CN105463197A - Method for recycling valuable metal from copper smelting white smoke - Google Patents

Method for recycling valuable metal from copper smelting white smoke Download PDF

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Publication number
CN105463197A
CN105463197A CN201510867122.5A CN201510867122A CN105463197A CN 105463197 A CN105463197 A CN 105463197A CN 201510867122 A CN201510867122 A CN 201510867122A CN 105463197 A CN105463197 A CN 105463197A
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China
Prior art keywords
arsenic
copper
zinc
leaching
content
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CN201510867122.5A
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Chinese (zh)
Inventor
孙宝辉
宋连民
周杰
夏举佩
苏毅
李国斌
罗中秋
宁勤科
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Xinjiang Wuxin Copper Co Ltd
Kunming University of Science and Technology
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Xinjiang Wuxin Copper Co Ltd
Kunming University of Science and Technology
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Priority to CN201510867122.5A priority Critical patent/CN105463197A/en
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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
    • C22B7/02Working-up flue dust
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00Obtaining lead
    • C22B13/04Obtaining lead by wet processes
    • C22B13/045Recovery from waste materials
    • 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
    • C22B15/0067Leaching or slurrying with acids or salts thereof
    • C22B15/0071Leaching or slurrying with acids or salts thereof containing sulfur
    • 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
    • C22B15/0084Treating solutions
    • C22B15/0089Treating solutions 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
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/20Obtaining zinc otherwise than by distilling
    • C22B19/22Obtaining zinc otherwise than by distilling with leaching with acids
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/30Obtaining zinc or zinc oxide from metallic residues or scraps
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • C22B7/007Wet processes by acid leaching
    • 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 invention relates to a method for recycling valuable metal from copper smelt white smoke and belongs to the technical field of resource recycling. The method includes the steps that the white smoke collected from a second electric field, a third electric field and a fourth electric field through an electric copper smelting smoke collection device serves as a raw material, a first-level power wave circulating cleaning solution serves as a leaching agent, the liquid-solid mass ratio is 8-10:1, leaching is conducted at the normal temperature, and lead-rich slag with the metal grade larger than 40wt% is obtained; sodium sulfide is added to a leaching solution for fractional precipitation so as to recycle copper and rich arsenic, the metal grade of copper-rich slag is larger than 40wt/%, the content of the arsenic in the arsenic-rich slag is larger than 35 wt%, finally, sodium carbonate is added for zinc precipitation, and the metal grade of the zinc-rich slag is larger than 45 wt/%; the valuable metal mentioned above can be used as raw materials for use or sale after being enriched, stockpiling or landfill requirements can be met after the metal is cured, and the arsenic open stub is formed. By the adoption of the method, circulating acid pickle serves as the leaching agent, the system waste acid treatment amount is reduced, valuable elements in the waste acid can be recycled, leaching operation and precipitation operation are conducted at the normal temperature, operation is convenient, and the method has good application and popularization value.

Description

The method of the white fume recovery valuable metal of a kind of Copper making
Technical field
The present invention relates to industrial solid castoff application technology as the second resource field, particularly the method for the white fume recovery valuable metal of a kind of Copper making.
Background technology
Copper is one of modern economy basic industry raw material sending out tendon, because it has conductive and heat-conductive, anti-tensile wear resisting property better, thus obtains sword widespread use in industry fields such as electric power electric, machinofacture, transport, building, the energy, military affairs.
Melting is the most important smelting process of copper smelting by pyrometallurgy, tradition melting method carries out in blast furnace, reverberatory furnace and electric furnace, the main drawback of this technique is: can not make full use of furnace charge medium sulphide content oxidation chemical reaction heat as energy, mineral fuel amount or power consumption large; Output S0 2flue gas concentration is low, produces sulfuric acid uneconomical, easily causes severe contamination to environment.Therefore traditional melting technology is replaced by efficient, energy-conservation and oligosaprobic intensified smelting novel process gradually.
From technological transformation and new projects' technical scheme of recent domestic several large factory, all using the technology of smelting system as emphasis, and select the advanced smelting technique and the equipment that are applicable to own characteristic, the large pole plate electrorefining of wherein copper ore concentrates batching-disk pelletizing-Ausmelt furnace melting-bessemerize-Rotary Anode Furnace pyrorefining-routine is the first-selected technique of current new upper Copper making.
The white smoke dust of Copper making derives from electric furnace flue gas and melting flue gas, and electric furnace flue gas main component is nitrogen and oxygen, and also containing a small amount of water vapor and sulfurous gas, temperature is generally at about 420 DEG C, and dustiness is about 30g/Nm 3; Melting flue gas main component is nitrogen, sulfurous gas and water vapor, and also containing a small amount of oxygen and sulphur trioxide, temperatures as high more than 1200 DEG C, dustiness is about 210g/Nm 3, reclaim after sensible heat through waste heat boiler, temperature drops to about 390 DEG C, and dustiness is down to 120g/Nm 3, assemble at this than dust that is great, coarse size.Mix from waste heat boiler melting flue gas out with electric furnace flue gas, mixture temperature about 300 DEG C, dustiness are at 105 ~ 110g/Nm 3, the high copper fumes one Returning smelting system through the trapping of dust precipitator first electric field is made feed stock for blast furnace and is used.Dust precipitator second and third, the flue dust collected of four electric fields due to containing more harmful impurity component, should not Returning smelting system, be the white smoke dust described in the application.
In mixed gas, sulfurous gas volume content is about 11 ~ 12%, is suitable for adopting double conversion double absorption relieving haperacidity, and it requires to be less than 0.5g/Nm to dust 3therefore, electric precipitator is only adopted to be difficult to meet relieving haperacidity requirement, washing adds dynamic wave dedusting and purifies gas, is the most common means of metallurgical tail gas relieving haperacidity, due in gas containing a large amount of objectionable impurities, washing water processing cost is high, usually take circulation cleaning mode to carry out, thus its remaining acid concentration after accumulation can reach about 5wt%, finally adds the heavy lead of sodium sulphite, limestone vegetation, lime dearsenification carry out wastewater treatment.
Because the white smoke dust of Copper making is the mixture being rich in valuable metal and harmful element, namely being a kind of dangerous solid waste, is also the resource that can be used, therefore, numerous scholars extract from single valuable metal or many metal recovery propose Counter-techniques route, as:
The Peng Cui of Wuhan Engineering Univ, with the white cigarette ash produced in Copper making process for raw material, have studied the leaching of valuable metal element in white cigarette ash, separation and recovery process, mainly born fruit: (1) leaches by successively adopting normal temperature water logging, hot acid-leaching and diluted acid heated oxide; (2) for the copper in cigarette ash leach liquor, using N902 as extraction agent, sulfuric acid is as reverse-extraction agent, and percentage extraction and back extraction ratio can reach more than 99% with optimal conditions; (4) adopt the zinc in sulfuration method co-precipitation leach liquor and arsenic, with optimal conditions, the deposition rate of zinc and arsenic is respectively 100% and 99%.
Ruan Shengshou, Lu Yongsuo adopt molten (pyrorefining) flow process of cigarette ash leaching-blast furnace smelting-lead bismuth alloy electrolysis-high bismuth anode sludge low temperature, the copper in synthetical recovery copper metallurgy electric precipitator dusts, zinc, paving, indium, lead, bismuth, gold and silver.Result shows: can comprehensively recovering valuable metal, environmental pollution little, and technico-economical comparison is better, has certain economic benefit.
The Liu Guoqing of Institutes Of Technology Of Jiangxi, adopt once leached by industrial sulphuric acid and a section of producing each batch of cigarette ash that solvent that solvent, waste electrolyte and trade effluent that water solvent, waste electrolyte and the production water prepared prepares prepare carries out, the secondary of one section of leach liquor leaches, the way leached for three times of one section of secondary leach liquor to be to improve copper, the Zn content in leach liquor, the treatment capacity, energy consumption etc. that reduce follow-up replacement deposition are of practical significance, the total leaching yield of leaching stage: Cu ﹥ 90%, Zn ﹥ 93%, Pb ﹤ 1%, Bi ﹤ 1%.
The Zhang Yan of Lanzhou University of Science & Technology, by the further investigation to certain Tong Ye company ash of copper converter, is applied to the comprehensive utilization of ash of copper converter by extraction process, propose the novel process of ash of copper converter comprehensive utilization.Ash of copper converter is after sulfuric acid leaching, and copper and the zinc of more than 90% all enter pickling liquor, and major part is plumbous enters acid leaching residue with the form of lead sulfate; Cigarette ash acid leaching residue is carried out to the technical process such as precipitation conversion-nitric acid dissolve-sulfuric acid depositing, obtained lead sulfate; Cigarette ash pickling liquor obtains the higher copper sponge of purity through iron replacement, can directly return the blowing refinement of the matte system; Cigarette ash acidleach carries copper liquid after oxidation, neutralization, hydrolysis deironing, and carry out triple-stage cross-flow extraction with P204 to deironing scavenging solution, organic phase has obtained the solution of zinc sulfate meeting electrowinning zinc needs after one-level back extraction.
CN102517449A proposes a kind of comprehensive recycling technique of valuable elements in smelting soot, the lead silver bismuth slag that after smelting ash adds sulfuric acid pulp two-stage leaching, press filtration is formed through superfusion, founding, electrolysis, refining, converter retailoring, obtain lead bullion, matte, smart bismuth and silver-zine slag, process recovery corresponding product and arsenic further.
CN103643044A provides the direct extracting copper of a kind of Bellamya aeruginosa wet method, zinc technology, its technical process is: leaching → organic matter removal → extraction copper → deironing, aluminium, chromium → extraction zinc → return leaching (open circuit 20-30%) without zinc solution, this invention can make more low-grade copper cigarette ash be able to resource recycling, there is conversion rate of products high, the advantage that added value is high.
CN102851707A provides the technique of a kind of alkaline leaching remanufacture electrolytic zinc powder and lead powder from smelting ash, process comprises leaching, lead powder decopper(ing), electrodeposition takes off lead-ingot casting, sodium sulphite deleading, arsenic removal antimony and electrodeposition zinc powder, is characterized in that: caustic lye of soda leaching agent and smelting ash are carried out Leaching reaction; Electrolysis lead powder decopper(ing) is added in leach liquor; Decopper(ing) liquid is through electrodeposition output electrolysis lead powder; Take sodium sulphite as deleading agent, precipitation separation takes off the remaining lead in plumbous liquid; Arsenic antimony in removing deleading liquid; Scavenging solution after arsenic removal antimony is again through electrodeposition output zinc powder, electrolysis waste solution returns to leach in operation and makes alkali leaching agent or carry out removing in cleaning section in waste liquid returning after foreign ion again to leach operation and make alkali leaching agent and recycle, and the method has the features such as simple to operate, less investment, adaptability to raw material wide, environmental friendliness.
CN103014355A provides a kind of Copper making cigarette ash many metals comprehensive recycling process, comprises the steps: (1) acidic leaching: adopt diluted acid to leach Copper making cigarette ash, obtain cigarette ash leach liquor and plumbous bismuth slag; (2) red arsenic copper removal: add uranium sulfide arsenic slag and red arsenic copper removal in cigarette ash leach liquor, preparation copper sulphide product; (3) the heavy arsenic of reduction: copper removal liquid sulphur dioxide reduction must sink arsenic liquid and white arsenic product; (4) secondary copper removal arsenic: add sodium sulphite again in heavy arsenic liquid, secondary copper removal arsenic.The method can by the various metals lixiviate in cigarette ash out, and the rate of recovery is high, and cost is low, profitable.
CN103981369A provides the many metals recovery processes of a kind of arsenic-containing smoke dust, and obtained containing the leach liquor of zinc, copper with containing arsenic, plumbous leached mud by Selectively leaching, leach liquor obtains copper and zinc by copper extraction and electrodeposition; Leached mud passes through H 2o 2and Na 2s 2o 3mixing dearsenic agent leaches and obtains arsenic leaching solution and leaded dearsenification slag, and arsenic leaching solution condensing crystal obtains sodium arseniate, and dearsenification leached mud carries lead by pyrogenic process and electrorefining obtains lead.This invention utilizes wet method and pyrogenic process associating metallurgical technology, and efficient recovery metallic copper, zinc, lead, make arsenic obtain recycling treatment, technique environmental protection.
From Copper making smoke dust, extracting and developing valuable metal research paper and Patents report are much, respectively there is feature, but make pickling agent with circulation of tail gas washing spent acid, adopt high liquid-solid ratio, normal temperature to leach, sodium sulphite sinks the rich arsenic of copper, and sodium carbonate sinks zinc also research report.
Summary of the invention
For solving above-mentioned prior art Problems existing, the object of the present invention is to provide the method for the white fume recovery valuable metal of a kind of Copper making, reclaim the valuable metal in the white flue dust of Copper making, enrichment is carried out to arsenic, to reduce the process total amount of arsenic-containing waste residue, reduce cost of disposal.The present invention makes pickling agent with copper metallurgy industry circulation cleaning spent acid, not only makes the free acid in spent acid obtain Appropriate application, also can realize valuable metal recovery in spent acid simultaneously, reduces system wastewater treatment capacity, reduces environmental protection treatment cost.
For achieving the above object, technical scheme of the present invention is:
A method for the white fume recovery valuable metal of Copper making, white flue dust adds pickling circulation spent acid and leaches under normal temperature, and copper, arsenic, zinc are proceeded to liquid phase, lead be enriched in slag mutually in, filtering separation, sinks zinc filtrate washing leaching cake by system, obtain lead-rich slag, make raw material and use by oneself or sell outward; Filtered liquid adds sodium sulphite and sinks copper, reclaims copper, as Copper making raw material with copper sulphide form; Continue to add sodium sulphite sink arsenic to reclaiming in the filtrate after copper, realize the enrichment of arsenic at this; In the filtrate being separated arsenic, add sodium sulfate sink zinc, reclaim zinc with the form of zinc carbonate, make raw material personal or take out.
A method for the white fume recovery valuable metal of Copper making, its basic step comprises as follows:
(1) the white smoke dust 1 part after the electric precipitation of the second stage is got, add the circulation cleaning waste liquid 8 ~ 10 parts from first order kinetics ripple, under normal temperature, lixiviate 30 ~ 45min is carried out in the reactive tank that band stirs, filter, wash, obtain the lead-rich slag that metallic lead content is greater than 40wt%, make raw material and use by oneself or take out;
(2) copper content analysis is carried out to leach liquor, add sulfuration to sink 0.9 ~ 1.1 times of sodium sulphite of copper theoretical amount and carry out heavy copper, operate in normal temperature band stir reactive tank in carry out, the heavy copper reaction times is 30min, reaction terminates rear pump to subsider standing separation, and supernatant liquor overflow is to rich arsenic groove, and sediment pump is separated to whizzer, filtrate is incorporated to medial launder, and filter cake is the rich copper ashes that metallic copper content is greater than 40wt%, is less than 7wt% containing arsenic;
(3) arsenic content analysis is carried out to leach liquor, add sulfuration to sink 0.8 ~ 1.0 times of sodium sulphite of arsenic theoretical amount and carry out heavy arsenic, operate in be with in the reactive tank of stirring and carry out under normal temperature, the heavy arsenic reaction times is 30min, reaction terminates rear standing 30min, supernatant liquor directly pumps into medial launder, and deposition liquid pump filters to flame filter press, arsenic content is greater than the rich arsenic slag of 35wt%;
(4) add sodium carbonate in the parting liquid after dearsenification and sink zinc, control ph 7.5 ± 0.5, reclaim zinc with the form of zinc carbonate, filter and obtain metallic zinc content and be greater than 45%, arsenic content is less than 5% rich cadmia.
Relative to prior art, beneficial effect of the present invention is:
A method for the white fume recovery valuable metal of Copper making, white flue dust adds pickling circulation spent acid and leaches under normal temperature, and copper, arsenic, zinc are proceeded to liquid phase, lead be enriched in slag mutually in, filtering separation, sinks zinc filtrate washing leaching cake by system, obtain lead-rich slag, make raw material and use by oneself or sell outward; Filtered liquid adds sodium sulphite and sinks copper, reclaims copper, as Copper making raw material with copper sulphide form; Continue to add sodium sulphite sink arsenic to reclaiming in the filtrate after copper, realize the enrichment of arsenic at this; In the filtrate being separated arsenic, add sodium sulfate sink zinc, reclaim zinc with the form of zinc carbonate, make raw material personal or take out.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, technical solution of the present invention is described in further detail:
Mass parts or mass percentage is in embodiment.
Embodiment 1:
As shown in Figure 1: (1) white smoke dust, first order kinetics ripple circulation spent acid main component are in table 1,2;
The white smoke dust main component of table 1
Table 2 first order kinetics ripple circulation spent acid main component
(2) get 40 tons, first order kinetics ripple circulation spent acid and pump into leaching groove, add white smoke dust 5 tons again, leaching 30min is stirred under normal temperature, filter, be incorporated in filtrate with heavy zinc liquid 1.5 tons of washing leaching cakes, by analysis, in filtrate, copper, zinc, arsenic content are respectively: 2.7g/L, 21.5g/L, 13.3g/L; Base filter cake quality of giving money as a gift is 1120kg, and lead content is 43.6wt%, and lead recovery is greater than 95.5%, and the solubility rate of copper, zinc, arsenic is respectively 92.6%, 97.5% and 95.5%;
(3) pickling liquor 40m is got 3by theoretical amount 0.8 needed for heavy copper extraordinarily effective content be 65wt% sodium sulphite 163kg solid sodium sulfide, reaction 30min is continued after reinforced end, pump is to subsider again, supernatant liquor pumps into dearsenification groove, settling, through centrifugation, obtains rich copper ashes 215kg, and rich copper ashes metallic copper content is 48wt% by analysis, arsenic content is 4.2wt%;
(4) in the heavy copper liquid of step (3), continue to add 1.0 times of above-mentioned sodium sulphite 1180kg of theoretical amount, reaction 30min is continued after reinforced end, pump is to subsider again, supernatant liquor overflow enters medial launder, settling is rich arsenic slag after filtration, rich arsenic slag amount (butt) is 1387kg, and arsenic content is 37.2wt% by analysis;
(5) continue to add solid sodium carbonate in the heavy arsenic liquid of step (4), it is 7.0 that reaction terminates rear survey pH value, pump is to subsider, supernatant liquor overflow enters medial launder, settling is rich cadmia after filtration, rich cadmia quality (butt) is 1788kg, and metallic zinc content is 46.3wt% by analysis, and arsenic content is 3.7wt%.
Embodiment 2:
(1) white smoke dust, first order kinetics ripple circulation spent acid main component are in table 3,4;
The white smoke dust main component of table 3
Table 4 first order kinetics ripple circulation spent acid main component
(2) get 40 tons, first order kinetics ripple circulation spent acid and pump into leaching groove, add white smoke dust 5 tons again, leaching 30min is stirred under normal temperature, filter, be incorporated in filtrate with heavy zinc liquid 1.5 tons of washing leaching cakes, by analysis, in filtrate, copper, zinc, arsenic content are respectively: 2.9g/L, 23.3g/L, 13.2g/L; Base filter cake quality of giving money as a gift is 1265kg, and lead content is 40.2wt%, and lead recovery is greater than 95.7%, and the solubility rate of copper, zinc, arsenic is respectively 92.8%, 98.6% and 95.1%;
(3) pickling liquor 40m3 is got, by theoretical amount 1.0 needed for heavy copper extraordinarily effective content be 65wt% sodium sulphite 222g solid sodium sulfide, reaction 30min is continued after reinforced end, pump is to subsider again, supernatant liquor pumps into dearsenification groove, settling, through centrifugation, obtains rich copper ashes 245kg, and rich copper ashes metallic copper content is 42.3wt% by analysis, arsenic content is 5.7wt%;
(4) in the heavy copper liquid of step (3), continue to add 0.9 times of above-mentioned sodium sulphite 1120kg of theoretical amount, reaction 30min is continued after reinforced end, pump is to subsider again, supernatant liquor overflow enters medial launder, settling is rich arsenic slag after filtration, rich arsenic slag amount (butt) is 1279kg, and arsenic content is 41.0wt% by analysis;
(5) continue to add solid sodium carbonate in the heavy arsenic liquid of step (4), it is 7.5 that reaction terminates rear survey pH value, pump is to subsider, supernatant liquor overflow enters medial launder, settling is rich cadmia after filtration, rich cadmia quality (butt) is 2095kg, and metallic zinc content is 42.3wt% by analysis, and arsenic content is 4.8wt%.
Embodiment 3:
(1) white smoke dust, first order kinetics ripple circulation spent acid main component are in table 5,6;
The white smoke dust main component of table 5
Table 6 first order kinetics ripple circulation spent acid main component
(2) get 40 tons, first order kinetics ripple circulation spent acid and pump into leaching groove, add white smoke dust 4 tons again, leaching 30min is stirred under normal temperature, filter, be incorporated in filtrate with heavy zinc liquid 1.5 tons of washing leaching cakes, by analysis, in filtrate, copper, zinc, arsenic content are respectively: 2.3g/L, 18.6g/L, 11.5g/L; Base filter cake quality of giving money as a gift is 811kg, and lead content is 48.2wt%, and lead recovery is greater than 95.5%, and the solubility rate of copper, zinc, arsenic is respectively 92.6%, 97.5% and 95.5%;
(3) pickling liquor 40m3 is got, by theoretical amount 1.1 needed for heavy copper extraordinarily effective content be the sodium sulphite 182kg solid sodium sulfide of 65wt%, reaction 30min is continued after reinforced end, pump is to subsider again, supernatant liquor pumps into dearsenification groove, settling, through centrifugation, obtains rich copper ashes 217g, and rich copper ashes metallic copper content is 40.5wt% by analysis, arsenic content is 6.8wt%;
(4) in the heavy copper liquid of step (3), continue to add 1.1 times of above-mentioned sodium sulphite 476kg of theoretical amount, reaction 30min is continued after reinforced end, pump is to subsider again, supernatant liquor overflow enters medial launder, settling is rich arsenic slag after filtration, rich arsenic slag amount (butt) is 1120kg, and arsenic content is 35.4wt% by analysis;
(5) continue to add solid sodium carbonate in the heavy arsenic liquid of step (4), it is 8.0 that reaction terminates rear survey pH value, pump is to subsider, supernatant liquor overflow enters medial launder, settling is rich cadmia after filtration, rich cadmia quality (butt) is 1610kg, and metallic zinc content is 40.2wt% by analysis, and arsenic content is 3.2wt%.
Embodiment 4:
(1) white smoke dust, first order kinetics ripple circulation spent acid main component are in table 7,8;
The white smoke dust main component of table 7
Table 8 first order kinetics ripple circulation spent acid main component
(2) get 40 tons, first order kinetics ripple circulation spent acid and pump into leaching groove, add white smoke dust 4.44 tons again, leaching 30min is stirred under normal temperature, filter, be incorporated in filtrate with heavy zinc liquid 1.5 tons of washing leaching cakes, by analysis, in filtrate, copper, zinc, arsenic content are respectively: 2.6g/L, 21.0g/L, 11.7/L; Base filter cake quality of giving money as a gift is 1215kg, and lead content is 41.5wt%, and lead recovery is 95.1%, and the solubility rate of copper, zinc, arsenic is respectively 92.2%, 98.3% and 95.7%;
(3) pickling liquor 40m3 is got, by theoretical amount 1.0 needed for heavy copper extraordinarily effective content be 65wt% sodium sulphite 197g solid sodium sulfide, reaction 30min is continued after reinforced end, pump is to subsider again, supernatant liquor pumps into dearsenification groove, settling, through centrifugation, obtains rich copper ashes 210kg, and rich copper ashes metallic copper content is 40.9wt% by analysis, arsenic content is 5.5wt%;
(4) in the heavy copper liquid of step (3), continue to add 0.9 times of above-mentioned sodium sulphite 1000kg of theoretical amount, reaction 30min is continued after reinforced end, pump is to subsider again, supernatant liquor overflow enters medial launder, settling is rich arsenic slag after filtration, rich arsenic slag amount (butt) is 1178kg, and arsenic content is 38.2wt% by analysis;
(5) continue to add solid sodium carbonate in the heavy arsenic liquid of step (4), it is 7.5 that reaction terminates rear survey pH value, pump is to subsider, supernatant liquor overflow enters medial launder, settling is rich cadmia after filtration, rich cadmia quality (butt) is 1860kg, and metallic zinc content is 41.7wt% by analysis, and arsenic content is 4.7wt%.
The above, be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, and any change of expecting without creative work or replacement, all should be encompassed within protection scope of the present invention.Therefore, the protection domain that protection scope of the present invention should limit with claims is as the criterion.

Claims (6)

1. the method for the white fume recovery valuable metal of Copper making, it is characterized in that, concrete preparation process comprises: the white flue dust collected with Copper making dust precipitator the second to four electric field is for raw material, first order kinetics ripple circulating cleaning solution is leaching agent, normal temperature acidleach is carried out in reactive tank, arsenic is proceeded to liquid phase, valuable metal copper again in fractional precipitation recovery flue dust and zinc, arsenic in solution is to carry out solidification treatment after sulfide enrichment, meet the stripping of GB GB5085.3-2007 toxicity and be less than 5mg/L, carry out landfill or directly stack, finally realizing the stabilization treatment of arsenic.
2. the method for the white fume recovery valuable metal of a kind of Copper making according to claim 1, it is characterized in that: white flue dust refers to second stage dust precipitator and the ash of dust-precipitator collection later, mainly leaded, zinc and arsenic oxide or sulfide, fine size, outward appearance is canescence.
3. the method for the white fume recovery valuable metal of a kind of Copper making according to claim 1, it is characterized in that: leaching medium is first order kinetics ripple circulating cleaning solution, sulfuric acid content is between 4.7wt ~ 5.5wt%, simultaneously containing lead, zinc, copper, arsenic, fluorine, it is a kind of waste liquid containing diluted acid and heavy metal, arsenic.
4. the method for the white fume recovery valuable metal of a kind of Copper making according to claim 1, it is characterized in that: the leaching operation of white flue dust is carried out at normal temperatures, liquid-solid mass ratio is 8 ~ 10, reaction times is 30 ~ 45min, soluble metal copper, zinc proceed to liquid phase with sulphate form, and arsenic then proceeds to liquid phase with the form of arsenus acid, and lead is insoluble in sulfuric acid, then still remain in slag, correlated response reaction is as follows:
CuO+H 2SO 4=CuSO 4+H 2O
ZnO+H 2SO 4=ZnSO 4+H 2O
As 2O 3+3H 2O=2H 3AsO 3
Wash through filtering, with when the heavy zinc filtrate of 1.5 times in white flue dust ash quantity after reaction terminates, this leaching is except in process, and lead recovery is greater than 95%, and metallic lead content is greater than 40wt%, and the solubility rate of copper, zinc, arsenic is greater than 92%, 97% and 95% respectively.
5. the method for the white fume recovery valuable metal of a kind of Copper making according to claim 4, it is characterized in that: in above-mentioned parting liquid, add theoretical amount 0.9 ~ 1.1 times of sodium sulphite sink copper, continue 0.8 ~ 1.0 times of heavy arsenic adding theoretical amount, respectively metallic copper content is greater than 40wt%, is less than the rich arsenic slag that the rich copper ashes of 7wt% and arsenic content is greater than 35% containing arsenic, heavy copper and heavy arsenic reaction times are 30min, temperature is normal temperature, and related chemistry reaction formula is as follows:
2AsO 3 3-+3S 2-+12H +=As 2S 3↓+6H 2O
Cu 2++S 2-=CuS↓
Zn 2++3S 2-=ZnS↓。
6. the method for the white fume recovery valuable metal of a kind of Copper making according to claim 1, it is characterized in that: add sodium carbonate in the parting liquid after dearsenification and sink zinc, zinc is reclaimed with the form of zinc carbonate, control ph 7.5 ± 0.5, in regenerant, metallic zinc content is greater than 45%, arsenic content is less than 5%, and reaction formula is as follows:
ZnSO 4+Na 2CO 3=ZnCO 3↓+Na 2SO 4
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CN105803209A (en) * 2016-04-21 2016-07-27 西北矿冶研究院 Method for recovering rare and precious metals from acid mud
CN106521167A (en) * 2016-10-11 2017-03-22 昆明理工大学 Comprehensive treatment method for high-arsenic lead zinc flue dust ash
CN106591586A (en) * 2016-12-02 2017-04-26 昆明理工大学 Method for recovering multiple kinds of metal from flue dust in copper smelting
CN106636656A (en) * 2016-09-19 2017-05-10 昆明理工大学 Method for recovering valuable metal from copper smelting white smoke
CN106756056A (en) * 2016-11-22 2017-05-31 昆明理工大学 A kind of method of Copper making white cigarette dirt dearsenification
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CN107502753A (en) * 2017-03-29 2017-12-22 河南中原黄金冶炼厂有限责任公司 A kind of method of Copper making white cigarette dirt acid leaching-extraction removal of impurities
CN107858519A (en) * 2017-10-30 2018-03-30 河南中原黄金冶炼厂有限责任公司 A kind of comprehensive processing technique of Copper making flue dust and arsenic sulfide slag
CN109136575A (en) * 2018-08-31 2019-01-04 唐山鹤兴废料综合利用科技有限公司 A kind of process of the more metallic dusts of wet-treating
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Publication number Priority date Publication date Assignee Title
CN105803209A (en) * 2016-04-21 2016-07-27 西北矿冶研究院 Method for recovering rare and precious metals from acid mud
CN106636656A (en) * 2016-09-19 2017-05-10 昆明理工大学 Method for recovering valuable metal from copper smelting white smoke
CN106521167A (en) * 2016-10-11 2017-03-22 昆明理工大学 Comprehensive treatment method for high-arsenic lead zinc flue dust ash
CN106521167B (en) * 2016-10-11 2018-10-02 昆明理工大学 A kind of integrated conduct method of high concn. arsenic and lead Zn dust ash
CN106756056A (en) * 2016-11-22 2017-05-31 昆明理工大学 A kind of method of Copper making white cigarette dirt dearsenification
CN106591586A (en) * 2016-12-02 2017-04-26 昆明理工大学 Method for recovering multiple kinds of metal from flue dust in copper smelting
CN107502753A (en) * 2017-03-29 2017-12-22 河南中原黄金冶炼厂有限责任公司 A kind of method of Copper making white cigarette dirt acid leaching-extraction removal of impurities
CN107459166A (en) * 2017-08-15 2017-12-12 昆明理工大学 The curing of sour recycling and arsenic in a kind of waste acid
CN107858519A (en) * 2017-10-30 2018-03-30 河南中原黄金冶炼厂有限责任公司 A kind of comprehensive processing technique of Copper making flue dust and arsenic sulfide slag
CN107858519B (en) * 2017-10-30 2019-08-02 河南中原黄金冶炼厂有限责任公司 A kind of comprehensive processing technique of Copper making flue dust and arsenic sulfide slag
CN109136575A (en) * 2018-08-31 2019-01-04 唐山鹤兴废料综合利用科技有限公司 A kind of process of the more metallic dusts of wet-treating
CN109136575B (en) * 2018-08-31 2020-08-14 唐山鹤兴废料综合利用科技有限公司 Technological method for processing multi-metal dust by wet method
CN111690815A (en) * 2019-03-13 2020-09-22 惠州Tcl环境科技有限公司 Heavy metal recovery method

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