CN106755655A

CN106755655A - A kind of recovery method for mixing the reduction of slag metallurgy melting

Info

Publication number: CN106755655A
Application number: CN201611133559.7A
Authority: CN
Inventors: 张力; 张武
Original assignee: Northeastern University China
Current assignee: Northeastern University China
Priority date: 2016-12-10
Filing date: 2016-12-10
Publication date: 2017-05-31

Abstract

A kind of recovery method for mixing the reduction of slag metallurgy melting, belongs to non-blast furnace ironmaking and comprehensive utilization of resources field.The method is used molten state blast furnace cinder and molten state slag, the melting reaction device for adding attemperator or slag liquid to flow out, it is mixed to form reaction mixing slag, real-time monitoring reaction mixing slag, by mass concentration≤1.0% for regulating and controlling to ensure temperature, well mixed and FeO；The reaction mixing slag for obtaining, is processed by separation and recovery, and slag can be used as additive, the clinker in slag cements, cement regulator, manufacture of cement, or the clinker for producing high added value.The method reaction time is short, metal recovery rate is high, low production cost, adaptability to raw material is strong, treating capacity is big, environment-friendly, economic well-being of workers and staff is high, the high temperature, chemism high and the height that make use of slag are fluxed, is a kind of new smelting reduction process.

Description

A kind of recovery method for mixing the reduction of slag metallurgy melting

Technical field

The invention belongs to non-blast furnace ironmaking and comprehensive utilization of resources field, and in particular to one kind mixing slag metallurgy melting is also Former recovery method.

Background technology

China's development of iron ＆ steel industry was rapid in recent years, and, more than 700,000,000 tons, crude steel yield is more than 900,000,000 tons for pig iron yield in 2015. Ironmaking, steel-making generated the Ferrous Metallurgy such as a large amount of blast furnace slags, slag slag and flue dust, by, blast furnace slag, slag, iron in 2015 Fe alloy slag and flue dust total amount already exceed 400,000,000 tons.

Blast furnace slag is generation in blast furnace reduction process, is metallurgical intermediate products, not only contains reducing substances, such as burnt Charcoal, coal dust, carbon, carbon dust etc., and contain high level CaO, MgO, SiO₂Deng flux for metallurgy and Fe containing component, China is annual More than 300,000,000 tons blast furnace slags are discharged, substantial amounts of CaO, MgO, SiO are taken away every year₂, coke, coal dust, carbon, carbon dust, iron component etc. have Valency component, therefore, blast furnace slag is a kind of important secondary resource.By the blast furnace cinder temperature of blast furnace releasing 1300 DEG C~1600 DEG C, substantial amounts of physical thermal is discharged every year, therefore, blast furnace cinder is also important physics thermal resource.

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 cinder and molten steel slag, contain abundant heat resource, contain substantial amounts of hot flux for metallurgy, Er Qiehan There are various valuable elements such as iron, phosphorus, the calcium of high level, be important secondary resource.Liquid molten blast furnace cinder and molten steel Dreg chemistry reactivity is strong, is all the slag system of excellent in physical and chemical performance, for the reduction of slag metallurgy melting provides necessity Condition.Meanwhile, the chemical composition of slag, mineral composition and clinker are extremely close, and blast furnace cinder also contains and clinker Close chemical composition.Annual China's clinker yield more than 1,200,000,000 tons, it is necessary to substantial amounts of mineral resources and physics thermal resource, Cost is more than 200,000,000,000.Blast furnace cinder and molten steel slag are not discarded objects, but metallurgical intermediate products.

The content of the invention

For the problem that prior art is present, the present invention provides a kind of recovery method for mixing the reduction of slag metallurgy melting, There is provided a kind of method that slag is metallurgical.The method is bathed using mixing slag as slag system by slag, realizes that slag is metallurgical molten Melt reduction, be that one kind reclaims the pig iron or steel, rich phosphorus phase by mixing slag melting and reducing, and realize the side of slag modifier treatment Method.The method reaction time is short, metal recovery rate is high, low production cost, adaptability to raw material is strong, treating capacity is big, it is environment-friendly, warp Ji income is high, can effectively solve environmental pollution, Metallurgical resources and heat energy high efficiente callback Utilizing question, is a kind of metallurgical new work of slag Skill, a kind of new smelting reduction process is improving and innovating for existing metallurgical technology, is to develop slag metallurgy first in the world Technique, slag is not discarded object, but metallurgical intermediate products.

The method that mixing slag metallurgy melting reduction of the invention is reclaimed, makes full use of steel to produce intermediate product-blast furnace The physics thermal resource and hot flux for metallurgy of slag and molten steel slag, and blast furnace cinder and molten steel slag chemism high, By the mixing of blast furnace cinder and molten steel slag, hot flux frit reaction is blown reducing substances and stirring, and slag bath is reduced, Realize mixing slag metallurgical, fused reduction iron-smelting makes the iron in mixing slag be reclaimed, and be realized with molten iron, the pig iron, steel form Rich phosphorus is mutually reclaimed and mixes that slag is quenched, and the slag for obtaining can be directly used as in slag cements, cement regulator, manufacture of cement Additive, clinker, or addition other components produce high added value clinker.

A kind of recovery method for mixing the reduction of slag metallurgy melting of the invention, follows the steps below：

Step 1, the metallurgy melting reduction of mixing slag

The melting reaction device that molten state blast furnace cinder and molten state slag, addition attemperator or slag can be flowed out, Reaction mixing slag is mixed to form, real-time monitoring reaction mixing slag ensures following (a), (b) and (c) three simultaneously by regulation and control Individual parameter：

A the temperature of () reaction mixing slag is in setting range；

B () reaction mixing slag is realized being sufficiently mixed；

In (c) reaction mixing slag, mass concentration≤1.0% of FeO；Regulation and control method is as follows：

Correspondence (a)：

Design temperature scope is 1300~1650 DEG C；

When reaction unit uses attemperator, the temperature range of reaction mixing slag is set as 1300~1580 DEG C；

When the melting reaction device that reaction unit can be flowed out using slag, the temperature range of reaction mixing slag is set as 1350~1650 DEG C；

Control to react the temperature for mixing slag and be in the method for design temperature scope：

When the temperature ＜ design temperature range lower limits of reaction mixing slag, by the heating function of reaction unit itself, Or to fuel and/or molten steel slag is added in reaction mixing slag, heat compensation is carried out, reach the temperature of reaction mixing slag In the range of design temperature；

It is metallurgical molten to being added in reaction mixing slag when the temperature ＞ design temperature range limits of reaction mixing slag One or more in agent, ferrous material or blast furnace cinder, are lowered the temperature, and the temperature of reaction mixing slag is reached design temperature In the range of；

Correspondence (b)：

The reaction mixing well-mixed hybrid mode of slag is the one kind in nature mixing or stirring；Described agitating mode It is the one kind in the following manner：Neutral gas stirring, electromagnetic agitation, mechanical agitation, neutral gas stirring are mutually tied with electromagnetic agitation Close or neutral gas stirring is combined with mechanical agitation.

Correspondence (c)：

As the mass concentration ＞ 1.0% of FeO, to reaction mixing slag in, be passed through reducibility gas or add reducing agent, Reaction mixing slag is set to meet parameter (c)；

Judge that the condition that step 1 terminates is：

In reaction mixing slag, when mass concentration≤1.0% of FeO, stop step 1 and operate, it is molten after being reduced Slag.

Step 2, separation and recovery：

Using the one kind in following methods：

Method one：When reaction unit uses attemperator, following steps are carried out：

(1) cool down：By the slag after reduction, room temperature is cooled to, obtains slow cooling slag；Wherein, metallic iron is deposited to reaction dress The bottom put, forms iron and sticks together；

(2) separate：The artificial iron that takes out sticks together；By containing metal iron layer in remaining slow cooling slag, granularity is crushed to for 20~400 μm, Residual metallic iron is isolated in ore grinding, magnetic separation；

(3) after isolating metallic iron, mine tailing is obtained；

(4) recycling of mine tailing has 2 kinds：1. as cement raw material, construction material, instead of rubble make aggregate, road material or Phosphate fertilizer is used；2. phosphorous Component seperation in mine tailing is gone out using hydrometallurgy, beneficiation method or ore dressing-hydrometallurgy combination method Come.

Method two：When the melting reaction device that reaction unit can flow out using slag, following steps are carried out：

Method I：Air cooling or water quenching after slag oxidation

(1) to the oxidizing gas that preheating is blown into the slag after reduction, as iron oxide content >=2wt%, injection is completed, 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 molten iron is sent to pneumatic steelmaking；

Method II：Slag treatment produces the clinker of high added value

(1) to addition melting converter slag, electric furnace melting and reducing slag, electric furnace melt oxidation steel in the slag after reduction One or more in slag, lime, flyash, basic iron lean ore, bauxite, blast furnace cinder, are sufficiently mixed, and 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 molten iron is sent to pneumatic steelmaking；

Method three：When the melting reaction device that reaction unit can flow out using slag, following steps are carried out：

(1) slag after reducing, cooling-sedimentation, slag-gold is separated, and obtains molten iron and slag；

(2) slag, carries out the outer slag treatment of stove；

(3) molten iron, is sent to pneumatic steelmaking；

Wherein, slag carries out the outer slag treatment of stove, using method A, method B, method C, method D, method E, method F or side One kind in method G：

Method A：Slag air cooling or water quenching

Slag Direct Air-Cooled or water quenching, it is ripe as the additive or cement in slag cements, cement regulator, manufacture of cement Material；

Method B：Air cooling or water quenching after slag oxidation

(1) slag after reducing is poured into the melting reaction device that dumpable attemperator or slag can flow out, Xiang Rong 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 0~1200 DEG C；

Method C：Slag treatment produces the clinker of high added value

(1) slag is poured into the melting reaction device that dumpable attemperator or slag can flow out, and adds melting converter Slag, electric furnace melting and reducing slag, electric furnace melt oxidation slag, lime, flyash, basic iron lean ore, bauxite, blast furnace cinder In one or more, be sufficiently mixed, obtain slag mixed material；

Method D：Slag pours devitrified glass or as mineral wool；

Method E：Part or all of slag returns to reaction mixing slag

Part or all of slag returns to the reaction mixing slag of step 1, used as hot flux for metallurgy, adjustment reaction mixing Slag composition, control reaction mixing slag temperature.

Method F：Slag point is but separated

Slag is poured into attemperator, and used as reaction mixing slag, separation and recovery is processed using step 2 method one.

Method G：The remelted reduction of slag

Slag is poured into attemperator, and slag is mixed as reacting, the reaction mixing slag in real-time monitoring attemperator, Ensure three parameters of above-mentioned (a), (b) and (c) simultaneously by regulation and control, regulation and control method is with the regulation and control method in above-mentioned steps 1；

Separation and recovery is located using method A, method D in step 2 method one or method three or the one kind in method E Reason.

Described molten state blast furnace cinder is obtained by slag notch, or blast furnace slag is heated into molten condition.

Described molten state slag is obtained by slag notch, or slag is heated into molten condition.

Described slag is one or two in pneumatic steelmaking slag or electric furnace steel making slag.

Described attemperator is dumpable attemperator or not dumpable attemperator；Dumpable attemperator It is insulation slag ladle, it raises temperature methods to add fuel；Not dumpable attemperator is thermal insulation pit, its liter of high-temperature side Method is addition fuel.

Described insulation slag ladle and thermal insulation pit, using preheating is preceding needed, preheating temperature is 100~1200 DEG C.

The melting reaction device that described slag 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 One kind in electric arc furnaces, mineral hot furnace, blast furnace or reverberatory furnace.

The temperature of described control mixing slag in the method for design temperature scope, to added in mixing slag fuel and During molten steel slag, fuel and molten steel slag are any ratio.

In the method for design temperature scope, the temperature of described fuel is the temperature of described control reaction mixing slag 0~1200 DEG C, the calorific value calculation Theoretical Mass of addition temperature and coal dust according to needed for of coal dust, the actual mass of addition is than reason By many 1~2wt.% of quality.

Described controls the temperature of reaction mixing slag in the method for design temperature scope, adds in mixing slag to reaction Need to be passed through oxidizing gas while entering fuel, fuel and oxidizing gas add reaction mixing molten by the way of injection Slag, described injection method is that inserted mode is in bottom blowing, side-blown or top blast using inside refractory lance intercalation reaction slag One or more.

In the method for design temperature scope, fuel is coal dust to the temperature of described control reaction mixing slag.

The temperature of described control reaction mixing slag in the method for design temperature scope, described flux for metallurgy be containing CaO or SiO₂Mineral, specially one or more of quartz sand, red mud, dolomite or lime stone；

The temperature of described control reaction mixing slag in the method for design temperature scope, the normal temperature or from smelting furnace Directly obtain the ferrous material with tapping temperature for common iron ore concentrate, common iron ore concentrate sintered ore deposit, common Iron Ore Pellets, 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, the zinc of Zinc Hydrometallurgy Process Red mud that leached mud, aluminum oxide production process are produced, flyash, copper smelting slag, pyrite cinder, zinc leach big kiln slag, ferronickel slag, In 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 Plant or several；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%.

In the method for design temperature scope, described ferrous material is powder to the temperature of described control reaction mixing slag Shape material or spherical material, wherein, granularity≤150 μm of granular material；Granular material adds reaction to mix in the way of being blown Slag, loading gas be air, nitrogen, argon gas, nitrogen-argon gas gaseous mixture, argon-oxygen, nitrogen-oxygen mixture, air- Argon gas gaseous mixture or air-nitrogen gaseous mixture；Described injection method is to be blown into powdery using inside refractory lance insertion slag Material.

The described material of titanium containing vanadium is titanium-containing blast furnace slag, slag with vanadium and titanium oxides, tailings in vanadium extraction, Tailing of titanium separation, low grade vanadium titanium Magnetic iron ore, v-ti magnetite concentrate, v-ti magnetite concentrate metallized pellet, the carbon containing pre-reduced pellet of v-ti magnetite concentrate, directly also One or more in former titanium, v-ti magnetite concentrate sintering deposit, v-ti magnetite concentrate pellet；

Described material containing Biobium rare-earth is blast furnace slag containing rare earth, slag containing niobium, carry niobium tailings, select rare-earth tailing, low-grade Biobium rare-earth ore deposit, Baiyunebo iron mine iron ore concentrate, Baiyunebo iron mine iron ore concentrate metallized pellet, Baiyunebo iron mine iron ore concentrate contain The rich rare earth slag of the iron ore concentrate sintered ore deposit of carbon pre-reduced pellet, Baiyunebo iron mine, Baiyunebo iron mine Iron Ore Pellets, blast furnace, Blast-Furnace Transition rare earth slag, molten one or more divided in rare earth slag；

In body series, it is 1. to protect reaction unit to add the material of titanium containing vanadium and/or the purpose containing Biobium rare-earth material Carbon containing insulation demoulding refractory material；2. reduction iron production can be realized.

Described control reaction mixing slag temperature is added in the method for design temperature scope in mixing slag to reaction During one or more in flux for metallurgy, ferrous material or blast furnace cinder, the mass ratio of several materials is any ratio.

The temperature of described control reaction mixing slag is in the method for design temperature scope, and described addition is metallurgical molten One or more in agent, ferrous material or blast furnace cinder, it is therefore intended that：

First, avoid temperature too high, protect melting reaction equipment, suppress in blast furnace cinder in the pig iron, molten steel slag granulated iron and The oxidation of 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 well-mixed method of described control, described neutral gas is inert gas or N₂In one kind or several Kind；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 blown into using inside refractory lance intercalation reaction mixing slag, plays enhancing and stirs The effect mixed.

When neutral gas is mixed gas, mixed proportion is any ratio.

Described reducibility gas are blast furnace gas, coke-stove gas, coal gas of converter, producer gas, natural gas or device Generation reclaim in tail gas one or more, the temperature of reducibility gas is 0~1200 DEG C, the relation of injection time and flow It is 1~90L/ (minkg) that the mode that is blown into of reducibility gas is to be blown using inside refractory lance intercalation reaction mixing slag Enter；The injection time of described reducibility gas is with flow depending on slag quality, temperature and the degree for needing reduction.

When reducibility gas are mixed gas, mixed proportion is any ratio.

Described reducing agent is blast furnace gas after coal dust, coke powder, bituminous coal, carbon containing blast furnace dust, carbon containing lead cadmia, dealuminzation Mud, zinc leach the one kind in big kiln slag or anthracite.

Described reducing agent is added inside reaction mixing slag by the way of injection, and loading gas is air, oxygen, richness In oxygen air, oxygen-nitrogen gaseous mixture, air-nitrogen gaseous mixture, oxygen-argon gas gaseous mixture, Air-Argon gaseous mixture one Plant or several；Described injection method uses spray gun to be sprayed into inside slag in the way of being blown, using in side-blown, top blast or bottom blowing One or more.

Oxidizing gas are sprayed into system, it is therefore intended that while reducing agent, fuel is added by reducing substances and combustion Material oxidation, makes C be oxidized to CO, further improves reaction speed, while improving slag temperature；

It is right in reaction mixing slag smelting reduction process in the method that described mixed melting metallurgy melting reduction is reclaimed Reaction mixing slag surface is persistently blown oxygen-enriched air；Wherein, it is blown using refractory lance, the oxygen volume of oxygen-enriched air Content is 25~35%；The temperature of oxygen-enriched air is 0~1200 DEG C, and the injection time is 1~90L/ (min with the relation of flow kg)；

It is blown acting as oxygen-enriched air：C reactions inside slag, generate CO, the not sufficiently combusted effusion from slag CO is acted on oxygen-enriched air, carries out second-time burning, improves reaction mixing slag temperature, reaction mixing slag is fully melted Reduction reaction；

After second-time burning, after remaining CO effusions, it is collected, recycles, Application way is：

1. return as reducing agent；2. return as thermal source；3. generating is returned to use；4. return to sintering deposit and do fuel.

The method that mixing slag metallurgy melting reduction of the invention is reclaimed, the rate of recovery of the corresponding Fe of method one for 92~ 96%；In method two, when being processed the slag after reduction using method I or method II, the rate of recovery of corresponding Fe is 85~90%；Method three, when carrying out slag treatment outside stove using method A, method B, method C, method D or method E, corresponding Fe The rate of recovery be 90~95%；Method three, when carrying out slag treatment outside stove using method F, the rate of recovery of corresponding Fe is 96 ~98%.

In the step 2, described hydrometallurgy is diluted acid leaching method, wherein, diluted acid leaching method is inorganic acidleach or has One kind in machine acidleach；Described inorganic acid selects one or more of sulfuric acid, hydrochloric acid or phosphoric acid；Organic acid selects oxalic acid, second One or more of acid or citric acid.

In the method that the mixing slag metallurgy melting reduction 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；The preheating temperature of the oxidizing gas is different because gas is different；The preheating temperature of oxidizing gas is 0~1200 DEG C, it is blown into inside described oxidizing gas insertion slag, inserted mode is one or more in bottom blowing, side-blown or top blast；

In the method that the mixing slag metallurgy melting reduction is reclaimed, described fuel is coal dust, preheating of fuel temperature It is 0~1200 DEG C.The calorific value calculation Theoretical Mass of the addition of coal dust temperature and coal dust according to needed for, the actual mass ratio of addition Many 1~the 2wt.% of Theoretical Mass；While adding fuel, oxidizing gas are passed through, fuel and oxidizing gas are using injection Mode is added inside slag, and inserted mode is one or more in bottom blowing, side-blown or top blast.

In the step 1, described injection reducing substances or stirring, it is therefore intended that ferriferous oxide is filled in ensureing slag Divide and be reduced to metallic iron Fe, it is ensured that iron granule is not oxidized in slag.The granulated iron that is mingled with molten steel slag and it is reduced Metal molten iron is realized aggregation, is grown up and sedimentation.

In described step 2, described is cooled to natural cooling or rotation cooling.

In described step 2, described one kind being settled into the sedimentation of natural subsidence, spun down or electromagnetism.

The step 2, described rotation cooling, spun down will be equipped with the attemperator or reaction dress of the slag after reduction Be placed on rotation platform, the rotary speed of rotation platform depending on slag quality and attemperator height or depth, during rotation Between depending on slag quality and slag solidification situation；The attemperator that will be equipped with the slag after reduction is placed in rotation on rotation platform Turn, it is therefore an objective to accelerate metallic iron to assemble, grow up and sedimentation, promote silico-calcium component, the enrichment of rich phosphorus phase and grow up, when shortening sedimentation Between, improving effect of settling, improve production efficiency realizes slag modifier treatment；

The step 2, in cooling procedure, silicon continues to migrate, is enriched in Silicon-rich with Calcium compounds in the mixing slag after reduction Calcium phase, and realize growing up, metal molten iron continues to assemble, grows up and sedimentation, and realization is grown up and sedimentation, phosphorus component continuation migration, It is enriched in Ca₂SiO₄-Ca₃(PO₄)₂Phase, is distributed in the boundary between Silicon-rich calcium phase and the two-phase of other mineral facies, is conducive to richness The mineral disaggregation of silico-calcium phase, beneficial to Mineral separation, free cao disappears with free oxidation magnesium in the mixing slag after reduction, gold Category iron almost disappears with ferriferous oxide, and mineral grindability increases, and realizes that slag is quenched.

A kind of method for mixing the reduction recovery of slag slag metallurgy melting of the invention, compared with prior art, the present invention The characteristics of and beneficial effect be：

(1) present invention makes full use of steel to produce the physics thermal resource and heat of intermediate product-blast furnace cinder and molten steel slag State flux for metallurgy, and blast furnace cinder and molten steel slag chemism high, by the mixing of blast furnace cinder and molten steel slag, heat State agent reaction, is blown reducing substances and stirring, and slag bath molten reduction is realized and mixes slag metallurgy, fused reduction iron-smelting, The iron in mixing slag is set to be reclaimed with molten iron, the pig iron, steel form；Slag treatment, cool down and separate, remaining granulated iron and continuation in slag The metallic iron being reduced is assembled, is grown up and sedimentation, and phosphorus component silico-calcium component is migrated, is enriched in rich phosphorus phase, Silicon-rich respectively in slag Calcium phase, and realize assembling, grow up and sedimentation, realizes reclaiming metallic iron or steel, rich phosphorus phase and slag quenched and efficiently separate recovery； The slag for obtaining can be directly used as additive, clinker in slag cements, cement regulator, manufacture of cement, or add it He produces the clinker of high added value at component, and can process hot solid material, while slag modifier treatment is realized, should It is wider with scope, reach the purpose of secondary resource high-efficiency comprehensive utilization.The method reaction time is short, the efficient economizing energy, metal The rate of recovery is high, low production cost, adaptability to raw material is strong, treating capacity is big, environment-friendly, economic well-being of workers and staff is high, can effectively solve metallurgy Resource and heat energy high efficiente callback, realize green metallurgical and energy-saving and emission-reduction, realize the efficient utilization of Metallurgical resources and thermal resource； It is a kind of slag New Metallurgical Technology, a kind of new smelting reduction process is improving and innovating for existing metallurgical technology, is in the world Slag metallurgical technology is proposed first, and slag is not discarded object, but important metallurgical intermediate products；

(2) gas, fuel and reducing agent are sprayed into inside slag, increase chemical reaction specific surface area, improve burning anti- Answer speed and reduction reaction speed.

(3) using neutral gas, electromagnetic agitation, mechanical agitation, reduction reaction speed is improve, promote metallic iron to assemble, Grow up and sedimentation, improve the rate of recovery, shorten the sedimentation time；

(4) reducibility gas or reducing agent are blown, reduction reaction speed is accelerated, and metal iron recovery is improved.

(5) the hot ferrous material for adding metallurgical furnace to come out of the stove, not only can be with the effectively save energy, reduces cost, Er Qiechong Divide and utilize thermal resource, improve the treating capacity of hot ferrous material, improve reaction speed and productivity ratio, reduce production cost, it is real Existing energy-saving and emission-reduction, realize green metallurgical；

(6) slag surface injection oxygen-enriched air, the not sufficiently combusted CO escaped from slag is acted on oxygen-enriched air, carried out Second-time burning, post-combustion rate is improved, and effectively reduces fuel consumption, and reaction mixing slag temperature is raised, and makes reaction mixing slag Abundant fusion reduction reaction is carried out, production cost is reduced；

(7) realize that unreacted CO is recycled, the effectively save energy；

(8) after slag cooling, metallic iron is deposited to bottom, forms iron and sticks together, and reclaims metallic iron, while being separated using magnetic separation surplus Containing metal iron layer, isolates residual metallic iron in remaining slow cooling slag, realizes granulated iron and iron oxidation in molten steel slag in blast furnace cinder The high efficiente callback of iron in thing, metal iron recovery is high；

(9) because metallic iron is deposited in bottom, therefore, it is small to sort slag amount, ore grinding, magnetic separation low cost, meanwhile, preservation Rich phosphorus in Silicon-rich calcium phase interface mutually contributes to silico-calcium mutually to dissociate；

(10) 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 the addition in slag cements, cement regulator, manufacture of cement Agent, further by add melting converter slag, electric furnace melting and reducing slag, electric furnace melt oxidation slag, lime, flyash, One or more in basic iron lean ore, bauxite, blast furnace cinder, adjust basicity, spray into oxidizing gas, and adjustment iron oxide contains Amount, generates ferrite, it is constituted closer to required clinker, and with A ore deposits high, the gluing mineral of the hydraulicity increase, Adhesivity increases, and the early strength of cement increases, can be directly as clinker；Titaniferous material is added in slag, increases water The intensity of mud, can prepare high-mark cement；

(11) free cao disappears with free oxidation magnesium, and metallic iron almost disappears with ferriferous oxide, it is easy to ore grinding, slag Realize quenched, Tailings utilization limiting factor disappears, and the recycling of mine tailing has 2 kinds：1. as cement raw material, construction material, generation Make aggregate, road material or phosphate fertilizer for rubble to use；2. hydrometallurgy, beneficiation method or ore dressing-hydrometallurgy combination method are used by tail Phosphorous Component seperation is out in ore deposit.Tailings utilization value is big, has a wide range of application.

(12) the method can be carried out continuously or discontinuously, meet industrial being actually needed.

(13) mixed by two kinds of slags, hot agent reaction, and be blown reducibility gas or reducing agent, bathed by slag, Reduction reaction speed is improved, fused reduction iron-smelting is realized, the ferriferous oxide in slag is fully reduced to metallic iron, slag- Gold is separated, and obtains molten iron and slag；Slag treatment, remaining granulated iron and the metallic iron for continuing to be reduced are assembled, grow up and sink in slag Drop,；

(14) in cooling procedure, iron component continues to migrate in slag, is enriched in metallic iron, phosphorus component continue Migration And Concentration in Rich phosphorus phase, and realize assembling, grow up, silicon continues to migrate, is enriched in Silicon-rich calcium phase with Calcium compounds in mixing slag, realizes growing up； Phosphorus component continues to migrate, is enriched in Ca in mixing slag₂SiO₄-Ca₃(PO₄)₂Phase, is distributed in the two of Silicon-rich calcium and other mineral facies Boundary between phase, beneficial to Mineral separation.Attemperator equipped with mixing slag is placed on rotation platform and rotates, and accelerates metal Iron, the aggregation of rich phosphorus phase, grow up and sedimentation, shorten the sedimentation time, improve effect of settling, improve production efficiency；

(15) method combined using manual sorting, magnetic separation, separation is deposited in the metallic iron of bottom, rich phosphorus phase, realizes mixed Close iron component, silico-calcium component, the high efficiente callback of phosphorus component in slag；Because follow-up separation process uses physical upgrading (magnetic Choosing) so that whole mixing slag technique has that short, simple to operate flow, iron, silicon, phosphorus, the calcium rate of recovery are high, is produced without waste water, tool There is the characteristics of efficient, cleaning, environmental protection；

(16) whole process is without thermal compensation or needs a small amount of thermal compensation, workable, low production cost；Whole process without Solid waste is produced, and reaction condition is gentle, realizes energy-saving and emission-reduction, is a kind of green metallurgical technique.

Specific embodiment

With reference to embodiment, the present invention is described in further detail.

Embodiment 1

A kind of recovery method for mixing the reduction of slag metallurgy melting, follows the steps below：

Step 1, the metallurgy melting reduction of mixing slag

To be obtained by slag notch and molten state blast furnace cinder and be heated to molten state electric furnace steel making slag, in mass ratio, melting State blast furnace cinder: electric furnace steel making slag=(200: 300) kg dispensings, in adding preheating temperature to be 1200 DEG C of thermal insulation pit, mixes Close and form reaction mixing slag, in slag mixed process, ferriferous oxide occurs fusion reduction reaction, real-time monitoring reaction in slag Mixing slag, following (a), (b) and (c) three parameters are ensured by regulation and control simultaneously：

A the temperature of () reaction mixing slag is 1300~1580 DEG C；B () reaction mixing slag is realized being sufficiently mixed；C () is anti- In should mixing slag, mass concentration≤1.0% of FeO；Regulation and control method is as follows：

Correspondence (a)：The temperature that mixing slag is reacted after mixing is 1544 DEG C, in setting range；

Correspondence (b)：Device adds agitating paddle, and using mechanical agitation, stir speed (S.S.) is 300r/min, makes reaction mixing slag Sufficiently mixing；

Correspondence (c)：The mass concentration of FeO is 1.8%, to reaction mixing slag in, it is mixed using refractory lance intercalation reaction Close inside slag, the relation of the coal gas of converter 2min that preheating temperature is 300 DEG C, injection time and flow is blown into the way of bottom blowing It is 60L/ (minkg) that the mass concentration of FeO is 1.0%, meets parameter (c)；

In reaction mixing slag smelting reduction process, temperature is persistently blown to reaction mixing slag surface using refractory lance It is 0 DEG C of oxygen-enriched air；The oxygen volume content of oxygen-enriched air is 35%；The injection time is 90L/ (min with the relation of flow kg)；

Step 2, separation and recovery：

Using method one：Carry out following steps：

(1) cool down：By the slag after reduction, room temperature is naturally cooled to, obtain slow cooling slag；Wherein, metallic iron is deposited to instead The bottom of device is answered, iron is formed and is sticked together；

(2) separate：The artificial iron that takes out sticks together；By containing metal iron layer in remaining slow cooling slag, granularity is crushed to for 20~400 μm, Residual metallic iron is isolated in ore grinding, magnetic separation；Metal iron recovery 96%；

(3) after isolating metallic iron, mine tailing is obtained；

(4) recycling of mine tailing：As cement raw material.

Embodiment 2

Step 1, the metallurgy melting reduction of mixing slag

The molten state pneumatic steelmaking slag that molten state blast furnace cinder will be obtained from slag notch and will be obtained from slag notch, by matter Amount ratio, molten state blast furnace cinder: pneumatic steelmaking slag=(50: 300) kg dispensings, converter is added, it is mixed to form reaction mixing molten Slag, real-time monitoring reaction mixing slag, following (a), (b) and (c) three parameters are ensured by regulation and control simultaneously：

A the temperature of () reaction mixing slag is at 1350~1650 DEG C；B () reaction mixing slag is realized being sufficiently mixed；C () is anti- In should mixing slag, mass concentration≤1.0% of FeO；Regulation and control method is as follows：

Correspondence (a)：The temperature of reaction mixing slag is 1655 DEG C, beyond design temperature scope, to adding normal temperature in device The common iron ore concentrate metallized pellet of degree of metalization >=70%, the common iron ore concentrate of content >=60% of normal temperature FeO it is carbon containing it is pre- also Protocorm group and material containing high-iron bauxite, three kinds of mass ratioes of material are 2: 1: 1, and the temperature of reaction mixing slag is 1470 DEG C, In setting range；

Correspondence (b)：Inside refractory lance intercalation reaction mixing slag, Ar gas is blown into side-blown mode, Ar gas Preheating temperature is 0 DEG C, and the injection time is 90L/ (minkg) with the relation of flow, reaction mixing slag is sufficiently mixed；

Correspondence (c)：The mass concentration of FeO is 1.6%, is loaded into air, to reaction mixing slag in, spray into carbon containing blast furnace Dust, zinc leach big kiln slag, zinc leaching residue and coke powder, and four corresponding mass ratio is 1: 1: 1: 1, makes reaction mixing slag Meet parameter (c)；

In reaction mixing slag smelting reduction process, temperature is persistently blown to reaction mixing slag surface using refractory lance It is 1200 DEG C of oxygen-enriched air；The oxygen volume content of oxygen-enriched air is 25%；The injection time is 60L/ with the relation of flow (min·kg)；

Zinc component, lead component, indium component and silver components are volatized into flue dust, and reacted flue dust is reclaimed, and obtain Zinc oxide and lead oxide, rate of recovery ＞ more than 95%, indium component recovery ＞ 90%, silver components rate of recovery ＞ 90%.

Step 2, separation and recovery：

Using method three, following steps are carried out：

(1) slag after reducing, natural subsidence, slag-gold is separated, and obtains molten iron and slag；(2) slag, melted outside stove Slag treatment；(3) molten iron, is sent to pneumatic steelmaking；Now, the rate of recovery of Fe is 95%；

Slag, carries out the outer slag treatment of stove, using method A：Slag air cooling or water quenching；

Slag direct-water-quenching, as cement regulator.

Embodiment 3

Step 1, the metallurgy melting reduction of mixing slag

The molten state blast furnace cinder that will be obtained by slag notch and the pneumatic steelmaking slag for being heated to molten state, in mass ratio, Molten state blast furnace cinder: pneumatic steelmaking slag=(20: 400) kg dispensings, add in blast furnace, it is mixed to form reaction mixing molten Slag, real-time monitoring reaction mixing slag, following (a), (b) and (c) three parameters are ensured by regulation and control simultaneously：

Correspondence (a)：The temperature of reaction mixing slag is 1660 DEG C, beyond design temperature scope, to being added in device from smelting Copper making slag, lead smelting slag, the common iron ore concentrate metallized pellet of thermal state metal rate >=70% that furnace is directly obtained With the carbon containing pre-reduced pellet of common iron ore concentrate of content >=60% of hot FeO, four mass ratio is 4: 3: 2: 1, in setting In the range of；

Correspondence (b)：Electromagnetic agitation is carried out to reaction mixing slag, reaction mixing slag is sufficiently mixed；

Correspondence (c)：When the mass concentration of FeO is 1.9%, inside refractory lance intercalation reaction mixing slag, with The mode of bottom blowing is blown into natural gas, and the temperature of natural gas is 0 DEG C, and the injection time is 1L/ (minkg) with the relation of flow, is made Reaction mixing slag meets parameter (c)；

In reaction mixing slag smelting reduction process, temperature is persistently blown to reaction mixing slag surface using refractory lance It is 900 DEG C of oxygen-enriched air；The oxygen volume content of oxygen-enriched air is 25%；The injection time is 70L/ with the relation of flow (min·kg)；

Step 2, separation and recovery：

Using method three, following steps are carried out：

(1) slag after reducing, natural cooling sedimentation, slag-gold is separated, and obtains molten iron and slag；(2) slag, carries out stove Outer slag treatment；(3) molten iron, is sent to pneumatic steelmaking；Now, the rate of recovery of Fe is 93%；

Slag, carries out the outer slag treatment of stove, using method B：Air cooling or water quenching after slag oxidation

(1) reduce after slag pour into dumpable insulation slag ladle, by refractory lance to slag inside, with top blast Mode is blown into the oxygen-nitrogen gaseous mixture that preheating temperature is 1000 DEG C, in oxygen-nitrogen gaseous mixture, the volume of oxygen and nitrogen Than being 3: 1；The flow of oxygen-nitrogen gaseous mixture is 60L/ (minkg), and now, slag temperature is 1470 DEG C, and injection terminates Afterwards, Fe in slag₂O₃It is 3.12wt%；Complete injection, the slag after being aoxidized；

(2) the slag Direct Air-Cooled after aoxidizing, as the additive in manufacture of cement.

Embodiment 4

Step 1, the metallurgy melting reduction of mixing slag

The blast furnace cinder that will warm up molten state and the pneumatic steelmaking slag for being heated to molten state, in mass ratio, blast furnace melts Slag: pneumatic steelmaking slag=(500: 560) kg dispensings, add in plasma heating furnace, it is mixed to form reaction mixing slag, real-time monitoring Reaction mixing slag, (a), (b) and (c) three parameters are ensured by regulation and control simultaneously：

Correspondence (a)：The temperature of reaction mixing slag is 1290 DEG C, and less than design temperature scope, device conducting self-heating makes anti- The temperature of slag should be mixed for 1350 DEG C, in setting range；

Correspondence (b)：Reaction mixing slag is stirred, agitating mode is N₂Stirring is combined with electromagnetic agitation；N₂It is pre- Hot temperature is 30 DEG C, and the injection time is 80L/ (minkg) with the relation of flow, and injection method is anti-using refractory lance insertion Should mix inside slag and be blown into the way of bottom blowing；

Correspondence (c)：The mass concentration of FeO is 1.6%, inside refractory lance intercalation reaction mixing slag, with bottom blowing Mode be blown into coke-stove gas, the preheating temperature of coke-stove gas is 500 DEG C, and the injection time is 10L/ (min with the relation of flow Kg), reaction mixing slag is made to meet parameter (c)；

In reaction mixing slag smelting reduction process, temperature is persistently blown to reaction mixing slag surface using refractory lance It is 200 DEG C of oxygen-enriched air；The oxygen volume content of oxygen-enriched air is 30%；The injection time is 20L/ with the relation of flow (min·kg)；

Step 2, separation and recovery：

Using method three, following steps are carried out：

(1) slag after reducing, electromagnetism cooling-sedimentation, slag-gold is separated, and obtains molten iron and slag；(2) slag, carries out stove Outer slag treatment；(3) molten iron, is sent to pneumatic steelmaking；Wherein, the rate of recovery of Fe is 92%；

Slag carries out the outer slag treatment of stove, using method C：Slag treatment produces the clinker of high added value

(1) slag is poured into dumpable melting reaction slag ladle, and now, slag temperature is 1490 DEG C, adds melting converter Slag, electric furnace melt oxidation slag, flyash, bauxite, are sufficiently mixed, and now, temperature of charge is 1350 DEG C, sprays into preheating temperature After spending the fuel-coal dust for 30 DEG C, temperature is 1450 DEG C, obtains slag mixed material；

(2) it is 600 DEG C of oxygen-argon gas mixed gas, oxygen and argon gas to preheating temperature is blown into slag mixed material Mixed volume ratio is 3: 1, and the injection time is 5min, and injection flow is 60L/ (minkg), when slag mixed material iron oxide contains It is 4wt% to measure, and completes the oxidation of slag mixed material, the slag mixed material after being aoxidized；

(3) the slag mixed material after aoxidizing, carries out air cooling, and the clinker of high added value is obtained.

Embodiment 5

Step 1, the metallurgy melting reduction of mixing slag

The blast furnace cinder that will warm up molten state and the pneumatic steelmaking slag for being heated to molten state, in mass ratio, blast furnace melts Slag: pneumatic steelmaking slag=(400: 350) kg dispensings, add in melting reaction slag ladle, reaction mixing slag is mixed to form, in real time Monitoring reaction mixing slag, regulation and control ensure (a), (b) and (c) simultaneously：

Correspondence (a)：The temperature of reaction mixing slag is 1450 DEG C, in setting range；

Correspondence (b)：Reaction mixing slag is stirred, agitating mode is that Ar stirrings are combined with mechanical agitation；Ar's Preheating temperature is 100 DEG C, and the injection time is 20L/ (minkg) with the relation of flow, and injection method is to be inserted using refractory lance Enter and be blown into side-blown mode inside reaction mixing slag；Churned mechanically stir speed (S.S.) is 200r/min；

Correspondence (c)：The mass concentration of FeO is 1.7%, inside refractory lance intercalation reaction mixing slag, with side-blown Mode be blown into blast furnace gas, the preheating temperature of blast furnace gas is 1000 DEG C, and the injection time is 10L/ with the relation of flow (minkg) reaction mixing slag, is made to meet parameter (c)；

In reaction mixing slag smelting reduction process, temperature is persistently blown to reaction mixing slag surface using refractory lance It is 200 DEG C of oxygen-enriched air；The oxygen volume content of oxygen-enriched air is 35%；The injection time is 30L/ (min with the relation of flow kg)；

Step 2, separation and recovery：

Using method three, following steps are carried out：

(1) slag after reducing, rotates cooling-sedimentation, and slag-gold is separated, and obtains molten iron and slag；(2) slag, carries out stove Outer slag treatment；(3) molten iron, is sent to pneumatic steelmaking；Wherein, the rate of recovery of Fe is 94%；

Slag, carries out the outer slag treatment of stove, using method D：Slag pours devitrified glass；

Embodiment 6

Step 1, the metallurgy melting reduction of mixing slag

The blast furnace cinder that will warm up molten state and the pneumatic steelmaking slag for being heated to molten state, in mass ratio, blast furnace melts Slag: pneumatic steelmaking slag=(560: 600) kg dispensings, add in melting reaction slag ladle, reaction mixing slag is mixed to form, in real time Monitoring reaction mixing slag, following (a), (b) and (c) three parameters are ensured by regulation and control simultaneously：

Correspondence (a)：Reaction mixing slag temperature is 1320 DEG C, less than design temperature, in device, adds fuel, fuel Temperature be 50 DEG C, the calorific value calculation Theoretical Mass of addition temperature and coal dust according to needed for of coal dust, the actual mass of addition The 1wt.% more than Theoretical Mass；Meanwhile, with side-blown mode, being passed through oxygen inside refractory lance intercalation reaction slag, oxygen Preheating temperature is 50 DEG C；After the completion of injection, the temperature for determining reaction mixing slag is 1550 DEG C, in setting range；

Correspondence (b)：Reaction mixing slag is stirred, agitating mode is electromagnetic agitation；Make reaction mixing slag abundant Mixing；

Correspondence (c)：The mass concentration of FeO is 1.0%, meets parameter (c)；

In reaction mixing slag smelting reduction process, temperature is persistently blown to reaction mixing slag surface using refractory lance It is 200 DEG C of oxygen-enriched air；The oxygen volume content of oxygen-enriched air is 25%；The injection time is 60L/ (min with the relation of flow kg)；

Step 2, separation and recovery：

Using method three, following steps are carried out：

(1) slag after reducing, spun down, slag-gold is separated, and obtains molten iron and slag；(2) slag, melted outside stove Slag treatment；(3) molten iron, is sent to pneumatic steelmaking；Wherein, the rate of recovery of Fe is 90%；

Slag, carries out the outer slag treatment of stove, using method E：Part or all of slag returns to reaction mixing slag

Whole slags return to the reaction mixing slag of step 1, as hot flux for metallurgy, adjustment reaction mixing slag into Point, control reaction mixing slag temperature, the temperature range for controlling is 1350~1580 DEG C.

Embodiment 7

Step 1, the metallurgy melting reduction of mixing slag

The blast furnace cinder that will warm up molten state and the electric furnace steel making oxidation slag for being heated to molten state are in mass ratio, high Stove slag: electric furnace steel making oxidation slag=(200: 250) kg, add formation reaction mixing slag, slag mixed process in converter In, in slag ferriferous oxide occur fusion reduction reaction, real-time monitoring reaction mixing slag, by regulation and control simultaneously ensure (a), (b) and (c) three parameters：

Correspondence (a)：The temperature of slag is 1651 DEG C after mixing, beyond the design temperature of reaction mixing slag；Add hot Common Iron Ore Pellets and the common iron ore concentrate sintered ore deposit of normal temperature, and refractory lance is used in the way of the injection of bottom blowing, add Particle mean size is 150 μm of blast furnace dust, electric furnace dust granular material and v-ti magnetite concentrate metallized pellet, four kinds of materials Mass ratio be 1: 1: 1: 0.1, be loaded into gas air-nitrogen mixture, reaction mixing slag temperature is 1520 DEG C；

Correspondence (b)：Reaction mixing slag is stirred, agitating mode is mechanical agitation, and stir speed (S.S.) is 100r/min, It is sufficiently mixed reaction mixing slag；

Correspondence (c)：The mass concentration of FeO is 2.0%, to the inside of reaction mixing slag, adds carbon containing lead cadmia and dealuminzation Blast furnace gas mud afterwards, two kinds of mass ratioes of material are 1: 1, and loadings gas is oxygen, reaction mixing slag is met parameter (c)；

In reaction mixing slag smelting reduction process, temperature is persistently blown to reaction mixing slag surface using refractory lance It is 300 DEG C of oxygen-enriched air；The oxygen volume content of oxygen-enriched air is 35%；The injection time is 30L/ with the relation of flow (min·kg)；

Zinc component, lead component volatilization enter flue dust, and reacted flue dust is reclaimed, and obtain zinc oxide and lead oxide, Rate of recovery ＞ more than 95%.

Step 2, separation and recovery：

Using method three, following steps are carried out：

(1) slag after reducing, natural subsidence, slag-gold is separated, and obtains molten iron and slag；(2) slag, melted outside stove Slag treatment；(3) molten iron, is sent to pneumatic steelmaking；

Wherein, slag carries out the outer slag treatment of stove, using method F：

Separation and recovery uses method one, is processed：

(1) cool down：Slag, rotation are cooled to room temperature, slow cooling slag is obtained.Metallic iron is deposited to the bottom of reaction unit, Iron is formed to stick together；

(2) separate：The artificial iron that takes out sticks together, and by containing metal iron layer in remaining slow cooling slag, is crushed to granularity for 20~400 μm, Residual metallic iron, metal iron recovery 97% are isolated in ore grinding, magnetic separation；

(3) after isolating metallic iron, mine tailing is obtained；

(4) mine tailing is recycled as：Using hydrometallurgical by phosphorous Component seperation in mine tailing out, in rich phosphorus phase P₂O₅Content is 23%, using 2wt% phosphoric acid, wherein, the solid-to-liquid ratio of gravity treatment richness phosphorus phase and phosphoric acid is 1: 2 (g: L), by P₂O₅Point Separate out and, P₂O₅The rate of recovery is 65%.

Embodiment 8

Step 1, the metallurgy melting reduction of mixing slag

The blast furnace cinder that will warm up molten state and the electric furnace steel making oxidation slag for being heated to molten state are in mass ratio, high Stove slag: electric furnace steel making oxidation slag=(200: 250) kg, add in ac arc furnace, reaction mixing slag is mixed to form, it is real When monitoring reaction mixing slag, regulation and control ensure (a), (b) and (c) three parameters simultaneously：

Correspondence (a)：Reaction mixing slag temperature is 1210 DEG C, electric arc furnaces conducting self-heating, and temperature is setting model to 1550 DEG C In enclosing；

Correspondence (c)：The mass concentration of FeO is 1.9%, inside refractory lance intercalation reaction mixing slag, with bottom blowing The preheating temperature of tail gas-CO, CO that reclaims of mode device for blowing be 1200 DEG C, injection time and flow are 10L/ (min Kg), reaction mixing slag is made to meet parameter (c)；

In reaction mixing slag smelting reduction process, temperature is persistently blown to reaction mixing slag surface using refractory lance It is 800 DEG C of oxygen-enriched air；The oxygen volume content of oxygen-enriched air is 25%；The injection time is 15L/ with the relation of flow (min·kg)；

Step 2, separation and recovery：

Using method three, following steps are carried out：

Wherein, slag carries out the outer slag treatment of stove, using method G：The remelted reduction of slag

Slag is poured into insulation slag ladle, real-time monitoring slag, ensures (a), (b) and (c) three as follows simultaneously by regulation and control Parameter, obtains the slag after secondary reduction：

A the temperature of () slag is at 1300~1580 DEG C；B () slag is realized being sufficiently mixed；C in () slag, the quality of FeO is dense Degree≤1.0%；

Regulation and control method is as follows：

Correspondence (a)：The temperature of slag is 1300 DEG C, in setting range；

Correspondence (b)：Reaction mixing slag is stirred, agitating mode is mechanical agitation, and stir speed (S.S.) is 200r/min, It is sufficiently mixed reaction mixing slag；

Correspondence (c)：The mass concentration of FeO is 0.9, and reaction mixing slag meets parameter (c)；

Separation and recovery is using the method A in method three：Slag air cooling or water quenching after reduction are processed：

Slag Direct Air-Cooled after reduction, as the additive in manufacture of cement.

Embodiment 9

Step 1, the metallurgy melting reduction of mixing slag

The molten state blast furnace cinder that will be obtained by slag notch and the pneumatic steelmaking slag for being heated to molten state, in mass ratio, Molten state blast furnace cinder: pneumatic steelmaking slag=(500: 400) kg dispensings, add in blast furnace, it is mixed to form reaction mixing molten Slag, real-time monitoring ensures (a), (b) and (c) three parameters simultaneously：

Correspondence (a)：The temperature of reaction mixing slag is 1657 DEG C, beyond design temperature scope, to being added in device from smelting Hot common iron ore concentrate sintered ore deposit, common iron ore concentrate DRI, normal temperature ferronickel slag and Bayan Obo that furnace is directly obtained The carbon containing pre-reduced pellet of iron ore iron ore concentrate, four kinds of corresponding mass ratios of material are 5: 3: 2: 0.2, determine reaction mixing slag Temperature is 1420 DEG C, in setting range；

Correspondence (c)：When the mass concentration of FeO is 1.9%, inside refractory lance intercalation reaction mixing slag, with The mode of top blast is blown into natural gas, and the temperature of natural gas is 0 DEG C, and the injection time is 1L/ (minkg) with the relation of flow, is made Reaction mixing slag meets parameter (c)；

In reaction mixing slag smelting reduction process, temperature is persistently blown to reaction mixing slag surface using refractory lance It is 800 DEG C of oxygen-enriched air；The oxygen volume content of oxygen-enriched air is 25%；The injection time is 60L/ with the relation of flow (min·kg)；

Step 2, separation and recovery：

Using method two, following steps are carried out：

Method I：Air cooling or water quenching after slag oxidation

(1) in the slag after reduction, by refractory lance to slag inside, being blown into preheating temperature in top blast mode is 1000 DEG C of oxygen, the flow of oxygen is that flow is 60L/ (minkg), and now, slag temperature is 1450 DEG C, and injection terminates Afterwards, Fe in slag₂O₃It is 3.46wt%, completes injection, the slag after being aoxidized；

(2) the slag Direct Air-Cooled after aoxidizing is used as cement regulator；

(3) melting reaction device bottom molten iron is sent to pneumatic steelmaking, and the rate of recovery of Fe is 90%.

Embodiment 10

Step 1, the metallurgy melting reduction of mixing slag

The blast furnace cinder that will warm up molten state and the pneumatic steelmaking slag for being heated to molten state, in mass ratio, blast furnace melts Slag: pneumatic steelmaking slag=(400: 360) kg dispensings, add in plasma heating furnace, it is mixed to form reaction mixing slag, real-time monitoring Reaction mixing slag, (a), (b) and (c) three parameters are ensured by regulation and control simultaneously：

Correspondence (a)：The temperature of reaction mixing slag is 1280 DEG C, and less than design temperature scope, device conducting self-heating makes anti- The temperature of slag should be mixed for 1350 DEG C, in setting range；

Correspondence (b)：Reaction mixing slag is stirred, agitating mode is N₂Stirring is combined with electromagnetic agitation；N₂It is pre- Hot temperature is 50 DEG C, and the injection time is 40L/ (minkg) with the relation of flow, and injection method is anti-using refractory lance insertion Should mix inside slag, be blown into the way of top blast；

Correspondence (c)：The mass concentration of FeO is 1.6%, inside refractory lance intercalation reaction mixing slag, with bottom blowing Mode is blown into the coke-stove gas that temperature is 500 DEG C, and the injection time is 10L/ (minkg), reaction mixing slag with discharge relation Meet parameter (c)；

Step 2, separation and recovery：

Using method two, following steps are carried out：

Method II：Slag treatment produces the clinker of high added value

(1) to electric furnace melting and reducing slag, lime, basic iron lean ore, blast furnace cinder is added in the slag after reduction, fully Mixing, now, temperature of charge is 1380 DEG C, and by plasma heating furnace conducting self-heating, temperature of charge is 1490 DEG C, obtains slag mixing Material；

(2) it is 800 DEG C of oxygen-nitrogen mixed gas, oxygen and nitrogen to preheating temperature is blown into slag mixed material Mixed volume ratio is 5: 1, and the injection time is 6min, and injection flow is 40L/ (minkg), when slag mixed material iron oxide contains It is 5.12wt% to measure, and completes the oxidation of slag mixed material, the slag mixed material after being aoxidized；

(4) melting reaction device bottom molten iron is sent to pneumatic steelmaking.

Claims

1. it is a kind of to mix the recovery method that slag metallurgy melting is reduced, it is characterised in that to follow the steps below：

Step 1, the metallurgy melting reduction of mixing slag

By molten state blast furnace cinder and molten state slag, the melting reaction device for adding attemperator or slag to flow out, mixing Reaction mixing slag is formed, real-time monitoring reaction mixing slag ensures following (a), (b) and (c) three ginsengs by regulation and control simultaneously Number：

A the temperature of () reaction mixing slag is in setting range；

B () reaction mixing slag is realized being sufficiently mixed；

In (c) reaction mixing slag, mass concentration≤1.0% of FeO；

Regulation and control method is as follows：

Correspondence (a)：

Design temperature scope is 1300~1650 DEG C；

When the melting reaction device that reaction unit can be flowed out using slag, the temperature range of reaction mixing slag is set as 1350 ~1650 DEG C；

When the temperature ＜ design temperature range lower limits of reaction mixing slag, by the heating function of reaction unit itself, or to Fuel and/or molten steel slag are added in reaction mixing slag, heat compensation is carried out, the temperature of reaction mixing slag is reached setting In temperature range；

When the temperature ＞ design temperature range limits of reaction mixing slag, add flux for metallurgy in mixing slag to reaction, contain One or more in iron material or blast furnace cinder, are lowered the temperature, and the temperature of reaction mixing slag is reached design temperature scope It is interior；

Correspondence (b)：

The reaction mixing well-mixed hybrid mode of slag is the one kind in nature mixing or stirring；Described agitating mode be with One kind under type：Neutral gas stirring, electromagnetic agitation, mechanical agitation, neutral gas stirring be combined with electromagnetic agitation or Neutral gas stirring is combined with mechanical agitation；

Correspondence (c)：

As the mass concentration ＞ 1.0% of FeO, to reaction mixing slag in, be passed through reducibility gas or add reducing agent, make anti- Slag should be mixed and meet parameter (c)；

Judge that the condition that step 1 terminates is：

In reaction mixing slag, when mass concentration≤1.0% of FeO, stop step 1 and operate, the slag after being reduced；

Step 2, separation and recovery：

Using the one kind in following methods：

(1) cool down：By the slag after reduction, room temperature is cooled to, obtains slow cooling slag；Wherein, metallic iron is deposited to reaction unit Bottom, forms iron and sticks together；

(2) separate：The artificial iron that takes out sticks together；By containing metal iron layer in remaining slow cooling slag, it is 20~400 μm to be crushed to granularity, ore grinding, Residual metallic iron is isolated in magnetic separation；

(3) after isolating metallic iron, mine tailing is obtained；

(4) recycling of mine tailing has 2 kinds：

1. as cement raw material, construction material, instead of rubble make aggregate, road material or phosphate fertilizer to use；

2. using hydrometallurgy, beneficiation method or ore dressing-hydrometallurgy combination method by phosphorous Component seperation in mine tailing out；

Method I：Air cooling or water quenching after slag oxidation

(1) to the oxidizing gas that preheating is blown into the slag after reduction, as iron oxide content >=2wt%, injection is completed, is obtained Slag after oxidation, wherein, the preheating temperature of oxidizing gas is 0~1200 DEG C；

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 II：Slag treatment produces the clinker of high added value

(1) to addition melting converter slag, electric furnace melting and reducing slag, electric furnace melt oxidation slag, stone in the slag after reduction One or more in ash, flyash, basic iron 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；

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；

(2) slag, carries out the outer slag treatment of stove；

(3) molten iron, is sent to pneumatic steelmaking；

Wherein, slag carries out the outer slag treatment of stove, using method A, method B, method C, method D, method E, method F or method G In one kind：

Method A：Slag air cooling or water quenching

Slag Direct Air-Cooled or water quenching, as additive or clinker in slag cements, cement regulator, manufacture of cement；

Method B：Air cooling or water quenching after slag oxidation

(1) slag after reducing is poured into the melting reaction device that dumpable attemperator or slag can flow out, in slag The oxidizing gas of preheating are blown into, 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；

Method C：Slag treatment produces the clinker of high added value

(1) slag is poured into the melting reaction device that dumpable attemperator or slag can flow out, add melting converter slag, In electric furnace melting and reducing slag, electric furnace melt oxidation slag, lime, flyash, basic iron lean ore, bauxite, blast furnace cinder One or more, are sufficiently mixed, and obtain slag mixed material；

Method D：Slag pours devitrified glass or as mineral wool；

Method E：Part or all of slag returns to reaction mixing slag

Part or all of slag returns to the reaction mixing slag of step 1, used as hot flux for metallurgy, adjustment reaction mixing slag Composition, control reaction mixing slag temperature；

Method F：Slag point is but separated

Slag is poured into attemperator, and used as reaction mixing slag, separation and recovery is processed using step 2 method one；

Method G：The remelted reduction of slag

Slag is poured into attemperator, and used as reaction mixing slag, the reaction mixing slag in real-time monitoring attemperator passes through Regulation and control ensure three parameters of above-mentioned (a), (b) and (c) simultaneously, and regulation and control method is with the regulation and control method in above-mentioned steps 1；

Separation and recovery is processed using method A, method D in step 2 method one or method three or the one kind in method E.

2. the recovery method that mixing slag metallurgy melting as claimed in claim 1 is reduced, it is characterised in that described molten state Blast furnace cinder is obtained by slag notch, or blast furnace slag is heated into molten condition；Described molten state slag is obtained by slag notch, or Slag is heated to molten condition；Described slag is one or two in pneumatic steelmaking slag or electric furnace steel making slag.

3. the recovery method that mixing slag metallurgy melting as claimed in claim 1 is reduced, it is characterised in that described insulation dress It is set to dumpable attemperator or not dumpable attemperator；Dumpable attemperator is insulation slag ladle, its liter of high temperature Degree method is addition fuel；Not dumpable attemperator is thermal insulation pit, and it raises temperature methods to add fuel；

Described insulation slag ladle and thermal insulation pit, using preheating is preceding needed, preheating temperature is 100~1200 DEG C；

The melting reaction device that described slag can flow out, is the dumpable fixation of melting reaction device or bottom with cinder notch Formula melting reaction device；Described dumpable melting reaction device is converter, induction furnace or dumpable melting reaction slag ladle In one kind；Fixed melting reaction device of the described bottom with cinder notch is plasma heating furnace, direct current electric arc furnace, alternating current arc One kind in stove, mineral hot furnace, blast furnace or reverberatory furnace.

4. the recovery method that mixing slag metallurgy melting as claimed in claim 1 is reduced, it is characterised in that described control is anti- The temperature of slag should be mixed in the method for design temperature scope, the temperature of described fuel is 0~1200 DEG C, the addition of coal dust The calorific value calculation Theoretical Mass of amount temperature and coal dust according to needed for, the actual mass of addition 1~2wt.% more than Theoretical Mass；

The temperature of described control reaction mixing slag adds combustion in the method for design temperature scope in mixing slag to reaction Need to be passed through oxidizing gas while material, fuel and oxidizing gas add reaction mixing slag, institute by the way of injection The injection method stated is that inserted mode is the one kind in bottom blowing, side-blown or top blast using inside refractory lance intercalation reaction slag Or it is several；

In the method for design temperature scope, fuel is coal dust to described control reaction mixing slag temperature；

Described control reaction mixing slag temperature in the method for design temperature scope, described flux for metallurgy be containing CaO or SiO₂Mineral, specially one or more of quartz sand, red mud, dolomite or lime stone；Described control reaction mixing is molten In the method for design temperature scope, described control reaction mixes the temperature of slag in the side of design temperature scope to the temperature of slag In method, the normal temperature or the ferrous material with tapping temperature is directly obtained for common iron ore concentrate, 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, in the common carbon containing pre-reduced pellet of iron ore concentrate Content >=60% of FeO；

In the method for design temperature scope, described ferrous material is powder to the temperature of described control reaction mixing slag Material or spherical material, wherein, the granularity≤150um of granular material；Granular material adds reaction mixing slag in the way of being blown, Loading gas is air, nitrogen, argon gas, nitrogen-argon gas gaseous mixture, argon-oxygen, nitrogen-oxygen mixture, Air-Argon Gaseous mixture or air-nitrogen gaseous mixture；Described injection method is to be blown into granular material using inside refractory lance insertion slag；

The described material of titanium containing vanadium is titanium-containing blast furnace slag, slag with vanadium and titanium oxides, tailings in vanadium extraction, Tailing of titanium separation, low-grade v-ti magnetite Ore deposit, v-ti magnetite concentrate, v-ti magnetite concentrate metallized pellet, the carbon containing pre-reduced pellet of v-ti magnetite concentrate, direct-reduction titanium, One or more in v-ti magnetite concentrate sintering deposit, v-ti magnetite concentrate pellet；

Described material containing Biobium rare-earth is blast furnace slag containing rare earth, slag containing niobium, carries niobium tailings, selects rare-earth tailing, low-grade niobium dilute Tu Kuang, Baiyunebo iron mine iron ore concentrate, Baiyunebo iron mine iron ore concentrate metallized pellet, Baiyunebo iron mine iron ore concentrate are carbon containing pre- The iron ore concentrate sintered ore deposit of reducting pellet, Baiyunebo iron mine, Baiyunebo iron mine Iron Ore Pellets, blast furnace richness rare earth slag, blast furnace Transition rare earth slag, molten one or more divided in rare earth slag.

5. the recovery method that mixing slag metallurgy melting as claimed in claim 1 is reduced, it is characterised in that described control is filled Divide in the method for mixing, described neutral gas is inert gas or N₂In one or more；The preheating temperature of neutral gas It it is 0~1200 DEG C, the injection time of neutral gas is 1~90L/ (minkg), the injection side of neutral gas with the relation of flow Formula is to be blown into using inside refractory lance intercalation reaction mixing slag.

6. the recovery method that mixing slag metallurgy melting as claimed in claim 1 is reduced, it is characterised in that described reproducibility In the recovery tail gas that gas is blast furnace gas, coke-stove gas, coal gas of converter, producer gas, natural gas or device are produced one Plant or several, the temperature of reducibility gas is 0~1200 DEG C, and the injection time is 1~90L/ (minkg) with the relation of flow, The mode that is blown into of reducibility gas is to be blown into using inside refractory lance intercalation reaction mixing slag；

Described reducing agent is blast furnace gas mud, zinc after coal dust, coke powder, bituminous coal, carbon containing blast furnace dust, carbon containing lead cadmia, dealuminzation Leach the one kind in big kiln slag or anthracite；

Described reducing agent is added inside reaction mixing slag by the way of injection, and loading gas is air, oxygen, oxygen-enriched sky One kind in gas, oxygen-nitrogen gaseous mixture, air-nitrogen gaseous mixture, oxygen-argon gas gaseous mixture, Air-Argon gaseous mixture or It is several；Described injection method uses spray gun to be sprayed into inside slag in the way of being blown, using in side-blown, top blast or bottom blowing Plant or several.

7. the recovery method that mixing slag metallurgy melting as claimed in claim 1 is reduced, it is characterised in that described mixing is melted Melt in the method that metallurgy melting reduction is reclaimed, in reaction mixing slag smelting reduction process, reaction mixing slag surface is continued Injection oxygen-enriched air；Wherein, it is blown using refractory lance, the oxygen volume content of oxygen-enriched air is 25~35%；It is oxygen-enriched The temperature of air is 0~1200 DEG C, and the injection time is 1~90L/ (minkg) with the relation of flow.

8. the recovery method that mixing slag metallurgy melting as claimed in claim 1 is reduced, it is characterised in that in the step 2, Described hydrometallurgy is diluted acid leaching method, wherein, diluted acid leaching method is the one kind in inorganic acidleach or organic acidleach；Described Inorganic acid selects one or more of sulfuric acid, hydrochloric acid or phosphoric acid；The one kind or several of organic acid from oxalic acid, acetic acid or citric acid Kind；

In the step 2, described fuel is coal dust, and preheating of fuel temperature is 0~1200 DEG C；The addition of coal dust is according to institute Need the calorific value calculation Theoretical Mass of temperature and coal dust, the actual mass of addition 1~2wt.% more than Theoretical Mass；Add fuel Meanwhile, oxidizing gas are passed through, fuel and oxidizing gas are added inside slag by the way of injection, and inserted mode is bottom Blow, one or more in side-blown or top blast；

In described step 2, described is cooled to natural cooling or rotation cooling；

9. the recovery method that the mixing slag metallurgy melting as described in claim 1 or 7 is reduced, it is characterised in that described oxygen Change property gas be air, oxygen, oxygen-enriched air, oxygen-nitrogen gaseous mixture, air-nitrogen gaseous mixture, oxygen-argon gas gaseous mixture, One or more in Air-Argon gaseous mixture；The preheating temperature of the oxidizing gas is different because gas is different；Oxidisability gas The preheating temperature of body is 0~1200 DEG C, is blown into inside described oxidizing gas insertion slag；Inserted mode is bottom blowing, side-blown Or one or more in top blast.

10. the recovery method that mixing slag metallurgy melting as claimed in claim 1 is reduced, it is characterised in that the correspondence of method one Fe the rate of recovery be 92~96%；It is right when being processed the slag after reduction using method I or method II in method two The rate of recovery of the Fe for answering is 85~90%；Method three, is carried out outside stove using method A, method B, method C, method D or method E During slag treatment, the rate of recovery of corresponding Fe is 90~95%；Method three is right when carrying out slag treatment outside stove using method F The rate of recovery of the Fe for answering is 96~98%.