CN107699700A - A kind of method that valuable component is reclaimed by slag containing nickel fibers - Google Patents

A kind of method that valuable component is reclaimed by slag containing nickel fibers Download PDF

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Publication number
CN107699700A
CN107699700A CN201710936072.0A CN201710936072A CN107699700A CN 107699700 A CN107699700 A CN 107699700A CN 201710936072 A CN201710936072 A CN 201710936072A CN 107699700 A CN107699700 A CN 107699700A
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slag
iron
copper
reaction
nickel
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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 CN201710936072.0A priority Critical patent/CN107699700A/en
Priority to PCT/CN2017/115642 priority patent/WO2019071787A1/en
Publication of CN107699700A publication Critical patent/CN107699700A/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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/02—Obtaining noble metals by dry processes
    • C22B11/021—Recovery of noble metals from waste materials
    • C22B11/023—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/02—Obtaining lead by dry processes
    • C22B13/025—Recovery from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/0056—Scrap treating
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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

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

Abstract

The present invention relates to a kind of method that valuable component is reclaimed by slag containing nickel fibers, it includes adding nickel fibers slag in reaction unit, and add calcium system mineral and additive, form mixing slag, mixing slag is heated to molten condition as reaction slag, is well mixed, monitors the reaction slag in real time, make mixed reaction slag by regulation and control while meet condition a and condition b, obtain reacted slag；S2, separation and recovery.The present invention can both make full use of melting nickel slag physics thermal resource and hot flux for metallurgy, cold conditions clinker can be handled again, by adding additive, it is well mixed, control slag oxygen position, realize slag metallurgy, realize copper in nickel fibers slag, iron separated in synchronization technology, and solve current clinker bulk deposition, problem of environmental pollution, and heavy metal contamination problem.

Description

A kind of method that valuable component is reclaimed by slag containing nickel fibers
Technical field
The invention belongs to slag metallurgical technology field, and in particular to a kind of side that valuable component is reclaimed by slag containing nickel fibers Method.
Background technology
During the pyrometallurgical smelting of nickel, a large amount of nickel fibers slags are produced, nickel fibers cinder ladle is included caused by " matte smelting " technique Nickel sedimentation clinker caused by dilution clinker, top blow smelting after Ni-B alloy slag, the blowing of " nickel convering of copper ice " technique.China Jinchuan is public Department carries out nickel ore concentrate smelting using " flash smelting " and " top blow smelting ", produces 1,000,000 tons of nickel fibers slags every year, adds up heap at present Storage is stored up more than 10,000,000 tons.The valuable component such as copper, iron, nickel, cobalt, zinc, lead, gold, silver in nickel fibers slag, it is long-term to stack, both Waste of resource, environment is polluted again.
Iron content is up to 50wt% in nickel fibers slag, 26wt% payable grades before remote superorder, Copper in Slag be up to 0.2wt% with On, wherein iron component mainly mutually exists with fayalite.At present, the research and utilization of nickel fibers slag mainly concentrates direct-reduction to carry iron Or deoxy iron-smelting.In reduction process, copper, nickel, the reduction of cobalt component enter molten iron, are unfavorable for follow-up steelmaking process.
Nickel fibers slag is not only important secondary resource etc., and contains a large amount of SiO2、CaO、MgO、Al2O3It is molten Deng metallurgy Agent, chemical reactivity is strong, is the slag system of excellent in physical and chemical performance, is hot metallurgical clinker, is ripe metallurgical slag System.How effectively using nickel fibers slag as reaction slag system, realize that copper in nickel fibers slag, iron separated in synchronization technology are current Needed for market.
The content of the invention
(1) technical problems to be solved
In order to solve the above mentioned problem of prior art, a kind of side that valuable component is reclaimed by slag containing nickel fibers of the present invention Method.The inventive method is a kind of new slag metallurgical technology, and not only reducing Copper in Slag makes Copper in Slag<0.1wt%, and realize The high efficiente callback of the components such as copper, nickel, cobalt, iron, gold, silver, lead, zinc, indium, bismuth, sodium, potassium, obtain low copper ferrous material (iron ore concentrate with The pig iron), and solve current clinker bulk deposition, problem of environmental pollution, and heavy metal contamination problem.
(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 slag containing nickel fibers, it comprises the following steps：
S1, clinker mixing：Nickel fibers slag is added in melting reaction device, and adds calcium system mineral and additive, is formed Slag is mixed, mixing slag is heated to molten condition as reaction slag, is well mixed, monitors the reaction slag in real time, lead to Crossing regulation and control makes mixed reaction slag while meets condition a and condition b, obtains reacted slag；
Wherein, the condition a be control reaction slag temperature be 1100~1500 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, are incubated 5~50min, and sedimentation separation obtains the richness of bottom Cupro-nickel phase, the Fe-riched phase layer and the Iron containing silicate minerals phase layer of middle and upper part of middle and lower part, while generate component containing zinc and leaded group The cigarette ash divided, golden component, silver components enter copper-rich nickel phase, and nickeliferous component, cobalt containing component respectively enter copper-rich nickel phase and Fe-riched 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 1100 DEG C of the temperature ＜ of the reaction slag, using the heating function of reaction unit itself, or into slag Fuel and the oxidising air of preheating are added, the temperature of reaction slag is reached in the range of design temperature, makes the temperature of reaction slag Degree reaches 1100~1500 DEG C；
As 1500 DEG C of the temperature ＞ of the reaction slag, nickel fibers slag, blast furnace slag, ferroalloy are added into reaction slag One or more in slag, slag, flux for metallurgy, ferrous material or fluorine-containing material, the temperature for making mixing slag reaches 1100~ 1500℃；
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；
As basicity CaO/SiO in the reaction slag2Ratio>When 1.5, to reaction slag in add acid material and/or Iron-containing acidic 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, Cu oxide, nickel oxide, cobalt/cobalt oxide and ferriferous oxide in the reaction slag is controlled to be reduced to metallic copper, gold respectively Belong to nickel, metallic cobalt and FeO, metal Ferrum content in slag<3%.Can be by adding one kind in reducing agent, carbon containing ferrous material Or two kinds regulated and controled, wherein, the dosage of the reducing agent is Cu oxide, nickel oxide, cobalt/cobalt oxide and iron oxygen in slag Compound is reduced to metallic copper, metallic nickel, metallic cobalt and FeO theoretical amount 110~140%；The carbon containing ferrous material is steel Iron dirt mud and cigarette ash, the carbon containing pre-reduced pellet of iron ore concentrate, iron ore concentrate carbonaceous metallized pellet, zinc hydrometallurgy volatilization kiln slag, coke Furnace dust mud and cigarette ash.
Method as described above, it is preferable that the nickel fibers slag is Ni-B alloy slag, copper ice caused by " matte smelting " technique The blowing slag after blowing slag, the blowing of " nickel convering of copper ice " technique after the blowing of nickel convering " technique through dilution clinker caused by dilution, Ni-B alloy slag caused by top blow smelting, Ni-B alloy slag caused by top blow smelting are one or more in slag through being settled caused by sedimentation； The nickel fibers slag is molten state or cold conditions, wherein, melting nickel fibers slag is obtained by nickel fibers stove slag notch, or by nickel fibers slag It is heated to molten condition；
Calcium system mineral are one kind in red mud after lime, lime stone, dolomite, carbide slag, red mud or removing sodium high calcium It is or several；The additive is SiO2、MgO、FeO、Fe2O3、MnO2、Al2O3、TiO2, Fe or Na2One or more in O.
Method as described above, it is preferable that the copper-contained material is blister copper copper fire refining slag, nominal group process, copper ashes, zinc Metallurgical slag, zinc abstraction cigarette ash and dirt mud, plumbum smelting slag, Pb-Zn tailings, lead copper matte, setting form, fire refining of crude lead slag, lead smelting Refine flue dust and cigarette ash, lead-acid battery, Copper making cigarette ash and dirt mud, composition brass, cupric rubbish, containing copper circuit board, tin metallurgical slag, tin tail One or more in ore deposit；Wherein, the zinc smelting dreg is zinc hydrometallurgy and zinc smelting dreg caused by pyrometallurgy of zinc, including is leached Slag, iron vitriol slag, copper-cadmium slag, goethite slag, bloodstone slag, volatilization kiln slag, zinc vertical retorting slag, blast furnace slag, fuming slag, vortex Clinker, electric furnace zinc smelting slag, the Zinc Hydrometallurgy Residue are entering stokehold, need to be dried, dewater treatment；Leaded 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 is smelted to produce by fuming furnace contains lead fume Change clinker；The copper ashes be cupric smelting slag, slag containing copper converting, dilution waste, flotation tailings, one kind in wet type copper smelting slag or A variety of, cupric smelting slag results from " matte smelting " process of the pyrometallurgical smelting process of copper；The slag containing copper converting results from copper Pyrometallurgical smelting process " Copper Matte Converting " process；Dilution waste is cupric smelting slag and waste after the dilution of slag containing copper converting, is floated Tailings is selected as cupric smelting slag and tailings after the ore dressing of slag containing copper converting.
Method as described above, it is preferable that the fuel and reducing agent be one kind in solid, liquid or gaseous fuel or It is a variety of, sprayed into a manner of being blown or feeding intake, during the injection, be loaded into 0~1200 DEG C of gas, the gas is oxidisability Gas；
The alkaline material is pulverized limestone, red mud, after removing sodium in high calcium red mud, carbide slag, dolomite dust or calcium lime powder One or more；The alkaline ferrous material is alkaline sintering deposit, alkaline iron ore concentrate, alkaline pre-reduced pellet, alkalinous metal One or more in pellet or slag；
Method as described above, it is preferable that the acid material is in silica, silica containing gold and silver, flyash, gangue It is one or more；The iron-containing acidic material is CaO/SiO2≤ 1 ferrous material, acid sinter ore, acid iron ore concentrate, acidity In pre-reduced pellet, acid metal pellet, copper ashes, leaded clinker, zinc smelting dreg, nickel fibers slag, ferroalloy slag, blast furnace slag It is one or more of.
Method as described above, it is preferable that the ferrous material is common iron ore concentrate, common iron ore concentrate DRI, Common iron ore concentrate sintered ore deposit, common Iron Ore Pellets, common iron ore concentrate metallized pellet, the carbon containing prereduction ball of common iron ore concentrate Group, slag, zinc smelting dreg, coke smelting smoke dust and dirt mud, steel flue dust and dirt mud, nickeliferous metallurgical slag, copper ashes, lead metallurgical slag, One or more after copper ashes, tin metallurgical slag, red mud, removing sodium in high calcium red mud, coal dust ash, pyrite cinder；The steel flue dust With dirt mud drum include blast furnace gas mud, bof sludge, electric furnace dust mud, heat (cold) roll sludge, sintering dust, pelletizing dust, go out ironworks Dust, blast furnace dust, electric stove dust ash, steel rolling iron scale；
The fluorine-containing material is fluorite, CaF2Or the one or more in fluorine-containing blast furnace slag；
The Zinc Hydrometallurgy Residue is needed to be dehydrated with dirt mud, dried.
Further, the solid fuel and reducing agent are in coal dust, coke powder, coke, flyash, bituminous coal or anthracite One or more, granular or powdery is shaped as, granular material granularity is 5~25mm, and granular material granularity is≤150 μm；It is described Liquid fuel is heavy oil with reducing agent, and the gaseous fuel and reducing agent are coal gas and/or natural gas.
Preferably, in the step S1, described to be well mixed to mix or being stirred naturally, agitating mode is argon gas Stirring, nitrogen gas stirring, nitrogen-argon gas mixing gas agitating, reducibility gas stirring, oxidizing gas stirring, electromagnetic agitation or machine One or more in tool stirring.
Method as described above, it is preferable that the copper-contained material, ferrous material and fluorine-containing material are pelletizing or powder Material or granulation；Wherein, granularity≤150 μm of granular material, granular material granularity are 5~25mm, side of the granular material to be blown Formula is sprayed into, and granular material is added in a manner of being blown or feeding intake, and argon gas, nitrogen of the gas for preheating are loaded into used in the injection One or more in gas, reducibility gas (coal gas and/or natural gas), oxidizing gas, the temperature of the preheating for 0~ 1200℃。
Wherein, copper-contained material and ferrous material are hot or cold conditions, wherein hot material is by metallurgical furnace discharging opening or slags tap Mouth directly obtains.
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 cupro-nickel phase, the rich iron at middle part and upper strata can be mutually respectively processed, or the rich iron and iron content of middle and upper part Silicate mineral is combined processing, and golden component migrates with silver components, enrichment enters copper-rich nickel phase, and part nickel cobalt component enters rich iron Phase, component containing zinc and leaded component volatilization, in the form of an oxide into fume recovery.
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 the weight percentage of slag ferrous oxide<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 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 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 1350~1670 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 1350~1670 DEG C；
As 1670 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 1350~1670 DEG C, wherein, the 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 slowly cooled to room temperature, obtains slow cooling slag；Wherein, Metallic iron is deposited to the bottom of reaction unit, forms iron and sticks together, by containing metal iron layer in remaining slow cooling slag, be crushed to granularity 20~ 400 μm, 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 nickel phase, it is sent to converter or converting furnace or the raw material as the separation of copper cobalt nickel；
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 nickel phase containing silver components, nickel, cobalt component respectively enter copper-rich nickel phase With Fe-riched phase；
S2-1-05, the Fe-riched phase layer carry out water quenching or air cooling pour into after attemperator slow cooling or through manual sorting with Gravity treatment, which combines, to be obtained, as blast furnace nickel metallurgy iron material or direct-reduction nickel metallurgy iron material or iron making by smelting reduction ferronickel raw material or flotation Carry copper raw material；In floatation process, float product is copper concentrate, nickel ore concentrate, nickel-containing alloys and iron ore concentrate, and iron ore concentrate refines as blast furnace Iron material or direct reduction iron making raw material or iron making by smelting reduction iron material；Wherein, the Direct Reduction is using rotary hearth furnace, tunnel Road kiln, underbody road, shaft furnace, rotary kiln or induction furnace are adopted as reduction apparatus using gas base or coal base reduction technology, gas-based reduction With natural gas and/or coal gas, coal base reduction uses the one or more in anthracite, bituminous 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；Coal gas is in slag caused by reduction Surface second burns, there is provided heat, and also the coal gas by being flowed out in stove can be as drying furnace charge and the thermal source of attemperator；
In addition, because containing potassium, sodium in red mud, dirt mud is with containing lead, zinc, bismuth, indium in steel cigarette ash, so it is former to add these During 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, after pouring into attemperator slow cooling Copper-rich nickel phase, it is sent to converter or converting furnace or the raw material as the separation of copper cobalt nickel.
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；Or used containing the Fe-riched phase Step S2-1-05 processing in method one；The molten state or the copper-rich nickel phase poured into after attemperator slow cooling, are sent to converter Or converting furnace or the raw material as the separation of copper cobalt nickel.
Method four, using the rotatable converter of slag with reaction slag ladle when, Iron-containing silicate ore deposit described in the molten state of acquisition Thing phase and 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 nickel phase, is sent to converter or converting furnace copper metallurgy, or be sent to again after broken magnetic separation separation metallic iron after slow cooling converter or converting furnace or Raw material as the separation of copper cobalt nickel.
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 cooled to room temperature, obtains slow cooling slag；The rich ambrose alloy is mutually deposited to reaction unit Bottom, form copper-rich nickel and 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, gold, silver component moves to copper-rich nickel phase, and nickel, cobalt component move to copper-rich nickel phase and rich iron respectively Phase；
S202, separation：The copper-rich nickel that artificial taking-up is deposited in bottom sticks together, and is sent to converter or converting furnace or as copper cobalt nickel point From raw material；The Fe-riched phase is as blast furnace ironmaking raw material or direct reduction iron making raw material or iron making by smelting reduction iron material or melting Reduction iron production raw material or flotation carry copper raw material；Float product is to make containing copper concentrate, nickel ore concentrate, nickel alloy and iron ore concentrate, iron ore concentrate For 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 in the step S1, described be well mixed is to mix naturally with being stirred, The mode being stirred is argon gas stirring, nitrogen gas stirring, nitrogen-argon gas mixing gas agitating, reducibility gas stirring, oxidation One or more in property 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；When carrying out cooling-sedimentation The type of cooling be natural cooling or rotation cooling or centrifugation cooling, with gravity separation method be separation by shaking table during the separation, slip Groove sorts or the two is combined.
Compared with prior art, it is characteristic of the invention that：
(1) method that valuable component is reclaimed by slag containing nickel fibers of the invention, can both handle hot molten slag, fully profit With melting nickel fibers slag physics thermal resource and hot flux for metallurgy, cold conditions clinker can be handled again, it is physico by adjusting slag Property is learned, using the physicochemical properties that nickeliferous slag is ripe, realizes nickeliferous slag metallurgical technology；And it is big to solve current clinker Amount accumulation, problem of environmental pollution, and heavy metal contamination problem；
(2) the slag metallurgical reaction in slag, addition have calcium system mineral, fayalite is disintegrated, ferriferous oxide is fully released Release, form the ferriferous oxide of free state, realize that Fe-riched phase is grown up and settled, the aggregation of Fe containing component in slag, grow up with Sedimentation, Fe-riched phase are gone back including a variety of in metallic iron, FeO phases, fayalite phase as blast furnace ironmaking or direct-reduction or melting The raw material of original ironmaking；Calcium system mineral effectively transform viscosity simultaneously, are viscosity reductions, contribute to cupric component to settle,
(3) copper component, nickel component, cobalt component, the gold and silver component mixed in slag migrates, is enriched in copper-rich nickel phase respectively, And realize and grow up and settle, wherein, copper-rich nickel mutually includes more in copper, white metal, copper ice nickel, copper-rich nickel cobalt phase, Fe containing component Kind, or part Cu, Ni and Co component enter Fe-riched phase；
(4) zinc component, the lead component mixed in slag is migrated, is enriched in cigarette ash, and realize recovery respectively；Part contains indium Component, bismuth component, component containing potassium, component volatilization containing sodium are reclaimed into flue dust；
(6) separation is deposited in copper-rich nickel phase, the ferriferous oxide of different parts, realizes copper component in slag, the height of iron component Effect recovery, Copper in Slag<0.1wt%, solid-state copper-contained material can be handled；
(7) slag is realized quenched, can be used as cement raw material or construction material or be made aggregate and road material instead of rubble；
(8) the inventive method adds additive, first, for reducing viscosity, second, for reducing fusing point, in certain temperature Contribute to copper-rich nickel mutually to settle under (1100~1450 DEG C), Fe-riched phase is obtained as low copper Fe-riched phase and iron content silicon after making sedimentation separation The copper content of hydrochlorate phase, wherein Fe-riched phase and Iron-containing silicate phase is less than 0.1%, can pass through direct-reduction or iron making by smelting reduction Iron, obtain iron ore concentrate and metallic iron；
(9) progress that the inventive method can be continuously or discontinuously, meets industrial needs.
(3) beneficial effect
The beneficial effects of the invention are as follows：
(1) raw material of the invention can be cold conditions clinker, cold conditions slag treatment, can not only realize copper component in clinker, Nickel component, cobalt component, golden component, silver components, bismuth component, sodium component, potassium component, iron component, zinc component, lead component valuable component Comprehensive utilization, can solve current clinker bulk deposition, problem of environmental pollution.
(2) raw material of the invention can be the liquid molten nickel fibers slag flowed out in slag notch, contain abundant heat energy Resource, there is the characteristics of high-temperature, high heat, take full advantage of slag physics thermal resource, the efficient economizing energy；Liquid molten copper Slag contains substantial amounts of hot flux for metallurgy, is the slag system of excellent in physical and chemical performance, realizes slag metallurgy.
(3) present invention blowing gas, controls oxygen gesture, makes copper component, nickel in slag by adjusting slag physicochemical properties Component, cobalt component, gold and silver component migrate, are enriched to copper-rich nickel phase, realize aggregation, grow up and settle.
(4) in the inventive method, adding cold conditions material, with melting nickel fibers slag to avoid slag temperature too high, improves and is incubated The life-span of device；Add cold conditions material and improve feed throughput with nickel fibers slag, can not only handle molten slag, Er Qieke To handle a small amount of cold conditions material, adaptability to raw material is strong；Adding cold conditions material realizes the chemical heat and slag physics of reaction release The efficient utilization of heat.
(5) present invention is by adjusting slag physicochemical properties, control oxygen gesture, while adds calcium system mineral, makes olivine Ferriferous oxide discharges in phase, is enriched in Fe-riched phase, realizes aggregation, grows up and settle, Fe-riched phase include metallic iron, FeO phases, It is a variety of in fayalite phase, as blast furnace ironmaking or direct-reduction or the raw material of fused reduction iron-smelting；Zinc component, lead in slag Component, indium component, bismuth component, sodium component, potassium component volatilization, are reclaimed into flue dust.
(6) in the inventive method natural cooling process, the addition of additive, copper component in slag, nickel component, cobalt component, Gold and silver component is enriched in copper-rich nickel phase, and realizes aggregation, grows up and settle, copper-rich nickel mutually include copper, white metal, copper ice nickel, It is a variety of in Cu, Ni and Co phase, Fe containing component, or part Cu, Ni and Co component enters Fe-riched phase, iron component is enriched in Fu Tie in slag Phase, and realize aggregation, grow up and settle, the attemperator equipped with slag, which is placed on rotation platform, to be rotated, and accelerates copper-rich nickel phase, richness The aggregation of iron phase, grow up and settle；The addition of fluorine-containing material, copper-rich nickel phase, Fe-riched phase is accelerated to grow up and settle.
(7) ferriferous oxide almost disappears in the inventive method slag, and the increase of mineral grindability, slag is realized quenched.
(8) method that the inventive method is separated using manual sorting, magnetic separation, gravity treatment or slag-gold, respectively to being distributed on Portion, middle part ferrosilicate mineral facies low with bottom, Fe-riched phase, copper-rich nickel are mutually separated, and realize copper component in slag, nickel group Divide, the high efficiente callback of cobalt component, gold and silver component, indium component, bismuth component, iron component, the Iron-containing silicate phase of acquisition and rich iron group The Copper in Slag divided<0.1wt%, in being deposited in due to copper-rich nickel phase, Fe-riched phase, bottom, therefore, it is small to sort slag amount, mineral Grindability increase, ore grinding, magnetic separation and gravity treatment cost are low；Follow-up separation process uses physical upgrading (magnetic separation or gravity treatment), separation Medium be water, in separation process will not generation environment pollution, slag handling technology has that flow is short, the simple to operate, rate of recovery Height, there is the characteristics of efficient, cleaning, environmentally friendly；Mine tailing makees aggregate as cement raw material, construction material, instead of rubble, road material makes With.
(9) present invention is mutually settled by copper-rich nickel, and the copper content of Iron-containing silicate phase and rich iron component is less than 0.1%, makees For blast furnace ironmaking or direct-reduction or the raw material of melting and reducing, metallic iron and molten iron are obtained.
(10) present invention had both made full use of liquid slag physics thermal resource and hot flux for metallurgy, can handle cold conditions stove again Slag, slag metallurgy is realized, copper component, nickel component, cobalt component, gold and silver component are enriched in copper-rich nickel phase in slag, and realize poly- Collect, grow up and settle, iron component is enriched in Fe-riched phase, realizes aggregation, grows up and settle, using manual sorting, magnetic separation, gravity treatment with The method that the sedimentation of slag-gold combines, separation are deposited in the copper-rich nickel phase and Fe-riched phase of different parts, realize copper component in slag, nickel, The high efficiente callback of cobalt, gold and silver component, iron component；Solid-state copper-contained material can be handled, this method technological process is short, metal recovery rate Height, production cost is low, adaptability to raw material is strong, treating capacity is big, environment-friendly, economic well-being of workers and staff is high, can solve Metallurgical resources and heat energy High efficiente callback Utilizing question.
Embodiment
A kind of method that valuable component is reclaimed by slag containing nickel fibers, specifically includes following steps：
Step 1, clinker mixes：
Nickel fibers slag will be contained, add in the melting reaction device that attemperator or slag can flow out and add calcium system mineral With additive, mixing slag is formed；
Mixing slag is heated to molten condition, forms reaction slag；It is well mixed, nickeliferous reaction is monitored in real time melts Slag, ensure following (a) and (b) two parameters, the slag after the completion of being reacted simultaneously by regulation and control；
(a) temperature for reacting slag is 1100~1500 DEG C；
(b) the basicity CaO/SiO of slag is reacted2Ratio=0.15~1.5；
Regulation and control method is：
Corresponding (a)：
Control reaction slag temperature be in the method for design temperature scope：
When reacting the temperature ＜ design temperature range lower limits of slag, by the heating function of reaction unit itself, or instead Answer and fuel and the oxidising air of preheating are added in slag, the temperature of reaction slag is reached in the range of design temperature；
When reacting the temperature ＞ design temperature range limits of slag, added into reaction slag nickel fibers slags, blast furnace slag, One or more in ferroalloy slag, slag, copper-contained material, flux for metallurgy, ferrous material or fluorine-containing material, make mixing slag Temperature reaches in the range of design temperature；
Corresponding (b)：
When reacting basicity CaO/SiO in slag2Ratio<When 0.15, add alkaline material into reaction slag or alkalescence contains One or more in iron material；
When reacting basicity CaO/SiO in slag2Ratio>When 1.5, acid material or iron-containing acidic are added into reaction slag One or more in material；
Step 2, separate and recover：
5~50min is incubated, the slag after the completion of reaction, is settled, slag-gold separation, the copper-rich nickel of acquisition bottom molten state, The Fe-riched phase of middle and lower part molten state and the Iron containing silicate minerals phase of middle and upper part molten state, while generate component containing zinc and leaded group Point, wherein, indium, bismuth, nickel, cobalt, gold, silver component move to the rich ambrose alloy phase, and part nickel cobalt component moves to Fe-riched phase；
Each phase is recycled 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 or converting furnace or the raw material as the separation of copper cobalt nickel are sent to；
(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, Cupro-nickel raw material is carried as blast furnace ironmaking raw material or direct-reduction nickel metallurgy iron material or iron making by smelting reduction ferronickel raw material or flotation；Flotation Product is copper concentrate, nickel ore concentrate, nickel-containing alloys and iron ore concentrate, 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；The Direct Reduction uses rotary hearth furnace, tunnel cave, underbody road, shaft furnace, rotary kiln or sensing Stove is as reduction apparatus, and using gas base or coal base reduction technology, gas-based reduction is natural gas and/or coal gas, and coal base reduction is nothing One or more in bituminous coal, bituminous coal, lignite, coking coal, coke powder or coke, reduction temperature are 900~1400 DEG C, basicity CaO/ SiO2Ratio=0.8~1.5.
Wherein, the Iron containing silicate minerals phase in step (1), slag treatment is carried out, using one kind in method A~G：
Method A：Iron containing silicate minerals are mutually used as cement raw material：
The water quenching of Iron containing silicate minerals phase or air cooling are directly as cement raw material or are further processed into the water of high added value Mud raw material.
Method B：Part or all of Iron containing silicate minerals mutually return to 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 content<1%, complete the oxidation of slag, the slag after being aoxidized, wherein, the preheating temperature of oxidizing gas for 0~ 1200℃；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, works as ferrous oxide content<1%, complete slag Oxidation, the slag after being aoxidized, wherein, the preheating temperature of oxidizing gas is 0~1190 DEG C；And in whole process, protect Demonstrate,prove (d) slag mixed material temperature>1450℃；Temprature control method is the same as the silicate slag temperature control in method D steps (1) Method；
(3) slag after aoxidizing, air cooling or water quenching are carried out, the clinker of high added value is made.
Method F：The 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 1350~1670 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~1670 DEG C；
When reacting 1350 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 1350~1670 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 1350~1670 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, making aggregate, road material or phosphate fertilizer as cement raw material, construction material, instead of rubble makes With；
Method II：Carry out following steps：
(a) the mixing slag after reducing, cooling-sedimentation, slag-gold separation, molten iron and the slag after reduction are obtained；
(b) slag after reducing, carries out the outer slag treatment of stove, and concrete mode is：Using 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) cold conditions copper-rich nickel phase, converter copper metallurgy or converting furnace or the raw material as the separation of copper cobalt nickel are sent to；
(2) Fe-riched phase layer mutually uses processing method described in method one one in one step process A~G with Iron containing silicate minerals Kind or several handled；
(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；Or used containing the Fe-riched phase in method one The step of (4) handled；
(2) molten state copper-rich nickel phase or after pouring into attemperator slow cooling, is sent to converter or converting furnace or as copper cobalt nickel point From raw material；
(3) part lead component, zinc component, indium component, bismuth component, sodium component, potassium component volatilization enter flue dust；
Method four：During using the rotatable converter of slag with reaction slag ladle, the slag after the completion of reaction carries out following steps：
(1) 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 nickel phase, converter or converting furnace or the raw material as the separation of copper cobalt nickel are sent to；
(3) part lead component, zinc component, indium component, bismuth component, sodium component, potassium component volatilization enter flue dust；
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 nickel is mutually deposited to reaction The bottom of device, form copper-rich nickel and stick together；Iron containing silicate minerals mutually float；It is slow among copper-rich nickel phase and Iron containing silicate minerals Cold slag is Fe-riched phase, while generates component containing zinc and leaded component；Gold and silver component moves to copper-rich nickel phase；
(2) separate：The copper-rich nickel that artificial taking-up is deposited in bottom sticks together, toward converter or converting furnace or as the separation of copper cobalt nickel Raw material；The Fe-riched phase layer at middle part is as blast furnace nickel metallurgy iron material or direct-reduction nickel metallurgy iron material or iron making by smelting reduction ferronickel raw material Or flotation carries copper raw material；In floatation process, float product is copper concentrate, nickel ore concentrate, nickel alloy and iron ore concentrate, iron ore concentrate conduct Blast furnace ironmaking raw material or direct reduction iron making raw material or iron making by smelting reduction iron material；
The Direct Reduction is using rotary hearth furnace, tunnel cave, underbody road, shaft furnace, rotary kiln or induction furnace as reduction Equipment, 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 direct reduction iron making raw material 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.
In method as described above, it is preferable that in described step 1 and 2, nickel fibers slag is molten state or cold conditions, wherein： Melt nickel fibers slag to be obtained by nickel fibers stove slag notch, or nickel fibers slag is heated to molten condition；Nickel fibers slag is " to make sulfonium to melt After blowing slag, the blowing of " nickel convering of copper ice " technique after refining " Ni-B alloy slag, the nickel convering of copper ice caused by technique " technique blowing Blow slag through Ni-B alloy slag caused by Ni-B alloy slag caused by dilution clinker caused by dilution, top blow smelting, top blow smelting through heavy It is one or more in sedimentation slag caused by drop；
Copper material is blister copper pyro-refining slag, copper ashes, nominal group process, zinc smelting dreg, zinc abstraction in described step 1 and 2 Cigarette ash and dirt mud, plumbum smelting slag, Pb-Zn tailings, lead copper matte, setting form, fire refining of crude lead slag, lead smelting ash and dirt mud, Lead-acid battery, Copper making cigarette ash and dirt mud, composition brass, cupric rubbish, containing one kind in copper circuit board, tin metallurgical slag, tailing or It is several；Zinc smelting dreg is zinc smelting dreg caused by zinc hydrometallurgy and pyrometallurgy of zinc, including leached mud, iron vitriol slag, copper-cadmium slag, pin iron Slag, bloodstone slag, volatilization kiln slag, zinc vertical retorting slag, blast furnace slag, fuming slag, vortex clinker, electric furnace zinc smelting slag；It is leaded Clinker is fuming furnace clinker and leaded smelting slag, and " reduction of ISP imperial smelting furnaces " or " sintering deposit blast furnace reduction " or " solid-state is high Lead skim reduction " or " liquid high lead dross reduction technique " reducing process produce leaded smelting slag, and leaded smelting slag passes through fuming furnace smelting Refining produces leaded fuming slag；
In described step 1 and 2, copper ashes is cupric smelting slag, slag containing copper converting, dilution waste, flotation tailings, wet method refining One or more in copper ashes, cupric smelting slag result from " matte smelting " process of the pyrometallurgical smelting process of copper；Containing copper converting Slag results from " Copper Matte Converting " process of the pyrometallurgical smelting process of copper；Dilution waste is cupric smelting slag and the dilution of slag containing copper converting Waste afterwards, flotation tailings are cupric smelting slag and tailings after the ore dressing of slag containing copper converting.
In method as described above, it is preferable that in described step 1 and 2, melting reaction device that slag can flow out is can The melting reaction device of rotation or the melting reaction device with 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 method as described above, it is preferable that in described step 1, calcium system mineral are specially lime, lime stone, white clouds One or more after stone, carbide slag, red mud or removing sodium in high calcium red mud；Additive is SiO2、MgO、FeO、Fe2O3、MnO2、 Al2O3、TiO2, Fe or Na2One or more in O.
In described step 1, ensure following (a) and (b) two parameters simultaneously by regulation and control, while ensure copper oxygen in slag Compound, nickel oxide, cobalt/cobalt oxide and ferriferous oxide are reduced to metallic copper, metallic nickel, metallic cobalt and FeO respectively, gold in slag Belong to iron content<3%.It can be regulated and controled by adding one or both of reducing agent, carbon containing ferrous material, wherein, it is described The dosage of reducing agent be slag in Cu oxide, nickel oxide, cobalt/cobalt oxide and ferriferous oxide be reduced to metallic copper, metallic nickel, The theoretical amount 110~140% of metallic cobalt and FeO；The carbon containing ferrous material is that steel dust and mud and cigarette ash, iron ore concentrate are carbon containing pre- Reducting pellet, iron ore concentrate carbonaceous metallized pellet, zinc hydrometallurgy volatilization kiln slag, coke furnace dust mud and cigarette ash.
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 oxidizing gas, nitrogen or one kind or more in argon gas for preheating Kind, 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, be shaped as granular or powdery, granular material granularity is 5~25mm, and granular material granularity is≤150 μm, liquid Fluid fuel is heavy oil with reducing agent, and gaseous fuel and reducing agent are coal gas and/or natural gas；
Flux for metallurgy is containing CaO or SiO in described step 1 and 22Mineral, specially quartz sand, containing gold and silver quartz One or more after sand, red mud, removing sodium in high calcium red mud, carbide slag, dolomite or lime stone；
Ferrous material is common iron ore concentrate, common iron ore concentrate DRI in described 1 and 2, common iron ore concentrate sintered Ore deposit, common Iron Ore Pellets, common iron ore concentrate metallized pellet, the carbon containing pre-reduced pellet of common iron ore concentrate, slag, zinc abstraction Slag, coke smelting smoke dust and dirt mud, steel flue dust and dirt mud, nickeliferous metallurgical slag, copper ashes, lead metallurgical slag, zinc smelting dreg, tin are smelted One or more after slag, red mud, removing sodium in high calcium red mud, coal dust ash, pyrite cinder；The steel flue dust includes height with dirt mud drum Stove gas mud, bof sludge, electric furnace dust mud, heat (cold) roll sludge, sintering dust, pelletizing dust, go out ironworks dust, blast furnace gas Ash, electric stove dust ash, steel rolling iron scale.
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.
The Zinc Hydrometallurgy Residue 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.
Fluorine-containing material is fluorite, CaF in described 1 and 22Or the one or more in fluorine-containing blast furnace slag；
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 step 1 is specifically inserted slag using refractory lance or is placed in anti-with being fed in 2 using injection method Answer slag top or side or bottom be blown into one or more.
In described step 1 and 2, in slag course of reaction, copper component, nickel component, cobalt component, gold and silver component are rich in slag Copper-rich nickel phase is combined in, and realizes aggregation, grow up and settle, iron component is enriched in Fe-riched phase, realizes aggregation, grows up and settle, melts Zinc component, lead component, indium component, bismuth component respectively enter fume recovery in slag.The temperature of described control mixing slag is being set In the method for determining temperature range：
When mixing the temperature ＞ design temperature upper limits of slag, nickel fibers slag, copper-contained material, flux for metallurgy, iron content are added One or more in material or fluorine-containing material, it is therefore an objective to avoid temperature too high, protect refractory material；Add the another of fluorine-containing material One effect be reduce viscosity, accelerate slag in copper-rich nickel phase, Fe-riched phase aggregation, grow up and settle.
In the step 1 and 2, when adjusting basicity, described alkaline material is red mud, calcium carbide after pulverized limestone, red mud, removing sodium One or more in slag, dolomite dust or calcium lime powder；Described alkaline ferrous material is CaO/SiO2>=1 chalybeate Material, described alkaline ferrous material are alkaline sintering deposit, alkaline iron ore concentrate, alkaline pre-reduced pellet, alkalinous metal pellet, steel One or more in slag or blast furnace slag.
In the step 1 and 2, when adjusting basicity, acid material is the one or more in silica, flyash, gangue； Iron-containing acidic material is CaO/SiO2≤ 1 ferrous material, iron-containing acidic material are acid sinter ore, acid iron ore concentrate, acidity Pre-reduced pellet, acid metal pellet, copper ashes, lead metallurgical slag, zinc smelting dreg, nickel fibers slag, tin metallurgical slag, ferroalloy slag, One or more in blast furnace slag；
In step 1, while ensureing (a) and (b) two parameters, it is sufficiently mixed slag, hybrid mode is nature Mix or be stirred, agitating mode is one kind in the following manner：Argon gas stirring, nitrogen gas stirring, nitrogen-argon gas mixing gas mixing Mix, reducibility gas stirring, oxidizing gas, electromagnetic agitation, the one or more in mechanical agitation, gas preheating temperature is 0 ~1200 DEG C；
In step 1 and 2, copper-rich nickel phase, Fe-riched phase are assembled, grow up and settle in slag, are advantageous to silicate floating, its In, copper-rich nickel mutually includes copper, white metal, copper ice nickel, copper-rich nickel cobalt phase, a variety of in Fe containing component, or part Cu, Ni and Co component Into Fe-riched phase, Fe-riched phase includes a variety of in metallic iron, FeO phases, fayalite phase；
In described step 1 and 2, oxidizing gas is the air of preheating, one kind in oxygen or oxygen-enriched air, injection side Formula be using refractory lance insert slag or be placed in reaction slag top or side or bottom be blown into one or more, preheating Temperature is 0~1200 DEG C；
In described step 2, Direct Reduction uses rotary hearth furnace, tunnel cave, underbody road, shaft furnace, rotary kiln or sensing Stove is as reduction apparatus, and using gas base or coal base reduction technology, gas-based reduction is natural gas and/or coal gas, and coal base reduction is nothing One or more in bituminous coal, bituminous coal, lignite, coking coal, coke powder or coke, reduction temperature are 900~1400 DEG C, basicity CaO/ SiO2Ratio=0.8~1.5；
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 step 2, it is necessary to during cooling-sedimentation, the wherein type of cooling is natural cooling or rotation cooling or centrifugation cooling, Subsidence style is natural subsidence or spun down or centrifugal sedimentation；
Further, rotate and be with the concrete operations centrifuged：Device equipped with the slag after the completion of reaction is placed in rotary flat On platform, rotated according to certain speed, rotary speed is depending on slag quality and attemperator height or depth, rotational time Depending on slag quality and slag solidification situation；Device equipped with the slag after the completion of reaction is placed on rotation platform and rotated, Purpose is to accelerate copper-rich nickel phase, Fe-riched phase aggregation, grow up and settle, and is advantageous to silicate floating, shortens the sedimentation time, it is heavy to improve Effect is dropped, improves 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 nickel phase, Fe-riched phase fall to middle and lower part；
In described step 2, copper component, nickel component, cobalt component, gold and silver component continue to be enriched with the slag after the completion of reaction In copper-rich nickel phase, realization is grown up and settled, or part is enriched in Fe-riched phase；Iron component continues to be enriched in Fu Tie in mixing slag Phase, and realize and grow up and settle.
In described step 2, during separation, can use gravity separation method be separation by shaking table, sluicing or the two mutually tie Close.
Such as using the method for the present invention, cupric≤0.1% in the slag of the Fe-riched phase finally obtained and Iron-containing silicate phase, most The rate of recovery of iron is >=91% afterwards, and the rate of recovery of zinc is >=92%, and the rate of recovery of lead is >=92%, the accumulation rate of nickel for >= 91%, the accumulation rate of cobalt is >=91%, and golden accumulation rate is >=90%, and silver-colored accumulation rate is >=90%.
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 1100~1500 DEG C；
(b) the reaction slag basicity CaO/SiO of cupric and iron2Ratio=0.15~1.5.
Embodiment 1
A kind of method that valuable component is reclaimed by slag containing nickel fibers, comprises the following steps：
Step 1, clinker mixes：
The melting nickel fibers slag that will be obtained by " making sulfonium technique " technique smelting furnace slag notch adds direct current electric arc furnace, adds simultaneously Enter lime, and SiO2、MgO、Al2O3, form mixing slag；Mixing slag is heated to molten condition, forms reaction slag, And reaction slag is set to realize that nature mixes；The slag of monitoring reaction in real time, ensure (a) and (b) two parameters simultaneously by regulation and control, obtain Slag after the completion of must reacting；Corresponding (a)：The temperature for reacting slag is 1660 DEG C, using in refractory lance intercalation reaction slag, Using nitrogen as gas is loaded into, the copper ashes of normal temperature powdery granularity≤150 μm is sprayed into, containing Bellamya aeruginosa, composition brass and cupric rubbish and cupric electricity Road plate, while blast furnace gas mud, electric furnace dust mud, bof sludge, common iron ore concentrate DRI and blast furnace dust are added, make Temperature is down to 1490 DEG C；(b)：Cupric reacts the basicity CaO/SiO of slag2Ratio=2.6, to reaction slag in add silica, Flyash and gangue mixture, cupric reaction slag basicity ratio is set to be down to 0.28；Metal Ferrum content is 1.1% in slag；
Step 2, separation and recovery uses method one：
45min is incubated, the slag after the completion of reaction slag-gold separation, obtains molten state copper-rich nickel dam, rich iron layer from settling With Iron containing silicate minerals phase, while generate zinc component and lead component and enter flue dust, progress following steps：(1) molten state iron content Silicate mineral phase, the outer slag treatment of stove is carried out, it is former as direct reduction iron making after silicate slag air cooling using method F Expect, in Direct Reduction, using rotary kiln as reduction apparatus, using gas-based reduction technology, gas-based reduction agent is natural gas And coal gas, reduction temperature are 950 DEG C, basicity CaO/SiO2Ratio is 0.8, uses electric furnace to melt point temperature for 1550 DEG C after reduction, Product is metal molten iron and slag；(2) molten state copper-rich nickel phase, is sent to converter；(3) Fe-riched phase layer pours into attemperator, air cooling Blast furnace ironmaking raw material is used as afterwards；(4) zinc component, indium component, lead component, bismuth component, potassium component, sodium component volatilization, with oxide Form enters fume recovery；Copper in Slag<0.1%, zinc recovery 92%, lead recovery 93%, indium recovery 92%, bismuth The rate of recovery is 94%, and the sodium rate of recovery is 95%, and the potassium rate of recovery is 96%, iron recovery 96%, and the accumulation rate of nickel is 93%, cobalt Accumulation rate be 95%, golden accumulation rate be 93%, silver-colored accumulation rate be 94%.Wherein, in all embodiments of the invention, Copper in Slag refers to the slag phase after the phase separation of copper-rich nickel, specially Fe-riched phase and the copper content in silicate mineral phase, nickel, the richness of cobalt Collection rate refers to that nickel, the content of cobalt are accounted in raw material in copper-rich nickel phase and corresponds to nickel, the percentage of cobalt total amount, and the accumulation rate of gold, silver is The content for referring to gold, silver in copper-rich nickel phase accounts for the percentage of gold, silver total amount in raw material.
Embodiment 2
A kind of method that valuable component is reclaimed by slag containing nickel fibers, comprises the following steps：
Step 1, clinker mixes：
It is anti-dumpable melting will to be added by the melting nickel fibers slag that " nickel convering of copper ice " technique converting furnace slag notch obtains Answer slag to fill, while add lime stone, dolomite, red mud and FeO and Fe2O3, form mixing slag；It it is 600 DEG C with preheating temperature Oxygen-enriched air granularity be 20mm anthracites and char particle, mixing slag is heated to molten condition, formation contains by and Natural GasInjecting Copper reacts slag；The slag of monitoring reaction in real time, ensure (a) and (b) two parameters simultaneously by regulation and control, after the completion of being reacted Slag；
Corresponding (a) cupric reaction slag temperature is 1660 DEG C, using in refractory lance intercalation reaction slag, using argon gas for load Gas, spray into normal temperature powdery granularity≤150 μm copper ashes, nickel fibers slag, containing Bellamya aeruginosa, composition brass and, steel sintering dust, agglomerates of sintered pellets Dust, go out ironworks dust, common iron ore concentrate DRI, temperature is down to 1480 DEG C；(b) cupric reaction slag basicity CaO/ SiO2Ratio is 2.4, and acid iron ore concentrate, acid pre-reduced pellet, leaded smelting slag, leaded fuming furnace are added into reaction slag The mixture of slag, cupric reaction slag basicity ratio is set to be down to 1.2；Metal Ferrum content is 3% in slag；
Step 2, separation and recovery uses method two：
50min is incubated, the slag natural subsidence after the completion of reaction, slag-gold separation, obtains molten state copper-rich nickel phase layer, richness Iron phase layer and silicate mineral phase, while zinc component, lead component and indium component are generated, into flue dust, it is subject in the form of an oxide Recovery, carry out following steps：
(1) Iron containing silicate minerals phase and Fe-riched phase are melted, slag treatment outside stove is carried out using method G, slag melting is also Original ironmaking, is comprised the following steps that：
(1-1) slag is poured into dumpable converter, and it is 20mm anthracites and bituminous coal that granularity is added into slag, is melted Melt reduction, the slag of monitoring reaction in real time, ensure that the temperature that following (a) reacts slag is 1350~1670 DEG C simultaneously by regulation and control, React the basicity CaO/SiO of slag (b)2Ratio=0.6~2.4 two parameter, the slag after the completion of being reacted；
Corresponding (a)：The temperature for reacting slag is 1460 DEG C, in temperature range；
Corresponding (b)：React basicity CaO/SiO in slag2When ratio is 0.8, in alkalinity ranges；
(1-2) oxidizing gas (oxygen-enriched air) of 200 DEG C of blowing preheated into slag carries out melting and reducing, forms reduction Mixing slag afterwards, and during injection, ensure that the temperature that (a) reacts slag is 1350~1670 DEG C simultaneously by regulation and control, React the basicity CaO/SiO of slag (b)2Ratio=0.6~2.4 two parameter,
(1-3) is separated and recovered：
(a) the mixing slag after reducing, natural subsidence, molten iron and the slag after reduction are obtained；
(b) slag after reducing, high added value cement raw material is made using method A processing in step 2 method one；
(c) molten iron, converter or electric furnace steel making are sent to；
(d) component containing zinc, leaded component, bismuth component and indium component volatilization, in the form of an oxide into fume recovery；
(e) component containing sodium, component volatilization containing potassium, into fume recovery；
(2) molten state copper-rich nickel phase, is sent to converter.
(3) zinc component and lead component volatilization, in the form of an oxide into fume recovery.
Zinc recovery is 95%, lead recovery 93%, indium recovery 96%, and the bismuth rate of recovery is 96%, the sodium rate of recovery For 97%, the potassium rate of recovery is 98%, Copper in Slag<0.1%, iron recovery 97%；The accumulation rate of nickel is 92%, the accumulation rate of cobalt For 96%, golden accumulation rate is 90%, and silver-colored accumulation rate is 90%.
Embodiment 3
A kind of method that valuable component is reclaimed by slag containing nickel fibers, comprises the following steps：
Step 1, clinker mixes：To be blown the melting nickel smelting that slag obtains through dilution stove slag notch by " nickel convering of copper ice " technique Slag is refined, adds reverberatory furnace, while adds lime stone and high calcium red mud after removing sodium, forms mixing slag；It it is 900 DEG C with preheating temperature Oxygen, injection granularity be 20mm anthracites, char particle and coal dust, and mixing slag is heated into molten condition, cupric is formed and reacts Slag, mechanical agitation mixing；The slag of monitoring reaction in real time, ensure (a) and (b) two parameters simultaneously by regulation and control, reacted After the completion of slag；
Corresponding (a)：The temperature of cupric reaction slag is 1685 DEG C, and acid metal pellet, copper are added into reaction slag Slag, while add carbon containing pre- containing Bellamya aeruginosa, leaded clinker, common Iron Ore Pellets, steel rolling scale oxide and common iron ore concentrate Reducting pellet, temperature is set to be down to 1420 DEG C；(b)：Cupric reacts the basicity CaO/SiO of slag2Ratio=2.3, to reaction slag Middle addition quartz sand, red mud, the mixture of zinc smelting dreg, the basicity ratio of cupric reaction slag is set to be down to 1.2；Molten metal in the dreg Iron content is 1.8%；
Step 2, separation and recovery uses method two：
35min is incubated, the slag natural subsidence after the completion of reaction, slag-gold separation, obtains molten state copper-rich nickel phase, Fu Tie Phase layer and silicate mineral phase, while component containing zinc and leaded component are generated, into flue dust, reclaim, carry out in the form of an oxide Following steps：
(1) molten state copper-rich nickel phase, is sent to converter；
(2) molten state Fe-riched phase layer is mutually used as direct-reduction nickel metallurgy iron material with silicate mineral；In reduction process, zinc group Point, lead component, bismuth component and indium component volatilization, into flue dust；In Direct Reduction, using rotary hearth furnace, reduction temperature is 1200 DEG C, basicity CaO/SiO2Ratio=1.0, granularity are≤150 μm of anthracite and coal dust；
(3) component containing zinc, indium component, bismuth component and leaded component volatilization, into fume recovery, Copper in Slag<0.1%, iron The rate of recovery be 96%, the rate of recovery of zinc is 93%, and the rate of recovery of lead is 92%, indium recovery 93%, and the bismuth rate of recovery is 94%；The accumulation rate of nickel is 93%, and the accumulation rate of cobalt is 97%, and golden accumulation rate is 91%, and silver-colored accumulation rate is 92%.
Embodiment 4
A kind of method that valuable component is reclaimed by slag containing nickel fibers, comprises the following steps：
Step 1, clinker mixes：The melting nickel fibers slag that top-blown bath smelting furnace slag notch is obtained adds plasma heating furnace, Add dolomite, MgO, Al simultaneously2O3And Fe, form mixing slag；Mixing slag is heated to molten condition, forms cupric Slag is reacted, and makes reaction slag electromagnetic agitation, realizes mixing；In real time monitoring reaction slag, by regulation and control simultaneously ensure (a) and (b) two parameters, the slag after the completion of being reacted；
The temperature of corresponding (a) cupric reaction slag is 1670 DEG C, added into reaction slag red mud, pyrite cinder, fluorite, Lead copper matte, lead-containing soot, soot containing zinc, setting form and Zinc Hydrometallurgy Residue, temperature is set to be down to 1440 DEG C；(b) cupric reaction slag Basicity CaO/SiO2Ratio is 2.0, and copper ashes is added into reaction slag, cupric reaction slag basicity ratio is down to 0.7；With Air, Natural GasInjecting, the char particle that granularity is 20mm, metal Ferrum content is 0.9% in slag；
Step 2, separation and recovery uses method two：
14min is incubated, the slag natural subsidence after the completion of reaction, slag-gold separation, obtains molten state copper-rich nickel phase, Fu Tie Phase layer and Iron containing silicate minerals phase, while component containing zinc and leaded component are generated, into flue dust, reclaim in the form of an oxide, Carry out following steps：
(1) molten state copper-rich nickel phase, is sent to converter；
(2) molten state Fe-riched phase layer changes with method F, oxidation in Iron containing silicate minerals phase step 2 separation and recovery method one Property magnetic separation separation：1. slag is poured into insulation slag ladle, the oxygen-enriched air that preheating temperature is 900 DEG C is sprayed into slag, realizes magnetic The conversion of iron ore；2. slow cooling magnetic separation separation, obtains iron ore concentrate and mine tailing to room temperature；
(3) partly component containing zinc, bismuth component, indium component and leaded component volatilization, are carried out into flue dust in the form of an oxide Recovery, Copper in Slag<0.1%, the rate of recovery of iron is 95%, and the rate of recovery of zinc is 92%, and the rate of recovery of lead is 92%, indium recovery For 93%, the bismuth rate of recovery is 94%；The accumulation rate of nickel is 93%, and the accumulation rate of cobalt is 94%, and golden accumulation rate is 92%, silver-colored Accumulation rate is 94%.
Embodiment 5
A kind of method that valuable component is reclaimed by slag containing nickel fibers, comprises the following steps：
Step 1, clinker mixes：Melting nickel of the smelting slag through sedimentation electric furnace slag notch acquisition will be produced by top-blown bath melting Metallurgical slag adds insulation slag ladle, while adds lime stone and Fe, forms mixing slag；It is 600 DEG C oxygen-enriched with preheating temperature Air, granularity≤150 μm bituminous coal is blown, mixing slag is heated to molten condition, form cupric reaction slag, and melt reaction Slag realizes mixing；The slag of monitoring reaction in real time, ensure (a) and (b) two parameters simultaneously by regulation and control, after the completion of being reacted Slag；
Corresponding (a)：The temperature of cupric reaction slag is 1430 DEG C；(b)：Cupric reacts the basicity CaO/SiO of slag2Ratio For 1.5, in claimed range；Metal Ferrum content is 2.2% in slag；
Step 2, separation and recovery uses method five：
Slag after the completion of reaction is poured into insulation slag ladle, is incubated 25min, the outer slag treatment of stove is carried out, carries out as follows Step：
(1) sedimentation cooling：Slag rotation after the completion of reaction is cooled to room temperature, obtains slow cooling slag；Copper-rich nickel is mutually deposited to The bottom of reaction unit, form copper-rich nickel and stick together；Iron containing silicate minerals mutually float；Copper-rich nickel phase metal stick together with silicate mineral Between slow cooling slag be Fe-riched phase, while generate component containing zinc and leaded component；
(2) separate：The copper-rich nickel that artificial taking-up is deposited in bottom sticks together, and product is sent to converter；The Fe-riched phase layer at middle part is direct It is sent to converter ironmaking；
(3) the Iron containing silicate minerals phase on top is manually taken out, silicate mine tailing is obtained, is used as cement raw material；
(4) partly component containing zinc is with containing lead volatility, in the form of an oxide into fume recovery, Copper in Slag<0.1%, iron The rate of recovery is 92%, and the rate of recovery of zinc is 94%, and the rate of recovery of lead is 95%；The accumulation rate of nickel is 95%, and the accumulation rate of cobalt is 93%, golden accumulation rate is 91%, and silver-colored accumulation rate is 92%.
Embodiment 6
A kind of method that valuable component is reclaimed by slag containing nickel fibers, comprises the following steps：
Step 1, clinker mixes：Will by " making sulfonium technique " technique smelting furnace slag notch obtain melting nickel fibers slag, by " copper Ice nickel convering " technique converting furnace slag notch obtain melting nickel fibers slag add ac arc furnace, while add lime, MgO, Al2O3、Fe2O3, form mixing slag；Mixing slag is heated to molten condition, cupric reaction slag is formed, sprays into preheating temperature The argon gas for 800 DEG C is spent, and reaction slag is realized mixing；In real time monitoring reaction slag, by regulation and control simultaneously ensure (a) and (b) two parameters, the slag after the completion of being reacted；
Corresponding (a)：The temperature of cupric reaction slag is 1080 DEG C, electric arc stove heat, temperature is risen to 1330 DEG C；(b)：Contain Copper reacts the basicity CaO/SiO of slag2Ratio is 0.1, and it is pre- that alkaline iron ore concentrate, converter mud, alkalescence are added into reaction slag High calcium red mud after reducting pellet, removing sodium, the basicity ratio of cupric reaction slag is set to rise to 0.3；Natural gas is sprayed into, melts metal in the dreg Iron content is 1.6%；
Step 2, separation and recovery uses method one：
38min is incubated, by the slag natural subsidence after the completion of reaction, slag-gold separation, obtains molten state copper-rich nickel phase, richness Iron phase and Iron containing silicate minerals phase, while component containing zinc and leaded component are generated, into flue dust, reclaim in the form of an oxide, Carry out following steps：
(1) Iron containing silicate minerals mutually use method A in step 2 separation and recovery method one, and water quenching is directly as cement raw Material；
(2) molten state copper-rich nickel phase, is sent to converter；
(3) Fe-riched phase layer pours into the raw material as direct-reduction nickel metallurgy iron after attemperator cooling；
(4) component containing zinc, leaded component, component containing indium and bismuth-containing component volatilization, are reclaimed, Copper in Slag into flue dust< 0.1%, the rate of recovery of iron is 91%, and the rate of recovery of zinc is 92%, and the rate of recovery of lead is 92%, and the sodium rate of recovery is 95%, and potassium returns Yield is 96%, and the accumulation rate of nickel is 94%, and the accumulation rate of cobalt is 92%, and golden accumulation rate is 91%, and silver-colored accumulation rate is 92%.
Embodiment 7
A kind of method that valuable component is reclaimed by slag containing nickel fibers, comprises the following steps：
Step 1, clinker mixes：Will by " making sulfonium technique " technique obtain cold conditions nickel fibers slag, by " nickel convering of copper ice " work The cold conditions nickel fibers slag that skill blowing slag obtains through dilution stove adds mineral hot furnace, while adds lime stone, SiO2, FeO and MgO, Form mixing slag；Mixing slag is heated to molten condition, forms cupric reaction slag, blowing preheated temperature is 900 DEG C Argon-nitrogen gaseous mixture, and reaction slag is realized mixing；In real time monitoring reaction slag, by regulation and control simultaneously ensure (a) and (b) two parameters, the slag after the completion of being reacted；
Corresponding (a)：The temperature of cupric reaction slag is 1320 DEG C；(b)：Cupric reacts the basicity CaO/SiO of slag2Ratio For 0.8, in claimed range；Using air, the μ m coal powder of injection granularity≤150 and natural gas, metal Ferrum content is in slag 2.7%；
Step 2, separation and recovery uses method four：
36min is incubated, by the slag natural subsidence after the completion of reaction, slag-gold separation, obtains molten state copper-rich nickel phase, richness Iron phase and Iron containing silicate minerals phase, while zinc component and lead component are generated, into flue dust, reclaimed, carried out with Z oxide forms Following steps：
(1) molten state copper-rich nickel phase, is sent to converter；
(2) molten state Fe-riched phase layer specifically uses the side in the separation and recovery method one of step 2 with Iron containing silicate minerals Method F, after water quenching, the raw material as direct-reduction nickel metallurgy iron；
(3) partly component containing zinc and 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 the rate of recovery of zinc is 93%, and the rate of recovery of lead is 92%；The accumulation rate of nickel is 93%, the enrichment of cobalt Rate is 95%, and golden accumulation rate is 91%, and silver-colored accumulation rate is 92%.
Embodiment 8
A kind of method that valuable component is reclaimed by slag containing nickel fibers, comprises the following steps：
Step 1, clinker mixes：Will by " making sulfonium technique " technique smelting furnace slag notch obtain melting nickel fibers slag, by " copper Ice nickel convering " technique blowing slag is obtained through dilution stove slag notch melting nickel fibers slag addition blast furnace, while add dolomite, Red mud, MgO, coke powder of the preheating temperature for 800 DEG C of oxygen granularity≤150 μm is used, and spray into coal gas, by mixing slag heating To molten condition, cupric reaction slag is formed, and reaction slag is realized mixing；The slag of monitoring reaction 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 cupric reaction slag is 1330 DEG C；(b)：Cupric reacts the basicity CaO/SiO of slag2Ratio For 1.0, in claimed range；Metal Ferrum content is 1.9% in slag；
Step 2, separation and recovery uses method three：
19min is incubated, by the slag natural subsidence after the completion of reaction, slag-gold separation, acquisition copper-rich nickel phase and middle and upper part Iron containing silicate minerals phase and Fe-riched phase, while component containing zinc and leaded component are generated, into flue dust, return in the form of an oxide Receive, carry out following steps：
(1) molten state Iron containing silicate minerals phase, smelting apparatus is poured into, carries out the outer slag treatment of stove, specifically use step 2 Separation and recovery method one in method B, the slag of middle and upper part is all returned to cupric reaction slag, as hot metallurgical molten Agent, adjustment cupric reaction slag composition, control cupric reaction slag temperature；
(2) molten state copper-rich nickel phase, converter or converting furnace are sent to；
(3) partly component containing zinc and leaded component volatilization, 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 92%, and the rate of recovery of lead is 94%, and the sodium rate of recovery is 95%, and the potassium rate of recovery is 96%, the accumulation rate of nickel is 91%, and the accumulation rate of cobalt is 97%, and golden accumulation rate is 92%, and silver-colored accumulation rate is 93%.
Embodiment 9
A kind of method that valuable component is reclaimed by slag containing nickel fibers, comprises the following steps：
Step 1, clinker mixes：Melting nickel smelting of the smelting slag through sedimentation electric furnace slag notch acquisition is produced by top-blown bath melting The melting nickel fibers slag that refining slag obtains with " nickel convering of copper ice " technique blowing slag through dilution stove slag notch adds side-blown converter, adds simultaneously Enter lime stone, form mixing slag；Preheating temperature is used to spray into≤150 μm of coke powders for 900 DEG C of air, by mixing slag heating To molten condition, cupric reaction slag is formed, and reaction slag is realized mixing；The slag of monitoring reaction 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 cupric reaction slag is 1340 DEG C；(b)：Cupric reacts the basicity CaO/SiO of slag2Ratio For 1.2, in claimed range；Metal Ferrum content is 2.1% in slag；
Step 2, separation and recovery uses method two：
31min is incubated, by the slag natural subsidence after the completion of reaction, slag-gold separation, acquisition copper-rich nickel phase and middle and upper part Fe-riched phase and Iron containing silicate minerals phase, while component containing zinc and leaded component are generated, into flue dust, return in the form of an oxide Receive, carry out following steps：(1) Fe-riched phase mutually pours into smelting apparatus with Iron containing silicate minerals, using the separation and recovery side of step 2 Method C in method one, middle and upper part slag is poured into devitrified glass；
(2) molten state copper-rich nickel phase, handled after slow cooling with the method four in step 2；(3) partly component containing zinc with Leaded component, in the form of an oxide into flue dust；
The Copper in Slag finally obtained<0.1%, the rate of recovery of iron is 94%, and the rate of recovery of zinc is 92%, and the rate of recovery of lead is 92%；The accumulation rate of nickel is 97%, and the accumulation rate of cobalt is 93%, and golden accumulation rate is 92%, and silver-colored accumulation rate is 92%.
Embodiment 10
A kind of method that valuable component is reclaimed by slag containing nickel fibers, comprises the following steps：
Step 1, clinker mixes：Melting nickel of the smelting slag through sedimentation electric furnace slag notch acquisition will be produced by top-blown bath melting Metallurgical slag, " nickel convering of copper ice " technique melting nickel fibers slag for being obtained through dilution stove slag notch of blowing slag and by top-blown bath melting Produce smelting slag through settle electric furnace slag notch obtain melting nickel fibers slag add thermal insulation pit, while add lime stone and Fe, form mixing slag；With oxygen-enriched air, granularity≤150 μm bituminous coal is blown, mixing slag is heated to molten condition, formed Cupric reacts slag, and reaction slag is realized mixing；The slag of monitoring reaction in real time, ensure (a) and (b) two simultaneously by regulation and control Individual parameter, the slag after the completion of being reacted；
Corresponding (a)：The temperature of cupric reaction slag is 1430 DEG C；(b)：Cupric reacts the basicity CaO/SiO of slag2Ratio For 0.5, in claimed range；Metal Ferrum content is 0.8% 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 cooled to room temperature, obtains slow cooling slag；Copper-rich nickel phase The bottom of reaction unit is deposited to, copper-rich is formed and sticks together；Iron containing silicate minerals mutually float；Among copper-rich nickel phase and silicate mineral Slow cooling slag is Fe-riched phase, while generates component containing zinc and leaded component；
(2) separate：The copper-rich nickel that artificial taking-up is deposited in bottom sticks together；After the Fe-riched phase layer direct-reduction at middle part, magnetic separation point From metal nickel-iron；
(3) the silicate mineral phase on top is manually taken out, is 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<0.1%, iron The rate of recovery is 91%, and the rate of recovery of zinc is 93%, and the rate of recovery of lead is 92%；The accumulation rate of nickel is 96%, and the accumulation rate of cobalt is 97%, golden accumulation rate is 91%, and silver-colored accumulation rate is 92%.
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 that valuable component is reclaimed by slag containing nickel fibers, it is characterised in that it comprises the following steps：
    S1, clinker mixing：Nickel fibers slag is added in reaction unit, and adds calcium system mineral and additive, forms mixing slag, Mixing slag is heated to molten condition as reaction slag, is well mixed, monitors the reaction slag in real time, make to mix by regulation and control Reaction slag after conjunction meets condition a and condition b simultaneously, obtains reacted slag；
    Wherein, the condition a is the slag temperature of control at 1100~1500 DEG C；
    The condition b is the basicity CaO/SiO of control slag2Ratio=0.15~1.5；
    S2, separation and recovery：The reacted slags of step S1,5~50min is incubated, sedimentation separation, obtains the copper-rich nickel of bottom Phase, the Fe-riched phase of middle and lower part and the Iron containing silicate minerals phase of middle and upper part, while the flue dust of component containing zinc and leaded component is generated, Golden component, silver components migration, enrichment enter copper-rich nickel phase, and nickeliferous component, cobalt containing component migrate into copper-rich nickel phase and Fe-riched phase； Each phase is recycled.
  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 1100 DEG C of temperature ＜, using the heating of reaction unit itself, or into slag add fuel with The oxidising air of preheating, the temperature of reaction slag is reached in the range of design temperature, the temperature of reaction slag is reached 1100 ~1500 DEG C；
    As 1500 DEG C of the temperature ＞ of the reaction slag, nickel fibers slag, copper-contained material, 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, it is well mixed, melts the reaction of mixing The temperature of slag reaches 1100~1500 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, control Cu oxide, nickel oxide, cobalt/cobalt oxide and ferriferous oxide in the reaction slag to be reduced to gold respectively Belong to copper, metallic nickel, metallic cobalt and FeO, metal Ferrum content in slag<3%.
  5. 5. the method as described in claim 1, it is characterised in that the nickel fibers slag be " matte smelting " technique caused by nickel melt The blowing slag after blowing slag, the blowing of " nickel convering of copper ice " technique after refining slag, the blowing of " nickel convering of copper ice " technique produces through dilution Dilution clinker, Ni-B alloy slag caused by top blow smelting, Ni-B alloy slag caused by top blow smelting through electric furnace settle caused by settle It is one or more in slag；The nickel fibers slag is molten state or cold conditions, wherein：Melting nickel fibers slag is obtained by nickel fibers stove slag notch , or nickel fibers slag is heated to molten condition；
    Calcium system mineral are one kind or several in high calcium red mud after lime, lime stone, dolomite, carbide slag, red mud or removing sodium Kind；
    The additive is SiO2、MgO、FeO、Fe2O3、MnO2、Al2O3、TiO2, Fe or Na2One or more in O.
  6. 6. method as claimed in claim 2, it is characterised in that the copper-contained material be blister copper pyro-refining slag, nominal group process, Copper ashes, zinc smelting dreg, zinc abstraction cigarette ash and dirt mud, Pb-Zn tailings, lead metallurgical slag, lead copper matte, setting form, fire refining of crude lead Slag, lead smelting ash and dirt mud, lead-acid battery, Copper making cigarette ash and dirt mud, composition brass, cupric rubbish, containing copper circuit board, tin smelt One or more in slag, tailing；Wherein, the zinc smelting dreg is zinc smelting dreg caused by zinc hydrometallurgy and pyrometallurgy of zinc, Including leached mud, iron vitriol slag, copper-cadmium slag, goethite slag, bloodstone slag, volatilization kiln slag, blast furnace slag, fuming slag, cyclone furnaces Slag, zinc vertical retorting slag, electric furnace zinc smelting slag；Leaded metallurgical slag is fuming furnace clinker and leaded smelting slag, and " ISP imperial smelting furnaces are also Original " or " sintering deposit blast furnace reduction " or " solid-state high lead dross reduction " or " liquid high lead dross reduction technique " reducing process, which produce, to be contained Lead smelting slag, leaded smelting slag is smelted by fuming furnace produces leaded fuming slag；The copper ashes is that cupric smelting slag, cupric blow The one or more in slag, dilution waste, flotation tailings, wet type copper smelting slag are refined, cupric smelting slag results from the pyrometallurgical smelting of copper " matte smelting " process of technique；The slag containing copper converting results from " Copper Matte Converting " process of the pyrometallurgical smelting process of copper；It is poor It is cupric smelting slag and waste after the dilution of slag containing copper converting to change waste, and flotation tailings is cupric smelting slag and the ore dressing of slag containing copper converting Tailings afterwards；
    The ferrous material is common iron ore concentrate, common iron ore concentrate DRI, common iron ore concentrate sintered ore deposit, common iron ore concentrate Pellet, common iron ore concentrate metallized pellet, the carbon containing pre-reduced pellet of common iron ore concentrate, slag, zinc smelting dreg, coke smelt cigarette Dirt and dirt mud, steel flue dust and dirt mud, nickeliferous metallurgical slag, copper ashes, lead metallurgical slag, zinc smelting dreg, tin metallurgical slag, red mud, removing sodium One or more in high calcium red mud, coal dust ash, pyrite cinder afterwards；The steel flue dust includes blast furnace gas mud with dirt mud drum, turned Furnace dust 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；
    The copper-contained material and ferrous material are hot or cold conditions, wherein hot material is direct by metallurgical furnace discharging opening or slag notch Obtain；The flux for metallurgy is containing CaO or SiO2Mineral and clinker；The fluorine-containing material is fluorite, CaF2Or fluorine-containing blast furnace slag In one or more；
    Zinc Hydrometallurgy Residue, wet type copper smelting slag and dirt mud need to through being dehydrated, dry；
    The fuel is the one or more in solid, liquid or gaseous fuel, and the fuel is added in a manner of being blown or feeding intake Enter, during the injection, use and be loaded into oxidizing gas of the gas for preheating, the temperature of the preheating is 0~1200 DEG C；
    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；The alkaline ferrous material is alkaline sintering deposit, alkaline iron ore concentrate, alkaline pre-reduced pellet, alkalinous metal ball One or more in group, slag or blast furnace slag；The acid material is in silica, silica containing gold and silver, flyash, gangue It is one or more；The iron-containing acidic material is CaO/SiO2≤ 1 ferrous material, acid sinter ore, acid iron ore concentrate, acidity Pre-reduced pellet, acid metal pellet, copper ashes, lead metallurgical slag, zinc smelting dreg, nickel fibers slag, tin metallurgical slag, ferroalloy slag, One or more in blast furnace slag.
  7. 7. method as claimed in claim 2, it is characterised in that the copper-contained material, ferrous material and fluorine-containing material are ball Group or granular material or granulation；Wherein, granularity≤150 μm of granular material, granular material granularity are 5~25mm, granular material Sprayed into a manner of injection, granular material is added in a manner of being blown or feeding intake, and the loading gas used in the injection is preheating Argon gas, nitrogen, reducibility gas, the one or more in oxidizing gas, the temperature of the preheating is 0~1200 DEG C.
  8. 8. such as the method any one of claim 1-7, it is characterised in that in the step S2 separation and recovery, carry out such as Lower processing：
    Containing copper-rich nickel phase described in hot or cold conditions, converter or converting furnace or the raw material as the separation of copper cobalt nickel are sent to；
    The component containing zinc and leaded component volatilization, in the form of an oxide into fume recovery；
    Nickeliferous component, cobalt containing component migrate into copper-rich nickel phase and Fe-riched phase；
    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：The part or all of molten state returns in the reaction slag and is 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 The weight percentage of slag ferrous oxide<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：
    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 0~1190 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：The iron content slag carries out reduction iron production, comprises 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 1350~1670 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 1350~1670 DEG C；
    As 1670 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 1350~1670 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 carry out water quenching or air cooling or pour into attemperator slow cooling or combined with gravity treatment through manual sorting to obtain containing the Fe-riched phase , put forward cupro-nickel original as blast furnace nickel metallurgy iron material or direct-reduction nickel metallurgy iron material or iron making by smelting reduction ferronickel raw material or flotation Material；Float product is containing copper concentrate, nickel ore concentrate, dilval and iron ore concentrate, and iron ore concentrate is gone back as blast furnace ironmaking raw material or directly Former iron-smelting raw material or iron making by smelting reduction iron material；The Direct Reduction using rotary hearth furnace, tunnel cave, underbody road, shaft furnace, return Rotary kiln or induction furnace are as reduction apparatus, and using gas base or coal base reduction, gas-based reduction uses natural gas and/or coal gas, coal base Reduction use anthracite, bituminous coal, lignite, coking coal, coke powder or coke in one or more, control reduction temperature be 900~ 1400 DEG C, control basicity CaO/SiO2Ratio=0.8~1.5.
  9. 9. method as claimed in claim 8, it is characterised in that the oxidizing gas for preheating air, oxygen, oxygen-enriched air, One kind in nitrogen-air, argon gas-air, oxygen-nitrogen, oxygen-argon gas, the temperature of the preheating is 0~1200 DEG C；Institute It is the one or more in solid, liquid or gaseous fuel that fuel, which is stated, with reducing agent, is sprayed into a manner of being blown or feeding intake, described Injection is loaded into oxidizing gas of the gas for preheating, and the temperature of the preheating is 0~1200 DEG C；The solid fuel and reducing agent For the one or more in coal dust, coke powder, coke, flyash, bituminous coal or anthracite, granular or powdery, granular material are shaped as Granularity is 5~25mm, and granular material granularity is≤150 μm, and the liquid fuel and reducing agent be heavy oil, the gaseous fuel and Reducing agent is 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, agitating mode is argon gas stirring, nitrogen gas stirring, nitrogen-argon gas mixing gas agitating, reducibility gas stirring, oxygen One or more in the property changed 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.
CN201710936072.0A 2017-10-10 2017-10-10 A kind of method that valuable component is reclaimed by slag containing nickel fibers Pending CN107699700A (en)

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CN111778407A (en) * 2020-05-22 2020-10-16 金川集团股份有限公司 Treatment method for converting sulfur-containing blister copper furnace slag in Kaldo furnace
CN111778408A (en) * 2020-05-22 2020-10-16 金川集团股份有限公司 Method for producing alloy by treating self-heating furnace slag with direct-current electric arc furnace
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CN114990348A (en) * 2022-05-30 2022-09-02 金川镍钴研究设计院有限责任公司 Method for producing blister copper from copper-nickel 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
CN115259840A (en) * 2022-08-31 2022-11-01 广东广青金属科技有限公司 Refractory material and preparation method thereof

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CN115259840A (en) * 2022-08-31 2022-11-01 广东广青金属科技有限公司 Refractory material and preparation method thereof

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Application publication date: 20180216