reacting for 0.5-1 hour at normal temperature, standing for layering, wherein an organic phase is bis (4325 zxft 3963-trimethylpentyl) phosphonic acid saponification liquid, the molar ratio of bis (2,4,4-trimethylpentyl) phosphonic acid to ammonia is 1.
7. The method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries according to claim 1, characterized by comprising the following steps: the volume ratio of the organic phase washed by water in the step (4) to the 1-bromo-2-methylpropane is 1:3-5, and the lower organic phase obtained after layering is distilled to separate the 1-bromo-2-methylpropane from the No. 260 solvent oil.
8. The method for preparing carbon-coated manganese phosphate from waste zinc-manganese batteries according to claim 1, characterized by comprising the following steps: the catalyst in the step (4) is one of nitric acid, perchloric acid and hypochlorous acid, the molar ratio of the catalyst to the upper organic phase is 1:3-5, and the pressure is 1-3Mpa.
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