CN105624412B - A kind of method that Combined Treatment is selected in Bellamya aeruginosa smelting - Google Patents
A kind of method that Combined Treatment is selected in Bellamya aeruginosa smelting Download PDFInfo
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- CN105624412B CN105624412B CN201610030159.7A CN201610030159A CN105624412B CN 105624412 B CN105624412 B CN 105624412B CN 201610030159 A CN201610030159 A CN 201610030159A CN 105624412 B CN105624412 B CN 105624412B
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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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
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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
- 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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- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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- 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 that Combined Treatment is selected in Bellamya aeruginosa smelting, Bellamya aeruginosa is milled to after requiring granularity and leached in aqueous, adding vulcanized sodium makes the metal ion mixed potential of whole slurry control requiring numerical value, add the pH value of sulfuric acid adjustment slurry to be maintained at simultaneously and require numerical value, filtered after continuing to stir a period of time after solution potential stabilization, leachate send wastewater treatment, leached mud direct flotation output copper concentrate and flotation tailings after the conversion of parlkaline ball milling after controlling metal ion mixed potential and pH value respectively output arsenones and zinc sulphide precipitation.The present invention reclaims valuable metal, these process tight associations using the method substep that control current potential vulcanization leaching and ore dressing are combined, and separate processes can not all reach the Expected Results of valuable metal selection separation in Bellamya aeruginosa.The leaching rate of arsenic and zinc reaches more than 95.0%, and copper direct yield reaches more than 98.0%.
Description
Technical field
The present invention relates to hydrometallurgy process in nonferrous metallurgy field, leached especially with control current potential vulcanization and ore dressing connection
Conjunction mode substep separates the Wet-process metallurgy method of valuable metal in Bellamya aeruginosa.
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, is had
The copper sulfide raw ore of economic worth 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 can
The property selected is good, be easy to enrichment, is used at pyrometallurgical smelting process by the copper sulfide concentrate of the cupric 20~30% of floatation process output
Reason, and cupric oxide ore flotability is poor, be difficult to beneficiation enrichment, is preferably directly processed using hydrometallurgical processes.
At present, about more than 80% mineral products copper is then copper sulfide concentrate by 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 then output largely contains the complicated flue dust of arsenic, lead, copper, zinc and bismuth, commonly referred to Bellamya aeruginosa.Due to
Volatile component is different different with smelting parameter in the copper concentrate of use, and the Bellamya aeruginosa composition of each copper metallurgy enterprise is not quite similar.Closely
Nian Lai, the rich ore in Copper Ores is reduced so that the grade reduction and impurity content increase of copper concentrate so that the composition of Bellamya aeruginosa becomes
Obtain more complicated.For the continuity and comprehensively recovering valuable metal of production, Bellamya aeruginosa is directly returned and made by domestic enterprise mostly
Sulfonium fusion process, but a series of problem is brought, the disposal ability of smelting furnace, the normal operation system of influence are reduced first
Degree；Secondly in Bellamya aeruginosa the impurity content such as Pb, As and Zn increase, not only cause the working of a furnace to deteriorate, and harmful element accumulation
Tough cathode product quality is influenceed, harmful element arsenic etc. causes follow-up relieving haperacidity operation catalyst cycle reduction again, therefore, with copper essence
The increase of harmful element content in ore deposit, it is necessary to which open circuit treatment is carried out to Bellamya aeruginosa.
Relevant Bellamya aeruginosa open circuit treatment has carried out long-term research both at home and abroad, is taking into full account the recovery of valuable metal resource
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 to be similar to, Bellamya aeruginosa is not introduced simply the matte smelting stove of copper concentrate, reduce Bellamya aeruginosa and main body is given 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 improving 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, while
The metals such as copper and zinc are made to be converted into soluble conformation, then calcining leaches the valuable metals such as separation 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 copper, arsenic and zinc etc. dissolve entrance using sulfuric acid system first
Solution, by separation and Extraction copper and zinc again after arsenic removal, leached mud reduction melting in blast furnace is enriched with lead and bismuth etc. to leachate
In lead bullion.Half wet process technical process index stabilization, is domestic using technique the most universal, but pyrogenic attack stage at present
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 is leached, and makes the sulfate of copper and zinc molten
Solution enters solution, and lead and bismuth then enter precipitation slag.Acid system 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
Be then realized in NaOH or vulcanized sodium system it can in cigarette ash arsenic leaching, leached mud is again using acidic leaching or straight
Connect method of smelting and reclaim valuable metal.No matter Bellamya aeruginosa is leached in which kind of system, and wet processing all thoroughly overcomes pyrogenic process work
The environmental impact issues that skill is present, but there are metal inferior separating effect and production cost exemplary shortcomings high, especially subsequently
The separation of valuable metal is still a problem in solution.Wet processing has significant environment compared with thermal process treatment Bellamya aeruginosa
Benefit, is the main development direction of Bellamya aeruginosa treatment.
Comprehensive Correlation these Bellamya aeruginosa handling process, 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 gradually, but treatment long flow path, high energy consumption, also just
To wet processing transition, wet processing process commercial Application, but existing technique is still present As evil difficult treatments, no
Thoroughly, equipment requirement is high, the low problem of economic benefit.Whote-wet method treatment 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, rational exploitation is a kind of economical, and efficient Bellamya aeruginosa handling process is still at present urgently
Problem to be solved.
The content of the invention
In order to overcome the shortcomings of traditional Bellamya aeruginosa processing method, the present invention is provided one kind and is leached and choosing using control current potential vulcanization
Ore deposit is combined mode substep and reclaims valuable metal, and metal recovery rate is high, environmental pollution is small and low cost Wet-process metallurgy method.
It is to reach above-mentioned purpose the technical solution adopted by the present invention：Bellamya aeruginosa is milled to and requires after granularity in aqueous
Leach, add vulcanized sodium to make the metal ion mixed potential of whole slurry control requiring numerical value, while adding sulfuric acid adjustment material
The pH value of slurry is maintained at and requires numerical value, is filtered after continuing to stir a period of time after solution potential stabilization, leachate control metal
Wastewater treatment is sent after Ar ion mixing current potential and pH value respectively output arsenones and zinc sulphide precipitation, leached mud turns through parlkaline ball milling
Direct flotation output copper concentrate after change, flotation tailings is the important source material for reclaiming lead and bismuth.The essence of the technical program is to use
Control current potential vulcanization and leach the method being combined with ore dressing recovery valuable metal, these process tight associations step by step, separate processes are all
The Expected Results of valuable metal selection separation in Bellamya aeruginosa can not be reached.
Control current potential vulcanization is leached
Bellamya aeruginosa is controlled current potential vulcanization in the aqueous solution containing vulcanized sodium and is leached.Bellamya aeruginosa ball milling simultaneously accounts for -0.074mm
100%, then by liquid-solid ratio（The ratio between liquid volume L and solid weight kg）Add water slurry at 1.0~3.0: 1, is subsequently adding solid
Vulcanized sodium makes the metal ion mixed potential of whole slurry be 50~150mV relative to calomel electrode, while adding industrial sulphuric acid
The pH value for adjusting solution maintains 0.1~1.0 all the time, and liquid is realized using plate compression mode after current potential stablizes 60~240min
Gu separating, leachate is separately recovered arsenic and zinc for controlling current potential sulfide precipitation, and leached mud is used for ore dressing and reclaims copper concentrate.Bellamya aeruginosa
The main chemical reactions that control current potential vulcanization leaching process occurs are as follows：
As2O3+2H2O=2H3AsO3（1）
CuO+Na2S+H2SO4=CuS↓+Na2SO4+H2O （2）
ZnO+H2SO4=ZnSO4+H2O （3）
CuSO4+Na2S=CuS↓+Na2SO4（4）
CuO•As2O3+Na2S+H2SO4+2H2O=CuS↓+2H3AsO3+Na2SO4（5）
The alkalescence ball milling conversion of 2 leached muds
Leached mud ball milling in alkaline system converts to remove sulfate radical.Leached mud presses liquid-solid ratio（Liquid volume L and solid
The ratio between weight kg）Adds water at 1.0~1.5: 1 be added in ball mill after pulp, while adding leached mud weight 1.0~10.0%
Sodium carbonate, is subsequently adding ball milling steel ball, controls ratio of grinding media to material（Steel ball weight kg and leached mud weight kg ratios）It is 3~10: 1 He
Two kinds of different-diameter steel ball number ratios（Diameter 10mm steel balls and diameter 5mm steel ball number ratios）It is 1: 5, starts ball mill and make
Drum's speed of rotation is maintained at 210-300r/min 1~3h of ball milling, and ball milling terminates rear mixed slurry and directly uses vacuum filter mode
Separation of solid and liquid is realized, conversion fluid send wastewater treatment, and conversion slag carries out flotation and recovery of copper.Leached mud alkalescence ball milling conversion process occurs
Main chemical reactions it is as follows：
PbSO4+Na2CO3=PbCO3+Na2SO4（6）
3 conversion slag flotations
Conversion slag is using the one thick one single-minded floatation process output copper sulfide concentrate swept.Conversion slag is sieved and makes -0.074um
More than 100% is accounted for, according to the one thick one single-minded operating duty swept, rougher process adds water to adjust pulp density to 25- to floatation process
30%, add beneficiation reagent, regulator sodium carbonate addition 1000-3000g/t, collecting agent butyl xanthate according to conversion slag per ton
5~200g/t and 5~100g/t are respectively with the addition of butyl black powder, the oily consumption of foaming agent two is 5~80g/t, to ore deposit
Air mass flow is poured in slurry for 20-30m3/ min, depth of foam is controlled in 100-200mm, time 12-20min；Refining process is not
Floating agent is added, it is 25-30% to add water adjustment pulp density, is 20-25m to air mass flow is poured in ore pulp3/ min, bubble
Foam thickness control is in 100-150mm, time 8-12min；It is 15-25% to scan process and add water adjustment pulp density, according to per ton
Bellamya aeruginosa adds beneficiation reagent, regulator sodium carbonate addition 500-1000g/t, collecting agent butyl xanthate and butyl black powder plus
Enter amount and be respectively 5~100g/t and 5~50g/t, the oily consumptions of foaming agent two are 5~40g/t, to pouring air mass flow in ore pulp
It is 1.5-4.5m3/ min, time 8-12min, refining process output copper sulfide concentrate, slurry uses dense separation after flotation, molten
Liquid is returned matches somebody with somebody ore deposit, and flotation tailings is the raw material for reclaiming lead and bismuth.
The heavy arsenic of control current potential vulcanization
Leachate controls metal ion mixed potential and pH value selective precipitation arsenones simultaneously.Leachate keeping temperature 30~
70 DEG C and 100~200r/min of rotating speed, being subsequently adding solid sodium sulfide makes the metal ion mixed potential of slurry relative to calomel
Electrode is -100~0mv, while the pH value for adding sulfuric acid adjustment slurry is 1.1~2.5, treats the follow-up continuous stirring of current potential value stabilization
Solid-liquor separation is realized using plate compression mode after 120-240min, solid product is arsenones, liquid is used to control current potential after arsenic removal
The heavy zinc operation of vulcanization.The main chemical reactions that control current potential vulcanization arsenic removal process occurs are as follows：
2H3AsO3+3Na2S+3H2SO4=As2S3↓+3Na2SO4+3H2O （7）
The 5 control heavy zinc of current potential vulcanization
Liquid controls metal ion mixed potential and pH value selective precipitation zinc sulphide simultaneously after arsenic removal.Liquid keeping temperature after arsenic removal
30~70 DEG C and 100~200r/min of rotating speed, be subsequently adding solid sodium sulfide make the metal ion mixed potential of slurry relative to
Calomel electrode is -200~-100mv, while the pH value for adding sulfuric acid adjustment slurry is 3.0~5.0, treats that current potential value stabilization is follow-up
Solid-liquor separation is realized using plate compression mode after continuous stirring 30-60min, solid product is zinc sulfide concentrates, except liquid send after zinc
Qualified discharge after wastewater treatment.The main chemical reactions that the heavy zinc process of control current potential vulcanization occurs are as follows：
ZnSO4+Na2S=ZnS↓+Na2SO4（8）
Described sulfuric acid is technical grade reagent, and its weight/mass percentage composition is not less than 98.0%.
Described vulcanized sodium is technical grade reagent, and its weight/mass percentage composition is not less than 60.0%.
The present invention is applied to the Bellamya aeruginosa for the treatment of copper concentrate fusion process output, and its main component scope is with mass percent
It is calculated as（%）：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.
It is suitable for the solid material of the cupric, arsenic and zinc for the treatment of Non-ferrous Metallurgy process output.
The present invention compares with traditional Bellamya aeruginosa processing method, has the advantage that：1st, the present invention is leached using control current potential vulcanization
Mode being combined with ore dressing and realizing that the substep of valuable metal in Bellamya aeruginosa is separated, metal good separating effect, process control is simple；2、
Arsenic and zinc selective dissolution in Bellamya aeruginosa are made using control current potential vulcanization leaching, and copper is then converted into copper sulfide precipitation, arsenic and zinc
Leaching rate reaches more than 95.0%；3rd, method for floating is used to reclaim copper, copper direct yield in copper sulfide concentrate form from conversion slag
Reach more than 98.0%；4th, from arsenic and zinc in control current potential vulcanization process fractional precipitation leachate etc. and output sulfide precipitation,
Precipitated metal rate is up to 99.9%；5th, present invention process process is simple, equipment investment is small, technical indicator is stable, labour intensity is small and
The advantages of low production cost.
Brief description of the drawings
Fig. 1：Present invention process schematic flow sheet.
Specific embodiment
Embodiment 1：The Bellamya aeruginosa of domestic certain enterprise's copper concentrate oxygen-enriched bottom-blowing stove bath smelting process output, its main component
Scope is by percentage to the quality（%）：Cu15.42, Pb22.68, As10.15, Zn3.27, Bi2.14 and S8.90.Technical grade sulphur
The weight/mass percentage composition of acid is not less than 98.0%, and the weight/mass percentage composition of technical grade vulcanized sodium is more than 60.0%.Bellamya aeruginosa ball milling is simultaneously
- 0.074mm is set to account for 100%, then by liquid-solid ratio（The ratio between liquid volume L and solid weight kg）Add water slurry at 2.0: 1, then
Adding solid sodium sulfide makes the metal ion mixed potential of whole slurry be 120mV relative to calomel electrode, while adding industry
The pH value of sulfuric acid adjustment solution maintains 0.8 all the time, realizes that liquid divides admittedly using plate compression mode after current potential stabilization 120min
From copper content is 0.01g/L in leachate, and copper and arsenic content are respectively 28.50 and 1.20% in leached mud.
Leached mud presses liquid-solid ratio（The ratio between liquid volume L and solid weight kg）Adds water at 1.2: 1 be added to ball mill after pulp
In, while adding sodium carbonate 18kg, ball milling steel ball is subsequently adding, control ratio of grinding media to material（Steel ball weight kg and leached mud weight kg
Ratio）It is 6: 1 and two kind of different-diameter steel ball number ratio（Diameter 10mm steel balls and diameter 5mm steel ball number ratios）It is 1: 5, opens
Dynamic ball mill simultaneously makes drum's speed of rotation be maintained at 240r/min ball milling 2h, and ball milling terminates rear mixed slurry and directly uses vacuum filter
Mode realizes separation of solid and liquid.Conversion slag sieves and -0.074um is accounted for more than 100%, and floatation process single-minded is swept according to one thick one
Operating duty, rougher process adds water to adjust pulp density to 28.0%, and beneficiation reagent, regulator are added according to conversion slag per ton
The addition of sodium carbonate addition 2000g/t, collecting agent butyl xanthate and butyl black powder is respectively 180g/t and 60g/t, foaming
The oily consumption of agent two is 30g/t, is 25m to air mass flow is poured in ore pulp3/ min, depth of foam is controlled in 180mm, time
15min；Refining process is added without floating agent, and it is 25% to add water adjustment pulp density, is to air mass flow is poured in ore pulp
22m3/ min, depth of foam is controlled in 100mm, time 8min；It is 16% to scan process and add water adjustment pulp density, according to every
Ton Bellamya aeruginosa adds beneficiation reagent, regulator sodium carbonate addition 800g/t, the addition of collecting agent butyl xanthate and butyl black powder
Amount is respectively 80g/t and 25g/t, and the oily consumption of foaming agent two is 20g/t, is 3.0m to air mass flow is poured in ore pulp3/ min,
Time 8min, refining process output copper sulfide concentrate, copper content is 58.4% in copper sulfide concentrate, and copper content is in flotation tailings
0.25%。
50 DEG C and rotating speed 120r/min of leachate keeping temperature, being subsequently adding solid sodium sulfide mixes the metal ion of slurry
It is -80mv that current potential is closed relative to calomel electrode, while the pH value for adding sulfuric acid adjustment slurry is 2.0, treats that current potential value stabilization is follow-up
Solid-liquor separation is realized using plate compression mode after continuous stirring 120min, arsenic content is 0.05g/L in liquid after arsenic removal, arsenones are produced
Arsenic content reaches 57.5% in thing.60 DEG C and rotating speed 120r/min of liquid keeping temperature after arsenic removal, being subsequently adding solid sodium sulfide makes material
The metal ion mixed potential of slurry is -180mv relative to calomel electrode, while the pH value for adding sulfuric acid adjustment slurry is 4.0, is treated
Solid-liquor separation is realized using plate compression mode after the follow-up continuous stirring 45min of current potential value stabilization, except Zn content is in liquid after zinc
0.03g/L, Zinc Content in Zinc Sulphide Concentrate content is 65.0%, except liquid send qualified discharge after wastewater treatment after zinc.
Claims (4)
1. a kind of method that Combined Treatment is selected in Bellamya aeruginosa smelting, it is characterised in that comprise the following steps：
A control current potential vulcanizations are leached
Bellamya aeruginosa is controlled current potential vulcanization in the aqueous solution containing vulcanized sodium and is leached：Bellamya aeruginosa ball milling simultaneously makes -0.074mm account for 100%,
Then add water slurry for 1.0~3.0: 1 by the ratio between liquid volume L and solid weight kg, be subsequently adding solid sodium sulfide make it is whole
The metal ion mixed potential of individual slurry is 50~150mV relative to calomel electrode, while adding industrial sulphuric acid adjustment solution
PH value maintains 0.1~1.0 all the time, and solid-liquor separation is realized using plate compression mode after current potential stablizes 60~240min, leaching
Go out liquid and be separately recovered arsenic and zinc for controlling current potential sulfide precipitation, leached mud is used for ore dressing and reclaims copper concentrate；
The alkalescence ball milling conversion of B leached muds
Leached mud ball milling in alkaline system converts to remove sulfate radical：Leached mud is by the ratio between liquid volume L and solid weight kg
It is to add water pulp after be added in ball mill at 1.0~1.5: 1, while the sodium carbonate of leached mud weight 1.0~10.0% is added, so
Ball milling steel ball is added afterwards, and it is 3~10: 1 to control ratio of grinding media to material, and two kinds of steel ball quantities of the steel ball of a diameter of 10mm and a diameter of 5mm
Amount starts ball mill and drum's speed of rotation is maintained at 210-300r/min 1~3h of ball milling than being 1: 5, and ball milling mixes after terminating
Slurry directly realizes separation of solid and liquid using vacuum filter mode, and conversion fluid send wastewater treatment, and conversion slag carries out flotation and recovery of copper；
C converts slag flotation
Conversion slag is using the one thick one single-minded floatation process output copper sulfide concentrate swept：Conversion slag is sieved and accounts for -0.074um
More than 100%, according to the one thick one single-minded operating duty swept, rougher process adds water to adjust pulp density to 25- to floatation process
30%, add beneficiation reagent according to conversion slag per ton：Regulator sodium carbonate is 1000-3000g/t, collecting agent butyl xanthate and fourth
Base black powder is respectively 5~200g/t and 5~100g/t, and No. two oil of foaming agent are 5~80g/t, to pouring air mass flow in ore pulp
It is 20-30m3/ min, depth of foam is controlled in 100-200mm, time 12-20min；Refining process is added without floating agent, plus
It is 25-30% to enter water adjustment pulp density, is 20-25m to air mass flow is poured in ore pulp3/ min, depth of foam is controlled in 100-
150mm, time 8-12min；It is 15-25% to scan process and add water adjustment pulp density, and ore dressing medicine is added according to Bellamya aeruginosa per ton
Agent：Regulator sodium carbonate is 500-1000g/t, and collecting agent butyl xanthate and butyl black powder are respectively 5~100g/t and 5~50g/
T, No. two oil of foaming agent are 5~40g/t, are 1.5-4.5m to air mass flow is poured in ore pulp3/ min, it is time 8-12min, selected
Process output copper sulfide concentrate, slurry uses dense separation after flotation, and solution is returned matches somebody with somebody ore deposit, and flotation tailings is to reclaim lead and bismuth
Raw material；
The D control heavy arsenic of current potential vulcanization
Leachate controls metal ion mixed potential and pH value selective precipitation arsenones simultaneously：30~70 DEG C of leachate keeping temperature
With the speed of agitator of 100~200r/min, being subsequently adding solid sodium sulfide makes the metal ion mixed potential of slurry relative to sweet
Mercury electrode is -100~0mv, while the pH value for adding sulfuric acid adjustment slurry is 1.1~2.5, treats the follow-up continuous stirring of current potential value stabilization
Solid-liquor separation is realized using plate compression mode after 120-240min, solid product is arsenones, liquid is used to control current potential after arsenic removal
The heavy zinc operation of vulcanization；
The E control heavy zinc of current potential vulcanization
Liquid controls metal ion mixed potential and pH value selective precipitation zinc sulphide simultaneously after arsenic removal：Liquid keeping temperature 30 after arsenic removal~
70 DEG C and the speed of agitator of 100~200r/min, being subsequently adding solid sodium sulfide makes the metal ion mixed potential of slurry relative
In calomel electrode be -200~-100mv, while add sulfuric acid adjustment slurry pH value be 3.0~5.0, after after current potential value stabilization
Continue to realize solid-liquor separation using plate compression mode after stirring 30-60min, solid product is zinc sulfide concentrates.
2. the method that Combined Treatment is selected in Bellamya aeruginosa smelting as claimed in claim 1, it is characterised in that described sulfuric acid is technical grade
Reagent, weight/mass percentage composition is not less than 98.0%.
3. the method that Combined Treatment is selected in Bellamya aeruginosa smelting as claimed in claim 1, it is characterised in that described vulcanized sodium is industry
Level reagent, weight/mass percentage composition is not less than 60.0%.
4. the method that Combined Treatment is selected in Bellamya aeruginosa smelting as claimed in claim 1, it is characterised in that：Its of the Bellamya aeruginosa is main
Composition range 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.
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| CN105950874B (en) * | 2016-06-30 | 2017-08-22 | 中南大学 | A kind of Copper making cigarette ash and the method for waste acid Combined Treatment |
| CN107661813B (en) * | 2016-07-29 | 2020-05-12 | 湖南隆洲驰宇科技有限公司 | Method for comprehensively recovering silver, lead and iron from electric precipitator dust |
| CN107354301B (en) * | 2017-07-19 | 2019-01-25 | 中南大学 | A method of improving arsenic-containing material arsenic-removing rate |
| CN110387464A (en) * | 2019-07-19 | 2019-10-29 | 江西铜业技术研究院有限公司 | A method of it will be enriched in sulphur arsenic in the complex materials of elemental sulfur and removes |
| CN110396597A (en) * | 2019-07-19 | 2019-11-01 | 江西铜业集团有限公司 | A kind of selecting smelting combination process of the high efficiency extraction lead bismuth from oxidation cleaning residue |
| CN110479500B (en) * | 2019-07-19 | 2022-02-08 | 江西铜业集团有限公司 | Floating-gravity combined process method for reducing sulfur and enriching bismuth of high-dispersion system of oxidation cleaning residues |
| CN111979412A (en) * | 2020-07-10 | 2020-11-24 | 华南师范大学 | Method for recovering lead and zinc in copper-sulfur tailings |
| CN112593082B (en) * | 2020-11-26 | 2022-09-27 | 山西北方铜业有限公司 | Method for separating copper and arsenic in contaminated acid liquid |
| CN112575200A (en) * | 2020-12-08 | 2021-03-30 | 衢州华友钴新材料有限公司 | Method for replacing and separating copper, zinc and manganese in inverse copper-manganese solution by using sulfide precipitation controlled electric position |
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| JP4417152B2 (en) * | 2004-03-25 | 2010-02-17 | Ｄｏｗａホールディングス株式会社 | Fly ash treatment method |
| CN1321200C (en) * | 2005-12-23 | 2007-06-13 | 朱永文 | Method for separating copper, arsenic and zinc from copper-smelting high-arsenic flue dust sulphuric acid leach liquor |
| CN101328539A (en) * | 2008-07-27 | 2008-12-24 | 郴州市金贵银业股份有限公司 | Oxidation oven ash hydrometallurgical leaching process |
| JP4921529B2 (en) * | 2009-07-29 | 2012-04-25 | パンパシフィック・カッパー株式会社 | Copper converter dust treatment method |
| CN101824543B (en) * | 2010-05-27 | 2011-07-06 | 中南大学 | Method for sulfidizing heavy metal waste and recovering valuable metals in heavy metal waste |
| CN103014355B (en) * | 2012-12-13 | 2014-12-24 | 马永涛 | Multi-metal comprehensive recycling process for copper smelting ash |
| CN104532007A (en) * | 2014-12-25 | 2015-04-22 | 安阳钢铁股份有限公司 | Method for comprehensively utilizing electric field dust-removal ash at head end of sintering machine and blast furnace gas ash |
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