CN105950874B - A kind of Copper making cigarette ash and the method for waste acid Combined Treatment - Google Patents
A kind of Copper making cigarette ash and the method for waste acid Combined Treatment Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/06—Obtaining bismuth
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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Abstract
A kind of method of Copper making cigarette ash and waste acid Combined Treatment, Copper making cigarette ash is mixed with waste acid size mixing after add oxidant control current potential Oxidation Leaching, make the copper in Bellamya aeruginosa, the dissolving metal such as arsenic and zinc enters leachate, the precipitated metal such as lead and bismuth enters leached mud, leachate, which adds oxidant, makes the As (III) in solution all be oxidized to As (V), then adding vulcanized sodium makes the copper in solution precipitate output copper concentrate with copper sulphide form, it is As (III) that liquid, which adds reducing agent by As in solution (V) Restore All, after copper removal, then adding vulcanized sodium makes the arsenic in solution be precipitated in arsenones form, qualified discharge after liquid is neutralized with alkali after final arsenic removal.The present invention is combined substep using control current potential Oxidation Leaching and control current potential oxidation of sulfureted and reduction-sulfurization simultaneously and is separated and recovered from Copper making cigarette ash and valuable metal in waste acid, realizes the cyclic utilization of waste in system, reaches treatment of wastes with processes of wastes against one another purpose.
Description
Technical field
The present invention relates to hydrometallurgy process in nonferrous metallurgy field, especially with control current potential Oxidation Leaching and control current potential
Oxidation of sulfureted and reduction-sulfurization are combined the hydrometallurgy side that mode is separated and recovered from valuable metal in Copper making cigarette ash and waste acid
Method.
Background technology
Copper is a kind of rose heavy non-ferrous metal, and its excellent physical and chemical performance is widely used in electric, state
The every field such as anti-industry, light industry, machine-building and building, aluminium is only second in the consumption of China's nonferrous materials.At present
The purposes ratio substantially situation of copper is：Electrical industry 48~49%, the communications industry 19~20%, building 14 ~ 16%, transport 7~10%,
Household electrical appliances with other 7~9%.Ten kinds of China, 44,170,000 tons of non-ferrous metal yield in 2014, wherein 24,380,000 tons of electrolytic aluminium, refined copper
7960000 tons, 5,830,000 tons of 4,220,000 tons of lead and zinc.Although world's copper yield is being continuously increased, because global economy increases, to copper
Demand be significantly increased, world wide production and consumption figure remain basically stable, but Chinese market copper supply breach it is still very big.
The copper mineral only more than 20 that nature has industrial application value is planted, and mainly has sulphide ore and the major class of oxide ore two, has
The copper sulfide raw ore of economic value mainly includes vitreous copper（Cu2S）, covellite（CuS）, bornite（Cu5FeS4）, tennantite
（Cu12As4S13）, tetrahedrite（Cu2As4S13）And chalcopyrite（CuFeS2）.The cupric oxide raw ore for having extraction value mainly includes red
Copper mine（Cu2O）, black copper ore（CuO）, chessy copper（2CuCO3·Cu(OH)2）, malachite（CuCO3·Cu(OH)2）, chrysocolla
（CuSiO3·2H2O）And blue stone（CuCO3 4H2O）.Selection of the composition of copper mine to smelting process is particularly important, and copper sulfide is optional
Property it is good, be easy to enrichment, the copper sulfide concentrate of the cupric 20~30% by floatation process output using pyrometallurgical smelting process processing,
And cupric oxide ore flotability is poor, be difficult to beneficiation enrichment, preferably directly handled using hydrometallurgical processes.
At present, about more than 80% mineral products copper is then that copper sulfide concentrate passes through pyrometallurgical smelting technique productions, i.e. copper concentrate
By matte smelting output copper matte regulus, copper matte regulus sequentially pass through bessemerize with pyro-refining output blister copper, blister copper is in sulfuric acid system
Electrorefining output tough cathode.During the matte smelting of copper, Pb, Zn, As, Bi and Sb present in copper concentrate etc. are volatile
Metal is volatized into flue gas, and these metals are in follow-up flue gas dust collection and lessivation difference output Bellamya aeruginosa and waste acid, Liang Zhesuo
The element species contained are roughly the same, but constituent content difference is larger.Further, since volatile component in the copper concentrate that each enterprise uses
Different different with smelting parameter, the Bellamya aeruginosa and waste acid composition of each copper metallurgy enterprise are not quite similar.In recent years, the rich ore in Copper Ores
Reduce so that the grade reduction and impurity content increase of copper concentrate so that Bellamya aeruginosa and the composition of waste acid become more complicated.
For the continuity and comprehensively recovering valuable metal of production, domestic enterprise, which mostly directly returns to Bellamya aeruginosa, to make sulfonium and melts
Refining process, but a series of problem is brought, the disposal ability of smelting furnace is reduced first, influences normal operating duty；Its
The increase of the impurity content such as Pb, As and Zn, not only causes the working of a furnace to deteriorate in secondary Bellamya aeruginosa, and the accumulation influence of harmful element is cloudy
Pole copper products quality, again harmful element arsenic etc. cause follow-up relieving haperacidity process catalyst cycle to reduce, therefore, with having in copper concentrate
The increase of evil constituent content, it is necessary to which open circuit processing is carried out to Bellamya aeruginosa.When acidity and impurity exceed certain scope, copper smelting
Refining waste acid needs purified treatment.The method of the waste acid processing of current document report is mainly neutralisation, the precipitation method, vulcanization method, life
Thing method and membrane separating method etc., waste acid is discharged after treatment.
Relevant Bellamya aeruginosa open circuit processing has carried out long-term research both at home and abroad, is taking into full account the recovery of valuable metal recycling
On the premise of many factors such as environmental protection, the handling process of formation is broadly divided into three kinds of pyrogenic process, half wet process and wet method.Pyrogenic process
Technique is Bellamya aeruginosa direct melting separating valuable metals in reverberatory furnace, electric arc furnaces or blast furnace, makes lead and bismuth and gold and silver etc.
Reduction enters lead bullion, and copper segregation is returned in the output arsenic trioxide flue dust that gathered dust after matte phase, arsenic volatilization, thermal process with Bellamya aeruginosa
Return matte smelting process it is similar, simply not by Bellamya aeruginosa introduce copper concentrate matte smelting stove, reduce Bellamya aeruginosa to main body give birth to
The influence of production. art, but it is low to there is valuable metal comprehensive recovery, high energy consumption, working condition difference and secondary pollution problems,
The open circuit of arsenic can not effectively be solved.Half wet process technique is then to be combined pyrogenic process and wet processing to improve in Bellamya aeruginosa to have
The separating effect of valency metal, it is different using sequencing with wet method according to pyrogenic process, there are pyrogenic process-wet processing and wet method-pyrogenic process work
Skill.Pyrogenic process-wet processing is then arsenic is volatized into flue dust using methods such as reduction roasting or sulfating roastings first, simultaneously
The metals such as copper and zinc are made to be converted into soluble conformation, then calcining leaches the separation valuable metal such as copper and zinc again, leached mud is enriched
The valuable metal such as lead and bismuth.And wet method-thermal process is then to leach to make the dissolving entrance such as copper, arsenic and zinc using sulfuric acid system first
Solution, leachate separation and Extraction copper and zinc again after arsenic removal, leached mud reduction melting in blast furnace is enriched with lead and bismuth etc.
In lead bullion.Half wet process technical process index is stable, is current domestic using technique the most universal, but pyrogenic attack stage
Production cost is high and causes secondary pollution.Wet processing is then Bellamya aeruginosa in neutral system, acid system or alkaline system
Leach.It is that normal pressure leaching and HTHP are leached Bellamya aeruginosa in aqueous that neutral system, which is leached, makes the sulfate of copper and zinc molten
Solution enters solution, and lead and bismuth then enter precipitation slag.Acid system, which is leached, to be leached in sulfuric acid system, makes copper, arsenic and zinc
It is dissolved in solution, and lead and bismuth precipitation enter leached mud, finally separating valuable metals from leachate again.Alkaline system is leached
It is then the leaching that arsenic in cigarette ash is realized in sodium hydroxide or vulcanized sodium system, leached mud uses acidic leaching or direct melting again
Method reclaims valuable metal.No matter Bellamya aeruginosa is leached in which kind of system, and wet processing all thoroughly overcomes thermal process presence
Environmental impact issues, but there is metal inferior separating effect and the high exemplary shortcomings of production cost, especially in subsequent solution
The separation of valuable metal is still a problem.Wet processing has significant environmental benefit compared with thermal process processing Bellamya aeruginosa,
It is the main development direction of Bellamya aeruginosa processing.
These Bellamya aeruginosa handling process of Comprehensive Correlation, thermal process by operating environment and environmental pollution influenceed gradually by
Substitution, pyrogenic process-wet method combined technique occupy the existing handling process principal status of public economy, but the long flow path of processing, high energy consumption, also to
Wet processing transition, wet processing process commercial Application, but existing technique still has arsenic harm reason difficulty is not thorough
Bottom, equipment requirement is high, the low problem of economic benefit.Whote-wet method processing is gradually in industrial applications with the advantage of its environmental protection, energy-conservation, but
The research and development of its technique are still not perfect enough, and exploitation is a kind of economical, and efficient Bellamya aeruginosa handling process is still urgently to be resolved hurrily at present
Problem.
Domestic widely used waste acid processing method has three kinds of lime neutralisation, molysite deposition method and vulcanization method, these sides
Method be not it is single use, often a variety of methods are combined together, such as lime-vulcanization method and lime-iron salt method, can be only achieved
Effective processing of waste acid.Rule is neutralized to use in the cheap solids such as lime, lime stone or carbide slurry and in waste acid
Sulfuric acid, for the process that intensified lime is neutralized, is often divided into multistage neutralization precipitation, such as typical three sections of adverse current stone in industrial production
Grey method etc..Lime neutralisation is that current domestic application is most also most basic waste acid handling process extensively, commonly used to handle arsenic
The relatively low acid waste water of content, for containing the higher waste acid of arsenic, in order to strengthen effect of removing arsenic, adds molysite to accelerate the de- of arsenic
Go out, in order to accelerate to precipitate separation process, add oxidant to improve effect of removing arsenic, the oxidant generally used has bleaching powder, height
Potassium manganate, sodium hypochlorite and hydrogen peroxide etc..This method is simple to operate, processing cost is low, but investment cost it is high, the water hardness
High, separation of solid and liquid is difficult, and cost of equipment maintenance is high, and waste residue is difficult to handle, it is easy to cause secondary pollution.It is to waste acid to vulcanize rule
It is heavy that middle addition vulcanized sodium, sodium thiosulfate or other organic sulfur compounds make the heavy metals such as As, Cu, Pb, Zn and Cd generate sulfide
Form sediment, the waste acid after vulcanization method processing, then the qualified discharge after lime neutralisation treatment.This method is high to processing content of beary metal
Waste acid especially has superiority, but precipitation slag belongs to the mixed sulfides of valuable metal, is unfavorable for later separation.Molysite deposition
Method is that ferrous sulfate is added into waste acid, arsenic is precipitated in ferric arsenate form while adding oxidant and carrying out oxidation, is mainly used to
Processing containing the higher waste acid of arsenic, with precipitation is rapid, arsenic removal efficiency high the features such as, but have that molysite consumption is big, waste residue is difficult to
The problem of effectively handling.
At present, it is often that a variety of methods are used in combination in industrial production, but essence is to use dilute in lime and in waste acid
Sulfuric acid, then remove beavy metal impurity by other chemical reagent.The problem of these waste acid handling process has two jointly：
One is that waste acid processing makes plurality of heavy metal precipitation enter gypsum tailings, adds the difficulty that waste residue is stacked and handled.Two be to make waste acid
In valuable metal enter waste residue, cause the waste of valuable metal, at the same valuable metal removing it is not thorough.Asked for the two
Topic, preferable waste acid processing method should effectively reclaim valuable metal in waste acid, realize that valuable metal is separated from each other again, most
Whole output is free of the gypsum tailings of heavy metal.So, exploitation is rationally and effective waste acid treating method is particularly urgent.
The content of the invention
In order to overcome the shortcomings of traditional copper smelting ash and waste acid processing method, the present invention provides a kind of simultaneously using control electricity
Position Oxidation Leaching and control current potential oxidation of sulfureted and reduction-sulfurization are combined substep and are separated and recovered from having in Copper making cigarette ash and waste acid
Valency metal, and metal recovery rate is high, environmental pollution is small and the simple Wet-process metallurgy method of technique.
To reach that above-mentioned purpose the technical solution adopted by the present invention is：Copper making cigarette ash is mixed with waste acid sizes mixing, Ran Houjia
Enter oxidant control current potential Oxidation Leaching, the dissolving metals such as the copper in Bellamya aeruginosa, arsenic and zinc is entered leachate, the metal such as lead and bismuth
Precipitation enters leached mud；Leachate, which adds oxidant and is increased to metal ion in solution mixed potential, requires numerical value, makes molten
As (III) in liquid is all oxidized to As (V), then adds vulcanized sodium and metal ion in solution mixed potential is reduced into copper removal
It is required that numerical value, makes the copper in solution precipitate output copper concentrate with copper sulphide form；Liquid adds reducing agent by the gold of solution after copper removal
Category Ar ion mixing current potential is reduced to and requires numerical value, then adds vulcanized sodium and is reduced to the metal ion mixed potential of solution and removes
Arsenic requires numerical value, the arsenic in solution is precipitated in arsenones form, qualified discharge after liquid is neutralized with alkali after arsenic removal.The technical program
Essence be and meanwhile using control current potential Oxidation Leaching and control current potential oxidation of sulfureted and reduction-sulfurization be combined substep be separated and recovered from
Copper making cigarette ash and valuable metal in waste acid, these process tight associations, separate processes can not all reach valuable metal selection point
From Expected Results.
Specific technical process and parameter are as follows：
1 control current potential Oxidation Leaching
Copper making cigarette ash adds oxidant control current potential Oxidation Leaching after being sized mixing with waste acid, makes the dissolving metals such as copper, arsenic and zinc
Into leachate, the precipitated metal such as lead and bismuth enters leached mud.Copper making waste acid presses liquid-solid ratio with cigarette ash（Liquid volume L is with consolidating
The ratio between body weight Kg）Size mixing at 5.1~8: 1, keeps 86~90 DEG C of mixed slurry temperature to add oxidizing dissolving, and control is whole
The metal ion mixed potential of slurry relative to calomel electrode be 501~520mV, treat current potential value stabilization it is follow-up it is continuous stirring 60~
Solid-liquor separation is realized using plate compression mode after 180min, leachate send control current potential oxidation of sulfureted process, and leached mud reclaims lead
With bismuth etc.；The main chemical reactions for controlling the generation of current potential Oxidation Leaching process are as follows：
As2O3+2H2O=2H3AsO3（1）
CuO+H2SO4=CuSO4+H2O （2）
ZnO+H2SO4=ZnSO4+H2O （3）
PbO+H2SO4=PbSO4↓+H2O （4）
CuO•As2O3+H2SO4+3H2O=CuSO4+2H3AsO3（5）
CuFeS2+8H2O2=CuSO4+FeSO4+8H2O （6）
3CuFeS2+8NaClO3=3CuSO4+3FeSO4+8NaCl （7）
2 control current potential oxidation of sulfureted
Leachate, which adds the oxidation of oxidant control current potential, makes As (III) all be oxidized to As (V), and solution controls metal after oxidation
Ar ion mixing current potential selective precipitation goes out copper concentrate.Oxidant is added into leachate, the metal ion of whole solution is mixed
Control of Electric potentials continues to stir 15~29min in 500~550mV after current potential is stable；Oxidated solution at 75~85 DEG C of temperature plus
Enter solid sodium sulfide, the metal ion mixed potential of solution is controlled in 180~250mV, treats that solution potential is stablized and continues to stir
Mix separation of solid and liquid after 60~90min, solid product is that liquid is used to control potential reduction sulfidation after copper sulfide concentrate, copper removal.Control
The main chemical reactions that current potential oxidation of sulfureted process occurs are as follows：
H3AsO3+H2O2=H3AsO4+H2O （1）
3H3AsO3+NaClO3=3H3AsO4+NaCl （2）
CuSO4+Na2S=CuS↓+Na2SO4（3）
CuSO4+Na2S2O3+2NaOH=CuS↓+2Na2SO4+H2O （4）
3 control potential reduction vulcanizations
Liquid, which adds reducing agent control potential reduction, after copper removal makes As (V) Restore All are As (III), and liquid controls gold again after reduction
Category Ar ion mixing current potential selective precipitation goes out arsenones.Liquid adds reducing agent after to copper removal, and the metal ion of whole solution is mixed
Control of Electric potentials is closed in 50~150mV, continues to stir 15~45min after current potential is stable；Liquid is at 75~85 DEG C of temperature after reduction
Add solid sodium sulfide, the metal ion mixed potential of solution controlled in -200~-300mV, treat solution potential it is stable and after
Separation of solid and liquid after 15~29min of continuous stirring, solid product is liquid continuation neutralisation treatment after arsenones, arsenic removal.Control potential reduction sulphur
The main chemical reactions for eliminating the generation of arsenic process are as follows：
H3AsO4+Na2SO3=H3AsO3+Na2SO4（5）
2H3AsO3+3Na2S+3H2SO4=As2S3↓+3Na2SO4+6H2O （6）
Liquid is neutralized after 4 arsenic removals
Liquid is neutralized to soda ash after arsenic removal requires qualified discharge after pH value.Solid soda ash is added in liquid after to arsenic removal, will be removed
The pH of liquid is neutralized to 7~9 after arsenic, realizes that liquid divides admittedly using plate compression mode after 60~90min of continuation stirring after pH is stable
From liquid qualified discharge after neutralization.
Described oxidant is one or both of hydrogen peroxide or sodium chlorate, and both are technical grade reagent, and industry is double
The weight/mass percentage composition of oxygen water is not less than 27.5%, and the weight/mass percentage composition of industrial sodium chlorate is not less than 95.0%.
Described reducing agent is the one or more in sodium sulfite, sulfur dioxide or sodium thiosulfate, and is industry
Level reagent.
Described vulcanized sodium is technical grade reagent, and wherein weight/mass percentage composition is not less than 60.0%；
The present invention is applied to the Bellamya aeruginosa and waste acid of processing copper concentrate matte smelting fume treatment process output, Bellamya aeruginosa
Main component is by percentage to the quality：Cu1.0~20.0, Pb1.0~30.0, As1.0~15.0, Zn1.0~10.0,
Bi0.1~10.0 and S1.0~15.0, unit are %；The main component concentration of waste acid is：Cu0.1~10.0, As1.0~15.0,
Zn1.0~5.0 and Bi0.1~10.0, unit are g/L.It is also suitable for handling cupric, the arsenic of Non-ferrous Metallurgy process output
With the solid or solution of zinc.
The present invention is compared with the processing method of traditional copper smelting ash and waste acid, is had the advantage that：1st, the present invention is adopted simultaneously
Substep, which is combined, with control current potential Oxidation Leaching and control current potential oxidation of sulfureted and reduction-sulfurization is separated and recovered from Copper making cigarette ash and dirt
Valuable metal in acid, metal good separating effect；2nd, the sulphur in waste acid is consumed with Bellamya aeruginosa in the control current potential Oxidation Leaching stage first
The leaching rate of acid, copper and arsenic respectively reaches 98.0% and more than 95.0%；3rd, secondly As is made in advance in the control current potential oxidation of sulfureted stage
(III) As (V) is all oxidized to, the rate of deposition of copper reaches more than 99.0%, and the rate of deposition of arsenic is less than 2.0%, effectively prevent control
Current potential vulcanizes the precipitation of copper removal process arsenic；4th, last in control potential reduction sulfurating stage, it is As (III) to make As (V) Restore All,
The purpose that arsenic is effectively precipitated can be reached, the rate of deposition of arsenic reaches more than 99.0%, reduce reagent consumption, improve arsenic precipitation
Rate；5th, the cigarette ash processing waste acid of present invention Copper making, realizes the cyclic utilization of waste in system, reaches treatment of wastes with processes of wastes against one another purpose；6、
The present invention has simple technical process, technical indicator stabilization, labor intensity small and the low advantage of production cost.
Brief description of the drawings
Fig. 1：Present invention process schematic flow sheet.
Embodiment
Embodiment 1：
The cigarette ash and waste acid of certain domestic enterprise's copper concentrate oxygen-enriched bottom-blowing stove bath smelting process output, Bellamya aeruginosa it is main into
Divide and be by percentage to the quality（%）：Cu15.8, Pb22.5, As9.8, Zn1.6, Bi2.9 and S10.4, its main component of waste acid
For（g/L）：Cu4.2, As12.4, Bi0.8 and Zn1.5.The weight/mass percentage composition of industrial grade hydrogen peroxide is not less than 27.5%, industry
The weight/mass percentage composition of level sodium sulfite is not less than 95.0%, and the weight/mass percentage composition of technical grade vulcanized sodium is not less than 60.0%.
Copper making waste acid presses liquid-solid ratio with cigarette ash（The ratio between liquid volume L and solid weight Kg）Size mixing at 7: 1, keeps compound
88 DEG C of slurry temperature degree adds oxidizing dissolving, and the metal ion mixed potential for controlling whole slurry is relative to calomel electrode
510mV, after realizing solid-liquor separation, the leaching of copper and arsenic using plate compression mode after the follow-up continuous stirring 120min of current potential value stabilization
Rate is respectively 98.2% and more than 95.3%；Oxidant is added into leachate, by the metal ion mixed potential control of whole solution
System continues to stir 25min in 540mV after current potential is stable；Oxidated solution adds solid sodium sulfide at 80 DEG C of temperature, by solution
Metal ion mixed potential control between 240mV, after solution potential stablize and continue stir 60min after separation of solid and liquid, copper
Rate of deposition with arsenic is respectively 99.8% and 1.4%；Liquid adds reducing agent after to copper removal, and the metal ion of whole solution is mixed into electricity
Position control continues to stir 30min in 130mV after current potential is stable；Liquid adds solid sodium sulfide at 80 DEG C of temperature after reduction, will
The metal ion mixed potential of solution is controlled between -290mV, the solid-liquid point after solution potential is stablized and continues stirring 20min
From solid product is arsenones, and the rate of deposition of arsenic reaches 99.0%；Solid soda ash is added after arsenic removal in liquid, pH value of solution=8 are adjusted,
Liquid qualified discharge after solid-liquor separation, neutralization is realized using plate compression mode after continuation stirring 60min after pH is stable.
Claims (5)
1. a kind of method of Copper making cigarette ash and waste acid Combined Treatment, it is characterised in that comprise the following steps：
(1) current potential Oxidation Leaching is controlled
Copper making waste acid volume L and cigarette ash weight kg sizes mixing by liquid-solid ratio 5.1~8: 1, keeps 86~90 DEG C of mixed slurry temperature
Oxidizing dissolving is added, it is 501~520mV relative to calomel electrode to control the metal ion mixed potential of whole slurry,
After realizing solid-liquor separation using plate compression mode after 60~180min of the follow-up continuous stirring of current potential value stabilization, leachate send control current potential
Oxidation of sulfureted process, leached mud reclaims lead and bismuth；
(2) current potential oxidation of sulfureted is controlled
Oxidant is added into leachate, the metal ion mixed potential of whole solution is controlled in 500~550mV, current potential is treated
Continue to stir 15~29min after stable；Oxidated solution adds solid sodium sulfide at 75~85 DEG C of temperature, by the metal of solution from
Sub- mixed potential control is in 180~250mV, the separation of solid and liquid after solution potential is stablized and continues 60~90min of stirring, solid production
Thing is that liquid is used to control potential reduction sulfidation after copper sulfide concentrate, copper removal；
(3) control potential reduction vulcanization
Liquid adds reducing agent after to copper removal, and the metal ion mixed potential of whole solution is controlled in 50~150mV, treats that current potential is steady
Continue to stir 15~45min after fixed；Liquid adds solid sodium sulfide at 75~85 DEG C of temperature after reduction, by the metal ion of solution
Mixed potential control is in -200~-300mV, the separation of solid and liquid after solution potential is stablized and continues 15~29min of stirring, solid production
Thing is that liquid continues with rear qualified discharge after arsenones, arsenic removal；
(4) liquid is neutralized after arsenic removal
Solid soda ash is added in liquid after to arsenic removal, the pH of liquid after arsenic removal is neutralized to 7~9, continue to stir 60 after pH is stable~
Liquid qualified discharge after solid-liquor separation, neutralization is realized using plate compression mode after 90min.
2. the method for Copper making cigarette ash as claimed in claim 1 and waste acid Combined Treatment, it is characterised in that described oxidant
For one or both of hydrogen peroxide or sodium chlorate, both are technical grade reagent, and the weight/mass percentage composition of industrial hydrogen peroxide is not
Less than 27.5%, the weight/mass percentage composition of industrial sodium chlorate is not less than 95.0%.
3. the method for Copper making cigarette ash as claimed in claim 1 and waste acid Combined Treatment, it is characterised in that described reducing agent
For the one or more in sodium sulfite, sulfur dioxide or sodium thiosulfate, and it is technical grade reagent.
4. the method for Copper making cigarette ash as claimed in claim 1 and waste acid Combined Treatment, it is characterised in that described vulcanized sodium
For technical grade reagent, wherein weight/mass percentage composition is not less than 60.0%.
5. the method for Copper making cigarette ash as claimed in claim 1 and waste acid Combined Treatment, it is characterised in that：Described Copper making
The main component of cigarette ash is by percentage to the quality：Cu1.0~20.0, Pb1.0~30.0, As1.0~15.0, Zn1.0~
10.0th, Bi0.1~10.0 and S1.0~15.0, unit is %；The main component concentration of copper waste acid is：Cu0.1~10.0,
As1.0~15.0, Zn1.0~5.0, Bi0.1~10.0 and H2SO410.0~240.0, unit is g/L.
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| CN107460329A (en) * | 2017-08-08 | 2017-12-12 | 中条山有色金属集团有限公司 | A kind of method that indium metal is reclaimed from Bellamya aeruginosa |
| CN107841626B (en) * | 2017-09-27 | 2019-02-05 | 昆明理工大学 | A kind of method of zinc hydrometallurgy kiln slag and waste acid Combined Treatment |
| CN109055780A (en) * | 2018-07-18 | 2018-12-21 | 河南中原黄金冶炼厂有限责任公司 | A kind of method of iron sulfonium processing pyrometallurgical smelting acid making system spent acid containing arsenic |
| CN110819814B (en) * | 2019-12-03 | 2021-01-26 | 山东国大黄金股份有限公司 | High-arsenic waste acid treatment method |
| CN111118307A (en) * | 2020-01-16 | 2020-05-08 | 湖南有色金属研究院 | Method for treating arsenic-containing waste residue by using industrial waste acid |
| AU2021230421A1 (en) * | 2020-03-02 | 2022-10-13 | Li-Cycle Corp. | A method for processing lithium iron phosphate batteries |
| CN112481505B (en) * | 2020-11-26 | 2022-11-08 | 江西睿锋环保有限公司 | Method for preparing basic zinc chloride by using high-chlorine smelting soot |
| CN115011810B (en) * | 2022-01-05 | 2023-09-12 | 昆明理工大学 | Leaching process for improving copper recovery rate in zinc roasting ore |
| CN114951228B (en) * | 2022-05-30 | 2023-03-28 | 南京理工大学 | Method for realizing co-treatment of fly ash and copper smelting waste acid |
| CN115369266B (en) * | 2022-08-19 | 2024-02-20 | 江西铜业股份有限公司 | Method for removing and recycling arsenic in chlorohydrochloric acid leaching solution |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009011316A1 (en) * | 2007-07-13 | 2009-01-22 | Dowa Metals & Mining Co., Ltd. | Method of treating copper-arsenic compound |
| CN102115165A (en) * | 2010-12-31 | 2011-07-06 | 马艳荣 | Method for preparing arsenic trioxide by arsenic-containing waste water |
| CN105567984A (en) * | 2016-01-18 | 2016-05-11 | 中南大学 | Method for potential controlled selection separation of copper refinery ash |
| CN105624412A (en) * | 2016-01-18 | 2016-06-01 | 中南大学 | Copper soot smelting and separation combined treatment method |
| CN105648214A (en) * | 2016-01-18 | 2016-06-08 | 中南大学 | Method for vulcanizing and separating valuable metal in solution through controlled potential |
-
2016
- 2016-06-30 CN CN201610501204.2A patent/CN105950874B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009011316A1 (en) * | 2007-07-13 | 2009-01-22 | Dowa Metals & Mining Co., Ltd. | Method of treating copper-arsenic compound |
| CN101743202A (en) * | 2007-07-13 | 2010-06-16 | 同和金属矿业有限公司 | Method of treating copper-arsenic compound |
| CN102115165A (en) * | 2010-12-31 | 2011-07-06 | 马艳荣 | Method for preparing arsenic trioxide by arsenic-containing waste water |
| CN105567984A (en) * | 2016-01-18 | 2016-05-11 | 中南大学 | Method for potential controlled selection separation of copper refinery ash |
| CN105624412A (en) * | 2016-01-18 | 2016-06-01 | 中南大学 | Copper soot smelting and separation combined treatment method |
| CN105648214A (en) * | 2016-01-18 | 2016-06-08 | 中南大学 | Method for vulcanizing and separating valuable metal in solution through controlled potential |
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