CN107699704A - A kind of method by cupric and the mixing slag recovery valuable component of iron - Google Patents

A kind of method by cupric and the mixing slag recovery valuable component of iron Download PDF

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Publication number
CN107699704A
CN107699704A CN201710936823.9A CN201710936823A CN107699704A CN 107699704 A CN107699704 A CN 107699704A CN 201710936823 A CN201710936823 A CN 201710936823A CN 107699704 A CN107699704 A CN 107699704A
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slag
iron
copper
smelting
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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Priority to PCT/CN2017/115649 priority patent/WO2019071794A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B3/00—General features in the manufacture of pig-iron
    • C21B3/04—Recovery of by-products, e.g. slag
    • C21B3/06—Treatment of liquid slag
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C22B7/004—Dry processes separating two or more metals by melting out (liquation), i.e. heating above the temperature of the lower melting metal component(s); by fractional crystallisation (controlled freezing)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The present invention relates to a kind of method by cupric and the mixing slag recovery valuable component of iron, it includes S1, clinker mixing：Copper ashes is added in melting reaction device, while one or more formed added in lead metallurgical slag, blast furnace slag, slag and ferroalloy slag mixes slag；Slag is heated to molten condition and forms reaction slag, is well mixed, monitors the reaction slag in real time, while makes the reaction slag after mixing by regulation and control, while meets condition a and condition b, obtains reacted slag；S2, separation and recovery.The present invention realizes the comprehensive utilization for realizing copper component in Non-ferrous metallurgical slag and Ferrous Metallurgy clinker, iron component, zinc component, lead component, gold, silver, phosphorus, calcium and silicon components valuable component, solves current clinker bulk deposition, problem of environmental pollution.

Description

A kind of method by cupric and the mixing slag recovery valuable component of iron
Technical field
The invention belongs to slag metallurgical technology field, and in particular to a kind of to reclaim valuable group by the mixing slag of cupric and iron The method divided.
Background technology
China is metallic copper, metallic lead, steel and the most country of ferroalloy yield in the world.The pyrometallurgical smelting process of copper " matte smelting-Copper Matte Converting " produces copper ashes, and copper ashes is the first solid waste in heavy non-ferrous metallurgy.The pyrometallurgical smelting mistake of lead Journey " sintering-blast furnace reduction-fuming furnace " directly refines the technique productions such as splicer's skill " oxidation blowing-high lead dross reduction-fuming furnace " Lead metallurgical slag is given birth to.Blast furnace slag, slag, ferro-alloy cinder are generated in steel manufacture process, is the first solid waste.
Copper ashes includes cupric smelting slag, slag containing copper converting, pyrometallurgical dilution waste, copper ashes flotation tailing, wet type copper smelting slag. During cupric smelting slag results from " matte smelting ", not only containing copper, iron, zinc, nickel, noble metal, and contain high level SiO2, the flux for metallurgy such as CaO, give off more than 20,000,000 tons every year, accumulative stockpiling is up to more than 200,000,000 tons at present.With metallurgy of copper skill The continuous development of art, traditional copper metallurgy technique just gradually by flash smelting, Rouyn-Noranda, Wa Niukefu, Ai Sa, Ausmelt, Mitsubishi, The new technologies such as Jin Feng, bottom blowing substitute, and copper content is high far above current 0.2%% copper mine payable grade, iron content up to 20% in slag Up to 50%, much larger than the average grade for smelting iron ore 29wt%.Also contain noble metal in slag, copper weld pool slag is a kind of important two Secondary resource.The molten copper smelting slag temperature released by smelting furnace is higher than 1100 DEG C, is important physics thermal resource.
" Copper Matte Converting " produces slag containing copper converting and (bessemerizes slag, flash blowing slag, top Bessemer blow slag, low blown converter to blow Refine slag etc.), copper content reaches 35% in slag, and iron content is up to 55%, also containing valuable components such as zinc, lead, noble metals.Melting contains Copper converting slag is also important physics thermal resource.
Cupric smelting slag uses Returning smelting stove or pyrogenic process dilution or beneficiation method, dilution or ore dressing effect with slag containing copper converting Fruit is bad, contains substantial amounts of heavy metal after pyrogenic process dilution or after flotation in copper ashes, can be to surrounding enviroment after a large amount of accumulations for a long time Pollute.After the dilution of copper ashes pyrogenic process or ore dressing, Copper in Slag>More than 0.4%, higher than the payable grade 0.2% of copper.Higher slag Cupric, it is unfavorable for follow-up reduction iron production.In reduction process, copper easily reduces and enters the pig iron.Steel can be reduced during more than 0.3% The weldability of material, and cause " hot-short " phenomenon of steel, make to crack during rolling.
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 contains the components such as copper, gold, silver, iron, zinc, lead, is important secondary resource. Lead metallurgical slag temperature is important physics thermal resource at >=1050 DEG C.
Blast furnace slag, slag and ferro-alloy cinder contain the metallic iron, ferriferous oxide, SiO of high level2, CaO, MgO etc. have Valency component is important secondary resource；Molten slag temperature >=1300 DEG C are given off by blast furnace, converter and ferro-alloy furnace, melted Blast furnace slag, molten steel slag and melting ferro-alloy cinder are also important physics thermal resource.These physics thermal resources can not be sharp very well With, and the accumulation of a large amount of slags not only occupies the space relatively arrived, and also brings serious environmental pollution.
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 reclaims valuable component by the mixing slag of cupric and iron Method.This method reaction time is short, technological process is short, metal recovery rate is high, production cost is low, treating capacity is big, it is environment-friendly, Economic well-being of workers and staff is high, can effectively solve Metallurgical resources and heat energy high efficiente callback Utilizing question；And problem of environmental pollution.The present invention provides Be a kind of new slag metallurgical technology, not only reduce Copper in Slag make, cupric in slag<0.1wt%, and realize copper, gold, silver, The high efficiente callback of iron, zinc, lead, indium, bismuth, sodium, potassium component, obtain low copper ferrous material (iron ore concentrate and the pig iron).
(2) technical scheme
In order to achieve the above object, the main technical schemes that the present invention uses include：
A kind of method that valuable component is reclaimed by the slag of cupric and iron, it comprises the following steps：
S1, clinker mixing：Copper ashes is added in melting reaction device, while adds lead metallurgical slag, blast furnace slag, slag and iron One or more formed in Fe alloy slag mixes slag；The mixing slag is heated to molten condition and forms reaction slag, mixing Uniformly, the slag of monitoring reaction in real time, make the reaction slag by regulation and control, while meet condition a and condition b, after being reacted Slag；
Wherein, the condition a is that slag temperature is 1050~1450 DEG C；
The condition b is the basicity CaO/SiO of slag2Ratio=0.15~1.5；
S2, separation and recovery：The reacted slags of step S1, are incubated 5~50min, sedimentation, and separation obtains the richness of bottom Copper phase, the Fe-riched phase at middle part and the Iron containing silicate minerals phase on top, while the flue dust of component containing zinc and leaded component is generated, gold Silver components enrichment enters copper-rich phase；Each phase is recycled.
Method as described above, it is preferable that in the step S1, the method for condition a regulation and control is：
As 1050 DEG C of the temperature ＜ of the reaction slag, using the heating function of reaction unit itself, or into slag Add fuel or molten copper slag, fusion of lead metallurgical slag, molten blast furnace slag, molten steel slag or the one kind or more for melting ferroalloy slag Kind, when spraying into fuel, while oxidizing gas is sprayed into, the temperature of reaction slag is reached 1050~1450 DEG C；
As 1450 DEG C of the temperature ＞ of the reaction slag, copper-contained material, nickel fibers slag, blast furnace are added into reaction slag One or more in slag, slag, ferroalloy slag, flux for metallurgy, ferrous material or fluorine-containing material, reach the temperature of mixing slag To 1050~1450 DEG C；
It is for the condition b methods regulated and controled：
As basicity CaO/SiO in the reaction slag2Ratio<When 0.15, to reaction slag in add alkaline material and/or Alkaline ferrous material；
When reacting basicity CaO/SiO in slag2Ratio>When 1.5, acid material and/or acidity are added into reaction slag Ferrous material.
Method as described above, it is preferable that the reaction unit be attemperator or rotatable melting reaction device or The melting reaction device that can be flowed out with cinder notch or iron mouth slag；Wherein, the attemperator is dumpable melting reaction slag Filling or thermal insulation pit；
The rotatable melting reaction device is converter, melting reaction slag ladle；
The melting reaction device that can be flowed out with cinder notch or iron mouth slag is plasma heating furnace, direct current electric arc furnace, exchange Electric arc furnaces, mineral hot furnace, blast furnace, blast furnace, induction furnace, furnace cupola, side-blowing bath smelting furnace, bottom blowing molten pool smelting furnace, top blast melt Pond smelting furnace, reverberatory furnace, Ausmelt furnace, Isa furnace, watt button can husband's bath smelting furnace, side-blown rotary furnace, bottom blowing rotary furnace, tops Blow back converter.
Method as described above, it is preferable that in the step S1, while meeting the condition a and b, should expire simultaneously Foot, controls that the slag keeps Cu oxide and ferriferous oxide is reduced to metallic copper and FeO, metal Ferrum content in slag<3%, By adding one or both of reducing agent, carbon containing ferrous material, wherein, the dosage of the reducing agent 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 or coke furnace dust mud and cigarette Ash.
Method as described above, it is preferable that the copper ashes be cupric smelting slag, slag containing copper converting, pyrometallurgical dilution waste, One or more of in flotation tailings, wet type copper smelting slag, cupric smelting slag results from " matte smelting " of the pyrometallurgical smelting process of copper Process, including this matt stove smelting slag, Flash Smelting Furnace smelting slag, noranda furnace smelting slag, Isa furnace smelting slag, Wa Niukefu stoves difficult to understand Smelting slag, Mitsubishi process smelting slag, Kaldo Furnace smelting slag, silver stove smelting slag, Shuikoushan method smelting slag, Te Niente meltings Slag, reverberatory smelting slag, electro-smelting slag, closed blast furnace smelting slag, low blown converter smelting slag, side-blown converter smelting slag；It is described to contain Copper converting slag results from " Copper Matte Converting " process of the pyrometallurgical smelting process of copper, including bessemerizes copper ashes, Flash Smelting Furnace blowing copper Slag, noranda furnace continuous converting copper ashes, top Bessemer blow copper ashes, side-blown converter blowing copper ashes, bottom convertor blowing copper ashes, top blast stove connect Continuous blowing copper ashes, side-blown converter continuous converting copper ashes, bottom convertor continuous converting copper ashes；The pyrometallurgical dilution waste is containing copper weld pool Waste after slag and the dilution of slag containing copper converting, flotation tailings are tailings after cupric smelting slag and the ore dressing of slag containing copper converting, wet type copper smelting Slag is waste caused by wet type copper smelting；The copper weld pool slag and copper converting slag are molten state or cold conditions, wherein：Molten copper smelting slag Obtained by the copper smelter slag notch of " matte smelting " process, or cupric smelting slag is heated to molten condition, melt copper converting Slag is obtained by the copper converting stove slag notch of " Copper Matte Converting " process, or copper converting slag is heated into molten condition, dilution waste by Dilution stove slag notch obtains, and obtains poor slugging being heated to molten condition；
The lead metallurgical slag includes fuming furnace clinker and leaded smelting slag, and lead metallurgical slag is molten state or cold conditions, wherein molten Melt state clinker by pyrometallurgical smelting of lead technique reduction phase slag notch or fuming furnace slag notch obtain；The blast furnace slag, slag with Ferroalloy slag is molten state, or cold conditions, wherein：Molten state clinker (including blast furnace slag, slag and ferroalloy slag) is obtained by slag notch , or cold conditions clinker (including blast furnace slag, slag and ferroalloy slag) is heated to molten condition；Affiliated slag is molten iron pre-desulfurization Slag (including desulfurization slag, desiliconization slag, dephosphorized slag), vessel slag, electroslag, VOD/VAD slags, VD slags, tundish waste；The iron closes Golden clinker is caused clinker in ferroalloy production process, including smelts clinker caused by carbon ferromanganese, smelts caused by ferrochrome Clinker caused by clinker, smelting ferronickel, clinker caused by smelting ferrovanadium, clinker caused by smelting duriron, smelt caused by ferro-niobium Clinker caused by clinker, Smelting Ferromolybdenum
The lead metallurgical slag is fuming furnace clinker and leaded smelting slag, " reduction of ISP imperial smelting furnaces " or " sintering deposit air blast Stove reduces " or the leaded smelting slag of " solid-state high lead dross reduction " or " liquid high lead dross reduction technique " reducing process generation, it is leaded molten Refine slag and the leaded fuming slag of generation is smelted by fuming furnace.
Method as described above, it is preferable that the fuel is the one or more in solid, liquid or gaseous fuel, with The mode for being blown or feeding intake sprays into, and is loaded into 0-1200 DEG C of gas, the gas is in oxidizing gas, argon gas, nitrogen It is one or more；
Method as described above, it is preferable that described copper-contained material is copper ashes, nominal group process, blister copper pyro-refining slag, zinc Metallurgical slag, zinc abstraction cigarette ash and dirt mud, Pb-Zn tailings, lead metallurgical slag, lead metallurgical slag nickel fibers slag, lead copper matte, setting form, lead bullion Pyro-refining lead-in-dreg fuming slag, lead smelting ash and dirt mud, lead-acid battery, Copper making cigarette ash and dirt mud, composition brass, cupric rubbish Rubbish, containing copper circuit board, tin metallurgical slag, tailing；It is caused with " blowing of copper sulphur " that copper ashes includes clinker caused by " matte smelting " Clinker, pyrogenic process dilution clinker, copper ashes flotation tailings, flotation tailings, wet type copper smelting slag；The lead metallurgical slag be fuming furnace clinker with Leaded smelting slag, " reduction of ISP imperial smelting furnaces " or " sintering deposit blast furnace reduction " or " solid-state high lead dross reduction " or " liquid is high Lead skim reducing process " reducing process produces leaded smelting slag, and leaded smelting slag is smelted by fuming furnace produces leaded fuming slag； The nickel fibers slag be Ni-B alloy slag caused by " matte smelting " technique, " nickel convering of copper ice " technique blowing after dilution clinker, It is one or more in nickel sedimentation clinker caused by top blow smelting；The zinc smelting dreg includes clinker and pyrogenic process caused by zinc hydrometallurgy Clinker caused by clinker caused by zinc metallurgy, wherein zinc hydrometallurgy is zinc leaching residue, after volatilize kiln slag, iron vitriol slag, copper-cadmium slag, pickling Iron vitriol slag, goethite slag, bloodstone slag are one or more, and pyrometallurgy of zinc slag is zinc vertical retorting clinker, cyclone smelting clinker, air blast Stove clinker, fuming slag, electroslag are one or more；
Described flux for metallurgy is containing CaO or SiO2Mineral, 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；Described ferrous material is common iron ore concentrate, general Logical iron ore concentrate DRI, it is common iron ore concentrate sintered ore deposit, common Iron Ore Pellets, common iron ore concentrate metallized pellet, general The carbon containing pre-reduced pellet of logical iron ore concentrate, slag, zinc smelting dreg, coke smelting smoke dust and dirt mud, steel flue dust and dirt mud nickel fibers High calcium red mud after high calcium red mud, lead metallurgical slag removing sodium after slag, copper ashes, lead metallurgical slag, zinc smelting dreg, tin metallurgical slag, red mud, removing sodium Coal dust ash, containing the one or more in copper tailing, pyrite cinder；The steel flue dust includes blast furnace gas mud, converter with dirt mud drum Dirt mud, electric furnace dust mud, heat or cold rolling sludge, sintering dust, pelletizing dust, go out ironworks dust, blast furnace dust, electric stove dust Ash, steel rolling iron scale；
Described fluorine-containing material is fluorite, CaF2Or the one or more in fluorine-containing blast furnace slag；The alkaline material is stone One or more after ashes, red mud, removing sodium in high calcium red mud, carbide slag, dolomite dust or calcium lime powder；Described alkalescence contains Iron material is CaO/SiO2>=1 ferrous material, alkaline sintering deposit, alkaline iron ore concentrate, alkaline pre-reduced pellet, alkalinous metal One or more in pelletizing, slag or blast furnace slag.
Method as described above, it is preferable that the acid material is silica, lead metallurgical slag silica containing gold and silver, flyash, coal One or more in spoil；The iron-containing acidic material be CaO/SiO2≤1 ferrous material, the iron-containing acidic material For, acid sinter ore, acid iron ore concentrate, acid pre-reduced pellet, acid metal pellet, copper ashes, lead smelt lead metallurgical slag, zinc One or more in metallurgical slag, nickel fibers slag, tin metallurgical slag, ferroalloy slag, blast furnace slag
The copper-contained material and ferrous material are hot or cold conditions, wherein hot material is by metallurgical furnace discharging opening or slag notch Directly obtain.Zinc Hydrometallurgy Residue, wet type copper smelting slag and dirt mud need to through being dehydrated, dry.
Further, the solid fuel is one kind or more 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 For heavy oil, the gaseous fuel is coal gas and/or natural gas.
Method as described above, it is preferable that in the step S1, it is well mixed to mix or being stirred naturally, its In, the mode being stirred is argon gas stirring, nitrogen gas stirring, nitrogen-argon gas mixing gas agitating, reducibility gas stir, One or more in oxidizing gas stirring, electromagnetic agitation or mechanical agitation；
Method as described above, it is preferable that in being separated and recovered in the step S2, the richness for being deposited in bottom The Iron containing silicate minerals of copper phase, the rich iron at middle part and upper strata can be mutually respectively processed, or the rich iron of middle and upper part and iron content silicon Hydrochlorate mineral facies combine processing, and golden component enters copper-rich phase, component containing zinc and leaded component volatilization with silver components migration, enrichment, Enter fume recovery in the form of an oxide.
Specifically, the separation and recovery in the step S2, with the following method any one of one to method five processing：
Method one, when can flow out melting reaction device using slag, walked as follows after the slag separation after the completion of reaction Suddenly：
S2-1-01, the Iron containing silicate minerals phase, carry out any of following method A-G processing；
Method A：Cement raw material is directly used as after water quenching or air cooling；
Method B：The part or all of Iron containing silicate minerals mutually return in the reaction slag and are used as hot metallurgy Flux；
Method C：For pouring devitrified glass or as mineral wool；Method D：The slag oxygen of the Iron containing silicate minerals phase Air cooling or water quenching, method include after change：Slag is retained in melting reaction device or slag is poured into attemperator, to iron content silicon In the slag of hydrochlorate, it is blown into temperature and is 0~1200 DEG C of preheating oxidizing gas, and ensure the slag temperature of silicate>1450 ℃；When slag ferrous oxide weight percent content<1%, the slag after being aoxidized；Slag Direct Air-Cooled after the oxidation Or water quenching, as the additive or clinker in slag cements, cement regulator, manufacture of cement；
Further, when Iron-containing silicate slag temperature<1450 DEG C, pre-heating fuel and the oxidizing gas of preheating are sprayed into, Combustion heat release, additional heat, or device conducting self-heating, make Iron-containing silicate slag temperature>1450℃；
Method E：The Iron containing silicate minerals are mutually used for the clinker for producing high added value, comprise the following steps：
E-1, Iron containing silicate minerals are mutually retained in melting reaction device or slag are poured into attemperator, to iron content silicon In the slag of hydrochlorate mineral facies, molten steel slag, lime, lime stone, ferro-alloy cinder, flyash, basic iron lean ore, alum clay are added One or more after ore deposit, molten blast furnace slag, red mud, removing sodium in high calcium red mud or carbide slag, are sufficiently mixed, and obtain slag mixing Material；
Preheating temperature is blown into E-2, upward slag mixed material and is 0~1190 DEG C of oxidizing gas, and ensures slag Mixed material temperature>1450℃；When ferrous oxide weight percent content<1%, the slag after being aoxidized；
Slag after E-3, the oxidation, air cooling or water quenching are carried out, the clinker of high added value is made；
Method F：The slag of the Iron containing silicate minerals phase is as blast furnace ironmaking raw material or direct reduction iron making raw material：Will After Iron-containing silicate slag air cooling, water quenching or slow cooling, as blast furnace ironmaking or direct reduction iron making raw material, after direct-reduction, adopt With 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 slag is poured into attemperator, separated using the modified magnetic separation of slag, including：It is molten into attemperator Slag, is blown into the oxidizing gas of 0~1200 DEG C of preheating, and ensures its slag temperature>1250℃；
Further, when slag temperature<1250 DEG C, spray into pre-heating fuel and the oxidizing gas of preheating, combustion heat release, benefit Heat, or device conducting self-heating are filled, makes slag temperature>1250℃；
By the slag slow cooling after above-mentioned oxidation to room temperature, crush, magnetic separation, product is magnetite concentrate and mine tailing, and mine tailing is made For construction material；
Method G：The Iron containing silicate minerals mutually carry out reduction iron production, comprise the following steps：
G-1, Iron containing silicate minerals are mutually retained in melting reaction device or the slag are poured into attemperator, or add Ferrous material, while reducing agent is added, melting and reducing is carried out, the slag of monitoring reaction in real time, meets condition simultaneously by regulation and control：Instead Answer the temperature of slag for 1350~1650 DEG C and react the basicity CaO/SiO of slag2Ratio=0.6~2.4, obtain reaction and complete Slag afterwards；
Wherein, the method for temperature for controlling reaction slag is：
When reaction slag 1350 DEG C of temperature ＜, by the heating of reaction unit itself, or into slag add fuel with The oxidizing gas of preheating, the temperature of reaction slag is set to reach 1350~1650 DEG C；
As 1650 DEG C of the temperature ＞ of reaction slag, flux for metallurgy, ferrous material or fluorine-containing material are added into reaction slag In one or more, the temperature of reaction slag is reached 11350~1650 DEG C, wherein, described flux for metallurgy be containing CaO or SiO2Mineral, high calcium red mud, carbide slag, dolomite or lime specially after quartz sand, quartz sand containing gold and silver, red mud, removing sodium One or more in stone；
The method of basicity for controlling reaction slag is：
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；
The oxidizing gas into slag after 0~1200 DEG C of preheating of injection is also needed to enter in G-2, the G-1 during melting and reducing Row melting and reducing, the slag formed after reduction；
G-3, separation and recovery：Carried out using one kind in following two methods：
Method I：Mixing slag after reduction is poured into insulation slag ladle, is cooled to room temperature, obtains slow cooling slag；Wherein, metal Iron is deposited to the bottom of reaction unit, forms iron and sticks together, by containing metal iron layer in remaining slow cooling slag, is crushed to 20~400 μm of granularity, Residual metallic iron and mine tailing are isolated in ore grinding, magnetic separation；
Method II：Mixing slag after reduction, cooling-sedimentation, slag-gold separation, obtain molten iron and the slag after reduction；Institute The slag after reduction is stated, slag treatment is carried out according to one or more of methods in method A~E；The molten iron, be sent to converter or Electric furnace steel making；
S2-1-02, the copper-rich phase, sent again after being sent to converter or converting furnace copper metallurgy or slow cooling crushing-magnetic selection 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；
S2-1-03, the part component containing zinc and leaded component volatilization, in the form of an oxide into fume recovery；
S2-1-04, partly contain golden component with entering copper-rich phase containing silver components；
It is former as blast furnace ironmaking after S2-1-05, the Fe-riched phase layer carry out water quenching or air cooling or pour into attemperator slow cooling Material or direct reduction iron making raw material or iron making by smelting reduction iron material or flotation are used as refining after carrying copper raw material or magnetic separation separation metallic iron The raw material of copper or direct reduction iron making；In Direct Reduction, after reduzate magnetic separation separation, metallic iron and mine tailing, tail are obtained Ore deposit returns to copper metallurgy system；In floatation process, float product is containing copper concentrate and iron ore concentrate, and copper concentrate returns to copper metallurgy system, iron essence Ore deposit 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 refining Copper system is united；The Direct Reduction is set using rotary hearth furnace, tunnel cave, underbody road, shaft furnace, rotary kiln or induction furnace as reduction Standby, using gas base or coal base reduction technology, gas-based reduction is natural gas and/or coal gas, and coal base reduction is anthracite, bituminous coal, brown One or more in coal, coking coal, coke powder or 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.
When method two, the melting reaction device that can be flowed out using slag, Fe-riched phase and the Iron-containing silicate ore deposit of acquisition One or more are handled thing phase processor method in one step process A~G described in method one, or after pouring into attemperator slow cooling Copper-rich phase, be sent to converter or converting furnace copper metallurgy, or converter or converting furnace copper metallurgy, or warp are sent to again after broken magnetic separation separation metallic iron After magnetic separation separates metallic iron or separates metallic iron without magnetic separation, direct-reduction, reduzate is after magnetic separation separates metallic iron, then send Toward converter or converting furnace copper metallurgy.
Method three, using the rotatable converter of slag with reaction slag ladle when, obtain molten state described in Iron containing silicate minerals Phase, one or more are handled processing method in one step process A~G described in method one；Contain the Fe-riched phase use side A kind of step S2-1-05 processing of method；The molten state or the copper-rich phase poured into after attemperator slow cooling, are sent to converter or blow Be sent to converter or converting furnace copper metallurgy again after furnace copper metallurgy, or broken magnetic separation separation metallic iron, or through magnetic separation separate metallic iron or without After magnetic separation separation metallic iron, direct-reduction, reduzate is after magnetic separation separates metallic iron, then is sent to converter or converting furnace copper metallurgy.
Method four, using the rotatable converter of slag with reaction slag ladle when, the molten state Iron containing silicate minerals phase of acquisition With Fe-riched phase, one or more are handled processing method in one step process A~G described in method one；The molten state copper-rich Mutually or after pouring into attemperator slow cooling, converter or converting furnace copper metallurgy are sent to, or is 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.
Method five：During using attemperator, or the melting reaction device that can be flowed out using slag, slag is poured into insulation dress When putting, following steps are carried out：
S201, sedimentation cooling：Slag is slowly cooled to room temperature, and obtains slow cooling slag；The copper-rich phase is deposited to reaction unit Bottom, formed copper-rich stick together；The Iron containing silicate minerals mutually float；Centre is that slow cooling slag is Fe-riched phase, while generation contains zinc Component and leaded component；Wherein, nickel, cobalt, gold, silver component move to copper-rich phase；
S202, separation：The copper-rich that artificial taking-up is deposited in bottom sticks together, or copper-rich sticks together after crushing-magnetic selection separates metallic iron and sent again 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；The Fe-riched phase mutually refines with Iron-containing silicate as blast furnace Iron material or direct reduction iron making raw material or iron making by smelting reduction iron material or iron making by smelting reduction iron material or flotation carry copper raw material or As copper metallurgy or the raw material of direct reduction iron making after magnetic separation separation metallic iron；In Direct Reduction, reduzate magnetic separation separation Afterwards, metallic iron and mine tailing are obtained, mine tailing returns to copper metallurgy system；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；
S203, the artificial Iron containing silicate minerals phase for taking out top, silicate phase is obtained as blast furnace ironmaking raw material or straight Connect reduction iron production raw material or iron making by smelting reduction iron material or cement raw material；
S204, part zinc component and lead component volatilization, in the form of an oxide into fume recovery；
S205, added with red mud or when dirt mud and these raw materials of steel cigarette ash, part indium component, bismuth component, group containing potassium Divide, component volatilization containing sodium, into fume recovery.
Method as described above, it is preferable that the oxidizing gas is the air of preheating, oxygen, oxygen-enriched air, nitrogen-sky One kind in gas, argon gas-air, oxygen-nitrogen, oxygen-argon gas.
Method as described above, it is preferable that it is described to be well mixed to mix or being stirred naturally, wherein, it is stirred and adopts Stirred with argon gas, nitrogen gas stirring, nitrogen-argon gas mixing gas agitating, reducibility gas stir, oxidizing gas stirs, electromagnetism stirs Mix or mechanical agitation in one or more；It is described to be settled into natural subsidence or spun down or centrifugation in the step S2 Sedimentation；Type of cooling when carrying out cooling-sedimentation is natural cooling or rotation cooling or centrifugation cooling, during the separation, uses gravity Separating method be separation by shaking table, sluicing or the two be combined.
Compared with prior art, it is characteristic of the invention that：
(1) method by cupric and the mixing slag recovery valuable component of iron of the invention, can both handle hot molten slag, Make full use of molten copper slag with fusion metallurgy slag (in fusion of lead metallurgical slag, molten blast furnace slag, molten steel slag, melting ferroalloy slag One or more) physics thermal resource and hot flux for metallurgy, cold conditions clinker can be handled again, mixed by slag mixing or cold conditions Close, it is metallurgical modified to realize slag；(2) the slag metallurgical reaction in slag is mixed, fayalite disintegrates, and ferriferous oxide is fully released Release, into Fe-riched phase, realization is grown up and settled, and Fe-riched phase includes a variety of in metallic iron, FeO phases, fayalite phase, work For blast furnace ironmaking or direct-reduction or the raw material of fused reduction iron-smelting；Metallic iron component in mixing slag is assembled, grows up and sink Drop；(3) copper component, gold and silver component in slag are mixed and is enriched in copper-rich phase respectively, and is realized and is grown up and settle, copper-rich phase includes Have a variety of in copper, white metal, matte, white metal, Fe containing component, or part copper component enters Fe-riched phase, and copper-rich phase, which is sent to, to be turned Stove or converting furnace copper metallurgy；(4) zinc component, the lead component mixed in slag is enriched in cigarette ash respectively, is reclaimed；(5) partly contain Indium component, bismuth component, component containing potassium, component volatilization containing sodium are reclaimed into flue dust；(6) mix slag in free cao with Magnesia disappears, and mixing slag is realized quenched；(7) method separated using manual sorting, magnetic separation, gravity treatment, slag gold, separation sedimentation The Fe-riched phase of copper-rich phase, middle part in bottom and the silicate mineral phase on top, realize mixing slag in copper component, golden component, The high efficiente callback of silver components, indium component, bismuth component, sodium component, potassium component, iron component, zinc component, lead component；(8) can handle Solid-state cupric, iron material, reach resource high-efficiency comprehensive utilization；(9) present invention contributes to copper-rich phase to settle using mixing slag, makes It is low copper Fe-riched phase and Iron-containing silicate phase to be obtained after sedimentation separation, and wherein Fe-riched phase and the copper content of Iron-containing silicate phase is less than 0.1%, metallic iron and molten iron can be obtained by direct-reduction or fused reduction iron-smelting；(10) present invention uses mixing slag, Whole process is without heating or a small amount of heat compensation.Whole process compensates flux for metallurgy without flux for metallurgy or on a small quantity, can locate Manage cold conditions material.The inventive method can be continuously or discontinuously progress, meet industrial production needs.
(3) beneficial effect
The beneficial effects of the invention are as follows：
(1) present invention realize copper component in Non-ferrous metallurgical slag and Ferrous Metallurgy clinker, iron component, zinc component, lead component, The comprehensive utilization of gold, silver, phosphorus, calcium and silicon components valuable component, solves current clinker bulk deposition, problem of environmental pollution；(2) originally Invention can handle ferro-alloy cinder, slag, blast furnace slag, lead metallurgical slag on a large scale and contain Cu-S ore, can solve heavy metal member Plain pollution problem, realize the recovery of heavy metal components；(3) present invention can handle a small amount of cold conditions cupric, ferrous material；(4) originally The raw material of invention can be the liquid molten copper ashes and fusion metallurgy slag (fusion of lead metallurgical slag, melting blast furnace flowed out in slag notch One or more in slag, molten steel slag, melting ferroalloy slag), there is the characteristics of high-temperature, high heat, take full advantage of molten Slag physics thermal resource；Mix and contain substantial amounts of hot flux for metallurgy in slag, be all the slag system of excellent in physical and chemical performance, Realize the efficient utilization of Metallurgical resources and thermal resource；The characteristics of taking full advantage of mixing slag high reactive chemistry activity, realizes Slag is metallurgical；(5) present invention is mixed by slag, insulation or blowing gas, is controlled oxygen gesture, is made copper group in slag, golden component Copper-rich phase is enriched to silver components, aggregation is realized, grows up and settle, iron component is enriched in copper-rich phase, realizes aggregation, grows up and sink Drop, lead component are enriched in cigarette ash with zinc component and reclaimed；Zinc component, lead component, indium component, bismuth component, sodium group in slag Divide, potassium component volatilization, reclaimed into flue dust；(6) in the inventive method, addition cold conditions material avoids molten with molten copper slag Slag temperature is too high, improves the life-span of attemperator；Add cold conditions material and molten copper slag and improve feed throughput, not only can be with Molten slag is handled, and a small amount of cold conditions material can be handled, adaptability to raw material is strong；Adding cold conditions material realizes slag metallurgy React the chemical heat of release and the efficient utilization of slag physical thermal；(7) in the inventive method infall process, copper component in slag, Gold and silver component is enriched in copper-rich phase respectively, and realizes aggregation, grows up and settle, and iron component is enriched in Fe-riched phase in slag, and in fact Now assemble, grow up and settle, phosphorus component, silicon components are enriched in silicate mineral phase with Calcium compounds respectively in slag, and realize Floating, copper-rich phase is sent to converter or converting furnace copper metallurgy, and low copper Fe-riched phase is used as blast furnace ironmaking or direct-reduction or melting and reducing The raw material of ironmaking, copper-rich phase include copper phase, white metal, matte phase, a variety of in Fe containing component, or part enters Fe-riched phase, richness Iron phase includes a variety of in metallic iron, FeO phases, fayalite phase；Attemperator equipped with slag, which is placed on rotation platform, to be rotated, Accelerate copper-rich phase, Fe-riched phase aggregation, grow up and settle；The addition of fluorine-containing material, accelerate copper-rich phase, the assembling of Fe-riched phase, long Greatly with sedimentation；(8) the inventive method is settled by copper-rich phase, and the copper content of Iron-containing silicate phase and rich iron component is less than 0.1%, Metallic iron and molten iron can be obtained as blast furnace ironmaking or direct-reduction or the raw material of fused reduction iron-smelting；(9) the inventive method The method settled using manual sorting, magnetic separation, gravity treatment, slag-gold, respectively to being distributed in top, middle part and the silicate mine of bottom Thing phase, Fe-riched phase, copper-rich phase are separated, and realize copper component in slag, gold and silver, iron component, silicon components, Calcium compounds and phosphorus component High efficiente callback；In being deposited in due to Fe-riched phase, copper-rich phase, bottom, it is small to sort slag amount, and sorting cost is low；Follow-up point Magnetic separation or gravity treatment are used from process, will not generation environment pollution；Because slag passes through modifier treatment, mine tailing as cement raw material, Construction material, make aggregate, the use of road material instead of rubble；(10) present invention can both handle hot molten slag, make full use of melting smelting The physics thermal resource and hot flux for metallurgy of golden slag, can handle cold conditions clinker and material again, using mixing slag metallurgical reaction, Slag metallurgy is realized, copper migration in slag, is enriched in copper-rich phase, and realizes aggregation, grow up and settle, the migration of iron component, richness Fe-riched phase is combined in, aggregation is realized, grows up and settle, silicon, calcium migrate with phosphorus component, are enriched in silicate mineral phase, realize and float, Separation is deposited in the copper-rich phase of bottom, the Fe-riched phase at middle part and the Iron containing silicate minerals phase on top, and realize has in mixing slag The high efficiente callback of valency component.This method technological process is short, metal recovery rate is high, production cost is low, adaptability to raw material is strong, treating capacity Greatly, it is environment-friendly, economic well-being of workers and staff is high, can effectively solve Metallurgical resources and heat energy high efficiente callback Utilizing question.
Embodiment
A kind of method by cupric and the mixing slag recovery valuable component of iron of the present invention, specifically includes following steps：
Step 1, clinker mixes：
By copper ashes (in cupric smelting slag, slag containing copper converting, pyrometallurgical dilution waste, copper ashes flotation tailing, wet type copper smelting slag It is one or more), add in the melting reaction device that insulation transposition or slag can flow out, and add lead metallurgical slag (fuming furnace stove Slag 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 the reaction slag of cupric and iron；It is well mixed, monitoring reaction in real time Slag, ensure following (a) and (b) two parameters, the slag after the completion of being reacted simultaneously by regulation and control；
(a) temperature of the reaction slag of cupric and iron is 1050~1450 DEG C；
(b) the basicity CaO/SiO of the reaction slag of cupric and iron2Ratio=0.15~1.5；
Regulation and control method is：
Corresponding (a)：The temperature for controlling the reaction slag of cupric and iron is in the method for design temperature scope：
When 1050 DEG C of the temperature ＜ design temperatures range lower limit of the reaction slag of cupric and iron, pass through reaction unit itself Heating function, or fuel or molten copper slag, fusion of lead metallurgical slag, molten blast furnace slag, molten steel slag or molten are added into slag Melt the one or more of ferroalloy slag, when spraying into fuel, while spray into the oxidizing gas of preheating, reach the temperature of slag and set Determine in 1050~1450 DEG C of temperature range；
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 Copper-contained material, nickel fibers slag, blast furnace slag, slag, ferroalloy slag, flux for metallurgy, ferrous material or fluorine-containing material are added in slag In one or more, the temperature of mixing slag is reached in 1050~1450 DEG C of design temperature scope；
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 1.5, acid material is added into reaction slag And/or iron-containing acidic material；
Step 2, separate and recover：
Slag after the completion of reaction, 5~50min is incubated, sedimentation, obtains bottom molten state copper-rich phase layer, middle part molten state Fe-riched phase and the molten state Iron containing silicate minerals phase on top, while generate the flue dust of component containing zinc and leaded component, gold and silver group Divide and move to copper-rich phase,
Each phase is handled 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, converter is sent to again after being sent to converter or converting furnace copper metallurgy or broken magnetic separation separation metallic iron or is blown Furnace copper metallurgy, or after magnetic separation separates metallic iron or separates metallic iron without magnetic separation, direct-reduction, reduzate separates through magnetic separation After metallic iron, then it is sent to converter or converting furnace copper metallurgy；
(3) part lead component, zinc component, indium component, bismuth component, sodium component, potassium component volatilization enter 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；The direct-reduction Process using rotary hearth furnace, tunnel cave, underbody road, shaft furnace, rotary kiln or induction furnace as reduction apparatus, using gas base or coal base also Former technology, gas-based reduction use natural gas and/or coal gas, and coal base reduction uses anthracite, bituminous coal, lignite, coking coal, coke powder or Jiao One or more in charcoal, it is 900~1400 DEG C to control reduction temperature, control 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 the 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) in the Iron-containing silicate slag into melting reaction device, the oxidizing gas of preheating is blown into, when slag aoxidizes Ferrous weight percent content<1%, the oxidation of slag is completed, the slag after being aoxidized, wherein, the preheating of oxidizing gas Temperature is 0~1200 DEG C；And in whole process, ensure (c) silicate slag temperature>1450℃；
The control method that corresponding (c) is used：
When Iron-containing silicate slag temperature<1450 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>1450℃；
(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) in the Iron-containing silicate slag into melting reaction device, molten steel slag, lime, lime stone, ferroalloy are added Red mud or one kind or several in carbide slag after clinker, flyash, basic iron lean ore, bauxite, molten blast furnace slag, red mud, removing sodium Kind, it is sufficiently mixed, obtains slag mixed material；
(2) oxidizing gas of preheating is blown into slag mixed material, when ferrous oxide weight percent content<1%, The oxidation of completion slag, the slag after being aoxidized, wherein, the preheating temperature of oxidizing gas is 0~1190 DEG C；And whole During, ensure (d) slag mixed material temperature>1440℃；Temprature control method melts with the silicate in method D steps (1) Slag temprature control method；
(3) slag after aoxidizing, air cooling or water quenching are carried out, the clinker of high added value is made.
Method F：The Iron containing silicate minerals phase slag is as blast furnace ironmaking raw material or direct reduction iron making raw material：It will contain After the slag air coolings of ferrosilicate mineral facies, 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 the Iron containing silicate minerals phase is poured into attemperator, separated using following methods：It is molten The modified magnetic separation separation of slag：Slag into attemperator, is blown into the oxidizing gas of 0~1200 DEG C of preheating, and ensures it 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 Choosing, product is magnetite concentrate and mine tailing, and mine tailing is as construction material.
Method G：Iron-containing silicate slag fused reduction iron-smelting：
(1) Iron-containing silicate slag is retained in melting reaction device or slag is poured into attemperator, to molten state Slag adds ferrous material, reducing agent, carries out melting and reducing, the slag of monitoring reaction in real time, ensures following (a) simultaneously by regulation and control Two parameter, slag reacted after the completion of (b)；
(a) temperature for reacting slag is 1350~1650 DEG C；
(b) the basicity CaO/SiO of slag is reacted2Ratio=0.6~2.4；
Regulation and control method is：
Corresponding (a)：
Control reaction slag temperature be in the method for design temperature scope：
When reacting 1350 DEG C of the temperature ＜ design temperatures range lower limit of slag, pass through the heating work(of reaction unit itself Can, or fuel and the oxidizing gas of preheating are added into slag, the temperature of reaction slag is reached design temperature scope 1350 In~1650 DEG C；
When reacting 1650 DEG C of the temperature ＞ design temperatures range limit of slag, added into reaction slag flux for metallurgy, One or more in ferrous material or fluorine-containing material, the temperature of reaction slag is set to reach 1350~1650 DEG C of design temperature scope It is interior；
Corresponding (b)：
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；
(2) oxidizing gas into slag after blowing preheated carries out melting and reducing, the slag formed after reduction, wherein： The preheating temperature of oxidizing gas is 0~1200 DEG C, and during injection, ensures (a) and (b) two ginsengs simultaneously by regulation and control Number：
(a) temperature of the slag after the completion of reacting is 1350~1650 DEG C；
(b) 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 steps (1)；
(3) separate and recover：
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 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, aggregate is made as cement raw material, construction material, instead of rubble, road material uses；
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 the separation and recovery method one of step 2 In method A~E in one or more, carry out slag treatment；
(c) molten iron, converter or electric furnace steel making are sent to；
(d) component containing zinc and leaded component volatilization, in the form of an oxide into fume recovery；
(e) part indium component, bismuth component, sodium component, potassium component volatilization enter 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) molten state copper-rich phase, is sent to converter copper metallurgy or converting furnace copper metallurgy, or is sent to and turns again after broken magnetic separation separation metallic iron Stove 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 After choosing separation metallic iron, then it is sent to converter or converting furnace copper metallurgy；
(2) molten state Fe-riched phase layer mutually uses processing method one step process A described in method one with Iron containing silicate minerals One or more are handled in~G；
(3) partly component containing zinc and leaded component volatilization, in the form of an oxide into fume recovery；
(4) part indium component, bismuth component, 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) molten state Iron containing silicate minerals phase, carries out slag treatment, and specific processing mode is：Using the separation of step 2 One or more of progress slag treatments in method A~G in recovery method one；Used containing the Fe-riched phase in method one Step (4) is handled；
(2) 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；
(3) part indium component, bismuth component, sodium component, potassium component volatilization enter fume recovery；
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) molten state Iron containing silicate minerals phase and Fe-riched phase, carry out slag treatment, and concrete mode is：Using step 2 The one or more in method A~G in separation and recovery method one are handled；
(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 through magnetic separation separate metallic iron or without magnetic separation separate metallic iron after, direct-reduction, reduzate warp After magnetic separation separation metallic iron, then it is sent to converter or converting furnace copper metallurgy；
(3) part indium component, bismuth component, sodium component, potassium component volatilization enter flue dust into soot oxidation thing；
Method five：During using attemperator, or the melting reaction device that can be flowed out using slag, slag is poured into insulation dress When putting, the slag after the completion of reaction carries out following steps：
(1) sedimentation cooling：Slag after the completion of reaction is cooled to room temperature, obtains slow cooling slag；Copper-rich phase is deposited to reaction dress The bottom put, form copper-rich and stick together；Iron containing silicate minerals mutually float；Slow cooling slag among copper-rich phase and Iron containing silicate minerals is 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 artificial taking-up is deposited in bottom is sticked together, and converter or converting furnace are sent to again after magnetic separation separation metallic iron Converter or converting furnace copper metallurgy are sent to after copper metallurgy, or broken magnetic separation separation metallic iron again, or metallic iron is separated or without magnetic separation through magnetic separation After separating metallic iron, direct-reduction, reduzate is after magnetic separation separates metallic iron, then is sent to converter or converting furnace copper metallurgy；Middle part Fe-riched phase layer carry copper raw material as blast furnace ironmaking raw material or direct reduction iron making raw material or iron making by smelting reduction iron material or flotation Or the raw material after magnetic separation separation metallic iron as copper metallurgy or direct-reduction；In floatation process, float product be containing copper concentrate with Iron ore concentrate, copper concentrate return to copper metallurgy system, and iron ore concentrate is as blast furnace ironmaking raw material or direct reduction iron making raw material or melting and reducing Iron-smelting raw material；Wherein, in Direct Reduction, after reduzate magnetic separation separation, metallic iron and mine tailing are obtained, mine tailing returns to refining Copper system is united；The Direct Reduction is set using rotary hearth furnace, tunnel cave, underbody road, shaft furnace, rotary kiln or induction furnace as reduction Standby, using gas base or coal base reduction technology, gas-based reduction uses natural gas and/or coal gas, and coal base reduction is using anthracite, cigarette One or more in coal, lignite, coking coal, coke powder or coke, it is 900~1400 DEG C to control reduction temperature, control 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 directly also Former iron-smelting raw material or iron making by smelting reduction iron material or as cement raw material, construction material, instead of rubble make aggregate, road material uses；
(4) part lead component, zinc component, indium component, bismuth component, sodium component, potassium component volatilization enter flue dust, with oxide Into flue dust.
Method as described above, it is preferable that in described step 1 and 2, copper ashes is cupric smelting slag, slag containing copper converting, poor Change one or more, cupric smelting slag in waste, flotation tailings, wet type copper smelting slag and result from " making for the pyrometallurgical smelting process of copper Sulfonium melting " process, including this difficult to understand matt stove smelting slag, Flash Smelting Furnace smelting slag, noranda furnace smelting slag, Isa furnace smelting slag, watt Niu Kefu stoves smelting slag, Mitsubishi process smelting slag, Kaldo Furnace smelting slag, silver stove smelting slag, Shuikoushan method smelting slag, Te Nien Special smelting slag, reverberatory smelting slag, electro-smelting slag, closed blast furnace smelting slag, low blown converter smelting slag, side-blown converter smelting slag； Slag containing copper converting results from " Copper Matte Converting " process of the pyrometallurgical smelting process of copper, including bessemerizes copper ashes, Flash Smelting Furnace blowing Copper ashes, noranda furnace continuous converting copper ashes, top Bessemer blow copper ashes, side-blown converter blowing copper ashes, bottom convertor blowing copper ashes, top blast stove Continuous converting copper ashes, side-blown converter continuous converting copper ashes, bottom convertor continuous converting copper ashes；Dilution waste is cupric smelting slag and cupric Waste after blowing slag dilution, flotation tailings are cupric smelting slag and tailings after the ore dressing of slag containing copper converting, and the wet type copper smelting slag produces It is born in wet type copper smelting technique；Copper weld pool slag and copper converting slag are molten state or cold conditions, wherein：Molten copper smelting slag is by " making sulfonium to melt The copper smelter slag notch of refining " process is obtained, or cupric smelting slag is heated into molten condition, and melting copper converting slag is by " copper matte regulus The copper converting stove slag notch of blowing " process is obtained, or copper converting slag is heated into molten condition, and dilution waste is slagged tap by dilution stove Mouth obtains, and obtains poor slugging being heated to molten condition；Lead metallurgical slag includes fuming furnace clinker and leaded smelting slag, and lead metallurgical slag is Molten state or cold conditions, wherein molten state clinker by pyrometallurgical smelting of lead technique reduction phase slag notch or fuming furnace slag notch obtain ；Blast furnace slag, slag and ferroalloy slag are molten state, or cold conditions, wherein：Molten state clinker (blast furnace slag, slag and ferroalloy Slag) obtained by slag notch, or cold conditions clinker (blast furnace slag, slag and ferroalloy slag) is heated to molten condition；Affiliated slag is Molten iron pre-desulfurization slag (desulfurization slag, desiliconization slag, dephosphorized slag), vessel slag, electroslag, VOD/VAD slags, VD slags, tundish waste；Institute Ferro-alloy cinder is stated as caused clinker in ferroalloy production process, including smelts clinker caused by carbon ferromanganese, smelt ferrochrome Clinker caused by caused clinker, smelting ferronickel, clinker caused by smelting ferrovanadium, clinker caused by smelting duriron, smelt ferro-niobium Clinker caused by caused clinker, Smelting Ferromolybdenum.
In described step 1 and 2, lead metallurgical slag is fuming furnace clinker and leaded smelting slag, " reduction of ISP imperial smelting furnaces " Or " sintering deposit blast furnace reduction " or " solid-state high lead dross reduction " or " liquid high lead dross reduction technique " reducing process produce it is leaded Smelting slag, leaded smelting slag is smelted by fuming furnace produces leaded fuming slag；
In described step 1 and 2, the melting reaction device that slag can flow out for rotatable melting reaction device or carries 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 device is converter, melting reaction slag ladle；
The described melting reaction device that can be flowed out with cinder notch or iron mouth slag is plasma heating furnace, direct current electric arc furnace, friendship Flow electric arc furnaces, mineral hot furnace, blast furnace, blast furnace, induction furnace, furnace cupola, side-blowing bath smelting furnace, bottom blowing molten pool smelting furnace, top blast Bath smelting furnace, reverberatory furnace, Ausmelt furnace, Isa furnace, watt button can husband's bath smelting furnace, side-blown rotary furnace, bottom blowing rotary furnace, Top blast rotary furnace.
In described step 1 and 2, described fuel and one kind or more that reducing agent is in solid, liquid or gaseous fuel Kind, sprayed into a manner of being blown or feeding intake, be loaded into gas as the one or more in the oxidizing gas, nitrogen, argon gas of preheating, Preheating temperature is 0~1200 DEG C；Solid fuel is in coal dust, coke powder, coke, flyash, bituminous coal or anthracite with reducing agent One or more, granular or powdery is shaped as, granular material granularity is 5~25mm, and granular material granularity is≤150 μm, liquid Fuel is heavy oil with reducing agent, and gaseous fuel and reducing agent are coal gas and/or natural gas；Described copper-contained material is copper ashes, choosing Copper tailing, blister copper pyro-refining slag, zinc smelting dreg, lead metallurgical slag, nickel fibers slag, lead copper matte, setting form, fire refining of crude lead slag Leaded fuming slag, lead-containing soot, lead-acid battery, containing Bellamya aeruginosa, composition brass, cupric rubbish or containing one kind in copper circuit board or several Kind；Copper ashes includes clinker caused by " matte smelting " and clinker, pyrogenic process dilution clinker, copper ashes flotation tail caused by " blowing of copper sulphur " Slag；Lead metallurgical slag is fuming furnace clinker and leaded smelting slag, " reduction of ISP imperial smelting furnaces " or " 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, and leaded smelting slag passes through cigarette Change stove and smelt the leaded fuming slag of generation；Nickel fibers slag is Ni-B alloy slag caused by " matte smelting " technique, " nickel convering of copper ice " It is one or more in nickel sedimentation clinker caused by dilution clinker, top blow smelting after technique blowing；Zinc smelting dreg refines including wet method Clinker caused by zinc and clinker caused by pyrometallurgy of zinc, wherein clinker caused by zinc hydrometallurgy are zinc leaching residue, volatilization kiln slag, iron Iron vitriol slag, goethite slag, bloodstone slag are one or more after alum slag, pickling, and zinc vertical retorting is zinc vertical retorting clinker, cyclone smelting Clinker, blast-furnace cinder, electroslag are one or more；Described flux for metallurgy is containing CaO or SiO2Mineral, be specially quartz One or more after sand, quartz sand containing gold and silver, red mud, removing sodium in high calcium red mud, carbide slag, dolomite or lime stone；It is described Ferrous material be common iron ore concentrate, common iron ore concentrate DRI, common iron ore concentrate sintered ore deposit, common iron ore pellets Ore deposit, common iron ore concentrate metallized pellet, the carbon containing pre-reduced pellet of common iron ore concentrate, slag, zinc smelting dreg, coke smelting smoke dust with Dirt mud, steel flue dust and dirt mud, nickel fibers slag, copper ashes,
After lead metallurgical slag, zinc smelting dreg, tin metallurgical slag, red mud, removing sodium in high calcium red mud, coal dust ash, pyrite cinder one Kind is several；The steel flue dust includes blast furnace gas mud, bof sludge, electric furnace dust mud, heat (cold) with dirt mud drum and rolls sludge, sintering Dust, pelletizing dust, go out ironworks dust, blast furnace dust, electric stove dust ash, steel rolling iron scale；
Fluorine-containing material after lead metallurgical slag removing sodium described in high calcium red mud is fluorite, CaF2Or one kind in fluorine-containing blast furnace slag or It is several；The copper-contained material and ferrous material are hot or cold conditions, wherein hot material is straight by metallurgical furnace discharging opening or slag notch Obtain；The zinc metallurgy slag of wet method and dirt mud need to through being dehydrated, dry.
In above-mentioned raw material, zinc smelting dreg contains indium and bismuth, lead, silver, zinc, bismuth with cigarette ash, lead metallurgical slag and cigarette ash；It is red Contain sodium and potassium in mud, steel flue dust contains indium, bismuth, silver, sodium and potassium with dirt mud, and above material has iron, lead metallurgical slag and zinc Metallurgical slag all contains copper, and Bellamya aeruginosa contains indium and bismuth with dirt mud, therefore in the method for invention, indium, bismuth, sodium, potassium, zinc, lead meeting Enter flue dust in the form of the oxide, so as to be reclaimed.
Method as described above, it is preferable that in the step 1 and 2, the temperature of control mixing slag is in design temperature scope Method in：
In described step 1 and 2, copper-contained material, ferrous material and fluorine-containing material are pelletizing or granular material or granulation； Wherein, granularity≤150 μm of granular material, granular material granularity are 5~25mm, and granular material is sprayed into a manner of being blown, grain Shape material is added in a manner of being blown or feeding intake, and is loaded into argon gas, nitrogen, reducibility gas (coal gas and/or day of the gas for preheating Right gas), the one or more in oxidizing gas, preheating temperature is 0~1200 DEG C；Described injection method is to use resistance to fire-fighting Rifle insert slag or be placed in reaction slag top or side or bottom be blown into one or more；
In described step 1 and 2, copper-contained material and ferrous material are hot or cold conditions, and described hot material is from smelting The hot material of direct output in golden stove, hot temperature of charge are 200~1750 DEG C.
In described step 1, the temperature of control mixing slag is in the method for design temperature scope：
When mixing the temperature ＞ design temperature upper limits of slag, copper-contained material, ferrous material, blast furnace slag, slag, iron are added One or more in Fe alloy slag, flux for metallurgy or fluorine-containing material, it is therefore an objective to avoid temperature too high, protect refractory material；Add Another effect of fluorine-containing material is to reduce viscosity, accelerates copper-rich phase in slag, rich matte phase, Fe-riched phase to assemble, grow up and sink Drop, be advantageous to silicate floating；
In described step 1, in slag course of reaction, copper component, gold and silver component are enriched in copper-rich phase, and realized in slag Assemble, grow up and settle, or part is enriched in Fe-riched phase, iron component discharges from olivine, is enriched in Fe-riched phase, realizes poly- Collect, grow up and settle, zinc component, lead component respectively enter flue dust in slag, reclaim in the form of an oxide；
In the step 1 and 2, when adjusting basicity, described alkaline material is pulverized limestone, red mud, high calcium red mud after removing sodium, One or more in carbide slag, dolomite dust or calcium lime powder；Described alkaline ferrous material is CaO/SiO2>=1 iron content In material, alkaline sintering deposit, alkaline iron ore concentrate, ferro-alloy cinder, slag, alkaline pre-reduced pellet or alkalinous metal pellet It is one or more of.
In the step 1 and 2, when adjusting basicity, described acid material is one kind in silica, flyash, gangue It is or a variety of；The iron-containing acidic material is CaO/SiO2≤ 1 acid sinter ore, acid iron ore concentrate, acid pre-reduced pellet, acidity One or more in metallized pellet, copper ashes, lead metallurgical slag, zinc smelting dreg, nickel fibers slag.
In the step 1 and 2, copper-rich phase, rich matte phase, Fe-riched phase are assembled, grow up and settle in slag, are advantageous to silicic acid Salt floats, copper-rich phase include it is a variety of in copper, white metal, matte, white metal or Fe containing component, or part copper component enter it is rich Iron phase, Fe-riched phase include a variety of in metallic iron, FeO phases, fayalite phase；
In described step 1 and 2, while ensureing (a) and (b) two parameters, it is sufficiently mixed mixing slag, mixing side Formula is that nature is mixed or is stirred, and agitating mode is one kind in the following manner：Argon gas stirring, nitrogen gas stirring, argon-nitrogen One or more in gaseous mixture, reducibility gas (coal gas and/or natural gas), electromagnetic agitation, mechanical agitation, gas preheating temperature Spend for 0~1200 DEG C；
In described step 1, ensure following (a) and (b) two parameters simultaneously by regulation and control, while ensure copper oxygen in slag Compound and ferriferous oxide are reduced to metallic copper and FeO, metal Ferrum content in slag<3%.Can be by adding reducing agent, carbon containing It is one or two kinds of in ferrous material, wherein, the dosage of the reducing agent be in slag copper and ferriferous oxide be 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 prereduction ball of iron ore concentrate Group, iron ore concentrate carbonaceous metallized pellet, zinc hydrometallurgy volatilization kiln slag or coke furnace dust mud and cigarette ash.
In described step 2, Direct Reduction is using rotary hearth furnace, tunnel cave, underbody road, 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, and coal base reduction is anthracite, cigarette One or more in coal, lignite, coking coal, coke powder, coke, reduction temperature are 900~1400 DEG C, basicity CaO/SiO2Ratio= 0.7~1.9,
In described step 1 and 2, oxidizing gas for preheating air, oxygen, oxygen-enriched air, argon gas-air, argon gas- One kind in oxygen, nitrogen-air, nitrogen-oxygen, preheating temperature are 0-1200 DEG C, and injection method is to be inserted using refractory lance Enter slag or be placed in reaction slag top or side or bottom be blown into one or more；
Cooling-sedimentation is needed in the step 2, during separation and recovery, wherein, the type of cooling is natural cooling or rotation cooling Or centrifugation cooling, subsidence style are natural subsidence or spun down or centrifugation cooling；
Further, rotate and the concrete operations of centrifugation cooling are：Device equipped with the slag after the completion of reaction is placed in rotation Turn on platform, rotated according to certain speed, rotary speed is depending on slag quality and attemperator height or depth, rotation Time is depending on slag quality and slag solidification situation；Device equipped with the slag after the completion of reaction is placed on rotation platform and revolved Turn, 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, when shortening sedimentation Between, improve effect of settling, improve production efficiency；
In described step 2, 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 with Fe-riched phase；
In described step 2, copper component, gold and silver component continue to migrate, are enriched in copper-rich phase in the slag after the completion of reaction With rich matte phase, and realize grow up and settle；Iron component continues to migrate respectively, is enriched in Fe-riched phase in mixing slag, and realizes Grow up and settle.
The method that valuable component is reclaimed by the slag of cupric and iron of the present invention, the mineral grindability increase finally obtained.
In method as described above, Copper in Slag≤0.1% that finally obtains, the rate of recovery of iron is >=90%, the recovery of zinc Rate is >=91%, and the rate of recovery of lead is >=92%, and golden accumulation rate is >=94%, and silver-colored accumulation rate is >=94%, indium recovery For >=94%, the bismuth rate of recovery is >=94%, and the sodium rate of recovery is >=95%, and the potassium rate of recovery is >=95%.
In order to preferably explain the present invention, in order to understand, by embodiment, the present invention is described in detail. Wherein, detection method used is not known what is pointed out with raw material in following examples, this area routine techniques can be used, unless separately It is described, percentage used is percetage by weight in the present invention.
When step (1) slag in example 1 below~10 mixes, pass through (a) and (b) the two parameters tools for regulating and controlling and ensureing Body is：
(a) temperature of the reaction slag of cupric and iron is 1050~1450 DEG C；
(b) the reaction slag basicity CaO/SiO of cupric and iron2Ratio=0.15~1.5；
Embodiment 1
A kind of method by cupric and the mixing slag recovery valuable component of iron, comprise the following steps：
Step 1, clinker mixes：The Ausmelt furnace cupric smelting slag obtained by matte smelting stove slag notch is gone out with converter The slag containing copper converting (vessel slag) that cinder notch obtains adds direct current electric arc furnace, while adds cold conditions blast furnace slag, VOD/VAD slags and smelting Ferro-alloy cinder caused by carbon ferromanganese, the leaded smelting slag of liquid high lead dross reduction stove, form mixing slag；Slag will be mixed Molten condition is heated to, forms the reaction slag of cupric and iron, and makes reaction slag electromagnetic agitation, realizes that nature mixes；In real time Monitoring reaction slag, ensure (a) and (b) two parameters, the slag after the completion of being reacted simultaneously by regulation and control；Corresponding (a)：Contain The temperature of the reaction slag of copper and iron is 1660 DEG C, using in refractory lance intercalation reaction slag, using nitrogen as gas is loaded into, is sprayed into The copper ashes of normal temperature powdery granularity≤150 μm, containing Bellamya aeruginosa, composition brass and cupric rubbish and containing copper circuit board, while add high tile This mud, electric furnace dust mud, bof sludge, common iron ore concentrate DRI and blast furnace dust, make temperature be down to 1380 DEG C；(b)： The basicity CaO/SiO of the reaction slag of cupric and iron2Ratio=2.8, silica, flyash and gangue are added into reaction slag Mixture, the reaction slag basicity ratio of cupric and iron is set to be down to 1.3；Metal Ferrum content is 0.8% in slag；
Step 2, separation and recovery uses method one：
6min is incubated, slag natural subsidence, slag-gold separation, obtains molten state copper-rich phase layer, Fe-riched phase and Iron-containing silicate Mineral facies, while zinc component and lead component are generated, carry out following steps：(1) Iron containing silicate minerals phase, carry out at the outer slag of stove Reason, using method F, after Iron-containing silicate slag air cooling, as direct reduction iron making raw material, carried out directly also using rotary kiln Original, using gas-based reduction technology, gas-based reduction agent is natural gas and coal gas, and reduction temperature is 900 DEG C, basicity CaO/SiO2Ratio For 0.8, metallic iron and slag are separately won to obtain using magnetoelectricity stove is molten after reduction, it is molten to divide temperature to be 1550 DEG C；(2) molten state copper-rich phase, It is sent to continuous-blowing furnace copper metallurgy；(3) Fe-riched phase pours into attemperator, and blast furnace ironmaking raw material is used as after air cooling；(4) zinc component, indium Component, lead component, bismuth component, potassium component, sodium component volatilization oxide form enter fume recovery, the Copper in Slag finally obtained< 0.1%, zinc recovery 92%, lead recovery 92%；Iron recovery is 93%, and golden accumulation rate is 96%, silver-colored enrichment Rate is 94%, indium recovery 94%, and the bismuth rate of recovery is 95%, and the sodium rate of recovery is 95%, and the potassium rate of recovery is 97%.Wherein, exist In all embodiments of the present invention, Copper in Slag refers to the slag phase after copper-rich phase separation, specially Fe-riched phase and silicate mineral phase In copper content, 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.
Embodiment 2
A kind of method by cupric and the mixing slag recovery valuable component of iron, comprise the following steps：
Step 1, clinker mixes：By by the Isa furnace cupric smelting slag that matte smelting stove slag notch obtains with being slagged tap with converter The slag containing copper converting (vessel slag) that mouth obtains adds dumpable melting reaction slag and filled, while adds by the melting of slag notch acquisition State smelts ferro-alloy cinder caused by ferrochrome, forms mixing slag；With oxygen-enriched air, Natural GasInjecting, granularity are that 20mm is smokeless Coal and char particle, mixing slag is heated to molten condition, forms the reaction slag of cupric and iron, and stir reaction slag electromagnetism Mix, realize 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；1660 DEG C of corresponding (a) cupric and iron reaction slag temperature, using in refractory lance intercalation reaction slag, using argon gas for load Gas, spray into normal temperature powdery granularity≤150 μm copper ashes, steel sintering dust, agglomerates of sintered pellets dust, go out ironworks dust, containing copper circuit Plate, common iron ore concentrate, common iron ore concentrate DRI and common iron ore concentrate sintered ore deposit, make temperature be down to 1360 DEG C；(b) cupric With iron reaction slag basicity CaO/SiO2Ratio is 2.7, and acid sinter ore, acid iron ore concentrate and acidity are added into reaction slag Pre-reduced pellet, cupric is reacted slag basicity ratio with iron and be down to 1.3；Metal Ferrum content is 2.9% in slag；
Step 2, separation and recovery uses method two：47min is incubated, slag spun down, slag-gold separation, obtains molten state Copper-rich phase layer, Fe-riched phase and Iron containing silicate minerals phase, generation zinc zinc component, lead component and indium component, into flue dust, carry out such as Lower step：(1) molten state silicate mineral phase pours into insulation slag ladle with Fe-riched phase, and slag is carried out using the method G in method one Fused reduction iron-smelting, comprise the following steps that：It is 20mm anthracites and bituminous coal that (1-1), which adds granularity into slag, melt also Original, monitoring reaction slag, by regulating and controlling to ensure that the temperature that following (a) reacts slag is 1350~1650 DEG C, and (b) reaction slag Basicity CaO/SiO2Ratio=0.6~2.4 two parameter, the slag after the completion of being reacted；Corresponding (a)：React the temperature of slag Spend for 1420, in temperature range；Corresponding (b)：React basicity CaO/SiO in slag2When ratio is 0.8, in alkalinity ranges； (1-2) oxygen-enriched air of 200 DEG C of blowing preheated into slag after the completion of reaction carries out melting and reducing, and mixing is molten after forming reduction Slag, and during injection, it is 1350~1650 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, settles slag-gold Separation, obtain molten iron and slag after reduction；(b) slag after reducing, high added value is made using method A processing in step 2 method one Cement raw material；(c) molten iron is sent to converter or electric furnace steel making；(d) component containing zinc, leaded component, bismuth component and indium component volatilization, with Oxide form enters fume recovery；(e) component containing sodium, component volatilization containing potassium, into fume recovery；(2) molten state copper-rich phase, It is sent to converter copper metallurgy；(3) zinc component and lead component volatilization, enter fume recovery, zinc recovery 92%, Copper in Slag with oxide <0.1%, lead recovery 92%；Iron recovery is 91%, indium recovery 96%, and the bismuth rate of recovery is 96%, and the sodium rate of recovery is 97%, the potassium rate of recovery is 98%, and golden accumulation rate is 94%, and silver-colored accumulation rate is 95%.
Embodiment 3
A kind of method by cupric and the mixing slag recovery valuable component of iron, comprise the following steps：
Step 1, clinker mixes：By the Ausmelt furnace cupric smelting slag obtained by matte smelting stove slag notch and and converter The slag containing copper converting (vessel slag) that slag notch obtains adds induction furnace, while adds the slag obtained by pneumatic steelmaking slag notch, Form mixing slag；With the oxygen that temperature is 600 DEG C, injection granularity is 20mm anthracites, char particle and coal dust, and mixing slag is added Heat forms the reaction slag of cupric and iron, and slag is realized mixing to molten condition；Monitoring slag in real time, it is same by regulating and controlling When ensure (a) and (b) two parameters, the slag after the completion of being reacted；Corresponding (a)：The temperature of the reaction slag of cupric and iron For 1685 DEG C, quartz sand, red mud, dolomite, lime stone, the big kiln slag of zinc hydrometallurgy are added into reaction slag, while add and contain Copper material, common Iron Ore Pellets, common iron ore concentrate metallized pellet and the carbon containing pre-reduced pellet of common iron ore concentrate, make temperature It is down to 1320 DEG C；(b)：The basicity CaO/SiO of the reaction slag of cupric and iron2Ratio=3.0, added into reaction slag acid The mixture of metallized pellet, cupric smelting slag and the slag containing copper converting, it is down to the basicity ratio of the reaction slag of cupric and iron 1.2；Metal Ferrum content is 2.1% in slag；
Step 2, separation and recovery uses method two：15min 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 and leaded component are generated, carry out following steps：(1) melt Melt state copper-rich phase, be sent to converter copper metallurgy；(2) molten state Fe-riched phase and Iron containing silicate minerals are mutually former as direct reduction iron making Material, direct-reduction product magnetic separation separation, obtains metallic iron and mine tailing, zinc component, lead component volatilization, in the form of an oxide into cigarette Dirt；In reduction process, using rotary hearth furnace, reduction temperature is 1200 DEG C, basicity CaO/SiO2Ratio=1.0；(3) component containing zinc with Leaded component volatilization, in the form of an oxide into fume recovery, Copper in Slag<0.08%, the rate of recovery of iron is 93%, the recovery of zinc Rate is 93%, and the rate of recovery of lead is 94%, and the sodium rate of recovery is 93%, and the potassium rate of recovery is 94%, and golden accumulation rate is 95%, silver-colored Accumulation rate is 96%, indium recovery 96%, and the bismuth rate of recovery is 95%.
Embodiment 4
A kind of method by cupric and the mixing slag recovery valuable component of iron, comprise the following steps：
Step 1, clinker mixes：The noranda furnace cupric smelting slag of cold conditions, copper dilution waste are added into plasma heating furnace, simultaneously The ferro-alloy cinder that the converter slag obtained by slag notch, electric furnace slag and smelting ferronickel obtain is added, forms mixing slag；Will Mixing slag is heated to molten condition, forms cupric and iron reaction slag, and makes the argon that reaction slag injection temperature is 1200 DEG C Gas, realize 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；The temperature of the reaction slag of corresponding (a) cupric and iron is 1650 DEG C, and red mud, coal dust ash, sulphur are added into reaction slag Sour slag, fluorite, lead copper matte, lead-containing soot, soot containing zinc, setting form and Zinc Hydrometallurgy Residue, temperature is set to be down to 1340 DEG C；(b) The reaction slag basicity CaO/SiO of cupric and iron2Ratio is 2.9, adds slag containing copper converting into reaction slag, makes cupric and iron Reaction slag basicity ratio is down to 1.1；Natural GasInjecting, and the char particle for being 20mm with air blown granularity, metallic iron in slag Content is 2.9%；
Step 2, separation and recovery uses method three：19min, slag natural subsidence after the completion of reaction are incubated, slag-gold separates, Molten state copper-rich phase, Fe-riched phase and Iron containing silicate minerals phase are obtained, and containing zinc and leaded component, carries out following steps：(1) melt Melt state copper-rich phase and molten state Fe-riched phase, be sent to converter copper metallurgy；(2) Iron containing silicate minerals mutually use the method A in method one, After water quenching, as cement raw material；(3) the partly bismuth of component containing zinc component, indium component and leaded component volatilization, enter in the form of an oxide Enter fume recovery, Copper in Slag<0.1%, the rate of recovery of iron is 90%, and the rate of recovery of zinc is 92%, and the rate of recovery of lead is 92%, indium The rate of recovery is 93%, and the bismuth rate of recovery is 94%, and golden accumulation rate is 95%, and silver-colored accumulation rate is 97%, and the sodium rate of recovery is 95%, The potassium rate of recovery is 96%.
Embodiment 5
A kind of method by cupric and the mixing slag recovery valuable component of iron, comprise the following steps：
Step 1, clinker mixes：The cupric smelting slag of cold conditions Mitsubishi process and copper ashes flotation tailing are added with wet type copper smelting slag Slag ladle is incubated, while adds the converter molten steel slag obtained by slag notch, forms mixing slag；It it is 800 DEG C with preheating temperature Air, injection granularity are 20mm bituminous coal and coal dust, mixing slag are heated into molten condition, the reaction for forming cupric and iron is melted Slag, and reaction slag is realized mixing；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 must reacting；Corresponding (a)：The reaction slag temperature of cupric and iron is 1210 DEG C；(b)：Cupric and iron reaction are molten Basicity of slag CaO/SiO2Ratio is 0.75, in claimed range；Metal Ferrum content is 1.4% in slag；
Step 2, separation and recovery insulation 16min, using method nine：Slag after the completion of reaction is subjected to following steps：(1) Sedimentation cooling：Slag rotation after the completion of reaction is cooled to room temperature, obtains slow cooling slag；Copper-rich phase is deposited to the bottom of reaction unit Portion, form metallic copper and stick together；Iron containing silicate minerals mutually float；Copper-rich phase metal sticks together is with slow cooling slag among Iron containing silicate minerals Fe-riched phase, while generate containing zinc and leaded component；(2) separate：The copper-rich that artificial taking-up is deposited in bottom sticks together, and is reduced directly, magnetic After choosing separation iron, product is sent to converter；The Fe-riched phase layer at middle part is routed directly to converter ironmaking；(3) iron content on top is manually taken out Silicate mineral phase, silicate mine tailing is obtained, is used as cement raw material；(4) part zinc component and lead component volatilization, with oxidation Thing form enters fume recovery, Copper in Slag<0.15%, the rate of recovery of iron is 96%, and the rate of recovery of zinc is 94%, the rate of recovery of lead For 93%, golden accumulation rate is 94%, and silver-colored accumulation rate is 96%.
Embodiment 6
A kind of method by cupric and the mixing slag recovery valuable component of iron, comprise the following steps：
Step 1, clinker mixes：The slag containing copper converting (vessel slag) obtained by converter slag notch is added into ac arc furnace, Ferro-alloy cinder caused by ferro-alloy cinder caused by cold conditions smelting ferrovanadium and smelting duriron is added simultaneously, forms mixing slag； Mixing slag is heated to molten condition, forms cupric and iron reaction slag, and makes reaction slag blowing preheated temperature be 400 DEG C Argon-nitrogen gaseous mixture, mixing；The slag of monitoring reaction in real time, ensure (a) (b) two parameter simultaneously by regulation and control, reacted After the completion of slag；Corresponding (a)：Cupric is 1040 DEG C with iron reaction slag temperature, and oxygen-enriched air, heavy oil are added into reaction slag With melting slag containing copper converting, temperature is set to rise to 1330 DEG C；(b)：Cupric and iron reaction slag basicity CaO/SiO2Ratio is 0.1, Alkaline iron ore concentrate and alkaline pre-reduced pellet are added into reaction slag, cupric is reacted slag basicity ratio with iron and rises to 0.4； Metal Ferrum content is 1.8% in slag；
Step 2, separation and recovery uses method one：21min is incubated, by the slag natural subsidence after the completion of reaction, slag-gold point From, molten state copper-rich phase, Fe-riched phase and Iron containing silicate minerals phase are obtained, and containing zinc and leaded component, progress following steps： (1) molten state Iron containing silicate minerals mutually use the method A of step 2 separation and recovery method one, and cement raw material is directly made in water quenching；(2) melt Melt state copper-rich phase, be sent to converter copper metallurgy；(3) after Fe-riched phase pours into attemperator cooling, direct reduction iron making；(4) zinc is partly contained With leaded component volatilization, in the form of an oxide into fume recovery, Copper in Slag<0.1%, the rate of recovery of iron is 91%, and zinc returns Yield is 94%, and the rate of recovery of lead is 92%, and golden accumulation rate is 94%, and silver-colored accumulation rate is 96%.
Embodiment 7
A kind of method by cupric and the mixing slag recovery valuable component of iron, comprise the following steps：
Step 1, clinker mixes：By the silver stove smelting slag obtained by matte smelting stove slag notch with being slagged tap by bessemerizing Slag containing copper converting (vessel slag), the copper ashes flotation tailings of mouth acquisition add mineral hot furnace, while add the smelting niobium of slag notch acquisition Clinker caused by clinker caused by iron and Smelting Ferromolybdenum, form mixing slag；Mixing slag is heated to molten condition, formation contains The reaction slag of copper and iron, and make reaction slag nitrogen-blow, realize mixing；The slag of monitoring reaction in real time, by regulating and controlling simultaneously Ensure (a) and (b) two parameters, the slag after the completion of being reacted；Corresponding (a)：The temperature of the reaction slag of cupric and iron is 1320℃；(b)：The basicity CaO/SiO of the reaction slag of cupric and iron2Ratio is 0.8；Natural GasInjecting, metallic iron in slag Content is 2.5%；
Step 2, separation and recovery uses method four：15min is incubated, by slag natural subsidence after the completion of reaction, slag-gold point From, acquisition molten state copper-rich phase, Fe-riched phase, Iron containing silicate minerals phase and zinc component and lead component, progress following steps：(1) Molten state copper-rich phase, send converter copper metallurgy；(2) molten state Fe-riched phase uses the method D in method one with Iron-containing silicate：(1) to The oxidizing gas that preheating temperature is 800 DEG C is blown into slag, slag temperature control is higher than 1350 DEG C；(2) it is molten after aoxidizing Pulp water is quenched, as clinker
(3) partly component containing zinc and leaded component volatilization, oxide enter fume recovery, Copper in Slag<0.1%, iron returns Yield is 91%, and the rate of recovery of zinc is 93%, and the rate of recovery of lead is 92%, and golden accumulation rate is 95%, and silver-colored accumulation rate is 97%.
Embodiment 8
A kind of method by cupric and the mixing slag recovery valuable component of iron, comprise the following steps：
Step 1, clinker mixes：By cold conditions Flash Smelting Furnace cupric smelting slag and flash blowing, copper ashes containing copper converting adds air blast Stove, while the blast furnace slag and electric furnace slag obtained by slag notch is added, form mixing slag；With the sky that preheating temperature is 600 DEG C Gas, injection granularity are 20mm bituminous coal and coal dust, and mixing slag is heated into molten condition, forms the reaction slag of cupric and iron, And reaction slag is set to realize mixing；The slag of monitoring reaction in real time, ensures (a) and (b) two parameters simultaneously by regulation and control, obtains anti- Slag after the completion of answering；Corresponding (a)：The temperature of the reaction slag of cupric and iron is 1330 DEG C；(b)：The reaction of cupric and iron is melted The basicity CaO/SiO of slag2Ratio is 1.0, in claimed range；Metal Ferrum content is 2.9% in slag；
Step 2, separation and recovery uses method three：10min is incubated, by slag natural subsidence after the completion of reaction, slag-gold point From, copper-rich phase and middle and upper part Iron containing silicate minerals phase are obtained, while generate containing zinc and leaded component, carry out following steps：(1) Molten state Iron containing silicate minerals phase, the method B of step 2 separation and recovery method one specifically is used, middle and upper part slag is all returned to Cupric and iron reaction slag, as hot flux for metallurgy, adjustment cupric and iron reaction slag composition, control its temperature；(2) melt State copper-rich phase Fe-riched phase, is sent to converting furnace copper metallurgy；(3) partly component containing zinc and leaded component volatilization, oxide return into flue dust Receive, Copper in Slag<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 94%, golden accumulation rate For 98%, silver-colored accumulation rate is 96%.
Embodiment 9
A kind of method by cupric and the mixing slag recovery valuable component of iron, comprise the following steps：
Step 1, clinker mixes：The cupric smelting slag that golden peak side-blowing bath smelting furnace slag notch obtains is obtained with converter cinder notch Slag containing copper converting (vessel slag), wet type copper smelting slag joining side blows back converter, while adds by the molten state of slag notch acquisition Blast furnace slag and VD slags, form mixing slag；Mixing slag is heated to molten condition, forms the reaction slag of cupric and iron, and Reaction slag is set to realize injection argon gas mixing；The slag of monitoring reaction in real time, ensure (a) and (b) two parameters simultaneously by regulation and control, Slag after the completion of being reacted；Corresponding (a)：The reaction slag temperature of cupric and iron is 1340 DEG C；(b)：Cupric and iron it is anti- Answer slag basicity CaO/SiO2Ratio is 1.2, is met the requirements；It is 20mm with the air blown granularity that preheating temperature is 1000 DEG C Char particle, metal Ferrum content is 2.5% in slag；
Step 2, separation and recovery uses method five：10min is incubated, by slag natural subsidence after the completion of reaction, slag-gold point From, acquisition molten state copper-rich phase, Fe-riched phase and middle and upper part Iron containing silicate minerals phase, and containing zinc and leaded component, carry out such as Lower step：(1) middle and upper part slag uses method C in step 2 separation and recovery method one, pours devitrified glass；(2) bottom molten state is rich Copper phase, Fe-riched phase are sent to converter copper metallurgy；(3) partly containing zinc and leaded component, in the form of an oxide into fume recovery, Copper in Slag <0.1%, the rate of recovery of iron is 93%, and the rate of recovery of zinc is 94%, and the rate of recovery of lead is 92%, and golden accumulation rate is 95%, silver Accumulation rate be 97%.
Embodiment 10
A kind of method by cupric and the mixing slag recovery valuable component of iron, comprise the following steps：
Step 1, clinker mixes：
By the melting cupric smelting slag of bottom blowing molten pool smelting furnace slag notch outflow and the cupric of bottom blowing continuous-blowing furnace outflow The slag that blows adds thermal insulation pit, while adds the melting converter slag of cinder notch acquisition, forms mixing slag；It is with preheating temperature 800 DEG C of oxygen-enriched air, granularity≤150 μm bituminous coal is blown, mixing slag is heated to molten condition, it is molten to form cupric reaction Slag, and reaction slag is realized mixing；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 obtaining；
Corresponding (a)：The temperature of cupric reaction slag is 1330 DEG C；(b)：Cupric reacts the basicity CaO/SiO of slag2Ratio For 0.9, in claimed range；Metal Ferrum content is 1.9% in slag；
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 slowly cooled to room temperature, and obtains slow cooling slag；Copper-rich Copper is mutually deposited to the bottom of reaction unit, forms copper-rich and sticks together；Iron containing silicate minerals mutually float；Copper-rich phase metal sticks together and silicate Slow cooling slag is Fe-riched phase among mineral, while generates component containing zinc and leaded component；
Fe-riched phase (2) separates：The copper-rich that artificial taking-up is deposited in bottom sticks together；After the Fe-riched phase layer direct-reduction at middle part, magnetic Choosing separation metallic iron, mine tailing return to the Iron containing silicate minerals phase that copper system system Fe-riched phase (3) manually takes out top, obtain silicate Mine tailing, used as cement raw material；
(4) part zinc component and lead component volatilization, in the form of an oxide into fume recovery, Copper in Slag<0.15%, iron The rate of recovery is 98%, and the rate of recovery of zinc is 96%, and the rate of recovery of lead is 94%, and golden accumulation rate is 95%, and silver-colored accumulation rate is 96%.
The above described is only a preferred embodiment of the present invention, being not the limitation that other forms are done to the present invention, appoint What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc. Imitate embodiment.But it is every without departing from technical solution of the present invention content, the technical spirit according to the present invention is to above example institute Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.

Claims (10)

  1. A kind of 1. method by cupric and the mixing slag recovery valuable component of iron, it is characterised in that it comprises the following steps：
    S1, clinker mixing：Copper ashes is added in melting reaction device, while adds lead metallurgical slag, blast furnace slag, slag and ferroalloy One or more formed in slag mixes slag；Slag is heated to molten condition and forms reaction slag, is well mixed, in real time prison Survey the reaction slag, while make the reaction slag after mixing by regulation and control, while meet condition a and condition b, after being reacted Slag；
    Wherein, the condition a be control reaction slag temperature be 1050~1450 DEG C；
    The condition b is the basicity CaO/SiO of control reaction slag2Ratio=0.15~1.5；
    S2, separation and recovery：The reacted slags of step S1,5~50min of insulation, the copper-rich phase of sedimentation separation acquisition bottom, The Fe-riched phase at middle part and the Iron containing silicate minerals phase on top, while generate the flue dust of component containing zinc and leaded component, gold and silver group Separating/enriching enters copper-rich phase；Each phase is handled.
  2. 2. the method as described in claim 1, it is characterised in that in the step S1, the method for the condition a regulation and control is：
    When it is described reaction slag 1050 DEG C of temperature ＜, using the heating of reaction unit itself, or into slag add fuel or Molten copper slag, fusion of lead metallurgical slag, molten blast furnace slag, molten steel slag or 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 1050~1450 DEG C；
    As 1450 DEG C of the temperature ＞ of the reaction slag, copper-contained material, nickel fibers slag, blast furnace slag, steel are added into reaction slag One or more in slag, ferroalloy slag, flux for metallurgy, ferrous material or fluorine-containing material, make the temperature of the reaction slag of mixing Reach 1050~1450 DEG C；
    The method of condition b regulation and control is：
    As basicity CaO/SiO in the reaction slag2Ratio<When 0.15, alkaline material and/or alkalescence are added into reaction slag Ferrous material；
    As basicity CaO/SiO in the reaction slag2Ratio>When 1.5, add acid material into reaction slag and/or acidity contains Iron material.
  3. 3. the method as described in claim 1, it is characterised in that the reaction unit is that attemperator or rotatable melting are anti- Answer device or the melting reaction device that can be flowed out with cinder notch or iron mouth slag；Wherein, the attemperator melts for dumpable Refining reaction slag fills or thermal insulation pit；
    The rotatable melting reaction device is converter, melting reaction slag ladle；
    The melting reaction device that can be flowed out with cinder notch or iron mouth slag is plasma heating furnace, direct current electric arc furnace, alternating current arc Stove, 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 melt Furnace, reverberatory furnace, Ausmelt furnace, Isa furnace, watt button can husband's bath smelting furnace, side-blown rotary furnace, bottom blowing rotary furnace, top blast time Converter.
  4. 4. the method as described in claim 1, it is characterised in that in the step S1, while meeting the condition a and b, It should simultaneously meet, Cu oxide and ferriferous oxide should be met to control in the slag to be reduced to metallic copper and FeO simultaneously, in slag Metal Ferrum content<3%.
  5. 5. the method as described in claim 1, it is characterised in that the copper ashes is cupric smelting slag, slag containing copper converting, pyrometallurgical One or more of in dilution waste, flotation tailings, wet type copper smelting slag, cupric smelting slag results from the pyrometallurgical smelting process of copper " matte smelting " process, including this difficult to understand matt stove smelting slag, Flash Smelting Furnace smelting slag, noranda furnace smelting slag, Isa furnace smelting slag, Wa Niukefu stoves smelting slag, Mitsubishi process smelting slag, Kaldo Furnace smelting slag, silver stove smelting slag, Shuikoushan method smelting slag, Te Ni Grace spy smelting slag, reverberatory smelting slag, electro-smelting slag, closed blast furnace smelting slag, low blown converter smelting slag, side-blown converter melting Slag；The slag containing copper converting results from " Copper Matte Converting " process of the pyrometallurgical smelting process of copper, including bessemerizes copper ashes, flash Stove blowing copper ashes, noranda furnace continuous converting copper ashes, top Bessemer blow copper ashes, side-blown converter blowing copper ashes, bottom convertor blowing copper ashes, Top blast stove continuous converting copper ashes, side-blown converter continuous converting copper ashes, bottom convertor continuous converting copper ashes；The pyrometallurgical dilution waste is Cupric smelting slag and waste after the dilution of slag containing copper converting, flotation tailings are tailings after cupric smelting slag and the ore dressing of slag containing copper converting, Wet type copper smelting slag is wet type copper smelting waste；The copper weld pool slag and copper converting slag are molten state or cold conditions, wherein：Melt copper weld pool Slag is obtained by the copper smelter slag notch of " matte smelting " process, or cupric smelting slag is heated into molten condition, and molten copper blows Refine slag to be obtained by the copper converting stove slag notch of " Copper Matte Converting " process, or copper converting slag is heated to molten condition, dilution waste Obtained by dilution stove slag notch, obtain and poor slugging is heated to molten condition；
    The lead metallurgical slag includes fuming slag and leaded smelting slag, and lead metallurgical slag is molten state or cold conditions, wherein molten state stove Slag by pyrometallurgical smelting of lead technique reduction phase slag notch or fuming furnace slag notch obtain；The blast furnace slag, slag and ferroalloy Slag is molten state, or cold conditions, wherein：Molten state clinker is obtained by slag notch, or cold conditions clinker is heated into molten condition；It is affiliated Slag is molten iron pre-desulfurization slag, vessel slag, electroslag, VOD/VAD slags, VD slags, tundish waste；The ferro-alloy cinder is iron Caused clinker during alloy production, including smelt clinker caused by carbon ferromanganese, smelt clinker caused by ferrochrome, smelt nickel Clinker caused by iron, clinker caused by smelting ferrovanadium, clinker caused by smelting duriron, smelt clinker caused by ferro-niobium, smelt molybdenum Clinker caused by iron.
  6. 6. method as claimed in claim 2, it is characterised in that the fuel is one kind in solid, liquid or gaseous fuel Or it is a variety of, sprayed into, be loaded into 0~1200 DEG C of gases, the gas is oxidizing gas, argon in a manner of being blown or feeding intake One or more in gas, nitrogen；
    Method as described above, it is preferable that described copper-contained material is copper ashes, nominal group process, blister copper pyro-refining slag, zinc abstraction Slag, zinc abstraction cigarette ash and dirt mud, Pb-Zn tailings, lead metallurgical slag, lead metallurgical slag nickel fibers slag, lead copper matte, setting form, lead bullion pyrogenic process Refine lead-in-dreg fuming slag, lead smelting ash and dirt mud, lead-acid battery, Copper making cigarette ash and dirt mud, composition brass, cupric rubbish, Containing the one or more in copper circuit board, tin metallurgical slag, tailing；The lead metallurgical slag is fuming furnace clinker and contains lead smelting Slag, " reduction of ISP imperial smelting furnaces " or " 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, and leaded smelting slag is smelted by fuming furnace produces leaded fuming slag；The nickel smelting Refining slag is Ni-B alloy slag caused by " matte smelting " technique, the dilution clinker after the blowing of " nickel convering of copper ice " technique, top blow smelting It is one or more in caused nickel sedimentation clinker；The zinc smelting dreg includes clinker caused by zinc hydrometallurgy and produced with pyrometallurgy of zinc Clinker, wherein clinker caused by zinc hydrometallurgy be zinc leaching residue, volatilization kiln slag, iron vitriol slag, copper-cadmium slag, iron vitriol slag after pickling, Goethite slag, bloodstone slag are one or more, and pyrometallurgy of zinc is zinc vertical retorting clinker, cyclone smelting clinker, blast-furnace cinder, cigarette It is one or more to change clinker, electroslag；Described flux for metallurgy is containing CaO or SiO2Mineral, specially quartz sand, containing gold and silver One or more after quartz sand, red mud, removing sodium in high calcium red mud, carbide slag, dolomite or lime stone；Described ferrous material It is common iron ore concentrate, common iron ore concentrate DRI, common iron ore concentrate sintered ore deposit, common Iron Ore Pellets, common iron are smart Ore deposit metallized pellet, the carbon containing pre-reduced pellet of common iron ore concentrate, slag, zinc smelting dreg, coke smelting smoke dust and dirt mud, steel cigarette High calcium red mud after dirt and dirt mud, nickel fibers slag, copper ashes, lead metallurgical slag, zinc smelting dreg, tin metallurgical slag, red mud, removing sodium, coal dust ash, One or more in pyrite cinder；The steel flue dust includes blast furnace gas mud, bof sludge, electric furnace dust mud, heat with dirt mud drum (cold) rolls sludge, sintering dust, pelletizing dust, goes out ironworks dust, blast furnace dust, electric stove dust ash, steel rolling iron scale；
    Fluorine-containing material after lead metallurgical slag removing sodium described in high calcium red mud is fluorite, CaF2Or the one or more in fluorine-containing blast furnace slag；
    The alkaline material be pulverized limestone, red mud, after removing sodium in high calcium red mud, carbide slag, dolomite dust or calcium lime powder one Kind is several；Described alkaline ferrous material is CaO/SiO2>=1 ferrous material, alkaline sintering deposit, alkaline iron ore concentrate, alkalescence One or more in pre-reduced pellet, alkalinous metal pellet or slag；
    The acid material is the one or more in silica, lead metallurgical slag silica containing gold and silver, flyash, gangue；The acid Property ferrous material is CaO/SiO2≤ 1 ferrous material, acid sinter ore, acid iron ore concentrate, acid pre-reduced pellet, acid gold Belong to pellet, copper ashes, lead metallurgical slag, zinc smelting dreg, nickel fibers slag, tin metallurgical slag, ferroalloy slag, one kind in blast furnace slag or several Kind.
  7. 7. such as the method any one of claim 1-6, it is characterised in that in the step S2 separation and recovery, carry out such as Lower processing：
    Copper-rich phase described in hot or cold conditions, it is sent to again 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, 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；
    The component containing zinc and leaded component volatilization, in the form of an oxide into flue dust；
    Containing the Iron containing silicate minerals phase and/or the Fe-riched phase, any of following method A-G processing is carried out；
    Method A：After water quenching or air cooling, directly as cement raw material；
    Method B：Partly or entirely return in the reaction slag and be used as hot flux for metallurgy；
    Method C：For pouring devitrified glass or as mineral wool；
    Method D：The Iron containing silicate minerals phase and/or the Fe-riched phase are retained in melting reaction device or are poured into guarantor Warm device, into slag, it is blown into temperature and is 0~1200 DEG C of preheating oxidizing gas, and ensure slag temperature>1450℃；When Slag ferrous oxide weight percent content<1%, the slag after being aoxidized；Slag Direct Air-Cooled or water after the oxidation Quench, 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 containing silicate minerals phase and/or the Fe-riched phase are retained in melting reaction device or pour into slag Attemperator, into slag, add molten steel slag, lime, lime stone, ferro-alloy cinder, flyash, basic iron lean ore, alum clay One or more after ore deposit, molten blast furnace slag, red mud, removing sodium in red mud or carbide slag, are sufficiently mixed, and obtain slag mixture Material；
    Preheating temperature is blown into E-2, upward slag mixed material and is 0~1200 DEG C of oxidizing gas, and ensures that slag mixes Temperature of charge>1450℃；When ferrous oxide weight percent 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 containing silicate minerals phase and/or the Fe-riched phase slag are as blast furnace ironmaking raw material or direct-reduction refining Iron material：After the slag air cooling of Iron containing silicate minerals phase and/or the Fe-riched phase, water quenching or slow cooling, 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 is metallic iron and mine tailing, Molten point of electric furnace, product is molten iron and slag；
    Or after the slag of the Iron containing silicate minerals phase and/or the Fe-riched phase is poured into attemperator, using following methods Separated：The modified magnetic separation separation of slag：Slag into attemperator, it is blown into the oxidisability gas of 0~1200 DEG C of preheating Body, and ensure 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, product is magnetite concentrate and mine tailing, and mine tailing is as construction material；
    Method G：Reduction iron production is carried out, is comprised the following steps：
    G-1, the slag of the Iron containing silicate minerals phase and/or the Fe-riched phase is retained in melting reaction device or will be molten Slag pours into attemperator, and ferrous material, reducing agent are added into molten state slag, carries out melting and reducing, and monitoring reaction in real time is molten Slag, meet condition simultaneously by regulation and control：The temperature for reacting slag is 1350~1650 DEG C and the basicity CaO/SiO of reaction slag2 Ratio=0.6~2.4, the slag after the completion of being reacted；
    Wherein, the method for temperature for controlling reaction slag is：
    As 1350 DEG C of the temperature ＜ of reaction slag, by the heating of reaction unit itself, or fuel and preheating are added into slag Oxidizing gas, the temperature of reaction slag is reached 1350~1650 DEG C；
    As 1650 DEG C of the temperature ＞ of reaction slag, added into reaction slag in flux for metallurgy, ferrous material or fluorine-containing material One or more, the temperature of reaction slag is set to reach 1350~1650 DEG C；Wherein, the flux for metallurgy is containing CaO or SiO2's Mineral；
    The method of basicity for controlling reaction slag is：
    When reacting basicity CaO/SiO in slag2Ratio<When 0.6, alkaline material and/or alkaline ferrous material are added into slag；
    When reacting basicity CaO/SiO in slag2Ratio>When 2.4, acid material and/or iron-containing acidic material is added into slag；
    The oxidizing gas into slag after 0~1200 DEG C of preheating of injection is also needed to be melted in G-2, the G-1 during melting and reducing Melt reduction, the slag formed after reduction；
    G-3, separation and recovery：Using one kind in following methods：
    Method I：Mixing slag after reduction is poured into insulation slag ladle, is cooled to room temperature, obtains slow cooling slag；Wherein, metallic iron sinks The bottom of reaction unit is dropped to, iron is formed and sticks together, by containing metal iron layer in remaining slow cooling slag, be crushed to 20~400 μm of granularity, grind Residual metallic iron and mine tailing are isolated in ore deposit, magnetic separation；
    Method II：Mixing slag after reduction, cooling-sedimentation, slag-gold separation, obtain molten iron and the slag after reduction；It is described to go back Slag after original, slag treatment is carried out according to one or more of methods in method A~E；The molten iron, it is sent to converter or electric furnace Steel-making；
    Or indium component, bismuth component, component containing sodium and component volatilization containing potassium, into flue dust；
    Or carry out water quenching or air cooling containing the Fe-riched phase layer or pour into attemperator slow cooling or combined through manual sorting with gravity treatment Obtain, copper raw material or magnetic separation are proposed 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 separation metallic iron；Float product is to be returned containing copper concentrate and iron ore concentrate, copper concentrate Freshening 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, exist In Direct Reduction, after reduzate magnetic separation separation, metallic iron and mine tailing are obtained, mine tailing returns to copper metallurgy system；It is described direct Reduction process uses rotary hearth furnace, tunnel cave, underbody road, shaft furnace, rotary kiln or induction furnace, utilizes gas base or coal base reduction, gas base Reduction uses natural gas and/or coal gas, and coal base reduction uses one kind in anthracite, bituminous coal, lignite, coking coal, coke powder or coke Or it is several, it is 900~1400 DEG C to control reduction temperature, control basicity CaO/SiO2Ratio=0.8~1.5.
  8. 8. method as claimed in claim 7, it is characterised in that the oxidizing gas is the air, oxygen, oxygen-enriched sky of preheating One kind in gas, nitrogen-air, argon gas-air, oxygen-nitrogen, oxygen-argon gas, the temperature of the preheating is 0~1200 DEG C.
  9. 9. method as claimed in claim 7, it is characterised in that the fuel and reducing agent are solid, liquid or gaseous fuel In one or more, sprayed into a manner of being blown or feeding intake, it is described injection be loaded into gas for preheating oxidizing gas, nitrogen Or the one or more in argon gas, the temperature of the preheating is 0~1200 DEG C；The solid fuel is coal dust, Jiao with reducing agent One or more in powder, coke, flyash, bituminous coal or anthracite, are shaped as granular or powdery, and granular material granularity is 5~ 25mm, granular material granularity are≤150 μm, and the liquid fuel and reducing agent are heavy oil, and the gaseous fuel is with reducing agent Coal gas and/or natural gas.
  10. 10. the method as described in claim 1, it is characterised in that described to be well mixed to mix naturally in the step S1 Or be stirred, wherein, the mode being stirred be argon gas stirring, nitrogen gas stirring, nitrogen-argon gas mixing gas agitating, and also One or more in originality Gas Stirring, oxidizing gas stirring, electromagnetic agitation or mechanical agitation；
    It is described to be settled into natural subsidence or spun down or centrifugal sedimentation in the step S2；It is cold during progress cooling-sedimentation But mode is natural cooling or rotation cooling or centrifugation cooling, is separation by shaking table, chute point with gravity separation method during the separation Select or the two is combined.
CN201710936823.9A 2017-10-10 2017-10-10 A kind of method by cupric and the mixing slag recovery valuable component of iron Pending CN107699704A (en)

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CN110698069A (en) * 2019-10-15 2020-01-17 昆明理工大学 Method for preparing microcrystalline glass by directly pouring molten copper slag and performing temperature-control condensation molding
CN110904340A (en) * 2019-12-10 2020-03-24 武翠莲 Method for removing harmful elements and impurities in iron-containing mixture by centrifugation
CN111139361A (en) * 2019-12-30 2020-05-12 东营方圆有色金属有限公司 Process method for utilizing valuable elements in all components of copper smelting waste slag
CN112375856A (en) * 2020-10-28 2021-02-19 东北大学 Method for improving iron content of converter slag and nickel slag and/or copper slag by melt coupling modification
CN112746139A (en) * 2021-01-01 2021-05-04 新疆互力佳源环保科技有限公司 Method for cooperatively treating waste lead-acid storage battery by using liquid steel slag
WO2022057882A1 (en) * 2020-09-18 2022-03-24 中南大学 Resource recycling method for copper smelting residue
CN114959276A (en) * 2022-04-12 2022-08-30 河南豫光金铅股份有限公司 Method for recovering lead, zinc and copper in smelting waste slag through side-blown smelting
CN115141938A (en) * 2021-03-29 2022-10-04 东北大学 Method for diluting copper smelting slag by using copper refining slag
CN115138448A (en) * 2022-07-25 2022-10-04 江苏省镔鑫钢铁集团有限公司 Method for partially replacing sintered limestone and dolomite with converter steel slag
CN115141937A (en) * 2021-03-29 2022-10-04 东北大学 Method for mixed dilution and iron component growth of copper-nickel smelting slag
CN115558797A (en) * 2022-10-12 2023-01-03 昆明理工大学 Comprehensive resource utilization process for high nickel matte oxygen pressure leaching slag

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CN110172593A (en) * 2019-06-13 2019-08-27 云南锡业股份有限公司铜业分公司 A kind of energy-saving and environment-friendly tin smelting system and smelting process
CN110698069A (en) * 2019-10-15 2020-01-17 昆明理工大学 Method for preparing microcrystalline glass by directly pouring molten copper slag and performing temperature-control condensation molding
CN110904340A (en) * 2019-12-10 2020-03-24 武翠莲 Method for removing harmful elements and impurities in iron-containing mixture by centrifugation
CN111139361A (en) * 2019-12-30 2020-05-12 东营方圆有色金属有限公司 Process method for utilizing valuable elements in all components of copper smelting waste slag
WO2022057882A1 (en) * 2020-09-18 2022-03-24 中南大学 Resource recycling method for copper smelting residue
CN112375856A (en) * 2020-10-28 2021-02-19 东北大学 Method for improving iron content of converter slag and nickel slag and/or copper slag by melt coupling modification
CN112746139A (en) * 2021-01-01 2021-05-04 新疆互力佳源环保科技有限公司 Method for cooperatively treating waste lead-acid storage battery by using liquid steel slag
CN115141938A (en) * 2021-03-29 2022-10-04 东北大学 Method for diluting copper smelting slag by using copper refining slag
CN115141937A (en) * 2021-03-29 2022-10-04 东北大学 Method for mixed dilution and iron component growth of copper-nickel smelting slag
CN114959276A (en) * 2022-04-12 2022-08-30 河南豫光金铅股份有限公司 Method for recovering lead, zinc and copper in smelting waste slag through side-blown smelting
CN114959276B (en) * 2022-04-12 2024-04-19 河南豫光金铅股份有限公司 Method for recycling lead, zinc and copper in smelting waste slag by side-blown smelting
CN115138448A (en) * 2022-07-25 2022-10-04 江苏省镔鑫钢铁集团有限公司 Method for partially replacing sintered limestone and dolomite with converter steel slag
CN115138448B (en) * 2022-07-25 2023-08-08 江苏省镔鑫钢铁集团有限公司 Method for partially replacing sintered limestone and dolomite with converter steel slag
CN115558797A (en) * 2022-10-12 2023-01-03 昆明理工大学 Comprehensive resource utilization process for high nickel matte oxygen pressure leaching slag
CN115558797B (en) * 2022-10-12 2023-07-18 昆明理工大学 Comprehensive utilization process for resources of high nickel matte oxygen pressure leaching slag

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