CN105695744B - A kind of many metal complete trails full price separation methods - Google Patents

A kind of many metal complete trails full price separation methods Download PDF

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CN105695744B
CN105695744B CN201610058342.8A CN201610058342A CN105695744B CN 105695744 B CN105695744 B CN 105695744B CN 201610058342 A CN201610058342 A CN 201610058342A CN 105695744 B CN105695744 B CN 105695744B
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copper
tin
zinc
ing
lead
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CN105695744A (en
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叶标
路永锁
宁建平
施文山
吴金宝
李华安
程进辰
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JIANGXI SELF-INDEPENDENCE ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd
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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
    • 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
    • C22B11/00—Obtaining noble metals
    • 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
    • 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
    • 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
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • 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
    • C22B25/00—Obtaining tin
    • C22B25/06—Obtaining tin from scrap, especially tin scrap
    • 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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/02—Obtaining antimony
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/14—Electrolytic production, recovery or refining of metals by electrolysis of solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
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  • Metallurgy (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Using low-grade cupric waste and copper ashes as raw material, realized by following main technical process the invention discloses a kind of many metal complete trails full price separation methods,（1）Raw material is through regeneration reducing stove reduction melting, and obtained black copper anode obtains metallic cathode copper products, and crude nickle sulphate product by electrorefining, realizes copper in raw material, nickel separation and reclaims；（2）Copper anode mud and zinc leaching residue have obtained mischzinn through electric furnace reduction melting, then by vacuum drying oven melting separation, antimonial lead product and thick tin are obtained, thick tin has obtained refined tin, i.e. tin slab product by electrorefining, realizes tin, lead, antimony separation and reclaims；（3）Smelting smoke dust is reclaimed with " leaching-extraction-electrodeposition " method and has obtained zinc ingot metal product, realizes zinc, tin, the separation of lead and the recovery of zinc；（4）Tin anode mud send noble metal recovery plant as concentration of precious metal material.Realize many metals to be completely separated, with significant economic, environmental protection and social benefit.

Description

A kind of many metal complete trails full price separation methods
Technical field
The invention provides a kind of many metal complete trails full price separation methods, belong to solid waste material recycling and non-ferrous metal Field of metallurgy, and in particular to cupric solid waste material recycling, various metals separation and comprehensive recycling technology.
Background technology
The copper ore resource shortage of China, it is impossible to the need for meeting the national economic development.In order to make up copper resource shortage phenomenon, For many years, China's also a large amount of cupric wastes of import while a large amount of import copper concentrates always.Show according to relevant information, to mesh Before untill, China has exceeded 200,000,000 tons in the waste non-ferrous metals resource that consumer field is accumulated, wherein up to 18,000,000 tons of waste and old copper Left and right, most of red copper, bronze, copper alloy and the electronics copper junk higher for grade, and it is the relatively low clinker of small part grade, wet Method smelts the copper ashes reclaimed.These contain copper-based solid waste, are produced in human consumption's process, metallurgical process, Ke Yizuo For the secondary resource of copper metal, reuse, reduce secondary pollution of the solid waste material to environment.Regeneration is engaged in using cupric waste The production of copper, which has, expands resources access, the energy that economizes on resources, reduces environmental pollution and increases social synthesis's benefit etc. many excellent Gesture.The metal that secondary resource is obtained can be utilized as first resource metalline with Infinite Cyclic.
Cupric waste, which is smelted, is generally divided into low-grade cupric waste smelting and the refining of cupric waste, in cupric waste refining furnace Refining process in the refining slag that produces contain 20%~25% copper, it is necessary to be recycled.
The method for recycling cupric waste both at home and abroad at present is a lot, can be divided mainly into two major classes：The first kind is will be high-quality The cupric waste Direct Rolling copper bar of amount is directly produced after the copper alloy of the corresponding trade mark for users to use, is referred to as directly utilization； Equations of The Second Kind be by cupric waste smelt into after positive plate through electrorefining into after cathode copper for users to use, referred to as indirect utilization.
Indirect utilization is generally to handle impure high composition brass using three-stage process, and three-stage process is to add cupric waste again Raw reduction furnace is molten to refine into copper, and copper adds converter and is smelt time blister copper, and secondary blister copper adds anode furnace and is smelt electrolysis after positive plate It is refined into the method for cathode copper.
But, cupric waste is added into anode furnace melting, by charge melted, oxidation, reduction, casting output cupric 99% More than, impurity content controls the anode copper in relatively low scope, then through electrorefining output criteria tough cathode.This method has life Production. art long flow path, tin nickel enter flue dust and slag formation vicious circle, recovery rate of valuable metals is low, high energy consumption, using level it is low, The problems such as environmental pollution is big, causes production cost can not to be in any more.With national related industry policy, Copper making industry standard condition Etc. the appearance successively of relevant laws and regulations, China, which regenerates Copper Processing Industry, to enter unprecedented competition period.Therefore exigence one The technological progress that new technology accelerates reclaimed copper enterprise is planted, processing cost is reduced, improves Environmental Protection Level and valuable metal synthetical recovery Ability.
The present invention have developed a kind of black copper direct pouring positive plate of regeneration reducing stove production, reclaim cloudy with electrolytic refining process Pole copper products so that copper resource in cupric waste, copper ashes, and associated valuable metals in black copper are enriched in the earth of positive pole, from Nickel sulfate product is reclaimed in electrolysis waste solution.
It has been highly developed technique that valuable metal is reclaimed in ore deposit copper anode mud.But cupric biowaste origin is complicated, cupric gives up The earth of positive pole that thing electrorefining is produced gold and silver composition transfer compared with ore deposit copper anode mud is big, and the tenor such as arsenic, antimony is relatively low, and Tin, lead content are higher (tin 30%, lead 17%, antimony 8%), and conventional art is not suitable for extracting the valuable gold in the cupric waste earth of positive pole Category.The present invention have developed valuable metal tin, lead, the recovery method of antimony in a kind of suitable cupric waste earth of positive pole.
Low-grade cupric waste and copper ashes pass through regeneration reducing stove melting, and copper anode mud passes through electro-smelting, while also obtaining Flue dust intermediate material is obtained, wherein rich in non-ferrous metals such as zinc, tin, lead, copper.
A kind of technique of remanufacture cathode copper and electrolytic zinc from smelting ash（Publication number：CN102851693A, it is open Day：2013.01.02）, elaborate zinc in reclaiming smelting cigarette ash, the technology of copper metal, the technology industrialization, Every economic and technical norms are good, and metallic zinc, copper recovery are all higher than 98%.Returned using the present invention from smelting smoke dust leached mud Receive valuable metal tin, lead.
Therefore, will be waste and old the invention provides a kind of method that various metals separation is extracted from waste and old composition brass, waste copper slag Metal dangerous waste material, is cashed as pure metal product, as one " eat dry squeeze net ", environmental protection, free of contamination technique skill Art.The valuable metals such as Recovering Copper, nickel, tin, lead, antimony, zinc, various metal recovery rates are high, energy consumption and operating cost all compare It is low, there is good economic benefit.
The content of the invention
It is an object of the invention to provide high, easy to operate, the environment-friendly various metals point of a kind of low cost, direct yield From method.
The present invention process technology scheme be：Pass through the melting of regeneration reducing stove, electro-smelting, vacuum distillation, cathode copper essence Refining, electrodeposition purification, electrolytic tin refining techniques, are extracted wherein rich in copper, nickel, tin, lead, antimony, zinc, the noble metal having, manufacture respectively Go out negative electrode copper products, crude nickle sulphate product, tin slab product, zinc ingot metal product, antimonial lead product and the tin anode rich in noble metal Mud material.
Realized by procedure below：（1）Cupric waste, copper ashes enter regeneration reducing stove melting, manufacture black copper alloy anode Plate；（2）Black copper positive plate enters electrorefining, extracts pure tough cathode；（3）Waste solution of copper electrolysis electrodeposition decopper(ing), evaporation and concentration, extract thick Nickel sulfate；（4）Copper anode mud leached mud and zinc leaching residue after decopper(ing) enter electro-smelting, produce mischzinn；（5）Tin-lead antimony Alloy enters vacuum drying oven distillation, the thick tin of separation and Extraction and antimonial lead；（6）Thick tin founding pours into thick tin anode plate and enters electrolysis essence Refining, extracts refined tin and founding is cast into tin slab；（7）Zinc oxide passes through in regeneration reducing stove flue dust, electric furnace dust：Leaching-extraction - electrodeposition is taken, metallic zinc is extracted and founding is cast into zinc ingot metal.
A kind of many metal complete trails full price separation methods comprise the following steps：
Step 1：By cupric waste, copper ashes and returning charge（Anode scrap, copper powder）65% -75%, flux（Lime stone, quartz）18%— 23% and reducing agent（Coke or carbon）7% -12% reduction melting in regeneration reducing stove, copper liquid alloy is through being cast into copper grade 62% -67% black copper anode.The grades such as clinker cupric, nickel, lead, tin flow into holding furnace, then return in side-blown converter below 3% Do further dilution processing.Regeneration reducing kiln gas is up to standard after desulphurization system is handled again after settling dedusting, bag collection Discharge.
Step 2：Black copper positive plate refer to metal content copper 62% -67%, tin 14% -16%, nickel 9% -13%, antimony 1.5% - 2.5%th, the metal alloy of lead 5% -6%, as electrolysis copper refining positive plate, minus plate is pure copper starting sheet, according to traditional copper electricity Solution refining routine techniques, must reach GB/T467 negative electrode copper products.Bath composition：Cu2+For 35-45g/L, H2SO4For 150-170g/L, additive be gelatin 100g/t copper, casein 20g/t copper, hydrochloric acid 10ml/t copper, current density be 100- 120A/m2, tank voltage is 0.35-0.5V, and electrolyte temperature is 60 DEG C-65 DEG C, and electrolyte circular flow is 25-50L/ Min, homopolarity centre-to-centre spacing 100mm.During electrolysis, copper, nickel metallic element are lost after electronics in black copper positive plate, and dissolving enters electrolyte In, copper ion obtains being deposited on minus plate after electronics on negative electrode, is electrolysed by some cycles, obtains meeting GB/T 467- The negative electrode copper products of 2010 standards.
Step 3：By periodicity electrolysis production, the nickel sulfate of finite concentration content, Ni are enriched in electrolyte2+For 35- 45g/L, each cycle removes the electrolysis waste solution of a certain amount of volume, first passes through two sections of electrodeposition decopper(ing)s, first paragraph decopper(ing) to cupric 15 g/L, second segment decopper(ing) to cupric 0.5g/L.
Step 4：By one section of electrodeposition decopper(ing), product is No. 2 cathode coppers.Two sections of decopper(ing)s are black copper powder.Electrodeposition decopper(ing) technology Condition：Using antimonial lead as anode, stainless steel is negative electrode, and tank voltage is 2-2.5V, and current density is 120-500A/m2, temperature Spend for 20 DEG C -40 DEG C, homopolarity centre-to-centre spacing 100mm.When decopper(ing) waste liquid cupric be less than 0.5g/L when, by liquid after decopper(ing) 90 DEG C- Negative pressure evaporation condensing crystallizing, obtains anhydrous nickel sulfate at 120 DEG C（Crude nickle sulphate）Sold as product, nigrotic acid returns to cupric electrolysis essence Refining system.Crude nickle sulphate chemical composition：Nickel 21% -25%, copper 1% -2%.Nigrotic acid sulfur acid is not less than 950g/L.
Step 5：Nigrotic acid is configured to 200g/L sulfuric acid solutions, is added and is reacted pH to terminal under cupric oxide powder, normal temperature and be 1.5, leachate copper ions reach more than 100g/L, send cathode copper production system.
Step 6：Flue dust send " leaching-extraction-electrodeposition " to produce zinc ingot metal product.Its zinc leaching residue send electro-smelting to extract tin Lead-antimony alloy.Zinc oxide leaches zinc under the conditions of Low acid at normal temperatures in flue dust, and leachate extracts zinc with P204 extractants, with containing Sulfuric acid solution is stripped the organic phase of zinc supported, obtains electrodeposition in zinc-rich solution, zinc-rich solution feeding electrolytic cell and extracts metallic zinc, Electrolytic zinc plate is cast into zinc ingot metal product by founding and sold.
Step 7：Copper anode mud leached mud power transmission stove after zinc leaching residue and decopper(ing) is smelted into mischzinn.Electro-smelting Technical conditions：It is copper anode mud in mass ratio by the copper anode mud leached mud and zinc leaching residue after decopper(ing) and reducing agent, slag former Or zinc leaching residue：Coke blacking：Slag former=2.5:0.4:After 1 ratio mixing, batch feed, the first batch of material accounts for the 1/3 of total amount Left and right；Smelting temperature is 1200 DEG C~1300 DEG C, and smelting time is 2h~2.5h, and when starting melting, current control is less Numerically, produce after certain amount clinker and crude tin alloy, then high current, while adding the second batch of material；Enter later every 2h One batch of material, whole furnace charges are put into electric furnace in 10~14h.The reduction of electro-smelting and slagging process are almost heated same with furnace charge Shi Fasheng, melt carries out conduct electricity heat and mass transfer by the convection circulation of overheat clinker near electrode, is layered, produces by clarification Mischzinn and clinker.Electric furnace flue gas is through settling dedusting, the qualified discharge after desulphurization system is handled again after bag collection.On State reducing agent and use coke, slag former uses quartz, calcium oxide, iron oxide.
Step 8：Leypewter passes through vacuum drying oven separated, and output antimonial lead is sold, and the thick tin of output is cast into tin sun Pole plate.Control 1200-1300 DEG C of the temperature of vacuum drying oven distillation.Residual voltage is less than 15Pa, distillation time 30-140 minutes in stove.
Step 9：Using thick tin as positive plate, pure tin is starting sheet, electrorefining output tin minus plate, then by founding into tin Ingot product.Bath composition：Sn2+18-28g/L, Sn4+<4g/L, H2SO485-98g/L, phenolsulfonic acid（Or cresol sulfonic acid） 16-25g/L, Cl-3.8-5g/L, Cr3+2—2.8g/L.35 DEG C-38 DEG C of electrolyte temperature, 6-7L/ of electrolyte internal circulating load Min, homopolarity centre-to-centre spacing 100mm, 85-100A/m of current density2。
Step 10：Tin anode mud is by removing tin pretreatment Hou Song noble metals factory.
The overall beneficial effect of the present invention：
（1）The present invention has reformed the technology of traditional smelting and refined copper, in regeneration after cupric waste, copper ashes are mixed Reduction furnace reduces concentration smelting, has manufactured low-grade black copper（Copper alloy）Anode be used for electrorefining, be separately recovered metallic copper, Nickel sulfate product, and the valuable metals such as tin, lead, antimony, noble metal are enriched in copper anode mud.Received in regeneration reducing stove flue dust The oxides such as zinc, tin, lead are collected.
（2）Copper anode mud leached mud and zinc leaching residue of the present invention after electric furnace reduction melting decopper(ing), have produced tin-lead Antimony alloy, is distilled by vacuum drying oven, has obtained antimonial lead product and thick tin, and thick tin obtains refined tin product tin by electrorefining Ingot, is further enriched noble metal in the earth of positive pole, improves the value of noble metal recycling.
（3）With zinc oxide fumes " leaching-extraction-electrodeposition " technology of original invention, zinc ingot metal product has been reclaimed. Tin, lead oxides are further enriched in zinc leaching residue.
（4）Many metals are realized using the present invention to be completely separated, and the purpose being separately recovered, create value, and metal The rate of recovery is high, reclaims wide in variety, operating cost is low, with significant economic, environmental protection and social benefit.
The major technique effect of the present invention：
（1）, by black copper positive plate electrorefining extract negative electrode copper products technical characterstic be that black copper needs not move through converter The process that blister copper and blister copper again pass by anode furnace Refining is blown into, technical advantage is black copper Direct Electrolysis refining output symbol GB/T 467-2010 standard cathode coppers are closed, and tin, lead, antimony, noble metal are concentrated in copper anode mud and be enriched with, nickel enters Electrolyte is reclaimed.Traditional handicraft be black copper again by bessemerizing, anode furnace pyro-refining, lead, antimony enrichment are entered into flue dust, portion Tin is divided to enter flue dust, part tin enters slag, and part of nickel enters slag, so operation can be such that valuable metal is dispersed in slag and flue dust, Always in system interior circulation, it is unfavorable for metal synthetical recovery and metal recovery rate is low, easily cause secondary environmental pollution, increases Cost recovery and operation difficulty.
（2）, mischzinn electro-smelting technical characterstic be furnace charge body self-heating cooking, thus heating is fast, heat transfer is fast, melting Cycle is short, the thermal efficiency is high；Heating energy source is cleaned, and furnace atmosphere is easily controlled, or even can be evacuated, and hot temperature is high, and temperature is held It is easy to control；There is no substantial amounts of flame and gas to release in heating process, pollute small, labour health condition is good, reduces environmental protection and sets Standby investment；Production process is easier to realize mechanization and automation.Because molten metal is in from beginning to end in whole fusion process In strong electric arc stirring, thus terminal uniform ingredients degree is high, and gross segregation is small, and is easy to the floating of each type impurity, can To obtain the purer composition of matrix than more uniform alloy melt.Metal recovery rate is high, easily operation, to adaptability to raw material By force, the stanniferous grade of alloy is high.
（3）, mischzinn first separate antimony, lead output antimonial lead and thick tin through vacuum drying oven.Antimonial lead is used as product Sell, using thick tin as positive plate, pure tin is starting sheet, electrorefining output tin minus plate, then by founding into tin slab technology Feature：Thick tin electrolytic refining process is a kind of Whote-wet method smelting process, no waste water, is produced without waste gas, without castaway slag, is in the world The state-of-the-art technique of non-ferrous metal metallurgy purification.Its maximum feature is：One-time investment is saved, sustainable development；The technique pair The adaptability of raw material extensively, can handle the complicated mischzinn such as high antimony；Tin slab product meets GB/T 728-2010 standards It is required that, metal recovery rate is high, and energy consumption is low, operating environment is friendly.
Brief description of the drawings
Fig. 1 is the technological process of the embodiment of the present invention 1.
Embodiment
The present invention can be so that the invention will be further described, however, the scope of the present invention is simultaneously by the following examples It is not limited to following embodiments.
Embodiment 1：
Step 1：Regeneration reducing stove reduction melting.Ingredient proportion is：Copper junk 65%（Wherein copper ashes brick 40%, copper powder ball material 2%th, cupric waste and anode scrap 23%）, flux 23%（Wherein lime stone 15%, quartz 8%）, reducing agent 12%（Coke or carbon）. According to regeneration reducing stove operating duty, to valuable metal reduction melting in material, oxide in air-breathing, flux and material is roused Slag making, melt is reduced by valuable metal when coke or carbon layer, is deposited to furnace bottom and is separated with clinker, it is ensured that clinker cupric, Nickel, lead, tin etc. are less than less than 3%, and zinc and part lead, the metallic vapour of tin enter flue with flue gas, and oxygen reaction in air, Enter in the form of an oxide in flue dust.Copper liquid is released from the outlet of copper liquid, the black copper positive plate of copper grade 65% is obtained through casting.Again Survive former kiln gas by sedimentation dedusting, bag collection and desulfurizing tower elution after qualified discharge.
Step 2：Black copper anode electrolysis is refined, and manufactures fine copper minus plate.Typical black copper anode plate chemical composition：Copper 65.4%, Tin 15.6%, nickel 10.8%, antimony 2.5%, lead 5.5%.Negative electrode is pure copper starting sheet, bath composition：Cu2+For 35g/L, H2SO4For 170g/L, additive be gelatin 100g/t copper, casein 20g/t copper, hydrochloric acid 10ml/t copper, current density is 100A/m2, groove electricity Press as 0.4V, electrolyte temperature is 65 DEG C, electrolyte circular flow is 35L/min, homopolarity centre-to-centre spacing 100mm.During electrolysis, black copper Copper, nickel metallic element are lost after electronics in positive plate, and dissolving enters in electrolyte, and copper ion obtains depositing after electronics on negative electrode On minus plate, it is electrolysed by some cycles, obtains meeting the negative electrode copper products of GB/T467-2010 standards.
Step 3：After black copper anodic cycle electrodissolution, the sulfuric acid of finite concentration content can be progressively enriched in the electrolytic solution Nickel, works as Ni2+During for 40g/L, the electrolysis waste solution of a certain amount of volume is removed, two sections of electrodeposition decopper(ing)s are first passed through, first paragraph decopper(ing) is extremely The g/L of cupric 15, second segment decopper(ing) to cupric 0.5g/L.
Step 4：By first paragraph electrodeposition decopper(ing), product is No. 2 cathode coppers, meets GB/T467-2010 tough cathode standard Product..Second segment decopper(ing) is black copper powder.Electrodeposition decopper(ing) technical conditions：Using antimonial lead as anode, stainless steel is negative electrode, groove Voltage is 2.5V, and first paragraph current density is 120A/m2, second segment current density is 400A/m2, temperature is 30 DEG C -35 DEG C, together Pole centre-to-centre spacing 100mm.When decopper(ing) waste liquid cupric is less than 0.5g/L, by liquid after decopper(ing), negative pressure evaporation is dense at 90 DEG C -120 DEG C Sheepshank is brilliant, obtains anhydrous nickel sulfate（Crude nickle sulphate）Sold as product, nigrotic acid returns to copper electrolyzing refining system.Crude nickle sulphate Study point：Nickel 24.6%, copper 1.5%.Nigrotic acid sulfur acid 950g/L.
Step 5：Nigrotic acid is configured to 200g/L sulfuric acid solutions, is added and is reacted pH to terminal under oxidation copper ashes, normal temperature and be 1.5, leachate copper ions reach more than 100g/L, send cathode copper production system.
Step 6：Flue dust send " leaching-extraction-electrodeposition " to produce zinc ingot metal product.Its zinc leaching residue send electro-smelting to extract tin Lead-antimony alloy.Zinc oxide leaches zinc under the conditions of Low acid at normal temperatures in flue dust, and leachate extracts zinc with P204 extractants, with containing Sulfuric acid solution is stripped the organic phase of zinc supported, obtains electrodeposition in zinc-rich solution, zinc-rich solution feeding electrolytic cell and extracts metallic zinc, Electrolytic zinc plate is cast into zinc ingot metal product by founding and sold.Zinc ingot metal chemical composition：Zinc 99.99%, lead 0.005%, cadmium 0.001%, copper 0.002%, meet the product of GB/T470-2008 zinc ingot metal standards.Typical zinc leaching residue chemical composition：Zinc 2.7%, tin 35.4%, lead 17.8%.Flue dust chemical composition：Zinc 25%, tin 30%, lead 10%.
Step 7：Copper anode mud leached mud power transmission stove is smelted into mischzinn after zinc leaching residue and decopper(ing).Electro-smelting skill Art condition：It is copper anode mud or zinc in mass ratio by copper anode mud leached mud after decopper(ing) and zinc leaching residue and reducing agent, slag former Leached mud：Coke blacking：Slag former=2.5:0.4:After 1 ratio mixing, batch feed, the first batch of material accounts for 1/3 of total amount or so； Smelting temperature be 1250 DEG C~1300 DEG C, smelting time is 2.5h, start melting when, current control it is less numerically, production After raw certain amount clinker and crude tin alloy, then high current, while adding the second batch of material；Enter a batch of material every 2h later, entirely Portion's furnace charge is put into electric furnace in 10h.The reduction of electro-smelting and slagging process almost with the heated generation simultaneously of furnace charge, melt according to By near electrode overheat clinker convection circulation carry out conduct electricity heat and mass transfer, by clarification be layered, produce mischzinn and Clinker.Electric furnace flue gas is through settling dedusting, the qualified discharge after desulfurizing tower elution processing again after bag collection.Above-mentioned reducing agent is Coke, slag former is quartz, calcium oxide, iron oxide.Typically mischzinn chemical composition is：Tin 50.8%, lead 31.3%, Antimony 14.2%.
Step 8：Leypewter passes through vacuum drying oven separated, and output antimonial lead is sold, and the thick tin of output is cast into tin sun Pole plate.Control 1200-1250 DEG C of the temperature of vacuum drying oven distillation.Residual voltage is less than 15Pa, distillation time 120 minutes in stove.Typically Slightly tin chemical composition is：Tin 95.1%, lead 0.8%, antimony 1.7%.Typical antimonial lead chemical composition：Tin 2.2%, lead 59.1%, antimony 34.3%。
Step 9：Using thick tin as positive plate, pure tin is starting sheet, electrorefining output tin minus plate, then by founding into tin Ingot product.Bath composition：Sn2+25g/L, Sn4+<4g/L, H2SO4 95g/L, phenolsulfonic acid（Or cresol sulfonic acid）20g/L, Cl- 3.8g/L, Cr3+ 2g/L.35 DEG C of electrolyte temperature, electrolyte internal circulating load 7L/min, homopolarity centre-to-centre spacing 100mm, current density 95A/m2.Typically tin slab chemical composition is：Tin 99.95%, lead 0.010%, antimony 0.014%.Meet GB/T728-2010 tin slab marks Accurate product.
Step 10：Tin anode mud is by removing tin pretreatment Hou Song noble metals factory.
Base metal is respectively obtained by embodiment 1 with one ton of copper junk and noble metal is as follows：
108~225kg of copper, tin 135.4kg, nickel 97.2kg, antimony 21.5kg, lead 54.0kg, gold 3.5g, silver 136.5g.
Embodiment 2：
Step 1：Regeneration reducing stove reduction melting.Ingredient proportion is：Copper junk 75%（Wherein copper ashes brick 40%, copper powder ball material 10%th, cupric waste and anode scrap 20%）, flux 18%（Wherein lime stone 12%, quartz 6%）, reducing agent 12%（Coke or carbon）. According to regeneration reducing stove operating duty, to valuable metal reduction melting in material, oxide in air-breathing, flux and material is roused Slag making, melt is reduced by valuable metal when coke or carbon layer, is deposited to furnace bottom and is separated with clinker, it is ensured that clinker cupric, Nickel, lead, tin etc. are less than less than 3%, and zinc and part lead, the metallic vapour of tin enter flue with flue gas, anti-with oxygen in air Should, in the form of an oxide into flue dust.Copper liquid is released from the outlet of copper liquid, the black copper positive plate of copper grade 67% is obtained through casting. Regeneration reducing kiln gas qualified discharge after sedimentation dedusting, bag collection and desulfurizing tower elution.
Step 2：Black copper anode electrolysis is refined, and manufactures fine copper minus plate.Typical black copper anode plate chemical composition：Copper 67%, tin 14.2%th, nickel 11.0%, antimony 2.0%, lead 5.4%.Negative electrode is pure copper starting sheet, bath composition：Cu2+For 35g/L, H2SO4For 170g/L, additive be gelatin 100g/t copper, casein 20g/t copper, hydrochloric acid 10ml/t copper, current density is 100A/m2, groove electricity Press as 0.4V, electrolyte temperature is 65 DEG C, electrolyte circular flow is 35L/min, homopolarity centre-to-centre spacing 100mm.During electrolysis, black copper Copper, nickel metallic element are lost after electronics in positive plate, and dissolving enters in electrolyte, and copper ion obtains depositing after electronics on negative electrode On minus plate, it is electrolysed by some cycles, obtains meeting the negative electrode copper products of GB/T467-2010 standards.
Step 3：After black copper anodic cycle electrodissolution, the sulfuric acid of finite concentration content can be progressively enriched in the electrolytic solution Nickel, works as Ni2+During for 45g/L, the electrolysis waste solution of a certain amount of volume is removed, two sections of electrodeposition decopper(ing)s are first passed through, first paragraph decopper(ing) is extremely The g/L of cupric 15, second segment decopper(ing) to cupric 0.5g/L.
Step 4：By first paragraph electrodeposition decopper(ing), product is No. 2 cathode coppers, meets GB/T467-2010 tough cathode standard Product.Second segment decopper(ing) is black copper powder.Electrodeposition decopper(ing) technical conditions：Using antimonial lead as anode, stainless steel is negative electrode, groove electricity Press as 2.5V, first paragraph current density is 200A/m2, second segment current density is 450A/m2, temperature be 35 DEG C -40 DEG C, homopolarity Centre-to-centre spacing 100mm.When decopper(ing) waste liquid cupric is less than 0.5g/L, by liquid after decopper(ing) at 100 DEG C negative pressure evaporation condensing crystallizing, obtain To anhydrous nickel sulfate（Crude nickle sulphate）Sold as product, nigrotic acid returns to copper electrolyzing refining system.Nigrotic acid returns to copper electrolyzing refining System.Crude nickle sulphate chemical composition：Nickel 24.6%, copper 1.5%.Nigrotic acid sulfur acid 950g/L.
Step 5：Nigrotic acid is configured to 200g/L sulfuric acid solutions, is added and is reacted pH to terminal under oxidation copper ashes, normal temperature and be 1.5, leachate copper ions reach more than 100g/L, send cathode copper production system.
Step 6：Flue dust send " leaching-extraction-electrodeposition " to produce zinc ingot metal product.Its zinc leaching residue send electro-smelting to extract tin Lead-antimony alloy.Zinc oxide leaches zinc under the conditions of Low acid at normal temperatures in flue dust, and leachate extracts zinc with P204 extractants, with containing Sulfuric acid solution is stripped the organic phase of zinc supported, obtains electrodeposition in zinc-rich solution, zinc-rich solution feeding electrolytic cell and extracts metallic zinc, Electrolytic zinc plate is cast into zinc ingot metal product by founding and sold.Zinc ingot metal chemical composition：Zinc 99.99%, lead 0.005%, cadmium 0.001%, copper 0.002%, meet the product of GB/T470-2008 zinc ingot metal standards.Typical zinc leaching residue chemical composition：Zinc 4.8%, tin 37.4%, lead 15.6%.Flue dust chemical composition：Zinc 30%, tin 20%, lead 15%.
Step 7：Copper anode mud leached mud power transmission stove is smelted into mischzinn after zinc leaching residue and decopper(ing).Electro-smelting skill Art condition：It is in mass ratio copper anode mud leached mud or zinc after decopper(ing) by copper anode mud and zinc leaching residue and reducing agent, slag former Leached mud：Coke blacking：Slag former=2.5:0.4:After 1 ratio mixing, batch feed, the first batch of material accounts for 1/3 of total amount or so； Smelting temperature be 1250 DEG C~1300 DEG C, smelting time is 2h, start melting when, current control it is less numerically, produce After certain amount clinker and crude tin alloy, then high current, while adding the second batch of material；Enter a batch of material every 2h later, all Furnace charge is put into electric furnace in 12h.The reduction of electro-smelting and slagging process are almost heated simultaneously with furnace charge to be occurred, and melt is relied on The convection circulation that clinker is overheated near electrode carries out conduct electricity heat and mass transfer, is layered by clarification, produces mischzinn and stove Slag.Electric furnace flue gas is through settling dedusting, the qualified discharge after desulfurizing tower elution processing again after bag collection.Above-mentioned reducing agent is burnt Charcoal, slag former is quartz, calcium oxide, iron oxide.Typically mischzinn chemical composition is：Tin 49.4%, lead 24.6%, antimony 14.2%。
Step 8：Leypewter passes through vacuum drying oven separated, and output antimonial lead is sold, and the thick tin of output is cast into tin sun Pole plate.Control 1250-1300 DEG C of the temperature of vacuum drying oven distillation.Residual voltage is less than 15Pa, distillation time 100 minutes in stove.Typically Slightly tin chemical composition is：Tin 94.8%, lead 0.7%, antimony 1.7%.Typical antimonial lead chemical composition：Tin 2.5%, lead 55.8%, antimony 36.3%。
Step 9：Using thick tin as positive plate, pure tin is starting sheet, electrorefining output tin minus plate, then by founding into tin Ingot product.Bath composition：Sn2+ 28g/L, Sn4+<4g/L, H2SO4 95g/L, phenolsulfonic acid（Or cresol sulfonic acid）20g/L, Cl- 3.8g/L, Cr3+ 2g/L.35 DEG C of electrolyte temperature, electrolyte internal circulating load 7L/min, homopolarity centre-to-centre spacing 100mm, current density 100A/m2.Typically tin slab chemical composition is：Tin 99.95%, lead 0.010%, antimony 0.014%.Meet GB/T728-2010 tin slabs The product of standard.
Step 10：Tin anode mud is by removing tin pretreatment Hou Song noble metals factory.
Base metal is respectively obtained by embodiment 2 with one ton of copper junk and noble metal is as follows：
124.6~225kg of copper, tin 117.3kg, nickel 84.3kg, antimony 18.8kg, lead 46.8kg, gold 3.1g, silver 118.3g.

Claims (1)

1. a kind of many metal complete trails full price separation methods, it is characterised in that comprise the following steps：
Step 1：By cupric waste, copper ashes and returning charge 65% -75%, flux 18% -23% and reducing agent including anode scrap and copper powder 7% -12% reduction melting in regeneration reducing stove, copper liquid alloy is through being cast into the black copper positive plate of copper grade 62% -67%；Clinker Cupric, nickel, lead, tin grade flow into holding furnace below 3%, then return further dilution processing is done in side-blown converter；Regeneration reducing Kiln gas is through settling dedusting, the qualified discharge after desulphurization system is handled again after bag collection, and flux is lime stone and quartz；Also Former agent is coke or carbon；
Step 2：Black copper positive plate refer to metal content copper 62% -67%, tin 14% -16%, nickel 9% -13%, antimony 1.5% -2.5%, The metal alloy of lead 5% -6%, as electrolysis copper refining positive plate, minus plate is pure copper starting sheet, according to traditional copper electrolyzing refining Routine techniques, must reach GB/T467 negative electrode copper products；
Bath composition：Cu2+For 35-45g/L, H2SO4For 150-170g/L, additive is gelatin 100g/t copper, casein 20g/t copper, hydrochloric acid 10ml/t copper, current density is 100-120A/m2, tank voltage is 0.35-0.5V, and electrolyte temperature is 60 DEG C-65 DEG C, electrolyte circular flow is 25-50L/min, homopolarity centre-to-centre spacing 100mm；During electrolysis, copper, nickel in black copper positive plate Metallic element is lost after electronics, and dissolving enters in electrolyte, and copper ion obtains being deposited on minus plate after electronics on negative electrode, warp Some cycles electrolysis is crossed, obtains meeting the negative electrode copper products of GB/T467-2010 standards；
Step 3：By periodicity electrolysis production, the nickel sulfate of finite concentration content, Ni are enriched in electrolyte2+For 35-45g/ L, each cycle removes the electrolysis waste solution of a certain amount of volume, first passes through two sections of electrodeposition decopper(ing)s, first paragraph decopper(ing) to cupric 15g/ L, second segment decopper(ing) to cupric 0.5g/L；
Step 4：By one section of electrodeposition decopper(ing), product is No. 2 cathode coppers；Two sections of decopper(ing)s are black copper powder；Electrodeposition decopper(ing) technical conditions：
Using antimonial lead as anode, stainless steel is negative electrode, and tank voltage is 2-2.5V, and current density is 120-500A/m2, temperature For 20 DEG C -40 DEG C, homopolarity centre-to-centre spacing 100mm；When decopper(ing) waste liquid cupric is less than 0.5g/L, by liquid after decopper(ing) 90 DEG C -120 DEG C when negative pressure evaporation condensing crystallizing, obtain anhydrous nickel sulfate i.e. crude nickle sulphate and sold as product, nigrotic acid return copper electrolyzing refining System；Crude nickle sulphate chemical composition：Nickel 21% -25%, copper 1% -2%；Nigrotic acid sulfur acid is not less than 950g/L；
Step 5：It is 1.5 that nigrotic acid, which is configured to react pH to terminal under 200g/L sulfuric acid solutions, addition cupric oxide powder, normal temperature, leaching Go out liquid copper ions and reach more than 100g/L, send cathode copper production system；
Step 6：Flue dust send " leaching-extraction-electrodeposition " to produce zinc ingot metal product；Its zinc leaching residue send electro-smelting to extract tin-lead antimony Zinc oxide leaches zinc under the conditions of Low acid at normal temperatures in alloy, flue dust, and leachate extracts zinc with P204 extractants, uses sulfur acid Solution is stripped the organic phase of zinc supported, obtains electrodeposition in zinc-rich solution, zinc-rich solution feeding electrolytic cell and extracts metallic zinc, electrolysis Zinc metal sheet is cast into zinc ingot metal product by founding and sold；
Step 7：Copper anode mud leached mud power transmission stove after zinc leaching residue and decopper(ing) is smelted into mischzinn；Electro-smelting technology Condition：It is copper anode mud or zinc in mass ratio by the copper anode mud leached mud and zinc leaching residue after decopper(ing) and reducing agent, slag former Leached mud：Coke blacking：Slag former=2.5:0.4:After 1 ratio mixing, batch feed, the first batch of material accounts for the 1/3 of total amount；Melting Temperature be 1200 DEG C~1300 DEG C, smelting time be 2h~2.5h, start melting when, current control it is less numerically, production After raw certain amount clinker and crude tin alloy, then high current, while adding the second batch of material；Enter a batch of material every 2h later, entirely Portion's furnace charge is put into electric furnace in 10~14h；The reduction of electro-smelting and slagging process are almost heated simultaneously with furnace charge to be occurred, and is melted Body carries out conduct electricity heat and mass transfer by the convection circulation of overheat clinker near electrode, is layered by clarification, produces the conjunction of tin-lead antimony Gold and clinker；Electric furnace flue gas is through settling dedusting, the qualified discharge after desulphurization system is handled again after bag collection；Above-mentioned reducing agent Using coke, slag former uses quartz, calcium oxide, iron oxide；
Step 8：Leypewter passes through vacuum drying oven separated, and output antimonial lead is sold, and the thick tin of output is cast into tin anode plate； Control 1200-1300 DEG C of the temperature of vacuum drying oven distillation；Residual voltage is less than 15Pa, distillation time 30-140 minutes in stove；
Step 9：Using thick tin as positive plate, pure tin is starting sheet, and electrorefining output tin minus plate, then process founding are produced into tin slab Product；Bath composition：Sn2+18-28g/L, Sn4+<4g/L, H2SO485-98g/L, 16-25g/ of phenolsulfonic acid or cresol sulfonic acid L, Cl-3.8-5g/L, Cr3+2—2.8g/L；In 35 DEG C-38 DEG C of electrolyte temperature, electrolyte 6-7L/min of internal circulating load, homopolarity The heart is away from 100mm, 85-100A/m of current density2；
Step 10：Tin anode mud is by removing tin pretreatment Hou Song noble metals factory.
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