CN107699701A - By the method containing zinc and the mixing slag recovery valuable component of iron - Google Patents

By the method containing zinc and the mixing slag recovery valuable component of iron Download PDF

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Publication number
CN107699701A
CN107699701A CN201710936807.XA CN201710936807A CN107699701A CN 107699701 A CN107699701 A CN 107699701A CN 201710936807 A CN201710936807 A CN 201710936807A CN 107699701 A CN107699701 A CN 107699701A
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slag
iron
copper
zinc
furnace
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张力
张武
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Northeastern University China
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Northeastern University China
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04Working-up slag
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00Obtaining noble metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00Obtaining lead
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/30Obtaining zinc or zinc oxide from metallic residues or scraps
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10Obtaining alkali metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20Obtaining alkaline earth metals or magnesium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B58/00Obtaining gallium or indium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001Dry processes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The present invention discloses a kind of by the method containing zinc and the mixing slag recovery valuable component of iron.It comprises the following steps:In S1, the melting reaction device that can flow out zinc smelting dreg, addition attemperator or slag, and the one or more added in lead metallurgical slag, blast furnace slag, slag and ferroalloy slag, form mixing slag;Mixing slag is heated to molten condition, forms reaction slag, the slag of monitoring reaction in real time, by regulating and controlling to react the temperature and basicity CaO/SiO of slag2Ratio, the slag after the completion of being reacted;The slag that S2, step obtain, sedimentation separation obtain Iron containing silicate minerals phase, copper-rich phase, Fe-riched phase, while generate and enter copper-rich phase containing zinc, leaded, containing indium Yu bismuth-containing component flue dust, the migration of gold and silver component, enrichment;Each phase is recycled.The present invention can reduce Copper in Slag (Copper in Slag<0.1wt%), the high efficiente callback production of valuable component can be realized, obtains low copper ferrous material, metal recovery rate is high, and production cost is low, environment-friendly, and economic well-being of workers and staff is high.

Description

By the method containing zinc and the mixing slag recovery valuable component of iron
Technical field
The invention belongs to comprehensive utilization of resources and slag metallurgical technology field, and in particular to a kind of by the mixing containing zinc and iron The method that slag reclaims valuable component.
Background technology
Zinc abstraction technique includes zinc hydrometallurgy and two kinds of techniques of zinc vertical retorting, and two kinds of techniques produce a large amount of zinc abstraction clinkers, Iron vitriol slag, goethite slag, bloodstone slag etc. wherein after zinc hydrometallurgy generation zinc leaching residue, iron vitriol slag, pickling, zinc vertical retorting produces Zinc vertical retorting clinker.Zinc abstraction clinker contains the secondary resources such as copper, iron, zinc, lead, indium, gold, silver, and wherein iron content is up to 50%, Payable grade (payable grade, the iron content of remote super iron ore>26wt%), copper content is up to 2%, remote super copper mine payable grade (payable grade, copper content>0.2wt%), Zn content is up to 25%.At present, zinc smelting dreg is using Rotary Kiln, fuming furnace, air blast The techniques such as stove, cyclone smelting carry out processing recovery, the only component such as recovery section lead, zinc, silver, and it is valuable not account for copper, iron, gold etc. The recovery of component, and high energy consumption, pollution are big.
At present, a large amount of zinc abstraction clinker accumulations, zinc abstraction clinker contain plurality of heavy metal ion, not only bring serious ring Border is polluted, and causes the wasting of resources.How to clean, be efficiently imperative using zinc abstraction clinker.
The pyrometallurgical smelting process " sintering-blast furnace reduction-fuming furnace " of lead or " oxidation blowing-high lead dross reduction-fuming In the techniques such as stove ", lead metallurgical slag is produced.Lead metallurgical slag includes leaded smelting slag and fuming slag." sintering deposit blast furnace reduction " Or " solid-state high lead dross reduction " or " liquid high lead dross reduction technique " reducing process produces leaded smelting slag, leaded smelting slag passes through Fuming furnace, which is smelted, produces fuming slag, and lead metallurgical slag (fuming furnace clinker and leaded smelting slag) contains copper, gold, silver, iron, zinc, lead It is important secondary resource etc. component.Lead metallurgical slag (leaded smelting slag or fuming furnace clinker) temperature at >=1100 DEG C, smelt by lead Slag is not only important physics thermal resource.
Blast furnace slag, slag and ferro-alloy cinder contain the metallic iron of high level, ferriferous oxide, chromated oxide, five oxidations Two phosphorus, SiO2, the valuable component such as CaO, MgO be important secondary resource;Melting is given off by blast furnace, converter and ferro-alloy furnace Slag temperature >=1300 DEG C, therefore, molten blast furnace slag, molten steel slag are also that important physical thermal provides with melting ferro-alloy cinder Source.Contain a large amount of SiO in zinc abstraction clinker, lead metallurgical slag, blast furnace slag, slag, ferro-alloy cinder2、CaO、MgO、Al2O3Deng smelting Golden flux, chemical reactivity is strong, is the slag system of excellent in physical and chemical performance, is metallurgical clinker.And flowed out by metallurgical furnace Fused zinc smelted furnace cinder, fusion of lead metallurgical slag, molten blast furnace slag, molten steel slag and melting ferro-alloy cinder, contain abundant heat Energy resource, containing a large amount of hot flux for metallurgy.Zinc abstraction clinker, lead metallurgical slag, blast furnace slag, slag and ferro-alloy cinder chemical group It is close into, mineral composition and clinker.
To sum up, largely accumulated containing zinc and iron metallurgical slag, clinker contains plurality of heavy metal ion, not only brings serious ring Border is polluted, and causes the wasting of resources.Therefore, how to clean, be using containing zinc and iron smelted furnace cinder recovery valuable component efficiently One urgent problem to be solved.
The content of the invention
(1) technical problems to be solved
In order to solve the above mentioned problem of prior art, the present invention provides a kind of valuable by the mixing slag recovery containing zinc and iron The method of component, this method can reduce Copper in Slag (Copper in Slag<0.1wt%), can realize copper, gold, silver, iron, zinc, lead, indium, The high efficiente callback and production of the components such as phosphorus, calcium, silicon, sodium, potassium, obtain low copper ferrous material (iron ore concentrate and the pig iron), metal recovery Rate is high, and production cost is low, environment-friendly, and economic well-being of workers and staff is high.
(2) technical scheme
In order to achieve the above object, the main technical schemes that the present invention uses are as follows:
A kind of method for reclaiming valuable component by the mixing slag containing zinc and iron, comprises the following steps:
S1, clinker mixing:By zinc smelting dreg, add in the melting reaction device that attemperator or slag can flow out, and add Enter the one or more in lead metallurgical slag, blast furnace slag, slag and ferroalloy slag, be stirred, form mixing slag;
Mixing slag is heated to molten condition, reaction slag is formed, is well mixed, the slag of monitoring reaction in real time, is passed through Regulation and control make reaction slag while meet two conditions of a and b, the slag after the completion of being reacted;
Wherein, a:The temperature of regulation and control reaction slag is 1100~1450 DEG C;
b:The basicity CaO/SiO of regulation and control reaction slag2Ratio=0.15~1.8;
S2, separation and recovery:The slag that step S1 is obtained, 5~50min is incubated, sedimentation separation, obtains middle and upper part iron content silicic acid Salt mineral facies, bottom copper-rich phase, middle and lower part Fe-riched phase, while generate component containing zinc, leaded component, component containing indium and bismuth-containing component Flue dust, gold and silver component migration, enrichment enter copper-rich phase;Each phase is recycled.
According to the present invention, in step sl, condition a regulation and control method is:
When the temperature of reaction slag<At 1100 DEG C, by the heating function of reaction unit itself, or combustion is added into slag It is material or fused zinc smelted furnace cinder, molten copper slag, melting nickel fibers slag, fusion of lead metallurgical slag, molten blast furnace slag, molten steel slag, molten Melt the one or more of ferroalloy slag, when spraying into fuel, while spray into the oxidizing gas of preheating, reach the temperature of reaction slag To in the range of 1100~1450 DEG C;
When the temperature of reaction slag>At 1450 DEG C, to reaction slag in add copper-contained material, zinc smelting dreg, lead-containing material, One or more in nickel fibers slag, blast furnace slag, slag, ferroalloy slag, flux for metallurgy, ferrous material, fluorine-containing material, make mixing The temperature of slag reaches in the range of 1100~1450 DEG C;
In step sl, condition b regulation and control method is:
As the basicity CaO/SiO of reaction slag2Ratio<When 0.15, alkaline material and/or alkalescence are added into reaction slag Ferrous material;
As the basicity CaO/SiO of reaction slag2Ratio>When 1.8, acid material and/or acidity are added into reaction slag Ferrous material.
According to the present invention, the attemperator is filled for dumpable melting reaction slag or thermal insulation pit;
The melting reaction device that the slag can flow out is rotatable melting reaction device or with cinder notch or iron mouth Melting reaction device;Wherein, the rotatable melting reaction device is converter, melting reaction slag ladle;It is described with cinder notch or The melting reaction device that iron mouth slag can flow out is plasma heating furnace, direct current electric arc furnace, ac arc furnace, mineral hot furnace, blast furnace, height Stove, induction furnace, furnace cupola, side-blowing bath smelting furnace, bottom blowing molten pool smelting furnace, top-blown bath smelting furnace, reverberatory furnace, Ausmelt Stove, Isa furnace, watt button can be in husband's bath smelting furnace, side-blown rotary furnace, bottom blowing rotary furnace, top blast rotary furnace one or more.
According to the present invention, in the step S1, while meeting the condition a and b, should meet simultaneously in the slag Copper and ferriferous oxide are reduced to metallic copper and FeO, metal Ferrum content in slag<3%.
By adding one or both of reducing agent, ferrous material containing solid carbon, reducing agent dosage is molten in slag Copper and ferriferous oxide are reduced to metallic copper and FeO theoretical amount 110~140% in slag;The carbon containing ferrous material is steel Dirt mud and cigarette ash, the carbon containing pre-reduced pellet of iron ore concentrate, iron ore concentrate carbonaceous metallized pellet, zinc hydrometallurgy volatilization kiln slag, coke-fired furnace Dirt mud and cigarette ash.
According to the present invention, the zinc smelting dreg is clinker caused by zinc hydrometallurgy, one in clinker caused by pyrometallurgy of zinc Kind or two kinds;Zinc smelting dreg is molten state or hot or cold conditions, and melting pyrometallurgy of zinc slag is by cyclone smelting stove, blast furnace, fuming Stove, electric furnace slag notch are obtained, and hot zinc smelting dreg is obtained by Rotary Kiln discharging opening, perpendicular tank slag hole, or zinc smelting dreg is heated To molten condition;
Wherein, clinker caused by the zinc hydrometallurgy is iron after zinc leaching residue, volatilization kiln slag, copper-cadmium slag, iron vitriol slag, pickling One or more in alum slag, goethite slag, bloodstone slag, clinker caused by the pyrometallurgy of zinc are zinc vertical retorting clinker, rotation One or more in whirlpool smelting slag, blast-furnace cinder, fuming furnace clinker, electroslag;Clinker caused by the zinc hydrometallurgy It is both needed to by drying, dewater treatment;Cyclone smelting clinker, blast-furnace cinder, fuming furnace clinker, electroslag are by smelting furnace slag notch Obtain, volatilization kiln slag is obtained by Rotary Kiln discharging opening, and zinc vertical retorting clinker is obtained by perpendicular tank discharging opening.
According to the present invention, the copper-contained material is copper ashes, nominal group process, blister copper pyro-refining slag, zinc smelting dreg, zinc abstraction Cigarette ash and dirt mud, lead zinc tailings, lead metallurgical slag, lead copper matte, setting form, fire refining of crude lead slag, lead smelting ash and dirt mud, lead Sour battery, Copper making cigarette ash and dirt mud, composition brass, cupric rubbish, containing in copper circuit board, tin metallurgical slag, nickel fibers slag, tailing It is one or more of;
The copper ashes is clinker caused by " matte smelting ", clinker, pyrogenic process dilution clinker, copper ashes caused by " blowing of copper sulphur " One or more in flotation tailings, wet type copper smelting slag;
The flux for metallurgy is containing CaO or SiO2Mineral and clinker, preferably quartz sand, quartz sand containing gold and silver, red mud, One or more after removing sodium in high calcium red mud, carbide slag, dolomite or lime stone;
The ferrous material is common iron ore concentrate, common iron ore concentrate DRI, common iron ore concentrate sintered ore deposit, common iron Concentrate pellet ore, common iron ore concentrate metallized pellet, the carbon containing pre-reduced pellet of common iron ore concentrate, slag, zinc smelting dreg, coke smelting Refine flue dust and dirt mud, steel flue dust and dirt mud, nickel fibers slag, copper ashes, lead metallurgical slag, zinc smelting dreg, tin metallurgical slag, red mud, take off One or more after sodium in high calcium red mud, coal dust ash, pyrite cinder;
The nickel fibers slag be Ni-B alloy slag caused by " matte smelting " technique, " nickel convering of copper ice " technique blowing after it is poor It is one or more in nickel sedimentation clinker caused by change clinker, top blow smelting;
The lead metallurgical slag is fuming furnace clinker and leaded smelting slag, wherein, " reduction of ISP imperial smelting furnaces " or " sinter Ore deposit blast furnace reduction " or " solid-state high lead dross reduction " or " liquid high lead dross reduction " technique produce leaded smelting slag, containing lead smelting Slag is smelted by fuming furnace produces leaded fuming slag;
The steel flue dust includes blast furnace gas mud, bof sludge, electric furnace dust mud, hot/cold rolled sludge, agglomerated powder with dirt mud drum Dirt, pelletizing dust, go out ironworks dust, blast furnace dust, electric stove dust ash, steel rolling iron scale;
The blast furnace slag, slag and ferroalloy slag are molten state or cold conditions, wherein, blast furnace slag, slag and the iron of molten state Fe alloy slag is obtained by slag notch, or the blast furnace slag, slag and ferroalloy slag of cold conditions are heated into molten condition;
The slag is one in molten iron pre-desulfurization slag, vessel slag, electroslag, VOD/VAD slags, VD slags, tundish waste Kind is a variety of;
The ferro-alloy cinder is caused clinker in ferroalloy production process, including smelts stove caused by carbon ferromanganese Slag, smelt clinker caused by ferrochrome, clinker caused by smelting ferronickel, clinker caused by smelting ferrovanadium, stove caused by smelting duriron Slag, smelt clinker caused by clinker caused by ferro-niobium and Smelting Ferromolybdenum;
The fluorine-containing material is fluorite, CaF2, one or more in fluorine-containing blast furnace slag;
The copper-contained material, ferrous material and fluorine-containing material are pelletizing or granular material or granulation;Wherein, granular material Granularity≤150 μm, granular material granularity is 5-25mm, and granular material is sprayed into a manner of being blown, granular material to be blown or The mode to feed intake adds, and is loaded into gas as the one or more in the argon gas of preheating, nitrogen, reducibility gas, oxidizing gas, Preheating temperature is 0-1200 DEG C.
According to the present invention, the alkaline material is pulverized limestone, red mud, high calcium red mud after removing sodium, carbide slag, dolomite dust or It is one or more of in calcium lime powder;The alkaline ferrous material is alkaline sintering deposit, slag, ferroalloy slag, alkaline iron ore concentrate, alkali One or more in property pre-reduced pellet, alkalinous metal pellet, alkali blast furnace slag;
The acid material is the one or more in silica, flyash, gangue;The iron-containing acidic material is acidity Sintering deposit, acid iron ore concentrate, acid pre-reduced pellet, acid metal pellet, copper ashes, lead metallurgical slag, zinc smelting dreg, nickel fibers One or more in slag, tin metallurgical slag, ferroalloy slag, acid blast furnace slag.
According to the present invention, separation and recovery in step s 2 is handled as follows:
Containing copper-rich phase described in hot or cold conditions, converter or converting furnace copper metallurgy, or slow cooling crushing-magnetic selection separation metal are sent to Converter or converting furnace copper metallurgy are sent to after iron again, or after magnetic separation separates metallic iron or separates metallic iron without magnetic separation, direct-reduction, Reduzate is after magnetic separation separates metallic iron, then is sent to converter or converting furnace copper metallurgy;
The component containing zinc, leaded component, bismuth-containing component and component volatilization containing indium, are returned into flue dust in the form of an oxide Receive;
Containing the Iron containing silicate minerals phase and/or the Fe-riched phase, carried out using any of following methods A-G Slag treatment:
Method A:After water quenching or air cooling, cement raw material is directly used in:
Method B:Return in reaction mixing slag and be used as hot flux for metallurgy:
Method C:For pouring devitrified glass or as mineral wool;
Method D:The iron content slag of the Iron containing silicate minerals phase and/or the Fe-riched phase is retained in melting reaction dress Attemperator is poured into putting or by slag, into iron content slag, is blown into the preheating oxidizing gas that temperature is 0~1200 DEG C, and Ensure silicate slag temperature>1460℃;When slag ferrous oxide content<1%, the slag after being aoxidized;After the oxidation Slag Direct Air-Cooled or water quenching, as the additive or clinker in slag cements, cement regulator, manufacture of cement;
Method E:For producing the clinker of high added value, method is as follows:
E-1, the iron content slag of the Iron containing silicate minerals phase and/or the Fe-riched phase is retained in melting reaction device It is interior or slag is poured into attemperator, into slag, add molten steel slag, lime, lime stone, ferro-alloy cinder, flyash, alkali Property iron lean ore, bauxite, molten blast furnace slag, red mud, the one or more after removing sodium in high calcium red mud or carbide slag, it is fully mixed Close, obtain slag mixed material;
E-2, the oxidizing gas that preheating temperature is 0~1200 DEG C is blown into the slag mixed material, and ensured molten Slag mixed material temperature>1460℃;Work as ferrous oxide content<1%, the slag after being aoxidized;
E-3, to the slag after the oxidation, carry out air cooling or water quenching, the clinker of high added value be made;
Method F:The iron content slag of the Iron containing silicate minerals phase and/or the Fe-riched phase as blast furnace ironmaking raw material or Direct reduction iron making raw material:By the iron content slag air cooling of the Iron containing silicate minerals phase and/or the Fe-riched phase, water quenching or slow After cold, as blast furnace ironmaking or direct reduction iron making raw material, after direct-reduction, using molten point of magnetic separation separation or electric furnace, magnetic separation production Thing is metallic iron and mine tailing, and molten point of electric furnace, product is molten iron and slag;
Or, after the iron content slag of the Iron containing silicate minerals phase and/or the Fe-riched phase is poured into attemperator, use Following methods are separated:The modified magnetic separation separation of slag:Slag into attemperator, preheating temperature is blown into as 0~1200 DEG C oxidizing gas, and ensure slag temperature>1250 DEG C, complete the conversion of magnetic iron ore in slag;Slag after oxidation is delayed It is cooled to room temperature, crushes, magnetic separation, product is magnetite concentrate and mine tailing, and mine tailing is as construction material;
Method G:The iron content slag fused reduction iron-smelting of the Iron containing silicate minerals phase and/or the Fe-riched phase, including Following steps:
G-1, the iron content slag of the Iron containing silicate minerals phase and/or the Fe-riched phase is retained in melting reaction device It is interior or slag is poured into attemperator, ferrous material, reducing agent are added into iron content slag, carries out melting and reducing, in real time monitoring Slag is reacted, meets following condition simultaneously by regulation and control:The temperature for reacting slag is 1350~1670 DEG C and the alkali of reaction slag Spend CaO/SiO2Ratio=0.6~2.4, the slag after the completion of being reacted;
G-2, the oxidizing gas into slag after blowing preheated carry out melting and reducing, the slag formed after reduction, wherein: The preheating temperature of oxidizing gas is 0~1200 DEG C, and during injection, meets following condition simultaneously by regulation and control:Reaction After the completion of slag temperature for 1350~1670 DEG C and reaction after the completion of slag basicity CaO/SiO2Ratio=0.6~ 2.4;
G-3, separated and recovered using one kind in following two methods:
Method I:Mixing slag after reduction is poured into insulation slag ladle, is slowly cooled to room temperature, obtains slow cooling slag;Metallic iron The bottom of reaction unit is deposited to, iron is formed and sticks together;By containing metal iron layer in remaining slow cooling slag, 20~400 μm of granularity is crushed to, is ground Residual metallic iron and mine tailing are isolated in ore deposit, magnetic separation;
Method II:Mixing slag after reduction, sedimentation, slag-gold separation, obtain molten iron and the slag after reduction;After reduction Slag, according to the one or more in A~E, carry out slag treatment;Molten iron is sent to converter or electric furnace steel making;
Or, containing the Fe-riched phase water quenching or air cooling or pour into attemperator slow cooling or combined through manual sorting with gravity treatment and obtain , carry copper raw material or magnetic separation point as blast furnace ironmaking raw material or direct reduction iron making raw material or iron making by smelting reduction iron material or flotation From after metallic iron as copper metallurgy or the raw material of direct reduction iron making;In floatation process, float product be containing copper concentrate and iron ore concentrate, Copper concentrate returns to copper metallurgy system, and iron ore concentrate is former as blast furnace ironmaking raw material or direct reduction iron making raw material or fused reduction iron-smelting Material;Wherein, in Direct Reduction, after reduzate magnetic separation separation, metallic iron and mine tailing are obtained, mine tailing returns to copper metallurgy system System;
The Direct Reduction is using any of rotary hearth furnace, tunnel cave, car-bottom furnace, shaft furnace, rotary kiln, induction furnace As reduction apparatus, using gas base or coal base reduction technology, gas base is natural gas and/or coal gas, coal base be anthracite, bituminous coal, One or more in lignite, coking coal, coke powder, coke, reduction temperature are 900~1400 DEG C, basicity CaO/SiO2Ratio=0.8 ~1.5;Coal gas caused by reduction is in slag surface second-time burning, there is provided heat, and also the coal gas by being flowed out in stove can be made For drying furnace charge and the thermal source of attemperator;
In addition, because containing potassium, sodium in red mud, dirt mud is with silver-colored containing lead, zinc, bismuth, indium in steel cigarette ash, so adding these During raw material, part indium component, bismuth component, component containing potassium, component volatilization containing sodium, in the form of an oxide into flue dust.
According to the present invention, in described step S2, the type of cooling is that natural cooling or rotation cooling or centrifugation cool down, sedimentation Mode is natural subsidence or spun down or centrifugal sedimentation;
It is described to be well mixed to mix or being stirred naturally, it is stirred as argon gas stirring, nitrogen gas stirring, nitrogen-argon One or more in gas mixing gas agitating, reducibility gas stirring, oxidizing gas stirring, electromagnetic agitation, mechanical agitation.
According to the present invention, the fuel and the one or more that reducing agent is in solid, liquid or gaseous fuel, with injection Or the mode to feed intake sprays into, the injection is loaded into gas as the one or more in the oxidizing gas, nitrogen or argon gas of preheating, The temperature of the preheating is 0~1200 DEG C;
The solid fuel and one kind or more that reducing agent is in coal dust, coke powder, coke, flyash, bituminous coal or anthracite Kind, granular or powdery is shaped as, granular material granularity is 5~25mm, and granular material granularity is≤150 μm, the liquid fuel It is heavy oil with reducing agent, the gaseous fuel and reducing agent are coal gas and/or natural gas;
The oxidizing gas is the air of preheating, oxygen, oxygen-enriched air, argon gas-air, argon-oxygen, nitrogen-sky One kind in gas, nitrogen-oxygen.
Compared with prior art, it is characteristic of the invention that:
(1) method for reclaiming valuable component by the mixing slag containing zinc and iron of the invention, can both handle hot molten slag, Make full use of melting zinc smelting dreg and fusion metallurgy slag (fusion of lead metallurgical slag, molten blast furnace slag, molten steel slag, melting ferroalloy One or more in slag) physics thermal resource and hot flux for metallurgy, cold conditions clinker can be handled again, pass through slag mixing or cold State mixes, and realizes slag metallurgy;And solve current clinker bulk deposition, problem of environmental pollution, and heavy metal contamination and ask Topic.
(2) the slag metallurgical reaction in slag is mixed, ferriferous oxide fully discharges, and forms the iron oxidation of free state Thing, growing up and settling for Fe-riched phase is realized, mix the aggregation of the metallic iron component in slag, grow up and settle, Fe-riched phase includes gold Belong to a variety of in iron, FeO phases, fayalite phase, as blast furnace ironmaking or direct-reduction or the raw material of fused reduction iron-smelting.
(3) copper component, gold and silver component in slag are mixed and is enriched in copper-rich phase respectively, copper-rich phase includes copper, white metal, ice Copper phase, containing a variety of in ferrous components, and realize and grow up and settle, or part copper component enters Fe-riched phase.
(4) component containing zinc in slag, leaded component, bismuth-containing component are mixed and is enriched in cigarette ash respectively with component containing indium, is added With recovery;Part component containing sodium, component volatilization containing potassium enter flue dust.
(5) silicon in slag is mixed, calcium migrates with phosphorus component, is enriched in Iron containing silicate minerals phase, floating.
(6) mix free cao in slag to disappear with magnesia, mixing slag is realized quenched.
(7) using the method for manual sorting, magnetic separation, gravity treatment or slag-gold sedimentation, separate be deposited in bottom copper-rich phase, under Portion's Fe-riched phase and the Iron containing silicate minerals phase of middle and upper part, realize copper component, gold and silver component, iron component, phosphorus, calcium in mixing slag With the high efficiente callback of silicon components, Copper in Slag<0.1wt%.
(8) solid-state cupric, iron material, including copper concentrate can be handled, while realizes slag modifier treatment, reaches resource height Effect comprehensive utilization.
(9) slag is realized quenched, and middle and upper part tailings is disappeared using limiting factor, can be used as cement raw material or construction material or Make aggregate and road material or as blast furnace ironmaking or the raw material or phosphate fertilizer of direct reduction iron making or fused reduction iron-smelting instead of rubble.
(10) this technique is using mixing slag, and whole process is without heating or a small amount of heat compensation;This technique is using mixing Slag, whole process compensate flux for metallurgy without flux for metallurgy or on a small quantity, can handle cold conditions material.
(11) progress that the inventive method can be continuously or discontinuously, meets industrial production needs.
(3) beneficial effect
The beneficial effect of invention:
(1) present invention realize copper in Non-ferrous metallurgical slag and Ferrous Metallurgy clinker, iron, zinc, lead, indium, gold, silver, phosphorus, calcium, The comprehensive utilization of sodium, potassium and silicon components valuable component, solve current clinker bulk deposition, problem of environmental pollution.
(2) present invention can handle ferro-alloy cinder, slag, blast furnace slag, lead metallurgical slag, zinc abstraction clinker on a large scale with containing Copper, iron material, can solve the problems, such as heavy metal contamination, realize the recovery of heavy metal components.
(3) present invention can handle a small amount of cold conditions cupric, ferrous material.
(4) raw material of the invention can be the liquid molten zinc abstraction clinker (>=1100 DEG C) and melting flowed out in slag notch Metallurgical slag (one or more in fusion of lead metallurgical slag, molten blast furnace slag, molten steel slag, melting ferroalloy slag, >=1100 DEG C), The characteristics of with high-temperature, high heat, take full advantage of slag physics thermal resource;Mix in slag containing substantial amounts of hot metallurgy Flux, all it is the slag system of excellent in physical and chemical performance, realizes the efficient utilization of Metallurgical resources and thermal resource;Make full use of The characteristics of mixing slag high reactive chemistry activity, realize slag metallurgy.
(5) present invention is mixed by slag, is controlled oxygen gesture, copper group in slag, golden component and silver components is enriched to copper-rich Phase, aggregation is realized, grows up and settles, zinc component, lead component, bismuth component, sodium component, potassium component and indium component volatilization, with oxidation Thing form is reclaimed into flue dust.
(6) in the inventive method, add cold conditions material and avoid that slag temperature is too high, improve the life-span of attemperator;Add Enter cold conditions material and improve feed throughput, can not only handle molten slag, and a small amount of cold conditions material, raw material can be handled Strong adaptability;Adding cold conditions material realizes chemical heat and the efficient utilization of slag physical thermal of the release of slag metallurgical reaction.
(7) during the inventive method natural subsidence, copper component, gold and silver component are enriched in copper-rich phase respectively in slag, and Aggregation is realized, grows up and settles;Iron component is enriched in Fe-riched phase in slag, and realizes aggregation, grows up and settle;Phosphorus group in slag Divide, silicon components are enriched in Iron containing silicate minerals phase with Calcium compounds, and realize floating respectively;Attemperator equipped with slag is placed in Rotated on rotation platform, accelerate copper-rich phase, Fe-riched phase aggregation, grow up and settle;The addition of fluorine-containing material, acceleration copper-rich phase, The aggregation of Fe-riched phase, grow up and settle.
(8) phosphorus component migrates, is enriched in Iron containing silicate minerals phase in the inventive method slag, and realizes floating;In on In portion's Iron containing silicate minerals phase, the increase of mineral grindability, slag is realized quenched.
(9) method that the inventive method is settled using manual sorting, magnetic separation, gravity treatment or slag-gold, respectively to being distributed on Portion, the Iron containing silicate minerals phase of middle part and bottom, Fe-riched phase, copper-rich phase are separated, realize copper component in slag, gold and silver, The high efficiente callback of iron component, indium component, bismuth component, sodium component, potassium component, silicon components, Calcium compounds and phosphorus component etc., Copper in Slag< 0.1wt%;
In being deposited in due to Fe-riched phase, copper-rich phase, bottom, therefore, it is small to sort slag amount, the increase of mineral grindability, point It is low from cost;Follow-up separation process uses magnetic separation or gravity treatment, and the medium of separation is water, will not generation environment pollution so that it is whole Individual slag handling technology has that flow is short, simple to operate, the rate of recovery is high, mine tailing as cement raw material, construction material, instead of rubble Make aggregate, road material or phosphate fertilizer or as blast furnace ironmaking or direct-reduction or the raw material of melting and reducing.
(10) Fe-riched phase can produce metallic iron and iron as blast furnace ironmaking or direct-reduction or the raw material of melting and reducing Water;Low copper Fe-riched phase is with Iron-containing silicate mutually as blast furnace ironmaking or direct-reduction or the raw material of slag melting and reducing, production gold Belong to iron and molten iron.
(11) present invention can both handle hot molten slag, make full use of molten copper slag and fusion metallurgy slag physics thermal resource and Hot flux for metallurgy, cold conditions clinker and material can be handled again, using slag metallurgical reaction is mixed, pass through slag mixing or cold conditions Heated after mixing, realize slag metallurgy, copper migration in slag, be enriched in copper-rich phase, and realize aggregation, grow up and settle;Iron Component migration, Fe-riched phase is enriched in, realizes aggregation, grow up and settle;Silicon, calcium and phosphorus component migration, it is enriched in Iron-containing silicate Mineral facies, realize and float, using the method for manual sorting, magnetic separation, gravity treatment or slag-gold sedimentation, separation is deposited in different parts Copper-rich phase, Fe-riched phase and the Iron containing silicate minerals phase on top, wherein, copper-rich phase include copper, white metal, matte phase, iron content into A variety of in point, Fe-riched phase includes a variety of in metallic iron, FeO phases, fayalite phase, valuable component in realization mixing slag High efficiente callback;Solid-state can be handled containing zinc, iron material, while realize slag modifier treatment.
Embodiment
The present invention proposes a kind of method for reclaiming valuable component by the mixing slag containing zinc and iron, and it comprises the following steps:
Step S1, clinker mixing:
By zinc smelting dreg, add in the melting reaction device that attemperator or slag can flow out, and add lead metallurgical slag (cigarette Change stove clinker and/or leaded smelting slag), blast furnace slag, one or more in slag and ferroalloy slag form mixing slags;
Mixing slag is heated to molten condition, forms reaction slag;It is well mixed, the slag of monitoring reaction in real time, pass through Regulation and control ensure following (a) and (b) two parameters, the slag after the completion of being reacted simultaneously;
(a) temperature for reacting slag is 1100~1450 DEG C;
(b) the basicity CaO/SiO of slag is reacted2Ratio=0.15~1.8;
Regulation and control method is:
Corresponding (a):Control reaction slag temperature be in the method for design temperature scope:
When reacting 1100 DEG C of the temperature < design temperatures range lower limit of slag, pass through the heating work(of reaction unit itself Can, or fuel or fused zinc smelted furnace cinder (cyclone smelting slag and/or blast furnace slag), molten copper slag, melting are added into slag Nickel fibers slag, fusion of lead metallurgical slag, molten blast furnace slag, molten steel slag, the one or more for melting ferroalloy slag, spray into fuel When, while the oxidizing gas of preheating is sprayed into, the temperature of reaction slag is reached in the range of design temperature;
When 1450 DEG C of the temperature > design temperatures range limit of the reaction slag of cupric and iron, the reaction to cupric and iron In slag add copper-contained material, zinc smelting dreg, lead-containing material, nickel fibers slag, blast furnace slag, slag, ferroalloy slag, flux for metallurgy, One or more in ferrous material, fluorine-containing material, make the temperature of mixing slag reach in the range of design temperature.
Corresponding (b):
As basicity CaO/SiO in the reaction slag of cupric and iron2Ratio<When 0.15, basic species are added into reaction slag Material and/or alkaline ferrous material;
As basicity CaO/SiO in the reaction slag of cupric and iron2Ratio>When 1.8, acid material is added into reaction slag And/or iron-containing acidic material.
Step S2, separation and recovery:
Be incubated 5~50min, the slag after the completion of reaction, sedimentation, the separation of slag-gold, acquisition bottom molten state copper-rich phase, in Bottom molten state Fe-riched phase and the molten state Iron containing silicate minerals phase of middle and upper part, at the same generate component containing zinc, leaded component and Component containing indium enters flue dust, wherein, gold, silver component moves to the copper-rich phase;Using one kind in following methods:
Method one:When can flow out melting reaction device using slag, the slag after the completion of reaction carries out following steps:
(1) molten state Iron containing silicate minerals phase, slag treatment is carried out;
(2) molten state copper-rich phase, be sent to converter or converting furnace copper metallurgy or broken magnetic separation separation metallic iron after be sent to again converter or Converting furnace copper metallurgy, or after magnetic separation separates metallic iron or separates metallic iron without magnetic separation, direct-reduction, reduzate is through magnetic separation point After metallic iron, then it is sent to converter or converting furnace copper metallurgy;
(3) component containing zinc, leaded component, component containing indium, bismuth-containing component, component containing sodium, component volatilization containing potassium, with oxide Into fume recovery;
(4) Fe-riched phase carries out water quenching or air cooling or pours into attemperator slow cooling or acquisition is combined with gravity treatment through manual sorting, Copper raw material or magnetic separation separation are carried as blast furnace ironmaking raw material or direct reduction iron making raw material or iron making by smelting reduction iron material or flotation As copper metallurgy or the raw material of direct reduction iron making after metallic iron;Float product is to return to refining containing copper concentrate and iron ore concentrate, copper concentrate Copper system is united, and iron ore concentrate is as blast furnace ironmaking raw material or direct reduction iron making raw material or iron making by smelting reduction iron material;Wherein, direct In reduction process, after reduzate magnetic separation separation, metallic iron and mine tailing are obtained, mine tailing returns to copper metallurgy system;
Direct Reduction using rotary hearth furnace, tunnel cave, underbody road, shaft furnace, rotary kiln or induction furnace as reduction apparatus, Using gas base or coal base reduction technology, gas-based reduction is natural gas and/or coal gas, coal base reduction be anthracite, bituminous coal, lignite, One or more in coking coal, coke powder or coke, reduction temperature are 900~1400 DEG C, basicity CaO/SiO2Ratio=0.8~ 1.5。
Wherein, the Iron containing silicate minerals phase in step (1), slag treatment is carried out, using one kind in method A~G:
Method A:Iron containing silicate minerals are mutually used as cement raw material:
The water quenching of Iron containing silicate minerals phase or air cooling are directly as cement raw material or are further processed into the water of high added value Mud raw material;
Method B:Part or all of Iron containing silicate minerals mutually return to cupric reaction slag:
Part or all of Iron containing silicate minerals mutually return to cupric reaction slag, and as hot flux for metallurgy, adjustment contains Copper reacts slag composition, control cupric reaction slag temperature;
Method C:Iron containing silicate minerals mutually pour devitrified glass or as mineral wools;
Method D:Air cooling or water quenching after the oxidation of Iron-containing silicate slag:
(1) Iron-containing silicate slag is retained in melting reaction device or slag is poured into attemperator, into slag, blows Enter the oxidizing gas of preheating, when slag ferrous oxide content<1%, the oxidation of slag is completed, the slag after being aoxidized, its In, the preheating temperature of oxidizing gas is 0~1200 DEG C;And in whole process, ensure (c) silicate slag temperature>1460 ℃;
The control method that corresponding (c) is used:
When Iron-containing silicate slag temperature<1460 DEG C, spray into pre-heating fuel with preheating oxidizing gas, combustion heat release, Additional heat, or device conducting self-heating, make silicate slag temperature>1460℃;
(2) slag Direct Air-Cooled or water quenching after aoxidizing, as adding in slag cements, cement regulator, manufacture of cement Add agent or clinker;
Method E:Iron-containing silicate slag treatment produces the clinker of high added value:
(1) Iron-containing silicate slag is retained in melting reaction device or slag is poured into attemperator, into slag, adds Enter molten steel slag, lime, lime stone, ferro-alloy cinder, flyash, basic iron lean ore, bauxite, molten blast furnace slag, red mud, de- One or more after sodium in high calcium red mud or carbide slag, are sufficiently mixed, and obtain slag mixed material;
(2) oxidizing gas of preheating is blown into slag mixed material, works as ferrous oxide content<1%, complete slag Oxidation, the slag after being aoxidized, wherein, the preheating temperature of oxidizing gas is 0~1200 DEG C;And in whole process, protect Demonstrate,prove (d) slag mixed material temperature>1460℃;Temprature control method is the same as the silicate slag temperature control in method D steps (1) Method;
(3) slag after aoxidizing, air cooling or water quenching are carried out, the clinker of high added value is made;
Method F:The slag of Iron containing silicate minerals phase is as blast furnace ironmaking raw material or direct reduction iron making raw material:By iron content After the slag air cooling of silicate mineral phase, water quenching or slow cooling, as blast furnace ironmaking or direct reduction iron making raw material, direct-reduction Afterwards, using molten point of magnetic separation separation or electric furnace, magnetic separation product is metallic iron and mine tailing, and molten point of electric furnace, product is molten iron and slag;
Or, after the slag of Iron containing silicate minerals phase is poured into attemperator, separated using following methods:Slag changes Property after magnetic separation separate:Slag into attemperator, is blown into the oxidizing gas of 0~1200 DEG C of preheating, and ensures its slag Temperature>1250 DEG C, complete the conversion of magnetic iron ore in slag;By the slag slow cooling after above-mentioned oxidation to room temperature, crush, magnetic separation, production Thing is magnetite concentrate and mine tailing, and mine tailing is as construction material.
Method G:Iron-containing silicate slag fused reduction iron-smelting:
G-1, the slag of Iron containing silicate minerals phase is retained in melting reaction device or slag poured into attemperator, Or ferrous material is added, reducing agent is added in slag, carries out melting and reducing, the slag of monitoring reaction in real time, is protected simultaneously by regulation and control Following (a1) and (b1) two parameters of card, the slag after the completion of being reacted;
(a1) temperature for reacting slag is 1350~1670 DEG C;
(b1) the basicity CaO/SiO of slag is reacted2Ratio=0.6~2.4.
Regulation and control method is:
Corresponding (a1):
Control reaction slag temperature be in the method for design temperature scope:
When reacting the temperature < design temperature range lower limits of slag, by the heating function of reaction unit itself, or to Fuel and the oxidizing gas of preheating are added in slag, the temperature of reaction slag is reached in the range of design temperature;
When reacting the temperature > design temperature range limits of slag, flux for metallurgy, chalybeate are added into reaction slag One or more in material or fluorine-containing material, make the temperature of reaction slag reach in the range of design temperature.
Corresponding (b1):
When reacting basicity CaO/SiO in slag2Ratio<When 0.6, alkaline material and/or alkaline iron content are added into slag Material;
When reacting basicity CaO/SiO in slag2Ratio>When 2.4, acid material and/or iron-containing acidic are added into slag Material.
G-2, the oxidizing gas into slag after blowing preheated carry out melting and reducing, the slag formed after reduction, wherein: The preheating temperature of oxidizing gas is 0~1200 DEG C, and during injection, is ensured simultaneously by regulation and control (a2) and (b2) two Parameter:
(a2) temperature of the slag after the completion of reacting is 1350~1670 DEG C;
(b2) the basicity CaO/SiO of the slag after the completion of reacting2Ratio=0.6~2.4.
Wherein, design temperature scope and basicity regulate and control method with method G-1 steps;
G-3, separation and recovery:
Using one kind in following methods:
Method I:Carry out following steps:
(a) cool down:Mixing slag after reduction is poured into insulation slag ladle, is slowly cooled to room temperature, obtains slow cooling slag;
(b) separate:Metallic iron is deposited to the bottom of reaction unit, forms iron and sticks together, and the artificial iron that takes out sticks together;By remaining slow cooling slag Middle containing metal iron layer, 20~400 μm of granularity is crushed to, residual metallic iron and mine tailing are isolated in ore grinding, magnetic separation;
(c) recycling of mine tailing, making aggregate, road material or phosphate fertilizer as cement raw material, construction material, instead of rubble makes With;
Method II:Carry out following steps:
(a) the mixing slag after reducing, cooling-sedimentation, slag-gold separation, molten iron and the slag after reduction are obtained;
(b) slag after reducing, carries out the outer slag treatment of stove, and concrete mode is:Using step S2 separation and recovery method The one or more in method A~E in one, carry out the outer slag treatment of stove;
(c) molten iron, converter or electric furnace steel making are sent to;
(d) partly component containing zinc, leaded component and component volatilization containing indium, in the form of an oxide into fume recovery.
(e) part indium component, bismuth component, sodium component, potassium component volatilization are reclaimed into flue dust;
(f) coal gas caused by reduction is in slag surface second-time burning, there is provided heat, and also the coal gas by being flowed out in stove can Using the thermal source as drying furnace charge and attemperator.
Method two:During the melting reaction device that can be flowed out using slag, the slag after the completion of reaction carries out following steps:
(1) the molten state Fe-riched phase and Iron containing silicate minerals phase obtained, using in method A~G described in method one One or more carry out slag treatment;
(2) molten state copper-rich phase, sent again after being sent to converter copper metallurgy or converting furnace copper metallurgy raw material, or broken magnetic separation separation metallic iron Toward converter or converting furnace copper metallurgy, or after magnetic separation separates metallic iron or separates metallic iron without magnetic separation, direct-reduction, reduzate After magnetic separation separates metallic iron, then it is sent to converter or converting furnace copper metallurgy;
(3) partly component containing zinc, leaded component, component containing indium and bismuth-containing component volatilization, enter fume recovery with oxide;
(4) part sodium component, potassium component volatilization enter flue dust.
Method three:During using the rotatable converter of slag with reaction slag ladle, the slag after the completion of reaction carries out following steps:
(1) the molten state Iron containing silicate minerals phase obtained, using one kind in method A~G described in method one or several Kind carries out slag treatment;
(2) after Fe-riched phase carries out water quenching or air cooling or pours into attemperator slow cooling, as blast furnace ironmaking raw material or directly also Original ironmaking, it is identical with the step of method one (4);
(3) molten state copper-rich phase or after pouring into attemperator slow cooling, is sent to converter or converting furnace copper metallurgy, or broken magnetic separation separation Converter or converting furnace copper metallurgy are sent to after metallic iron again, or after magnetic separation separates metallic iron or separates metallic iron without magnetic separation, directly Reduction, reduzate is after magnetic separation separates metallic iron, then is sent to converter or converting furnace copper metallurgy;
(4) partly component containing zinc, leaded component, component containing indium and bismuth-containing component volatilization, enter fume recovery with oxide;
(5) part sodium component, potassium component volatilization enter flue dust.
Method four:During using the rotatable converter of slag with reaction slag ladle, the slag after the completion of reaction carries out following steps:
(1) the molten state Iron containing silicate minerals phase and Fe-riched phase obtained, using in method A~G described in method one One or more carry out slag treatment;
(2) molten state copper-rich phase, converter or converting furnace copper metallurgy are sent to, or are sent to again after broken magnetic separation separation metallic iron after slow cooling Converter or converting furnace copper metallurgy, or after magnetic separation separates metallic iron or separates metallic iron without magnetic separation, direct-reduction, reduzate warp After magnetic separation separation metallic iron, then it is sent to converter or converting furnace copper metallurgy;
(3) partly component containing zinc, leaded component, component containing indium and bismuth-containing component volatilization, enter fume recovery with oxide;
(4) part sodium component, potassium component volatilization enter flue dust.
Method five:Using attemperator or the melting reaction device that can be flowed out using slag, slag is poured into attemperator When, the slag after the completion of reaction carries out following steps:
(1) sedimentation cooling:Slag after the completion of reaction is slowly cooled to room temperature, and obtains slow cooling slag;Copper-rich phase is deposited to instead The bottom of device is answered, copper-rich is formed and sticks together;Iron containing silicate minerals mutually float;Copper-rich phase metal stick together among Iron containing silicate minerals Slow cooling slag be Fe-riched phase, while generate component containing zinc and leaded component;Gold and silver component moves to copper-rich phase;
(2) separate:The copper-rich that the taking-up of artificial or Gravity separation is deposited in bottom sticks together;
Converter is sent to again after being sent to converter or converting furnace copper metallurgy, or broken magnetic separation separation metallic iron after magnetic separation separation metallic iron again Or converting furnace copper metallurgy, or after magnetic separation separates metallic iron or separates metallic iron without magnetic separation, direct-reduction, reduzate is through magnetic separation After separating metallic iron, then it is sent to converter or converting furnace copper metallurgy;The Fe-riched phase layer at middle part is as blast furnace ironmaking raw material or direct-reduction Iron-smelting raw material or iron making by smelting reduction iron material or flotation are used as copper metallurgy or direct-reduction after carrying copper raw material or magnetic separation separation metallic iron Raw material;In floatation process, float product is to return to copper metallurgy system, iron ore concentrate conduct containing copper concentrate and iron ore concentrate, copper concentrate Blast furnace ironmaking raw material or direct reduction iron making raw material or iron making by smelting reduction iron material;Wherein, in Direct Reduction, also originate in After thing magnetic separation separation, metallic iron and mine tailing are obtained, mine tailing returns to copper metallurgy system;
Direct Reduction using rotary hearth furnace, tunnel cave, underbody road, shaft furnace, rotary kiln or induction furnace as reduction apparatus, Using gas base or coal base reduction technology, gas-based reduction is natural gas and/or coal gas, coal base reduction be anthracite, bituminous coal, lignite, One or more in coking coal, coke powder or coke, reduction temperature are 900~1400 DEG C, basicity CaO/SiO2Ratio=0.8~ 1.5;
(3) the Iron containing silicate minerals phase on top is manually taken out, as blast furnace ironmaking raw material or direct reduction iron making raw material Or iron making by smelting reduction iron material:Make aggregate as cement raw material, construction material, instead of rubble, road material uses;
(4) partly component containing zinc, leaded component, component containing indium and bismuth-containing volatilize, and enter fume recovery with oxide;
(5) part sodium component, potassium component volatilization enter flue dust.
In described step S1 and S2, zinc abstraction clinker is clinker caused by zinc hydrometallurgy and clinker caused by pyrometallurgy of zinc One or both of, wherein clinker caused by zinc hydrometallurgy be zinc leaching residue, volatilization kiln slag, iron vitriol slag, iron vitriol slag after pickling, One or more in goethite slag, bloodstone slag, clinker caused by pyrometallurgy of zinc are zinc vertical retorting clinker, cyclone smelting stove One or more in slag, blast-furnace cinder, fuming furnace clinker, electric-furnace slag.
Zinc abstraction clinker is molten state, hot or cold conditions, wherein:Zinc Hydrometallurgy Residue needs drying, dewater treatment, and vortex melts Furnace slag, blast-furnace cinder, fuming furnace clinker, electroslag are obtained by smelting furnace slag notch, and volatilization kiln slag is by Rotary Kiln discharging opening Obtain, zinc vertical retorting clinker is obtained by perpendicular tank slag hole, or zinc smelting dreg is heated into molten condition.
In described step S1 and S2, the temperature (cyclone smelting slag and/or blast furnace slag) >=1100 of zinc smelting dreg is melted DEG C, temperature >=1500 DEG C of molten steel slag, molten blast furnace slag >=1300 DEG C, melt ferro-alloy cinder >=1500 DEG C, fusion of lead smelting Refine slag >=1000 DEG C.
In described step S1 and S2, the melting reaction device that slag can flow out is rotatable melting reaction device or band There is the melting reaction device of cinder notch or iron mouth.
Wherein:Described attemperator fills for dumpable melting reaction slag, thermal insulation pit.Described rotatable melting Reaction unit is converter, melting reaction slag ladle.The described melting reaction device that can be flowed out with cinder notch or iron mouth slag for etc. Ion stove, direct current electric arc furnace, ac arc furnace, mineral hot furnace, blast furnace, blast furnace, induction furnace, furnace cupola, side-blowing bath smelting furnace, Bottom blowing molten pool smelting furnace, top-blown bath smelting furnace, reverberatory furnace, Ausmelt furnace, Isa furnace, watt button can husband's bath smelting furnace, sides Blow back the one or more in converter, bottom blowing rotary furnace, top blast rotary furnace.
In described step S1, in the case of regulating and controlling to ensure above-mentioned (a) and (b) two parameters,
Metallic copper and FeO are reduced to by ensureing in slag copper and ferriferous oxide, metal Ferrum content in slag simultaneously<3%. By adding one or both of reducing agent, ferrous material containing solid carbon, in slag reducing agent dosage be in slag copper and Ferriferous oxide is reduced to metallic copper and FeO theoretical amount 110~140%;The carbon containing ferrous material is steel dust and mud and cigarette Ash, the carbon containing pre-reduced pellet of iron ore concentrate, iron ore concentrate carbonaceous metallized pellet, zinc hydrometallurgy volatilization kiln slag, coke furnace dust mud and cigarette Ash.
In described step S1 and S2, described fuel and the one or more that reducing agent is in solid, liquid or gas, Sprayed into a manner of injection, for the one or more in the oxidizing gas, nitrogen, argon gas of preheating, preheating temperature is 0~1200 ℃.Solid fuel and the one or more that reducing agent is in coal dust, flyash, coke powder, coke, bituminous coal or anthracite, are shaped as Granular or powdery or bulk, the granularity of granular material is 5~25 μm, and the granularity of granular material is≤150 μm, and liquid fuel is with going back Former agent is heavy oil, and gaseous fuel and reducing agent are one or both of coal gas and/or natural gas.
In described step S1 and S2, copper-contained material is copper ashes, nominal group process, blister copper pyro-refining slag, zinc smelting dreg, zinc Smelting ash and dirt mud, lead zinc tailings, lead metallurgical slag, lead copper matte, setting form, fire refining of crude lead slag, lead smelting ash and dirt Mud, lead-acid battery, Copper making cigarette ash and dirt mud, composition brass, cupric rubbish, containing copper circuit board, tin metallurgical slag, nickel fibers slag, tin tail One or more in ore deposit.
Wherein, copper ashes is clinker caused by " matte smelting ", clinker, pyrogenic process dilution clinker, copper caused by " blowing of copper sulphur " One or more in slag flotation tailings, wet type copper smelting slag.
Zinc smelting dreg is zinc smelting dreg caused by zinc hydrometallurgy and pyrometallurgy of zinc, including leached mud, iron vitriol slag, copper-cadmium slag, Goethite slag, bloodstone slag, volatilization kiln slag, zinc vertical retorting slag, electric furnace zinc smelting slag.
Lead metallurgical slag is fuming furnace clinker and leaded smelting slag, and " reduction of ISP imperial smelting furnaces " or " sintering deposit blast furnace is also It is former " or the leaded smelting slag of " solid-state high lead dross reduction " or " liquid high lead dross reduction technique " reducing process generation, leaded smelting slag Smelted by fuming furnace and produce leaded fuming slag.
Nickel fibers slag is Ni-B alloy slag caused by " matte smelting " technique, the dilution stove after the blowing of " nickel convering of copper ice " technique It is one or more in nickel sedimentation clinker caused by slag, top blow smelting.
Flux for metallurgy is containing CaO or SiO2Mineral and clinker, specially quartz sand, quartz sand containing gold and silver, red mud, removing sodium One or more in high calcium red mud, carbide slag, dolomite or lime stone afterwards.
Blast furnace slag, slag and ferroalloy slag are molten state, or cold conditions, wherein:Molten state clinker (lead metallurgical slag, blast furnace slag, Slag and ferroalloy slag) obtained by slag notch, or cold conditions clinker (lead metallurgical slag, blast furnace slag, slag and ferroalloy slag) is heated To molten condition.Slag be molten iron pre-desulfurization slag (desulfurization slag, desiliconization slag, dephosphorized slag), vessel slag, electroslag, VOD/VAD slags, VD slags, tundish waste.Ferro-alloy cinder is caused clinker in ferroalloy production process, including is smelted caused by carbon ferromanganese Clinker, smelt clinker caused by ferrochrome, clinker caused by smelting ferronickel, clinker caused by smelting ferrovanadium, caused by smelting duriron Clinker, smelt clinker caused by ferro-niobium, clinker caused by Smelting Ferromolybdenum.
Ferrous material is common iron ore concentrate, common iron ore concentrate DRI, common iron ore concentrate sintered ore deposit, common iron ore concentrate Pellet, common iron ore concentrate metallized pellet, the carbon containing pre-reduced pellet of common iron ore concentrate, slag, zinc smelting dreg, coke smelt cigarette After dirt and dirt mud, steel flue dust and dirt mud, nickel fibers slag, copper ashes, lead metallurgical slag, zinc smelting dreg, tin metallurgical slag, red mud, removing sodium One or more in high calcium red mud, coal dust ash, pyrite cinder.
Copper-contained material and ferrous material are hot or cold conditions, wherein hot material is direct by metallurgical furnace discharging opening or slag notch Obtain.
Zinc Hydrometallurgy Residue and dirt mud need to through being dehydrated, dry.
Steel flue dust and dirt mud drum include blast furnace gas mud, bof sludge, electric furnace dust mud, hot/cold rolled sludge, sintering dust, Pelletizing dust, go out ironworks dust, blast furnace dust, electric stove dust ash, steel rolling iron scale.
In above-mentioned raw material, zinc smelting dreg contains indium, bismuth, lead, silver and zinc with cigarette ash, lead metallurgical slag and cigarette ash;Red mud In contain sodium and potassium, steel flue dust contains indium, bismuth, silver, sodium and potassium with dirt mud, and above material has iron;Lead metallurgical slag and zinc smelting Refining slag all contains copper, and Bellamya aeruginosa contains indium and bismuth with dirt mud, and in the method for invention, indium, bismuth, sodium, potassium, zinc, lead can be with oxidations The form of thing enters flue dust, so as to be reclaimed.
Fluorine-containing material is fluorite, CaF2Or the one or more in fluorine-containing blast furnace slag.
In described step S1 and S2, copper-contained material, ferrous material and fluorine-containing material are pelletizing or granular material or system Grain;Wherein, the granularity of granular material is 5~25 μm, and the granularity of granular material is≤150 μm, and granular material is in a manner of being blown Spray into, be loaded into gas as one kind in the argon gas of preheating, nitrogen, reducibility gas (coal gas and/or natural gas), oxidizing gas Or it is a variety of, preheating temperature is 0~1200 DEG C, and described injection method is to insert slag using refractory lance or be placed in reaction slag Top or side or bottom be blown into one or more.
Copper-contained material and ferrous material are hot or cold conditions, and described hot material is the heat of the direct output from metallurgical furnace State material, hot temperature of charge are 200~1750 DEG C.
In described step S1 and S2, in slag course of reaction, copper component, gold and silver component are enriched in copper-rich phase in slag, And realize aggregation, grow up and settle, copper-rich phase include copper, white metal, matte phase, containing a variety of in ferrous components, and realize and grow up Enter Fe-riched phase with sedimentation, or part.Iron component is enriched in Fe-riched phase, realizes aggregation, grows up and settle, Fe-riched phase includes metal It is a variety of in iron, FeO phases, fayalite phase, as blast furnace ironmaking or direct-reduction or the raw material of fused reduction iron-smelting;Silicon, calcium Migrated with phosphorus component, be enriched in Iron containing silicate minerals phase;Zinc component, lead component, indium component, bismuth component respectively enter in slag Flue dust, reclaim in the form of the oxide.
In described step S1, the temperature of control mixing slag is in the method for design temperature scope:
When mixing the temperature > design temperature upper limits of slag, zinc smelting dreg, copper-contained material, ferrous material, blast furnace are added One or more in slag, slag, ferroalloy slag, flux for metallurgy or fluorine-containing material, it is therefore an objective to avoid temperature too high, protect fire resisting Material;Another effect for adding fluorine-containing material is to reduce viscosity, accelerates copper-rich phase in slag, Fe-riched phase aggregation, grows up and sink Drop, be advantageous to silicate floating.
In the step S1 and S2, when adjusting basicity, described alkaline material is pulverized limestone, high calcium is red after red mud, removing sodium It is one or more of in mud, carbide slag, dolomite dust or calcium lime powder;Described alkaline ferrous material is CaO/SiO2>=1 iron content Material;The alkaline ferrous material is alkaline sintering deposit, slag, ferroalloy slag, alkaline iron ore concentrate, alkaline pre-reduced pellet or alkali Property metallized pellet, one or more of in alkali blast furnace slag.
In the step S1 and S2, when adjusting basicity, described acid material is one in silica, flyash, gangue Kind is a variety of;Described iron-containing acidic material is CaO/SiO2≤ 1 ferrous material;Described iron-containing acidic material burns to be acid Tie ore deposit, acid iron ore concentrate, acid pre-reduced pellet, acid metal pellet, copper ashes, lead metallurgical slag, zinc smelting dreg, nickel fibers Slag, tin metallurgical slag, ferroalloy slag, the one or more of acid blast furnace slag.
In described step S1 and S2, copper-rich phase, Fe-riched phase are assembled, grow up and settle in slag, are advantageous on silicate Floating, copper-rich phase includes a variety of in copper, white metal, matte phase, ferrous components, or part is enriched in Fe-riched phase.
In described step S1, while ensureing (a) and (b) two parameters, it is sufficiently mixed mixing slag, hybrid mode To mix or being stirred naturally, it is stirred as one kind in the following manner:Argon gas stirring, nitrogen gas stirring, argon-nitrogen mix Close the one or more in gas, reducibility gas (coal gas and/or natural gas), oxidizing gas, electromagnetic agitation, mechanical agitation.
In described step S2, Direct Reduction is using rotary hearth furnace, tunnel cave, car-bottom furnace, shaft furnace, rotary kiln, sensing Stove is as reduction apparatus, and using gas base or coal base reduction technology, gas base is natural gas and/or coal gas, coal base reduction be anthracite, One or more in bituminous coal, lignite, coking coal, coke powder, coke, reduction temperature are 900~1400 DEG C, basicity CaO/SiO2Ratio =0.7~1.9.
In described step S1 and S2, oxidizing gas is the air of preheating, oxygen, oxygen-enriched air, nitrogen-oxygen, nitrogen One kind in gas-air, argon gas-air, argon-oxygen, preheating temperature are 0-1200 DEG C, and described injection method is using resistance to Fire-fighting rifle inserts slag or is placed in cupric and the reaction slag top of iron or side is blown into.
In described step S2, the type of cooling is natural cooling or rotation cooling or centrifugation cooling, and subsidence style is nature Sedimentation or spun down or centrifugal sedimentation.
In described step S2, rotating the concrete operations cooled down with centrifugation is:Device equipped with the slag after the completion of reaction Be placed on rotation platform, rotated according to certain speed, rotary speed according to slag quality and attemperator height or depth and Fixed, rotational time is depending on slag quality and slag solidification situation;Device equipped with the slag after the completion of reaction is placed in rotation Rotated on platform, it is therefore an objective to accelerate copper-rich phase, Fe-riched phase aggregation, grow up and settle, be advantageous to silicate (rich phosphorus phase) floating, contracting Settling time.
In described step S2, in the slag cooling procedure after the completion of reaction, because density is different different from mineral size, Most of copper-rich phase falls to middle and lower part, and Fe-riched phase falls to middle and upper part.
In described step S2, copper component, gold and silver component continue to migrate, are enriched in copper-rich in the slag after the completion of reaction Phase, and realize and grow up and settle, or part copper component is enriched in Fe-riched phase;Iron component continues migration, richness respectively in mixing slag Fe-riched phase is combined in, and is realized and is grown up and settle.
In described step S2, gravity separation method be separation by shaking table, sluicing or the two be combined.
Using the method for the present invention, in the slag of the Fe-riched phase finally obtained and Iron containing silicate minerals phase, Copper in Slag≤ 0.1%, the rate of recovery of iron is >=96%, and the rate of recovery of zinc is >=95%, and the rate of recovery of lead is >=95%, the rate of recovery of indium for >= 91%, golden accumulation rate is >=91%, and silver-colored accumulation rate is >=91%, and the accumulation rate of nickel is >=92%, the accumulation rate of cobalt for >= 94%, the rate of recovery of bismuth is >=91%, and the rate of recovery of sodium is >=92%, and the rate of recovery of potassium is >=93%.
Wherein, Copper in Slag refer to copper-rich be separated after slag phase, specially Fe-riched phase with Iron containing silicate minerals phase Copper content, nickel, the accumulation rate of cobalt refer to that nickel, the content of cobalt are accounted in raw material in copper-rich phase and correspond to nickel, the percentage of cobalt total amount, The accumulation rate of gold, silver refers to that the content of gold, silver in copper-rich phase accounts for the percentage of gold, silver total amount in raw material.
In order to preferably explain the present invention, in order to understand, by following examples, the present invention is described in detail.Its In, processing method used is not known what is pointed out with raw material in following examples, can use this area routine techniques, unless otherwise Illustrate, percentage used is percetage by weight in the present invention.
Embodiment 1
A kind of method for reclaiming valuable component by the mixing slag containing zinc and iron, comprises the following steps:
Step 1, clinker mixes:Zinc smelting dreg (cold conditions zinc leaching residue) is added into direct current electric arc furnace, while adds cold conditions height Clinker, VOD/VAD slags and ferro-alloy cinder caused by smelting carbon ferromanganese, the cold conditions of liquid high lead dross reduction stove contain lead smelting Slag, form mixing slag;Mixing slag is heated to molten condition, forms the reaction slag of cupric and iron, and make reaction slag Electromagnetic agitation, realize that nature mixes;The slag of monitoring reaction in real time, ensure (a) and (b) two parameters simultaneously by regulation and control, obtain Slag after the completion of reaction;
Corresponding (a):The temperature of the reaction slag of cupric and iron is 1660 DEG C, using in refractory lance intercalation reaction slag, Using nitrogen as gas is loaded into, the copper ashes of normal temperature powdery granularity≤150 μm is sprayed into, containing Bellamya aeruginosa, composition brass and cupric rubbish and cupric electricity Road plate, while add blast furnace gas mud, electric furnace dust mud, bof sludge, common iron ore concentrate, common iron ore concentrate DRI and height Stove gas ash, temperature is set to be down to 1380 DEG C;
(b):The basicity CaO/SiO of the reaction slag of cupric and iron2Ratio=1.8, silica, powder are added into reaction slag Coal ash and gangue mixture, the reaction slag basicity ratio of cupric and iron is set to be down to 1.4;Metal Ferrum content is in slag 0.5%.
Step 2, separation and recovery uses method one:
48min is incubated, slag natural subsidence, slag-gold separation, obtains molten state copper-rich phase, Fe-riched phase and Iron-containing silicate Mineral facies, while component containing zinc, leaded component, bismuth-containing component and component containing indium are generated, into fume recovery, walked as follows Suddenly:
(1) molten state Iron containing silicate minerals phase, the outer slag treatment of stove is carried out, it is empty using method F, Iron-containing silicate slag After cold, as direct reduction iron making raw material, it is reduced directly using rotary kiln, utilizes gas-based reduction technology, gas-based reduction agent For natural gas and coal gas, reduction temperature is 900 DEG C, basicity CaO/SiO2Ratio is 0.8, is separately won after reduction using magnetoelectricity stove is molten Metallic iron and slag, it is molten to divide temperature to be 1550 DEG C;
(2) molten state copper-rich phase, it is sent to converter copper metallurgy;
(3) molten state Fe-riched phase pours into attemperator, and blast furnace ironmaking raw material is used as after air cooling;
(4) component containing zinc, leaded component, bismuth-containing component, component containing indium, component containing sodium and component volatilization containing potassium enter flue dust Recovery.
The Copper in Slag finally obtained<0.1%, zinc recovery 97%, lead recovery 96%, iron recovery 98%, The rate of recovery of indium is 92%, and the rate of recovery of bismuth is 91%, and golden accumulation rate is 92%, and silver-colored accumulation rate is 91%, the recovery of sodium Rate is 93%, and the rate of recovery of potassium is 94%.
Embodiment 2
A kind of method for reclaiming valuable component by the mixing slag containing zinc and iron, comprises the following steps:
Step 1, clinker mixes:Zinc smelting dreg (the volatilization kiln slag obtained by Rotary Kiln discharging opening) is added into dumpable melt Refining reaction slag fills, while adds the ferro-alloy cinder as caused by the molten state of slag notch acquisition smelts ferrochrome, forms mixing slag; It is 20mm anthracites and char particle with oxygen-enriched air that preheating temperature is 1000 DEG C injection granularity, and Natural GasInjecting, mixing is molten Slag is heated to molten condition, forms the reaction slag of cupric and iron, and makes reaction slag electromagnetic agitation, realizes mixing;Prison in real time Reaction slag is surveyed, ensures (a) and (b) two parameters, slag after the completion of being reacted simultaneously by regulation and control;
1660 DEG C of corresponding (a) cupric and iron reaction slag temperature, using in refractory lance intercalation reaction slag, using argon gas as Carrier gas, spray into normal temperature powdery granularity≤150 μm copper ashes, containing Bellamya aeruginosa, composition brass and cupric rubbish, containing copper circuit board, common iron essence Ore deposit, common iron ore concentrate DRI and common iron ore concentrate sintered ore deposit, make temperature be down to 1400 DEG C;
(b) cupric and iron reaction slag basicity CaO/SiO2Ratio is 2.7, to reaction slag in add acid sinter ore, Acid iron ore concentrate and acid pre-reduced pellet, cupric is reacted slag basicity ratio with iron and be down to 1.6;Metal Ferrum content in slag For 2.9%.
Step 2, separation and recovery uses method two:
50min is incubated, the slag natural subsidence after the completion of reaction, slag-gold separation, obtains molten state copper-rich phase, Fe-riched phase With Iron containing silicate minerals phase, while component containing zinc, leaded component, bismuth-containing component and component containing indium are generated, into fume recovery, Carry out following steps:
(1) Iron containing silicate minerals phase and Fe-riched phase, slag treatment outside stove, slag iron making by smelting reduction are carried out using method G Iron, comprise the following steps that:
(1-1) above-mentioned iron content slag is poured into dumpable converter, and it is 20mm anthracites and cigarette that granularity is added into slag Coal, melting and reducing is carried out, the slag of monitoring reaction in real time, ensure that the temperature that following (a) reacts slag is 1350 simultaneously by regulation and control ~1670 DEG C, and (b) reaction slag basicity CaO/SiO2Ratio=0.6~2.4 two parameter, it is molten after the completion of being reacted Slag;
Corresponding (a):The temperature for reacting slag is 1400 DEG C, in temperature range;
Corresponding (b):React basicity CaO/SiO in slag2When ratio is 0.8, in alkalinity ranges.
(1-2) 200 DEG C of oxygen-enriched air of blowing preheated into slag after the completion of reaction carry out melting and reducing, are mixed after forming reduction Slag is closed, and during injection, it is 1350~1670 DEG C to ensure that (a) reacts slag temperature simultaneously by regulation and control, and (b) reaction Slag basicity CaO/SiO2Ratio=0.6~2.4 two parameter;
(1-3) is separated and recovered:
(a) slag is mixed after reducing, sedimentation slag-gold separation, obtains molten iron and slag after reduction;
(b) slag after reducing, high added value cement raw material is made using method A processing in step S2 methods one;
(c) molten iron is sent to converter or electric furnace steel making;
(d) bismuth-containing component, component containing sodium and component containing potassium enter fume recovery;
(2) molten state copper-rich phase is sent to converter copper metallurgy;
(3) component containing zinc, leaded component, bismuth-containing component, component containing indium, component containing sodium and component volatilization containing potassium enter flue dust Recovery.
The Copper in Slag finally obtained<0.1%, zinc recovery 96%, lead recovery 97%, iron recovery 96%, The rate of recovery of indium is 92%, and the rate of recovery of bismuth is 92%, and golden accumulation rate is 93%, and silver-colored accumulation rate is 93%, the recovery of sodium Rate is 94%, and the rate of recovery of potassium is 93%.
Embodiment 3
A kind of method for reclaiming valuable component by the mixing slag containing zinc and iron, comprises the following steps:
Step 1, clinker mixes:Zinc smelting dreg (cold conditions volatilization kiln slag) is added into direct current electric arc furnace, while added by converter The slag that slag notch obtains is made steel, forms mixing slag;With the oxygen that preheating temperature is 400 DEG C, injection granularity is that 20mm is smokeless Coal, char particle and coal dust, mixing slag is heated to molten condition, forms the reaction slag of cupric and iron, and it is mixed to realize slag Close;Monitoring slag in real time, ensure (a) and (b) two parameters, the slag after the completion of being reacted simultaneously by regulation and control;
Corresponding (a):The temperature of the reaction slag of cupric and iron is 1685 DEG C, and acid metal ball is added into reaction slag Group, copper smelting slag and slag containing copper converting, while add containing Bellamya aeruginosa, lead metallurgical slag, common Iron Ore Pellets, steel rolling iron oxide Phosphorus and the carbon containing pre-reduced pellet of common iron ore concentrate, make temperature be down to 1420 DEG C;
(b):The basicity CaO/SiO of the reaction slag of cupric and iron2Ratio=2.4, acid gold is added into reaction slag Belong to the mixture of pellet, cupric smelting slag and the slag containing copper converting, be down to the basicity ratio of the reaction slag of cupric and iron 1.6;Metal Ferrum content is 2.1% in slag.
Step 2, separation and recovery uses method two:
40min is incubated, slag natural subsidence, slag-gold separation, obtains molten state copper-rich phase, Fe-riched phase and Iron-containing silicate Mineral facies, while component containing zinc, leaded component, bismuth-containing component and component containing indium are generated, reclaimed, carried out as follows into flue dust Step:
(1) molten state copper-rich phase, it is sent to converter copper metallurgy;
(2) molten state Fe-riched phase and Iron containing silicate minerals are mutually used as direct reduction iron making raw material, in reduction process, part Zinc component, lead component, indium component and bismuth component volatilization enter flue dust;In Direct Reduction, using rotary hearth furnace, reduction temperature is 1200 DEG C, basicity CaO/SiO2Ratio=1.0, reducing agent are the anthracite and fine coal that granularity is≤150 μm;
(3) component containing zinc, leaded component, bismuth-containing component and component volatilization containing indium enter fume recovery.
The Copper in Slag finally obtained<0.1%, the rate of recovery of iron is 98%, and the rate of recovery of zinc is 97%, and the rate of recovery of lead is 96%, the rate of recovery of indium is 94%, and the rate of recovery of bismuth is 93%, and golden accumulation rate is 91%, and silver-colored accumulation rate is 92%.
Embodiment 4
A kind of method for reclaiming valuable component by the mixing slag containing zinc and iron, comprises the following steps:
Step 1, clinker mixes:Cold conditions zinc smelting dreg (iron vitriol slag) is added into plasma heating furnace, while adds and is obtained by slag notch The ferro-alloy cinder that converter slag, electric furnace slag and the smelting ferronickel obtained obtains, form mixing slag;Mixing slag is heated to Molten condition, cupric and iron reaction slag are formed, and make the argon gas that reaction slag blowing preheated temperature is 400 DEG C, realize mixing; The slag of monitoring reaction in real time, ensure (a) and (b) two parameters, the slag after the completion of being reacted simultaneously by regulation and control;
The temperature of the slag of corresponding (a) cupric and iron is 1670 DEG C, and red mud, pyrite cinder, firefly are added into reaction slag Stone, lead copper matte, lead-containing soot, soot containing zinc, setting form and Zinc Hydrometallurgy Residue, temperature is set to be down to 1450 DEG C;
(b) cupric answers slag basicity CaO/SiO with iron2Ratio is 2.9, adds slag containing copper converting into reaction slag, makes Cupric is down to 1.7 with iron reaction slag basicity ratio;Natural GasInjecting, and be 900 DEG C of air blown granularity with preheating temperature For 20mm char particle, metal Ferrum content is 1.8% in slag.
Step 2, separation and recovery uses method two:32min is incubated, slag natural subsidence, slag-gold separation, obtains molten state Copper-rich phase, Fe-riched phase and Iron containing silicate minerals phase, while component containing zinc, leaded component, bismuth-containing component and component containing indium are generated, Into flue dust, reclaimed in the form of an oxide, carry out following steps:
(1) molten state copper-rich phase, it is sent to converter copper metallurgy;
(2) molten state Fe-riched phase and method F, oxidation modification in Iron containing silicate minerals phase step S2 separation and recovery methods one Magnetic separation separates:1. slag is poured into insulation slag ladle, the oxygen-enriched air that preheating temperature is 900 DEG C is sprayed into slag, realizes magnet The conversion of ore deposit;2. slow cooling magnetic separation separation, obtains iron ore concentrate and mine tailing to room temperature;
(3) component containing zinc, leaded component, bismuth-containing component and component volatilization containing indium enter fume recovery.
The Copper in Slag finally obtained<0.1%, the rate of recovery of iron is 96%, and the rate of recovery of zinc is 96%, and the rate of recovery of lead is 95%, the rate of recovery of indium is 92%, and the rate of recovery of bismuth is 92%, and golden accumulation rate is 93%, and silver-colored accumulation rate is 92%.
Embodiment 5
A kind of method for reclaiming valuable component by the mixing slag containing zinc and iron, comprises the following steps:
Step 1, clinker mixes:By zinc smelting dreg (the melting cyclone smelting stove that hot zinc vertical retorting clinker, slag notch obtain Slag, melting blast-furnace cinder and electroslag) insulation slag ladle is added, while add the converter molten steel slag obtained by slag notch, shape Into mixing slag;With the air that preheating temperature is 800 DEG C, injection granularity is 20mm bituminous coal and coal dust, and mixing slag is heated to Molten condition, forms the reaction slag of cupric and iron, and reaction slag is realized mixing;The slag of monitoring reaction in real time, passes through tune Control ensures (a) and (b) two parameters, the slag after the completion of being reacted simultaneously;
Corresponding (a):The reaction slag temperature of cupric and iron is 1410 DEG C;
(b):Cupric and iron reaction slag basicity CaO/SiO2Ratio is 1.5, in claimed range;Metallic iron in slag Content is 2.2%.
Step 2, separation and recovery uses method five:
Slag after the completion of reaction is poured into insulation slag ladle, is incubated 28min, carries out slag treatment, carries out following steps:
(1) sedimentation cooling:Slag rotation after the completion of reaction is cooled to room temperature, obtains slow cooling slag;Copper-rich-white metal mutually sinks The bottom of reaction unit is dropped to, copper-rich is formed and sticks together;Iron containing silicate minerals mutually float;Copper-rich sticks together and slow cooling among silicate mineral Slag is Fe-riched phase, while generates component containing zinc, component containing indium, bismuth-containing component and leaded component;
(2) separate:The metallic copper that artificial taking-up is deposited in bottom sticks together;After the Fe-riched phase layer magnetic separation separation metallic iron at middle part, It is routed directly to converter copper metallurgy;
(3) the silicate mineral phase on top is manually taken out, silicate mine tailing is obtained, is used as cement raw material;
(4) component containing zinc, component containing indium, bismuth-containing component and leaded component volatilization, into fume recovery.
The Copper in Slag finally obtained<0.15%, the rate of recovery of iron is 98%, and the rate of recovery of zinc is 97%, the rate of recovery of lead For 96%, the rate of recovery of indium is 93%, and the rate of recovery of bismuth is 92%, and golden accumulation rate is 96%, and silver-colored accumulation rate is 93%.
Embodiment 6
A kind of method for reclaiming valuable component by the mixing slag containing zinc and iron, comprises the following steps:
Step 1, clinker mixes:Cold conditions zinc smelting dreg (iron vitriol slag, goethite slag, bloodstone slag after pickling) is added and exchanged Electric arc furnaces, while ferro-alloy cinder caused by ferro-alloy cinder caused by cold conditions smelting ferrovanadium and smelting duriron is added, formed mixed Close slag;Mixing slag is heated to molten condition, forms cupric and iron reaction slag, blowing preheated temperature is 600 DEG C of argon Gas-nitrogen mixture, mixing;The slag of monitoring reaction in real time, ensure (a) and (b) two parameter simultaneously by regulation and control, acquisition has been reacted Into rear slag;
Corresponding (a):Cupric is 1040 DEG C with iron reaction slag temperature, and it is 800 DEG C that preheating temperature is added into reaction slag Oxygen-enriched air and heavy oil, add melting slag containing copper converting, temperature is risen to 1330 DEG C;
(b):Cupric and iron reaction slag basicity CaO/SiO2Ratio is 0.1, to reaction slag in add alkaline iron ore concentrate, High calcium red mud after converter mud, alkaline pre-reduced pellet, removing sodium, cupric is reacted slag basicity ratio with iron and rise to 0.4;Slag Middle metal Ferrum content is 1.2%.
Step 2, separation and recovery uses method one:
38min is incubated, slag natural subsidence, slag-gold separation, obtains molten state copper-rich phase, Fe-riched phase and Iron-containing silicate Mineral facies, while generate component containing zinc, component containing indium, bismuth-containing component and leaded component volatilization and reclaimed into flue dust, carry out Following steps:
(1) molten state Iron containing silicate minerals mutually use the method A of step S2 separation and recovery methods one, and cement raw is directly made in water quenching Material;
(2) molten state copper-rich phase, it is sent to converter copper metallurgy;
(3) Fe-riched phase pours into direct reduction iron making after attemperator cooling;
(4) component containing zinc, component containing indium, bismuth-containing component, leaded component, component containing sodium and component volatilization containing potassium, into cigarette Dirt reclaims.
The Copper in Slag finally obtained<0.1%, the rate of recovery of iron is 97%, and the rate of recovery of zinc is 96%, and the rate of recovery of lead is 96%, the rate of recovery of indium is 93%, and the rate of recovery of bismuth is 94%, and golden accumulation rate is 93%, and silver-colored accumulation rate is 92%, sodium The rate of recovery is 93%, and the rate of recovery of potassium is 95%.
Embodiment 7
A kind of method for reclaiming valuable component by the mixing slag containing zinc and iron, comprises the following steps:
Step 1, clinker mixes:Zinc smelting dreg (cold conditions zinc vertical retorting clinker) is added into mineral hot furnace, while adds slag notch Clinker caused by clinker caused by the smelting ferro-niobium of acquisition and Smelting Ferromolybdenum, form mixing slag;Mixing slag is heated to melting Melt state, form the reaction slag of cupric and iron, and make the nitrogen that reaction slag blowing preheated temperature is 1100 DEG C, realize mixed Close;The slag of monitoring reaction in real time, ensure (a) and (b) two parameters, the slag after the completion of being reacted simultaneously by regulation and control;
Corresponding (a):The temperature of the reaction slag of cupric and iron is 1320 DEG C;
(b):The basicity CaO/SiO of the reaction slag of cupric and iron2Ratio is 0.8, in claimed range;Using 200 DEG C air spray into the μ m coal powder of granularity≤150, and spray into natural gas, metal Ferrum content is 1.5% in slag.
Step 2, separation and recovery uses method four:
32min, slag natural subsidence are incubated, slag-gold separates to obtain molten state copper-rich phase, Fe-riched phase, Iron containing silicate minerals Phase, while component containing zinc, leaded component, bismuth-containing component and component containing indium are generated, reclaimed into flue dust, walked as follows Suddenly:
(1) molten state copper-rich phase, converter copper metallurgy is sent;
(2) molten state Fe-riched phase specifically uses the method in step S2 separation and recovery method one with Iron containing silicate minerals F, after water quenching, the raw material as direct reduction iron making;
(3) component containing zinc, leaded component, bismuth-containing component and component volatilization containing indium enter fume recovery.
The Copper in Slag finally obtained<0.1%, the rate of recovery of iron is 96%, and the rate of recovery of zinc is 97%, and the rate of recovery of lead is 97%, the rate of recovery of indium is 94%, and the rate of recovery of bismuth is 95%, and golden accumulation rate is 93%, and silver-colored accumulation rate is 91%.
Embodiment 8
A kind of method for reclaiming valuable component by the mixing slag containing zinc and iron, comprises the following steps:
Step 1, clinker mixes:Zinc smelting dreg (the melting cyclone smelting clinker obtained by slag notch) is added into blast furnace, The blast furnace slag and electric furnace slag obtained by slag notch is added simultaneously, forms mixing slag;It is 600 DEG C of air with preheating temperature, Injection granularity is 20mm bituminous coal and coal dust, and mixing slag is heated into molten condition, forms the reaction slag of cupric and iron, and make React slag and realize mixing;The slag of monitoring reaction in real time, ensure (a) and (b) two parameters simultaneously by regulation and control, acquisition has been reacted Slag after;
Corresponding (a):The temperature of the reaction slag of cupric and iron is 1330 DEG C;
(b):The basicity CaO/SiO of the reaction slag of cupric and iron2Ratio is 1.0, in claimed range;It is golden in slag It is 2.6% to belong to iron content.
Step 2, separation and recovery uses method three:
Be incubated 19min, slag natural subsidence, the separation of slag-gold, acquisition copper-rich phase and middle and upper part Iron containing silicate minerals phase and Fe-riched phase, while component containing zinc, leaded component, bismuth-containing component and component containing indium are generated, reclaimed, carried out as follows into flue dust Step:
(1) molten state Iron containing silicate minerals phase slag, smelting apparatus is poured into, carries out the outer slag treatment of stove, it is specific using step Method B in rapid S2 separation and recovery method one, the slag of middle and upper part is all returned to cupric reaction slag, as hot smelting Golden flux, adjustment cupric reaction slag composition, control cupric reaction slag temperature;
(2) molten state copper-rich phase, converter or converting furnace copper metallurgy are sent to;
(3) component containing zinc, leaded component, bismuth-containing component and component volatilization containing indium enter fume recovery;
(4) after Fe-riched phase carries out water quenching or air cooling or pours into attemperator slow cooling, as blast furnace ironmaking raw material or directly also Original ironmaking.
The Copper in Slag finally obtained<0.1%, the rate of recovery of iron is 97%, and the rate of recovery of zinc is 95%, and the rate of recovery of lead is 96%, the rate of recovery of indium is 93%, and the rate of recovery of bismuth is 92%, and golden accumulation rate is 91%, and silver-colored accumulation rate is 92%.
Embodiment 9
A kind of method for reclaiming valuable component by the mixing slag containing zinc and iron, comprises the following steps:
Step 1, clinker mixes:Zinc smelting dreg (the melting blast-furnace cinder obtained by slag notch) joining side will be blown back and turned Stove, while the molten state blast furnace slag and VD slags obtained by slag notch is added, form mixing slag;Mixing slag is heated to melting State, the slag of cupric and iron is formed, blowing preheated temperature is 800 DEG C of argon gas, slag is realized mixing;Monitoring reaction in real time Slag, ensure (a) and (b) two parameters, the slag after the completion of being reacted simultaneously by regulation and control;
Corresponding (a):The slag temperature of cupric and iron is 1340 DEG C;
(b):The slag basicity CaO/SiO of cupric and iron2Ratio is 1.2, is met the requirements;It it is 900 DEG C with preheating temperature Air blown granularity be 20mm char particle, metal Ferrum content is 2.7% in slag.
Step 2, separation and recovery uses method two:
30min, slag natural subsidence are incubated, slag-gold separates, and obtains molten state copper-rich phase, the rich iron of middle and upper part of bottom The iron content slag of phase and Iron containing silicate minerals phase, while component containing zinc, leaded component, bismuth-containing component and component containing indium are generated, Into fume recovery, following steps are carried out:
(1) the iron content slag of middle and upper part pours into smelting apparatus, using method C in step S2 separation and recovery methods one, middle and upper part Slag pours devitrified glass;
(2) bottom molten state copper-rich phase, it is sent to converter copper metallurgy;
(3) component containing zinc, leaded component, bismuth-containing component and component volatilization containing indium enter fume recovery.
The Copper in Slag finally obtained<0.1%, the rate of recovery of iron is 98%, and the rate of recovery of zinc is 96%, and the rate of recovery of lead is 97%, the rate of recovery of indium is 94%, and the rate of recovery of bismuth is 93%, and golden accumulation rate is 90%, and silver-colored accumulation rate is 92%.
Embodiment 10
A kind of method for reclaiming valuable component by the mixing slag containing zinc and iron, comprises the following steps:
Step 1, clinker mixes:Zinc smelting dreg (the melting electroslag obtained by slag notch) adds thermal insulation pit, adds simultaneously Enter by the molten steel slag that slag notch obtains and melting cupric smelting slag, form mixing slag;It is 200 DEG C oxygen-enriched with preheating temperature Air, granularity≤150 μm bituminous coal is blown, mixing slag is heated to molten condition, form cupric reaction slag, and melt reaction Slag realizes mixing;The slag of monitoring reaction in real time, ensure (a) and (b) two parameters simultaneously by regulation and control, after the completion of being reacted Slag;
Corresponding (a):The temperature of cupric reaction slag is 1430 DEG C;
(b):Cupric reacts the basicity CaO/SiO of slag2Ratio is 1.5, in claimed range;Metallic iron contains in slag Measure as 1.9%.
Step 2, separation and recovery uses method five:
Slag after the completion of reaction is subjected to following steps:
(1) sedimentation cooling:48min is incubated, the slag after the completion of reaction is cooled to room temperature, obtains slow cooling slag;Copper-rich phase sinks The bottom of reaction unit is dropped to, copper-rich is formed and sticks together;Iron containing silicate minerals mutually float;Copper-rich phase metal stick together with silicate mineral Between slow cooling slag be Fe-riched phase, while generate component containing zinc and leaded component;
(2) separate:The copper-rich that artificial taking-up is deposited in bottom sticks together;After the Fe-riched phase magnetic separation separation metallic iron at middle part, send Toward converter copper metallurgy;
(3) the Iron containing silicate minerals phase on top is manually taken out, silicate mine tailing is obtained, is used as cement raw material;
(4) component containing zinc, leaded component, bismuth-containing component and component containing indium enter fume recovery.
The Copper in Slag finally obtained<0.1%, the rate of recovery of iron is 97%, and the rate of recovery of zinc is 97%, and the rate of recovery of lead is 96%, the rate of recovery of indium is 94%, and the rate of recovery of bismuth is 91%, and golden accumulation rate is 93%, and silver-colored accumulation rate is 92%.
It is to be appreciated that the description carried out above to the specific embodiment of the present invention is simply to illustrate that the skill of the present invention Art route and feature, its object is to allow those skilled in the art to understand present disclosure and implement according to this, but The present invention is not limited to above-mentioned particular implementation.Every various change made within the scope of the claims is repaiied Decorations, it should all cover within the scope of the present invention.

Claims (10)

  1. It is 1. a kind of by the method containing zinc and the mixing slag recovery valuable component of iron, it is characterised in that to comprise the following steps:
    S1, clinker mixing:By zinc smelting dreg, add in the melting reaction device that attemperator or slag can flow out, and add lead One or more in metallurgical slag, blast furnace slag, slag and ferroalloy slag, are stirred, and form mixing slag;
    Mixing slag is heated to molten condition, reaction slag is formed, is well mixed, the slag of monitoring reaction in real time, passes through regulation and control Make reaction slag while meet two conditions of a and b, the slag after the completion of being reacted;
    Wherein, a:The temperature of regulation and control reaction slag is 1100~1450 DEG C;
    b:The basicity CaO/SiO of regulation and control reaction slag2Ratio=0.15~1.8;
    S2, separation and recovery:The slag that step S1 is obtained, 5~50min is incubated, sedimentation separation, obtains middle and upper part Iron-containing silicate ore deposit Thing phase, bottom copper-rich phase, middle and lower part Fe-riched phase, while generate component containing zinc, leaded component, the cigarette of component containing indium and bismuth-containing component Dirt, the migration of gold and silver component, enrichment enter copper-rich phase;Each phase is recycled.
  2. It is 2. according to claim 1 by the method containing zinc and the mixing slag recovery valuable component of iron, it is characterised in that: In step S1, condition a regulation and control method is:
    When the temperature of reaction slag<At 1100 DEG C, by the heating function of reaction unit itself, or into slag add fuel or Fused zinc smelted furnace cinder, molten copper slag, melting nickel fibers slag, fusion of lead metallurgical slag, molten blast furnace slag, molten steel slag, molten iron The one or more of Fe alloy slag, when spraying into fuel, while the oxidizing gas of preheating is sprayed into, reach the temperature of reaction slag In the range of 1100~1450 DEG C;
    When the temperature of reaction slag>At 1450 DEG C, copper-contained material, zinc smelting dreg, lead-containing material, nickel smelting are added into reaction slag The one or more in slag, blast furnace slag, slag, ferroalloy slag, flux for metallurgy, ferrous material, fluorine-containing material are refined, make mixing slag Temperature reach in the range of 1100~1450 DEG C;
    In step sl, condition b regulation and control method is:
    As the basicity CaO/SiO of reaction slag2Ratio<When 0.15, alkaline material and/or alkaline iron content are added into reaction slag Material;
    As the basicity CaO/SiO of reaction slag2Ratio>When 1.8, acid material and/or iron-containing acidic thing is added into reaction slag Material.
  3. It is 3. according to claim 1 by the method containing zinc and the mixing slag recovery valuable component of iron, it is characterised in that:Institute Attemperator is stated as dumpable melting reaction slag filling or thermal insulation pit;
    The melting reaction device that the slag can flow out is rotatable melting reaction device or the melting with cinder notch or iron mouth Reaction unit;Wherein, the rotatable melting reaction device is converter, melting reaction slag ladle;It is described to carry cinder notch or iron mouth The melting reaction device that slag can flow out be plasma heating furnace, direct current electric arc furnace, ac arc furnace, mineral hot furnace, blast furnace, blast furnace, Induction furnace, furnace cupola, side-blowing bath smelting furnace, bottom blowing molten pool smelting furnace, top-blown bath smelting furnace, reverberatory furnace, Ausmelt furnace, Isa furnace, watt button can be in husband's bath smelting furnace, side-blown rotary furnace, bottom blowing rotary furnace, top blast rotary furnace one or more.
  4. It is 4. according to claim 1 by the method containing zinc and the mixing slag recovery valuable component of iron, it is characterised in that: In the step S1, while meeting the condition a and b, it should meet that copper and ferriferous oxide are reduced to gold in the slag simultaneously Belong to copper and FeO, metal Ferrum content in slag<3%.
  5. It is 5. according to claim 1 by the method containing zinc and the mixing slag recovery valuable component of iron, it is characterised in that:Institute It is one or both of clinker caused by zinc hydrometallurgy, clinker caused by pyrometallurgy of zinc to state zinc smelting dreg;Zinc smelting dreg is molten Melt state or hot or cold conditions, melting pyrometallurgy of zinc slag is obtained by cyclone smelting stove, blast furnace, fuming furnace, electric furnace slag notch, hot Zinc smelting dreg is obtained by Rotary Kiln discharging opening, perpendicular tank slag hole, or zinc smelting dreg is heated into molten condition;
    Wherein, clinker caused by the zinc hydrometallurgy is siderotil after zinc leaching residue, volatilization kiln slag, copper-cadmium slag, iron vitriol slag, pickling One or more in slag, goethite slag, bloodstone slag, clinker caused by the pyrometallurgy of zinc are zinc vertical retorting clinker, vortex One or more in smelting slag, blast-furnace cinder, fuming furnace clinker, electroslag;Clinker caused by the zinc hydrometallurgy is equal Drying, dewater treatment need to be passed through;Cyclone smelting clinker, blast-furnace cinder, fuming furnace clinker, electroslag are obtained by smelting furnace slag notch , volatilization kiln slag is obtained by Rotary Kiln discharging opening, and zinc vertical retorting clinker is obtained by perpendicular tank discharging opening.
  6. It is 6. according to claim 2 by the method containing zinc and the mixing slag recovery valuable component of iron, it is characterised in that:Institute State copper-contained material be copper ashes, nominal group process, blister copper pyro-refining slag, zinc smelting dreg, zinc abstraction cigarette ash and dirt mud, lead zinc tailings, Lead metallurgical slag, lead copper matte, setting form, fire refining of crude lead slag, lead smelting ash and dirt mud, lead-acid battery, Copper making cigarette ash with Dirt mud, composition brass, cupric rubbish, containing the one or more in copper circuit board, tin metallurgical slag, nickel fibers slag, tailing;
    The copper ashes is clinker caused by " matte smelting ", clinker, pyrogenic process dilution clinker, copper ashes flotation caused by " blowing of copper sulphur " One or more in tailings, wet type copper smelting slag;
    The flux for metallurgy is containing CaO or SiO2Mineral and clinker, preferably quartz sand, quartz sand containing gold and silver, red mud, removing sodium One or more in high calcium red mud, carbide slag, dolomite or lime stone afterwards;
    The ferrous material is common iron ore concentrate, common iron ore concentrate DRI, common iron ore concentrate sintered ore deposit, common iron ore concentrate Pellet, common iron ore concentrate metallized pellet, the carbon containing pre-reduced pellet of common iron ore concentrate, slag, zinc smelting dreg, coke smelt cigarette After dirt and dirt mud, steel flue dust and dirt mud, nickel fibers slag, copper ashes, lead metallurgical slag, zinc smelting dreg, tin metallurgical slag, red mud, removing sodium One or more in high calcium red mud, coal dust ash, pyrite cinder;
    The nickel fibers slag is Ni-B alloy slag caused by " matte smelting " technique, the dilution stove after the blowing of " nickel convering of copper ice " technique It is one or more in nickel sedimentation clinker caused by slag, top blow smelting;
    The lead metallurgical slag is fuming furnace clinker and leaded smelting slag, wherein, " reduction of ISP imperial smelting furnaces " or " sintering deposit drum Wind furnace reduction " or " solid-state high lead dross reduction " or " liquid high lead dross reduction " technique produce leaded smelting slag, and leaded smelting slag leads to Cross fuming furnace and smelt the leaded fuming slag of generation;
    The steel flue dust and dirt mud drum include blast furnace gas mud, bof sludge, electric furnace dust mud, hot/cold rolled sludge, sintering dust, Pelletizing dust, go out ironworks dust, blast furnace dust, electric stove dust ash, steel rolling iron scale;
    The blast furnace slag, slag and ferroalloy slag are molten state or cold conditions, wherein, blast furnace slag, slag and the ferroalloy of molten state Slag is obtained by slag notch, or the blast furnace slag, slag and ferroalloy slag of cold conditions are heated into molten condition;The slag is that molten iron is pre- One or more in desulfurization slag, vessel slag, electroslag, VOD/VAD slags, VD slags, tundish waste;The ferro-alloy cinder is Caused clinker in ferroalloy production process, including smelt clinker caused by carbon ferromanganese, smelt clinker caused by ferrochrome, smelt Clinker caused by ferronickel, clinker caused by smelting ferrovanadium, clinker caused by smelting duriron, smelt clinker and smelting caused by ferro-niobium Clinker caused by molybdenum-iron;
    The fluorine-containing material is fluorite, CaF2, one or more in fluorine-containing blast furnace slag;
    The copper-contained material, ferrous material and fluorine-containing material are pelletizing or granular material or granulation;Wherein, the grain of granular material ≤ 150 μm of degree, granular material granularity is 5-25mm, and granular material is sprayed into a manner of being blown, and granular material is to be blown or feed intake Mode add, be loaded into gas as the argon gas of preheating, nitrogen, reducibility gas, the one or more in oxidizing gas, preheating Temperature is 0-1200 DEG C.
  7. It is 7. according to claim 2 by the method containing zinc and the mixing slag recovery valuable component of iron, it is characterised in that:Institute Alkaline material is stated as one or more in high calcium red mud, carbide slag, dolomite dust or calcium lime powder after pulverized limestone, red mud, removing sodium; The alkaline ferrous material is alkaline sintering deposit, slag, ferroalloy slag, alkaline iron ore concentrate, alkaline pre-reduced pellet, alkalinous metal One or more in pellet, alkali blast furnace slag;
    The acid material is the one or more in silica, flyash, gangue;The iron-containing acidic material sinters to be acid Ore deposit, acid iron ore concentrate, acid pre-reduced pellet, acid metal pellet, copper ashes, lead metallurgical slag, zinc smelting dreg, nickel fibers slag, One or more in tin metallurgical slag, ferroalloy slag, acid blast furnace slag.
  8. 8. according to any described methods for reclaiming valuable component by the mixing slag containing zinc and iron of claim 1-7, its feature It is:Separation and recovery in step s 2 is handled as follows:
    Containing copper-rich phase described in hot or cold conditions, after being sent to converter or converting furnace copper metallurgy, or slow cooling crushing-magnetic selection separation metallic iron Converter or converting furnace copper metallurgy are sent to again, or after magnetic separation separates metallic iron or separates metallic iron without magnetic separation, are reduced directly, reduction Product is after magnetic separation separates metallic iron, then is sent to converter or converting furnace copper metallurgy;
    The component containing zinc, leaded component, bismuth-containing component and component volatilization containing indium, in the form of an oxide into fume recovery;
    Containing the Iron containing silicate minerals phase and/or the Fe-riched phase, slag is carried out using any of following methods A-G Processing:
    Method A:After water quenching or air cooling, cement raw material is directly used in:
    Method B:Return in reaction mixing slag and be used as hot flux for metallurgy:
    Method C:For pouring devitrified glass or as mineral wool;
    Method D:The iron content slag of the Iron containing silicate minerals phase and/or the Fe-riched phase is retained in melting reaction device Or slag is poured into attemperator, into iron content slag, it is blown into temperature and is 0~1200 DEG C of preheating oxidizing gas, and ensure Silicate slag temperature>1460℃;When slag ferrous oxide content<1%, the slag after being aoxidized;It is molten after the oxidation Slag Direct Air-Cooled or water quenching, as the additive or clinker in slag cements, cement regulator, manufacture of cement;
    Method E:For producing the clinker of high added value, method is as follows:
    E-1, the iron content slag of the Iron containing silicate minerals phase and/or the Fe-riched phase is retained in melting reaction device or Slag is poured into attemperator, into slag, adds molten steel slag, lime, lime stone, ferro-alloy cinder, flyash, basic iron One or more after lean ore, bauxite, molten blast furnace slag, red mud, removing sodium in high calcium red mud or carbide slag, are sufficiently mixed, obtain Obtain slag mixed material;
    E-2, preheating temperature is blown into as 0~1200 DEG C of oxidizing gas into the slag mixed material, and ensure that slag mixes Close temperature of charge>1460℃;Work as ferrous oxide content<1%, the slag after being aoxidized;
    E-3, to the slag after the oxidation, carry out air cooling or water quenching, the clinker of high added value be made;
    Method F:The iron content slag of the Iron containing silicate minerals phase and/or the Fe-riched phase is as blast furnace ironmaking raw material or directly Reduction iron production raw material:By iron content slag air cooling, water quenching or the slow cooling of the Iron containing silicate minerals phase and/or the Fe-riched phase Afterwards, as blast furnace ironmaking or direct reduction iron making raw material, after direct-reduction, using molten point of magnetic separation separation or electric furnace, magnetic separation product For metallic iron and mine tailing, molten point of electric furnace, product is molten iron and slag;
    Or, after the iron content slag of the Iron containing silicate minerals phase and/or the Fe-riched phase is poured into attemperator, use is following Method is separated:The modified magnetic separation separation of slag:Slag into attemperator, it is 0~1200 DEG C to be blown into preheating temperature Oxidizing gas, and ensure slag temperature>1250 DEG C, complete the conversion of magnetic iron ore in slag;By the slag slow cooling after oxidation extremely Room temperature, crush, magnetic separation, product is magnetite concentrate and mine tailing, and mine tailing is as construction material;
    Method G:The iron content slag fused reduction iron-smelting of the Iron containing silicate minerals phase and/or the Fe-riched phase, including it is as follows Step:
    G-1, the iron content slag of the Iron containing silicate minerals phase and/or the Fe-riched phase is retained in melting reaction device or Slag is poured into attemperator, ferrous material, reducing agent are added into iron content slag, carries out melting and reducing, in real time monitoring reaction Slag, meet following condition simultaneously by regulation and control:The temperature for reacting slag is 1350~1670 DEG C and the basicity of reaction slag CaO/SiO2Ratio=0.6~2.4, the slag after the completion of being reacted;
    G-2, the oxidizing gas into slag after blowing preheated carry out melting and reducing, the slag formed after reduction, wherein:Oxidation Property gas preheating temperature be 0~1200 DEG C, and during injection, meet following condition simultaneously by regulation and control:Reaction is completed The temperature of slag afterwards is 1350~1670 DEG C of basicity CaO/SiO with the slag after the completion of reaction2Ratio=0.6~2.4;
    G-3, separated and recovered using one kind in following two methods:
    Method I:Mixing slag after reduction is poured into insulation slag ladle, is slowly cooled to room temperature, obtains slow cooling slag;Metallic iron settles To the bottom of reaction unit, form iron and stick together;By containing metal iron layer in remaining slow cooling slag, 20~400 μm of granularity is crushed to, ore grinding, Residual metallic iron and mine tailing are isolated in magnetic separation;
    Method II:Mixing slag after reduction, cooling-sedimentation, slag-gold separation, obtain molten iron and the slag after reduction;After reduction Slag, according to the one or more in A~E, carry out slag treatment;Molten iron is sent to converter or electric furnace steel making;
    Or, containing the Fe-riched phase water quenching or air cooling or pour into attemperator slow cooling or acquisition is combined with gravity treatment through manual sorting, Copper raw material or magnetic separation separation are carried as blast furnace ironmaking raw material or direct reduction iron making raw material or iron making by smelting reduction iron material or flotation As copper metallurgy or the raw material of direct reduction iron making after metallic iron;In floatation process, float product is containing copper concentrate and iron ore concentrate, copper Concentrate returns to copper metallurgy system, and iron ore concentrate is as blast furnace ironmaking raw material or direct reduction iron making raw material or iron making by smelting reduction iron material; Wherein, in Direct Reduction, after reduzate magnetic separation separation, metallic iron and mine tailing are obtained, mine tailing returns to copper metallurgy system;
    The Direct Reduction is using the conduct of any of rotary hearth furnace, tunnel cave, car-bottom furnace, shaft furnace, rotary kiln, induction furnace Reduction apparatus, using gas base or coal base reduction technology, gas base is natural gas and/or coal gas, coal base be anthracite, bituminous coal, lignite, One or more in coking coal, coke powder, coke, reduction temperature are 900~1400 DEG C, basicity CaO/SiO2Ratio=0.8~ 1.5。
  9. It is 9. according to claim 8 by the method containing zinc and the mixing slag recovery valuable component of iron, it is characterised in that:Institute In the step S2 stated, the type of cooling is natural cooling or rotation cooling or centrifugation cooling, and subsidence style is natural subsidence or rotation Sedimentation or centrifugal sedimentation;
    It is described to be well mixed to mix or being stirred naturally, it is stirred and is mixed for argon gas stirring, nitrogen gas stirring, nitrogen-argon gas Close the one or more in gas agitating, reducibility gas stirring, oxidizing gas stirring, electromagnetic agitation, mechanical agitation.
  10. It is 10. according to claim 8 by the method containing zinc and the mixing slag recovery valuable component of iron, it is characterised in that: The fuel and the one or more that reducing agent is in solid, liquid or gaseous fuel, are sprayed into, institute in a manner of being blown or feeding intake State injection and be loaded into gas as the one or more in the oxidizing gas of preheating, nitrogen or argon gas, the temperature of the preheating for 0~ 1200℃;
    The solid fuel and the one or more that reducing agent is in coal dust, coke powder, coke, flyash, bituminous coal or anthracite, shape Shape is granular or powdery, and granular material granularity is 5~25mm, and granular material granularity is≤150 μm, the liquid fuel and reduction Agent is heavy oil, and the gaseous fuel and reducing agent are coal gas and/or natural gas;
    The oxidizing gas is the air of preheating, oxygen, oxygen-enriched air, argon gas-air, argon-oxygen, nitrogen-air, nitrogen One kind in gas-oxygen.
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CN108676942A (en) * 2018-05-18 2018-10-19 廖辉明 The materials such as a kind of iron content and/or zinc lead bronze tin cooperate with processing recovery method with molten steel slag
CN110423889A (en) * 2019-08-21 2019-11-08 安徽工业大学 A kind of hot galvanizing line alkali cleaning sewage sludge harmlessness disposing and resource utilization method
CN110904340A (en) * 2019-12-10 2020-03-24 武翠莲 Method for removing harmful elements and impurities in iron-containing mixture by centrifugation
CN111647704A (en) * 2020-05-19 2020-09-11 北京科技大学 Zinc recovery method based on HIsmelt smelting reduction furnace

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CN106755656A (en) * 2016-12-10 2017-05-31 东北大学 A kind of method that slag metallurgy one-step method is reclaimed
CN106755652A (en) * 2016-12-10 2017-05-31 东北大学 A kind of method that titanium-containing slag metallurgy one-step method is reclaimed
CN106755651A (en) * 2016-12-10 2017-05-31 东北大学 A kind of method reclaimed containing rare earth and/or niobium slag metallurgy one-step method

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CN106755654A (en) * 2016-12-10 2017-05-31 东北大学 A kind of method of slag metallurgy melting also original production

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108676942A (en) * 2018-05-18 2018-10-19 廖辉明 The materials such as a kind of iron content and/or zinc lead bronze tin cooperate with processing recovery method with molten steel slag
CN110423889A (en) * 2019-08-21 2019-11-08 安徽工业大学 A kind of hot galvanizing line alkali cleaning sewage sludge harmlessness disposing and resource utilization method
CN110904340A (en) * 2019-12-10 2020-03-24 武翠莲 Method for removing harmful elements and impurities in iron-containing mixture by centrifugation
CN111647704A (en) * 2020-05-19 2020-09-11 北京科技大学 Zinc recovery method based on HIsmelt smelting reduction furnace

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