CN106755652A - A kind of method that titanium-containing slag metallurgy one-step method is reclaimed - Google Patents

A kind of method that titanium-containing slag metallurgy one-step method is reclaimed Download PDF

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CN106755652A
CN106755652A CN201611133555.9A CN201611133555A CN106755652A CN 106755652 A CN106755652 A CN 106755652A CN 201611133555 A CN201611133555 A CN 201611133555A CN 106755652 A CN106755652 A CN 106755652A
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slag
vanadium
reaction
titanium
iron
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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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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B3/00—General features in the manufacture of pig-iron
    • C21B3/04—Recovery of by-products, e.g. slag
    • C21B3/06—Treatment of liquid slag
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B11/00—Making pig-iron other than in blast furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B3/00—General features in the manufacture of pig-iron
    • C21B3/04—Recovery of by-products, e.g. slag
    • C21B3/06—Treatment of liquid slag
    • C21B3/08—Cooling slag
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2200/00—Recycling of non-gaseous waste material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Furnace Details (AREA)

Abstract

A kind of method that titanium-containing slag metallurgy one-step method is reclaimed, belongs to non-blast furnace ironmaking and comprehensive utilization of resources field.Method：1) two or three material mix in molten state blast furnace titanium-containing slag, molten state slag with vanadium and titanium oxides, ferrous material, the melting reaction device for adding slag liquid to flow out, it is mixed to form reaction mixing slag, reaction mixing slag in real-time monitoring device, by regulating and controlling to ensure control reaction slag basicity CaO/SiO2Ratio=0.6~2.4, and the temperature of slag bath is 1300~1600 DEG C, the slag after the completion of being reacted；2) separate and recover：By the slag cooling treatment after the completion of reaction, or by the slag separating treatment after the completion of reaction.The inventive method, the Fe of tax rate high is obtained with step mixing, is applied after the layer treatment of silicate mineral phase, and effectively rate of recovery ferriferous oxide and rich titanium phase layer, adequately achieves the secondary utilization of titanium-containing slag.

Description

A kind of method that titanium-containing slag metallurgy one-step method is reclaimed
Technical field
The invention belongs to non-blast furnace ironmaking and comprehensive utilization of resources field, and in particular to a kind of titanium-containing slag metallurgy one-step method The method of recovery.
Background technology
Titanium-containing slag and slag are all important secondary resources.
Slag results from steelmaking process, is metallurgical intermediate products, and its metal Ferrum content is more than 10%, ferriferous oxide content It is more than 25%, and contains certain free cao and phosphorus pentoxide.More than 1.5 hundred million tons, annual band discharge every year in China More than 15,000,000 tons of metallic iron is walked, more than 30,000,000 tons of ferriferous oxide also takes away a large amount of free caos, five oxidations two The valuable components such as phosphorus, silica, therefore, slag is a kind of important secondary resource.The molten steel slag temperature that steelmaking process is released Degree is higher than 1550 DEG C, and substantial amounts of physical thermal is discharged every year, therefore, molten steel slag is also important physics thermal resource.
Blast furnace titanium-containing slag and molten steel slag, contain abundant heat resource, containing substantial amounts of hot flux for metallurgy, and And various valuable elements such as iron, titanium, phosphorus, the calcium containing high level, it is important secondary resource.Blast furnace titanium-containing slag is reduction Property slag, molten steel slag is oxidisability slag, and chemical reactivity is strong, is all the slag system of excellent in physical and chemical performance, is Metallurgical clinker.Meanwhile, slag chemical composition, mineral composition and clinker are extremely close, slag chemical composition and clinker Chemical composition is close, and annual China produces clinker more than 1,200,000,000 tons, it is necessary to the mineral resources such as substantial amounts of lime stone, clay With physics thermal resource, more than 200,000,000,000, China's lime stone, clay mineral resource only can also be exploited 50 years cost.
How titanium-containing slag and molten steel slag are effectively efficiently comprehensively utilized, reduce cost recovery, being one has to be solved Problem.
The content of the invention
For the problem that prior art is present, the present invention provides a kind of method that titanium-containing slag metallurgy one-step method is reclaimed.Should Method takes full advantage of the acidic flux and basic solvent contained in slag, realizes by mixing the new method that a step is reclaimed.
The method that titanium-containing slag metallurgy one-step method of the invention is reclaimed, comprises the following steps：
Step 1, the mixing of the step of slag one：
Two or three material in molten state blast furnace titanium-containing slag, molten state slag with vanadium and titanium oxides, ferrous material is mixed Dispensing, the melting reaction device that the material addition slag after mix can be flowed out, is mixed to form reaction mixing slag, in real time Monitoring reaction slag, following (a), (b) two parameters, the slag after the completion of being reacted are ensured by regulation and control simultaneously；
A () will control reaction slag basicity CaO/SiO2Ratio=0.6~2.4；
B () ensures that the temperature of slag bath is 1300~1600 DEG C；
Regulation and control method is：
Correspondence (a)：
The basicity CaO/SiO in slag is reacted2During ratio ＜ 0.6, contain to addition alkaline material in reaction slag or alkalescence One or more in iron material；
The basicity CaO/SiO in slag is reacted2During ratio ＞ 2.4, contain to acid material or acidity is added in reaction slag One or more in iron material；
Correspondence (b)：
Control to react mixing slag temperature and be in the method for design temperature scope：
When reaction mixing slag temperature ＜ design temperature range lower limits, by the heating function of reaction unit itself, make Reaction mixing slag temperature meets 1300~1600 DEG C；
When reaction mixing slag temperature ＞ design temperature range limits when, to reaction mixing slag in add flux for metallurgy, One or more in ferrous material or blast furnace cinder, make the temperature of reaction mixing slag meet 1300~1600 DEG C；
Step 2, separation and recovery：
Using the one kind in following methods：
Method one, the slag after the completion of reaction carries out cooling treatment：
Slag after the completion of reaction is poured into attemperator, following steps are carried out：
(1) by the slag after the completion of reaction, be cooled to room temperature, obtain slow cooling slag, wherein, slow cooling slag from bottom toward top according to Secondary is that the iron of the sedimentation of iron containing vanadium metal sticks together, iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer and rich vanadium phase layer and silicate mine Thing phase layer；
(2) artificial taking-up sticks together and silicate mineral phase layer containing vanadium iron, will contain vanadium metal iron layer, oxide ferroelectric layer, rich titanium phase Layer and rich vanadium phase layer, crush, by the way that after direct-reduction, iron and ferriferous oxide are selected in magnetic separation, while obtaining rich titanium thing phase with richness Vanadium mineral phase；
(3) recycling of silicate mineral phase has 2 kinds：1. as cement raw material, construction material, instead of rubble bone is made Material, road material or phosphate fertilizer are used；2. hydrometallurgy, beneficiation method or ore dressing-hydrometallurgy combination method are used by phosphorous Component seperation Out.
Method two, separating treatment is carried out by the slag after the completion of reaction：
(1) by the slag after the completion of reaction, sedimentation, slag-gold is separated, and obtains vanadium-bearing hot metal molten iron, iron layer containing vanadium metal, iron Oxide skin(coating), rich titanium phase layer and rich vanadium phase layer and silicate mineral phase layer；
(2) by silicate mineral phase layer, the outer slag treatment of stove is carried out；
(3) vanadium-bearing hot metal is sent to vanadium extraction by converter blowing steel-making；
(4) iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer and rich vanadium phase layer, after water quenching or air cooling, refine as blast furnace Iron material or direct reduction iron making；It is broken, through direct-reduction after, crush, iron and ferriferous oxide are selected in magnetic separation, while obtaining richness Titanium mineral phase and solution vanadium-rich mineral phase；
Wherein, silicate mineral phase layer, carries out the outer slag treatment of stove, using the one kind in method A, method B or method C：
Method A, silicate mineral phase layer is used as cement raw material：
Silicate mineral phase layer makes the cement raw material of high added value directly as cement raw material or further treatment；
Method B, part or all of silicate mineral phase layer returns to reaction mixing slag：
Part or all of silicate mineral phase layer returns to reaction mixing slag, used as hot flux for metallurgy, adjustment mixing Slag composition, control mixing slag temperature；
Method C, silicate mineral phase layer pours devitrified glass or as mineral wool；
Method three：Slag after the completion of reaction carries out separating treatment：
Slag after the completion of reaction, sedimentation, slag-gold is separated, acquisition vanadium-bearing hot metal, iron layer containing vanadium metal, oxide ferroelectric layer, Rich titanium phase layer and rich vanadium phase layer and silicate mineral phase layer, carry out following steps：
(1) iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer and rich vanadium phase layer and silicate mineral phase layer, water quenching or After air cooling, as blast furnace ironmaking raw material or direct reduction iron making or fused reduction iron-smelting；
(2) vanadium-bearing hot metal, is sent to vanadium extraction by converter blowing steel-making；
Wherein, iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer is directly gone back with rich vanadium phase layer and silicate mineral phase layer After original, granularity is crushed to for 20~400 μm, iron and ferriferous oxide are selected in magnetic separation, while obtaining rich titanium mineral phase with rich navajoite Thing phase and silicate mineral phase；
The method for subsequent processing of silicate mineral phase is using method A, method B in method two or the one kind in method C；
Method four：Slag after the completion of reaction is directly processed, using in method method D, method E or method F The method of kind：
Method D, slag Direct Air-Cooled or water quenching after the completion of reaction：
(1) melting reaction device top slag Direct Air-Cooled or water quenching, purposes have 4 kinds：1. slag cements；2. cement adjustment Agent；3. the additive in manufacture of cement；4. clinker；
(2) melting reaction device bottom vanadium-bearing hot metal is sent to vanadium extraction by converter blowing steel-making；
Method E, air cooling or water quenching after slag oxidation after the completion of reaction：
(1) it is complete as slag iron oxide content >=2wt% to the oxidizing gas that preheating is blown into slag after the completion of reaction Into injection, the slag after being aoxidized, wherein, the preheating temperature of oxidizing gas is 0~1200 DEG C；
Wherein, in whole process, it is ensured that slag temperature >=1450 DEG C, the control method for using for：
As 1450 DEG C of temperature ＜, pre-heating fuel, combustion heat release, additional heat, or device conducting self-heating are sprayed into, make slag temperature Degree is at >=1450 DEG C；
(2) slag Direct Air-Cooled or water quenching after aoxidizing, purposes have 4 kinds：1. slag cements；2. cement regulator；3. water Additive in mud production；4. clinker；
(3) melting reaction device bottom vanadium-bearing hot metal is sent to vanadium extraction by converter blowing steel-making；
Method F, slag treatment produces the clinker of high added value：
(1) add melting converter slag, electric furnace melting and reducing slag, electric furnace melt oxidation slag, lime, flyash, alkali Property iron lean ore, bauxite, titaniferous blast furnace cinder, one or more in ordinary blast slag, be sufficiently mixed, obtain slag mixing Material；
(2) to the oxidizing gas that preheating is blown into slag mixed material, when slag mixed material iron oxide content >= 2wt%, completes to be blown, the slag mixed material after being aoxidized, wherein, the preheating temperature of oxidizing gas is 0~1200 DEG C；
Wherein, in whole process, it is ensured that slag mixed material temperature >=1450 DEG C, the control method for using for：
As 1450 DEG C of temperature ＜, pre-heating fuel, combustion heat release, additional heat, or device conducting self-heating are sprayed into, mix slag Temperature of charge is closed at >=1450 DEG C；
(3) the slag mixed material after aoxidizing, carries out air cooling or water quenching, and the clinker of high added value is obtained；
(4) melting reaction device bottom vanadium-bearing hot metal is sent to pneumatic steelmaking
Method five：Slag after the completion of reaction, cooling-sedimentation, slag-gold is separated, and obtains vanadium-bearing hot metal, iron layer containing vanadium metal, Oxide ferroelectric layer and silicate phase slag, carry out following steps：
(1) vanadium-bearing hot metal, is sent to vanadium extraction by converter blowing steel-making；
(2) iron layer containing vanadium metal, silicate phase and ferriferous oxide slag are poured into attemperator, as follows G, method One kind in H or method I is processed：
Method G, slag Direct Air-Cooled or water quenching：
(1) melting reaction device top slag Direct Air-Cooled or water quenching, purposes have 4 kinds：1. slag cements；2. cement adjustment Agent；3. the additive in manufacture of cement；4. clinker；
Method H, air cooling or water quenching after slag oxidation：
(1) to the oxidizing gas that preheating is blown into the slag after the completion of reaction, as slag iron oxide content >=2wt%, Complete to be blown, the slag after being aoxidized, wherein, the preheating temperature of oxidizing gas is 0~1200 DEG C；
Wherein, in whole process, it is ensured that slag temperature >=1450 DEG C, the control method for using for：
As 1450 DEG C of temperature ＜, pre-heating fuel, combustion heat release, additional heat, or device conducting self-heating are sprayed into, make slag temperature Degree is at >=1450 DEG C；
(2) slag Direct Air-Cooled or water quenching after aoxidizing, purposes have 4 kinds：1. slag cements；2. cement regulator；3. water Additive in mud production；4. clinker；
Method I, slag treatment produces the clinker of high added value：
(1) melting converter slag, electric furnace melting and reducing slag, electric furnace melt oxidation slag, lime, flyash, alkali are added Property iron lean ore, bauxite, one or more in blast furnace cinder, be sufficiently mixed, obtain slag mixed material；
(2) to the oxidizing gas that preheating is blown into slag mixed material, when slag mixed material iron oxide content >= 2wt%, completes to be blown, the slag mixed material after being aoxidized, wherein, the preheating temperature of oxidizing gas is 0~1200 DEG C；
Wherein, in whole process, it is ensured that slag mixed material temperature >=1450 DEG C, the control method for using for：
As 1450 DEG C of temperature ＜, pre-heating fuel, combustion heat release, additional heat, or device conducting self-heating are sprayed into, mix slag Temperature of charge is closed at >=1450 DEG C；
(3) the slag mixed material after aoxidizing, carries out air cooling or water quenching, and the clinker of high added value is obtained.
Described molten state titanium-containing slag is obtained by slag notch, or titanium-containing slag is heated into molten condition.
Described titanium-containing slag is one or more in titaniferous blast furnace cinder or electro-titanium slag.
Described titaniferous blast furnace cinder, contains TiO2Mass fraction≤4%.
Described molten state slag with vanadium and titanium oxides is obtained by slag notch, or slag with vanadium and titanium oxides is heated into molten condition.
Described slag with vanadium and titanium oxides is one or more in pneumatic steelmaking slag or electric furnace steel making oxidation slag.
Described slag with vanadium and titanium oxides, contains TiO2Mass fraction be 0.3~6%, contain V2O5Mass fraction be 0.3 ~5%.
Described ferrous material is normal temperature or directly obtains the common iron ore concentrate with temperature, common iron ore concentrate from smelting furnace Sintering deposit, common Iron Ore Pellets, common iron ore concentrate metallized pellet, common iron ore concentrate DRI, common iron ore concentrate Carbon containing pre-reduced pellet, common slag, molten iron pre-desulfurization slag, blast furnace dust, blast furnace dust, converter dust, electric furnace dust, oxygen Change red mud, flyash, copper smelting slag, sulfuric acid burning that iron sheet, the zinc leaching residue of Zinc Hydrometallurgy Process, aluminum oxide production process are produced Slag, zinc leach big kiln slag, ferronickel slag, lead and zinc smelting dreg, material containing high-iron bauxite, the material of titanium containing vanadium, material containing Biobium rare-earth, nickel One or more in metallurgical slag or lead metallurgical slag.Described tapping temperature is 600~1550 DEG C；
Middle degree of metalization >=70% of described common iron ore concentrate metallized pellet, the common carbon containing pre-reduced pellet of iron ore concentrate Middle FeO content >=60%.
The material of titanium containing vanadium be normal temperature or from smelting furnace directly obtain with tapping temperature titanium-containing blast furnace slag, slag with vanadium and titanium oxides, Tailings in vanadium extraction, Tailing of titanium separation, low-grade vanadium titano-magnetite, v-ti magnetite concentrate, direct reduction of V-Ti magnetite iron, v-ti magnetite The carbon containing pre-reduced pellet of concentrate metallized pellet, v-ti magnetite concentrate, v-ti magnetite concentrate sintering deposit, v-ti magnetite concentrate pelletizing One or more in ore deposit, ilmenite concentrate.
In the step 1 (a), during adjustment basicity, described alkaline material is pulverized limestone, red mud, dolomite dust or raw stone One kind in ashes；Described alkaline ferrous material is CaO/SiO2>=1 ferrous material；Described alkaline ferrous material is alkali Property sintering deposit, alkaline iron ore concentrate, alkaline pre-reduced pellet or alkalinous metal pellet in one kind；
Described acid material is silica；Described iron-containing acidic material is CaO/SiO2≤ 1 ferrous material；Described Iron-containing acidic material is acid sinter ore, acid iron ore concentrate, acid pre-reduced pellet, acid metal pellet, copper smelting slag, zinc Leach the one kind in big kiln slag, ferronickel slag, lead and zinc smelting dreg, nickel fibers slag or lead metallurgical slag；
Described ferrous material and the material of titanium containing vanadium are granular material or spherical material, wherein, the granularity of granular material≤ 150μm；Granular material adds reaction mixing slag by carrier gas injection of neutral gas；
The melting reaction device that described slag liquid can flow out, is that dumpable melting reaction device or bottom carry cinder notch Fixed melting reaction device；Described dumpable melting reaction device is converter, induction furnace or dumpable melting reaction One kind in slag ladle；Fixed melting reaction device of the described bottom with cinder notch is plasma heating furnace, direct current electric arc furnace, exchange Electric arc furnaces or mineral hot furnace are a kind of.
Described attemperator internal layer is insulation demoulding refractory material；Described insulation demoulding refractory material be it is siliceous, half In siliceous, clayey, High-Alumina, magnesia, dolomite matter, olivine matter, spinel, cold conditions blast furnace slag, cold conditions slag one Plant or several.
The effect of described insulation demoulding refractory material has two：1) attemperator is protected, its life-span is improved；2) cooling is made Good slow cooling slag is easy to be removed from attemperator.
In the method that described titanium-containing slag metallurgy one-step method is reclaimed, in step 1, containing ferrous material or containing vanadium in raw material During titanium material, the method for the melting reaction device that each material addition slag liquid can flow out is：First by molten state blast furnace cinder or melting In state molten steel slag adding apparatus, then with neutral gas or oxidizing gas as carrier gas, ferrous material or contain to being blown in device Vanadium titanium material.
In the method that described titanium-containing slag metallurgy one-step method is reclaimed, described oxidizing gas are air, oxygen, oxygen-enriched One kind in air, oxygen-nitrogen gaseous mixture, air-nitrogen gaseous mixture, oxygen-argon gas gaseous mixture, Air-Argon gaseous mixture Or it is several；Described injection method is to be blown into using inside refractory lance intercalation reaction mixing slag.
In the method that described control is sufficiently stirred for, neutral gas is that neutral gas is inert gas or N2In one kind or Two kinds；The preheating temperature of neutral gas is 0~1200 DEG C, and the injection time of neutral gas is 1~90L/ with the relation of flow (minkg), the injection method of neutral gas is to be sprayed into using refractory lance, wherein, neutral gas can from bottom of device or Side sprays into, and plays a part of enhancing stirring.
Described inert gas is argon gas.
When neutral gas is mixed gas, mixed proportion is any ratio.
Described control reaction mixing slag temperature is added in the method for design temperature scope in mixing slag to reaction When ferrous material and titanium-containing slag, ferrous material and titanium-containing slag are any ratio.
Described control reaction mixing slag temperature in the method for design temperature scope, described addition ferrous material And/or slag containing vanadium, it is therefore intended that：
First, avoid temperature too high, protect melting reaction device, grain in the pig iron, molten steel slag in suppression titaniferous blast furnace cinder The oxidation of iron and reduced metal iron, improves the rate of recovery of metallic iron；
2nd, scale treatment ferrous material, improves the productivity ratio of metallic iron.
In the method that described titanium-containing slag metallurgy one-step method is reclaimed, in step 1, reaction mixing slag is stirred, Agitating mode is the one kind in the following manner：Neutral gas stirring, electromagnetic agitation, mechanical agitation, neutral gas stirring and electromagnetism Stirring is combined or neutral gas stirring is combined with mechanical agitation.
In the step 2, described attemperator is the one kind being incubated in slag ladle or thermal insulation pit；Described insulation slag ladle And thermal insulation pit, using preheating is preceding needed, preheating temperature is 100~1200 DEG C.
When neutral gas is mixed gas, mixed proportion is any ratio.
Described attemperator is the one kind being incubated in slag ladle or thermal insulation pit；Described insulation slag ladle and thermal insulation pit, Using preheating is preceding needed, preheating temperature is 300~1200 DEG C.
Described step 2, in method one, the type of cooling is natural cooling or rotation cooling.
In described step 2, subsidence style is the sedimentation of spun down, natural subsidence or electromagnetism.
Described step 2, rotation cools down and is with the concrete operations of sedimentation：Attemperator equipped with slag after the completion of reaction is put In on rotation platform, rotated according to certain speed, rotary speed according to slag quality and attemperator height or depth depending on, Rotational time is depending on slag quality and slag solidification situation, it is therefore an objective to accelerate iron containing vanadium metal, rich titanium phase, rich vanadium phase to gather Collect, grow up and sedimentation, shorten the sedimentation time, improve effect of settling, improve production efficiency.
The gravity separation method be separation by shaking table, sluicing or the two be combined.
Described step 2, direct reduction iron making is carried out in stove is reduced directly, and the direct-reduction stove is revolution One kind in kiln, shaft furnace, rotary hearth furnace, car-bottom furnace or tunnel cave.
Described step 2, corresponding method three, ferriferous oxide with rich titanium phase layer as direct reduction iron making when, iron is aoxidized Thing be crushed to granularity for 20~400 μm with rich titanium phase layer, and residual metallic iron and silicate phase are isolated in ore grinding, magnetic separation.
In the method that described titanium-containing slag metallurgy one-step method is reclaimed, the rate of recovery of Fe is 92~96%.
The method that titanium-containing slag metallurgy one-step method of the invention is reclaimed, compared with prior art, has the beneficial effect that：
(1) add the hot ferrous material come out of the stove of metallurgical furnace, make full use of thermal resource, not only can with the effectively save energy, Reduces cost, and the treating capacity of hot ferrous material is improved, productivity ratio and reaction speed are improved, production cost is reduced, realize Energy-saving and emission-reduction, realize green metallurgical；
(2) using neutral gas, electromagnetic agitation, mechanical agitation, mixing velocity is improve, promotes metallic iron and ferriferous oxide Assemble, grow up and sedimentation, improve the rate of recovery, shorten the sedimentation time.
(3) gas is sprayed into inside slag, increases chemical reaction specific surface area, improves combustion velocity anti-with reduction Answer speed.
(4) present invention takes full advantage of hot molten slag chemism high, contains a large amount of hot flux for metallurgy and a large amount of physics Thermal resource, is kept molten by, and realizes hot flux for metallurgy reaction, and the large solid-state ferrous material of melt process is realized large The slag of solid-state ferrous material is metallurgical.Green metallurgical and energy-saving and emission-reduction are realized, Metallurgical resources is realized efficient with thermal resource Utilize；It is a kind of slag New Metallurgical Technology, a kind of new slag recovery process is improving and innovating for existing metallurgical technology, is Propose slag metallurgical technology first in the world, slag is not discarded object, but important metallurgical intermediate products；
(5) slag realize it is quenched after, free cao and free oxidation magnesium disappear in slag, and metallic iron almost disappears, can Mill property increases, and mineral hydraulic C2S increases, and can be directly used as adding in slag cements, cement regulator or manufacture of cement Plus agent, further by adding melting converter slag, electric furnace melting and reducing slag, electric furnace melt oxidation slag, lime, fine coal One or more mixing in ash, basic iron lean ore, adjust basicity, spray into oxidizing gas, adjust iron oxide content, generate iron Hydrochlorate, makes it be constituted closer to required clinker, and with A ore deposits high, the gluing mineral of the hydraulicity increase, and adhesivity increases Plus, the early strength of cement increases, and titaniferous material can be added in slag directly as clinker, increases the intensity of cement, High-mark cement can be prepared.
(6) the inventive method reaction time is short, metal recovery rate is high, low production cost, adaptability to raw material strong, treating capacity Greatly, environment-friendly and economic well-being of workers and staff is high, is a kind of new slag melting recovery process.
Specific embodiment
Embodiment 1
A kind of method that titanium-containing slag metallurgy one-step method is reclaimed, comprises the following steps：
Step 1, the mixing of the step of slag one：
By by the molten state titaniferous blast furnace cinder of tap cinder mouthful outflow, and the molten state converter obtained by slag slag notch Slag with vanadium and titanium oxides, adds in melting reaction slag ladle, is sufficiently mixed, and reaction mixing slag is formed, while slag mixes, using resistance to Inside fire-fighting rifle intercalation reaction mixing slag, the argon gas that preheating temperature is 100 DEG C is blown into, the injection time is with the relation of flow 85L/ (minkg), makes reaction mixing slag realize being sufficiently stirred for；And real-time monitoring reaction slag, ensure that (a) is anti-by regulating and controlling Slag temperature should be mixed for 1300~1650 DEG C；Basicity CaO/SiO in (b) reaction slag2Ratio=0.6~2.4；Reacted After the completion of slag；
Correspondence (a)：The temperature of reaction mixing slag is 1680 DEG C, and beyond setting range, addition red mud and degree of metalization are The 85% common iron ore concentrate metallized pellet of normal temperature, the two mass ratio is 2: 1, and uses refractory lance, is mixed with argon-nitrogen Gas is carrier gas, inside intercalation reaction slag, converter dust and electric furnace dust is sprayed into by the way of side-blown, and the two mass ratio is 1: 1, reaction mixing slag temperature is down to 1620 DEG C；
(b)：Basicity CaO/SiO in reaction slag2Ratio=0.85, in setting range；
Step 2, separation and recovery uses method one：
Slag after the completion of reaction is poured into attemperator, following steps are carried out：
(1) by the slag after the completion of reaction, naturally cool to room temperature, obtain slow cooling slag, wherein, slow cooling slag from bottom up The iron that portion is followed successively by the sedimentation of iron containing vanadium metal sticks together, iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer and rich vanadium phase layer and silicic acid Salt mineral facies layer；
(2) artificial taking-up sticks together and silicate mineral phase layer containing vanadium iron, will contain vanadium metal iron layer, oxide ferroelectric layer, rich titanium phase Layer and rich vanadium phase layer, crush, by the way that after direct-reduction, iron and ferriferous oxide are selected in magnetic separation, while obtaining rich titanium thing phase with richness Vanadium mineral phase；
(3) silicate mineral phase layer, uses as cement raw material.
The present embodiment, the rate of recovery of Fe is 92.5%.
Embodiment 2
A kind of method that titanium-containing slag metallurgy one-step method is reclaimed, follows the steps below：
Step 1, the mixing of the step of slag one：
The Copper making slag that will be directly obtained from smelting furnace and the molten state converter slag obtained from slag exit are matched somebody with somebody Material, in Copper making slag and molten steel slag addition induction furnace, will obtain reaction mixing slag, and real-time monitoring reaction slag passes through Regulation and control ensure following (a), (b) two parameters simultaneously；
To ensure basicity CaO/SiO after (a) dispensing2Ratio=0.6~2.4；
After dispensing, basicity CaO/SiO2Ratio is 0.4 ＜ 0.6, is sintered to red mud and hot alkalescence is added in reaction slag Ore deposit, both mass ratioes are 1: 1；After regulation, basicity CaO/SiO2Ratio is 0.7, in setting range；
B () ensures that the temperature of slag bath is 1300~1600 DEG C, the slag after the completion of being reacted；
Reaction mixing slag temperature is 1380 DEG C, in setting range；
Reaction mixing slag is stirred, agitating mode is stirred for neutral gas；Neutral gas is N2, N2Preheating temperature It is 1200 DEG C to spend, and the injection time is 90L/ (minkg) with the relation of flow, and injection method is to spray into insert using refractory lance It is blown into the way of top blast inside reaction mixing slag；
Step 2, separation and recovery is using the method F in method four：Slag treatment produces the clinker of high added value
(1) melting converter slag, electric furnace melting and reducing slag, electric furnace melt oxidation slag, lime, flyash, alkali are added Property iron lean ore, bauxite, one or more in blast furnace cinder, be sufficiently mixed, obtain slag mixed material；
(2) to the oxygen that preheating temperature is 280 DEG C is blown into slag mixed material, when slag mixed material iron oxide content >=2wt%, completes injection, the slag mixed material after being aoxidized；And in whole process, it is ensured that slag mixed material temperature >=1450 DEG C, as 1450 DEG C of temperature ＜, by plasma heating furnace conducting self-heating, make slag mixed material temperature >=1450 DEG C；
(3) the slag mixed material after aoxidizing, carries out water quenching, and the clinker of high added value is obtained；
(4) plasma heating furnace bottom vanadium-bearing hot metal is sent to pneumatic steelmaking；
And by the fume recovery to being produced in course of reaction, obtain zinc oxide.
The present embodiment, the rate of recovery of Fe is 94.6%.
Embodiment 3
A kind of method that titanium slag metallurgy one-step method is reclaimed, comprises the following steps：
Step 1, the mixing of the step of slag one：
By converter obtain molten state molten steel slag, and the iron ore concentrate sintered ore deposit of normal temperature copper smelting slag, normal temperature, normal temperature nickel slag, Normal temperature lead metallurgical slag and normal temperature lead cadmia, pour into ac arc furnace, are sufficiently mixed, and form reaction mixing slag, slag mixing Meanwhile, inside refractory lance intercalation reaction mixing slag, it is blown into the argon gas that preheating temperature is 400 DEG C, injection time and stream The relation of amount is 90L/ (minkg), and electromagnetic agitation is carried out while to reaction mixing slag injection argon gas, mixes reaction molten Slag is realized being sufficiently stirred for；And real-time monitoring reaction mixing slag, it is molten after the completion of being reacted by regulating and controlling to ensure (a) and (b) Slag；：
A () reaction mixing slag is 1300~1650 DEG C；
Basicity CaO/SiO in (b) reaction slag2Ratio=0.6~2.4
Correspondence (a)：The temperature of reaction mixing slag is 1480 DEG C, in setting range；
Correspondence (b)：Basicity CaO/SiO in reaction slag2Ratio=2.6, in mass ratio 1: 3: 1, to reaction slag in plus Enter dolomite, lead and zinc smelting dreg and the mixture with lead metallurgical slag, make basicity CaO/SiO in reaction slag2It is down to 2.4；
Step 2, separation and recovery is using the method D in method four, slag Direct Air-Cooled or water quenching after the completion of reaction：
(1) direct current electric arc furnace top slag Direct Air-Cooled or water quenching, purposes have 4 kinds：1. slag cements；2. cement adjustment Agent；3. the additive in manufacture of cement；4. clinker；
(2) direct current electric arc furnace bottom vanadium-bearing hot metal is sent to pneumatic steelmaking.
The present embodiment, the rate of recovery of Fe is 95.1%.
Embodiment 4
A kind of method that titanium-containing slag metallurgy one-step method is reclaimed, follows the steps below：
Step 1, the mixing of the step of slag one：
Hot common iron ore concentrate metallized pellet, the molten state blast furnace titanium-containing slag that is obtained from slag outlet and often will be melted Warm material containing high-iron bauxite carries out dispensing, adds in direct current electric arc furnace, obtains reaction mixing slag, and real-time monitoring reaction is molten Slag, following (a), (b) two parameters, the slag after the completion of being reacted are ensured by regulation and control simultaneously；Wherein, common iron ore concentrate gold The middle degree of metalization for belonging to pellet is 75%, is loaded into gas for oxygen that preheating temperature is 200 DEG C；
To ensure basicity CaO/SiO after (a) dispensing2Ratio=0.6~2.4；
B () ensures that the temperature of slag bath is 1300~1600 DEG C；
Correspondence (a), after dispensing, basicity CaO/SiO2Ratio is 0.5 ＜ 0.6, to adding calcium lime powder, white in reaction slag Marble dust and alkaline iron ore concentrate, three kinds of mass ratioes of material are 1: 1: 1；After regulation, basicity CaO/SiO2Ratio is 1.0, is being set Determine in scope；
Correspondence (b), reaction mixing slag temperature is 1260 DEG C, less than design temperature scope, by direct current electric arc furnace itself Heating, makes reaction mixing slag temperature for 1335 DEG C, in setting range；
Reaction mixing slag is stirred, agitating mode is that neutral gas stirring and mechanical agitation are combined；
Neutral gas is Ar, and the preheating temperature of Ar is 5 DEG C, and the injection time is 150L/ (minkg) with the relation of flow, Injection method is to be sprayed into inside intercalation reaction mixing slag using refractory lance, is blown into side-blown mode；
Churned mechanically stir speed (S.S.) is 50r/min；
Step 2, separation and recovery uses method three：
Slag after the completion of reaction, spun down, slag-gold is separated, and obtains vanadium-bearing hot metal, iron layer containing vanadium metal, iron oxidation Nitride layer, rich titanium phase layer and rich vanadium phase layer and silicate mineral phase layer, carry out following steps：
(1) iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer and rich vanadium phase layer and silicate mineral phase layer, water quenching or After air cooling, as blast furnace ironmaking raw material or direct reduction iron making or fused reduction iron-smelting；
(2) vanadium-bearing hot metal, is sent to vanadium extraction by converter blowing steel-making；
Wherein, iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer is directly gone back with rich vanadium phase layer and silicate mineral phase layer After original, granularity is crushed to for 20~400 μm, iron and ferriferous oxide are selected in magnetic separation, while obtaining rich titanium mineral phase with rich navajoite Thing phase and silicate mineral phase.
Silicate mineral phase layer returns to reaction mixing slag.
The present embodiment, the rate of recovery of Fe is 92.8%.
Embodiment 5
A kind of method that titanium-containing slag metallurgy one-step method is reclaimed, follows the steps below：
Step 1, the mixing of the step of slag one：
The molten state obtained by the carbon containing pre-reduced pellet of normal temperature acidity iron ore concentrate, normal temperature titanium-containing blast furnace slag and from slag outlet Electric furnace refines the slag of titanium steel containing vanadium, carries out dispensing, adds in plasma heating furnace, is mixed to form reaction mixing slag, real-time monitoring reaction Slag, following (a), (b) two parameters are ensured by regulation and control simultaneously；
To ensure basicity CaO/SiO after (a) dispensing2Ratio=0.6~2.4；
B () ensures that the temperature of slag bath is 1300~1600 DEG C, the slag after the completion of being reacted；
Correspondence (a), after dispensing, basicity CaO/SiO2Ratio is 2.0, in setting range；
Correspondence (b), reaction mixing slag temperature is 1282 DEG C, less than design temperature scope, is added by plasma heating furnace itself Heat, makes reaction mixing slag temperature for 1305 DEG C, in setting range；
Reaction mixing slag is stirred, agitating mode is mechanical agitation, and stir speed (S.S.) is 150r/min；
Step 2, separation and recovery uses method two, the outer slag treatment of stove to use method A：
(1) by the slag after the completion of reaction, electromagnetism sedimentation, slag-gold is separated, and obtains vanadium-bearing hot metal, iron layer containing vanadium metal, iron Oxide skin(coating), rich titanium phase layer and rich vanadium phase layer and silicate mineral phase layer；
(2) by silicate mineral phase layer, the outer slag treatment of stove is carried out；
(3) vanadium-bearing hot metal is sent to vanadium extraction by converter blowing steel-making；
(4) iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer and rich vanadium phase layer, after water quenching or air cooling, refine as blast furnace Iron material or direct reduction iron making；It is broken, through direct-reduction after, crush, iron and ferriferous oxide are selected in magnetic separation, while obtaining richness Titanium mineral phase and solution vanadium-rich mineral phase；
(5) silicate mineral phase layer makes the cement raw material of high added value directly as cement raw material or further treatment.
(6) by fume recovery, zinc oxide is obtained.
The present embodiment, the rate of recovery of Fe is 92.4%.
Embodiment 6
A kind of method that titanium-containing slag metallurgy one-step method is reclaimed, follows the steps below：
Step 1, the mixing of the step of slag one：
The blast furnace titanium-containing slag and normal temperature electric furnace steel making slag with vanadium and titanium oxides that will be obtained from slag notch carry out dispensing, by each material In adding plasma heating furnace, be mixed to form reaction mixing slag, real-time monitoring reaction slag, ensured simultaneously by regulation and control following (a), (b) two parameters；
To ensure basicity CaO/SiO after (a) dispensing2Ratio=0.6~2.4；
B () ensures that the temperature of slag bath is 1300~1600 DEG C, the slag after the completion of being reacted；
Correspondence (a), after dispensing, basicity CaO/SiO2Ratio be 2.62 ＞ 2.4, to reaction slag in add copper smelting slag and Zinc leaches big kiln slag, and two kinds of mass ratioes of material are 1: 1；After regulation, basicity CaO/SiO2Ratio is 1.7, in setting range；
Correspondence (b) controls reaction to mix slag temperature：
Reaction mixing slag temperature is 1250 DEG C, less than design temperature, by the heating function of plasma heating furnace itself, is made anti- Slag temperature should be mixed for 1600 DEG C, in setting range；
Reaction mixing slag is stirred, agitating mode is electromagnetic agitation, is sufficiently mixed reaction mixing slag；
By the fume recovery to being produced in course of reaction, zinc oxide is obtained；
Step 2, separation and recovery uses method two, the outer slag treatment of stove to be returned using method B, whole silicate mineral phase layers To reaction mixing slag：
(1) by the slag after the completion of reaction, natural subsidence, slag-gold is separated, and obtains vanadium-bearing hot metal molten iron, iron containing vanadium metal Layer, oxide ferroelectric layer, rich titanium phase layer and rich vanadium phase layer and silicate mineral phase layer；
(2) by silicate mineral phase layer, the outer slag treatment of stove is carried out；
(3) vanadium-bearing hot metal is sent to vanadium extraction by converter blowing steel-making；
(4) iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer and rich vanadium phase layer, after water quenching or air cooling, refine as blast furnace Iron material or direct reduction iron making；It is broken, through direct-reduction after, crush, iron and ferriferous oxide are selected in magnetic separation, while obtaining richness Titanium mineral phase and solution vanadium-rich mineral phase；
(5) whole silicate mineral phase layers return to reaction mixing slag, used as hot flux for metallurgy, adjustment mixing slag Composition, control mixing slag temperature.
The present embodiment, the rate of recovery of Fe is 93.3%.
Embodiment 7
A kind of method that titanium-containing slag metallurgy one-step method is reclaimed, follows the steps below：
Step 1, the mixing of the step of slag one：
Blast furnace cinder, normal temperature electric furnace dust and the hot Baiyunebo iron mine iron ore concentrate metallization ball that will be obtained from slag notch Group carries out dispensing, in each material addition ac arc furnace, will obtain reaction mixing slag, real-time monitoring reaction slag, by adjusting Control ensures following (a), (b) two parameters simultaneously；
To ensure basicity CaO/SiO after (a) dispensing2Ratio=0.6~2.4；
B () ensures that the temperature of slag bath is 1300~1600 DEG C, the slag after the completion of being reacted；
Correspondence (a), after dispensing, basicity CaO/SiO2Ratio is 2.56 ＞ 2.4, to addition silica, nickel smelting in reaction slag Refining slag and lead metallurgical slag, three kinds of mass ratioes of material are 3: 2: 1；After regulation, basicity CaO/SiO2Ratio is 2.05, in setting model In enclosing；
Control to react mixing slag temperature and be in the method for design temperature scope：
Reaction mixing slag temperature is 1246 DEG C, less than design temperature, by the heating function of ac arc furnace itself, is made Reaction mixing slag temperature is 1589 DEG C, in setting range；
Nature mixing is carried out to reaction mixing slag, reaction mixing slag is sufficiently mixed；
By the fume recovery to being produced in course of reaction, zinc oxide is obtained；
Step 2, separation and recovery is using the method H in method five, air cooling or water quenching after slag oxidation：
Slag after the completion of reaction, rotates cooling-sedimentation, and slag-gold is separated, and obtains vanadium-bearing hot metal, iron layer containing vanadium metal, iron Oxide skin(coating) and silicate phase slag, carry out following steps：
(1) vanadium-bearing hot metal, is sent to vanadium extraction by converter blowing steel-making；
(2) iron layer containing vanadium metal, silicate phase and ferriferous oxide slag are poured into attemperator, to molten after the completion of reaction The oxidizing gas of preheating are blown into slag, as slag iron oxide content >=2wt%, complete to be blown, the slag after being aoxidized, its In, the preheating temperature of oxidizing gas is 500 DEG C；
Wherein, in whole process, it is ensured that slag temperature >=1450 DEG C, the control method for using for：
As 1450 DEG C of temperature ＜, pre-heating fuel, combustion heat release, additional heat, or device conducting self-heating are sprayed into, make slag temperature Degree is at >=1450 DEG C；
(2) the slag Direct Air-Cooled after aoxidizing is used as the additive in manufacture of cement.
The present embodiment, the rate of recovery of Fe is 94.1%.
Embodiment 8
A kind of method that titanium-containing slag metallurgy one-step method is reclaimed, follows the steps below：
Step 1, the mixing of the step of slag one：
It is the Copper making slag that will obtain electric furnace steel making slag with vanadium and titanium oxides from slag notch and directly obtain from smelting furnace, hot Common iron ore concentrate sintered ore deposit carries out dispensing, by each material addition direct current electric arc furnace, is mixed to form reaction mixing slag, in real time prison Reaction slag is surveyed, ensures following (a), (b) two parameters simultaneously by regulation and control；
To ensure basicity CaO/SiO after (a) dispensing2Ratio=0.6~2.4；
B () ensures that the temperature of slag bath is 1300~1600 DEG C, the slag after the completion of being reacted；
Correspondence (a), after dispensing, basicity CaO/SiO2Ratio is 1.2, in setting range；
Correspondingly (b), control to react mixing slag temperature and be in the method for design temperature scope：
Reaction mixing slag temperature is 1280 DEG C, less than design temperature, by the heating function of direct current electric arc furnace itself, is made Reaction mixing slag temperature is 1595 DEG C, in setting range；
Reaction mixing slag is stirred, agitating mode is electromagnetic agitation, is sufficiently mixed reaction mixing slag；
Step 2, separation and recovery uses method three：Slag after the completion of reaction carries out separating treatment：
Slag after the completion of reaction, spun down, slag-gold is separated, and obtains vanadium-bearing hot metal, iron layer containing vanadium metal, iron oxidation Nitride layer, rich titanium phase layer and rich vanadium phase layer and silicate mineral phase layer, carry out following steps：
(1) iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer and rich vanadium phase layer and silicate mineral phase layer, water quenching or After air cooling, as blast furnace ironmaking raw material or direct reduction iron making or fused reduction iron-smelting；
(2) vanadium-bearing hot metal, is sent to vanadium extraction by converter blowing steel-making；
Wherein, iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer is directly gone back with rich vanadium phase layer and silicate mineral phase layer After original, granularity is crushed to for 20~400 μm, iron and ferriferous oxide are selected in magnetic separation, while obtaining rich titanium mineral phase with rich navajoite Thing phase and silicate mineral phase；
Silicate mineral phase layer pours devitrified glass or as mineral wool.
The present embodiment, the rate of recovery of Fe is 95%.
Embodiment 9
A kind of method that titanium-containing slag metallurgy one-step method is reclaimed, follows the steps below：
Step 1, the mixing of the step of slag one：
Blast furnace cinder, molten state electric furnace steel making slag, the content of hot FeO that will be obtained from slag notch are for 60% common iron is smart The carbon containing pre-reduced pellet of ore deposit, ferronickel dross of coming out of the stove is directly obtained from smelting furnace carry out dispensing, add in plasma heating furnace, reacted Mixing slag, real-time monitoring reaction slag, following (a), (b) two parameters are ensured by regulation and control simultaneously；
To ensure basicity CaO/SiO after (a) dispensing2Ratio=0.6~2.4；
B () ensures that the temperature of slag bath is 1300~1600 DEG C, the slag after the completion of being reacted；
Correspondence (a), after dispensing, basicity CaO/SiO2Ratio is 0.5 ＜ 0.6, to addition pulverized limestone, alkalescence in reaction slag Metallized pellet and alkaline pre-reduced pellet, three kinds of mass ratioes of material are 2: 2: 1；After regulation, basicity CaO/SiO2Ratio is 0.9, in setting range；
Correspondingly (b), control to react mixing slag temperature and be in the method for design temperature scope：
Reaction mixing slag temperature is 1220 DEG C, less than design temperature, by the heating function of plasma heating furnace itself, is made anti- Slag temperature should be mixed for 1452 DEG C, in setting range；
Reaction mixing slag is stirred, agitating mode is electromagnetic agitation, is sufficiently mixed reaction mixing slag；
Step 2, separation and recovery uses method four：Slag after the completion of reaction is directly processed, method D：Reaction is completed Slag Direct Air-Cooled afterwards：
(1) melting reaction device top slag Direct Air-Cooled or water quenching, purposes have 4 kinds：1. slag cements；2. cement adjustment Agent；3. the additive in manufacture of cement；4. clinker；
(2) melting reaction device bottom vanadium-bearing hot metal is sent to vanadium extraction by converter blowing steel-making.
The present embodiment, the rate of recovery of Fe is 96%.

Claims (10)

1. a kind of method that titanium-containing slag metallurgy one-step method is reclaimed, it is characterised in that comprise the following steps：
Step 1, the mixing of the step of slag one：
By two or three material mix in molten state blast furnace titanium-containing slag, molten state slag with vanadium and titanium oxides, ferrous material, The melting reaction device that material addition slag after mix can be flowed out, is mixed to form reaction mixing slag, real-time monitoring Reaction slag, following (a), (b) two parameters, the slag after the completion of being reacted are ensured by regulation and control simultaneously；
A () will control reaction slag basicity CaO/SiO2Ratio=0.6~2.4；
B () ensures that the temperature of slag bath is 1300~1600 DEG C；
Regulation and control method is：
Correspondence (a)：
The basicity CaO/SiO in slag is reacted2During ratio ＜ 0.6, to addition alkaline material in reaction slag or alkaline ferrous material In one or more；
The basicity CaO/SiO in slag is reacted2During ratio ＞ 2.4, to the acid material of addition or iron-containing acidic material in reaction slag In one or more；
Correspondence (b)：
Control to react mixing slag temperature and be in the method for design temperature scope：
When reaction mixing slag temperature ＜ design temperature range lower limits, by the heating function of reaction unit itself, make reaction Mixing slag temperature meets 1300~1600 DEG C；
When reaction mixing slag temperature ＞ design temperature range limits, to addition flux for metallurgy, iron content in reaction mixing slag One or more in material or blast furnace cinder, make the temperature of reaction mixing slag meet 1300~1600 DEG C；
Step 2, separation and recovery：
Using the one kind in following methods：
Method one, the slag after the completion of reaction carries out cooling treatment：
Slag after the completion of reaction is poured into attemperator, following steps are carried out：
(1) by the slag after the completion of reaction, room temperature is cooled to, obtains slow cooling slag, wherein, slow cooling slag is followed successively by from bottom toward top The iron of the sedimentation of iron containing vanadium metal sticks together, iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer and rich vanadium phase layer and silicate mineral phase Layer；
(2) artificial taking-up sticked together containing vanadium iron and silicate mineral phase layer, will contain vanadium metal iron layer, oxide ferroelectric layer, rich titanium phase layer with Rich vanadium phase layer, crushes, by the way that after direct-reduction, iron and ferriferous oxide are selected in magnetic separation, while obtaining rich titanium thing phase with rich navajoite Thing phase；
(3) recycling of silicate mineral phase has 2 kinds：1. as cement raw material, construction material, make aggregate, road instead of rubble Material or phosphate fertilizer are used；2. using hydrometallurgy, beneficiation method or ore dressing-hydrometallurgy combination method by phosphorous Component seperation out；
Method two, separating treatment is carried out by the slag after the completion of reaction：
(1) by the slag after the completion of reaction, sedimentation, slag-gold is separated, and obtains vanadium-bearing hot metal molten iron, iron layer containing vanadium metal, iron oxidation Nitride layer, rich titanium phase layer and rich vanadium phase layer and silicate mineral phase layer；
(2) by silicate mineral phase layer, the outer slag treatment of stove is carried out；
(3) vanadium-bearing hot metal is sent to vanadium extraction by converter blowing steel-making；
(4) iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer and rich vanadium phase layer, it is former as blast furnace ironmaking after water quenching or air cooling Material or direct reduction iron making；It is broken, through direct-reduction after, crush, iron and ferriferous oxide are selected in magnetic separation, while obtaining rich titanium ore Thing phase and solution vanadium-rich mineral phase；
Wherein, silicate mineral phase layer, carries out the outer slag treatment of stove, using the one kind in method A, method B or method C：
Method A, silicate mineral phase layer is used as cement raw material：
Silicate mineral phase layer makes the cement raw material of high added value directly as cement raw material or further treatment；
Method B, part or all of silicate mineral phase layer returns to reaction mixing slag：
Part or all of silicate mineral phase layer returns to reaction mixing slag, used as hot flux for metallurgy, adjustment mixing slag Composition, control mixing slag temperature；
Method C, silicate mineral phase layer pours devitrified glass or as mineral wool；
Method three：Slag after the completion of reaction carries out separating treatment：
Slag after the completion of reaction, sedimentation, slag-gold is separated, and obtains vanadium-bearing hot metal, iron layer containing vanadium metal, oxide ferroelectric layer, Fu Tai Phase layer and rich vanadium phase layer and silicate mineral phase layer, carry out following steps：
(1) iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer and rich vanadium phase layer and silicate mineral phase layer, water quenching or air cooling Afterwards, as blast furnace ironmaking raw material or direct reduction iron making or fused reduction iron-smelting；
(2) vanadium-bearing hot metal, is sent to vanadium extraction by converter blowing steel-making；
Wherein, iron layer containing vanadium metal, oxide ferroelectric layer, rich titanium phase layer and rich vanadium phase layer and the layer direct-reduction of silicate mineral phase Afterwards, granularity is crushed to for 20~400 μm, and iron and ferriferous oxide are selected in magnetic separation, while obtaining rich titanium mineral phase and solution vanadium-rich mineral With silicate mineral phase；
The method for subsequent processing of silicate mineral phase is using method A, method B in method two or the one kind in method C；
Method four：Slag after the completion of reaction is directly processed, using one kind side in method method D, method E or method F Method：
Method D, slag Direct Air-Cooled or water quenching after the completion of reaction：
(1) melting reaction device top slag Direct Air-Cooled or water quenching, purposes have 4 kinds：1. slag cements；2. cement regulator； 3. the additive in manufacture of cement；4. clinker；
(2) melting reaction device bottom vanadium-bearing hot metal is sent to vanadium extraction by converter blowing steel-making；
Method E, air cooling or water quenching after slag oxidation after the completion of reaction：
(1) to the oxidizing gas that preheating is blown into slag after the completion of reaction, as slag iron oxide content >=2wt%, spray is completed Blow, the slag after being aoxidized, wherein, the preheating temperature of oxidizing gas is 0~1200 DEG C；
Wherein, in whole process, it is ensured that slag temperature >=1450 DEG C, the control method for using for：
As 1450 DEG C of temperature ＜, pre-heating fuel, combustion heat release, additional heat, or device conducting self-heating are sprayed into, slag temperature is existed ≥1450℃；
(2) slag Direct Air-Cooled or water quenching after aoxidizing, purposes have 4 kinds：1. slag cements；2. cement regulator；3. cement life Additive in product；4. clinker；
(3) melting reaction device bottom vanadium-bearing hot metal is sent to vanadium extraction by converter blowing steel-making；
Method F, slag treatment produces the clinker of high added value：
(1) add melting converter slag, electric furnace melting and reducing slag, electric furnace melt oxidation slag, lime, flyash, basic iron One or more in lean ore, bauxite, titaniferous blast furnace cinder, ordinary blast slag, are sufficiently mixed, and obtain slag mixture Material；
(2) to the oxidizing gas that preheating is blown into slag mixed material, as slag mixed material iron oxide content >=2wt%, Complete to be blown, the slag mixed material after being aoxidized, wherein, the preheating temperature of oxidizing gas is 0~1200 DEG C；
Wherein, in whole process, it is ensured that slag mixed material temperature >=1450 DEG C, the control method for using for：
As 1450 DEG C of temperature ＜, pre-heating fuel, combustion heat release, additional heat, or device conducting self-heating are sprayed into, make slag mixture Material temperature degree is at >=1450 DEG C；
(3) the slag mixed material after aoxidizing, carries out air cooling or water quenching, and the clinker of high added value is obtained；
(4) melting reaction device bottom vanadium-bearing hot metal is sent to pneumatic steelmaking
Method five：Slag after the completion of reaction, cooling-sedimentation, slag-gold is separated, and obtains vanadium-bearing hot metal, iron layer containing vanadium metal, iron oxygen Compound layer and silicate phase slag, carry out following steps：
(1) vanadium-bearing hot metal, is sent to vanadium extraction by converter blowing steel-making；
(2) iron layer containing vanadium metal, silicate phase and ferriferous oxide slag are poured into attemperator, as follows G, method H or One kind in method I is processed：
Method G, slag Direct Air-Cooled or water quenching：
(1) melting reaction device top slag Direct Air-Cooled or water quenching, purposes have 4 kinds：1. slag cements；2. cement regulator； 3. the additive in manufacture of cement；4. clinker；
Method H, air cooling or water quenching after slag oxidation：
(1) to the oxidizing gas that preheating is blown into the slag after the completion of reaction, as slag iron oxide content >=2wt%, complete Injection, the slag after being aoxidized, wherein, the preheating temperature of oxidizing gas is 0~1200 DEG C；
Wherein, in whole process, it is ensured that slag temperature >=1450 DEG C, the control method for using for：
As 1450 DEG C of temperature ＜, pre-heating fuel, combustion heat release, additional heat, or device conducting self-heating are sprayed into, slag temperature is existed ≥1450℃；
(2) slag Direct Air-Cooled or water quenching after aoxidizing, purposes have 4 kinds：1. slag cements；2. cement regulator；3. cement life Additive in product；4. clinker；
Method I, slag treatment produces the clinker of high added value：
(1) melting converter slag, electric furnace melting and reducing slag, electric furnace melt oxidation slag, lime, flyash, basic iron are added One or more in lean ore, bauxite, blast furnace cinder, are sufficiently mixed, and obtain slag mixed material；
(2) to the oxidizing gas that preheating is blown into slag mixed material, as slag mixed material iron oxide content >=2wt%, Complete to be blown, the slag mixed material after being aoxidized, wherein, the preheating temperature of oxidizing gas is 0~1200 DEG C；
Wherein, in whole process, it is ensured that slag mixed material temperature >=1450 DEG C, the control method for using for：
When temperature≤1450 DEG C, pre-heating fuel, combustion heat release, additional heat, or device conducting self-heating are sprayed into, make slag mixture Material temperature degree is at >=1450 DEG C；
(3) the slag mixed material after aoxidizing, carries out air cooling or water quenching, and the clinker of high added value is obtained.
2. the method that the titanium-containing slag metallurgy one-step method according to right will go 1 is reclaimed, it is characterised in that described molten state Titanium-containing slag is obtained by slag notch, or titanium-containing slag is heated into molten condition, and described titanium-containing slag is titaniferous blast furnace cinder Or one or more in electro-titanium slag；Described molten state slag with vanadium and titanium oxides is obtained by slag notch, or slag with vanadium and titanium oxides is added Heat is to molten condition；Described slag with vanadium and titanium oxides is one or more in pneumatic steelmaking slag or electric furnace steel making oxidation slag.
3. the method that the titanium-containing slag metallurgy one-step method according to right will go 1 is reclaimed, it is characterised in that described chalybeate Expect to directly obtain the common iron ore concentrate with temperature, common iron ore concentrate sintered ore deposit, common iron ore concentrate ball for normal temperature or from smelting furnace It is nodulizing, common iron ore concentrate metallized pellet, common iron ore concentrate DRI, the carbon containing pre-reduced pellet of common iron ore concentrate, common Slag, molten iron pre-desulfurization slag, blast furnace dust, blast furnace dust, converter dust, electric furnace dust, iron scale, Zinc Hydrometallurgy Process Zinc leaching residue, the red mud that produces of aluminum oxide production process, flyash, copper smelting slag, pyrite cinder, zinc leach big kiln slag, nickel In scum, lead and zinc smelting dreg, material containing high-iron bauxite, the material of titanium containing vanadium, material containing Biobium rare-earth, nickel fibers slag or lead metallurgical slag One or more；
Middle degree of metalization >=70% of described common iron ore concentrate metallized pellet, in the common carbon containing pre-reduced pellet of iron ore concentrate Content >=60% of FeO；
The described material of titanium containing vanadium be normal temperature or from smelting furnace directly obtain the titanium-containing blast furnace slag with temperature, slag with vanadium and titanium oxides, Tailings in vanadium extraction, Tailing of titanium separation, low-grade vanadium titano-magnetite, v-ti magnetite concentrate, v-ti magnetite concentrate metallized pellet, vanadium titanium magnetic One kind in the carbon containing pre-reduced pellet of iron ore concentrate, direct-reduction titanium, v-ti magnetite concentrate sintering deposit, v-ti magnetite concentrate pellet Or it is several.
4. the method that the titanium-containing slag metallurgy one-step method according to right will go 1 is reclaimed, it is characterised in that described slag liquid can The melting reaction device of outflow, is the dumpable fixed melting reaction device of melting reaction device or bottom with cinder notch； Described dumpable melting reaction device is the one kind in converter, induction furnace or dumpable melting reaction slag ladle；Described Fixed melting reaction device of the bottom with cinder notch is plasma heating furnace, direct current electric arc furnace, ac arc furnace or mineral hot furnace are a kind of；
Described attemperator internal layer is insulation demoulding refractory material；Described insulation demoulding refractory material be siliceous, semi silica, One kind or several in clayey, High-Alumina, magnesia, dolomite matter, olivine matter, spinel, cold conditions blast furnace slag, cold conditions slag Kind.
5. the method that the titanium-containing slag metallurgy one-step method according to right will go 1 is reclaimed, it is characterised in that former in institute's step 1 When containing ferrous material or vanadium-containing material in material, the method for the melting reaction device that each material addition slag liquid can flow out is：First will In molten state blast furnace cinder or molten state molten steel slag adding apparatus, then with neutral gas or oxidizing gas as carrier gas, to dress Put middle injection ferrous material or vanadium-containing material；
Described oxidizing gas are air, oxygen, oxygen-enriched air, oxygen-nitrogen gaseous mixture, air-nitrogen gaseous mixture, oxygen One or more in gas-argon gas gaseous mixture, Air-Argon gaseous mixture；Described injection method is to be inserted using refractory lance It is blown into inside reaction mixing slag；
Described neutral gas is inert gas or N2In one or more；The preheating temperature of neutral gas is 0~1200 DEG C, The injection time of neutral gas is 1~90L/ (minkg) with the relation of flow, and the injection method of neutral gas is to use fire resisting Spray gun is sprayed into and is blown into inside intercalation reaction mixing slag.
6. the method that the titanium-containing slag metallurgy one-step method according to right will go 1 is reclaimed, it is characterised in that described fuel is Coal dust；To needing to be passed through oxidizing gas while adding fuel in reaction mixing slag, fuel and oxidizing gas are using spray The mode blown adds mixing slag, and described injection method is using inside refractory lance intercalation reaction slag；Described oxidation Property gas be air, oxygen, oxygen-enriched air, oxygen-nitrogen gaseous mixture, air-nitrogen gaseous mixture, oxygen-argon gas gaseous mixture, sky One or more in gas-argon gas gaseous mixture；Described oxidizing gas are using inside refractory lance intercalation reaction mixing slag It is blown into.
7. the method that the titanium-containing slag metallurgy one-step method according to right will go 1 is reclaimed, it is characterised in that in step 1, to anti- Slag should be mixed to be stirred, agitating mode is the one kind in the following manner：Neutral gas stirring, electromagnetic agitation, mechanical agitation, Neutral gas stirring is combined with electromagnetic agitation or neutral gas stirring is combined with mechanical agitation；
In the method that described control is sufficiently stirred for, neutral gas is that neutral gas is inert gas or N2In one or two； The preheating temperature of neutral gas is 0~1200 DEG C, and the injection time of neutral gas is 1~90L/ (min with the relation of flow Kg), the injection method of neutral gas is to be sprayed into using refractory lance, wherein, neutral gas can spray from bottom of device or side Enter.
8. the method that the titanium-containing slag metallurgy one-step method according to right will go 1 is reclaimed, it is characterised in that described insulation dress It is set to the one kind in insulation slag ladle or thermal insulation pit；Described insulation slag ladle and thermal insulation pit, using preceding need preheating, preheating temperature It is 300~1200 DEG C.
9. the method that the titanium-containing slag metallurgy one-step method according to right will go 1 is reclaimed, it is characterised in that the step 2, institute That states is cooled to natural cooling or rotation cooling；The gravity separation method be separation by shaking table, sluicing or the two be combined；It is described Direct reduction iron making is carried out in stove is reduced directly, and the direct-reduction stove is rotary kiln, shaft furnace, rotary hearth furnace, car-bottom furnace Or the one kind in tunnel cave.
10. the method that the titanium-containing slag metallurgy one-step method according to right will go 1 is reclaimed, it is characterised in that the rate of recovery of Fe It is 92~96%.
CN201611133555.9A 2016-12-10 2016-12-10 A kind of method that titanium-containing slag metallurgy one-step method is reclaimed Pending CN106755652A (en)

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CN107460306A (en) * 2017-08-11 2017-12-12 攀钢集团研究院有限公司 Titanium slag releasing agent and its application method
WO2019071787A1 (en) * 2017-10-10 2019-04-18 东北大学 Method for recovering valuable components from smelting slag containing nickel
WO2019071795A1 (en) * 2017-10-10 2019-04-18 东北大学 Manufacturing method using copper-containing slag
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WO2019071789A1 (en) * 2017-10-10 2019-04-18 东北大学 Method for recovering valuable components from zinc smelting slag
WO2019071790A1 (en) * 2017-10-10 2019-04-18 东北大学 Method for recovering valuable components from mixed slag containing zinc and iron
CN110343874A (en) * 2018-04-03 2019-10-18 上海广谋能源技术开发有限公司 A method of titanium or titanium alloy is directly produced using titanium ore
CN110496699A (en) * 2019-07-12 2019-11-26 昆明理工大学 A method of recycling fe from ion dust mud contaning
CN111348654A (en) * 2020-04-02 2020-06-30 昆明理工大学 Method for granulating industrial silicon slag by water quenching and separating silicon and slag

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CN106191344A (en) * 2016-07-18 2016-12-07 东北大学 A kind of slag melting and reducing that mixes produces the method with modifier treatment

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CN106048106A (en) * 2016-07-18 2016-10-26 东北大学 Smelting reduction recovery and thermal refining method for rare-earth-niobium-containing slag mixture
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Publication number Priority date Publication date Assignee Title
CN107460306A (en) * 2017-08-11 2017-12-12 攀钢集团研究院有限公司 Titanium slag releasing agent and its application method
CN107460306B (en) * 2017-08-11 2019-05-17 攀钢集团研究院有限公司 Titanium slag release agent and its application method
WO2019071787A1 (en) * 2017-10-10 2019-04-18 东北大学 Method for recovering valuable components from smelting slag containing nickel
WO2019071795A1 (en) * 2017-10-10 2019-04-18 东北大学 Manufacturing method using copper-containing slag
WO2019071792A1 (en) * 2017-10-10 2019-04-18 东北大学 Production method based on smelting reduction of slag containing zinc and iron
WO2019071789A1 (en) * 2017-10-10 2019-04-18 东北大学 Method for recovering valuable components from zinc smelting slag
WO2019071790A1 (en) * 2017-10-10 2019-04-18 东北大学 Method for recovering valuable components from mixed slag containing zinc and iron
CN110343874A (en) * 2018-04-03 2019-10-18 上海广谋能源技术开发有限公司 A method of titanium or titanium alloy is directly produced using titanium ore
CN110496699A (en) * 2019-07-12 2019-11-26 昆明理工大学 A method of recycling fe from ion dust mud contaning
CN111348654A (en) * 2020-04-02 2020-06-30 昆明理工大学 Method for granulating industrial silicon slag by water quenching and separating silicon and slag
CN111348654B (en) * 2020-04-02 2022-09-02 昆明理工大学 Method for granulating industrial silicon slag by water quenching and separating silicon and slag

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