CN108374093B - A kind of processing method of sulfide removal of impurities slag - Google Patents

A kind of processing method of sulfide removal of impurities slag Download PDF

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CN108374093B
CN108374093B CN201810191153.7A CN201810191153A CN108374093B CN 108374093 B CN108374093 B CN 108374093B CN 201810191153 A CN201810191153 A CN 201810191153A CN 108374093 B CN108374093 B CN 108374093B
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蒋央芳
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蒋央芳
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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
    • C22B7/04Working-up slag
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/22Alkali metal sulfides or polysulfides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00Ammonia; Compounds thereof
    • C01C1/24Sulfates of ammonium
    • C01C1/244Preparation by double decomposition of ammonium salts with sulfates
    • 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
    • C22B15/0063Hydrometallurgy
    • C22B15/0065Leaching or slurrying
    • C22B15/0078Leaching or slurrying with ammoniacal solutions, e.g. ammonium hydroxide
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B17/00Obtaining cadmium
    • C22B17/04Obtaining cadmium 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
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/34Obtaining zinc oxide
    • 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
    • C22B23/0407Leaching processes
    • C22B23/0446Leaching processes with an ammoniacal liquor or with a hydroxide of an alkali or alkaline-earth metal
    • 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
    • C22B23/0453Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/306Ketones or aldehydes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00Obtaining manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/12Dry methods smelting of sulfides or formation of mattes by gases
    • 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 sulfide removal of impurities slag.Material is dried to moisture content lower than 1%, then by broken sieving, material after sieving is restored in hydrogen atmosphere, it is absorbed after the gas after reduction is drawn by air-introduced machine simultaneously using sodium hydroxide, metal powder is passed through to the leaching of ammonia and carbonate, cobalt ambrose alloy is separated with other metals, the separation of zinc-manganese and cadmium lead is realized by the difference of metal activity again, pass through extraction and oxidation again, realize same, cobalt and nickel separation, the separation of lead cadmium is realized in the separation that zinc-manganese is realized by oxidation using sulfuric acid leaching.Process of the present invention is short, simple process, and can be realized the separation and recycling of full constituent, and the rate of recovery is high, and finally obtained product purity is high, and added value of product is big, realizes the recycling of sulphion and recycles, the influence to environment is small.

Description

A kind of processing method of sulfide removal of impurities slag
Technical field
The present invention relates to a kind of processing methods of sulfide removal of impurities slag, belong to Waste Disposal Technology field.
Background technique
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 raw in cobalt nickel Leaching 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, which mainly has sulphide ore and oxide ore, especially sulphide ore mostly, other metals, so not only to examine 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 it is ferrous oxidising at ferric iron, for except iron, there are also amarillite methods. It can generally be cleaned using vulcanized sodium for 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 lower pH fishes out 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, partial size etc..
If directly selecting high pressure hydrogen reduction, do not need to synthesize this step.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.
Sulfide slag is obtained in sulfide dedoping step, the component in sulfide slag is as follows:
Meanwhile the parameters such as sample detection its granularity, specific surface area, it is as a result as follows:
Index BET D10 D50 D90
Quantity 15-20m2/g 3-5μm 8-10μm 15-20μm
Conventional treatment process be by sulfide after sulfating roasting acid dissolution, then separate again to recycling wherein Metal, but this technique has the following problems:
1. sulfating roasting can generate to obtain sulfur dioxide, energy consumption is high, and sulfur dioxide passes through the sulfurous acid that absorption obtains Salt is little to cobalt nickel fibers purposes, to be unfavorable for the recycling of sulphite.
2. the material after sulfating roasting, after peracid is molten, all metallic elements are all dissolved and come out, lead to the later period Separation, impurity removal long flow path, and the rate of recovery of various metals is not high.
Summary of the invention
In view of this, process is short, simple process, and energy the present invention provides a kind of processing method of sulfide removal of impurities slag Enough realize the separation and recycling of full constituent, the rate of recovery is high, and finally obtained product purity is high, and added value of product is big, realizes It the recycling of sulphion and recycles, the influence to environment is small.
The present invention solves above-mentioned technical problem by following technological means:
A kind of processing method of sulfide removal of impurities slag, is following steps:
(1) it pre-processes, material is dried to moisture content lower than 1%, then by broken, 100-200 mesh is crossed after screening Sieve;
(2) hydrogen reducing restores the material after sieving in hydrogen atmosphere, while the gas after reduction is passed through air inducing Power traction is absorbed after going out using sodium hydroxide, and the recovery time is 5-6 hours, and reduction temperature is 350-450 DEG C, obtains mixed metal powder End;
(3) metal powder being put into closed reactor and is leached, leachate is the mixed solution of ammonium hydroxide and ammonium carbonate, It is passed through air, extraction temperature is 50-60 DEG C, and extraction time is 4-5 hours, it then filters, obtains the first filtrate and the first filter residue, Beta-diketone extracting agent is added in first filtrate and extracts copper therein, then is stripped using sulfuric acid, copper-bath is obtained, by concentration Crystallization obtains cupric sulphate crystal, and the raffinate after extracting copper is passed through ozone, is 35-45 DEG C in temperature and is stirred to react 2-3 hours, passes through Cobaltic hydroxide precipitating and nickel filtrate is obtained by filtration, obtained nickel filtrate is added oxalic acid, obtains nickel oxalate;
Ferrous sulfate solution is added in (4) first filter residues, and temperature is 40-60 DEG C and is stirred to react 2-3 hours, then filters, obtains To the second filtrate and the second filter residue, the second obtained filtrate is passed through oxygen after except iron, is 110-140 DEG C in temperature, pressure To be stirred to react under 2-2.5atm 2-3 hours, manganese dioxide precipitate and filtrate containing zinc is obtained by filtration, bicarbonate is added in filtrate containing zinc Then ammonium obtains nano zine oxide by calcining by precipitation reaction;
(5) the second filter residue addition sulfuric acid is dissolved, by third filter residue and third filtrate, third filtrate is obtained by filtration After except iron, cadmium sulfate solution is obtained.
Dry process tiles material to material thickness no more than 3cm, dries under ventilated environment.
Hydrogen reduction in the step (2), the flow velocity of hydrogen are 1-3m/s, the molal quantity and material of the hydrogen being passed through The ratio between middle metal total moles are 4-5:1, and the wind speed that air-introduced machine is drawn is 1-3m/s, and the concentration of sodium hydroxide absorbing liquid is 8- 10mol/L absorbs and uses spray-absorption, and lead is done in absorbing liquid return when the concentration of sodium hydroxide is lower than 1mol/L in liquid to be absorbed The cleaner of cadmium.
Anti-corrosion glass steel layer is coated in air-introduced machine and air inducing pipeline in step (2).
When metal powder leaches in closed reactor in the step (3), the mass ratio of metal powder and leachate is 1:3-4, the concentration of ammonium hydroxide is 3-5mol/L in leachate, and the concentration of ammonium carbonate is 1-1.2mol/L, is passed through air per hour Amount is 5-8 times of leachate total volume, and leaching process maintains stirring, mixing speed 100-150r/min, the first filtrate Beta-diketone extracting agent extracting copper process is added, extracts counter-current extraction technique, the proportion of beta-diketone extracting agent is that volume parts are 10- 15% beta-diketon, the TBP that the sulfonated kerosene and volume parts that volume parts are 60-75% are 10-30%, extraction series are 3- 5 grades, series 2-3 grade is washed, is stripped series 3-4 grades, the volume flow ratio of the extractant of extraction process and the first filtrate is 1: 0.3-0.5, the detergent of washing process and the volume flow ratio of extractant are 5-6:1, and detergent is using 0.1-0.5mol/L's The volume flow ratio of sulfuric acid solution, stripping process extractant and strip liquor is 1:0.1-0.15, and back extraction is using 1.5-2mol/L's Sulfuric acid solution, the raffinate after extracting copper are passed through ozone process, and the molal quantity of the ozone of addition is the raffinate weight after extracting copper 3-5 times of the molal quantity of cobalt, the time for being passed through ozone is 1.5-2 hours, and speed of agitator is 120-150r/min when being stirred to react.
Oxalic acid process is added in nickel filtrate in the step (3), and the molar ratio of nickel is 1.1-1.2 times in oxalic acid and nickel filtrate, The time that oxalic acid is added is 0.5-1 hour, and the temperature that oxalic acid process is added is 40-50 DEG C, and adding after oxalic acid in temperature is 40-50 The reaction was continued at DEG C 1-2 hours, speed of agitator 120-150r/min, then after filtration washing, obtains purity and is greater than 98.5%, the nickel oxalate that granularity is 3-5 microns, the pH that sulfuric acid regulation solution is added in filtered filtrate is 3-3.5, is then concentrated Crystallization obtains ammonia sulfate crystal.
The concentration of ferrous sulfate solution is 1-1.2mol/L, the molal quantity of ferrous sulfate and the first filter in the step (4) The ratio between total mole number of zinc and manganese is 1.15-1.2:1 in slag, maintains the pH4-4.5 of reaction process, the second filtrate iron removal For temperature is increased to 85-90 DEG C, is passed through air, stirring is filtered after 1-2 hours, and iron precipitates to realize with hydroxide scum Except iron, except being passed through oxygen after iron, the purity of oxygen is greater than 99%, the molal quantity of the molal quantity for the oxygen being passed through and the second filtrate it Than for 1:0.2-0.25, the manganese dioxide precipitate being obtained by filtration is dried after the washing of the sulfuric acid solution of 0.2-0.5mol/L, warp It crosses air-flow to be crushed and sieve, obtains battery electrode manganese dioxide, mole of zinc in the molal quantity and filtrate containing zinc of ammonium hydrogen carbonate is added The ratio between number is 3-3.2:1, and dispersing agent is added in zinc-containing solution, and the dispersant concentration of addition is 0.1-0.2%, and ammonium hydrogen carbonate is added Time be 0.5-1 hour, then temperature be 40-45 DEG C be stirred to react 15-30min, washed after filtering, then drying break It is broken, using 600-650 DEG C calcining 1.5-2 hours, obtain nano zine oxide after broken, ammonium bicarbonate precipitation is filtered The pH that sulfuric acid regulation solution is added in filtrate is 3-3.5, and then condensing crystallizing obtains ammonia sulfate crystal.
Third filter residue is dried after washing in the step (5), obtains the lead sulfate that purity is greater than 98.5%, warp Cadmium sulfate solution after crossing except iron, the pH for adjusting solution is 1.5-2, ammonium sulfide solution is then added, the ammonium sulfide of addition rubs Your number is 1.1-1.15 times of cadmium molal quantity, and the temperature of maintenance process is 30-40 DEG C, and the time that ammonium sulfide solution is added is 30- 60min, the reaction was continued after adding 30-60min, are then filtered, and the sulfuric acid scrubbing of 0.5-1mol/L is added in filter residue, obtain purity Greater than 99%, granularity is 1-1.5 microns of cadmium sulfide.
Cobaltic hydroxide precipitating uses pure water again after sulfuric acid scrubbing in the step (3), then broken by drying It after broken sieving, is calcined in the case where temperature is 900-950 DEG C of inert atmosphere, obtains battery-grade cobaltosic oxide, granularity is 3-5 microns, Tap density is greater than 2.4g/mL.
This patent realizes that sulfide is transformed into metal simple-substance by hydrogen reducing, and the hydrogen sulfide generated is by spray Absorption obtains vulcanized sodium, to realize the recycling of sulphion, can return to cobalt metallurgy of nickel and removing heavy metals elsewhere, then passes through The leaching for crossing ammonia and carbonate separates cobalt ambrose alloy with other metals, then by the difference of metal activity realize zinc-manganese and The separation of cadmium lead, then by extraction and oxidation, realize same, cobalt and nickel separation, the separation of zinc-manganese is realized by oxidation, using sulphur Ore Leaching realizes the separation of lead cadmium, while most waste water is ammonium sulfate waste water, obtains ammonium sulfate by condensing crystallizing, can It recycles.
The beneficial effects of the present invention are:
1. process flow is short, easy to operate, the most waste water of generation is ammonium sulfate waste water, is obtained by condensing crystallizing To ammonium sulfate, recoverable.
2., so that vulcanized slag is reduced to metal simple-substance, hydrogen sulfide is absorbed using sodium hydroxide by hydrogen reducing To vulcanized sodium, vulcanized sodium, which returns, continues removing impurity by means of precipitation heavy metal, realizes the recycling of sulphion, in turn avoids the pollution of environment.
3. technique realizes the recycling of metal full constituent, the recycling including cobalt nickel LEAD CADMIUM zinc-manganese, and recovery method letter Single, the rate of recovery is high, and the purity is high of product, and added value is high.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in detail, a kind of sulfide removal of impurities slag of the present embodiment Processing method is following steps:
(1) it pre-processes, material is dried to moisture content lower than 1%, then by broken, 100-200 mesh is crossed after screening Sieve;
(2) hydrogen reducing restores the material after sieving in hydrogen atmosphere, while the gas after reduction is passed through air inducing Power traction is absorbed after going out using sodium hydroxide, and the recovery time is 5-6 hours, and reduction temperature is 350-450 DEG C, obtains mixed metal powder End;
(3) metal powder being put into closed reactor and is leached, leachate is the mixed solution of ammonium hydroxide and ammonium carbonate, It is passed through air, extraction temperature is 50-60 DEG C, and extraction time is 4-5 hours, it then filters, obtains the first filtrate and the first filter residue, Beta-diketone extracting agent is added in first filtrate and extracts copper therein, then is stripped using sulfuric acid, copper-bath is obtained, by concentration Crystallization obtains cupric sulphate crystal, and the raffinate after extracting copper is passed through ozone, is 35-45 DEG C in temperature and is stirred to react 2-3 hours, passes through Cobaltic hydroxide precipitating and nickel filtrate is obtained by filtration, obtained nickel filtrate is added oxalic acid, obtains nickel oxalate;
Ferrous sulfate solution is added in (4) first filter residues, and temperature is 40-60 DEG C and is stirred to react 2-3 hours, then filters, obtains To the second filtrate and the second filter residue, the second obtained filtrate is passed through oxygen after except iron, is 110-140 DEG C in temperature, pressure To be stirred to react under 2-2.5atm 2-3 hours, manganese dioxide precipitate and filtrate containing zinc is obtained by filtration, bicarbonate is added in filtrate containing zinc Then ammonium obtains nano zine oxide by calcining by precipitation reaction;
(5) the second filter residue addition sulfuric acid is dissolved, by third filter residue and third filtrate, third filtrate is obtained by filtration After except iron, cadmium sulfate solution is obtained.
Dry process tiles material to material thickness no more than 3cm, dries under ventilated environment.
Hydrogen reduction in the step (2), the flow velocity of hydrogen are 1-3m/s, the molal quantity and material of the hydrogen being passed through The ratio between middle metal total moles are 4-5:1, and the wind speed that air-introduced machine is drawn is 1-3m/s, and the concentration of sodium hydroxide absorbing liquid is 8- 10mol/L absorbs and uses spray-absorption, and lead is done in absorbing liquid return when the concentration of sodium hydroxide is lower than 1mol/L in liquid to be absorbed The cleaner of cadmium.
Anti-corrosion glass steel layer is coated in air-introduced machine and air inducing pipeline in step (2).
When metal powder leaches in closed reactor in the step (3), the mass ratio of metal powder and leachate is 1:3-4, the concentration of ammonium hydroxide is 3-5mol/L in leachate, and the concentration of ammonium carbonate is 1-1.2mol/L, is passed through air per hour Amount is 5-8 times of leachate total volume, and leaching process maintains stirring, mixing speed 100-150r/min, the first filtrate Beta-diketone extracting agent extracting copper process is added, extracts counter-current extraction technique, the proportion of beta-diketone extracting agent is that volume parts are 10- 15% beta-diketon, the TBP that the sulfonated kerosene and volume parts that volume parts are 60-75% are 10-30%, extraction series are 3- 5 grades, series 2-3 grade is washed, is stripped series 3-4 grades, the volume flow ratio of the extractant of extraction process and the first filtrate is 1: 0.3-0.5, the detergent of washing process and the volume flow ratio of extractant are 5-6:1, and detergent is using 0.1-0.5mol/L's The volume flow ratio of sulfuric acid solution, stripping process extractant and strip liquor is 1:0.1-0.15, and back extraction is using 1.5-2mol/L's Sulfuric acid solution, the raffinate after extracting copper are passed through ozone process, and the molal quantity of the ozone of addition is the raffinate weight after extracting copper 3-5 times of the molal quantity of cobalt, the time for being passed through ozone is 1.5-2 hours, and speed of agitator is 120-150r/min when being stirred to react.
Oxalic acid process is added in nickel filtrate in the step (3), and the molar ratio of nickel is 1.1-1.2 times in oxalic acid and nickel filtrate, The time that oxalic acid is added is 0.5-1 hour, and the temperature that oxalic acid process is added is 40-50 DEG C, and adding after oxalic acid in temperature is 40-50 The reaction was continued at DEG C 1-2 hours, speed of agitator 120-150r/min, then after filtration washing, obtains purity and is greater than 98.5%, the nickel oxalate that granularity is 3-5 microns, the pH that sulfuric acid regulation solution is added in filtered filtrate is 3-3.5, is then concentrated Crystallization obtains ammonia sulfate crystal.
The concentration of ferrous sulfate solution is 1-1.2mol/L, the molal quantity of ferrous sulfate and the first filter in the step (4) The ratio between total mole number of zinc and manganese is 1.15-1.2:1 in slag, maintains the pH4-4.5 of reaction process, the second filtrate iron removal For temperature is increased to 85-90 DEG C, is passed through air, stirring is filtered after 1-2 hours, and iron precipitates to realize with hydroxide scum Except iron, except being passed through oxygen after iron, the purity of oxygen is greater than 99%, the molal quantity of the molal quantity for the oxygen being passed through and the second filtrate it Than for 1:0.2-0.25, the manganese dioxide precipitate being obtained by filtration is dried after the washing of the sulfuric acid solution of 0.2-0.5mol/L, warp It crosses air-flow to be crushed and sieve, obtains battery electrode manganese dioxide, mole of zinc in the molal quantity and filtrate containing zinc of ammonium hydrogen carbonate is added The ratio between number is 3-3.2:1, and dispersing agent is added in zinc-containing solution, and the dispersant concentration of addition is 0.1-0.2%, and ammonium hydrogen carbonate is added Time be 0.5-1 hour, then temperature be 40-45 DEG C be stirred to react 15-30min, washed after filtering, then drying break It is broken, using 600-650 DEG C calcining 1.5-2 hours, obtain nano zine oxide after broken, ammonium bicarbonate precipitation is filtered The pH that sulfuric acid regulation solution is added in filtrate is 3-3.5, and then condensing crystallizing obtains ammonia sulfate crystal.
Third filter residue is dried after washing in the step (5), obtains the lead sulfate that purity is greater than 98.5%, warp Cadmium sulfate solution after crossing except iron, the pH for adjusting solution is 1.5-2, ammonium sulfide solution is then added, the ammonium sulfide of addition rubs Your number is 1.1-1.15 times of cadmium molal quantity, and the temperature of maintenance process is 30-40 DEG C, and the time that ammonium sulfide solution is added is 30- 60min, the reaction was continued after adding 30-60min, are then filtered, and the sulfuric acid scrubbing of 0.5-1mol/L is added in filter residue, obtain purity Greater than 99%, granularity is 1-1.5 microns of cadmium sulfide.
Cobaltic hydroxide precipitating uses pure water again after sulfuric acid scrubbing in the step (3), then broken by drying It after broken sieving, is calcined in the case where temperature is 900-950 DEG C of inert atmosphere, obtains battery-grade cobaltosic oxide, granularity is 3-5 microns, Tap density is greater than 2.4g/mL.
Embodiment 1
A kind of processing method of sulfide removal of impurities slag, is following steps:
(1) it pre-processes, material is dried to moisture content lower than 1%, then by broken, 150 meshes are crossed after screening;
(2) hydrogen reducing restores the material after sieving in hydrogen atmosphere, while the gas after reduction is passed through air inducing Power traction is absorbed after going out using sodium hydroxide, and the recovery time is 5.5 hours, and reduction temperature is 390 DEG C, obtains mixed metal powder;
(3) metal powder being put into closed reactor and is leached, leachate is the mixed solution of ammonium hydroxide and ammonium carbonate, It is passed through air, extraction temperature is 55 DEG C, and extraction time is 4.5 hours, then filters, obtains the first filtrate and the first filter residue, will First filtrate is added beta-diketone extracting agent and extracts copper therein, then is stripped using sulfuric acid, obtains copper-bath, ties by concentration Crystalline substance obtains cupric sulphate crystal, and the raffinate after extracting copper is passed through ozone, is 42 DEG C in temperature and is stirred to react 2.5 hours, passed through Filter obtains cobaltic hydroxide precipitating and nickel filtrate, and obtained nickel filtrate is added oxalic acid, obtains nickel oxalate;
Ferrous sulfate solution is added in (4) first filter residues, and temperature is 52 DEG C and is stirred to react 2.5 hours, then filters, and obtains the Two filtrates and the second filter residue, the second obtained filtrate are passed through oxygen after except iron, are 135 DEG C in temperature, pressure 2.3atm Under be stirred to react 2.5 hours, be obtained by filtration manganese dioxide precipitate and filtrate containing zinc, ammonium hydrogen carbonate is added in filtrate containing zinc, by heavy It forms sediment and reacts, then obtain nano zine oxide by calcining;
(5) the second filter residue addition sulfuric acid is dissolved, by third filter residue and third filtrate, third filtrate is obtained by filtration After except iron, cadmium sulfate solution is obtained.
Dry process tiles material to material thickness no more than 3cm, dries under ventilated environment.
Hydrogen reduction in the step (2), the flow velocity of hydrogen are 2.1m/s, the molal quantity and material of the hydrogen being passed through The ratio between middle metal total moles are 4.3:1, and the wind speed that air-introduced machine is drawn is 2m/s, and the concentration of sodium hydroxide absorbing liquid is 9mol/L, It absorbs and uses spray-absorption, absorbing liquid is returned to the removal of impurities for doing lead cadmium when the concentration of sodium hydroxide is lower than 1mol/L in liquid to be absorbed Agent.
Anti-corrosion glass steel layer is coated in air-introduced machine and air inducing pipeline in step (2).
When metal powder leaches in closed reactor in the step (3), the mass ratio of metal powder and leachate is 1:3.3, the concentration of ammonium hydroxide is 4mol/L in leachate, and the concentration of ammonium carbonate is 1.1mol/L, and the amount for being passed through air per hour is 7 times of leachate total volume, leaching process maintain stirring, mixing speed 142r/min, and beta-diketon is added in the first filtrate Extractant extracting copper process extracts counter-current extraction technique, and the proportion of beta-diketone extracting agent is the beta-diketon that volume parts are 12%, The TBP that the sulfonated kerosene and volume parts that volume parts are 73% are 15%, extraction series are 4 grades, wash 3 grades of series, back extraction 4 grades of series, the volume flow ratio of the extractant of extraction process and the first filtrate is 1:0.41, the detergent of washing process and extraction The volume flow ratio of agent is 5.6:1, and detergent uses the sulfuric acid solution of 0.35mol/L, stripping process extractant and strip liquor Volume flow ratio is 1:0.12, and back extraction uses the sulfuric acid solution of 1.8mol/L, and the raffinate after extracting copper is passed through ozone process, adds The molal quantity of the ozone entered is 4 times of the molal quantity of the raffinate weight cobalt after extracting copper, and the time for being passed through ozone is 1.8 hours, Speed of agitator is 140r/min when being stirred to react.
Oxalic acid process is added in nickel filtrate in the step (3), and the molar ratio of nickel is 1.12 times in oxalic acid and nickel filtrate, is added The time of oxalic acid is 0.8 hour, and the temperature that oxalic acid process is added is 44 DEG C, add be 48 DEG C in temperature after oxalic acid at the reaction was continued 1.5 hours, speed of agitator 140r/min, then after filtration washing, purity is obtained greater than 98.5%, granularity is 4.5 micro- The nickel oxalate of rice, the pH that sulfuric acid regulation solution is added in filtered filtrate is 3.3, and then condensing crystallizing obtains ammonia sulfate crystal.
The concentration of ferrous sulfate solution is 1.12mol/L, the molal quantity of ferrous sulfate and the first filter residue in the step (4) The ratio between total mole number of middle zinc and manganese is 1.19:1, maintains the pH4.3 of reaction process, the second filtrate iron removal is, by temperature 88 DEG C are increased to, air is passed through, stirring is filtered after 1.5 hours, and iron removes iron with hydroxide scum precipitating to realize, except logical after iron Enter oxygen, the purity of oxygen is greater than 99%, and the ratio between the molal quantity for the oxygen being passed through and the molal quantity of the second filtrate are 1:0.22, mistake Obtained manganese dioxide precipitate is filtered after the washing of the sulfuric acid solution of 0.35mol/L, drying is crushed and is sieved by air-flow, obtained To battery electrode manganese dioxide, it is 3.1:1 that the ratio between molal quantity of zinc in the molal quantity and filtrate containing zinc of ammonium hydrogen carbonate, which is added, molten containing zinc Dispersing agent is added in liquid, the dispersant concentration of addition is 0.15%, and the time that ammonium hydrogen carbonate is added is 0.8 hour, then in temperature Degree is stirred to react 25min for 42 DEG C, washs after filtering, and then drying is broken, calcines 1.8 hours using 635 DEG C, by broken After obtain nano zine oxide, the pH that sulfuric acid regulation solution is added in the filtered filtrate of ammonium bicarbonate precipitation is 3.3, then concentration knot Crystalline substance obtains ammonia sulfate crystal.
Third filter residue is dried after washing in the step (5), obtains the lead sulfate that purity is greater than 98.5%, warp Cadmium sulfate solution after crossing except iron, the pH for adjusting solution is 1.8, and ammonium sulfide solution, mole of the ammonium sulfide of addition is then added Number is 1.12 times of cadmium molal quantity, and the temperature of maintenance process is 35 DEG C, and the time that ammonium sulfide solution is added is 45min, adds it The reaction was continued afterwards 50min, is then filtered, and the sulfuric acid scrubbing of 0.8mol/L is added in filter residue, obtains purity greater than 99%, granularity is 1.3 microns of cadmium sulfide.
Cobaltic hydroxide precipitating uses pure water again after sulfuric acid scrubbing in the step (3), then broken by drying It after broken sieving, is calcined in the case where temperature is 930 DEG C of inert atmospheres, obtains battery-grade cobaltosic oxide, granularity is 4.2 microns, jolt ramming Density is greater than 2.4g/mL.
The index of finally obtained product of the invention is as follows, and the index of copper sulfate crystal is as follows:
Index Main content Fe Cd Na Ni
Numerical value 99.1% 21ppm 8ppm 20ppm 25ppm
Co Zn Mn Pb Al Ca
41ppm 12ppm 7ppm 2ppm 1.3ppm 2.7ppm
The rate of recovery of copper is 98.7%
The index of battery-grade cobaltosic oxide is as follows:
The rate of recovery 98.1% of cobalt.
The index of nickel oxalate is as follows:
Index Main content Fe Cd Na Co
Numerical value 98.7% 12ppm 8ppm 28ppm 42ppm
Mg Zn Mn Pb Al Ca
17ppm 12ppm 17ppm 3ppm 1.3ppm 2.7ppm
Sulfate radical Chloride ion Apparent density Dmin D10 D50
52ppm 22ppm 0.4g/mL 0.9 micron 1.7 micron 4.5 micron
D90 Specific surface area Tap density
9.7 micron 12.1m2/g 0.97g/mL
The rate of recovery of nickel is 98.3%.
The index of battery electrode manganese dioxide is as follows:
Index Main content Fe Cd Na Co
Numerical value 99.1% 22ppm 8ppm 35ppm 22ppm
Mg Zn Ni Pb Al Ca
45ppm 15ppm 17ppm 3ppm 1.3ppm 5.8ppm
Sulfate radical Chloride ion Apparent density Dmin D10 D50
85ppm 22ppm 0.98g/mL 1.2 micron 3.8 micron 7.5 micron
D90 Specific surface area Tap density
11.2 microns 21.5m2/g 1.8g/mL
The rate of recovery of manganese is 97.8%.
The index of nano zine oxide is as follows:
The rate of recovery of zinc is 98.6%.
The purity of lead sulfate is 98.6%, and the rate of recovery of lead is 98.7%.
The purity of cadmium sulfide is 99.3%, and the rate of recovery of cadmium is 98.5%.
Embodiment 2
A kind of processing method of sulfide removal of impurities slag, is following steps:
(1) it pre-processes, material is dried to moisture content lower than 1%, then by broken, 175 meshes are crossed after screening;
(2) hydrogen reducing restores the material after sieving in hydrogen atmosphere, while the gas after reduction is passed through air inducing Power traction is absorbed after going out using sodium hydroxide, and the recovery time is 5.3 hours, and reduction temperature is 440 DEG C, obtains mixed metal powder;
(3) metal powder being put into closed reactor and is leached, leachate is the mixed solution of ammonium hydroxide and ammonium carbonate, It is passed through air, extraction temperature is 53 DEG C, and extraction time is 4.7 hours, then filters, obtains the first filtrate and the first filter residue, will First filtrate is added beta-diketone extracting agent and extracts copper therein, then is stripped using sulfuric acid, obtains copper-bath, ties by concentration Crystalline substance obtains cupric sulphate crystal, and the raffinate after extracting copper is passed through ozone, is 38 DEG C in temperature and is stirred to react 2.3 hours, passed through Filter obtains cobaltic hydroxide precipitating and nickel filtrate, and obtained nickel filtrate is added oxalic acid, obtains nickel oxalate;
Ferrous sulfate solution is added in (4) first filter residues, and temperature is 55 DEG C and is stirred to react 2.7 hours, then filters, and obtains the Two filtrates and the second filter residue, the second obtained filtrate are passed through oxygen after except iron, are 135 DEG C in temperature, pressure 2.1atm Under be stirred to react 2.7 hours, be obtained by filtration manganese dioxide precipitate and filtrate containing zinc, ammonium hydrogen carbonate is added in filtrate containing zinc, by heavy It forms sediment and reacts, then obtain nano zine oxide by calcining;
(5) the second filter residue addition sulfuric acid is dissolved, by third filter residue and third filtrate, third filtrate is obtained by filtration After except iron, cadmium sulfate solution is obtained.
Dry process tiles material to material thickness no more than 3cm, dries under ventilated environment.
Hydrogen reduction in the step (2), the flow velocity of hydrogen are 2.1m/s, the molal quantity and material of the hydrogen being passed through The ratio between middle metal total moles are 4.3:1, and the wind speed that air-introduced machine is drawn is 2m/s, and the concentration of sodium hydroxide absorbing liquid is 9mol/L, It absorbs and uses spray-absorption, absorbing liquid is returned to the removal of impurities for doing lead cadmium when the concentration of sodium hydroxide is lower than 1mol/L in liquid to be absorbed Agent.
Anti-corrosion glass steel layer is coated in air-introduced machine and air inducing pipeline in step (2).
When metal powder leaches in closed reactor in the step (3), the mass ratio of metal powder and leachate is 1:3.3, the concentration of ammonium hydroxide is 4mol/L in leachate, and the concentration of ammonium carbonate is 1.1mol/L, and the amount for being passed through air per hour is 7 times of leachate total volume, leaching process maintain stirring, mixing speed 142r/min, and beta-diketon is added in the first filtrate Extractant extracting copper process extracts counter-current extraction technique, and the proportion of beta-diketone extracting agent is the beta-diketon that volume parts are 12%, The TBP that the sulfonated kerosene and volume parts that volume parts are 73% are 15%, extraction series are 4 grades, wash 3 grades of series, back extraction 4 grades of series, the volume flow ratio of the extractant of extraction process and the first filtrate is 1:0.41, the detergent of washing process and extraction The volume flow ratio of agent is 5.6:1, and detergent uses the sulfuric acid solution of 0.35mol/L, stripping process extractant and strip liquor Volume flow ratio is 1:0.12, and back extraction uses the sulfuric acid solution of 1.8mol/L, and the raffinate after extracting copper is passed through ozone process, adds The molal quantity of the ozone entered is 4 times of the molal quantity of the raffinate weight cobalt after extracting copper, and the time for being passed through ozone is 1.8 hours, Speed of agitator is 140r/min when being stirred to react.
Oxalic acid process is added in nickel filtrate in the step (3), and the molar ratio of nickel is 1.12 times in oxalic acid and nickel filtrate, is added The time of oxalic acid is 0.8 hour, and the temperature that oxalic acid process is added is 44 DEG C, add be 48 DEG C in temperature after oxalic acid at the reaction was continued 1.5 hours, speed of agitator 140r/min, then after filtration washing, purity is obtained greater than 98.5%, granularity is 4.3 micro- The nickel oxalate of rice, the pH that sulfuric acid regulation solution is added in filtered filtrate is 3.3, and then condensing crystallizing obtains ammonia sulfate crystal.
The concentration of ferrous sulfate solution is 1.12mol/L, the molal quantity of ferrous sulfate and the first filter residue in the step (4) The ratio between total mole number of middle zinc and manganese is 1.19:1, maintains the pH4.3 of reaction process, the second filtrate iron removal is, by temperature 88 DEG C are increased to, air is passed through, stirring is filtered after 1.5 hours, and iron removes iron with hydroxide scum precipitating to realize, except logical after iron Enter oxygen, the purity of oxygen is greater than 99%, and the ratio between the molal quantity for the oxygen being passed through and the molal quantity of the second filtrate are 1:0.22, mistake Obtained manganese dioxide precipitate is filtered after the washing of the sulfuric acid solution of 0.35mol/L, drying is crushed and is sieved by air-flow, obtained To battery electrode manganese dioxide, it is 3.1:1 that the ratio between molal quantity of zinc in the molal quantity and filtrate containing zinc of ammonium hydrogen carbonate, which is added, molten containing zinc Dispersing agent is added in liquid, the dispersant concentration of addition is 0.15%, and the time that ammonium hydrogen carbonate is added is 0.8 hour, then in temperature Degree is stirred to react 25min for 42 DEG C, washs after filtering, and then drying is broken, calcines 1.8 hours using 635 DEG C, by broken After obtain nano zine oxide, the pH that sulfuric acid regulation solution is added in the filtered filtrate of ammonium bicarbonate precipitation is 3.3, then concentration knot Crystalline substance obtains ammonia sulfate crystal.
Third filter residue is dried after washing in the step (5), obtains the lead sulfate that purity is greater than 98.5%, warp Cadmium sulfate solution after crossing except iron, the pH for adjusting solution is 1.8, and ammonium sulfide solution, mole of the ammonium sulfide of addition is then added Number is 1.12 times of cadmium molal quantity, and the temperature of maintenance process is 35 DEG C, and the time that ammonium sulfide solution is added is 45min, adds it The reaction was continued afterwards 50min, is then filtered, and the sulfuric acid scrubbing of 0.8mol/L is added in filter residue, obtains purity greater than 99%, granularity is 1.5 microns of cadmium sulfide.
Cobaltic hydroxide precipitating uses pure water again after sulfuric acid scrubbing in the step (3), then broken by drying It after broken sieving, is calcined in the case where temperature is 930 DEG C of inert atmospheres, obtains battery-grade cobaltosic oxide, granularity is 4.4 microns, jolt ramming Density is greater than 2.4g/mL.
The index of finally obtained product of the invention is as follows, and the index of copper sulfate crystal is as follows:
Index Main content Fe Cd Na Ni
Numerical value 99.2% 21ppm 8ppm 18ppm 25ppm
Co Zn Mn Pb Al Ca
38ppm 12ppm 8ppm 2ppm 1.3ppm 4.5ppm
The rate of recovery of copper is 98.8%
The index of battery-grade cobaltosic oxide is as follows:
Index Co Fe Cd Na Ni
Numerical value 72.6% 11ppm 8ppm 31ppm 28ppm
Mg Zn Mn Pb Al Ca
12ppm 17ppm 17ppm 2ppm 1.8ppm 4.2ppm
Sulfate radical Chloride ion Apparent density Dmin D10 D50
52ppm 12ppm 1.82g/mL 0.85 micron 1.9 micron 4.4 micron
D90 Specific surface area Tap density
9.1 micron 8.8m2/g 2.57g/mL
The rate of recovery 98.1% of cobalt.
The index of nickel oxalate is as follows:
Index Main content Fe Cd Na Co
Numerical value 98.8% 11ppm 8ppm 28ppm 43ppm
Mg Zn Mn Pb Al Ca
17ppm 12ppm 19ppm 3ppm 1.3ppm 2.7ppm
Sulfate radical Chloride ion Apparent density Dmin D10 D50
55ppm 22ppm 0.4g/mL 1.0 micron 1.9 micron 4.3 micron
D90 Specific surface area Tap density
9.8 micron 12.7m2/g 1.01g/mL
The rate of recovery of nickel is 98.4%.
The index of battery electrode manganese dioxide is as follows:
Index Main content Fe Cd Na Co
Numerical value 99.1% 23ppm 7ppm 45ppm 22ppm
Mg Zn Ni Pb Al Ca
45ppm 25ppm 17ppm 3ppm 1.3ppm 5.8ppm
Sulfate radical Chloride ion Apparent density Dmin D10 D50
97ppm 28ppm 0.96g/mL 1.5 micron 3.9 micron 7.5 micron
D90 Specific surface area Tap density
11.8 microns 22.1m2/g 1.78g/mL
The rate of recovery of manganese is 97.9%.
The index of nano zine oxide is as follows:
Index Main content Fe Cd Na Co
Numerical value 99.3% 12ppm 7ppm 21ppm 25ppm
Mg Mn Ni Pb Al Ca
17ppm 49ppm 18ppm 3ppm 3.1ppm 2.9ppm
Sulfate radical Chloride ion Apparent density Dmin D10 D50
32ppm 12ppm 0.27g/mL 0.02 micron 0.35 micron 0.51 micron
D90 Specific surface area Tap density Primary particle size
0.99 micron 61.2m2/g 0.55g/mL 61nm
The rate of recovery of zinc is 98.8%.
The purity of lead sulfate is 98.6%, and the rate of recovery of lead is 98.8%.
The purity of cadmium sulfide is 99.3%, and the rate of recovery of cadmium is 98.8%.
Embodiment 3
A kind of processing method of sulfide removal of impurities slag, is following steps:
(1) it pre-processes, material is dried to moisture content lower than 1%, then by broken, 125 meshes are crossed after screening;
(2) hydrogen reducing restores the material after sieving in hydrogen atmosphere, while the gas after reduction is passed through air inducing Power traction is absorbed after going out using sodium hydroxide, and the recovery time is 5.5 hours, and reduction temperature is 375 DEG C, obtains mixed metal powder;
(3) metal powder being put into closed reactor and is leached, leachate is the mixed solution of ammonium hydroxide and ammonium carbonate, It is passed through air, extraction temperature is 53 DEG C, and extraction time is 4.4 hours, then filters, obtains the first filtrate and the first filter residue, will First filtrate is added beta-diketone extracting agent and extracts copper therein, then is stripped using sulfuric acid, obtains copper-bath, ties by concentration Crystalline substance obtains cupric sulphate crystal, and the raffinate after extracting copper is passed through ozone, is 39 DEG C in temperature and is stirred to react 2.7 hours, passed through Filter obtains cobaltic hydroxide precipitating and nickel filtrate, and obtained nickel filtrate is added oxalic acid, obtains nickel oxalate;
Ferrous sulfate solution is added in (4) first filter residues, and temperature is 47 DEG C and is stirred to react 2.8 hours, then filters, and obtains the Two filtrates and the second filter residue, the second obtained filtrate are passed through oxygen after except iron, are 128 DEG C in temperature, pressure 2.4atm Under be stirred to react 2.6 hours, be obtained by filtration manganese dioxide precipitate and filtrate containing zinc, ammonium hydrogen carbonate is added in filtrate containing zinc, by heavy It forms sediment and reacts, then obtain nano zine oxide by calcining;
(5) the second filter residue addition sulfuric acid is dissolved, by third filter residue and third filtrate, third filtrate is obtained by filtration After except iron, cadmium sulfate solution is obtained.
Dry process tiles material to material thickness no more than 3cm, dries under ventilated environment.
Hydrogen reduction in the step (2), the flow velocity of hydrogen are 2.1m/s, the molal quantity and material of the hydrogen being passed through The ratio between middle metal total moles are 4.7:1, and the wind speed that air-introduced machine is drawn is 2.8m/s, and the concentration of sodium hydroxide absorbing liquid is 9.5mol/L absorbs and uses spray-absorption, does absorbing liquid return when the concentration of sodium hydroxide is lower than 1mol/L in liquid to be absorbed The cleaner of lead cadmium.
Anti-corrosion glass steel layer is coated in air-introduced machine and air inducing pipeline in step (2).
When metal powder leaches in closed reactor in the step (3), the mass ratio of metal powder and leachate is 1:3.4, the concentration of ammonium hydroxide is 4.2mol/L in leachate, and the concentration of ammonium carbonate is 1.12mol/L, is passed through the amount of air per hour It is 7 times of leachate total volume, leaching process maintains stirring, mixing speed 135r/min, and β-two is added in the first filtrate Ketone extractant extracting copper process extracts counter-current extraction technique, and the proportion of beta-diketone extracting agent is the β-two that volume parts are 12% Ketone, the TBP that the sulfonated kerosene and volume parts that volume parts are 74% are 14%, extraction series are 4 grades, wash 3 grades of series, instead The volume flow ratio of 4 grades of series of extraction, the extractant of extraction process and the first filtrate is 1:0.41, the detergent and extraction of washing process The volume flow ratio for taking agent is 5.3:1, and detergent uses the sulfuric acid solution of 0.2mol/L, stripping process extractant and strip liquor Volume flow ratio is 1:0.13, and back extraction uses the sulfuric acid solution of 1.7mol/L, and the raffinate after extracting copper is passed through ozone process, adds The molal quantity of the ozone entered is 4.2 times of the molal quantity of the raffinate weight cobalt after extracting copper, and the time for being passed through ozone is 1.8 small When, speed of agitator is 141r/min when being stirred to react.
Oxalic acid process is added in nickel filtrate in the step (3), and the molar ratio of nickel is 1.13 times in oxalic acid and nickel filtrate, is added The time of oxalic acid is 0.8 hour, and the temperature that oxalic acid process is added is 45 DEG C, add be 45 DEG C in temperature after oxalic acid at the reaction was continued 1.3 hours, speed of agitator 128r/min, then after filtration washing, purity is obtained greater than 98.5%, granularity is 3.8 micro- The nickel oxalate of rice, the pH that sulfuric acid regulation solution is added in filtered filtrate is 3.35, and then condensing crystallizing obtains ammonia sulfate crystal.
The concentration of ferrous sulfate solution is 1.12mol/L, the molal quantity of ferrous sulfate and the first filter residue in the step (4) The ratio between total mole number of middle zinc and manganese is 1.18:1, maintains the pH4.3 of reaction process, the second filtrate iron removal is, by temperature 88 DEG C are increased to, air is passed through, stirring is filtered after 1.3 hours, and iron removes iron with hydroxide scum precipitating to realize, except logical after iron Enter oxygen, the purity of oxygen is greater than 99%, and the ratio between the molal quantity for the oxygen being passed through and the molal quantity of the second filtrate are 1:0.23, mistake Obtained manganese dioxide precipitate is filtered after the washing of the sulfuric acid solution of 0.4mol/L, drying is crushed and is sieved by air-flow, obtained Battery electrode manganese dioxide, it is 3.12:1 that the ratio between molal quantity of zinc in the molal quantity and filtrate containing zinc of ammonium hydrogen carbonate, which is added, molten containing zinc Dispersing agent is added in liquid, the dispersant concentration of addition is 0.15%, and the time that ammonium hydrogen carbonate is added is 0.8 hour, then in temperature Degree is stirred to react 22min for 43 DEG C, washs after filtering, and then drying is broken, calcines 1.8 hours using 615 DEG C, by broken After obtain nano zine oxide, the pH that sulfuric acid regulation solution is added in the filtered filtrate of ammonium bicarbonate precipitation is 3.2, then concentration knot Crystalline substance obtains ammonia sulfate crystal.
Third filter residue is dried after washing in the step (5), obtains the lead sulfate that purity is greater than 98.5%, warp Cadmium sulfate solution after crossing except iron, the pH for adjusting solution is 1.8, and ammonium sulfide solution, mole of the ammonium sulfide of addition is then added Number is 1.12 times of cadmium molal quantity, and the temperature of maintenance process is 33 DEG C, and the time that ammonium sulfide solution is added is 50min, adds it The reaction was continued afterwards 40min, is then filtered, and the sulfuric acid scrubbing of 0.8mol/L is added in filter residue, obtains purity greater than 99%, granularity is 1.2 microns of cadmium sulfide.
Cobaltic hydroxide precipitating uses pure water again after sulfuric acid scrubbing in the step (3), then broken by drying It after broken sieving, is calcined in the case where temperature is 938 DEG C of inert atmospheres, obtains battery-grade cobaltosic oxide, granularity is 4.7 microns, jolt ramming Density is greater than 2.4g/mL.
The index of finally obtained product of the invention is as follows, and the index of copper sulfate crystal is as follows:
Index Main content Fe Cd Na Ni
Numerical value 99.2% 11ppm 12ppm 21ppm 21ppm
Co Zn Mn Pb Al Ca
38ppm 14ppm 8ppm 2ppm 4.3ppm 4.5ppm
The rate of recovery of copper is 98.7%
The index of battery-grade cobaltosic oxide is as follows:
The rate of recovery 98.2% of cobalt.
The index of nickel oxalate is as follows:
Index Main content Fe Cd Na Co
Numerical value 98.7% 21ppm 8ppm 28ppm 44ppm
Mg Zn Mn Pb Al Ca
19ppm 12ppm 19ppm 3ppm 4.3ppm 5.1ppm
Sulfate radical Chloride ion Apparent density Dmin D10 D50
75ppm 22ppm 0.41g/mL 1.2 micron 2.1 micron 3.8 micron
D90 Specific surface area Tap density
9.9 micron 12.9m2/g 1.00g/mL
The rate of recovery of nickel is 98.5%.
The index of battery electrode manganese dioxide is as follows:
Index Main content Fe Cd Na Co
Numerical value 99.2% 33ppm 7ppm 55ppm 24ppm
Mg Zn Ni Pb Al Ca
48ppm 25ppm 17ppm 3ppm 3ppm 6ppm
Sulfate radical Chloride ion Apparent density Dmin D10 D50
87ppm 28ppm 0.94g/mL 1.7 micron 4.3 micron 8.3 micron
D90 Specific surface area Tap density
11.9 microns 24.3m2/g 1.82g/mL
The rate of recovery of manganese is 98.0%.
The index of nano zine oxide is as follows:
The rate of recovery of zinc is 98.9%.
The purity of lead sulfate is 98.7%, and the rate of recovery of lead is 98.7%.
The purity of cadmium sulfide is 99.2%, and the rate of recovery of cadmium is 98.9%.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the 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 scope of the claims of invention.

Claims (9)

1. a kind of processing method of sulfide removal of impurities slag, which is characterized in that be following steps:
(1) it pre-processes, material is dried to moisture content lower than 1%, then by broken, 100-200 mesh is crossed after screening;
(2) hydrogen reducing restores the material after sieving in hydrogen atmosphere, while the gas after reduction is passed through air inducing power traction It is absorbed after out using sodium hydroxide, the recovery time is 5-6 hours, and reduction temperature is 350-450 DEG C, obtains mixed metal powder;
(3) metal powder is put into closed reactor and is leached, leachate is the mixed solution of ammonium hydroxide and ammonium carbonate, is passed through Air, extraction temperature are 50-60 DEG C, and extraction time is 4-5 hours, then filter, obtain the first filtrate and the first filter residue, by the One filtrate is added beta-diketone extracting agent and extracts copper therein, then is stripped using sulfuric acid, copper-bath is obtained, by condensing crystallizing Cupric sulphate crystal is obtained, the raffinate after extracting copper is passed through ozone, is 35-45 DEG C in temperature and is stirred to react 2-3 hours, passed through Filter obtains cobaltic hydroxide precipitating and nickel filtrate, and obtained nickel filtrate is added oxalic acid, obtains nickel oxalate;
Ferrous sulfate solution is added in (4) first filter residues, and temperature is 40-60 DEG C and is stirred to react 2-3 hours, then filters, and obtains the Two filtrates and the second filter residue, the second obtained filtrate are passed through oxygen after except iron, are 110-140 DEG C in temperature, pressure 2- It being stirred to react under 2.5atm 2-3 hours, manganese dioxide precipitate and filtrate containing zinc is obtained by filtration, ammonium hydrogen carbonate is added in filtrate containing zinc, By precipitation reaction, nano zine oxide then is obtained by calcining;
(5) the second filter residue addition sulfuric acid is dissolved, by third filter residue and third filtrate is obtained by filtration, third filtrate is passed through After iron, cadmium sulfate solution is obtained.
2. a kind of processing method of sulfide removal of impurities slag according to claim 1, it is characterised in that: dry process is by material Tiling to material thickness is not more than 3cm, dries under ventilated environment.
3. a kind of processing method of sulfide removal of impurities slag according to claim 1, it is characterised in that: in the step (2) Hydrogen reduction, the flow velocity of hydrogen are 1-3m/s, and the ratio between metal total moles are 4- in the molal quantity and material of the hydrogen being passed through 5:1, the wind speed that air-introduced machine is drawn are 1-3m/s, and the concentration of sodium hydroxide absorbing liquid is 8-10mol/L, absorb and are inhaled using spray It receives, absorbing liquid is returned to the cleaner for doing lead cadmium when the concentration of sodium hydroxide is lower than 1mol/L in liquid to be absorbed.
4. a kind of processing method of sulfide removal of impurities slag according to claim 1, it is characterised in that: air inducing in step (2) Anti-corrosion glass steel layer is coated in machine and air inducing pipeline.
5. a kind of processing method of sulfide removal of impurities slag according to claim 1, it is characterised in that: in the step (3) When metal powder leaches in closed reactor, the mass ratio of metal powder and leachate is 1:3-4, and ammonium hydroxide is dense in leachate Degree is 3-5mol/L, and the concentration of ammonium carbonate is 1-1.2mol/L, and the amount for being passed through air per hour is the 5-8 of leachate total volume Times, leaching process maintains stirring, mixing speed 100-150r/min, and beta-diketone extracting agent extracting copper is added in the first filtrate Process extracts counter-current extraction technique, and the proportion of beta-diketone extracting agent is the beta-diketon that volume parts are 10-15%, volume parts The TBP that sulfonated kerosene and volume parts for 60-75% are 10-30%, extraction series are 3-5 grades, wash series 2-3 grades, instead The volume flow ratio of series 3-4 grades of extraction, the extractant of extraction process and the first filtrate is 1:0.3-0.5, the washing of washing process The volume flow ratio of agent and extractant is 5-6:1, and detergent uses the sulfuric acid solution of 0.1-0.5mol/L, stripping process extractant Volume flow ratio with strip liquor is 1:0.1-0.15, and back extraction uses the sulfuric acid solution of 1.5-2mol/L, the raffinate after extracting copper Liquid is passed through ozone process, and the molal quantity of the ozone of addition is 3-5 times of the molal quantity of the raffinate weight cobalt after extracting copper, is passed through smelly The time of oxygen is 1.5-2 hours, and speed of agitator is 120-150r/min when being stirred to react.
6. a kind of processing method of sulfide removal of impurities slag according to claim 1, it is characterised in that: in the step (3) Oxalic acid process is added in nickel filtrate, and the molar ratio of nickel is 1.1-1.2 times in oxalic acid and nickel filtrate, and the time that oxalic acid is added is 0.5-1 Hour, the temperature that oxalic acid process is added is 40-50 DEG C, add be 40-50 DEG C in temperature after oxalic acid at the reaction was continued 1-2 hours, Speed of agitator is 120-150r/min, then after filtration washing, obtains purity greater than 98.5%, granularity is 3-5 microns Nickel oxalate, the pH that sulfuric acid regulation solution is added in filtered filtrate is 3-3.5, and then condensing crystallizing obtains ammonia sulfate crystal.
7. a kind of processing method of sulfide removal of impurities slag according to claim 1, it is characterised in that: in the step (4) The concentration of ferrous sulfate solution is 1-1.2mol/L, in the molal quantity of ferrous sulfate and the first filter residue the total mole number of zinc and manganese it Than maintaining the pH4-4.5 of reaction process for 1.15-1.2:1, the second filtrate iron removal is that temperature is increased to 85-90 DEG C, It is passed through air, stirring is filtered after 1-2 hour, and iron is precipitated to realize with hydroxide scum except iron, except being passed through oxygen, oxygen after iron Purity be greater than 99%, the ratio between molal quantity of the molal quantity for the oxygen being passed through and the second filtrate is 1:0.2-0.25, is obtained by filtration Manganese dioxide precipitate after the washing of the sulfuric acid solution of 0.2-0.5mol/L, drying is broken by air-flow and sieve, and obtains electricity Pond electrode manganese dioxide, it is 3-3.2:1, zinc-containing solution that the ratio between molal quantity of zinc in the molal quantity and filtrate containing zinc of ammonium hydrogen carbonate, which is added, Middle addition dispersing agent, the dispersant concentration of addition are 0.1-0.2%, and the time that ammonium hydrogen carbonate is added is 0.5-1 hours, are then existed Temperature is 40-45 DEG C and is stirred to react 15-30min, washs after filtering, and then drying is broken, using 600-650 DEG C of calcining 1.5- 2 hours, nano zine oxide is obtained after broken, the pH that sulfuric acid regulation solution is added in the filtered filtrate of ammonium bicarbonate precipitation is 3-3.5, then condensing crystallizing obtains ammonia sulfate crystal.
8. a kind of processing method of sulfide removal of impurities slag according to claim 1, it is characterised in that: in the step (5) Third filter residue is dried after washing, obtains the lead sulfate that purity is greater than 98.5%, by except the cadmium sulfate solution after iron, The pH for adjusting solution is 1.5-2, and ammonium sulfide solution is then added, and the molal quantity of the ammonium sulfide of addition is the 1.1- of cadmium molal quantity 1.15 times, the temperature of maintenance process is 30-40 DEG C, and the time that ammonium sulfide solution is added is 30-60min, is continued after adding anti- 30-60min to be answered, is then filtered, the sulfuric acid scrubbing of 0.5-1mol/L is added in filter residue, and it obtains purity and is greater than 99%, granularity 1-1.5 The cadmium sulfide of micron.
9. a kind of processing method of sulfide removal of impurities slag according to claim 1, it is characterised in that: in the step (3) Cobaltic hydroxide precipitating uses pure water again after sulfuric acid scrubbing, is 900- in temperature then after drying broken sieving It is calcined under 950 DEG C of inert atmospheres, obtains battery-grade cobaltosic oxide, granularity is 3-5 microns, and tap density is greater than 2.4g/mL.
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