CN108588425A - A kind of processing method of cobalt metallurgy of nickel waste water slag - Google Patents

A kind of processing method of cobalt metallurgy of nickel waste water slag Download PDF

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CN108588425A
CN108588425A CN201810375178.2A CN201810375178A CN108588425A CN 108588425 A CN108588425 A CN 108588425A CN 201810375178 A CN201810375178 A CN 201810375178A CN 108588425 A CN108588425 A CN 108588425A
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nickel
cobalt
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方嘉城
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方嘉城
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0026Pyrometallurgy
    • C22B15/0028Smelting or converting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/20Obtaining zinc otherwise than by distilling
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/30Obtaining zinc or zinc oxide from metallic residues or scraps
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001Dry processes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The present invention discloses a kind of processing method of cobalt metallurgy of nickel waste water slag.Water slurryization stirring is added in waste water slag, carbon dioxide gas is then passed through into pulp material, filtration washing obtains washes slag;Obtained washes slag and coke, silica, waste cupron is put into togerther melting in high temperature melting furnace, copper water after melting is flowed out from furnace bottom, mold postcooling is flowed into metal derby, metal derby is put into progress electrolytical refined copper in electrolytic cell and obtains tough cathode, calcium oxide is added in electrolyte, then by filtering, it obtains the first filtrate and obtains the raffinate of the nickel containing cobalt by copper extraction line extracting copper, raffinate obtains cobaltic hydroxide after peroxidating, again cobaltosic oxide is obtained with cobalt acetate mixed calcining, solution after oxidation passes through extraction and separation, it obtains nickel sulfate and obtains nickel sulfate hexahydrate crystal by condensing crystallizing.Flow of the present invention is short, simple for process, and can realize the separation and recycling of full constituent, and the rate of recovery is high, and added value of product is high.

Description

A kind of processing method of cobalt metallurgy of nickel waste water slag
Technical field
The present invention relates to a kind of processing methods of cobalt metallurgy of nickel waste water slag, belong to Waste Disposal Technology field.
Background technology
Cobalt nickel is greatly improved as the status of strategic resource in the industry, in hard alloy, function ceramics, catalyst, army It is widely used in terms of industrial and commercial bank's industry, high-energy battery, there is the title of industrial monosodium glutamate.The production of cobalt nickel is based on hydrometallurgy.It is broadly divided into Following steps:
It leaches.As the hydrometallurgical first step, the height of leaching rate directly determines efficiency and benefit.Raw ore is by broken After broken, screening, enrichment and other processing, the process that the valuable metal inside mineral is transferred in solution.It is given birth in cobalt nickel Being leached in production mainly has acidic leaching, potassium cloride, ammonia leach and hyperbaric oxygen soaks etc..The auxiliary material mainly used has dense sulphur Acid, concentrated hydrochloric acid, chlorine, sulfur dioxide, ammonium hydroxide, air, sodium chlorate, hydrogen peroxide, manganese dioxide, sodium sulfite etc..General cobalt Nickel minerals mainly has sulphide ore and oxide ore, especially sulphide ore to have other metals mostly, so not only to be examined when leaching The leaching for considering cobalt nickel, it is also contemplated that the comprehensive reutilization of other valuable metals.
Removal of impurities is the significant process of product guarantee in cobalt metallurgy of nickel.For some a large amount of foreign ions, such as iron ion, Aluminium ion, it is main to consider chemical subtraction method, directly add sodium carbonate or sodium hydroxide to adjust pH in 3.5-4.0, due to ferrous iron It is relatively high to precipitate pH, thus generally can oxidizer make ferrous oxidising at ferric iron, also have amarillite method for removing iron. Can generally vulcanized sodium be used to clean lead cadmium copper, the general pH that adjusts is in 1.8-2.0 or so.Certainly due to consideration that integrating back It receives, first can remove other impurities again after relatively low pH drags for copper with other extractants.It, can be with for manganese, zinc, a small amount of iron-aluminum-manganese chromium It is removed with extraction.Common extractant has P204, P507, cyanex272.
The qualified cobalt nickel solution of extraction production need to produce presoma with precipitating reagent, and main presoma is carbonate, oxalic acid Salt.If producing crystal, such as nickel sulfate hexahydrate crystal, cobaltous sulfate crystal, then this step, direct concentration and evaporation crystallization are not needed.One As synthesis presoma use to add mode, control certain process pH and terminal pH, reaction temperature, reaction time etc..Control Certain pattern, grain size etc..
If directly selecting high pressure hydrogen reduction, this step need not be synthesized.If with high-temperature hydrogen reduction, presoma After broken, certain air temperature and current amount is controlled in reduction furnace, is then crushed, be vacuum-packed.
It is required to outer row leaching slag washing water, the raffinate of extraction, the mother liquor of liquid phase synthesis and wash water, by chemical precipitation Precipitation by metallic ion therein to be got off, waste water slag is obtained, waste water slag is based on hydroxide, with the extension of pilling up time, It will produce to obtain some oxides and carbonate, the component of waste water slag is as follows:
Since the metal species wherein contained are more, and each constituent content is similar, and conventional treatment process is difficult by it It all recycles, is precipitated, zinc, cobalt, nickel, copper are recycled, other elements are again using sulfide after the general dissolving using acid Into in waste water, after being then deposited again, into waste water slag, to cause the elements such as magnesium, calcium, manganese in waste water gradual Enrichment, and can not achieve various valuable metals all of not meeting the requirement now to environment.
Invention content
In view of this, the present invention provides a kind of processing method of cobalt metallurgy of nickel waste water slag, by the processing of carbon dioxide, Calcium sulfate can be converted in calcium carbonate, while be washed using water, by waste water slag sulfate radical and sodium salt wash, avoid Pyrometallurgical smelting process causes a large amount of sulfur dioxide and salt to evaporate, and blocks dust arrester installation, more easily uses pyrogenic attack Waste water slag, while waste water slag and waste cupron being put into togerther in smelting furnace and carry out reduction melting so that the metals such as cobalt nickel with it is same It rises and enters among copper water, and Ca, Mg and Fe etc. enters in clinker, clinker density is light, swims in copper water, to realize Ca, Mg and Fe Be recovered in cigarette ash together Deng the separation with cobalt ambrose alloy, while by tin, zinc, lead and a small amount of copper, then again in cigarette ash realize tin, The separation of zinc, lead and a small amount of copper, copper return do electrolyte, then recycle to obtain tough cathode, while cobalt nickel by electrorefining Into in electrolyte, copper is recycled after extraction, using oxidation, to obtain cobaltic hydroxide, by cobaltic hydroxide with Calcining obtains battery-grade cobaltosic oxide after cobalt acetate mixing, and technical grade sulfuric acid nickel is obtained using extraction and back extraction.
The present invention solves above-mentioned technical problem by following technological means:
A kind of processing method of cobalt metallurgy of nickel waste water slag, is following steps:
(1) it pre-processes, water slurryization stirring is added in waste water slag, then carbon dioxide gas is passed through into pulp material, in temperature Degree is stirred to react into solid material sulfate radical content for 25-45 DEG C and is less than 500ppm, then filters, and hot water washing is added in filter residue It is less than 0.1g/L to sulfate radical content in washings, obtains washes slag;
(2) the washes slag that step (1) obtains is put into togerther high melt with coke, silica, waste cupron Melting in stove, smelting temperature is 950-1150 DEG C, while maintaining a concentration of 500-1000ppm of the carbon monoxide in smelting furnace, External air blast enters in smelting furnace simultaneously, and smelting time is 4-6 hours, while smelting furnace top is provided with dust arrester installation, flue gas After dust arrester installation is gathered dust, using outer row after spray-absorption, the copper water after melting is flowed out from furnace bottom, after flowing into mold It is cooled to metal derby, clinker is raked off;
(3) metal derby in step (2) is put into progress electrolytical refined copper in electrolytic cell and obtains tough cathode, electrolyte cycle Using being handled after being more than 0.5mol/L to cobalt nickel total concentration therein, the pH that calcium oxide adjusts solution is added in this electrolyte The first filtrate and the first filter residue are obtained then by filtering for 4-4.5, the first filter residue return composite waste slag is located in advance Reason, the first filtrate extract line extracting copper by copper, are then stripped to obtain new electrolyte back in electrolytic cell with sulfuric acid, extraction The raffinate of the nickel containing cobalt after copper;
(4) battery grade cobalt sulfate or LITHIUM BATTERY nickel sulfate tune is added in the raffinate that will arrive the nickel containing cobalt that step (3) obtains It is 10 to save the cobalt nickel molar ratio in solution:1, chlorine is passed into sodium hydroxide solution, pH to the 11-11.5 of solution is adjusted, Then it is added under stirring in the raffinate of the nickel containing cobalt after adjusting, it is 4-5 hours that the time, which is added, and reaction temperature is 45-60 DEG C, then after filtering, the second filtrate and the second filter residue are obtained, by the second residue washing, then by the object after washing After pure water pulp is added in material, after cobalt acetate stirring and dissolving is added, spray drying, under an inert atmosphere calcining obtains four oxygen of LITHIUM BATTERY Change three cobalts;
(5) the second filtrate for obtaining step (4) pass through P204 counter-current extractions, then pass through two sections of countercurrent reextractions, first Section countercurrent reextraction obtains nickel sulfate solution, and second segment countercurrent reextraction obtains containing calcium solution, and nickel sulfate solution is obtained by condensing crystallizing To technical grade sulfuric acid nickel.
The washings that step (1) obtains obtain sulfate crystal by condensing crystallizing, and the vapor evaporated is by condensation After obtain pure water.
Washes slag and the mass ratio of coke, silica, waste cupron are 5-10 in the step (2):1-2:0.3- 0.6:20-30, the copper content in waste cupron are more than 85%, the tailings and shale and stick that obtained clinker is obtained with cobalt metallurgy of nickel Soil adds water molding after ball milling together, is put into high temperature furnace and calcines after compacting, and temperature is 700-750 DEG C, calcination time It is 6-8 hours, obtains floor tile, the mass ratio for tailings, shale and the clay that clinker, cobalt metallurgy of nickel obtain is 4-8:1-2:1-2:4- 5。
The material that gathers dust to gather dust in step (2) is added sodium hydroxide and is calcined in rotary kiln, and gather dust material and sodium hydroxide Mass ratio be 1:0.2-0.3, calcination temperature are 330-350 DEG C, and calcination time is 2-3 hours, and obtained calcining material is by washing It washs to obtain the solution and filter residue of tin-zinc containing, sulfuric acid is added in filter residue, dioxygen water dissolution is then added and obtains copper-bath and sulphur Lead plumbate filter residue, copper-bath, which returns, prepares electrolyte, and ammonium sulfide is added in the solution of tin-zinc containing, is 45-55 DEG C of reaction in temperature, It obtains zinc precipitation and solution of tin, solution of tin obtains sodium stannate by condensing crystallizing, obtained zinc precipitates after sulfating roasting Dilute sulfuric acid is added to dissolve to obtain solution of zinc sulfate, zinc sulfate crystal is obtained by condensing crystallizing.
It is 5-6 grades that the first filtrate obtained in the step (3), which extracts series when carrying out extracting copper, organic phase when extraction Volume flow ratio with water phase is 3-4:1, extractant is copper chelating extractant, and sodium hydroxide is added when extracting the second level and adjusts out The pH of the water phase of the second level is 2.5-3, and back extraction is stripped using 2-3 stage countercurrents, a concentration of 0.8-1.2mol/L of sulfuric acid.
A concentration of 1-1.2mol/L of sodium hydroxide solution, the second residue washing use pH for 3-4's in the step (4) Hydrochloric acid solution washs, and the mass ratio of the second filter residue and hydrochloric acid solution is 1:Then 8-10 uses pure water to washings again PH is 6-6.5, and the ratio between molal quantity of cobalt is 2 in the molal quantity of cobalt and the cobalt acetate of addition in the material after washing:1, spraying is dry Material particular diameter after dry is 8-15 microns, and calcination time is 7-9 hours under inert atmosphere, and calcination time is 700-850 DEG C, is obtained Calcining material by air-flow crushing and screening after obtain battery-grade cobaltosic oxide.
The series of counter-current extraction is 10-12 grades in the step (5), and the volume ratio of P204 is 20- in P204 extractants 25%, diluent is sulfonated kerosene, and the saponification rate of P204 is 75-85%, adjusts the volume flow ratio of extractant and the second filtrate So that the content of nickel maintains 2-5mg/L in raffinate, for the strip liquor that first segment countercurrent reextraction uses for sulfuric acid solution, sulfuric acid is molten A concentration of 1-1.5mol/L of liquid, the molar ratio of nickel is 2 in the hydrochloric acid and extractant in strip liquor:1.02-1.05, first segment are inverse The back extraction series of stream back extraction is 10-12 grades, and the strip liquor that second segment countercurrent reextraction uses is hydrochloric acid solution, the concentration of hydrochloric acid solution Back extraction series for 2-3mol/L, second segment countercurrent reextraction is 7-9 grades.
At present due to cobalt metallurgy of nickel during, can generally be associated with copper, using electrorefining after pyrometallurgical smelting, can will give up Grain slag and copper scap carry out pyrogenic attack admixed together, technological process is short, and uses this technique, can reduce in waste water slag Sulfate radical and salt content avoid a large amount of generations of a large amount of sulfur dioxide generation and salt from causing to block dust arrester installation, waste water slag Doping than high, and technological process is short, realizes efficiently using for whole components, obtains the oxidation of LITHIUM BATTERY four three of high added value Cobalt and technical grade sulfuric acid nickel, while clinker can be used by processing as floor tile, cigarette ash can recycle zinc, lead by processing With the recycling of tin.
This technological process is short, and realizes the recycling of full constituent, and the rate of recovery of each component is high, obtained added value of product It is high.
Contain nickel in obtained cobaltosic oxide, realize the doping of nickel, to improve capacity.
The beneficial effects of the invention are as follows:
1. technological process is short, the recycling of nickel cobalt copper zinc is realized, while Ca, Mg and Fe therein etc. is used to prepare floor tile.
2. technique cleverly precipitates conversion using carbon dioxide, to convert calcium sulfate to calcium carbonate, thus will Sulfate radical is converted into soluble sulfate radical, then passes through pure water, reduces the concentration of sulfate radical and salt, then by reduction Melting, to which cobalt nickel to be enriched in copper, and calcium and magnesium etc. is enriched in slag, and zinc, lead, tin etc. enter in cigarette ash, realize component Separation, using electrorefining, oxidation and extraction and separation, to realize the separation and recycling of copper, cobalt and nickel.
3. environmental friendly property is good, the generation of a large amount of sulfur dioxide is avoided.
Specific implementation mode
Below with reference to specific embodiment, the present invention is described in detail, a kind of cobalt metallurgy of nickel waste water slag of the present embodiment Processing method, be following steps:
(1) it pre-processes, water slurryization stirring is added in waste water slag, then carbon dioxide gas is passed through into pulp material, in temperature Degree is stirred to react into solid material sulfate radical content for 25-45 DEG C and is less than 500ppm, then filters, and hot water washing is added in filter residue It is less than 0.1g/L to sulfate radical content in washings, obtains washes slag;
(2) the washes slag that step (1) obtains is put into togerther high melt with coke, silica, waste cupron Melting in stove, smelting temperature is 950-1150 DEG C, while maintaining a concentration of 500-1000ppm of the carbon monoxide in smelting furnace, External air blast enters in smelting furnace simultaneously, and smelting time is 4-6 hours, while smelting furnace top is provided with dust arrester installation, flue gas After dust arrester installation is gathered dust, using outer row after spray-absorption, the copper water after melting is flowed out from furnace bottom, after flowing into mold It is cooled to metal derby, clinker is raked off;
(3) metal derby in step (2) is put into progress electrolytical refined copper in electrolytic cell and obtains tough cathode, electrolyte cycle Using being handled after being more than 0.5mol/L to cobalt nickel total concentration therein, the pH that calcium oxide adjusts solution is added in this electrolyte The first filtrate and the first filter residue are obtained then by filtering for 4-4.5, the first filter residue return composite waste slag is located in advance Reason, the first filtrate extract line extracting copper by copper, are then stripped to obtain new electrolyte back in electrolytic cell with sulfuric acid, extraction The raffinate of the nickel containing cobalt after copper;
(4) battery grade cobalt sulfate or LITHIUM BATTERY nickel sulfate tune is added in the raffinate that will arrive the nickel containing cobalt that step (3) obtains It is 10 to save the cobalt nickel molar ratio in solution:1, chlorine is passed into sodium hydroxide solution, pH to the 11-11.5 of solution is adjusted, Then it is added under stirring in the raffinate of the nickel containing cobalt after adjusting, it is 4-5 hours that the time, which is added, and reaction temperature is 45-60 DEG C, then after filtering, the second filtrate and the second filter residue are obtained, by the second residue washing, then by the object after washing After pure water pulp is added in material, after cobalt acetate stirring and dissolving is added, spray drying, under an inert atmosphere calcining obtains four oxygen of LITHIUM BATTERY Change three cobalts;
(5) the second filtrate for obtaining step (4) pass through P204 counter-current extractions, then pass through two sections of countercurrent reextractions, first Section countercurrent reextraction obtains nickel sulfate solution, and second segment countercurrent reextraction obtains containing calcium solution, and nickel sulfate solution is obtained by condensing crystallizing To technical grade sulfuric acid nickel.
The washings that step (1) obtains obtain sulfate crystal by condensing crystallizing, and the vapor evaporated is by condensation After obtain pure water.
Washes slag and the mass ratio of coke, silica, waste cupron are 5-10 in the step (2):1-2:0.3- 0.6:20-30, the copper content in waste cupron are more than 85%, the tailings and shale and stick that obtained clinker is obtained with cobalt metallurgy of nickel Soil adds water molding after ball milling together, is put into high temperature furnace and calcines after compacting, and temperature is 700-750 DEG C, calcination time It is 6-8 hours, obtains floor tile, the mass ratio for tailings, shale and the clay that clinker, cobalt metallurgy of nickel obtain is 4-8:1-2:1-2:4- 5。
The material that gathers dust to gather dust in step (2) is added sodium hydroxide and is calcined in rotary kiln, and gather dust material and sodium hydroxide Mass ratio be 1:0.2-0.3, calcination temperature are 330-350 DEG C, and calcination time is 2-3 hours, and obtained calcining material is by washing It washs to obtain the solution and filter residue of tin-zinc containing, sulfuric acid is added in filter residue, dioxygen water dissolution is then added and obtains copper-bath and sulphur Lead plumbate filter residue, copper-bath, which returns, prepares electrolyte, and ammonium sulfide is added in the solution of tin-zinc containing, is 45-55 DEG C of reaction in temperature, It obtains zinc precipitation and solution of tin, solution of tin obtains sodium stannate by condensing crystallizing, obtained zinc precipitates after sulfating roasting Dilute sulfuric acid is added to dissolve to obtain solution of zinc sulfate, zinc sulfate crystal is obtained by condensing crystallizing.
It is 5-6 grades that the first filtrate obtained in the step (3), which extracts series when carrying out extracting copper, organic phase when extraction Volume flow ratio with water phase is 3-4:1, extractant is copper chelating extractant, and sodium hydroxide is added when extracting the second level and adjusts out The pH of the water phase of the second level is 2.5-3, and back extraction is stripped using 2-3 stage countercurrents, a concentration of 0.8-1.2mol/L of sulfuric acid.
A concentration of 1-1.2mol/L of sodium hydroxide solution, the second residue washing use pH for 3-4's in the step (4) Hydrochloric acid solution washs, and the mass ratio of the second filter residue and hydrochloric acid solution is 1:Then 8-10 uses pure water to washings again PH is 6-6.5, and the ratio between molal quantity of cobalt is 2 in the molal quantity of cobalt and the cobalt acetate of addition in the material after washing:1, spraying is dry Material particular diameter after dry is 8-15 microns, and calcination time is 7-9 hours under inert atmosphere, and calcination time is 700-850 DEG C, is obtained Calcining material by air-flow crushing and screening after obtain battery-grade cobaltosic oxide.
The series of counter-current extraction is 10-12 grades in the step (5), and the volume ratio of P204 is 20- in P204 extractants 25%, diluent is sulfonated kerosene, and the saponification rate of P204 is 75-85%, adjusts the volume flow ratio of extractant and the second filtrate So that the content of nickel maintains 2-5mg/L in raffinate, for the strip liquor that first segment countercurrent reextraction uses for sulfuric acid solution, sulfuric acid is molten A concentration of 1-1.5mol/L of liquid, the molar ratio of nickel is 2 in the hydrochloric acid and extractant in strip liquor:1.02-1.05, first segment are inverse The back extraction series of stream back extraction is 10-12 grades, and the strip liquor that second segment countercurrent reextraction uses is hydrochloric acid solution, the concentration of hydrochloric acid solution Back extraction series for 2-3mol/L, second segment countercurrent reextraction is 7-9 grades.
Embodiment 1
A kind of processing method of cobalt metallurgy of nickel waste water slag, is following steps:
(1) it pre-processes, water slurryization stirring is added in waste water slag, then carbon dioxide gas is passed through into pulp material, in temperature Degree for 42 DEG C be stirred to react into solid material sulfate radical content be less than 500ppm, then filter, filter residue be added hot water wash to Sulfate radical content is less than 0.1g/L in washings, obtains washes slag;
(2) the washes slag that step (1) obtains is put into togerther high melt with coke, silica, waste cupron Melting in stove, smelting temperature is 1050 DEG C, while maintaining a concentration of 800ppm of the carbon monoxide in smelting furnace, while external drum Wind enters in smelting furnace, and smelting time is 5.2 hours, while smelting furnace top is provided with dust arrester installation, and flue gas is by the dress that gathers dust It sets after being gathered dust, using outer row after spray-absorption, the copper water after melting is flowed out from furnace bottom, flows into mold postcooling into metal Block, clinker are raked off;
(3) metal derby in step (2) is put into progress electrolytical refined copper in electrolytic cell and obtains tough cathode, electrolyte cycle Using being handled after being more than 0.5mol/L to cobalt nickel total concentration therein, the pH that calcium oxide adjusts solution is added in this electrolyte It is 4.3, then by filtering, obtains the first filtrate and the first filter residue, the first filter residue return composite waste slag is pre-processed, First filtrate extracts line extracting copper by copper, is then stripped to obtain new electrolyte back in electrolytic cell with sulfuric acid, extracting copper The raffinate of the nickel containing cobalt afterwards;
(4) battery grade cobalt sulfate or LITHIUM BATTERY nickel sulfate tune is added in the raffinate that will arrive the nickel containing cobalt that step (3) obtains It is 10 to save the cobalt nickel molar ratio in solution:1, chlorine is passed into sodium hydroxide solution, adjusts the pH to 11.2 of solution, then It is added under stirring in the raffinate of the nickel containing cobalt after adjusting, it is 4.8 hours that the time, which is added, reaction temperature 52 DEG C, then after filtering, the second filtrate and the second filter residue are obtained, then the second residue washing adds the material after washing After entering pure water pulp, after cobalt acetate stirring and dissolving is added, spray drying, under an inert atmosphere calcining obtains the oxidation of LITHIUM BATTERY four three Cobalt;
(5) the second filtrate for obtaining step (4) pass through P204 counter-current extractions, then pass through two sections of countercurrent reextractions, first Section countercurrent reextraction obtains nickel sulfate solution, and second segment countercurrent reextraction obtains containing calcium solution, and nickel sulfate solution is obtained by condensing crystallizing To technical grade sulfuric acid nickel.
The washings that step (1) obtains obtain sulfate crystal by condensing crystallizing, and the vapor evaporated is by condensation After obtain pure water.
Washes slag and the mass ratio of coke, silica, waste cupron are 8.5 in the step (2):1.8:0.45: 25, the copper content in waste cupron is more than 85%, together with the tailings and shale and clay that obtained clinker is obtained with cobalt metallurgy of nickel After ball milling plus water is molded, and is put into high temperature furnace and is calcined after compacting, and temperature is 725 DEG C, and calcination time is 7.5 hours, Floor tile is obtained, the mass ratio for tailings, shale and the clay that clinker, cobalt metallurgy of nickel obtain is 5.5:1.5:1.7:4.8.
The material that gathers dust to gather dust in step (2) is added sodium hydroxide and is calcined in rotary kiln, and gather dust material and sodium hydroxide Mass ratio be 1:0.25, calcination temperature is 345 DEG C, and calcination time is 2.5 hours, and obtained calcining material is contained by washing Sulfuric acid is added in filter residue by the solution and filter residue of tin zinc, and dioxygen water dissolution is then added and obtains copper-bath and lead sulfate filter residue, Copper-bath, which returns, prepares electrolyte, and ammonium sulfide is added in the solution of tin-zinc containing, is 48 DEG C of reactions in temperature, obtain zinc precipitation and Solution of tin, solution of tin obtain sodium stannate by condensing crystallizing, and it is molten that obtained zinc precipitates the addition dilute sulfuric acid after sulfating roasting Solution obtains solution of zinc sulfate, and zinc sulfate crystal is obtained by condensing crystallizing.
It is 6 grades that the first filtrate obtained in the step (3), which extracts series when carrying out extracting copper, when extraction organic phase with The volume flow ratio of water phase is 3.5:1, extractant is copper chelating extractant, and sodium hydroxide is added when extracting the second level and adjusts out the The pH of the water phase of two level is 2.8, and back extraction is stripped using 3 stage countercurrents, a concentration of 1.1mol/L of sulfuric acid.
A concentration of 1.1mol/L of sodium hydroxide solution in the step (4), the second residue washing use pH for 3.5 salt The mass ratio of acid solution wash, the second filter residue and hydrochloric acid solution is 1:9.2, then use again pure water to washings pH for 6.25, the ratio between the molal quantity of cobalt is 2 in the molal quantity of cobalt and the cobalt acetate of addition in the material after washing:1, after spray drying Material particular diameter is 12 microns, and calcination time is 8.2 hours under inert atmosphere, and calcination time is 810 DEG C, and obtained calcining material passes through Battery-grade cobaltosic oxide is obtained after air-flow crushing and screening.
The series of counter-current extraction is 11 grades in the step (5), and the volume ratio of P204 is 22% in P204 extractants, dilution Agent is sulfonated kerosene, and the saponification rate of P204 is 79%, and the volume flow ratio for adjusting extractant and the second filtrate makes in raffinate The content of nickel maintains 3.5mg/L, the strip liquor that first segment countercurrent reextraction uses for sulfuric acid solution, sulfuric acid solution it is a concentration of 1.35mol/L, the molar ratio of nickel is 2 in the hydrochloric acid and extractant in strip liquor:1.035, the back extraction grade of first segment countercurrent reextraction Number is 11 grades, and the strip liquor that second segment countercurrent reextraction uses is hydrochloric acid solution, a concentration of 2.5mol/L of hydrochloric acid solution, second segment The back extraction series of countercurrent reextraction is 8 grades.
Obtained tough cathode complies with standard the standard of tough cathode.
The index of obtained battery-grade cobaltosic oxide is as follows:
Index Cobalt content D10 D50 D90
Numerical value 72.7% 1.9 micron 5.8 micron 9.1 micron
Index BET Pine dress Tap density Angle of repose
Numerical value 9.5m2/g 1.85g/mL 2.49g/mL 13°
Index Ni Ca Mn Zn
Numerical value 1200ppm 12.5ppm 21.5ppm 18.5ppm
Index Na Cd Mg C
Numerical value 21.5ppm 0.6ppm 12.8ppm 42ppm
Index Sulfate radical Chlorion
Numerical value 66ppm 17ppm
The purity of technical grade sulfuric acid nickel is 99.1%, and the purity of lead sulfate is 98.1%, and the purity of zinc sulfate is 99%, tin The purity of sour sodium is 87.8%.
The flexural strength of floor tile is 4.5Mpa, compression strength 41Mpa.
Final cobalt, nickel, lead, zinc, tin the rate of recovery be respectively 97.8%, 98.1%, 98.6%, 96.8% and 97.8%, The synthesis of copper returns rate and is more than 99%.
Embodiment 2
A kind of processing method of cobalt metallurgy of nickel waste water slag, is following steps:
(1) it pre-processes, water slurryization stirring is added in waste water slag, then carbon dioxide gas is passed through into pulp material, in temperature Degree for 42 DEG C be stirred to react into solid material sulfate radical content be less than 500ppm, then filter, filter residue be added hot water wash to Sulfate radical content is less than 0.1g/L in washings, obtains washes slag;
(2) the washes slag that step (1) obtains is put into togerther high melt with coke, silica, waste cupron Melting in stove, smelting temperature is 985 DEG C, while maintaining a concentration of 800ppm of the carbon monoxide in smelting furnace, while external drum Wind enters in smelting furnace, and smelting time is 5.2 hours, while smelting furnace top is provided with dust arrester installation, and flue gas is by the dress that gathers dust It sets after being gathered dust, using outer row after spray-absorption, the copper water after melting is flowed out from furnace bottom, flows into mold postcooling into metal Block, clinker are raked off;
(3) metal derby in step (2) is put into progress electrolytical refined copper in electrolytic cell and obtains tough cathode, electrolyte cycle Using being handled after being more than 0.5mol/L to cobalt nickel total concentration therein, the pH that calcium oxide adjusts solution is added in this electrolyte It is 4.25, then by filtering, obtains the first filtrate and the first filter residue, the first filter residue return composite waste slag is located in advance Reason, the first filtrate extract line extracting copper by copper, are then stripped to obtain new electrolyte back in electrolytic cell with sulfuric acid, extraction The raffinate of the nickel containing cobalt after copper;
(4) battery grade cobalt sulfate or LITHIUM BATTERY nickel sulfate tune is added in the raffinate that will arrive the nickel containing cobalt that step (3) obtains It is 10 to save the cobalt nickel molar ratio in solution:1, chlorine is passed into sodium hydroxide solution, adjusts the pH to 11.35 of solution, so It is added under stirring afterwards in the raffinate of the nickel containing cobalt after adjusting, it is 4.5 hours that the time, which is added, reaction temperature 52 DEG C, then after filtering, the second filtrate and the second filter residue are obtained, then the second residue washing adds the material after washing After entering pure water pulp, after cobalt acetate stirring and dissolving is added, spray drying, under an inert atmosphere calcining obtains the oxidation of LITHIUM BATTERY four three Cobalt;
(5) the second filtrate for obtaining step (4) pass through P204 counter-current extractions, then pass through two sections of countercurrent reextractions, first Section countercurrent reextraction obtains nickel sulfate solution, and second segment countercurrent reextraction obtains containing calcium solution, and nickel sulfate solution is obtained by condensing crystallizing To technical grade sulfuric acid nickel.
The washings that step (1) obtains obtain sulfate crystal by condensing crystallizing, and the vapor evaporated is by condensation After obtain pure water.
Washes slag and the mass ratio of coke, silica, waste cupron are 8.3 in the step (2):1.5:0.46: 26, the copper content in waste cupron is more than 85%, together with the tailings and shale and clay that obtained clinker is obtained with cobalt metallurgy of nickel After ball milling plus water is molded, and is put into high temperature furnace and is calcined after compacting, and temperature is 720 DEG C, and calcination time is 7.5 hours, Floor tile is obtained, the mass ratio for tailings, shale and the clay that clinker, cobalt metallurgy of nickel obtain is 6:1.8:1.6:4.6.
The material that gathers dust to gather dust in step (2) is added sodium hydroxide and is calcined in rotary kiln, and gather dust material and sodium hydroxide Mass ratio be 1:0.27, calcination temperature is 345 DEG C, and calcination time is 2.8 hours, and obtained calcining material is contained by washing Sulfuric acid is added in filter residue by the solution and filter residue of tin zinc, and dioxygen water dissolution is then added and obtains copper-bath and lead sulfate filter residue, Copper-bath, which returns, prepares electrolyte, and ammonium sulfide is added in the solution of tin-zinc containing, is 49 DEG C of reactions in temperature, obtain zinc precipitation and Solution of tin, solution of tin obtain sodium stannate by condensing crystallizing, and it is molten that obtained zinc precipitates the addition dilute sulfuric acid after sulfating roasting Solution obtains solution of zinc sulfate, and zinc sulfate crystal is obtained by condensing crystallizing.
It is 6 grades that the first filtrate obtained in the step (3), which extracts series when carrying out extracting copper, when extraction organic phase with The volume flow ratio of water phase is 3.6:1, extractant is copper chelating extractant, and sodium hydroxide is added when extracting the second level and adjusts out the The pH of the water phase of two level is 2.8, and back extraction is stripped using 3 stage countercurrents, a concentration of 0.95mol/L of sulfuric acid.
A concentration of 1.15mol/L of sodium hydroxide solution, the second residue washing use pH for 3.5 in the step (4) Hydrochloric acid solution washs, and the mass ratio of the second filter residue and hydrochloric acid solution is 1:9.1, then use pure water to the pH of washings again It is 6.3, the ratio between molal quantity of cobalt is 2 in the molal quantity of cobalt and the cobalt acetate of addition in the material after washing:1, after spray drying Material particular diameter be 12 microns, calcination time is 8.1 hours under inert atmosphere, and calcination time is 815 DEG C, obtained calcining material warp Battery-grade cobaltosic oxide is obtained after crossing air-flow crushing and screening.
The series of counter-current extraction is 11 grades in the step (5), and the volume ratio of P204 is 24% in P204 extractants, dilution Agent is sulfonated kerosene, and the saponification rate of P204 is 79%, and the volume flow ratio for adjusting extractant and the second filtrate makes in raffinate The content of nickel maintains 4.1mg/L, the strip liquor that first segment countercurrent reextraction uses for sulfuric acid solution, sulfuric acid solution it is a concentration of 1.3mol/L, the molar ratio of nickel is 2 in the hydrochloric acid and extractant in strip liquor:1.04, the back extraction series of first segment countercurrent reextraction It it is 11 grades, the strip liquor that second segment countercurrent reextraction uses is hydrochloric acid solution, a concentration of 2.7mol/L of hydrochloric acid solution, and second segment is inverse The back extraction series of stream back extraction is 9 grades.
Obtained tough cathode complies with standard the standard of tough cathode.
The index of obtained battery-grade cobaltosic oxide is as follows:
Index Cobalt content D10 D50 D90
Numerical value 72.6% 1.8 micron 5.9 micron 9.2 micron
Index BET Pine dress Tap density Angle of repose
Numerical value 9.7m2/g 1.85g/mL 2.48g/mL 13°
Index Ni Ca Mn Zn
Numerical value 1195ppm 13ppm 24ppm 18.5ppm
Index Na Cd Mg C
Numerical value 21.9ppm 0.7ppm 12.8ppm 45ppm
Index Sulfate radical Chlorion
Numerical value 66ppm 17ppm
The purity of technical grade sulfuric acid nickel is 99.2%, and the purity of lead sulfate is 98.2%, and the purity of zinc sulfate is 98.9%, The purity of sodium stannate is 87.8%.
The flexural strength of floor tile is 4.7Mpa, compression strength 42Mpa.
Final cobalt, nickel, lead, zinc, tin the rate of recovery be respectively 97.9%, 98.2%, 98.6%, 96.8% and 97.7%, The synthesis of copper returns rate and is more than 99%.
Embodiment 3
A kind of processing method of cobalt metallurgy of nickel waste water slag, is following steps:
(1) it pre-processes, water slurryization stirring is added in waste water slag, then carbon dioxide gas is passed through into pulp material, in temperature Degree for 42 DEG C be stirred to react into solid material sulfate radical content be less than 500ppm, then filter, filter residue be added hot water wash to Sulfate radical content is less than 0.1g/L in washings, obtains washes slag;
(2) the washes slag that step (1) obtains is put into togerther high melt with coke, silica, waste cupron Melting in stove, smelting temperature is 1080 DEG C, while maintaining a concentration of 850ppm of the carbon monoxide in smelting furnace, while external drum Wind enters in smelting furnace, and smelting time is 5.2 hours, while smelting furnace top is provided with dust arrester installation, and flue gas is by the dress that gathers dust It sets after being gathered dust, using outer row after spray-absorption, the copper water after melting is flowed out from furnace bottom, flows into mold postcooling into metal Block, clinker are raked off;
(3) metal derby in step (2) is put into progress electrolytical refined copper in electrolytic cell and obtains tough cathode, electrolyte cycle Using being handled after being more than 0.5mol/L to cobalt nickel total concentration therein, the pH that calcium oxide adjusts solution is added in this electrolyte It is 4.3, then by filtering, obtains the first filtrate and the first filter residue, the first filter residue return composite waste slag is pre-processed, First filtrate extracts line extracting copper by copper, is then stripped to obtain new electrolyte back in electrolytic cell with sulfuric acid, extracting copper The raffinate of the nickel containing cobalt afterwards;
(4) battery grade cobalt sulfate or LITHIUM BATTERY nickel sulfate tune is added in the raffinate that will arrive the nickel containing cobalt that step (3) obtains It is 10 to save the cobalt nickel molar ratio in solution:1, chlorine is passed into sodium hydroxide solution, adjusts the pH to 11.3 of solution, then It is added under stirring in the raffinate of the nickel containing cobalt after adjusting, it is 4.2 hours that the time, which is added, reaction temperature 52 DEG C, then after filtering, the second filtrate and the second filter residue are obtained, then the second residue washing adds the material after washing After entering pure water pulp, after cobalt acetate stirring and dissolving is added, spray drying, under an inert atmosphere calcining obtains the oxidation of LITHIUM BATTERY four three Cobalt;
(5) the second filtrate for obtaining step (4) pass through P204 counter-current extractions, then pass through two sections of countercurrent reextractions, first Section countercurrent reextraction obtains nickel sulfate solution, and second segment countercurrent reextraction obtains containing calcium solution, and nickel sulfate solution is obtained by condensing crystallizing To technical grade sulfuric acid nickel.
The washings that step (1) obtains obtain sulfate crystal by condensing crystallizing, and the vapor evaporated is by condensation After obtain pure water.
Washes slag and the mass ratio of coke, silica, waste cupron are 8.5 in the step (2):1.3:0.52: 28, the copper content in waste cupron is more than 85%, together with the tailings and shale and clay that obtained clinker is obtained with cobalt metallurgy of nickel After ball milling plus water is molded, and is put into high temperature furnace and is calcined after compacting, and temperature is 726 DEG C, and calcination time is 7 hours, is obtained The mass ratio of the tailings, shale and the clay that are obtained to floor tile, clinker, cobalt metallurgy of nickel is 6:1.8:1.6:4.8.
The material that gathers dust to gather dust in step (2) is added sodium hydroxide and is calcined in rotary kiln, and gather dust material and sodium hydroxide Mass ratio be 1:0.25, calcination temperature is 345 DEG C, and calcination time is 2.8 hours, and obtained calcining material is contained by washing Sulfuric acid is added in filter residue by the solution and filter residue of tin zinc, and dioxygen water dissolution is then added and obtains copper-bath and lead sulfate filter residue, Copper-bath, which returns, prepares electrolyte, and ammonium sulfide is added in the solution of tin-zinc containing, is 49 DEG C of reactions in temperature, obtain zinc precipitation and Solution of tin, solution of tin obtain sodium stannate by condensing crystallizing, and it is molten that obtained zinc precipitates the addition dilute sulfuric acid after sulfating roasting Solution obtains solution of zinc sulfate, and zinc sulfate crystal is obtained by condensing crystallizing.
It is 6 grades that the first filtrate obtained in the step (3), which extracts series when carrying out extracting copper, when extraction organic phase with The volume flow ratio of water phase is 3.3:1, extractant is copper chelating extractant, and sodium hydroxide is added when extracting the second level and adjusts out the The pH of the water phase of two level is 2.8, and back extraction is stripped using 3 stage countercurrents, a concentration of 0.9mol/L of sulfuric acid.
A concentration of 1.1mol/L of sodium hydroxide solution in the step (4), the second residue washing use pH for 3.8 salt The mass ratio of acid solution wash, the second filter residue and hydrochloric acid solution is 1:9.2, then use again pure water to washings pH for 6.35, the ratio between the molal quantity of cobalt is 2 in the molal quantity of cobalt and the cobalt acetate of addition in the material after washing:1, after spray drying Material particular diameter is 13 microns, and calcination time is 8.2 hours under inert atmosphere, and calcination time is 795 DEG C, and obtained calcining material passes through Battery-grade cobaltosic oxide is obtained after air-flow crushing and screening.
The series of counter-current extraction is 11 grades in the step (5), and the volume ratio of P204 is 23% in P204 extractants, dilution Agent is sulfonated kerosene, and the saponification rate of P204 is 81%, and the volume flow ratio for adjusting extractant and the second filtrate makes in raffinate The content of nickel maintains 4.2mg/L, the strip liquor that first segment countercurrent reextraction uses for sulfuric acid solution, sulfuric acid solution it is a concentration of 1.3mol/L, the molar ratio of nickel is 2 in the hydrochloric acid and extractant in strip liquor:1.04, the back extraction series of first segment countercurrent reextraction It it is 12 grades, the strip liquor that second segment countercurrent reextraction uses is hydrochloric acid solution, a concentration of 2.8mol/L of hydrochloric acid solution, and second segment is inverse The back extraction series of stream back extraction is 8 grades.
Obtained tough cathode complies with standard the standard of tough cathode.
The index of obtained battery-grade cobaltosic oxide is as follows:
Index Cobalt content D10 D50 D90
Numerical value 72.4% 1.7 micron 5.7 micron 9.1 micron
Index BET Pine dress Tap density Angle of repose
Numerical value 9.6m2/g 1.81g/mL 2.48g/mL 12°
Index Ni Ca Mn Zn
Numerical value 1191ppm 18ppm 28ppm 21ppm
Index Na Cd Mg C
Numerical value 25ppm 0.3ppm 21ppm 41ppm
Index Sulfate radical Chlorion
Numerical value 69ppm 21ppm
The purity of technical grade sulfuric acid nickel is 99.1%, and the purity of lead sulfate is 98.4%, and the purity of zinc sulfate is 98.7%, The purity of sodium stannate is 87.9%.
The flexural strength of floor tile is 4.5Mpa, compression strength 43Mpa.
Final cobalt, nickel, lead, zinc, tin the rate of recovery be respectively 98.1%, 98.1%, 98.7%, 96.8% and 97.9%, The synthesis of copper returns rate and is more than 99%.
Finally illustrate, the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although with reference to compared with Good embodiment describes the invention in detail, it will be understood by those of ordinary skill in the art that, it can be to the skill of the present invention Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this In the right of invention.

Claims (7)

1. a kind of processing method of cobalt metallurgy of nickel waste water slag, which is characterized in that be following steps:
(1) it pre-processes, water slurryization stirring is added in waste water slag, then carbon dioxide gas is passed through into pulp material, is in temperature 25-45 DEG C is stirred to react into solid material sulfate radical content and is less than 500ppm, then filters, filter residue is added hot water and washs to washing It washs sulfate radical content in water and is less than 0.1g/L, obtain washes slag;
(2) the washes slag that step (1) obtains is put into togerther with coke, silica, waste cupron in high temperature melting furnace Melting, smelting temperature is 950-1150 DEG C, while maintaining a concentration of 500-1000ppm of the carbon monoxide in smelting furnace, simultaneously External air blast enters in smelting furnace, and smelting time is 4-6 hours, while smelting furnace top is provided with dust arrester installation, and flue gas passes through After dust arrester installation is gathered dust, using outer row after spray-absorption, the copper water after melting is flowed out from furnace bottom, flows into mold postcooling At metal derby, clinker is raked off;
(3) metal derby in step (2) is put into progress electrolytical refined copper in electrolytic cell and obtains tough cathode, electrolyte recycles It is handled after being more than 0.5mol/L to cobalt nickel total concentration therein, it is 4- that this electrolyte, which is added calcium oxide to adjust the pH of solution, 4.5, then by filtering, the first filtrate and the first filter residue are obtained, the first filter residue return composite waste slag is pre-processed, the One filtrate extracts line extracting copper by copper, is then stripped to obtain new electrolyte back in electrolytic cell, after extracting copper with sulfuric acid The nickel containing cobalt raffinate;
(4) battery grade cobalt sulfate is added for the raffinate that will arrive the nickel containing cobalt that step (3) obtains or the adjusting of LITHIUM BATTERY nickel sulfate is molten Cobalt nickel molar ratio in liquid is 10:1, chlorine is passed into sodium hydroxide solution, adjusts pH to the 11-11.5 of solution, then It is added under stirring in the raffinate of the nickel containing cobalt after adjusting, it is 4-5 hours that the time, which is added, reaction temperature 45- 60 DEG C, then after filtering, the second filtrate and the second filter residue are obtained, by the second residue washing, then by the material after washing After pure water pulp is added, after cobalt acetate stirring and dissolving is added, spray drying, under an inert atmosphere calcining obtains the oxidation of LITHIUM BATTERY four Three cobalts;
(5) the second filtrate for obtaining step (4) passes through P204 counter-current extractions, then passes through two sections of countercurrent reextractions, and first segment is inverse Stream back extraction obtains nickel sulfate solution, and second segment countercurrent reextraction obtains containing calcium solution, and nickel sulfate solution obtains work by condensing crystallizing Industry grade nickel sulfate.
2. a kind of processing method of cobalt metallurgy of nickel waste water slag according to claim 1, it is characterised in that:Step (1) obtains Washings obtain sulfate crystal by condensing crystallizing, the vapor evaporated obtains pure water after condensation.
3. a kind of processing method of cobalt metallurgy of nickel waste water slag according to claim 1, it is characterised in that:The step (2) The mass ratio of middle washes slag and coke, silica, waste cupron is 5-10:1-2:0.3-0.6:20-30, in waste cupron Copper content is more than 85%, adds water after ball milling together with the tailings and shale and clay that obtained clinker is obtained with cobalt metallurgy of nickel Molding, is put into high temperature furnace after compacting and calcines, and temperature is 700-750 DEG C, and calcination time is 6-8 hours, obtains floor tile, stove The mass ratio for tailings, shale and the clay that slag, cobalt metallurgy of nickel obtain is 4-8:1-2:1-2:4-5.
4. a kind of processing method of cobalt metallurgy of nickel waste water slag according to claim 1, it is characterised in that:It is received in step (2) What dirt obtained gather dust, and sodium hydroxide is added in material is calcined in rotary kiln, and the mass ratio of gather dust material and sodium hydroxide is 1:0.2-0.3, Calcination temperature is 330-350 DEG C, and calcination time is 2-3 hour, obtained calcining material by washing obtain the solution of tin-zinc containing with Sulfuric acid is added in filter residue by filter residue, and dioxygen water dissolution is then added and obtains copper-bath and lead sulfate filter residue, copper-bath returns It returns and prepares electrolyte, ammonium sulfide is added in the solution of tin-zinc containing, is 45-55 DEG C of reaction in temperature, obtains zinc precipitation and solution of tin, tin Solution obtains sodium stannate by condensing crystallizing, and obtained zinc precipitates the addition dilute sulfuric acid after sulfating roasting and dissolves to obtain sulfuric acid Zinc solution obtains zinc sulfate crystal by condensing crystallizing.
5. a kind of processing method of cobalt metallurgy of nickel waste water slag according to claim 1, it is characterised in that:The step (3) In obtained the first filtrate series is extracted when carrying out extracting copper is 5-6 grades, the volume flow ratio of organic phase and water phase when extraction For 3-4:1, extractant is copper chelating extractant, and the pH that the water phase that sodium hydroxide adjusts out the second level is added when extracting the second level is 2.5-3, back extraction are stripped using 2-3 stage countercurrents, a concentration of 0.8-1.2mol/L of sulfuric acid.
6. a kind of processing method of cobalt metallurgy of nickel waste water slag according to claim 1, it is characterised in that:The step (4) A concentration of 1-1.2mol/L of middle sodium hydroxide solution, the second residue washing use pH to be washed for the hydrochloric acid solution of 3-4, the second filter The mass ratio of slag and hydrochloric acid solution is 1:Then 8-10 uses pure water to the pH of washings for 6-6.5, the object after washing again The ratio between molal quantity of cobalt is 2 in the molal quantity of cobalt and the cobalt acetate of addition in material:1, the material particular diameter after spray drying is 8-15 Micron, calcination time is 7-9 hours under inert atmosphere, and calcination time is 700-850 DEG C, and obtained calcining material passes through air-flow crushing With battery-grade cobaltosic oxide is obtained after screening.
7. a kind of processing method of cobalt metallurgy of nickel waste water slag according to claim 1, it is characterised in that:The step (5) The series of middle counter-current extraction is 10-12 grades, and the volume ratio of P204 is 20-25% in P204 extractants, and diluent is sulfonated kerosene, The saponification rate of P204 is 75-85%, and the volume flow ratio for adjusting extractant and the second filtrate makes the content of nickel in raffinate tie up It holds in 2-5mg/L, the strip liquor that first segment countercurrent reextraction uses is sulfuric acid solution, a concentration of 1-1.5mol/L of sulfuric acid solution, The molar ratio of nickel is 2 in hydrochloric acid and extractant in strip liquor:The back extraction series of 1.02-1.05, first segment countercurrent reextraction are 10- 12 grades, the strip liquor that second segment countercurrent reextraction uses is hydrochloric acid solution, a concentration of 2-3mol/L of hydrochloric acid solution, second segment adverse current The back extraction series of back extraction is 7-9 grades.
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