CN106399692A - Concentration smelting method for resource utilization of copper-containing solid waste - Google Patents

Concentration smelting method for resource utilization of copper-containing solid waste Download PDF

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CN106399692A
CN106399692A CN201610867705.2A CN201610867705A CN106399692A CN 106399692 A CN106399692 A CN 106399692A CN 201610867705 A CN201610867705 A CN 201610867705A CN 106399692 A CN106399692 A CN 106399692A
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copper
smelting
slag
solid waste
fuming
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CN106399692B (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

The invention provides a concentration smelting method for resource utilization of copper-containing solid waste. Oxygen is introduced into the copper-containing solid waste in a lime solution for oxidation transformation, transformed slag and other copper-containing solid waste ingredients are mixed, the moisture content of a mixture, the copper content and the mass ratio of FeO:SiO2:CaO are each kept in the required range, meanwhile starch is added, and bricks are made; the mixture bricks and coke are alternately added to a smelting furnace, oxygen-enriched air is introduced for concentration smelting, a heavy-phase melt produced through smelting controls a cooling process for separating produced coarse copper and ice copper, the molten slag in a fuming furnace is subjected to matte smelting dilution and fuming for recovering copper and tin, and the molten slag is finely ground and then separated for further recovering the copper. According to the key of the concentration smelting method, calcium sulfate is used as a new sulfur-fixing agent, then the starch is used as a binder and a reducing agent at the same time, then the harmless disposal and resource utilization of the copper-containing solid waste are achieved by controlling the copper content in the molten slag, and finally recovery of the copper and tin in the molten slag is achieved by the adoption of matte smelting dilution and fuming.

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, especially with wet method conversion and the pyrometallurgical smelting side of combining 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, are only second to aluminum 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%.44,170,000 tons of ten kinds of non-ferrous metal yield of China in 2014, wherein 24,380,000 tons of electrolytic aluminium, refined copper 7960000 tons, 4,220,000 tons of lead and 5,830,000 tons of 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 the copper of Chinese market supply breach still very big.
The copper mineral only more than 20 that nature has industrial application value is planted, and mainly has sulphide ore and oxide ore two big class, sulfur Change copper washability is good, be easy to enrichment, adopts pyrometallurgical smelting work through the copper sulfide concentrate of the cupric 20～30% of floatation process output Skill is processed, and cupric oxide ore flotability is poor, be difficult to beneficiation enrichment, preferably directly adopts hydrometallurgical processes to process.At present, about More than 80% mineral products copper be then copper sulfide concentrate through pyrometallurgical smelting technique productions, that is, copper concentrate is through matte smelting output Copper matte regulus, copper matte regulus sequentially passes through to be bessemerized 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 country, China's copper resource reserves are extremely poor, China's self-produced copper essence every year 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 become development bottleneck restriction because Element.Reclaimed copper has made significant contribution for China's copper consumption demand, has also sought outlet for the copper resource of China.China in recent years The ratio that reclaimed copper accounts for refined copper total output totally assumes steady-state growth trend, and China's refined copper yield in 2010 is 457.3 ten thousand t, its Middle reclaimed copper 176.2 ten thousand t, reclaimed copper yield accounts for the 38.5% of refined copper yield.
Cupric solid waste resource refer to the mankind produce, consumption, life and other activities in produce solid-state, semi-solid or Many or few waste material containing metal copper resource, it has contaminative, resource and social feature.That is in society Can develop 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 meanwhile, cupric solid waste is the resource with 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 in decontamination process containing heavy metal produce copper sludge, Environmental protection mud, the electroplating sludge that electroplating industry produces, copper sponge and old circuit board cracking and sorting that all kinds of process industries produce Copper powder going out etc..This kind of material generally has four features：
One is that cupric solid waste water content is high, cannot be removed using conventional filter press solid separation method and combine water, such as electroplate Mud, its water content up to 60 ~ 80%, if this part moisture does not remove it is impossible to carry out pyrometallurgical smelting process；Two is complicated component, In the cupric solid waste such as wet-precipitated slag and electroplating sludge, often contain the heavy metals such as more lead, zinc, chromium, this kind of cupric solid waste If imappropriate process will cause huge harm to ecological environment around；Three is that in cupric solid waste, copper content difference is larger, copper The copper grade of powder, copper sponge and copper sludge 60 ~ 90%, and the copper content of electroplating sludge and environmental protection mud then mostly below 15% even Lower, that is, in copper-contained material, main metal ingredient fluctuation is larger, if this kind of material is directly entered stove melting, can cause a lot of problems； Four is the problem of cupric solid waste sulfur, and in cupric solid waste, sulfur is mainly existed with sulfate or sulphided form, in follow-up fusion process Not only high energy consumption, and vent gas treatment difficulty is big, and absorption product is gypsum tailings is also a kind of solid waste, and it stores up problem Letter is to be solved.
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 Produce copper to compare, often produce 1t reclaimed copper energy-conservation 1054Kg mark 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 thermal process and two kinds of wet processing.
Fire metallurgy process is then cupric solid waste through reduction melting output blister copper, then uses reverberatory furnace pyro-refining output Positive plate, positive plate is 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 carry out cupric solid waste in reverberatory furnace casting positive plate after pyro-refining, then Again through electrorefining output tough cathode.Two-stage nitration rule be by cupric solid waste first in blast furnace reduction melting output blister copper, Or copper-contained material first reduction melting output blister copper in converter, then in reflection ingle method refine output positive plate, then Again through electrorefining output tough cathode.Three-stage process is then through more black of shaft smelting output impurity by cupric solid waste Copper, black copper blows in converter and obtains blister copper after removing the impurity such as lead and stannum, blister copper output positive plate after reverberatory refining, Eventually pass electrorefining output tough cathode.As can be seen that one-stage process and two-stage method are suitable only for impure less the containing of process Copper solid waste, and three-stage process is suitable for processing impure more cupric solid waste.The core of pyrometallurgical smelting technique is to be melted using pyrogenic process Smelting method makes copper and impurity reduction enter blister copper, then bessemerizes or refining process imurity-removal metal in follow-up.At pyrogenic process Science and engineering skill has the advantages that flow process is short, low cost and the response rate are high.
Cupric solid waste wet dissolution method is mainly dissolved copper by hydrometallurgical processes, and copper-containing solution is through purifying to remove Remove impurities, purer copper-containing solution obtains tough cathode using electrodeposition method again.Although Wet-process metallurgy method has flow process letter Singly, the advantages of metal good separating effect and metal recovery rate are high, but there are material bad adaptability, processing cost height and the three wastes and produce Measure big shortcoming so that the method is difficult to be widely popularized.
So select which kind of PROCESS FOR TREATMENT cupric solid waste, need to take into full account environmental conservation, the utilization of resources and processing cost Etc. factor, especially it is unable to output secondary pollution, so, developing a kind of efficient cupric fixed-end forces technique is still at present urgently The problem solving.
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 In conjunction with 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 little-pyrogenic process connection Close metallurgical method.
For reaching above-mentioned purpose the technical solution used in the present invention it is：Cupric solid waste is passed through dioxygen oxidation in lime solution Conversion, makes sulfur be completely converted into calcium sulfate precipitation and enters conversion slag, conversion slag is mixed with other cupric solid waste dispensings, makes mixture The moisture of material, copper content and FeO: SiO2: CaO mass ratio is kept at claimed range, adds one in mixed material simultaneously Prepare fragment of brick 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, so that the stannum in material is entered in smelting slag and flue dust by controlling copper content in smelting slag, The heavy phase melt of melting output is periodically released, and controls cooling system separation output blister copper and matte, smelting slag is in fuming furnace Make sulfonium dilution and fuming is separately recovered copper and stannum, copper is reclaimed in levigate rear ore dressing to smelting slag further again, and melting flue gas is through gathering dust And with qualified discharge after Alkali absorption.The core of the present invention is to make the sulfur in cupric solid waste complete initially with alkaline pressure oxidation conversion Portion is converted into calcium sulfate, reclaims sulfur in order to reduction melting process with copper sulphide form；Next to that using starch simultaneously as viscous Knot agent and reducing agent, not only increase the intensity of agglomerate, and enhance reduction melting process；It is that reduction melting process makes again Copper in raw material and noble metal etc. reduce and are enriched in heavy phase melt, and heavy phase melt is divided using control cooling system selectivity again From output blister copper and matte, it is finally using making sulfonium dilution and fuming process realizes the recovery of copper and stannum in smelting slag.These rings Section tight association, collective effect achieves the purpose of cupric solid wastes recycling utilization.
Specific technical process and parameter are as follows：
1 lime pressure oxidation conversion
Cupric solid waste is passed through dioxygen oxidation conversion in lime solution, makes sulfur be completely converted into calcium sulfate precipitation and enters conversion slag, Make water and valuables oxidation removal；Prepare the lime solution that molar concentration is 0.5～2.0mol/L, by liquid-solid ratio（Liquid volume Ratio with solid weight）2～4: 1 addition cupric solid waste, mixed slurry is added in autoclave, controlling reaction temperature React 1.0～3.0h under the conditions of 100～200 DEG C and partial pressure of oxygen 0.1～1.0MPa, be cooled to 60 DEG C after the completion of reaction and liquid divides admittedly From conversion slag send next step dispensing, and conversional solution returns and uses；Lime pressure aoxidizes the main chemical reactions of conversion process generation such as Under：
Ca(OH)2+MeSO4=Me(OH)2+CaSO4（1）
Ca(OH)2+MeS+2O2=Me(OH)2+CaSO4（2）
2 dispensing brickmaking
Conversion slag prepares fragment of brick with other cupric solid waste dispensings and after adding a certain proportion of starch；Conversion slag is solid with other cuprics Useless dispensing, makes FeO: SiO in mixed material2: CaO mass ratio is maintained at（1.0～1.5）∶1.0∶（0.4～0.6）, make to mix simultaneously The moisture of compound material and copper content control respectively 15.0～25.0% and 40.0～60.0%, then allocate mixed material quality again into 1.0～5.0% starch, is then prepared into the fragment of brick that specification is length × width × height=200 × 120 × 100mm, naturally stacks Can be used as qualified furnace charge after 1～3 day and enter stove melting.
3 reduction melting
Qualified furnace charge and coke are divided and is proportionally added into reduction melting in smelting furnace, smelted product is periodically released, control cold But system separation output blister copper and matte；Above-mentioned qualified fragment of brick and coke alternately add according to the ratio that weight compares 1: 0.10～0.25 Enter in smelting furnace, be passed through the oxygen-enriched air melting that concentration is 26.0 ~ 40.0%, by controlling the percent mass of copper in smelting slag Content is 2.0～4.5%, so that stannum and zinc is enriched in respectively in smelting slag and flue dust, and melting cycle is 1.5～3.0h, melting output Heavy phase melt and smelting slag periodically release and be contained in respectively in cast iron mold, smelting slag send subsequently makes sulfonium dilution, melting Flue gas uses qualified discharge after sodium hydroxide solution drip washing after gathering dust；The heavy phase melt being contained in cast iron mold adopts blowing Mode cools down, and control blowing amount is 50～100m3/ min and blow-time are 15～90min, when heavy phase bath surface temperature is When 650～850 DEG C, heavy phase melt liquate output blister copper is biphase with matte, keeps bath surface temperature to be to take advantage of when 500～650 DEG C Thermal release, the further Refining of blister copper, smelting slag makes sulfonium fuming further.
4 make sulfonium dilution and fuming
Smelting slag is made sulfonium dilution in fuming furnace simultaneously and is reclaimed copper and fuming volatilization stannum；It is contained in the liquid smelting in cast iron mold Slag is directly added into fuming furnace, adds granularity to cross the fine coal of 200 mesh by smelting slag and fine coal mass ratio 1: 0.25～0.40, simultaneously plus The high-sulfur low copper cupric solid waste entering smelting slag part by weight 1.0-5.0% carries out making sulfonium dilution, keep air capacity be 100～ 300m3/ min blow 90-120min, gas gather dust the flue dust obtaining be reclaim stannum raw material, fuming slag is put into cold in V-type slag chute But, V-type slag chute bottom is matte, and the slag at V-type slag chute top is sold as cement raw material.
The present invention is applied to the various cupric solid wastes of process, 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 is compared with cupric solid waste traditional treatment method, has the advantage that：1st, the present invention adopts lime pressure to aoxidize Method for transformation makes moisture and oxidation operation removing in cupric solid waste, and sulfur is completely converted into calcium sulfate and as new solid sulfur Agent, in sequential reduction fusion process with matte form output, the conversion ratio of sulfur reaches 99.0%, considerably reduces melting flue gas The concentration of middle sulfur, improves operating environment；2nd, the dispensing brickmaking process of the present invention, the cupric solid waste of different grades is arranged in pairs or groups and is made Enter in furnace charge copper content control 40～60%, decrease the yield of follow-up fusion process slag, improve the response rate of copper,；Allocate shallow lake into Powder not only increased the intensity of fragment of brick in brickmaking process as binding agent, and reduce fusion process and enhance also as reducing agent Former effect；3rd, the reduction melting process of the present invention, by controlling in smelting slag copper content 2.0～4.5%, by valuable metal also In former entrance blister copper, matte or flue dust, by metal-cured for poisonous and harmful in smelting slag, realize the resource 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 is realized making sulfonium dilution and fuming, makes Tin disulfide be volatized into flue dust, makes copper sulfide enter matte, reaches melting Slag dilution and fuming are separately recovered the purpose of stannum and copper；5th, the present invention has that technical process technical specification is stable, labor intensity is little And the advantages of low production cost.
Brief description
Fig. 1：Present invention process schematic flow sheet.
Specific embodiment
Embodiment 1：
The cupric solid waste that the present invention is processed has three kinds, and the first is electroplating sludge, and its main component is by weight percentage （%）：Cu5.3, Sn1.2, Zn3.8, Pb0.50, Sb0.4, S8.4 and H2O72.5；Second is copper sponge, its main component with Percentage by weight is calculated as（%）：Cu82.4, Pb1.3, Sb1.4 and S0.3；The third is wet method mud, and its main component is with weight hundred Ratio is divided to be calculated as（%）：Cu35.6, Sn3.5, Zn1.8, Pb3.2, Sb3.2 and S4.5；In technical grade quick lime, CaO percent mass contains Amount is more than 75.0%, and in coke, the weight/mass percentage composition of fixed carbon is more than 75%, the quality of copper and sulfur in high-sulfur low copper cupric solid waste Percentage composition is respectively 2.0～5.0% and 5.0～8.0%.
First, compound concentration is the lime solution of 1.0mol/L, adds the first solid with the third cupric by liquid-solid ratio 3: 1 Useless, mixed slurry is added in Stainless Steel autoclave, anti-under the conditions of 150 DEG C and partial pressure of oxygen 0.6MPa of controlling reaction temperature Answer 2.0h, after the completion of reaction, be cooled to 60 DEG C and solid-liquor separation；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 ratio keeps 16.5%, 54.0% and 1.3: 1.0: 0.5 respectively, joins simultaneously 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, is qualified furnace charge after naturally stacking 2 days；Above-mentioned qualified fragment of brick and coke are alternately added according to the ratio that weight compares 1: 0.10 To in smelting furnace, it is passed through the oxygen-enriched air melting that concentration is 28.0%, the weight/mass percentage composition controlling copper in smelting slag is 2.5%, Melting cycle is 2.5h, and the heavy phase melt of melting output and smelting slag are periodically released and be contained in respectively in cast iron mold, weight Phase melt is cooled down using blowing mode, and control blowing amount is 60m3/ min and blow-time are 25min, keep heavy phase bath surface Temperature is to separate while hot when 580 DEG C, the further Refining of blister copper；The liquid smelting slag being contained in cast iron mold directly hangs in Fuming furnace, adds granularity to cross the fine coal of 200 mesh by smelting slag and fine coal mass ratio 1: 0.30, is simultaneously introduced smelting slag part by weight 4.0% high-sulfur low copper cupric solid waste, holding air capacity is 240m3/ min blows 100min, and the gas flue dust obtaining that gathers dust is back Receive the raw material of stannum, fuming slag puts into cooling in V-type slag chute, V-type slag chute bottom is matte, and the slag at V-type slag chute top is as cement Raw material is sold.

Claims (2)

1. a kind of cupric solid wastes recycling using concentration smelting method it is characterised in that comprising the following steps：
（1）Lime pressure Oxidation Leaching
Prepare the lime solution that molar concentration is 0.5～2.0mol/L, by solid with the liquid of the ratio of solid weight Kg by liquid volume L Ratio for 2～4: 1 addition cupric solid waste, mixed slurry is added in autoclave, 100～200 DEG C of controlling reaction temperature and React 1.0～3.0h under the conditions of partial pressure of oxygen 0.1～1.0MPa, after the completion of reaction, be cooled to 60 DEG C and solid-liquor separation, conversion slag send Next step dispensing, conversional solution returns and uses；
（2）Dispensing brickmaking
Conversion slag and other cupric solid waste dispensings, make FeO: SiO in mixed material2: CaO mass ratio is maintained at（1.0～1.5）∶ 1.0∶（0.4～0.6）, make the moisture of mixed material simultaneously and copper content control respectively 15.0～25.0% and 40.0～ 60.0%, then allocate the starch of mixed material quality 1.0～5.0% again into, be then prepared into specification be length × width × height= The fragment of brick of 200 × 120 × 100mm, enters stove melting as qualified furnace charge after naturally stacking 1～3 day;
（3）Reduction melting
Above-mentioned qualified fragment of brick and coke are alternately added in smelting furnace according to the ratio that weight compares 1: 0.10～0.25, are passed through concentration Oxygen-enriched air melting for 26.0 ~ 40.0%, by control smelting slag in copper weight/mass percentage composition be 2.0～4.5%, make stannum 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 drip washing；The heavy phase melt being contained in cast iron mold is cooled down using blowing mode, and control blowing amount is 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 is biphase with matte, keeps bath surface temperature to be to separate while hot when 500～650 DEG C, the further refine of blister copper Purification, smelting slag makes sulfonium fuming further；
（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, and the high-sulfur low copper cupric solid waste being simultaneously introduced 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, gas gathers dust the flue dust obtaining for reclaiming stannum Raw material, fuming slag puts in V-type slag chute cooling, and V-type slag chute bottom is matte, and the slag at V-type slag chute top is as cement raw material Sell.
2. cupric solid wastes recycling as claimed in claim 1 utilizes concentration smelting method 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, Pb01～15.0, Sb0.1～10.0 and S0.1～10.0.
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CN109136560A (en) * 2018-06-27 2019-01-04 东营方圆有色金属有限公司 The method that hot copper ashes produces copper-based antibacterial alloy material is handled using bottom convertor
CN110052106A (en) * 2019-05-15 2019-07-26 开平市新龙回收加工厂有限公司 Cupric industrial sludge comprehensive administration of three wastes system and method
CN110055412A (en) * 2019-04-28 2019-07-26 广东飞南资源利用股份有限公司 A kind of method of cupric tin electroplating sludge and desulfurized gesso of flue gas slag cooperative disposal and synthetical recovery copper and tin
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
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
CN110408785A (en) * 2019-08-28 2019-11-05 中南大学 A kind of method that noble metal is extracted in copper-based solid waste collaboration melting 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
CN110976481A (en) * 2019-12-09 2020-04-10 洛南环亚源铜业有限公司 Copper-containing hazardous waste treatment process
CN111647749A (en) * 2020-05-26 2020-09-11 中国恩菲工程技术有限公司 Separation method of copper-containing solid waste
CN112030002A (en) * 2020-09-10 2020-12-04 江西理工大学 Method for producing blister copper by directly oxygen-enriched smelting from waste circuit boards
CN113652552A (en) * 2021-08-20 2021-11-16 广东飞南资源利用股份有限公司 Comprehensive recovery method of copper pyrogenic refining slag
CN114317992A (en) * 2021-12-30 2022-04-12 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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Cited By (18)

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CN109136560A (en) * 2018-06-27 2019-01-04 东营方圆有色金属有限公司 The method that hot copper ashes produces copper-based antibacterial alloy material is handled using bottom convertor
CN110055412A (en) * 2019-04-28 2019-07-26 广东飞南资源利用股份有限公司 A kind of method of cupric tin electroplating sludge and desulfurized gesso of flue gas slag cooperative disposal and synthetical recovery copper and tin
CN110052106A (en) * 2019-05-15 2019-07-26 开平市新龙回收加工厂有限公司 Cupric industrial sludge comprehensive administration of three wastes system and method
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
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
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
CN110408785A (en) * 2019-08-28 2019-11-05 中南大学 A kind of method that noble metal is extracted in copper-based solid waste collaboration melting enrichment
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
CN110976481A (en) * 2019-12-09 2020-04-10 洛南环亚源铜业有限公司 Copper-containing hazardous waste treatment process
CN111647749A (en) * 2020-05-26 2020-09-11 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
CN112030002A (en) * 2020-09-10 2020-12-04 江西理工大学 Method for producing blister copper by directly oxygen-enriched smelting from waste circuit boards
CN113652552A (en) * 2021-08-20 2021-11-16 广东飞南资源利用股份有限公司 Comprehensive recovery method of copper pyrogenic refining slag
CN114317992A (en) * 2021-12-30 2022-04-12 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
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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