CN108588425B - Treatment method of cobalt-nickel metallurgy wastewater slag - Google Patents
Treatment method of cobalt-nickel metallurgy wastewater slag Download PDFInfo
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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Abstract
The invention discloses a method for treating cobalt-nickel metallurgy wastewater slag. Adding water into the waste water slag, pulping and stirring, introducing carbon dioxide gas into the pulp, filtering and washing to obtain washing waste water slag; the obtained washing waste water slag, coke, silicon dioxide and waste copper materials are put into a high-temperature smelting furnace to be smelted, smelted copper water flows out of the furnace bottom, flows into a die and is cooled into metal blocks, the metal blocks are put into an electrolytic bath to be electrolyzed and refined into copper to obtain cathode copper, calcium oxide is added into electrolyte, then the electrolyte is filtered, first filtrate is obtained, copper is extracted by a copper extraction line to obtain raffinate containing cobalt and nickel, the raffinate is oxidized to obtain cobaltous hydroxide, then the cobaltous hydroxide is mixed with cobalt acetate and is calcined to obtain cobaltosic oxide, and oxidized solution is extracted and separated to obtain nickel sulfate, and nickel sulfate is concentrated and crystallized to obtain nickel sulfate crystals. The method has the advantages of short flow, simple process, high recovery rate and high added value of products, and can realize separation and recovery of all components.
Description
Technical Field
The invention relates to a method for treating cobalt-nickel metallurgy wastewater slag, belonging to the technical field of waste treatment.
Background
The cobalt nickel is used as strategic resource, has greatly improved industrial position, is widely applied to hard alloy, functional ceramic, catalyst, military industry and high-energy battery, and is called industrial monosodium glutamate. The production of cobalt and nickel is mainly hydrometallurgy. The method mainly comprises the following steps:
and (4) leaching. As the first step of hydrometallurgy, the leaching rate directly determines the efficiency and the benefit. The method is characterized by comprising the process of transferring valuable metals in the ores into a solution after crushing, screening, enriching and other treatments of raw ores. The leaching in the cobalt nickel production mainly comprises acid leaching, chlorination leaching, ammonia leaching, high pressure oxygen leaching and the like. The main auxiliary materials used include concentrated sulfuric acid, concentrated hydrochloric acid, chlorine, sulfur dioxide, ammonia water, air, sodium chlorate, hydrogen peroxide, manganese dioxide, sodium sulfite and the like. Generally, the cobalt-nickel ore mainly comprises sulphide ore and oxide ore, and particularly the sulphide ore mostly contains other metals, so that the leaching of cobalt and nickel is considered, and the comprehensive recycling of other valuable metals is also considered.
Impurity removal is an important process for product guarantee in cobalt-nickel metallurgy. For a large amount of impurity ions, such as iron ions and aluminum ions, chemical impurity removal methods are mainly considered, sodium carbonate or sodium hydroxide is directly added to adjust the pH value to be 3.5-4.0, an oxidant is generally added to oxidize ferrous iron into ferric iron due to the high pH value of ferrous iron precipitate, and a jarosite method is also used for removing iron. For lead, cadmium and copper, sodium sulfide is generally adopted to remove impurities, and the pH is generally adjusted to be about 1.8-2.0. Of course, other extracting agents can be used for removing other impurities after the copper is fished at lower pH in consideration of comprehensive recovery. The manganese, zinc and a small amount of iron, aluminum, manganese and chromium can be removed by an extraction method. Common extractants are P204, P507, cyanex 272.
The qualified cobalt-nickel solution is produced by extraction, a precipitator is needed to produce a precursor, and the main precursor is carbonate and oxalate. If crystals such as nickel sulfate crystals, cobalt sulfate crystals and the like are produced, the step is not needed, and the crystals are directly concentrated, evaporated and crystallized. Generally, the precursor is synthesized by adopting a counter-addition mode, and certain process pH, end-point pH, reaction temperature, reaction time and the like are controlled. Controlling certain morphology, particle size and the like.
If high pressure hydrogen reduction is directly used, this step of synthesis is not required. If high-temperature hydrogen is used for reduction, the precursor is crushed, then the temperature and the air flow are controlled in a reduction furnace, and then the crushed precursor is packaged in vacuum.
The leaching slag washing water, the extracted raffinate, the liquid-phase synthesized mother liquor and the washing water are discharged outside, metal ions in the leaching slag washing water are precipitated through chemical precipitation to obtain waste water slag, the waste water slag mainly comprises hydroxide, and oxide and carbonate can be generated and obtained along with the extension of stacking time, and the waste water slag comprises the following components:
because the metals contained in the waste water are various and the content of each component is almost the same, the conventional treatment process is difficult to completely recycle the waste water, generally, sulfides are adopted for precipitation after acid dissolution, zinc, cobalt, nickel and copper are recovered, other elements enter the waste water again, and then the other elements enter waste water slag after being precipitated again, so that the elements such as magnesium, calcium, manganese and the like in the waste water are gradually enriched, the complete utilization of various valuable metals cannot be realized, and the requirement on the environment at present is not met.
Disclosure of Invention
In view of the above, the invention provides a method for treating cobalt-nickel metallurgical waste water slag, which can convert calcium sulfate into calcium carbonate through carbon dioxide treatment, simultaneously adopts water to wash, washes sulfate radicals and sodium salts in the waste water slag, avoids a large amount of sulfur dioxide and salt volatilization in a pyrometallurgical smelting process, blocks a dust collecting device, more conveniently adopts a pyrometallurgical method to treat the waste water slag, simultaneously puts the waste water slag and waste copper materials into a smelting furnace for reduction smelting, so that metals such as cobalt-nickel and the like enter copper water together with the metals, and calcium-magnesium-iron and the like enter the slag, the slag has light density and floats on the copper water, thereby realizing the separation of calcium-magnesium-iron and the like from the cobalt-nickel-copper, simultaneously recovering tin, zinc, lead and a small amount of copper into soot, realizing the separation of tin, zinc, lead and a small amount of copper in the soot, returning the copper to be used as electrolyte, and then obtaining cathode copper through electrolytic refining, meanwhile, cobalt and nickel enter the electrolyte, copper is recovered after extraction, and oxidation is carried out, so that cobaltous hydroxide is obtained, the cobaltous hydroxide and cobalt acetate are mixed and calcined, so that battery-grade cobaltosic oxide is obtained, and the industrial-grade nickel sulfate is obtained through extraction and back extraction.
The invention solves the technical problems by the following technical means:
a treatment method of cobalt-nickel metallurgy wastewater slag comprises the following steps:
(1) pretreating, namely adding wastewater slag into water, pulping and stirring, introducing carbon dioxide gas into the pulp, stirring and reacting at the temperature of 25-45 ℃ until the content of sulfate radicals in solid materials is lower than 500ppm, filtering, and adding hot water into filter residues for washing until the content of sulfate radicals in washing water is lower than 0.1g/L to obtain washing wastewater slag;
(2) putting the washing wastewater slag obtained in the step (1), coke, silicon dioxide and waste copper materials into a high-temperature smelting furnace for smelting at 1150 ℃ at 950, maintaining the concentration of carbon monoxide in the smelting furnace at 1000ppm, blowing external air into the smelting furnace for 4-6 hours, arranging a dust collection device at the upper part of the smelting furnace, collecting dust of flue gas by the dust collection device, spraying and absorbing the dust, discharging the flue gas to the outside, allowing the smelted copper water to flow out of the furnace bottom, flowing into a mold, cooling the molten copper water into metal blocks, and raking out slag;
(3) putting the metal blocks in the step (2) into an electrolytic cell for electrolytic copper refining to obtain cathode copper, recycling the electrolyte until the total concentration of cobalt and nickel in the electrolyte is more than 0.5mol/L, then treating the electrolyte, adding calcium oxide into the electrolyte to adjust the pH value of the solution to be 4-4.5, then filtering the solution to obtain first filtrate and first filter residue, returning the first filter residue to be mixed with wastewater slag for pretreatment, extracting copper from the first filtrate through a copper extraction line, then performing back extraction with sulfuric acid to obtain new electrolyte, returning the new electrolyte to the electrolytic cell, and extracting copper to obtain raffinate containing cobalt and nickel;
(4) adding the raffinate containing cobalt and nickel obtained in the step (3) into battery-grade cobalt sulfate or battery-grade nickel sulfate to adjust the molar ratio of cobalt and nickel in the solution to be 10:1, introducing chlorine into a sodium hydroxide solution, adjusting the pH value of the solution to be 11-11.5, adding the chlorine into the adjusted raffinate containing cobalt and nickel under a stirring state for 4-5 hours at the reaction temperature of 45-60 ℃, filtering to obtain a second filtrate and a second filter residue, washing the second filter residue, adding the washed materials into pure water to make a slurry, adding cobalt acetate, stirring and dissolving the cobalt acetate, performing spray drying, and calcining under an inert atmosphere to obtain battery-grade cobaltosic oxide;
(5) and (3) carrying out countercurrent extraction on the second filtrate obtained in the step (4) through P204, then carrying out two-stage countercurrent back extraction, wherein the first-stage countercurrent back extraction is used for obtaining a nickel sulfate solution, the second-stage countercurrent back extraction is used for obtaining a calcium-containing solution, and the nickel sulfate solution is concentrated and crystallized to obtain industrial-grade nickel sulfate.
And (2) concentrating and crystallizing the washing water obtained in the step (1) to obtain sodium sulfate crystals, and condensing the evaporated water vapor to obtain pure water.
In the step (2), the mass ratio of the washing waste water slag to the coke, the silicon dioxide and the waste copper material is 5-10:1-2:0.3-0.6:20-30, the copper content in the waste copper material is more than 85%, the obtained slag, the tailings obtained by cobalt-nickel metallurgy, the shale and the clay are subjected to ball milling and then water adding forming, the obtained slag, the tailings obtained by cobalt-nickel metallurgy, the shale and the clay are placed into a high temperature furnace for calcination at the temperature of 700 ℃ and 750 ℃ for 6-8 hours after pressing, so that the floor tiles are obtained, and the mass ratio of the tailings, the shale and the clay obtained by the slag and cobalt-nickel metallurgy is 4-8:1-2:1-2: 4-5.
Adding sodium hydroxide into the dust collection material obtained by collecting dust in the step (2) to calcine in a rotary kiln, wherein the mass ratio of the dust collection material to the sodium hydroxide is 1:0.2-0.3, the calcination temperature is 330-.
The extraction stage number of the first filtrate obtained in the step (3) is 5-6 stages when copper is extracted, the volume flow ratio of an organic phase to a water phase during extraction is 3-4:1, the extractant is a copper chelating extractant, sodium hydroxide is added during the second stage of extraction to adjust the pH of the water phase of the second stage to be 2.5-3, 2-3 stages of counter-current back extraction are adopted for back extraction, and the concentration of sulfuric acid is 0.8-1.2 mol/L.
In the step (4), the concentration of the sodium hydroxide solution is 1-1.2mol/L, the second filter residue is washed by hydrochloric acid solution with the pH value of 3-4, the mass ratio of the second filter residue to the hydrochloric acid solution is 1:8-10, then pure water is used for washing until the pH value of washing water is 6-6.5, the ratio of the mole number of cobalt in the washed material to the mole number of cobalt in the added cobalt acetate is 2:1, the particle size of the spray-dried material is 8-15 microns, the calcination time is 7-9 hours under inert atmosphere and is 850 ℃, the calcination material obtained is subjected to airflow crushing and screening to obtain the battery-grade cobaltosic oxide.
The stage number of the countercurrent extraction in the step (5) is 10-12, the volume ratio of P204 in the P204 extractant is 20-25%, the diluent is sulfonated kerosene, the saponification rate of P204 is 75-85%, the volume flow ratio of the extractant to the second filtrate is adjusted to ensure that the content of nickel in the raffinate is maintained at 2-5mg/L, the stripping solution adopted by the first stage of countercurrent back extraction is sulfuric acid solution, the concentration of the sulfuric acid solution is 1-1.5mol/L, the molar ratio of hydrochloric acid in the stripping solution to nickel in the extractant is 2:1.02-1.05, the back extraction stage number of the first stage of countercurrent back extraction is 10-12, the back extraction solution adopted by the second stage of countercurrent back extraction is hydrochloric acid solution, the concentration of the hydrochloric acid solution is 2-3mol/L, and the back extraction stage number of the second stage of countercurrent back extraction is 7-9.
At present because in the cobalt nickel metallurgical process, generally can have copper along with, adopt electrolytic refining after the pyrometallurgical process, can mix waste water sediment and useless miscellaneous copper and carry out the pyrometallurgical process together, the process flow is short, and adopt this technology, sulfate radical and salt content in the waste water sediment can be reduced, avoid the production of a large amount of sulfur dioxide and salt to lead to blockking up dust arrester installation in a large number, the doping ratio of waste water sediment is high, and the process flow is short, the effective utilization of whole components has been realized, battery level cobaltosic oxide and industrial grade nickel sulfate of high added value are obtained, the slag can regard as the ceramic tile to use through handling simultaneously, the recovery of zinc, lead and tin can be retrieved through handling to the cigarette ash.
The process flow is short, the recovery of all components is realized, the recovery rate of each component is high, and the added value of the obtained product is high.
The obtained cobaltosic oxide contains nickel, so that the doping of the nickel is realized, and the capacity is improved.
The invention has the beneficial effects that:
1. the process flow is short, the recovery of nickel, cobalt, copper and zinc is realized, and meanwhile, calcium, magnesium, iron and the like in the process flow are used for preparing the floor tiles.
2. The process ingeniously adopts carbon dioxide to perform precipitation conversion, so that calcium sulfate is converted into calcium carbonate, sulfate radicals are converted into soluble sulfate radicals, then the sulfate radicals and the salt are washed by pure water to reduce the concentration of the sulfate radicals and the salt, then reduction smelting is performed, cobalt and nickel are enriched into copper, calcium, magnesium and the like are enriched into slag, zinc, lead, tin and the like enter soot, separation of components is realized, and then electrolytic refining, oxidation and extraction separation are performed, so that separation and recovery of copper, cobalt and nickel are realized.
3. The process has good environmental protection property, and avoids the generation of a large amount of sulfur dioxide.
Detailed Description
The invention will be described in detail with reference to specific examples, wherein the method for treating cobalt-nickel metallurgical wastewater slag comprises the following steps:
(1) pretreating, namely adding wastewater slag into water, pulping and stirring, introducing carbon dioxide gas into the pulp, stirring and reacting at the temperature of 25-45 ℃ until the content of sulfate radicals in solid materials is lower than 500ppm, filtering, and adding hot water into filter residues for washing until the content of sulfate radicals in washing water is lower than 0.1g/L to obtain washing wastewater slag;
(2) putting the washing wastewater slag obtained in the step (1), coke, silicon dioxide and waste copper materials into a high-temperature smelting furnace for smelting at 1150 ℃ at 950, maintaining the concentration of carbon monoxide in the smelting furnace at 1000ppm, blowing external air into the smelting furnace for 4-6 hours, arranging a dust collection device at the upper part of the smelting furnace, collecting dust of flue gas by the dust collection device, spraying and absorbing the dust, discharging the flue gas to the outside, allowing the smelted copper water to flow out of the furnace bottom, flowing into a mold, cooling the molten copper water into metal blocks, and raking out slag;
(3) putting the metal blocks in the step (2) into an electrolytic cell for electrolytic copper refining to obtain cathode copper, recycling the electrolyte until the total concentration of cobalt and nickel in the electrolyte is more than 0.5mol/L, then treating the electrolyte, adding calcium oxide into the electrolyte to adjust the pH value of the solution to be 4-4.5, then filtering the solution to obtain first filtrate and first filter residue, returning the first filter residue to be mixed with wastewater slag for pretreatment, extracting copper from the first filtrate through a copper extraction line, then performing back extraction with sulfuric acid to obtain new electrolyte, returning the new electrolyte to the electrolytic cell, and extracting copper to obtain raffinate containing cobalt and nickel;
(4) adding the raffinate containing cobalt and nickel obtained in the step (3) into battery-grade cobalt sulfate or battery-grade nickel sulfate to adjust the molar ratio of cobalt and nickel in the solution to be 10:1, introducing chlorine into a sodium hydroxide solution, adjusting the pH value of the solution to be 11-11.5, adding the chlorine into the adjusted raffinate containing cobalt and nickel under a stirring state for 4-5 hours at the reaction temperature of 45-60 ℃, filtering to obtain a second filtrate and a second filter residue, washing the second filter residue, adding the washed materials into pure water to make a slurry, adding cobalt acetate, stirring and dissolving the cobalt acetate, performing spray drying, and calcining under an inert atmosphere to obtain battery-grade cobaltosic oxide;
(5) and (3) carrying out countercurrent extraction on the second filtrate obtained in the step (4) through P204, then carrying out two-stage countercurrent back extraction, wherein the first-stage countercurrent back extraction is used for obtaining a nickel sulfate solution, the second-stage countercurrent back extraction is used for obtaining a calcium-containing solution, and the nickel sulfate solution is concentrated and crystallized to obtain industrial-grade nickel sulfate.
And (2) concentrating and crystallizing the washing water obtained in the step (1) to obtain sodium sulfate crystals, and condensing the evaporated water vapor to obtain pure water.
In the step (2), the mass ratio of the washing waste water slag to the coke, the silicon dioxide and the waste copper material is 5-10:1-2:0.3-0.6:20-30, the copper content in the waste copper material is more than 85%, the obtained slag, the tailings obtained by cobalt-nickel metallurgy, the shale and the clay are subjected to ball milling and then water adding forming, the obtained slag, the tailings obtained by cobalt-nickel metallurgy, the shale and the clay are placed into a high temperature furnace for calcination at the temperature of 700 ℃ and 750 ℃ for 6-8 hours after pressing, so that the floor tiles are obtained, and the mass ratio of the tailings, the shale and the clay obtained by the slag and cobalt-nickel metallurgy is 4-8:1-2:1-2: 4-5.
Adding sodium hydroxide into the dust collection material obtained by collecting dust in the step (2) to calcine in a rotary kiln, wherein the mass ratio of the dust collection material to the sodium hydroxide is 1:0.2-0.3, the calcination temperature is 330-.
The extraction stage number of the first filtrate obtained in the step (3) is 5-6 stages when copper is extracted, the volume flow ratio of an organic phase to a water phase during extraction is 3-4:1, the extractant is a copper chelating extractant, sodium hydroxide is added during the second stage of extraction to adjust the pH of the water phase of the second stage to be 2.5-3, 2-3 stages of counter-current back extraction are adopted for back extraction, and the concentration of sulfuric acid is 0.8-1.2 mol/L.
In the step (4), the concentration of the sodium hydroxide solution is 1-1.2mol/L, the second filter residue is washed by hydrochloric acid solution with the pH value of 3-4, the mass ratio of the second filter residue to the hydrochloric acid solution is 1:8-10, then pure water is used for washing until the pH value of washing water is 6-6.5, the ratio of the mole number of cobalt in the washed material to the mole number of cobalt in the added cobalt acetate is 2:1, the particle size of the spray-dried material is 8-15 microns, the calcination time is 7-9 hours under inert atmosphere and is 850 ℃, the calcination material obtained is subjected to airflow crushing and screening to obtain the battery-grade cobaltosic oxide.
The stage number of the countercurrent extraction in the step (5) is 10-12, the volume ratio of P204 in the P204 extractant is 20-25%, the diluent is sulfonated kerosene, the saponification rate of P204 is 75-85%, the volume flow ratio of the extractant to the second filtrate is adjusted to ensure that the content of nickel in the raffinate is maintained at 2-5mg/L, the stripping solution adopted by the first stage of countercurrent back extraction is sulfuric acid solution, the concentration of the sulfuric acid solution is 1-1.5mol/L, the molar ratio of hydrochloric acid in the stripping solution to nickel in the extractant is 2:1.02-1.05, the back extraction stage number of the first stage of countercurrent back extraction is 10-12, the back extraction solution adopted by the second stage of countercurrent back extraction is hydrochloric acid solution, the concentration of the hydrochloric acid solution is 2-3mol/L, and the back extraction stage number of the second stage of countercurrent back extraction is 7-9.
Example 1
A treatment method of cobalt-nickel metallurgy wastewater slag comprises the following steps:
(1) pretreating, namely adding wastewater slag into water, pulping and stirring, introducing carbon dioxide gas into the pulp, stirring and reacting at 42 ℃ until the content of sulfate radicals in solid materials is lower than 500ppm, filtering, and adding hot water into filter residues for washing until the content of sulfate radicals in washing water is lower than 0.1g/L to obtain washing wastewater slag;
(2) putting the washing wastewater slag obtained in the step (1), coke, silicon dioxide and waste copper materials into a high-temperature smelting furnace for smelting at 1050 ℃, maintaining the concentration of carbon monoxide in the smelting furnace to be 800ppm, simultaneously blowing external air into the smelting furnace for 5.2 hours, arranging a dust collecting device at the upper part of the smelting furnace, discharging flue gas after dust collection by the dust collecting device and spraying absorption, allowing the smelted copper water to flow out of the furnace bottom, flowing into a mold, cooling into metal blocks, and raking out slag;
(3) putting the metal blocks in the step (2) into an electrolytic cell for electrolytic refining of copper to obtain cathode copper, recycling the electrolyte until the total concentration of cobalt and nickel in the electrolyte is more than 0.5mol/L, then treating the electrolyte, adding calcium oxide into the electrolyte to adjust the pH of the solution to be 4.3, then filtering the solution to obtain first filtrate and first filter residue, returning the first filter residue to be mixed with wastewater residues for pretreatment, extracting copper from the first filtrate through a copper extraction line, then performing back extraction with sulfuric acid to obtain new electrolyte, returning the new electrolyte to the electrolytic cell, and extracting copper to obtain raffinate containing cobalt and nickel;
(4) adding the raffinate containing cobalt and nickel obtained in the step (3) into battery-grade cobalt sulfate or battery-grade nickel sulfate to adjust the molar ratio of cobalt and nickel in the solution to be 10:1, introducing chlorine into a sodium hydroxide solution, adjusting the pH value of the solution to be 11.2, adding the chlorine into the adjusted raffinate containing cobalt and nickel under a stirring state for 4.8 hours at a reaction temperature of 52 ℃, filtering to obtain a second filtrate and a second filter residue, washing the second filter residue, adding the washed materials into pure water for slurrying, adding cobalt acetate, stirring and dissolving, performing spray drying, and calcining under an inert atmosphere to obtain battery-grade cobaltosic oxide;
(5) and (3) carrying out countercurrent extraction on the second filtrate obtained in the step (4) through P204, then carrying out two-stage countercurrent back extraction, wherein the first-stage countercurrent back extraction is used for obtaining a nickel sulfate solution, the second-stage countercurrent back extraction is used for obtaining a calcium-containing solution, and the nickel sulfate solution is concentrated and crystallized to obtain industrial-grade nickel sulfate.
And (2) concentrating and crystallizing the washing water obtained in the step (1) to obtain sodium sulfate crystals, and condensing the evaporated water vapor to obtain pure water.
In the step (2), the mass ratio of the washing waste water slag to the coke, the silicon dioxide and the waste copper material is 8.5:1.8:0.45:25, the copper content in the waste copper material is more than 85%, the obtained slag, the tailings obtained by cobalt-nickel metallurgy, the shale and the clay are subjected to ball milling and then water adding forming, the obtained slag, the tailings obtained by cobalt-nickel metallurgy, the shale and the clay are placed into a high-temperature furnace to be calcined after being pressed, the temperature is 725 ℃, and the calcination time is 7.5 hours, so that the floor tiles are obtained, and the mass ratio of the tailings obtained by the slag and the cobalt-nickel metallurgy, the shale and the clay is 5.5:1.5: 1.7.
Adding sodium hydroxide into the dust collection material obtained by collecting dust in the step (2) to calcine in a rotary kiln, wherein the mass ratio of the dust collection material to the sodium hydroxide is 1:0.25, the calcination temperature is 345 ℃, the calcination time is 2.5 hours, washing the obtained calcined material to obtain a solution containing tin and zinc and filter residue, adding sulfuric acid into the filter residue, adding hydrogen peroxide to dissolve the filter residue to obtain a copper sulfate solution and a lead sulfate filter residue, returning the copper sulfate solution to prepare an electrolyte, adding ammonium sulfide into the solution containing tin and zinc to react at the temperature of 48 ℃ to obtain a zinc precipitate and a tin solution, concentrating and crystallizing the tin solution to obtain sodium stannate, roasting and sulfating the obtained zinc precipitate, adding dilute sulfuric acid to dissolve the obtained zinc precipitate to obtain a zinc sulfate solution, and concentrating and crystallizing to obtain zinc sulfate crystals.
And (3) extracting the first filtrate obtained in the step (3) by 6 stages, wherein the volume flow ratio of an organic phase to a water phase is 3.5:1 during extraction, the extractant is a copper chelating extractant, sodium hydroxide is added during the second stage of extraction to adjust the pH of the water phase of the second stage to be 2.8, 3-stage counter-current back extraction is adopted for back extraction, and the concentration of sulfuric acid is 1.1 mol/L.
In the step (4), the concentration of the sodium hydroxide solution is 1.1mol/L, the second filter residue is washed by hydrochloric acid solution with the pH value of 3.5, the mass ratio of the second filter residue to the hydrochloric acid solution is 1:9.2, then the second filter residue is washed by pure water until the pH value of washing water is 6.25, the ratio of the mole number of cobalt in the washed material to the mole number of cobalt in the added cobalt acetate is 2:1, the particle size of the spray-dried material is 12 micrometers, the calcination time is 8.2 hours in an inert atmosphere and is 810 ℃, and the obtained calcined material is subjected to airflow crushing and screening to obtain the battery-grade cobaltosic oxide.
The stage number of the countercurrent extraction in the step (5) is 11, the volume ratio of P204 in the P204 extractant is 22%, the diluent is sulfonated kerosene, the saponification rate of P204 is 79%, the volume flow ratio of the extractant to the second filtrate is adjusted to maintain the content of nickel in the raffinate at 3.5mg/L, the stripping solution adopted in the first stage of countercurrent back extraction is sulfuric acid solution, the concentration of the sulfuric acid solution is 1.35mol/L, the molar ratio of hydrochloric acid in the stripping solution to nickel in the extractant is 2:1.035, the stripping stage number of the first stage of countercurrent back extraction is 11, the stripping solution adopted in the second stage of countercurrent back extraction is hydrochloric acid solution, the concentration of the hydrochloric acid solution is 2.5mol/L, and the stripping stage number of the second stage of countercurrent back extraction is 8.
The obtained cathode copper meets the standard of standard cathode copper.
The indexes of the obtained battery grade cobaltosic oxide are as follows:
| index (I) | Cobalt content | D10 | D50 | D90 |
| Numerical value | 72.7％ | 1.9 micron | 5.8 micron | 9.1 micron |
| Index (I) | BET | Loose-pack | Tap density | Angle of repose |
| Numerical value | 9.5m2/g | 1.85g/mL | 2.49g/mL | 13° |
| Index (I) | Ni | Ca | Mn | Zn |
| Numerical value | 1200ppm | 12.5ppm | 21.5ppm | 18.5ppm |
| Index (I) | Na | Cd | Mg | C |
| Numerical value | 21.5ppm | 0.6ppm | 12.8ppm | 42ppm |
| Index (I) | Sulfate radical | Chloride ion | ||
| Numerical value | 66ppm | 17ppm |
The purity of industrial grade nickel sulfate is 99.1%, the purity of lead sulfate is 98.1%, the purity of zinc sulfate is 99%, and the purity of sodium stannate is 87.8%.
The breaking strength of the floor tile is 4.5MPa, and the compressive strength is 41 MPa.
Finally, the recovery rates of cobalt, nickel, lead, zinc and tin are respectively 97.8%, 98.1%, 98.6%, 96.8% and 97.8%, and the comprehensive recovery rate of copper is more than 99%.
Example 2
A treatment method of cobalt-nickel metallurgy wastewater slag comprises the following steps:
(1) pretreating, namely adding wastewater slag into water, pulping and stirring, introducing carbon dioxide gas into the pulp, stirring and reacting at 42 ℃ until the content of sulfate radicals in solid materials is lower than 500ppm, filtering, and adding hot water into filter residues for washing until the content of sulfate radicals in washing water is lower than 0.1g/L to obtain washing wastewater slag;
(2) putting the washing wastewater slag obtained in the step (1), coke, silicon dioxide and waste copper materials into a high-temperature smelting furnace for smelting at the smelting temperature of 985 ℃, maintaining the concentration of carbon monoxide in the smelting furnace to be 800ppm, simultaneously blowing external air into the smelting furnace for 5.2 hours, arranging a dust collecting device at the upper part of the smelting furnace, discharging flue gas after dust collection by the dust collecting device and spraying absorption, allowing the smelted copper water to flow out of the furnace bottom, flowing into a mold, cooling into metal blocks, and raking out slag;
(3) putting the metal blocks in the step (2) into an electrolytic cell for electrolytic refining of copper to obtain cathode copper, recycling the electrolyte until the total concentration of cobalt and nickel in the electrolyte is more than 0.5mol/L, then treating the electrolyte, adding calcium oxide into the electrolyte to adjust the pH of the solution to be 4.25, then filtering the solution to obtain first filtrate and first filter residue, returning the first filter residue to be mixed with wastewater residues for pretreatment, extracting copper from the first filtrate through a copper extraction line, then performing back extraction with sulfuric acid to obtain new electrolyte, returning the new electrolyte to the electrolytic cell, and extracting copper to obtain raffinate containing cobalt and nickel;
(4) adding the raffinate containing cobalt and nickel obtained in the step (3) into battery-grade cobalt sulfate or battery-grade nickel sulfate to adjust the molar ratio of cobalt and nickel in the solution to be 10:1, introducing chlorine into a sodium hydroxide solution, adjusting the pH value of the solution to be 11.35, adding the chlorine into the adjusted raffinate containing cobalt and nickel under a stirring state for 4.5 hours at a reaction temperature of 52 ℃, filtering to obtain a second filtrate and a second filter residue, washing the second filter residue, adding the washed materials into pure water to pulp, adding cobalt acetate, stirring and dissolving, spray drying, and calcining in an inert atmosphere to obtain battery-grade cobaltosic oxide;
(5) and (3) carrying out countercurrent extraction on the second filtrate obtained in the step (4) through P204, then carrying out two-stage countercurrent back extraction, wherein the first-stage countercurrent back extraction is used for obtaining a nickel sulfate solution, the second-stage countercurrent back extraction is used for obtaining a calcium-containing solution, and the nickel sulfate solution is concentrated and crystallized to obtain industrial-grade nickel sulfate.
And (2) concentrating and crystallizing the washing water obtained in the step (1) to obtain sodium sulfate crystals, and condensing the evaporated water vapor to obtain pure water.
In the step (2), the mass ratio of the washing waste water slag to the coke, the silicon dioxide and the waste copper material is 8.3:1.5:0.46:26, the copper content in the waste copper material is more than 85%, the obtained slag, the tailings obtained by cobalt-nickel metallurgy, the shale and the clay are subjected to ball milling and then water adding forming, the obtained slag, the tailings obtained by cobalt-nickel metallurgy, the shale and the clay are placed into a high-temperature furnace for calcination at the temperature of 720 ℃ for 7.5 hours after pressing, so that the floor tiles are obtained, and the mass ratio of the tailings, the shale and the clay obtained by the slag and cobalt-nickel metallurgy is 6:1.8:1.6: 4.6.
Adding sodium hydroxide into the dust collection material obtained by collecting dust in the step (2) to calcine in a rotary kiln, wherein the mass ratio of the dust collection material to the sodium hydroxide is 1:0.27, the calcining temperature is 345 ℃, the calcining time is 2.8 hours, washing the obtained calcined material to obtain a solution containing tin and zinc and filter residue, adding sulfuric acid into the filter residue, adding hydrogen peroxide to dissolve the filter residue to obtain a copper sulfate solution and a lead sulfate filter residue, returning the copper sulfate solution to prepare an electrolyte, adding ammonium sulfide into the solution containing tin and zinc to react at the temperature of 49 ℃ to obtain a zinc precipitate and a tin solution, concentrating and crystallizing the tin solution to obtain sodium stannate, roasting and sulfating the obtained zinc precipitate, adding dilute sulfuric acid to dissolve the obtained zinc precipitate to obtain a zinc sulfate solution, and concentrating and crystallizing to obtain zinc sulfate crystals.
And (3) extracting the first filtrate obtained in the step (3) by 6 stages when copper is extracted, wherein the volume flow ratio of an organic phase to a water phase is 3.6:1 during extraction, the extractant is a copper chelating extractant, sodium hydroxide is added during the second stage of extraction to adjust the pH of the water phase of the second stage to be 2.8, 3-stage counter-current back extraction is adopted for back extraction, and the concentration of sulfuric acid is 0.95 mol/L.
In the step (4), the concentration of the sodium hydroxide solution is 1.15mol/L, the second filter residue is washed by hydrochloric acid solution with the pH value of 3.5, the mass ratio of the second filter residue to the hydrochloric acid solution is 1:9.1, then the second filter residue is washed by pure water until the pH value of washing water is 6.3, the ratio of the mole number of cobalt in the washed material to the mole number of cobalt in the added cobalt acetate is 2:1, the particle size of the spray-dried material is 12 micrometers, the calcination time is 8.1 hours in an inert atmosphere and is 815 ℃, and the obtained calcined material is subjected to airflow crushing and screening to obtain the battery-grade cobaltosic oxide.
The stage number of the countercurrent extraction in the step (5) is 11, the volume ratio of P204 in the P204 extractant is 24%, the diluent is sulfonated kerosene, the saponification rate of P204 is 79%, the volume flow ratio of the extractant to the second filtrate is adjusted to maintain the content of nickel in the raffinate at 4.1mg/L, the stripping solution adopted in the first stage of countercurrent back extraction is sulfuric acid solution, the concentration of the sulfuric acid solution is 1.3mol/L, the molar ratio of hydrochloric acid in the stripping solution to nickel in the extractant is 2:1.04, the stripping stage number of the first stage of countercurrent back extraction is 11, the stripping solution adopted in the second stage of countercurrent back extraction is hydrochloric acid solution, the concentration of the hydrochloric acid solution is 2.7mol/L, and the stripping stage number of the second stage of countercurrent back extraction is 9.
The obtained cathode copper meets the standard of standard cathode copper.
The indexes of the obtained battery grade cobaltosic oxide are as follows:
| index (I) | Cobalt content | D10 | D50 | D90 |
| Numerical value | 72.6％ | 1.8 micron | 5.9 micron | 9.2 micron |
| Index (I) | BET | Loose-pack | Tap density | Angle of repose |
| Numerical value | 9.7m2/g | 1.85g/mL | 2.48g/mL | 13° |
| Index (I) | Ni | Ca | Mn | Zn |
| Numerical value | 1195ppm | 13ppm | 24ppm | 18.5ppm |
| Index (I) | Na | Cd | Mg | C |
| Numerical value | 21.9ppm | 0.7ppm | 12.8ppm | 45ppm |
| Index (I) | Sulfate radical | Chloride ion | ||
| Numerical value | 66ppm | 17ppm |
The purity of the industrial grade nickel sulfate is 99.2 percent, the purity of the lead sulfate is 98.2 percent, the purity of the zinc sulfate is 98.9 percent, and the purity of the sodium stannate is 87.8 percent.
The breaking strength of the floor tile is 4.7MPa, and the compressive strength is 42 MPa.
Finally, the recovery rates of cobalt, nickel, lead, zinc and tin are respectively 97.9%, 98.2%, 98.6%, 96.8% and 97.7%, and the comprehensive recovery rate of copper is more than 99%.
Example 3
A treatment method of cobalt-nickel metallurgy wastewater slag comprises the following steps:
(1) pretreating, namely adding wastewater slag into water, pulping and stirring, introducing carbon dioxide gas into the pulp, stirring and reacting at 42 ℃ until the content of sulfate radicals in solid materials is lower than 500ppm, filtering, and adding hot water into filter residues for washing until the content of sulfate radicals in washing water is lower than 0.1g/L to obtain washing wastewater slag;
(2) putting the washing wastewater slag obtained in the step (1), coke, silicon dioxide and waste copper materials into a high-temperature smelting furnace for smelting at 1080 ℃, simultaneously maintaining the concentration of carbon monoxide in the smelting furnace at 850ppm, simultaneously blowing external air into the smelting furnace for 5.2 hours, simultaneously arranging a dust collection device at the upper part of the smelting furnace, discharging flue gas after dust collection by the dust collection device and spraying absorption, allowing the smelted copper water to flow out of the furnace bottom, flowing into a mold and cooling into metal blocks, and raking out slag;
(3) putting the metal blocks in the step (2) into an electrolytic cell for electrolytic refining of copper to obtain cathode copper, recycling the electrolyte until the total concentration of cobalt and nickel in the electrolyte is more than 0.5mol/L, then treating the electrolyte, adding calcium oxide into the electrolyte to adjust the pH of the solution to be 4.3, then filtering the solution to obtain first filtrate and first filter residue, returning the first filter residue to be mixed with wastewater residues for pretreatment, extracting copper from the first filtrate through a copper extraction line, then performing back extraction with sulfuric acid to obtain new electrolyte, returning the new electrolyte to the electrolytic cell, and extracting copper to obtain raffinate containing cobalt and nickel;
(4) adding the raffinate containing cobalt and nickel obtained in the step (3) into battery-grade cobalt sulfate or battery-grade nickel sulfate to adjust the molar ratio of cobalt and nickel in the solution to be 10:1, introducing chlorine into a sodium hydroxide solution, adjusting the pH value of the solution to be 11.3, adding the chlorine into the adjusted raffinate containing cobalt and nickel under a stirring state for 4.2 hours at a reaction temperature of 52 ℃, filtering to obtain a second filtrate and a second filter residue, washing the second filter residue, adding the washed materials into pure water to pulp, adding cobalt acetate, stirring and dissolving, spray drying, and calcining in an inert atmosphere to obtain battery-grade cobaltosic oxide;
(5) and (3) carrying out countercurrent extraction on the second filtrate obtained in the step (4) through P204, then carrying out two-stage countercurrent back extraction, wherein the first-stage countercurrent back extraction is used for obtaining a nickel sulfate solution, the second-stage countercurrent back extraction is used for obtaining a calcium-containing solution, and the nickel sulfate solution is concentrated and crystallized to obtain industrial-grade nickel sulfate.
And (2) concentrating and crystallizing the washing water obtained in the step (1) to obtain sodium sulfate crystals, and condensing the evaporated water vapor to obtain pure water.
In the step (2), the mass ratio of the washing waste water slag to the coke, the silicon dioxide and the waste copper material is 8.5:1.3:0.52:28, the copper content in the waste copper material is more than 85%, the obtained slag, the tailings obtained by cobalt-nickel metallurgy, the shale and the clay are subjected to ball milling and then water adding forming, the obtained slag, the tailings obtained by cobalt-nickel metallurgy, the shale and the clay are placed into a high-temperature furnace for calcination at 726 ℃ for 7 hours after being pressed to obtain the floor tiles, and the mass ratio of the tailings obtained by the slag and the cobalt-nickel metallurgy, the shale and the clay is 6:1.8:1.6: 4.8.
Adding sodium hydroxide into the dust collection material obtained by collecting dust in the step (2) to calcine in a rotary kiln, wherein the mass ratio of the dust collection material to the sodium hydroxide is 1:0.25, the calcination temperature is 345 ℃, the calcination time is 2.8 hours, washing the obtained calcined material to obtain a solution containing tin and zinc and filter residue, adding sulfuric acid into the filter residue, adding hydrogen peroxide to dissolve the filter residue to obtain a copper sulfate solution and a lead sulfate filter residue, returning the copper sulfate solution to prepare an electrolyte, adding ammonium sulfide into the solution containing tin and zinc to react at the temperature of 49 ℃ to obtain a zinc precipitate and a tin solution, concentrating and crystallizing the tin solution to obtain sodium stannate, roasting and sulfating the obtained zinc precipitate, adding dilute sulfuric acid to dissolve the obtained zinc precipitate to obtain a zinc sulfate solution, and concentrating and crystallizing to obtain zinc sulfate crystals.
And (3) extracting the first filtrate obtained in the step (3) by 6 stages, wherein the volume flow ratio of an organic phase to a water phase is 3.3:1 during extraction, the extractant is a copper chelating extractant, sodium hydroxide is added during the second stage of extraction to adjust the pH of the water phase of the second stage to be 2.8, 3-stage counter-current back extraction is adopted for back extraction, and the concentration of sulfuric acid is 0.9 mol/L.
In the step (4), the concentration of the sodium hydroxide solution is 1.1mol/L, the second filter residue is washed by hydrochloric acid solution with the pH value of 3.8, the mass ratio of the second filter residue to the hydrochloric acid solution is 1:9.2, then the second filter residue is washed by pure water until the pH value of washing water is 6.35, the ratio of the mole number of cobalt in the washed material to the mole number of cobalt in the added cobalt acetate is 2:1, the particle size of the spray-dried material is 13 micrometers, the calcination time is 8.2 hours under inert atmosphere and is 795 ℃, and the obtained calcined material is subjected to airflow crushing and screening to obtain the battery-grade cobaltosic oxide.
The stage number of the countercurrent extraction in the step (5) is 11, the volume ratio of P204 in the P204 extractant is 23%, the diluent is sulfonated kerosene, the saponification rate of P204 is 81%, the volume flow ratio of the extractant to the second filtrate is adjusted to maintain the content of nickel in the raffinate at 4.2mg/L, the stripping solution adopted in the first stage of countercurrent back extraction is sulfuric acid solution, the concentration of the sulfuric acid solution is 1.3mol/L, the molar ratio of hydrochloric acid in the stripping solution to nickel in the extractant is 2:1.04, the stripping stage number of the first stage of countercurrent back extraction is 12, the stripping solution adopted in the second stage of countercurrent back extraction is hydrochloric acid solution, the concentration of the hydrochloric acid solution is 2.8mol/L, and the stripping stage number of the second stage of countercurrent back extraction is 8.
The obtained cathode copper meets the standard of standard cathode copper.
The indexes of the obtained battery grade cobaltosic oxide are as follows:
| index (I) | Cobalt content | D10 | D50 | D90 |
| Numerical value | 72.4％ | 1.7 micron | 5.7 microns | 9.1 micron |
| Index (I) | BET | Loose-pack | Tap density | Angle of repose |
| Numerical value | 9.6m2/g | 1.81g/mL | 2.48g/mL | 12° |
| Index (I) | Ni | Ca | Mn | Zn |
| Numerical value | 1191ppm | 18ppm | 28ppm | 21ppm |
| Index (I) | Na | Cd | Mg | C |
| Numerical value | 25ppm | 0.3ppm | 21ppm | 41ppm |
| Index (I) | Sulfate radical | Chloride ion | ||
| Numerical value | 69ppm | 21ppm |
The purity of the industrial grade nickel sulfate is 99.1 percent, the purity of the lead sulfate is 98.4 percent, the purity of the zinc sulfate is 98.7 percent, and the purity of the sodium stannate is 87.9 percent.
The breaking strength of the floor tile is 4.5MPa, and the compressive strength is 43 MPa.
Finally, the recovery rates of cobalt, nickel, lead, zinc and tin are respectively 98.1%, 98.7%, 96.8% and 97.9%, and the comprehensive recovery rate of copper is more than 99%.
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 (7)
1. A treatment method of cobalt-nickel metallurgy wastewater slag is characterized by comprising the following steps:
(1) pretreating, namely adding wastewater slag into water, pulping and stirring, introducing carbon dioxide gas into the pulp, stirring and reacting at the temperature of 25-45 ℃ until the content of sulfate radicals in solid materials is lower than 500ppm, filtering, and adding hot water into filter residues for washing until the content of sulfate radicals in washing water is lower than 0.1g/L to obtain washing wastewater slag;
(2) putting the washing wastewater slag obtained in the step (1), coke, silicon dioxide and waste copper materials into a high-temperature smelting furnace for smelting at 1150 ℃ at 950, maintaining the concentration of carbon monoxide in the smelting furnace at 1000ppm, blowing external air into the smelting furnace for 4-6 hours, arranging a dust collection device at the upper part of the smelting furnace, collecting dust of flue gas by the dust collection device, spraying and absorbing the dust, discharging the flue gas to the outside, allowing the smelted copper water to flow out of the furnace bottom, flowing into a mold, cooling the molten copper water into metal blocks, and raking out slag;
(3) putting the metal blocks in the step (2) into an electrolytic cell for electrolytic copper refining to obtain cathode copper, recycling the electrolyte until the total concentration of cobalt and nickel in the electrolyte is more than 0.5mol/L, then treating the electrolyte, adding calcium oxide into the electrolyte to adjust the pH value of the solution to be 4-4.5, then filtering the solution to obtain first filtrate and first filter residue, returning the first filter residue to be mixed with wastewater slag for pretreatment, extracting copper from the first filtrate through a copper extraction line, then performing back extraction with sulfuric acid to obtain new electrolyte, returning the new electrolyte to the electrolytic cell, and extracting copper to obtain raffinate containing cobalt and nickel;
(4) adding the raffinate containing cobalt and nickel obtained in the step (3) into battery-grade cobalt sulfate or battery-grade nickel sulfate to adjust the molar ratio of cobalt and nickel in the solution to be 10:1, introducing chlorine into a sodium hydroxide solution, adjusting the pH value of the solution to be 11-11.5, adding the chlorine into the adjusted raffinate containing cobalt and nickel under a stirring state for 4-5 hours at the reaction temperature of 45-60 ℃, filtering to obtain a second filtrate and a second filter residue, washing the second filter residue, adding the washed materials into pure water to make a slurry, adding cobalt acetate, stirring and dissolving the cobalt acetate, performing spray drying, and calcining under an inert atmosphere to obtain battery-grade cobaltosic oxide;
(5) and (3) carrying out countercurrent extraction on the second filtrate obtained in the step (4) through P204, then carrying out two-stage countercurrent back extraction, wherein the first-stage countercurrent back extraction is used for obtaining a nickel sulfate solution, the second-stage countercurrent back extraction is used for obtaining a calcium-containing solution, and the nickel sulfate solution is concentrated and crystallized to obtain industrial-grade nickel sulfate.
2. The method for treating the cobalt-nickel metallurgical waste water slag according to claim 1, which is characterized by comprising the following steps: and (2) concentrating and crystallizing the washing water obtained in the step (1) to obtain sodium sulfate crystals, and condensing the evaporated water vapor to obtain pure water.
3. The method for treating the cobalt-nickel metallurgical waste water slag according to claim 1, which is characterized by comprising the following steps: in the step (2), the mass ratio of the washing waste water slag to the coke, the silicon dioxide and the waste copper material is 5-10:1-2:0.3-0.6:20-30, the copper content in the waste copper material is more than 85%, the obtained slag, the tailings obtained by cobalt-nickel metallurgy, the shale and the clay are subjected to ball milling and then water adding forming, the obtained slag, the tailings obtained by cobalt-nickel metallurgy, the shale and the clay are placed into a high temperature furnace for calcination at the temperature of 700 ℃ and 750 ℃ for 6-8 hours after pressing, so that the floor tiles are obtained, and the mass ratio of the tailings, the shale and the clay obtained by the slag and cobalt-nickel metallurgy is 4-8:1-2:1-2: 4-5.
4. The method for treating the cobalt-nickel metallurgical waste water slag according to claim 1, which is characterized by comprising the following steps: adding sodium hydroxide into the dust collection material obtained by collecting dust in the step (2) to calcine in a rotary kiln, wherein the mass ratio of the dust collection material to the sodium hydroxide is 1:0.2-0.3, the calcination temperature is 330-.
5. The method for treating the cobalt-nickel metallurgical waste water slag according to claim 1, which is characterized by comprising the following steps: the extraction stage number of the first filtrate obtained in the step (3) is 5-6 stages when copper is extracted, the volume flow ratio of an organic phase to a water phase during extraction is 3-4:1, the extractant is a copper chelating extractant, sodium hydroxide is added during the second stage of extraction to adjust the pH of the water phase of the second stage to be 2.5-3, 2-3 stages of counter-current back extraction are adopted for back extraction, and the concentration of sulfuric acid is 0.8-1.2 mol/L.
6. The method for treating the cobalt-nickel metallurgical waste water slag according to claim 1, which is characterized by comprising the following steps: in the step (4), the concentration of the sodium hydroxide solution is 1-1.2mol/L, the second filter residue is washed by hydrochloric acid solution with the pH value of 3-4, the mass ratio of the second filter residue to the hydrochloric acid solution is 1:8-10, then pure water is used for washing until the pH value of washing water is 6-6.5, the ratio of the mole number of cobalt in the washed material to the mole number of cobalt in the added cobalt acetate is 2:1, the particle size of the spray-dried material is 8-15 microns, the calcination time is 7-9 hours under inert atmosphere and is 850 ℃, the calcination material obtained is subjected to airflow crushing and screening to obtain the battery-grade cobaltosic oxide.
7. The method for treating the cobalt-nickel metallurgical waste water slag according to claim 1, which is characterized by comprising the following steps: the stage number of the countercurrent extraction in the step (5) is 10-12, the volume ratio of P204 in the P204 extractant is 20-25%, the diluent is sulfonated kerosene, the saponification rate of P204 is 75-85%, the volume flow ratio of the extractant to the second filtrate is adjusted to ensure that the content of nickel in the raffinate is maintained at 2-5mg/L, the stripping solution adopted by the first stage of countercurrent back extraction is sulfuric acid solution, the concentration of the sulfuric acid solution is 1-1.5mol/L, the molar ratio of hydrochloric acid in the stripping solution to nickel in the extractant is 2:1.02-1.05, the back extraction stage number of the first stage of countercurrent back extraction is 10-12, the back extraction solution adopted by the second stage of countercurrent back extraction is hydrochloric acid solution, the concentration of the hydrochloric acid solution is 2-3mol/L, and the back extraction stage number of the second stage of countercurrent back extraction is 7-9.
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| CN105886770A (en) * | 2015-01-26 | 2016-08-24 | 昆明冶金高等专科学校 | Efficient enrichment method for precious metal secondary resources |
| CN107058745A (en) * | 2017-04-21 | 2017-08-18 | 青海快驴电动汽车科技有限公司 | A kind of method that valuable metal is extracted in cobalt metallurgical waste |
| CN107666022A (en) * | 2017-09-25 | 2018-02-06 | 湖南工业大学 | Lithium, the recovery method of nickel cobalt manganese in a kind of discarded tertiary cathode material |
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