CN106399692B - A kind of concentration smelting method that cupric solid wastes recycling utilizes - Google Patents

A kind of concentration smelting method that cupric solid wastes recycling utilizes Download PDF

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CN106399692B
CN106399692B CN201610867705.2A CN201610867705A CN106399692B CN 106399692 B CN106399692 B CN 106399692B CN 201610867705 A CN201610867705 A CN 201610867705A CN 106399692 B CN106399692 B CN 106399692B
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copper
slag
smelting
cupric
solid waste
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CN106399692A (en
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刘伟锋
孙百奇
刘亮强
杨天足
陈霖
张杜超
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Guangzhou Huarui Environmental Technology Co.,Ltd.
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Central South University
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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
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/0028—Smelting or converting
    • C22B15/0052—Reduction smelting or converting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • 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
    • 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
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A kind of concentration smelting method that cupric solid wastes recycling utilizes, cupric solid waste are passed through dioxygen oxidation conversion in lime solution, and conversion slag mixes with other cupric solid waste dispensings, makes moisture, the copper content and FeO: SiO of mixed material2: CaO mass ratioes are kept at claimed range, fragment of brick is prepared after adding starch simultaneously, compound fragment of brick and coke are alternately added in smelting furnace, it is passed through oxygen-enriched air and carries out concentration smelting, the heavy phase melt control cooling system separation output blister copper and matte of melting output, smelting slag makes sulfonium dilution in fuming furnace and copper and tin is separately recovered in fuming, and copper is further reclaimed in levigate rear ore dressing to smelting slag again.The core of the present invention is calcium sulfate first as new sulphur-fixing agent, next to that binding agent and reducing agent are used as using starch simultaneously, it is the innoxious and recycling by controlling copper content in smelting slag to realize cupric solid waste again, is finally using making sulfonium dilution and fuming process realizes the recovery of copper and tin in smelting slag.

Description

A kind of concentration smelting method that cupric solid wastes recycling utilizes
Technical field
The present invention relates to metallurgical process in nonferrous metallurgy field, is converted especially with wet method with the pyrometallurgical smelting side of being combined The metallurgical method of formula Treatment of Copper solid waste.
Background technology
Copper is a kind of rose heavy non-ferrous metal, 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, sulphur Change copper washability is good, is easy to be enriched with, and the copper sulfide concentrate of the cupric 20~30% by floatation process output uses pyrometallurgical smelting work Skill processing, and cupric oxide ore flotability is poor, is difficult to beneficiation enrichment, is preferably directly handled using hydrometallurgical processes.At present, about More than 80% mineral products copper is then that copper sulfide concentrate passes through pyrometallurgical smelting technique productions, i.e. copper concentrate passes through matte smelting output Copper matte regulus, copper matte regulus is successively by bessemerizing and pyro-refining output blister copper, blister copper electrorefining output negative electrode in sulfuric acid system Copper.
Although China is the first in the world Chan Tong big countries, China's copper resource reserves are extremely poor, and self-produced copper is smart every year in China Ore deposit amount is only the 24% of China's year copper concentrate consumption, and this item data is aculeate to reflect that China depends on import resource unduly Present situation.The external dependence degree of China's copper concentrate in 2010 be 75%, resource problem further turn into development bottleneck restrict because Element.Reclaimed copper is that significant contribution has been made in China's copper consumption demand, has also sought outlet for the copper resource in China.China in recent years Steady-state growth trend is totally presented in the ratio that reclaimed copper accounts for refined copper total output, and China's refined copper yield in 2010 is 457.3 ten thousand t, its The middle t of reclaimed copper 176.2 ten thousand, reclaimed copper yield account for the 38.5% of refined copper yield.
Cupric solid waste resource refer to the mankind production, consumption, life and other activities in caused solid-state, semisolid or More or few waste material containing metal copper resource, it has contaminative, resource and social feature.That is in society Can develop it is inevitable with the generation of cupric solid waste in human lives' process, due to containing heavy metal copper, therefore cupric solid waste Disposal situation is directly connected to the safety problem of ecological environment, and at the same time, cupric solid waste is the resource for having certain values again. Therefore from environmental protection and two aspects of resource, how to handle cupric solid waste well is all an important topic.
The wide material sources of cupric solid waste, complicated component, mainly include decontamination process containing heavy metal in caused copper sludge, Environmentally friendly mud, electroplating sludge caused by electroplating industry, copper sponge caused by all kinds of process industries and old circuit board cracking and sorting Copper powder gone out etc..This kind of material generally has four features：
First, cupric solid waste water content is high, can not be removed with reference to water using the plate compression solid separation method of routine, such as Electroplating sludge, its water content are up to 60 ~ 80%, if this partial moisture does not remove, can not carry out pyrometallurgical smelting processing；Second, composition Complexity, in the cupric solid waste such as wet-precipitated slag and electroplating sludge, often containing the heavy metals such as more lead, zinc, chromium, this kind of cupric If the imappropriate processing of solid waste will cause huge harm to ecological environment around；Third, in cupric solid waste copper content difference compared with Greatly, the copper grade of copper powder, copper sponge and copper sludge is 60 ~ 90%, and the copper content of electroplating sludge and environmentally friendly mud then mostly 15% with Under it is even lower, i.e., the fluctuation of main metal ingredient is larger in copper-contained material, if this kind of material is directly entered into stove melting, can cause a lot Problem；Fourth, the problem of cupric solid waste sulphur, sulphur mainly exists with sulfate or sulphided form in cupric solid waste, in follow-up melting Process not only high energy consumption, and vent gas treatment difficulty is big, absorption product are that gypsum tailings is also a kind of solid waste, and its heap is sent one's regards to Also letter is to be solved for topic；
Compared with primary copper mine, cupric solid waste metals resources are more rich, grade is higher, processing procedure energy consumption is lower, with ore deposit Production copper is compared, and often produces 1t reclaimed coppers energy-conservation 1054kg marks coal, water saving 395m3, reduce solid waste discharge 380t, reduce dioxy Change sulphur emissions 0.14t.Cupric solid waste belongs to typical cupric secondary resource, and similar with cupric secondary resource, its processing method is also divided For two kinds of thermal process and wet processing.
Fire metallurgy process is then that cupric solid waste passes through reduction melting output blister copper, then with reverberatory furnace pyro-refining output Positive plate, positive plate pass through electrorefining output tough cathode.Because the property of cupric solid waste is different, metallurgist develops one section Method, two-phase method and three-stage process.One-stage process is then to cast positive plate after cupric solid waste is carried out into pyro-refining in reverberatory furnace, then Pass through electrorefining output tough cathode again.Two-phase method be then by cupric solid waste first in blast furnace reduction melting output blister copper, Or the first reduction melting output blister copper in converter of copper-contained material, output positive plate then is refined in reflection ingle method, then Pass through electrorefining output tough cathode again.Three-stage process is then by more black of shaft smelting output impurity by cupric solid waste Copper, black copper blow in converter and obtain blister copper after the removing impurity such as lead and tin, blister copper output positive plate after reverberatory refining, Finally pass through electrorefining output tough cathode.As can be seen that one-stage process and two-stage method are suitable only for handling impure less contain Copper solid waste, and three-stage process is suitable for handling impure more cupric solid waste.The core of pyrometallurgical smelting technique is melted using pyrogenic process Smelting method reduces copper and impurity and enters blister copper, then is bessemerized or refining process imurity-removal metal follow-up.At pyrogenic process Science and engineering skill has the advantages of flow is short, cost is low and the rate of recovery is high.
Hydrometallurgical processes mainly by cupric solid waste with wet dissolution method dissolve copper, copper-containing solution by purification with except Impurities are removed, purer copper-containing solution obtains tough cathode using electrodeposition method again.Although Wet-process metallurgy method has flow simple Singly, the advantages that metal good separating effect and metal recovery rate is high, but material bad adaptability, processing cost height and three wastes production be present Measure the shortcomings that big so that this method is difficult to be widely popularized.
So from which kind of PROCESS FOR TREATMENT cupric solid waste, it is necessary to take into full account environmental protection, the utilization of resources and processing cost Etc. factor, output secondary pollution is especially unable to, so, it is still at present urgently to develop a kind of efficient cupric fixed-end forces technique Solve the problems, such as.
The content of the invention
In order to overcome the shortcomings of cupric solid waste traditional treatment method, the present invention provides a kind of wet method conversion and pyrometallurgical smelting phase With reference to Treatment of Copper solid waste, and the wet method that copper recovery is high, sulfur curable rate is high, processing cost is low and environmental pollution is small-pyrogenic process connection Close metallurgical method.
It is to reach above-mentioned purpose the technical solution adopted by the present invention：Cupric solid waste is passed through dioxygen oxidation in lime solution Conversion, sulphur is completely converted into calcium sulfate precipitation and enter conversion slag, conversion slag mixes with other cupric solid waste dispensings, makes mixture The moisture of material, copper content and FeO: SiO2: CaO mass ratioes are kept at claimed range, while one is added into mixed material Fragment of brick is prepared after the starch of certainty ratio, then compound fragment of brick and coke alternating portions are added in smelting furnace, are passed through simultaneously Oxygen-enriched air carries out concentration smelting, the tin in material is entered in smelting slag and cigarette ash by controlling copper content in smelting slag, The heavy phase melt of melting output is periodically released, and control cooling system separation output blister copper and matte, smelting slag is in fuming furnace Make sulfonium dilution and copper and tin is separately recovered in fuming, copper is further reclaimed in levigate rear ore dressing to smelting slag again, and melting flue gas is by gathering dust And with qualified discharge after Alkali absorption.The core of the present invention is to make the sulphur in cupric solid waste complete using alkaline pressure oxidation conversion first Portion is converted into calcium sulfate, in order to which reduction melting process reclaims sulphur with copper sulphide form；Next to that using starch simultaneously as viscous Agent and reducing agent are tied, not only increases the intensity of agglomerate, and enhance reduction melting process；It is that reduction melting process makes again Copper and noble metal in raw material etc. are reduced and are enriched in heavy phase melt, and heavy phase melt is selectively divided using control cooling system again It is finally using making sulfonium dilution and fuming process realizes the recovery of copper and tin in smelting slag from output blister copper and matte.These rings Tight association is saved, collective effect realizes the purpose that cupric solid wastes recycling utilizes.
Specific technical process and parameter are as follows：
The oxidation conversion of 1 lime pressure
Cupric solid waste is passed through dioxygen oxidation conversion in lime solution, sulphur is completely converted into calcium sulfate precipitation and enters conversion Slag, make water and valuables oxidation removal；The lime solution that molar concentration is 0.5~2.0mol/L is prepared, by liquid-solid ratio（Liquid bulk Product the ratio between L and solid weight kg）Add cupric solid waste at 2~4: 1, and mixed slurry is added in autoclave, control reaction 1.0~3.0h is reacted under the conditions of 100~200 DEG C of temperature and 0.1~1.0MPa of partial pressure of oxygen, 60 DEG C and liquid are cooled to after the completion of reaction Gu separation, conversion slag send next step dispensing, and conversion fluid, which returns, to be used；The primary chemical that lime pressure oxidation conversion process occurs is anti- Should be as follows：
Ca(OH)2+MeSO4=Me(OH)2+CaSO4（1）
Ca(OH)2+MeS+2O2=Me(OH)2+CaSO4（2）
2 dispensing brickmaking
Convert slag and other cupric solid waste dispensings and prepare fragment of brick after adding a certain proportion of starch；Conversion slag contains with other Copper solid waste dispensing, makes FeO: SiO in mixed material2: CaO mass ratioes are maintained at（1.0~1.5）∶1.0∶（0.4~0.6）, simultaneously The moisture and copper content for making mixed material control in 15.0~25.0% and 40.0~60.0% respectively, are then incorporated mixed material again The starch of quality 1.0~5.0%, the fragment of brick that specification is length × width × height=200 × 120 × 100mm is then prepared into, it is natural Qualified furnace charge, which is can be used as, after stacking 1~3 day enters stove melting.
Reduction melting
Qualified furnace charge and coke point are proportionally added into reduction melting in smelting furnace, smelted product is periodically released, control Cooling system separation output blister copper and matte processed；Above-mentioned qualified fragment of brick and coke are handed over according to the ratio of weight ratio 1: 0.10~0.25 For being added in smelting furnace, the oxygen-enriched air melting that concentration is 26.0 ~ 40.0% is passed through, by the quality for controlling copper in smelting slag Percentage composition is 2.0~4.5%, tin and zinc is enriched in respectively in smelting slag and flue dust, and melting cycle is 1.5~3.0h, melting The heavy phase melt and smelting slag of output are periodically released and are contained in respectively in cast iron mold, and smelting slag, which is sent, subsequently makes sulfonium dilution, Qualified discharge after melting flue gas is eluted after gathering dust with sodium hydroxide solution；The heavy phase melt being contained in cast iron mold uses Blowing mode cools down, and it is 50~100m to control blowing amount3/ min and blow-time are 15~90min, when heavy phase bath surface temperature Spend for 650~850 DEG C when, heavy phase melt liquate output blister copper and matte two-phase, it is 500~650 DEG C to keep bath surface temperature When separate while hot, the further Refining of blister copper, smelting slag further makes sulfonium fuming.
Make sulfonium dilution and fuming
Smelting slag makes sulfonium dilution recovery copper and fuming volatilization tin simultaneously in fuming furnace；The liquid being contained in cast iron mold Smelting slag is directly added into fuming furnace, the fine coal of 200 mesh is crossed by smelting slag and the addition of fine coal mass ratio 1: 0.25~0.40 granularity, together When add the smelting slag part by weight 1.0-5.0% low copper cupric solid waste of high-sulfur and carry out making sulfonium dilution, keep air capacity be 100~ 300m3/ min blowing 90-120min, the flue dust that gas gathers dust to obtain is the raw material of recovery tin, and fuming slag is put into cold in V-type slag chute But, V-type slag chute bottom is matte, and the slag at the top of V-type slag chute is sold as cement raw material.
The present invention is applied to handle various cupric solid wastes, and its main component scope is by weight percentage（%）：Cu1.0 ~90.0, Sn1.0~15.0, Zn1.0~15.0, Pb01~15.0, Sb0.1~10.0 and S0.1~10.0.
The present invention has the advantage that compared with cupric solid waste traditional treatment method：1st, the present invention is aoxidized using lime pressure Method for transformation makes moisture and oxidation operation removing in cupric solid waste, and sulphur is completely converted into calcium sulfate and as new solid sulphur Agent, in sequential reduction fusion process, output, the conversion ratio of sulphur reach 99.0% in the form of matte, considerably reduce melting flue gas The concentration of middle sulphur, improves operating environment；2nd, dispensing brickmaking process of the invention, the cupric solid waste of different grades is arranged in pairs or groups and made Enter in furnace charge copper content control 40~60%, reduce the yield of follow-up fusion process slag, improve the rate of recovery of copper,；Supplying is formed sediment Powder not only adds the intensity of fragment of brick in brickmaking process as binding agent, and reduces fusion process and enhanced also as reducing agent Former effect；3rd, reduction melting process of the invention, by controlling in smelting slag copper content 2.0~4.5%, by valuable metal also Original enters in blister copper, matte or cigarette ash, will be poisonous and harmful metal-cured in smelting slag, i.e., realizes the recycling profit of solid waste simultaneously With with two purposes of harmless treatment, smelting efficiency is substantially increased using oxygen-enriched air；4th, the present invention adds in fuming furnace High-sulfur cupric solid waste, which is realized, makes sulfonium dilution and fuming, artificial gold is volatized into flue dust, copper sulfide is entered matte, reach melting The purpose of tin and copper is separately recovered in slag dilution and fuming；5th, the present invention has technical process technical indicator stabilization, labor intensity small The advantage such as low with production cost.
Brief description of the drawings
Fig. 1：Present invention process schematic flow sheet.
Embodiment
Embodiment 1：
The cupric solid waste that the present invention is handled has three kinds, and the first is electroplating sludge, and its main component is by weight percentage For（%）：Cu5.3, Sn1.2, Zn3.8, Pb0.50, Sb0.4, S8.4 and H2O72.5；Second is copper sponge, its main component It is by weight percentage（%）：Cu82.4, Pb1.3, Sb1.4 and S0.3；The third is wet method mud, and its main component is with weight Percentages are（%）：Cu35.6, Sn3.5, Zn1.8, Pb3.2, Sb3.2 and S4.5；CaO mass percentage in technical grade quick lime Content is more than 75.0%, and the weight/mass percentage composition of fixed carbon is more than 75% in coke, the matter of copper and sulphur in the low copper cupric solid waste of high-sulfur It is respectively 2.0~5.0% and 5.0~8.0% to measure percentage composition.
First, compound concentration is 1.0mol/L lime solution, and add the first by liquid-solid ratio 3: 1 consolidates with the third cupric It is useless, mixed slurry is added in Stainless Steel autoclave, it is anti-under the conditions of 150 DEG C of controlling reaction temperature and partial pressure of oxygen 0.6MPa 2.0h is answered, 60 DEG C and solid-liquor separation are cooled to after the completion of reaction；Slag and other two kinds of cupric solid waste dispensings will be converted, make mixture The moisture of material, copper content and FeO: SiO2: CaO mass ratioes keep 16.5%, 54.0% and 1.3: 1.0: 0.5 respectively, while match somebody with somebody again Enter the starch of mixed material quality 4.6%, be then prepared into the brick that specification is length × width × height=200 × 120 × 100mm Block, it is qualified furnace charge after stacking 2 days naturally；Above-mentioned qualified fragment of brick and coke are alternately added according to the ratio of weight ratio 1: 0.10 Into smelting furnace, the oxygen-enriched air melting that concentration is 28.0% is passed through, the weight/mass percentage composition for controlling copper in smelting slag is 2.5%, Melting cycle is 2.5h, and the heavy phase melt and smelting slag of melting output are periodically released and be contained in respectively in cast iron mold, weight Phase melt is cooled down using blowing mode, and it is 60m to control blowing amount3/ min and blow-time are 25min, keep heavy phase bath surface Temperature separates while hot when being 580 DEG C, the further Refining of blister copper；The liquid smelting slag being contained in cast iron mold is directly hung in Fuming furnace, add granularity by smelting slag and fine coal mass ratio 1: 0.30 and cross the fine coal of 200 mesh, while add smelting slag part by weight The 4.0% low copper cupric solid waste of high-sulfur, holding air capacity are 240m3/ min blowing 100min, the flue dust that gas gathers dust to obtain are back The raw material of tin is received, fuming slag is put into V-type slag chute and cools down, and V-type slag chute bottom is matte, and the slag at the top of V-type slag chute is as cement Raw material is sold.

Claims (2)

1. a kind of concentration smelting method that cupric solid wastes recycling utilizes, it is characterised in that comprise the following steps：
（1）Lime pressure Oxidation Leaching
The lime solution that molar concentration is 0.5~2.0mol/L is prepared, is consolidated by the liquid by liquid volume L and the ratio between solid weight kg Than adding cupric solid waste for 2~4: 1, mixed slurry is added in autoclave, 100~200 DEG C of controlling reaction temperature and 1.0~3.0h is reacted under the conditions of 0.1~1.0MPa of partial pressure of oxygen, 60 DEG C and solid-liquor separation are cooled to after the completion of reaction, conversion slag is sent Next step dispensing, conversion fluid, which returns, to be used；
（2）Dispensing brickmaking
Slag and other cupric solid waste dispensings are converted, are made FeO: SiO in mixed material2: CaO mass ratioes are maintained at（1.0~1.5）∶ 1.0∶（0.4~0.6）, while make the moisture of mixed material and copper content control respectively 15.0~25.0% and 40.0~ 60.0%, be then incorporated the starch of mixed material quality 1.0~5.0% again, be then prepared into specification for length × width × height= 200 × 120 × 100mm fragment of brick, enter stove melting as qualified furnace charge after stacking 1~3 day naturally;
（3）Reduction melting
Above-mentioned qualified fragment of brick and coke are alternately added in smelting furnace according to the ratio of weight ratio 1: 0.10~0.25, are passed through concentration Be 2.0~4.5% by controlling the weight/mass percentage composition of copper in smelting slag for 26.0 ~ 40.0% oxygen-enriched air melting, make tin and Zinc is enriched in smelting slag and flue dust respectively, and melting cycle is 1.5~3.0h, the heavy phase melt of melting output and smelting slag cycle Property release and be contained in respectively in cast iron mold, smelting slag send and subsequently makes sulfonium dilution, and melting flue gas uses hydroxide after gathering dust Qualified discharge after sodium solution elution；The heavy phase melt being contained in cast iron mold is cooled down using blowing mode, controls the blowing amount to be 50~100m3/ min and blow-time are 15~90min, when heavy phase bath surface temperature is 650~850 DEG C, heavy phase melt Liquate output blister copper and matte two-phase, holding bath surface temperature separate while hot when being 500~650 DEG C, and blister copper further refines Purification, smelting slag further make sulfonium fuming；
（4）Make sulfonium dilution and fuming
The liquid smelting slag being contained in cast iron mold is directly added into fuming furnace, by smelting slag and fine coal mass ratio 1: 0.25~ 0.40 addition granularity crosses the fine coal of 200 mesh, while the low copper cupric solid waste of the high-sulfur for adding smelting slag part by weight 1.0-5.0% is entered Row makes sulfonium dilution, and holding air capacity is 100~300m3/ min blowing 90-120min, the flue dust that gas gathers dust to obtain are recovery tin Raw material, fuming slag is put into V-type slag chute and cools down, and V-type slag chute bottom is matte, and the slag at the top of V-type slag chute is as cement raw material Sell.
2. the concentration smelting method that cupric solid wastes recycling as claimed in claim 1 utilizes, it is characterised in that：Cupric solid waste master The composition range is wanted to be by weight percentage：Cu5.0~90.0, Sn1.0~15.0, Zn1.0~15.0, Pb0.5~15.0, Sb0.1~10.0 and S0.1~10.0.
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CN110052106B (en) * 2019-05-15 2024-04-19 开平市新龙回收加工厂有限公司 Comprehensive treatment system and method for three wastes of copper-containing industrial sludge
CN110387475A (en) * 2019-08-28 2019-10-29 中南大学 A kind of method that copper-based solid waste collaboration matte smelting strengthens enriching noble metals
CN110331299A (en) * 2019-08-28 2019-10-15 中南大学 A kind of method that enriching noble metals are strengthened in copper-based solid waste collaborative SCM melting
CN110408785B (en) * 2019-08-28 2021-08-17 中南大学 Method for extracting noble metals by copper-based solid waste synergistic smelting enrichment
CN110724821A (en) * 2019-10-31 2020-01-24 万载志成实业有限公司 Method for comprehensively recovering valuable metals from low-grade multi-metal hazardous wastes
CN110976481B (en) * 2019-12-09 2021-10-08 洛南环亚源铜业有限公司 Copper-containing hazardous waste treatment process
CN111647749B (en) * 2020-05-26 2022-03-11 中国恩菲工程技术有限公司 Separation method of copper-containing solid waste
CN112030002B (en) * 2020-09-10 2022-12-30 江西理工大学 Method for producing blister copper by directly carrying out oxygen-enriched smelting on waste circuit boards
CN113652552B (en) * 2021-08-20 2023-03-10 广东飞南资源利用股份有限公司 Comprehensive recovery method of copper pyrogenic refining slag
CN114317992B (en) * 2021-12-30 2022-09-16 耒阳市焱鑫有色金属有限公司 Method for recovering copper and silver from waste slag of fuming furnace
CN114350968A (en) * 2021-12-31 2022-04-15 高诺(衡阳)产业园发展有限责任公司 High-efficiency energy-saving copper fire refining process

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