CN106048108B - A kind of method of titaniferous mixing slag melting and reducing recycling and modifier treatment - Google Patents

A kind of method of titaniferous mixing slag melting and reducing recycling and modifier treatment Download PDF

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CN106048108B
CN106048108B CN201610565007.7A CN201610565007A CN106048108B CN 106048108 B CN106048108 B CN 106048108B CN 201610565007 A CN201610565007 A CN 201610565007A CN 106048108 B CN106048108 B CN 106048108B
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slag
titaniferous
titanium
mixing
iron
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CN106048108A (en
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张力
张武
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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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
    • C22B34/1222—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes using a halogen containing agent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
    • C22B34/1227—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes using an oxygen containing agent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • 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

Abstract

A kind of method of titaniferous mixing slag melting and reducing recycling and modifier treatment：1) titaniferous blast furnace cinder and the molten steel slag of titanium containing vanadium are mixed to form titaniferous mixing slag, by the temperature control of titaniferous mixing slag in design temperature scope；2) oxidizing gas is blown, carries out melting and reducing and oxidation；During ensure titaniferous mixing slag temperature in the range of design temperature, and in titaniferous mixing slag, Low-valent Titanium is oxidized to high price titanium, and ferriferous oxide is reduced into metallic iron；3) separated and recovered according to reaction unit difference.The present invention realizes the high efficiente callback of titanium component in mixing slag, iron component, vanadium component, phosphorus component and free oxidation Calcium compounds, can handle cold conditions containing vanadium, titanium, iron material, realize slag modifier treatment, resource high-efficiency comprehensive utilization；Reaction time of the invention is short, metal recovery rate is high, production cost is low, adaptability to raw material is strong, treating capacity is big, environmental-friendly, economic well-being of workers and staff is high, can effectively solve Metallurgical resources and thermal energy high efficiente callback Utilizing question.

Description

A kind of method of titaniferous mixing slag melting and reducing recycling and modifier treatment
Technical field
The invention belongs to non-blast furnace ironmaking and comprehensive utilization of resources field, and in particular to a kind of titaniferous mixing slag melting is also The method of original recycling and modifier treatment.
Background technology
China is titanium resource big country, possesses abundant v-ti magnetite ore resources, is mainly distributed on Pan Xi and Chengde area.Vanadium Titanomagnetite is the grandidierite of a variety of valuable element symbiosis such as iron, vanadium, titanium, chromium, phosphorus, copper, nickel, cobalt, scandium, niobium, zirconium, yttrium.By Research of technique for many years, China select smelting work using " vanadium titano-magnetite ore dressing-blast furnace ironmaking-molten iron blows vanadium slag-pneumatic steelmaking " Skill flow, vanadium slag-sodium or calcification baking technique flow, realize the extensive utilization of vanadium titano-magnetite, and generate titaniferous The solid waste such as blast furnace slag, slag with vanadium and titanium oxides, tailings in vanadium extraction.Iron containing high level in the discarded object of titanium containing vanadium, vanadium, titanium, A variety of valuable elements such as chromium, phosphorus, are important secondary resources.
Titanium-containing blast furnace slag results from the blast furnace ironmaking process of vanadium titano-magnetite, its TiO2Content is 4~30%, pig iron containing vanadium Content is 4~8%, and pentoxide content is 0.1~0.5%, and is containing valuable element, titanium-containing blast furnace slags such as chromium, gallium, scandiums A kind of important secondary resource；The titaniferous blast furnace cinder temperature released by blast furnace is optionally greater than 1300 DEG C, and annual discharge is substantial amounts of Physical thermal, therefore, titaniferous blast furnace cinder are also important physics thermal resource.
Slag with vanadium and titanium oxides results from the steelmaking process of vanadium titano-magnetite, its TiO2Content is 0.5~10%, metal Ferrum content For 4~12%, iron oxygen content is 10~35%, and pentoxide content is 0.5~5%, phosphorus pentoxide content for 0.2~ 6%, chromic oxide content is 0.1~5%, and contains certain free cao (10% or so).Slag with vanadium and titanium oxides is one The important secondary resource of kind；The molten steel slag of titanium containing vanadium temperature is optionally greater than 1500 DEG C, discharges substantial amounts of physical thermal every year, therefore, The molten steel slag of titanium containing vanadium is also important physics thermal resource.
Titanium-containing blast furnace slag and slag with vanadium and titanium oxides belong to the thing such as people's dressing, titaniferous, vanadium, iron, phosphorus, calcium together and mutually disperse tiny, category hardly possible Ore deposit is handled, its problem of complex utilization is not yet efficiently solved.More than 20,000,000 tons titanium-containing blast furnace slags, accumulation are discharged every year in China Exceed more than one hundred million tons of titanium-containing blast furnace slags, TiO of more than 15,000,000 tons equivalent to accumulation2, more than 15,000,000 tons of pig iron containing vanadium, five oxygen Change more than 300,000 tons of two vanadium, trillion in total value.Meanwhile more than 7,000,000 tons v-bearing steel slags are discharged every year, accumulate more than 2000 More than ten thousand tons, TiO of more than 600,000 tons equivalent to accumulation2, more than 4,000,000 tons of metallic iron, more than 600,000 tons of vanadic anhydride, five Aoxidize more than 150,000 tons of two phosphorus, more than 2,000,000 tons of free cao, total value more than one hundred billion.A large amount of titanium-contained slag (titanium-containing blast furnace slag with Slag with vanadium and titanium oxides) bulk deposition, not only waste of resource, but also pollution environment.
Titanium-containing blast furnace slag and slag with vanadium and titanium oxides are important Metallurgical resources, not only containing valuable components such as iron, vanadium, titanium, chromium, Also contain substantial amounts of CaO, SiO2Deng flux for metallurgy.The comprehensive utilization to titanium-containing blast furnace slag and slag with vanadium and titanium oxides has been made greatly both at home and abroad Quantifier elimination, achieves certain achievement, although however, many methods are technically feasible, due to economically, environmentally can not OK, commercial Application and exploitation still be cannot be used for so far.
At present, researchers to the comprehensive utilizating research of titanium-containing blast furnace slag and slag with vanadium and titanium oxides and vanadium extraction waste such as Under：
The comprehensive utilization of one, titanium-containing blast furnace slags
Titanium is carried including alkaline process, acid system carries titanium, preparation proposes titanium, high temperature modified-analysis containing titanium alloy, the nitridation of titanium-containing blast furnace slag carbon Go out-Mineral separation, as construction material the methods of.
Alkalinity extraction titanium alkali consumption is big, considers that recycling sodium salt will greatly increase the complexity of cost and a full set of technique, titanium Concentration effect it is also not very good, Ti content is still higher in poor titanium phase, deals with improperly there may be new pollution, at the same time The problems such as producing more serious air pollution and huge energy consumption with alkali process blast furnace slag under high temperature.
Sulfuric acid or hydrochloric acid method extraction separation titanium-containing blast furnace slag, sour consumption is big, produces a large amount of spent acid and tailings, serious dirty Contaminate environment.Hydrochloric acid leaching natural cooling titanium-containing blast furnace slag is a kind of approach using titanium-containing blast furnace slag, however, meeting after salt Ore Leaching Generation is a large amount of to leach residues, and leaching residue does not have suitable purposes, that is to say, that can produce new discard after salt Ore Leaching again Thing.
Due to needing titanium and silicon seldom as the steel grade of alloying agents at the same time, the application range of titanium silicon is narrow, and dosage is small, It can not solve the problems, such as that steel climbing high slag quantity is big, this is the key point that the technical solution is difficult to realize industrialization.In addition, also Although former residue has a potential hydraulicity, residual titanium amount is still higher, it is necessary to further reduce its content, but may cause into Ben Taigao.
To carry titanium be a kind of approach using titanium-containing blast furnace slag to the nitridation of titanium-containing blast furnace slag carbon, also there are some distinct disadvantages, such as Electric furnace carbonization this excessive key issue of power consumption does not solve, and the electricity charge account for more than the 70~80% of carbide slag totle drilling cost, produces big The chloride residue of amount, brings serious secondary pollution, in addition, also exposing furnace bottom and some smelting furnaces has more serious foam The problems such as slag, production are difficult to continuous.
Direct-water-quenching, as cement raw material, or as construction material, but cement raw material requires TiO in slag2≤ 10wt%, If TiO2＞ 10wt%, it is impossible to as cement raw material.As cast stone, mineral wool etc., treating capacity is small.
The above variety of problems utilized for titanium-containing blast furnace slag, the present inventor is once in Patent No. 200610134260.3 " from titanium-containing blast furnace slag separation production rich-titanium material method " and Patent No. 201110072575.0 " one kind use titaniferous blast furnace Two kinds of methods using titanium-containing blast furnace slag are proposed in the method that slag produces synthetic rutile ", although both the above method has The characteristics for the treatment of capacity is big, but still have following shortcoming：
1. the method in two above patent can only realize a kind of efficiently using for the i.e. titaniferous blast furnace cinder of clinker, chemistry is living Property it is low, temperature is low, and processing cost is high, and iron, titanium component migration, be enriched with and effect of growing up is poor, and the rate of recovery is low, is only capable of realizing iron, titanium Group recycles, and is not carried out effective enrichment of valuable element；2. the method in two above patent can only utilize a kind of clinker That is titaniferous blast furnace cinder, single clinker-titanium-containing blast furnace slag slag temperature is low, it is necessary to compensate big calorimetric, of high cost, complicated； 3. cold conditions titanium-containing blast furnace slag cannot be handled；4. it is required to add SiO in two above patent2、CaO、CaF2Deng additive, adding Add agent to make slag rapid drop in temperature during adding, waste a part of heat in slag, therefore, it is necessary to compensate heat Amount, waste of energy, increases cost, increases the complexity of processing procedure；5. the separation method used in both the above invention is The method that gravity treatment is combined with flotation and hydrometallurgical mode, FLOTATION SEPARATION and hydrometallurgy separation process be easy to cause environment Pollution.
The comprehensive utilization of two, slag with vanadium and titanium oxides
At present, titaniferous slag mainly using water quenching technology, slag " vexed tank " treatment process, magnetic separation recovery metal in the dreg iron, But the rate of recovery is low, residual metallic iron content is up to 5% in slag, which only considers to recycle metal in the dreg iron, does not account for recycling Content is up to more than 30% ferriferous oxide in slag.Water quenching technology, slag " vexed tank " treatment process consumption great lot of water resources, produce Corrosivity hot steam, heat cannot recycle, water resource cannot circulate, and a large amount of thermal resources hardly result in utilization.Meanwhile dissociate in slag CaO and MgO reduces the stabilization of slag volume, and the ferriferous oxide of high level adds the difficulty of ore grinding, limits slag Using.The comprehensive utilization of vanadium component, is also in conceptual phase in slag with vanadium and titanium oxides, and there has been no on the recycling for titanium. Therefore, slag with vanadium and titanium oxides bulk deposition, not only pollutes environment, but also waste of resource.
Blast furnace liquid melts titanium-containing blast furnace slag and molten steel slag containing vanadium, contains abundant heat resource, containing substantial amounts of Hot flux for metallurgy, and a variety of valuable elements such as the iron containing high level, vanadium, titanium, chromium, phosphorus, calcium, are important secondary money Source.Liquid molten titanium-containing blast furnace slag is reproducibility slag, and molten steel slag containing vanadium is oxidisability slag, is all that physicochemical properties are excellent Good slag system.
Based on this, in view of the problems of the existing technology, the present inventor is once in Patent No. ZL201310290767.8 " one In the method that ferrotitanium vanadium calcium is separated kind from titaniferous mixing slag ", there is provided it is a kind of from titaniferous mixing slag (titaniferous blast furnace cinder and The molten steel slag of titanium containing vanadium) in separation ferrotitanium vanadium calcium method, which has the following advantages that：(1) raw material is flowed out in slag notch Liquid molten titanium-containing blast furnace slag (>=1300 DEG C) and slag (>=1500 DEG C), there is high-temperature, high heat, fully profit With slag physics thermal resource, the efficient economizing energy；(2) due to having the free oxygen of high-content in liquid molten titanium-containing blast furnace slag Change calcium, the titanium suboxide in liquid molten converter slag with high-content, under the high temperature conditions with high chemism, holds Easily realize vanadium, titanium, iron, Calcium compounds migration and enrichment, can recycle at the same time mixing slag in titanium component, iron component, vanadium component with Free oxidation Calcium compounds, reach the efficient synthetical recovery of secondary resource, recycle titaniferous blast furnace cinder and the molten steel slag of titanium containing vanadium Physics thermal resource；(3) physical upgrading (magnetic separation or gravity treatment) is used in follow-up separation process, separated medium is water, and water is selecting It can be circulated during ore deposit, thus will not generation environment pollution in separation process so that whole titaniferous mixing slag technique has Flow is short, easy to operate, iron, vanadium, titanium, the calcium rate of recovery are high, is produced without waste water, has the characteristics that efficient, cleaning, environmental protection；(4) weight The tailing that choosing separation obtains can be produced as the quality raw materials of production high-mark cement, whole processing procedure without solid waste； (5) whole process need not add any additive, and workable without any thermal compensation, production cost is low.
Although above method has the characteristics that obvious, following shortcoming is still had：(1) hot molten slag can only be handled (titaniferous blast furnace cinder and the molten steel slag of titanium containing vanadium), it is impossible to handle cold conditions titanium containing vanadium material；(2) (titaniferous is high for titaniferous mixing slag Stove slag and the molten steel slag of titanium containing vanadium) in reduction-state material oxidation heat liberation, slag temperature is excessive, is easily damaged insulation and demoulds furnace lining Material and tank body, reduce its service life；(3) reduction-state in titaniferous mixing slag (titaniferous blast furnace cinder and the molten steel slag of titanium containing vanadium) Material oxidation heat liberation, slag temperature is excessive, and it is ferriferous oxide to mix metallic iron accelerated oxidation in slag, and the sedimentation of metallic iron subtracts Few, the rate of recovery of metallic iron declines；(4) titaniferous mixing slag reduction-state material oxidation heat liberation, slag temperature is excessive, causes a large amount of Thermal resource wastes；(5) metal iron recovery is low, has only recycled metallic iron in mixing slag, does not account for iron oxygen in mixing slag The reduction and recycling of compound；(6) reproducibility and reproducibility of titaniferous blast furnace cinder are not made full use of；(7) slag is only accounted for The recycling of middle elemental vanadium, does not recycle and contains barium oxide in slag；(8) without control slag oxygen gesture, mix iron in slag and aoxidize Thing partial reduction, partial reduction iron is reoxidized, and therefore, ferriferous oxide content is higher in slag, it is difficult to ore grinding；(9) rich titanium phase-calcium Titanium ore does not settle mutually, and slag amount is big, and ore grinding cost, magnetic separation cost and gravity treatment are of high cost；(10) without recycling phosphorus component；(11) Slag does not carry out modifier treatment, and Tailings utilization is restricted.
The content of the invention
In view of the problems of the existing technology, the present invention provides a kind of titaniferous mixing slag melting and reducing recycling and quenched place The method of reason.This method is that one kind recycles pig iron containing vanadium or V-alloyed steel, rich titanium phase, rich vanadium phase, rich phosphorus phase by titaniferous mixing slag With the method for slag modifier treatment；This method reaction time is short, metal recovery rate is high, production cost is low, adaptability to raw material is strong, place Reason amount is big, environmental-friendly, economic well-being of workers and staff is high, can effectively solve Metallurgical resources and thermal energy high efficiente callback Utilizing question；Present invention side Method is a kind of new melting and reducing oxidation technology.
The recycling of titaniferous mixing slag melting and reducing and the method for modifier treatment of the present invention, makes full use of titaniferous blast furnace cinder With the molten steel slag physics thermal resource of titanium containing vanadium and hot flux for metallurgy, and the reproducibility of titaniferous blast furnace cinder and the molten steel of titanium containing vanadium The oxidisability of slag, is mixed by two kinds of slags, and injection oxidizing gas, realizes melting and reducing and oxidation：1. mix slag In titanium component obtained under oxidizing atmosphere fully oxidized, ferriferous oxide is fully reduced to metallic iron；2. mix in slag The component of iron containing vanadium metal aggregation, grow up and settle；3. the titanium in mixing slag migrates with Calcium compounds, is enriched in Perovskite Phase, And realize and grow up and settle；4. the vanadium component in mixing slag migrates, is enriched in metal iron phase and rich vanadium phase respectively, and realizes length Greatly with sedimentation；5. the phosphorus component in mixing slag migrates, is enriched in Ca2SiO4-Ca3(PO4)2Phase, is distributed in Perovskite Phase interface； 6. the free cao mixed in slag disappears with magnesia, ferriferous oxide is reduced into metallic iron, and mixing slag is realized quenched；Adopt The method that manually sorting, magnetic separation are combined with gravity treatment, separation are deposited in iron containing vanadium metal, rich barium oxide phase, the calcium titanium of bottom Ore deposit phase, realizes the high efficiente callback of titanium component in mixing slag, iron component, vanadium component, phosphorus component and free oxidation Calcium compounds；Can be with Solid-state is handled containing vanadium, titanium, iron material, while realizes slag modifier treatment, reaches resource high-efficiency comprehensive utilization；
Specifically include following steps：
Step 1, slag mixes：
In mass ratio, titaniferous blast furnace cinder: molten steel slag=100 of titanium containing vanadium: (1~1000) dispensing, addition attemperator, In drumped melting reaction device or fixed melting reaction device, titaniferous mixing slag is formed, it is anti-that melting and reducing occurs Should；By the temperature control of titaniferous mixing slag in the range of design temperature；
Wherein：
Design temperature scope is 1400~1600 DEG C；
When reaction unit uses attemperator, the temperature range of titaniferous mixing slag is set as 1400~1600 DEG C；
When reaction unit uses drumped melting reaction device or fixed melting reaction device, titaniferous mixing is molten The temperature range of slag is set as 1450~1600 DEG C；
The temperature for controlling titaniferous mixing slag is in the method for design temperature scope：
When the temperature ＜ design temperature range lower limits of titaniferous mixing slag, by the heating function of reaction unit itself, Or fuel and/or the molten steel slag of titanium containing vanadium are added into titaniferous mixing slag, the temperature of titaniferous mixing slag is reached setting temperature In the range of degree；
When the temperature ＞ design temperature range limits of titaniferous mixing slag, the thing of titanium containing vanadium is added into titaniferous mixing slag One or more in material, ferrous material, fluorine-containing material or titaniferous blast furnace cinder, make the temperature of titaniferous mixing slag reach setting In temperature range；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, blowing preheated rear oxidation gas；Wherein, oxidizing gas is pre- Hot temperature is 0~1200 DEG C, and the relation of oxidizing gas time and flow is 1~105L/ (minkg)；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Regulation and control method is：
Corresponding (a)：
The temperature of titaniferous mixing slag is controlled in the method for design temperature scope using in step 1；
Corresponding (b)：
When reproducibility is insufficient in titaniferous mixing slag, reducing agent is added into titaniferous mixing slag, makes titaniferous mixing molten In slag, ferriferous oxide is reduced into metallic iron；
Step 3, separate and recover：
Using one kind in following methods：
One, is when reaction unit uses attemperator, using method A, method B or method C：
When reaction unit is using not drumped attemperator or drumped attemperator, using method A：
(1) by the mixing slag after reduction-oxidation, it is cooled to room temperature, obtains slow cooling slag；
(2) iron containing vanadium metal is deposited to the bottom of reaction unit, forms iron and sticks together, and manually takes out iron and sticks together；By remaining slow cooling slag In iron layer containing vanadium metal, be crushed to granularity as 20~400 μm, remaining iron containing vanadium metal is isolated in ore grinding, magnetic separation；
(3) to going iron removaling to stick together and the slow cooling slag of the iron layer containing vanadium metal, separated using gravity separation method, obtain titanium essence Ore deposit, rich vanadium concentrate and tailings；
(4) recycling of tailing has 2 kinds：1. make as cement raw material, construction material, instead of rubble aggregate, road material or Phosphate fertilizer uses；2. it will be isolated using hydrometallurgy, beneficiation method or ore dressing-hydrometallurgy combination method in tailing containing phosphorus component Come；
Only when reaction unit uses drumped attemperator, using method B or method C：
Method B：
(1) by the greenhouse cooling of the mixing slag after reduction-oxidation to 1150~1250 DEG C, by the reduction on middle part and top After mixing slag after oxidation is poured out, air-cooled or water quenching, as cement raw material or construction material；
(2) by the mixing slag after the reduction-oxidation of lower part, still in drumped attemperator, reduced as method A Mixing slag after oxidation is handled；
Method C：
(1) by the mixing slag after reduction-oxidation, sedimentation slag-gold separation, obtains vanadium-bearing hot metal and containing after reduction-oxidation Vanadium titanium slag；
(2) TiO of titanium slag containing vanadium after reduction-oxidation2Mass fraction≤10% when, directly by after reduction-oxidation After titanium slag containing vanadium is poured out, air-cooled or water quenching, as cement raw material or construction material；
(3) vanadium-bearing hot metal is sent to pneumatic steelmaking；
Two, are when reaction unit uses drumped melting reaction device or fixed melting reaction device, using side Method D：
(1) by the mixing slag after reduction-oxidation, sedimentation slag-gold separation, obtains vanadium-bearing hot metal and containing after reduction-oxidation Vanadium titanium slag；
(2) by the titanium slag containing vanadium after reduction-oxidation, the outer slag treatment of stove is carried out；
(3) vanadium-bearing hot metal is sent to pneumatic steelmaking；
Wherein, the outer slag treatment of stove uses method D-1 or method D-2：
Method D-1：The TiO of titanium slag containing vanadium after reduction-oxidation2Mass fraction≤10% when, directly by reduction-oxidation After titanium slag containing vanadium afterwards is poured out, air-cooled or water quenching, as cement raw material or construction material；
Method D-2：Titanium slag containing vanadium after reduction-oxidation is poured into attemperator, is melted according to the method in step 2 Melt reduction and oxidation, separation and recovery uses method A, method B or method C.
In the step 1, temperature >=1300 DEG C of titaniferous blast furnace cinder, temperature >=1500 of the molten steel slag of titanium containing vanadium ℃。
In the step 1, titaniferous blast furnace cinder is obtained by tap cinder mouth；The molten steel slag of titanium containing vanadium is by slag slag notch Obtain；
In the step 1, titaniferous blast furnace cinder, contains TiO2Mass fraction be 4~30%；The molten steel of titanium containing vanadium Slag, contains TiO2Mass fraction be 0.3~6%, contain V2O5Mass fraction be 0.3~5%.
The molten steel slag of titanium containing vanadium, is converter titanium containing vanadium molten steel slag or electric furnace titanium containing vanadium melt oxidation slag.
The attemperator is drumped attemperator or not drumped attemperator；Not drumped insulation dress It is set to thermal insulation pit；It is addition fuel that it, which raises temperature methods,.Drumped attemperator is drumped insulation slag ladle；Its Temperature methods are raised to add fuel.
The drumped melting reaction device is drumped converter, drumped melting reaction slag fills or sensing Stove.
The fixed melting reaction device carries the reaction unit of cinder notch or iron mouth for bottom；Described is fixed anti- It is plasma heating furnace, direct current electric arc furnace, ac arc furnace, mineral hot furnace, blast furnace or reverberatory furnace to answer device.
Attemperator, drumped melting reaction device or the fixed melting reaction device internal layer is carbon containing guarantor Temperature demoulding refractory material；The carbon containing insulation demoulding refractory material is to contain carbon composite refractory, is specially that carbon is carbon, stone One or more in ink, asphalt Jiao, metallurgical coke, pitch, anthracite, bituminous coal or lignite, refractory material are siliceous, half silicon Matter, clayey, High-Alumina, magnesia, dolomite matter, olivine matter, spinel, cold conditions titanium-containing blast furnace slag or cold conditions titanium steel containing vanadium One or more in slag.The effect of the carbon containing insulation demoulding refractory material has two：(1) attemperator is protected, is improved Its service life, the slow cooling slag that (2) get well cooling are easy to remove from attemperator.
The temperature of the control titaniferous mixing slag is same into titaniferous mixing slag in the method for design temperature scope When add fuel and during the molten steel slag of titanium containing vanadium, fuel and the molten steel slag of titanium containing vanadium are any ratio.
For the temperature of the control titaniferous mixing slag in the method for design temperature scope, preheating of fuel temperature is 0 ~1200 DEG C, temperature >=1500 DEG C of the molten steel slag of titanium containing vanadium.
The temperature of the control titaniferous mixing slag is in the method for design temperature scope, and fuel is by the way of injection Add titaniferous mixing slag.The injection method is to be inserted into slag using refractory lance or be placed in slag top or side is blown into Fuel.
For the temperature of the control titaniferous mixing slag in the method for design temperature scope, fuel is coal dust.
The temperature of the control mixing slag adds in the method for design temperature scope when at the same time into mixing slag When fuel and the molten steel slag of titanium containing vanadium, fuel and the molten steel slag of titanium containing vanadium are any ratio.
The temperature of the control titaniferous mixing slag is in the method for design temperature scope, when the temperature of titaniferous mixing slag When spending ＜ design temperature range lower limits, fuel and/or the molten steel slag of titanium containing vanadium are added into titaniferous mixing slag, carries out heat benefit Repay.
For the temperature of the control titaniferous mixing slag in the method for design temperature scope, the material of titanium containing vanadium is titaniferous height Clinker, slag with vanadium and titanium oxides, tailings in vanadium extraction, Tailing of titanium separation, low-grade vanadium titano-magnetite, v-ti magnetite concentrate, vanadium titano-magnetite are straight Connect reduced iron, the carbon containing pre-reduced pellet of v-ti magnetite concentrate metallized pellet, v-ti magnetite concentrate, v-ti magnetite concentrate sintering One or more in ore deposit, v-ti magnetite concentrate pellet；Ferrous material is common iron ore concentrate, the direct-reduction of common iron ore concentrate Iron, common iron ore concentrate sintered ore deposit, common Iron Ore Pellets, common iron ore concentrate metallized pellet, common iron ore concentrate it is carbon containing it is pre- also Protocorm group, common slag, blast furnace dust, blast furnace dust, converter dust, iron scale, Zinc Hydrometallurgy Process zinc leaching residue, Red mud that aluminum oxide production process produces, coal dust ash, the one or more in pyrite cinder；Fluorine-containing material be fluorite and/or CaF2。
The temperature of the control titaniferous mixing slag is in the method for design temperature scope, the material of titanium containing vanadium, chalybeate Material and fluorine-containing material are pelletizing or granular material；Wherein, granularity≤150 μm of granular material, side of the granular material to be blown Formula add titaniferous mixing slag, loading gas be air, argon gas, nitrogen-air Mixture, nitrogen-oxygen mixture or air- Argon gas gaseous mixture.The injection method is to be inserted into slag using refractory lance or be placed in slag top or side is blown into powder Material.
The temperature of the control titaniferous mixing slag is in the method for design temperature scope, when the temperature of titaniferous mixing slag When spending the ＞ design temperature upper limits, the material of titanium containing vanadium, ferrous material, fluorine-containing material or one kind or several in titaniferous blast furnace cinder are added Kind, it is therefore an objective to avoid temperature excessive, protect carbon containing insulation demoulding refractory material, suppress pig iron containing vanadium in titaniferous blast furnace cinder, contain The oxidation of granulated iron containing vanadium and the metallic iron being reduced in vanadium titanium molten steel slag, improves the rate of recovery of metallic iron.
The temperature of the control titaniferous mixing slag is in the method for design temperature scope, when the temperature of titaniferous mixing slag When spending the ＞ design temperature upper limits, another effect for adding fluorine-containing material is to reduce viscosity, accelerates iron containing vanadium metal, richness in slag Titanium phase, rich vanadium phase, rich phosphorus phase aggregation, grow up and settle.
The temperature of the control titaniferous mixing slag adds the cold conditions thing of titanium containing vanadium in the method for design temperature scope One or more in material, ferrous material, fluorine-containing material, titaniferous blast furnace cinder, reduce temperature, ensure in gas process is sprayed Remaining Low-valent Titanium (Ti2+, Ti3+) it is fully oxidized be high price titanium (Ti4+), ensure remaining high price iron (Fe in mixing slag3+, Fe2+) It is reduced sufficiently as metallic iron Fe, ensures that iron granule is not oxidized in slag.
In the step 1, reproducibility titaniferous blast furnace cinder is with oxidisability titanium containing vanadium molten steel slag mixed process, reducing Property titaniferous blast furnace cinder middle or low price titanium (Ti2+, Ti3+) it is oxidized to high price titanium (Ti4+), (Fe in oxidisability titanium containing vanadium molten steel slag3+, Fe2+) it is reduced to Fe and Fe2+。
The oxidizing gas be air, oxygen, oxygen-enriched air, nitrogen-oxygen mixture, nitrogen-air Mixture, One kind in oxygen-argon gas gaseous mixture or Air-Argon gaseous mixture.The preheating temperature of the oxidizing gas because gas is different and It is different.
The oxidizing gas is inserted into slag or is placed in slag top or side using refractory lance is blown into oxidisability gas Body.
The oxidizing gas injection time determines with flow according to slag quality, temperature and reduction-oxidation degree.
In the step 2 and step 3, reducing agent is one kind in coal dust, coke powder, bituminous coal or anthracite.
In the step 2 (2), corresponding (b), when titaniferous mixing slag reproducibility is insufficient, into slag, injection supplement is gone back Former agent.
In the step 2 (2), guarantee parameter (b), which is embodied in titaniferous mixing slag, sufficient reproducibility, in reality In production, generally judge in titaniferous mixing slag whether is reproducibility with the mass percent of ferriferous oxide in titaniferous mixing slag It is sufficient.
Step 2 melting and reducing is with oxidizing process, ensureing remaining Low-valent Titanium (Ti in titaniferous mixing slag2+, Ti3 +) it is fully oxidized be high price titanium (Ti4+), ensure remaining high price iron (Fe in titaniferous mixing slag3+, Fe2+) be reduced sufficiently as gold Belong to iron Fe, ensure that iron granule is not oxidized in titaniferous mixing slag, the mistake of the melting and reducing and oxidation+blowing gas Cheng Zhong, in titaniferous blast furnace cinder in pig iron containing vanadium, the molten steel slag of titanium containing vanadium granulated iron containing vanadium and the metallic iron being reduced realize aggregation, Grow up and settle.
The step 3, in method A (1), the type of cooling is natural cooling or rotation cooling.
The step 3, in method A (1), the concrete operations for rotating cooling are：Equipped with the mixing slag after redox Attemperator be placed on rotating platform, rotated according to certain speed, rotary speed is high according to slag quality and attemperator Depending on degree or depth, rotational time is depending on slag quality and slag solidification situation；By equipped with the mixing slag after redox Attemperator be placed on rotating platform and rotate, it is therefore an objective to accelerate metallic iron, Perovskite Phase, rich vanadium phase aggregation, grow up and sink Drop, shortens the sedimentation time, improves effect of settling, improves production efficiency.
The step 3, in method A (1), in cooling procedure, since density is different different from mineral size, largely contains Vanadium metal iron, titaniferous group and component containing vanadium fall to bottom.
The step 3, in method A (3), to going iron removaling to stick together and the slow cooling slag upper, middle and lower portion of the iron layer containing vanadium metal, point Not Cai Yong gravity separation method separated, obtain ilmenite concentrate, rich vanadium concentrate and tailings；
The step 3, in method A (1), titanium continues to migrate, is enriched with Calcium compounds in the mixing slag after reduction-oxidation In Perovskite Phase, and realize and grow up and settle；Vanadium component continues to migrate respectively, is enriched in gold in mixing slag after reduction-oxidation Belong to iron phase and rich barium oxide phase, and realize and grow up and settle；Phosphorus component continues migration, richness in mixing slag after reduction-oxidation Combine in Ca2SiO4-Ca3(PO4)2Phase, the boundary being distributed between the two-phase of perovskite and other mineral facies；After redox Mix ferriferous oxide, free cao and free oxidation magnesium in slag to disappear, slag is realized quenched.
The step 3, in method A (3), gravity separation method be separation by shaking table, sluicing or the two be combined.
The step 3, in method A (4), hydrometallurgy is diluted acid leaching method, wherein diluted acid leaching method be inorganic acidleach, One kind in organic acidleach.The inorganic acid selects sulfuric acid, hydrochloric acid, the one or more of phosphoric acid, and organic acid selects oxalic acid, second One or more in acid, citric acid.
The step 3, in the method A, metal iron recovery is 90~97%, and main thing is mutually the titanium of perovskite TiO in concentrate2Mass fraction be 35~52%, the rate of recovery of titanium is 60~80%；In the method B, metallic iron returns Yield is 90~95%, and main thing is mutually TiO in the ilmenite concentrate of perovskite2Mass fraction be 35~52%, the recycling of titanium Rate is 58~76%.
The method of the recycling of titaniferous mixing slag melting and reducing and modifier treatment, quenched process are opened from raw material mixing Begin until the free cao in lasting generation, slag and the disappearance of free oxidation magnesium always of separation and recovery process, ferriferous oxide Disappear with metallic iron or almost disappear, slag is realized quenched.
The recycling of titaniferous mixing slag and the method for modifier treatment of the present invention, metal iron recovery height is titaniferous mixing slag Gas is sprayed, pig iron containing vanadium in titaniferous blast furnace cinder assembled, grow up and is sunk with granulated iron containing vanadium in the molten steel slag of titanium containing vanadium Drop, and make ferriferous oxide (FeO, Fe in molten mixing slag2O3) metallic iron is fully reduced to, realize aggregation, grow up and settle.
The method of the recycling of titaniferous mixing slag melting and reducing and modifier treatment of the present invention, the increase of mineral grindability.
The recycling of titaniferous mixing slag and the method for modifier treatment of the present invention, rich phosphorus distributed mutually is in perovskite and other mineral Boundary between the two-phase of phase is the mineral disaggregation for being conducive to Perovskite Phase, beneficial to Mineral separation；
The method of the recycling of titaniferous mixing slag melting and reducing and modifier treatment of the present invention, compared with prior art, this hair The characteristics of bright is：
The present invention takes full advantage of titaniferous blast furnace cinder and the hot smelting in the molten steel slag physics of titanium containing vanadium thermal resource, slag The reproducibility and oxidisability of golden flux and titaniferous blast furnace cinder and the molten steel slag of titanium containing vanadium, are aoxidized by two kinds of slag mixed injections Property gas, realize melting and reducing and oxidation, control oxygen gesture, ferriferous oxide is fully reduced to metallic iron, titanium group in slag Get fully oxidized；It is a kind of method of new melting and reducing；
Start to gather containing vanadium iron and the metallic iron being reduced in the pig iron, the molten steel slag of titanium containing vanadium in titaniferous blast furnace cinder at the same time Collect, grow up, after close to certain size；Start to settle, be largely deposited to slag and stick together bottom, form monoblock ingot iron；
After blowing gas, mix titanium in slag and migrated with Calcium compounds, be enriched in Perovskite Phase, and realize and grow up and sink Drop, the migration of elemental vanadium component, be enriched in metal iron phase, Low Valent Vanadium oxide concentration in rich barium oxide phase, and realize grow up with Sedimentation, phosphorus component migration, be enriched in Ca2SiO4-Ca3(PO4)2Phase, preservation is in Perovskite Phase interface；
After slag cooling, slow cooling slag is separated with the ingot iron settled, recycles iron containing vanadium metal, while using magnetic separation separation slag Stick together the remaining iron containing vanadium metal in bottom, realizes the pig iron in titaniferous blast furnace cinder, granulated iron containing vanadium and iron in the molten steel slag of titanium containing vanadium The high efficiente callback of iron in oxide, metal iron recovery are high；
Since rich titanium phase (Perovskite Phase), rich vanadium phase (rich barium oxide phase) are deposited in lower part, slag amount need to be sorted Small, ore grinding, magnetic separation and gravity treatment cost are low, meanwhile, rich phosphorus of the preservation in Perovskite Phase interface mutually contribute to Perovskite Phase dissociation with Ore dressing；
The recycling of elemental vanadium in slag is not only realized, but also realizes the enrichment containing barium oxide, grows up, settles with dividing From；
Free cao disappears with free oxidation magnesium, and metallic iron almost disappears with ferriferous oxide, and slag realizes quenched, tailing Disappeared using limiting factor, cement raw material or construction material can be used as or make aggregate and road material or phosphate fertilizer or using wet instead of rubble Method metallurgical method will contain phosphorus component and separate, and Tailings utilization value is big, has a wide range of application.
The method of the present invention can be continuously or discontinuously progress, meet industrial needs.
The beneficial effects of the invention are as follows：
(1) reaction unit internal layer of the invention demoulds refractory material using carbon containing insulation, not only protects attemperator, and And slow cooling slag after cooling is set to be easy to remove from attemperator；
(2) raw material of the invention is that the liquid molten titanium-containing blast furnace slag (>=1300 DEG C) that is flowed out in slag notch and titanium containing vanadium melt Melt slag (>=1500 DEG C), contain abundant heat resource, there is high-temperature, high heat, take full advantage of slag Physics thermal resource, the efficient economizing energy；Liquid molten titanium-containing blast furnace slag contains substantial amounts of hot metallurgy with the molten steel slag of titanium containing vanadium Flux, is all the slag system of excellent in physical and chemical performance, realizes the efficient utilization of Metallurgical resources and thermal resource；Liquid molten Titanium-containing blast furnace slag is reproducibility slag, and the molten steel slag of titanium containing vanadium is oxidisability slag, takes full advantage of the high reactionization of two kinds of slags The characteristics of learning activity；
(3) present invention realizes melting and reducing and oxidation by two kinds of slag mixing, is blown oxidizing gas, controls oxygen Gesture, not only makes the pig iron in titaniferous blast furnace cinder assemble, grow up and settle with granulated iron containing vanadium in the molten steel slag of titanium containing vanadium, but also makes to contain Ferriferous oxide (FeO, Fe in titanium molten steel slag2O3) metallic iron is fully reduced to, realize aggregation, grow up and settle；
(4) in the method for the present invention, adding cold conditions material and heat fusing titanium-containing blast furnace slag, to avoid slag temperature excessive, protects Carbon containing insulation demoulding refractory material, improves the service life of attemperator；Suppress the pig iron, the molten steel slag of titanium containing vanadium in titaniferous blast furnace cinder In granulated iron containing vanadium and the metallic iron being reduced oxidation, improve the rate of recovery of metallic iron；Add cold conditions material and heat fusing titaniferous Blast furnace slag improves feed throughput, can not only handle molten slag, but also can handle a small amount of cold conditions material, and raw material adapts to Property is strong；Adding cold conditions material realizes the chemical heat of slag oxidation reaction release and the efficient utilization of slag physical thermal；
(5) two kinds of slag mixing of the present invention realize melting and reducing and oxidation, are blown oxidizing gas, control oxygen gesture, low Valency titanyl turns to high price titanium, mixes titanium in slag and is migrated with Calcium compounds, is enriched in Perovskite Phase, and realizes and grow up and settle；Vanadium Oxide is fully reduced to elemental vanadium and Low Valent Vanadium, migrates, is enriched in metal iron phase and rich barium oxide phase, and grows up and sink Drop, not only realizes the recycling for the elemental vanadium in slag of knowing clearly, but also the enrichment containing barium oxide in slag, grows up and settle；
(6) in the method for the present invention natural cooling process, iron component, titanium component, vanadium component and phosphorus component move respectively in slag Move, be enriched in iron containing vanadium metal, rich titanium phase, rich vanadium phase, rich phosphorus phase, and realize aggregation, grow up and settle；Insulation equipped with slag Device, which is placed on rotating platform, to be rotated, accelerate iron containing vanadium metal, rich titanium phase, rich vanadium phase, rich phosphorus phase aggregation, grow up and settle, Shorten the sedimentation time, improve effect of settling, improve production efficiency；The addition of fluorine-containing material, accelerate iron containing vanadium metal, richness titanium phase, Rich vanadium phase, rich phosphorus phase aggregation, grow up and settle, shorten the sedimentation time, improve effect of settling；
(7) phosphorus component migrates, is enriched in Ca in the method for the present invention mixing slag2SiO4-Ca3(PO4)2Phase, is distributed in calcium titanium Boundary between the two-phase of ore deposit and other mineral facies, beneficial to Mineral separation；Free cao disappears with free oxidation magnesium, metal Iron almost disappears with ferriferous oxide, and free calcium oxide disappears with magnesia in slag, the increase of mineral grindability, and slag, which is realized, to be adjusted Matter；
(8) method that the method for the present invention is combined using manual sorting, magnetic separation with gravity treatment, separation are deposited in the golden containing vanadium of bottom Belong to iron, rich barium oxide phase, Perovskite Phase, realize titanium component, iron component, vanadium component, phosphorus component and free oxygen in mixing slag Change the high efficiente callback of Calcium compounds；Since rich titanium phase, iron containing vanadium metal, rich vanadium are mutually deposited in bottom, slag amount need to be sorted Small, the increase of mineral grindability, ore grinding, magnetic separation and gravity treatment cost are low；Follow-up separation process is using physical upgrading (magnetic separation or again Choosing), separated medium be water, and water can circulate in ore dressing process, thus in separation process will not generation environment pollute so that Whole titaniferous mixing slag technique has that short flow, easy to operate, iron, vanadium, titanium, the calcium rate of recovery are high, are produced without waste water, has high The characteristics of effect, cleaning, environmental protection；Since slag passes through modifier treatment, the recycling of tailing has 2 kinds：1. as cement raw material, build Material is built, makees aggregate instead of rubble, road material or phosphate fertilizer use；2. using hydrometallurgy, beneficiation method or ore dressing-hydrometallurgy connection It is legal to be separated in tailing containing phosphorus component；, Tailings utilization value is big, has a wide range of application；
(9) the method for the present invention whole process without thermal compensation or needs a small amount of thermal compensation, and workable, production cost is low；
(10) present invention take full advantage of in slag physics thermal resource, slag the oxidisability of hot flux for metallurgy and slag with Reproducibility, realizes melting and reducing and oxidation, and iron component, titanium component, vanadium component and phosphorus component are migrated, be enriched in respectively in slag Iron containing vanadium metal, rich titanium phase, rich vanadium phase, rich phosphorus phase, and realize aggregation, grow up and settle, realize titanium component, iron in mixing slag The high efficiente callback of component, vanadium component, phosphorus component and free oxidation Calcium compounds, and cold conditions can be handled containing vanadium, titanium, iron material, Realize slag modifier treatment at the same time, reach secondary resource high-efficiency comprehensive utilization.This method reaction time is short, metal recovery rate is high, Production cost is low, adaptability to raw material is strong, treating capacity is big, environmental-friendly, economic well-being of workers and staff is high, can effectively solve Metallurgical resources and thermal energy High efficiente callback Utilizing question.
Brief description of the drawings
The recycling of titaniferous mixing slag melting and reducing and the technological process of the method for modifier treatment of Fig. 1 embodiment of the present invention Figure.
Embodiment
The titaniferous mixing slag melting and reducing recycling of following embodiments and process flow chart such as Fig. 1 of the method for modifier treatment It is shown.
The solid-to-liquid ratio arrived involved in following embodiments, refers to the quality of tailing and the volume ratio of leachate, unit g：L.
Embodiment 1
A kind of titaniferous mixing slag melting and reducing recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
In by the 410kg liquid moltens titanium-containing blast furnace slag flowed out in slag notch and 40kg converters, the molten steel slag of titanium containing vanadium pours into Layer has the drumped insulation slag ladle of graphite-dolomite matter complex heat-preservation demoulding refractory material, is thoroughly mixed to form titaniferous mixing Slag, occurs fusion reduction reaction；
Slag temperature is 1394 DEG C after mixing, less than 1400~1600 DEG C of scopes of design temperature in titaniferous mixing slag； Refractory lance is inserted into mixing slag and is blown into coal dust 2kg, the temperature of mixing slag is increased to 1426 DEG C；Wherein：
Titaniferous blast furnace cinder, is containing component and its mass percent：20.34wt%TiO2, 22.26wt%CaO, 8.12wt%MgO, 10.89wt%Al2O3, 2.96wt%FeO and 20.46wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium contains component and its mass percent is：3.26wt%V2O5, TFe20.68wt%, 40.89wt%CaO, 12.36wt%SiO2, 3.62wt%TiO2, 2.47wt%MgO, 1.22wt%MnO, 1.64wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, oxygen after blowing preheated, common injecting oxygen 18min；Wherein, oxygen Preheating temperature be 30 DEG C, the relation of oxygen time and flow is 1L/ (minkg)；The injection method of oxygen is using fire resisting Spray gun insertion titaniferous mixing slag is blown into oxygen.
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is at 1400~1600 DEG C；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a), reduction is measured with oxidizing process mixes slag temperature as 1456~1466 DEG C, in setting range；
Corresponding (b), reduction and oxidizing process, remaining Low-valent Titanium are oxidized to high price titanium, and remaining ferriferous oxide is reduced into metal Iron；
Step 3, separation and recovery uses method A：
(1) by the mixing slag after reduction-oxidation, cooled to room temperature, obtains slow cooling slag；
(2) iron containing vanadium metal is deposited to the bottom of reaction unit, forms iron and sticks together, and manually takes out iron and sticks together；By remaining slow cooling slag In iron layer containing vanadium metal, be crushed to granularity as 20~400 μm, remaining iron containing vanadium metal is isolated in ore grinding, magnetic separation；Metallic iron recycles Rate 92%, full iron is 0.792wt% in this step mine tailings；
(3) to going iron removaling to stick together and the lower part slow cooling slag of the slow cooling slag of the iron layer containing vanadium metal, through chute one roughing, shaking table one It is secondary selected, scan twice, upper, middle part is through chute one roughing, and shaking table primary cleaning, once purging selection, will contain titanium component and gangue Phase separation, it is mutually ilmenite concentrate, the chats of magnesium aluminate spinel containing vanadium and the tailing of Perovskite Phase to obtain main thing, TiO in ilmenite concentrate2's Mass fraction is 48.41%, V in the chats of magnesium aluminate spinel containing vanadium2O5Mass fraction be 8.71%, P in rich phosphorus phase2O5Matter It is 28% to measure fraction,
(4) tailing uses 2% dilute sulfuric acid, by solid-to-liquid ratio 1: 2, phosphorus pentoxide is separated, phosphorous recovery 80%.
Embodiment 2
A kind of titaniferous mixing slag recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
By the liquid molten 100kg titanium-containing blast furnace slags flowed out in slag notch and 1000kg converters, the molten steel slag of titanium containing vanadium pours into Internal layer has the thermal insulation pit of carbon-magnesia complex heat-preservation demoulding refractory material, is thoroughly mixed to form titaniferous mixing slag, melts Reduction reaction；Slag temperature is 1570 DEG C after mixing, is set in the temperature of titaniferous mixing slag in the range of 1400~1600 DEG C；Its In：
Titaniferous blast furnace cinder, is containing component and its mass percent：22.65wt%TiO2, 19.79wt%CaO, 9.31wt%MgO, 11.96wt%Al2O3, 3.26wt%FeO and 19.48wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium contains component and its mass percent：2.29wt%V2O5, TFe18.79wt%, 41.64wt%CaO, 11.36wt%SiO2, 3.92wt%TiO2, 3.54wt%MgO, 1.43wt%MnO, 1.37wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, air after blowing preheated, common blows air 5min；Wherein, air Preheating temperature be 900 DEG C, the relation of air time and flow is 105L/ (minkg)；The injection method of air is using resistance to Fire-fighting rifle is placed in mixing slag top and is blown into；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1400~1600 DEG C of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：
Oxidation-reduction process measures mixing slag temperature and is up to 1620 DEG C；Since temperature is higher by setting value, mixed to titaniferous Titanium-containing blast furnace slag 2kg, common the iron ore concentrate carbon containing pre-reduced pellet 1kg and slag with vanadium and titanium oxides 2kg of room temperature are added in slag, makes to contain The temperature of titanium mixing slag is reduced to 1550~1560 DEG C, in setting range；
Corresponding (b)：
In oxidation-reduction process, reproducibility deficiency in titaniferous mixing slag is showed, coke powder is added into titaniferous mixing slag 3kg, makes in titaniferous mixing slag, and remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Step 3, separation and recovery uses method A：
(1) the mixing slag after reduction-oxidation, rotation are cooled to room temperature, obtain slow cooling slag；Wherein, the tool of cooling is rotated Gymnastics conduct：Attemperator equipped with the mixing slag after redox is placed on rotating platform, is revolved according to certain speed Turn, for rotary speed depending on slag quality and attemperator height or depth, rotational time solidifies feelings according to slag quality and slag Depending on condition；
(2) iron containing vanadium metal is deposited to the bottom of reaction unit, forms iron and sticks together, and manually takes out iron and sticks together；By remaining slow cooling slag In iron layer containing vanadium metal, be crushed to granularity as 20~400 μm, remaining iron containing vanadium metal is isolated in ore grinding, magnetic separation；Metallic iron recycles Rate 93%, full iron is 0.463wt% in this step mine tailings；
(3) to going iron removaling to stick together and the slow cooling slag lower part of the iron layer containing vanadium metal, through chute one roughing, shaking table primary cleaning, Scan twice, titanium component will be contained and be separated with gangue, obtain ilmenite concentrate, the magnesium aluminate spinel containing vanadium that main thing is mutually Perovskite Phase Chats and tailing, TiO in ilmenite concentrate2Mass fraction be 38.31%, V in the chats of magnesium aluminate spinel containing vanadium2O5Mass fraction For 9.58%, P in rich phosphorus phase2O5Mass fraction be 29%；
(4) tailing is used as phosphate fertilizer.
Embodiment 3
A kind of titaniferous mixing slag recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
In by the liquid molten 400kg titanium-containing blast furnace slags flowed out in slag notch and 45kg converters, the molten steel slag of titanium containing vanadium pours into Layer has the thermal insulation pit of metallurgical coke-High-Alumina complex heat-preservation demoulding refractory material, is thoroughly mixed to form titaniferous mixing slag, occurs Fusion reduction reaction；Slag temperature is 1420 DEG C after mixing；In 1400~1600 DEG C of the temperature controlling range of titaniferous mixing slag； Wherein：
Titaniferous blast furnace cinder, is containing component and its mass percent：21.96wt%TiO2, 20.37wt%CaO, 8.75wt%MgO, 11.62wt%Al2O3, 4.4.46wt%FeO and 19.28wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium, contains component and its mass percent：1.79wt%V2O5, TFe18.76wt%, 43.84wt%CaO, 12.92wt%SiO2, 3.94wt%TiO2, 3.78wt%MgO, 1.21wt%MnO, 1.26wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, oxygen after blowing preheated, common injecting oxygen 5min；Wherein, oxygen Preheating temperature be 1200 DEG C, the relation of oxygen time and flow is 40L/ (minkg)；The injection method of oxygen is using resistance to Fire-fighting rifle is placed in mixing slag side and is blown into.
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in 1400~1600 DEG C of setting；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：Reduction-oxidation process, it is 1462~1467 DEG C to measure mixing slag temperature, in the range of design temperature；
Corresponding (b)：Reduction-oxidation process, remaining Low-valent Titanium are oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Step 3, separation and recovery uses method A：
(1) by the mixing slag after reduction-oxidation, cooled to room temperature, obtains slow cooling slag；Wherein, cooling means is rotated With embodiment 2；
(2) iron containing vanadium metal is deposited to the bottom of reaction unit, forms iron and sticks together, and manually takes out iron and sticks together；By remaining slow cooling slag In iron layer containing vanadium metal, be crushed to granularity as 20~400 μm, remaining iron containing vanadium metal is isolated in ore grinding, magnetic separation；Metallic iron recycles Rate 91%, full iron 0.872wt% in this step mine tailings；
(3) to going iron removaling to stick together and the slow cooling slag upper, middle and lower portion of the iron layer containing vanadium metal, the progress of gravity separation method is respectively adopted Separation, slow cooling slag in lower part is through chute roughing twice, and shaking table primary cleaning, is scanned twice, and upper, middle part is shaken through chute roughing twice Selected twice, the once purging selection of bed, will contain titanium component and be separated with gangue, obtain main thing and be mutually the ilmenite concentrate of Perovskite Phase, contain Vanadium magnesium aluminate spinel chats and tailing, TiO in ilmenite concentrate2Mass fraction be 44.27%, in the chats of magnesium aluminate spinel containing vanadium V2O5Mass fraction be 8.89%, P in rich phosphorus phase2O5Mass fraction be 28%；
(4) tailing is used as phosphate fertilizer.
Embodiment 4
A kind of titaniferous mixing slag recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
In by the liquid molten 400kg titanium-containing blast furnace slags flowed out in slag notch and 65kg converters, the molten steel slag of titanium containing vanadium pours into Layer has the drumped insulation slag ladle of pitch-semi silica complex heat-preservation demoulding refractory material, and it is molten to be thoroughly mixed to form titaniferous mixing Slag, occurs fusion reduction reaction；Slag temperature is 1440 DEG C after mixing；1400~1600 are set in the temperature of titaniferous mixing slag In the range of DEG C；Wherein：
Titaniferous blast furnace cinder, is containing component and its mass percent：18.69wt%TiO2, 21.32wt%CaO, 9.26wt%MgO, 12.31wt%Al2O3, 4.49wt%FeO and 20.14wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium, contains component and mass percent：3.12wt%V2O5, TFe20.51wt%, 41.19wt%CaO, 9.34wt%SiO2, 5.79wt%TiO2, 1.24wt%MgO, 2.31wt%MnO, 1.30wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, air after blowing preheated, common blows air 4min；Wherein, air Preheating temperature is 1000 DEG C, and the relation of air time and flow is 87L/ (minkg)；The injection method of air is using fire resisting Spray gun insertion mixing slag is blown into；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1400~1600 DEG C of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：Reduction-oxidation process, it is 1500~1510 DEG C to measure mixing slag temperature, in design temperature scope；
Corresponding (b)：Reduction-oxidation process, remaining Low-valent Titanium are oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Step 3, separation and recovery uses method A：
(1) the mixing slag after reduction-oxidation, rotation are cooled to room temperature, obtain slow cooling slag；Wherein, cooling means is rotated With embodiment 2；
(2) iron containing vanadium metal is deposited to the bottom of reaction unit, forms iron and sticks together, and manually takes out iron and sticks together；By remaining slow cooling slag In iron layer containing vanadium metal, be crushed to granularity as 20~400 μm, remaining iron containing vanadium metal is isolated in ore grinding, magnetic separation；Metallic iron recycles Rate 93%, all iron content 0.502wt% in this step mine tailings；
(3) to going iron removaling to stick together and the slow cooling slag upper, middle and lower portion of the iron layer containing vanadium metal, the progress of gravity separation method is respectively adopted Separation, slow cooling slag in lower part is through chute one roughing, and shaking table primary cleaning, is scanned twice, and upper, middle part is shaken through chute one roughing Bed primary cleaning, once purging selection, will contain titanium component and be separated with gangue, obtain main thing and be mutually the ilmenite concentrate of Perovskite Phase, contain Vanadium magnesium aluminate spinel chats and tailing, TiO in ilmenite concentrate2Mass fraction be 49.31%, in the chats of magnesium aluminate spinel containing vanadium V2O5Mass fraction be 8.98%, P in rich phosphorus phase2O5Mass fraction be 27%, Gravity separation, phosphorous recovery 60%；
(4) tailing is used as construction material.
Embodiment 5
A kind of titaniferous mixing slag recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
In by the liquid molten 400kg titanium-containing blast furnace slags flowed out in slag notch and 80kg converters, the molten steel slag of titanium containing vanadium pours into Layer has the drumped insulation slag ladle of bituminous coal-spinel complex heat-preservation demoulding refractory material, is thoroughly mixed to form titaniferous mixing Slag, occurs fusion reduction reaction；Slag temperature is 1450 DEG C after mixing；Titaniferous mixing slag temperature setting 1400~ In the range of 1600 DEG C；Wherein：
Titaniferous blast furnace cinder, is containing component and its mass percent：19.31wt%TiO2, 19.69wt%CaO, 9.84wt%MgO, 13.28wt%Al2O3, 4.47wt%FeO and 20.26wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium, contains component and its mass percent：0.62wt%V2O5, TFe18.74wt%, 41.32wt%CaO, 12.74wt%SiO2, 4.78wt%TiO2, 3.14wt%MgO, 1.29wt%MnO, 1.87wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, air after blowing preheated, common blows air 4min；Wherein, air Preheating temperature is 0 DEG C, and the relation of air time and flow is 23L/ (minkg)；The injection method of air is to use resistance to fire-fighting Rifle insertion mixing slag is blown into；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1400~1600 DEG C of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：Reduction-oxidation process, it is 1468~1476 DEG C to measure mixing slag temperature, in setting range；
Corresponding (b)：Reduction-oxidation process, remaining Low-valent Titanium are oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Step 3, separation and recovery uses method A：
(1) by the mixing slag after reduction-oxidation, cooled to room temperature, obtains slow cooling slag；
(2) iron containing vanadium metal is deposited to the bottom of reaction unit, forms iron and sticks together, and manually takes out iron and sticks together；By remaining slow cooling slag In iron layer containing vanadium metal, be crushed to granularity as 20~400 μm, remaining iron containing vanadium metal is isolated in ore grinding, magnetic separation；Metallic iron recycles Rate 91%, all iron content 0.519wt% in slag；
(3) to going iron removaling to stick together and the slow cooling slag upper, middle and lower portion of the iron layer containing vanadium metal, the progress of gravity separation method is respectively adopted Separation, lower part slow cooling slag, through chute roughing twice, shaking table primary cleaning, is scanned twice, and upper, middle part is shaken through chute one roughing Bed primary cleaning, once purging selection, will contain titanium component and be separated with gangue, obtain main thing and be mutually the ilmenite concentrate of Perovskite Phase, contain Vanadium magnesium aluminate spinel chats and tailing, TiO in ilmenite concentrate2Mass fraction be 42.87%, in the chats of magnesium aluminate spinel containing vanadium V2O5Mass fraction be 8.71%, P in rich phosphorus phase2O5Mass fraction be 28%；
(4) tailing uses 2% dilute sulfuric acid, separates phosphorus pentoxide by solid-to-liquid ratio 1: 2, phosphorous recovery 75%.
Embodiment 6
A kind of titaniferous mixing slag recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
By the liquid molten 400kg titanium-containing blast furnace slags flowed out in slag notch and 50kg electric furnaces, the melt oxidation of titanium containing vanadium slag falls Entering internal layer has the thermal insulation pit of carbon-clayey complex heat-preservation demoulding refractory material, is thoroughly mixed to form titaniferous mixing slag, occurs Fusion reduction reaction；Slag temperature is 1430 DEG C after mixing；1400~1600 DEG C of scopes are set in the temperature of titaniferous mixing slag It is interior；Wherein；
Titaniferous blast furnace cinder, contains component and its mass percent：12.46wt%TiO2, 21.37wt%CaO, 11.26wt%MgO, 16.14wt%Al2O3, 5.09wt%FeO and 19.48wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium, contains component and its mass percent：2.32wt%V2O5, TFe18.76wt%, 42.25wt%CaO, 11.96wt%SiO2, 4.89wt%TiO2, 3.26wt%MgO, 1.45wt%MnO, 1.69wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, oxygen after blowing preheated, common injecting oxygen 7min；Wherein, oxygen Preheating temperature is 900 DEG C, and the relation of oxygen time and flow is 9L/ (minkg)；The injection method of oxygen is to use resistance to fire-fighting Rifle insertion mixing slag is blown into；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1400~1600 DEG C of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：Reduction-oxidation process is surveyed, and slag temperature must be mixed as 1483~1491 DEG C, in setting range；
Corresponding (b)：Reduction-oxidation process is surveyed, and remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metal Iron；
Step 3, separation and recovery uses method A：
(1) by the mixing slag after reduction-oxidation, cooled to room temperature, obtains slow cooling slag；
(2) iron containing vanadium metal is deposited to the bottom of reaction unit, forms iron and sticks together, and manually takes out iron and sticks together；By remaining slow cooling slag In iron layer containing vanadium metal, be crushed to granularity as 20~400 μm, remaining iron containing vanadium metal is isolated in ore grinding, magnetic separation；Metallic iron recycles Rate 92%, all iron content 0.741wt% in this step mine tailings；
(3) to going iron removaling to stick together and the slow cooling slag upper, middle and lower portion of the iron layer containing vanadium metal, the progress of gravity separation method is respectively adopted Separation, lower part slow cooling slag one roughing, shaking table primary cleaning, is scanned twice, and upper, middle part is through chute one roughing, and shaking table is once Selected, once purging selection, will contain titanium component and be separated with gangue, obtain ilmenite concentrate, the magnalium containing vanadium that main thing is mutually Perovskite Phase Spinelle chats and tailing, TiO in ilmenite concentrate2Mass fraction be 36.39%, V in the chats of magnesium aluminate spinel containing vanadium2O5Matter It is 8.07% to measure fraction, P in rich phosphorus phase2O5Mass fraction be 26%；
(4) tailing is used as phosphate fertilizer.
Embodiment 7
A kind of titaniferous mixing slag recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
By the liquid molten 40kg titanium-containing blast furnace slags flowed out in slag notch and 400kg electric furnaces, the melt oxidation of titanium containing vanadium slag falls Entering internal layer has the thermal insulation pit of carbon-spinel matter complex heat-preservation demoulding refractory material, is thoroughly mixed to form mixing slag, occurs molten Melt reduction reaction；Slag temperature is 1580 DEG C after mixing；Set in the temperature of titaniferous mixing slag in the range of 1400~1600 DEG C； Wherein；
Titaniferous blast furnace cinder, is containing component and its mass percent：29.48wt%TiO2, 19.67wt%CaO, 5.38wt%MgO, 12.27wt%Al2O3, 2.47wt%FeO and 17.74wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium, contains component and its mass percent：1.34wt%V2O5, TFe18.72wt%, 41.19wt%CaO, 12.37wt%SiO2, 4.96wt%TiO2, 3.19wt%MgO, 1.89wt%MnO, 1.29wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, oxygen after blowing preheated, common injecting oxygen 14min；Wherein, oxygen Preheating temperature is 180 DEG C, and the relation of oxygen time and flow is 1.8L/ (minkg)；The injection method of oxygen is using fire resisting Spray gun insertion mixing slag is blown into；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1400~1600 DEG C of design temperature
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：Reduction-oxidation process measures mixing slag temperature and is up to 1618 DEG C, since temperature is higher by setting value, to Slag with vanadium and titanium oxides 2kg is added in titaniferous mixing slag, the temperature for making titaniferous mixing slag is 1520~1525 DEG C, in design temperature Scope；
Corresponding (b)：In oxidation-reduction process, reproducibility deficiency in titaniferous mixing slag is showed, into titaniferous mixing slag Coke powder 2kg is added, is made in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Step 3, separation and recovery uses method A：
(1) the mixing slag after reduction-oxidation, rotation are cooled to room temperature, obtain slow cooling slag；Wherein, cooling means is rotated With embodiment 2；
(2) iron containing vanadium metal is deposited to the bottom of reaction unit, forms iron and sticks together, and manually takes out iron and sticks together；By remaining slow cooling slag In iron layer containing vanadium metal, be crushed to granularity as 20~400 μm, remaining iron containing vanadium metal is isolated in ore grinding, magnetic separation；Metallic iron recycles Rate 93%, all iron content 0.879wt% in this step mine tailings；
(3) to going iron removaling to stick together and the slow cooling slag upper, middle and lower portion of the iron layer containing vanadium metal, the progress of gravity separation method is respectively adopted Separation, through chute one roughing, shaking table primary cleaning, is scanned lower part slow cooling slag twice, will be contained titanium component and is separated with gangue, and obtain It is mutually ilmenite concentrate, the chats of magnesium aluminate spinel containing vanadium and the tailing of Perovskite Phase to main thing, TiO in ilmenite concentrate2Mass fraction For 37.28%, V in the chats of magnesium aluminate spinel containing vanadium2O5Mass fraction be 9.18%；P in rich phosphorus phase2O5Mass fraction be 29%；
(4) tailing is used as phosphate fertilizer.
Embodiment 8
A kind of titaniferous mixing slag recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
The melt oxidation of titanium containing the vanadium slag by the liquid molten 200kg titanium-containing blast furnace slags flowed out in slag notch and 200kg electric furnaces Pouring into internal layer has the thermal insulation pit of carbon-olivine matter complex heat-preservation demoulding refractory material, is thoroughly mixed to form mixing slag, sends out Raw fusion reduction reaction；Slag temperature is 1440 DEG C after mixing；1400~1600 DEG C of models are set in the temperature of titaniferous mixing slag In enclosing；Wherein：
Titaniferous blast furnace cinder, is containing component and its mass percent：4.37wt%TiO2, 256.28wt%CaO, 9.77wt%MgO, 16.14wt%Al2O3, 2.89wt%FeO and 22.98wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium, contains component and its mass percent：0.39wt%V2O5, TFe18.72wt%, 42.26wt%CaO, 12.17wt%SiO2, 4.96wt%TiO2, 3.15wt%MgO, 1.57wt%MnO, 1.91wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, oxygen after blowing preheated, common injecting oxygen 2min；Wherein, oxygen Preheating temperature is 1050 DEG C, and the relation of oxygen time and flow is 20L/ (minkg)；The injection method of oxygen is using fire resisting Spray gun insertion mixing slag is blown into；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1400~1600 DEG C of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：It is 1470~1480 DEG C that reduction process, which measures mixing slag temperature, in setting range；
Corresponding (b)：In oxidation-reduction process, reproducibility deficiency in titaniferous mixing slag is showed, into titaniferous mixing slag Coke powder 1kg is added, is made in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Step 3, separation and recovery uses method A：
(1) the mixing slag after reduction-oxidation, rotation are cooled to room temperature, obtain slow cooling slag；Wherein, cooling means is rotated With embodiment 2；
(2) iron containing vanadium metal is deposited to the bottom of reaction unit, forms iron and sticks together, and manually takes out iron and sticks together；By remaining slow cooling slag In iron layer containing vanadium metal, be crushed to granularity as 20~400 μm, remaining iron containing vanadium metal is isolated in ore grinding, magnetic separation；Metallic iron recycles Rate is 92%, all iron content 0.879wt% in this step mine tailings；
(3) to going iron removaling to stick together and the slow cooling slag upper, middle and lower portion of the iron layer containing vanadium metal, the progress of gravity separation method is respectively adopted Separation, through chute one roughing, shaking table primary cleaning, will contain titanium component and be separated with gangue, and obtain main thing lower part slow cooling slag It is mutually ilmenite concentrate, the chats of magnesium aluminate spinel containing vanadium and the tailing of Perovskite Phase, TiO in ilmenite concentrate2Mass fraction be 32.19%, V in the chats of magnesium aluminate spinel containing vanadium2O5Mass fraction be 8.20%, P in rich phosphorus phase2O5Mass fraction be 27%；
(4) tailing is used as phosphate fertilizer.
Embodiment 9
A kind of titaniferous mixing slag recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
The melt oxidation of titanium containing the vanadium slag by the liquid molten 100kg titanium-containing blast furnace slags flowed out in slag notch and 500kg electric furnaces Pouring into internal layer has the thermal insulation pit of graphite-slag with vanadium and titanium oxides complex heat-preservation demoulding refractory material, is thoroughly mixed to form mixing slag, Generation fusion reduction reaction；Slag temperature is 1470 DEG C after mixing；1400~1600 DEG C are set in the temperature of titaniferous mixing slag In the range of；Wherein；
Titaniferous blast furnace cinder, is containing component and its mass percent：29.97wt%TiO2, 19.17wt%CaO, 5.69wt%MgO, 11.98wt%Al2O3, 2.47wt%FeO and 16.26wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium, contains component and its mass percent：2.14wt%V2O5, TFe16.71wt%, 43.26wt%CaO, 12.38wt%SiO2, 0.53wt%TiO2, 2.96wt%MgO, 1.85wt%MnO, 1.79wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, oxygen after blowing preheated, common injecting oxygen 4min；Wherein, oxygen Preheating temperature is 280 DEG C, and the relation of oxygen time and flow is 10L/ (minkg)；The injection method of oxygen is using fire resisting Spray gun insertion mixing slag is blown into；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1400~1600 DEG C of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：Reduction-oxidation process is surveyed, and slag temperature must be mixed as 1520~1530 DEG C, in the range of design temperature；
Corresponding (b)：In oxidation-reduction process, reproducibility deficiency in titaniferous mixing slag is showed, into titaniferous mixing slag Coke powder 2kg is added, is made in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Step 3, separation and recovery uses method A：
(1) by the mixing slag after reduction-oxidation, cooled to room temperature, obtains slow cooling slag；
(2) iron containing vanadium metal is deposited to the bottom of reaction unit, forms iron and sticks together, and manually takes out iron and sticks together；By remaining slow cooling slag In iron layer containing vanadium metal, be crushed to granularity as 20~400 μm, remaining iron containing vanadium metal is isolated in ore grinding, magnetic separation；Metallic iron recycles Rate is 93%, this step mine tailings all iron content 0.794wt%；
(3) to going iron removaling to stick together and the slow cooling slag upper, middle and lower portion of the iron layer containing vanadium metal, the progress of gravity separation method is respectively adopted Separation, through chute one roughing, shaking table primary cleaning, is scanned lower part slow cooling slag twice, will be contained titanium component and is separated with gangue, and obtain It is mutually ilmenite concentrate, the chats of magnesium aluminate spinel containing vanadium and the tailing of Perovskite Phase to main thing, TiO in ilmenite concentrate2Mass fraction 37.38%, V in the chats of magnesium aluminate spinel containing vanadium2O5Mass fraction be 9.15%, P in rich phosphorus phase2O5Mass fraction be 28%；
(4) tailing uses 2% citric acid, and solid-to-liquid ratio 1: 2 separates phosphorus pentoxide, phosphorous recovery 70%.
Embodiment 10
A kind of titaniferous mixing slag recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
The melt oxidation of titanium containing the vanadium slag by the liquid molten 400kg titanium-containing blast furnace slags flowed out in slag notch and 360kg electric furnaces Pouring into internal layer has the drumped insulation slag ladle of asphalt-titanium-containing blast furnace slag complex heat-preservation demoulding refractory material, is sufficiently mixed Titaniferous mixing slag is formed, fusion reduction reaction occurs；Slag temperature is 1430 DEG C after mixing；In the temperature of titaniferous mixing slag In the range of 1400~1600 DEG C of setting；Wherein；
Titaniferous blast furnace cinder, is containing component and its mass percent：13.41wt%TiO2, 21.49wt%CaO, 9.87wt%MgO, 15.37wt%Al2O3, 4.43wt%FeO and 20.28wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium, contains component and its mass percent：2.24wt%V2O5, TFe16.94wt%, 42.86wt%CaO, 11.29wt%SiO2, 4.86wt%TiO2, 2.98wt%MgO, 1.94wt%MnO, 1.78wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, oxygen after blowing preheated, common injecting oxygen 7min；Wherein, oxygen Preheating temperature is 300 DEG C, and the relation of oxygen time and flow is 50L/ (minkg)；The injection method of oxygen is using fire resisting Spray gun insertion mixing slag is blown into；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1400~1600 DEG C of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：It is 1470~1478 DEG C that reduction-oxidation process, which measures mixing slag temperature, in setting range；
Corresponding (b)：In oxidation-reduction process, reproducibility deficiency in titaniferous mixing slag is showed, into titaniferous mixing slag Coal dust 1kg is added, is made in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Step 3, separation and recovery uses method A：
(1) by the mixing slag after reduction-oxidation, cooled to room temperature, obtains slow cooling slag；
(2) iron containing vanadium metal is deposited to the bottom of reaction unit, forms iron and sticks together, and manually takes out iron and sticks together；By remaining slow cooling slag In iron layer containing vanadium metal, be crushed to granularity as 20~400 μm, remaining iron containing vanadium metal is isolated in ore grinding, magnetic separation；Metallic iron recycles Rate is 92%, all iron content 0.778wt% in this step mine tailings；
(3) to going iron removaling to stick together and the slow cooling slag upper, middle and lower portion of the iron layer containing vanadium metal, the progress of gravity separation method is respectively adopted Separation；Through chute one roughing, shaking table primary cleaning, is scanned lower part slow cooling slag twice, will be contained titanium component and is separated with gangue, and obtain It is mutually ilmenite concentrate, the chats of magnesium aluminate spinel containing vanadium and the tailing of Perovskite Phase to main thing, TiO in ilmenite concentrate2Mass fraction is 38.28%, V in the chats of magnesium aluminate spinel containing vanadium2O5Mass fraction be 8.51%, P in rich phosphorus phase2O5Mass fraction be 27%；
(4) tailing uses 2% hydrochloric acid, separates phosphorus pentoxide by solid-to-liquid ratio 1: 2, phosphorous recovery 70%.
Embodiment 11
A kind of titaniferous mixing slag recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
By the liquid molten 40kg titanium-containing blast furnace slags flowed out in slag notch and 400kg electric furnaces, the melt oxidation of titanium containing vanadium slag falls Entering internal layer has the drumped melting reaction slag ladle of metallurgical coke-spinel complex heat-preservation demoulding refractory material, is sufficiently mixed shape Into titaniferous mixing slag, fusion reduction reaction occurs；Slag temperature is 1610 DEG C after mixing；
1450~1600 DEG C of scopes are set higher than the temperature in titaniferous mixing slag；The side that refractory lance is used to be blown Formula, adds the converter dust granular material 4kg that particle mean size is 140 μm, loading gas is air, makes the temperature of titaniferous mixing slag Degree is reduced to 1580 DEG C；Wherein：
Titaniferous blast furnace cinder, is containing component and its mass percent：4wt%TiO2, 25.49wt%CaO, 1.06wt% MgO, 14.35wt%Al2O3, 4.56wt%FeO and 21.03wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium, contains component and its mass percent：0.3wt%V2O5, TFe16.94wt%, 45.32wt%CaO, 10.36wt%SiO2, 3.54wt%TiO2, 2.67wt%MgO, 1.85wt%MnO, 1.64wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, oxygen-enriched air after blowing preheated, is blown oxygen-enriched air 5min altogether；Its In, the percent by volume of oxygen is 22% in oxygen-enriched air, and oxygen-enriched air preheating temperature is 1200 DEG C, oxygen-enriched air time and stream The relation of amount is 60L/ (minkg)；The injection method of oxygen-enriched air is to be placed in slag side using refractory lance insertion to be blown into；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1450~1600 DEG C of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：Oxidation-reduction process measures mixing slag temperature and is up to 1655 DEG C；Since temperature is higher by setting value, to V-ti magnetite concentrate metallized pellet 3kg is blown into titaniferous mixing slag, the temperature for making titaniferous mixing slag is reduced to 1560~ 1570 DEG C, in setting range；
Corresponding (b)：In oxidation-reduction process, reproducibility deficiency in titaniferous mixing slag is showed, into titaniferous mixing slag Bituminous coal 2kg is added, is made in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Step 3, separation and recovery uses method B：
(1) by the greenhouse cooling of the mixing slag after reduction-oxidation to 1250 DEG C, after the reduction-oxidation on middle part and top Mixing slag water quenching, as cement raw material or construction material；
(2) by the mixing slag after the reduction-oxidation of lower part, still there is metallurgical coke-spinel complex heat-preservation demoulding in internal layer In the melting reaction slag ladle of refractory material, proceed as follows：
By the mixing slag after the reduction-oxidation of lower part, rotation is cooled to room temperature, and obtains slow cooling slag；Wherein, rotation cooling Operation be：Attemperator equipped with the mixing slag after redox is placed on rotating platform, is revolved according to certain speed Turn, for rotary speed depending on slag quality and attemperator height or depth, rotational time solidifies feelings according to slag quality and slag Depending on condition；
Iron containing vanadium metal is deposited to the bottom of reaction unit, forms iron and sticks together, and manually takes out iron and sticks together；It will contain in remaining slow cooling slag Vanadium metal iron layer, is crushed to granularity as 20~400 μm, remaining iron containing vanadium metal is isolated in ore grinding, magnetic separation；The rate of recovery of metallic iron For 91%, all iron content 0.652wt% in this step mine tailings；
To going iron removaling to stick together and the slow cooling slag upper, middle and lower portion of the iron layer containing vanadium metal, gravity separation method is respectively adopted and is divided From；Through chute one roughing, shaking table primary cleaning, is scanned lower part slow cooling slag twice, will be contained titanium component and is separated with gangue, and obtain Main thing is mutually ilmenite concentrate, the chats of magnesium aluminate spinel containing vanadium and the tailing of Perovskite Phase, TiO in ilmenite concentrate2Mass fraction be 35.00%, V in the chats of magnesium aluminate spinel containing vanadium2O5Mass fraction be 9.21%；P in rich phosphorus phase2O5Mass fraction be 26%；
Tailing uses 2% hydrochloric acid, and solid-to-liquid ratio 1: 2 separates phosphorus pentoxide, phosphorous recovery 60%.
Embodiment 12
A kind of titaniferous mixing slag recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
The melt oxidation of titanium containing the vanadium slag by the liquid molten 150kg titanium-containing blast furnace slags flowed out in slag notch and 500kg electric furnaces Pouring into internal layer has the converter of graphite-magnesia complex heat-preservation demoulding refractory material, is thoroughly mixed to form titaniferous mixing slag, occurs molten Melt reduction reaction；Slag temperature is 1610 DEG C after mixing；
1450~1600 DEG C of scopes are set higher than the temperature in titaniferous mixing slag；V-ti magnetite essence is added to mixing slag Ore deposit carbon containing pre-reduced pellet 2kg and fluorite 1kg, makes the temperature of titaniferous mixing slag be reduced to 1570 DEG C；Wherein：
Titaniferous blast furnace cinder, is containing component and its mass percent：30wt%TiO2, 15.64wt%CaO, 8.32wt%MgO, 10.79wt%Al2O3, 3.54wt%FeO and 18.45wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium, contains component and its mass percent：5.00wt%V2O5, TFe15.49wt%, 41.78wt%CaO, 15.11wt%SiO2, 2.54wt%TiO2, 1.86wt%MgO, 1.79wt%MnO, 1.62wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, nitrogen-air Mixture after blowing preheated, common nitrogen-blow-sky Gas gaseous mixture 10min；Wherein, the percent by volume of nitrogen is 40% in nitrogen-air Mixture, and nitrogen-air Mixture is pre- Hot temperature is 500 DEG C, and the relation of nitrogen-air Mixture time and flow is 40L/ (minkg)；Nitrogen-air Mixture Injection method is to be placed in mixing slag top using refractory lance to be blown into；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1450~1600 DEG C of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：Oxidation-reduction process measures mixing slag temperature and is up to 1618 DEG C；Since temperature is higher by setting value, to The carbon containing pre-reduced pellet 1kg of titanium magnet ore concentrate is blown into titaniferous mixing slag, the temperature of titaniferous mixing slag is reduced to 1575 ~1582 DEG C, in setting range；
Corresponding (b)：In oxidation-reduction process, reproducibility deficiency in titaniferous mixing slag is showed, into titaniferous mixing slag Anthracite 2.5kg is added, is made in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into gold Belong to iron；
Step 3, separation and recovery uses method D：
(1) by the mixing slag after reduction-oxidation, sedimentation slag-gold separation, obtains vanadium-bearing hot metal with containing vanadium after reduction-oxidation Titanium slag；
(2) by the titanium slag containing vanadium after reduction-oxidation, the outer slag treatment of stove is carried out, using method D-1：Measure reduction-oxidation The TiO of titanium slag containing vanadium afterwards2Mass fraction be 8.9%≤10%, it is directly that the titanium slag containing vanadium after reduction-oxidation is air-cooled, use Make cement raw material or construction material；
(3) vanadium-bearing hot metal is sent to pneumatic steelmaking.
Embodiment 13
A kind of titaniferous mixing slag recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
The melt oxidation of titanium containing the vanadium slag by the liquid molten 420kg titanium-containing blast furnace slags flowed out in slag notch and 380kg electric furnaces Pouring into internal layer has the direct current electric arc furnace of pitch-olivine matter complex heat-preservation demoulding refractory material, is thoroughly mixed to form titaniferous mixing Slag, occurs fusion reduction reaction；Slag temperature is 1380 DEG C after mixing；
1450~1600 DEG C of scopes are set less than the temperature in titaniferous mixing slag；Pass through direct current electric arc furnace conducting self-heating work( Can, the temperature of titaniferous mixing slag is increased to 1450 DEG C；Wherein：
Titaniferous blast furnace cinder, is containing component and its mass percent：15.64wt%TiO2, 20.64wt%CaO, 9.98wt%MgO, 16.31wt%Al2O3, 5.01wt%FeO and 21.61wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium, contains component and its mass percent：2.56wt%V2O5, TFe15.36wt%, 40.25wt%CaO, 11.39wt%SiO2, 5.35wt%TiO2, 2.64wt%MgO, 1.92wt%MnO, 1.59wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, oxygen-argon gas gaseous mixture after blowing preheated, common injecting oxygen-argon Gas gaseous mixture 6min；Wherein, the percent by volume of oxygen is 50% in oxygen-argon gas gaseous mixture, oxygen-argon gas charge heating Temperature is 800 DEG C, and the relation of oxygen-argon gas gaseous mixture time and flow is 80L/ (minkg)；Oxygen-argon gas gaseous mixture Injection method is to be inserted into mixing slag using refractory lance to be blown into；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1450~1600 DEG C of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：It is 1470~1475 DEG C that reduction-oxidation process, which measures mixing slag temperature, in setting range；
Corresponding (b)：In oxidation-reduction process, reproducibility deficiency in titaniferous mixing slag is showed, into titaniferous mixing slag Bituminous coal 2.0kg is added, is made in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metal Iron；
Step 3, separation and recovery uses method D：
(1) by the mixing slag after reduction-oxidation, sedimentation slag-gold separation, obtains vanadium-bearing hot metal and containing after reduction-oxidation Vanadium titanium slag：
(2) by the titanium slag containing vanadium after reduction-oxidation, the outer slag treatment of stove is carried out, using method D-1：
Measure the TiO of the titanium slag containing vanadium after reduction-oxidation2Mass fraction=9.8≤10% when, directly by reduction-oxidation The water quenching of titanium slag containing vanadium afterwards, as cement raw material or construction material；
(3) vanadium-bearing hot metal is sent to pneumatic steelmaking.
Embodiment 14
A kind of titaniferous mixing slag recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
By the liquid molten 400kg titanium-containing blast furnace slags flowed out in slag notch and 100kg converters, the molten steel slag of titanium containing vanadium pours into Internal layer has the mineral hot furnace of anthracite-clayey complex heat-preservation demoulding refractory material, is thoroughly mixed to form titaniferous mixing slag, occurs Fusion reduction reaction；Slag temperature is 1389 DEG C after mixing；
1450~1600 DEG C of scopes are set less than the temperature in titaniferous mixing slag；By mineral hot furnace conducting self-heating function, The temperature of titaniferous mixing slag is set to be increased to 1462 DEG C；Wherein；
Titaniferous blast furnace cinder, is containing component and its mass percent：10.65wt%TiO2, 22.68wt%CaO, 9.08wt%MgO, 17.62wt%Al2O3, 5.05wt%FeO and 21.03wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium, contains component and its mass percent：5.21wt%V2O5, TFe15.68wt%, 40.01wt%CaO, 12.12wt%SiO2, 4.86wt%TiO2, 2.66wt%MgO, 1.90wt%MnO, 1.71wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, nitrogen-oxygen mixture after blowing preheated, common nitrogen-blow-oxygen Gas gaseous mixture 8min；Wherein, the percent by volume of nitrogen is 60% in nitrogen-oxygen mixture, nitrogen-oxygen mixture preheating Temperature is 480 DEG C, and the relation of nitrogen-oxygen mixture time and flow is 10L/ (minkg)；Nitrogen-oxygen mixture Injection method is to be inserted into mixing slag using refractory lance to be blown into；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1450~1600 DEG C of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：It is 1480~1488 DEG C that reduction-oxidation process, which measures mixing slag temperature, in setting range；
Corresponding (b)：In oxidation-reduction process, reproducibility deficiency in titaniferous mixing slag is showed, into titaniferous mixing slag Anthracite 1.8kg is added, is made in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into gold Belong to iron；
Step 3, separation and recovery uses method D：
(1) by the mixing slag after reduction-oxidation, sedimentation slag-gold separation, obtains vanadium-bearing hot metal and containing after reduction-oxidation Vanadium titanium slag；
(2) by the titanium slag containing vanadium after reduction-oxidation, the outer slag treatment of stove is carried out：
(3) vanadium-bearing hot metal is sent to pneumatic steelmaking；
Wherein, the outer slag treatment of stove uses method D-2：
Titanium slag containing vanadium after reduction-oxidation is poured into the insulation of bituminous coal-High-Alumina complex heat-preservation demoulding refractory material Hole, then proceeds as follows：
1. into the titanium slag containing vanadium after reduction-oxidation, nitrogen-oxygen mixture after blowing preheated, common nitrogen-blow-oxygen Gas gaseous mixture 2min；Wherein, the percent by volume of nitrogen is 60% in nitrogen-oxygen mixture, nitrogen-oxygen mixture preheating Temperature is 500 DEG C, and the relation of nitrogen-oxygen mixture time and flow is 12L/ (minkg)；Nitrogen-oxygen mixture Injection method is to be inserted into mixing slag using refractory lance to be blown into；
2. control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1400~1600 DEG C of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：It is 1422~1429 DEG C that reduction-oxidation process, which measures mixing slag temperature, in setting range；
Corresponding (b)：Remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
3. separation and recovery uses method A：
By the slag after reduction-oxidation, cooled to room temperature, obtains slow cooling slag；
Iron containing vanadium metal is deposited to the bottom of reaction unit, forms iron and sticks together, and manually takes out iron and sticks together；It will contain in remaining slow cooling slag Vanadium metal iron layer, is crushed to granularity as 20~400 μm, remaining iron containing vanadium metal is isolated in ore grinding, magnetic separation；Metal iron recovery 95%, full iron is 0.665wt% in this step mine tailings；
To going iron removaling to stick together and the slow cooling slag upper, middle and lower portion of the iron layer containing vanadium metal, gravity separation method is respectively adopted and is divided From；Through chute one roughing, shaking table primary cleaning, is scanned lower part slow cooling slag twice, will be contained titanium component and is separated with gangue, and obtain Main thing is mutually ilmenite concentrate, the chats of magnesium aluminate spinel containing vanadium and the tailing of Perovskite Phase, TiO in ilmenite concentrate2Mass fraction be 48.96%, V in the chats of magnesium aluminate spinel containing vanadium2O5Mass fraction be 9.65%；P in rich phosphorus phase2O5Mass fraction be 30%；
Tailing uses 2% hydrochloric acid, separates phosphorus pentoxide by solid-to-liquid ratio 1: 2, phosphorous recovery 80%.
Embodiment 15
A kind of titaniferous mixing slag recycling and the method for modifier treatment, specifically include following steps：
Step 1, slag mixes：
By the liquid molten 380kg titanium-containing blast furnace slags flowed out in slag notch and 480kg converters, the molten steel slag of titanium containing vanadium pours into Internal layer has the converter of burnt-siliceous complex heat-preservation demoulding refractory material of asphalt, is thoroughly mixed to form titaniferous mixing slag, occurs Fusion reduction reaction；Slag temperature is 1632 DEG C after mixing；
1450~1600 DEG C of scopes are set higher than the temperature in titaniferous mixing slag；Common iron ore concentrate is added to mixing slag Metallized pellet 1.5kg, makes the temperature of titaniferous mixing slag be reduced to 1560 DEG C；Wherein：
Titaniferous blast furnace cinder, is containing component and its mass percent：10.94wt%TiO2, 21.49wt%CaO, 9.95wt%MgO, 14.39wt%Al2O3, 6.66wt%FeO and 22.61wt%SiO2, surplus is other impurities；
The molten steel slag of titanium containing vanadium, contains component and its mass percent：1.32wt%V2O5, TFe16.59wt%, 43.12wt%CaO, 13.33wt%SiO2, 5.06wt%TiO2, 3.68wt%MgO, 2.67wt%MnO, 2.00wt%Al2O3, Surplus is other impurities；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, oxygen after blowing preheated, common injecting oxygen 6min；Wherein, oxygen Preheating temperature is 1000 DEG C, and the relation of oxygen time and flow is 45L/ (minkg)；The injection method of air is using fire resisting Spray gun insertion mixing slag is blown into；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1450~1600 DEG C of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；With The progress of reaction, slag reproducibility deficiency, adds coal dust 1kg, ferriferous oxide is reduced into metallic iron；
Corresponding (a)：Oxidation-reduction process measures mixing slag temperature and is up to 1612 DEG C；Since temperature is higher by setting value, to Common iron ore concentrate metallized pellet 1kg is added in titaniferous mixing slag, the temperature for making titaniferous mixing slag is reduced to 1580~ 1585 DEG C, in setting range；
Corresponding (b)：In oxidation-reduction process, reproducibility deficiency in titaniferous mixing slag is showed, into titaniferous mixing slag Coal dust 2kg is added, is made in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Step 3, separation and recovery uses method D：
(1) by the mixing slag after reduction-oxidation, sedimentation slag-gold separation, obtains vanadium-bearing hot metal and containing after reduction-oxidation Vanadium titanium slag；
(2) by the titanium slag containing vanadium after reduction-oxidation, the outer slag treatment of stove is carried out：
(3) vanadium-bearing hot metal is sent to pneumatic steelmaking；
Wherein, the use method D-2 of the outer slag treatment of stove：
1. the titanium slag containing vanadium after reduction-oxidation is poured into asphalt Jiao-spinel complex heat-preservation demoulds refractory material Insulation slag fill, then proceed as follows：
Into the titanium slag containing vanadium after reduction-oxidation, oxygen after blowing preheated, common injecting oxygen 3min；Wherein, oxygen mixes It is 960 DEG C to close gas preheating temperature, and the relation of oxygen mixed gas time and flow is 40L/ (minkg)；Oxygen mixture The injection method of body is to be inserted into mixing slag using refractory lance to be blown into；
2. control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of 1400~1600 DEG C of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Corresponding (a)：It is 1570~1576 DEG C that reduction-oxidation process, which measures mixing slag temperature, in setting range；
Corresponding (b)：Remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
3. separation and recovery uses method C：
By the mixing slag after reduction-oxidation, sedimentation slag-gold separation, obtains vanadium-bearing hot metal and the titanium containing vanadium after reduction-oxidation Slag；
The TiO of titanium slag containing vanadium after reduction-oxidation2Mass fraction=8.5%≤10% when, directly by reduction-oxidation The water quenching of titanium slag containing vanadium afterwards, as cement raw material or construction material.

Claims (12)

1. a kind of method of titaniferous mixing slag melting and reducing recycling and modifier treatment, it is characterised in that comprise the following steps：
Step 1, slag mixes：
In mass ratio, titaniferous blast furnace cinder: molten steel slag=100 of titanium containing vanadium: (1~1000) dispensing, adds attemperator, can incline In melting reaction device or fixed melting reaction device, titaniferous mixing slag is formed, fusion reduction reaction occurs；Will The temperature control of titaniferous mixing slag is in the range of design temperature；
Wherein：
Design temperature scope is 1400~1600 DEG C；
When reaction unit uses attemperator, the temperature range of titaniferous mixing slag is set as 1400~1600 DEG C；
When reaction unit uses drumped melting reaction device or fixed melting reaction device, titaniferous mixing slag Temperature range is set as 1450~1600 DEG C；
The temperature for controlling titaniferous mixing slag is in the method for design temperature scope：
When the temperature ＜ design temperature range lower limits of titaniferous mixing slag, by the heating function of reaction unit itself, or to Fuel and/or the molten steel slag of titanium containing vanadium are added in titaniferous mixing slag, the temperature of titaniferous mixing slag is reached design temperature model In enclosing；
When the temperature ＞ design temperature range limits of titaniferous mixing slag, added into titaniferous mixing slag titanium containing vanadium material, One or more in ferrous material, fluorine-containing material or titaniferous blast furnace cinder, make the temperature of titaniferous mixing slag reach setting temperature In the range of degree；
Step 2, melting and reducing and oxidation：
(1) blowing gas：Into titaniferous mixing slag, blowing preheated rear oxidation gas；Wherein, the preheating temperature of oxidizing gas Spend for 0~1200 DEG C, the relation of oxidizing gas time and flow is 1~105L/ (minkg)；
(2) control reduction and oxidizing process：
During injection, ensure (a) and (b) two parameters at the same time by regulation and control：
(a) temperature of titaniferous mixing slag is in the range of design temperature；
(b) in titaniferous mixing slag, remaining Low-valent Titanium is oxidized to high price titanium, and remaining ferriferous oxide is reduced into metallic iron；
Regulation and control method is：
Corresponding (a)：
The temperature of titaniferous mixing slag is controlled in the method for design temperature scope using in step 1；
Corresponding (b)：
When reproducibility is insufficient in titaniferous mixing slag, reducing agent is added into titaniferous mixing slag, is made in titaniferous mixing slag, Ferriferous oxide is reduced into metallic iron；
Step 3, separate and recover：
Using one kind in following methods：
One, is when reaction unit uses attemperator, using method A, method B or method C：
When reaction unit is using not drumped attemperator or drumped attemperator, using method A：
(1) by the mixing slag after reduction-oxidation, it is cooled to room temperature, the slow cooling slag of acquisition；
(2) iron containing vanadium metal is deposited to the bottom of reaction unit, forms iron and sticks together, and manually takes out iron and sticks together；It will contain in remaining slow cooling slag Vanadium metal iron layer, is crushed to granularity as 20~400 μm, remaining iron containing vanadium metal is isolated in ore grinding, magnetic separation；
(3) to going iron removaling to stick together and the slow cooling slag of the iron layer containing vanadium metal, separated using gravity separation method, obtain ilmenite concentrate, richness Vanadium concentrate and tailings；
(4) recycling of tailing has 2 kinds：1. make aggregate, road material or phosphate fertilizer as cement raw material, construction material, instead of rubble Use；2. it will be separated using hydrometallurgy, beneficiation method or ore dressing-hydrometallurgy combination method in tailing containing phosphorus component；
Only when reaction unit uses drumped attemperator, using method B or method C：
Method B：
(1) by the greenhouse cooling of the mixing slag after reduction-oxidation to 1150~1250 DEG C, by the reduction-oxidation on middle part and top After mixing slag afterwards is poured out, air-cooled or water quenching, as cement raw material or construction material；
(2) by the mixing slag after the reduction-oxidation of lower part, still in drumped attemperator, as method A reduction-oxidations Mixing slag afterwards is handled；
Method C：
(1) by the mixing slag after reduction-oxidation, sedimentation slag-gold separation, obtains vanadium-bearing hot metal and the titanium containing vanadium after reduction-oxidation Slag；
(2) TiO of titanium slag containing vanadium after reduction-oxidation2Mass fraction≤10% when, directly by the titanium containing vanadium after reduction-oxidation After slag is poured out, air-cooled or water quenching, as cement raw material or construction material；
(3) vanadium-bearing hot metal is sent to pneumatic steelmaking；
Two, are when reaction unit uses drumped melting reaction device or fixed melting reaction device, using method D：
(1) by the mixing slag after reduction-oxidation, sedimentation slag-gold separation, obtains vanadium-bearing hot metal and the titanium containing vanadium after reduction-oxidation Slag：
(2) by the titanium slag containing vanadium after reduction-oxidation, the outer slag treatment of stove is carried out；
(3) vanadium-bearing hot metal is sent to pneumatic steelmaking；
Wherein, the outer slag treatment of stove uses method D-1 or method D-2：
Method D-1：The TiO of titanium slag containing vanadium after reduction-oxidation2Mass fraction≤10% when, directly by after reduction-oxidation After titanium slag containing vanadium is poured out, air-cooled or water quenching, as cement raw material or construction material；
Method D-2：Titanium slag containing vanadium after reduction-oxidation is poured into attemperator, melt also according to the method in step 2 It is former to use method A, method B or method C with oxidation, separation and recovery.
2. the method for titaniferous mixing slag melting and reducing recycling according to claim 1 and modifier treatment, it is characterised in that In the step 1, titaniferous blast furnace cinder is obtained by tap cinder mouth, and temperature >=1300 DEG C of titaniferous blast furnace cinder are described Titaniferous blast furnace cinder, contains TiO2Mass fraction be 4~30%；The molten steel slag of titanium containing vanadium is obtained by slag slag notch, containing vanadium Temperature >=1500 DEG C of titanium molten steel slag, the titanium containing vanadium molten steel slag, contain TiO2Mass fraction be 0.3~6%, contain There is V2O5Mass fraction be 0.3~5%.
3. the method for titaniferous mixing slag melting and reducing recycling according to claim 2 and modifier treatment, it is characterised in that The molten steel slag of titanium containing vanadium, is converter titanium containing vanadium molten steel slag or electric furnace titanium containing vanadium melt oxidation slag.
4. the method for titaniferous mixing slag melting and reducing recycling according to claim 1 and modifier treatment, it is characterised in that The attemperator is drumped attemperator or not drumped attemperator；The not drumped attemperator For thermal insulation pit；The drumped attemperator is drumped insulation slag ladle；The drumped melting reaction dress It is set to drumped converter, drumped melting reaction slag fills or induction furnace；Fixed melting reaction device carries slag for bottom The reaction unit of mouth or iron mouth；The fixed reaction unit is plasma heating furnace, direct current electric arc furnace, ac arc furnace, ore deposit heat Stove, blast furnace or reverberatory furnace.
5. the method for titaniferous mixing slag melting and reducing recycling according to claim 1 and modifier treatment, it is characterised in that Attemperator, drumped melting reaction device or the fixed melting reaction device internal layer demoulds resistance to for carbon containing insulation Fiery material；The carbon containing insulation demoulding refractory material is to contain carbon composite refractory, is specially that carbon is carbon, graphite, oil One or more in pitch coke, metallurgical coke, pitch, anthracite, bituminous coal or lignite, refractory material are siliceous, semi silica, clay In matter, High-Alumina, magnesia, dolomite matter, olivine matter, spinel, cold conditions titanium-containing blast furnace slag or cold conditions slag with vanadium and titanium oxides It is one or more of.
6. the method for titaniferous mixing slag melting and reducing recycling according to claim 1 and modifier treatment, it is characterised in that The temperature of described control titaniferous mixing slag in the method for design temperature scope, into mixing slag addition fuel and/or During the molten steel slag of titanium containing vanadium, preheating of fuel temperature is 0~1200 DEG C, temperature >=1500 DEG C of the molten steel slag of titanium containing vanadium；Fuel Using using refractory lance insertion slag or being placed in slag top or side is blown into fuel；Fired when being added at the same time into mixing slag When material and the molten steel slag of titanium containing vanadium, fuel and the molten steel slag of titanium containing vanadium are any ratio；
The 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, direct reduction of V-Ti magnetite iron, v-ti magnetite concentrate metallized pellet, v-ti magnetite concentrate are carbon containing One or more in pre-reduced pellet, v-ti magnetite concentrate sinter, v-ti magnetite concentrate pellet；Ferrous material is common Iron ore concentrate, common iron ore concentrate direct reduced iron, common iron ore concentrate sintered ore deposit, common Iron Ore Pellets, common iron ore concentrate metal Pellet, the carbon containing pre-reduced pellet of common iron ore concentrate, common slag, blast furnace dust, blast furnace dust, converter dust, iron oxide Skin, the zinc leaching residue of Zinc Hydrometallurgy Process, aluminum oxide production process produce red mud, coal dust ash, one kind in pyrite cinder or It is several；Fluorine-containing material is fluorite and/or CaF2。
7. the method for titaniferous mixing slag melting and reducing recycling according to claim 6 and modifier treatment, it is characterised in that Fuel is coal dust.
8. the method for titaniferous mixing slag melting and reducing recycling according to claim 6 and modifier treatment, it is characterised in that The material of titanium containing vanadium, ferrous material and fluorine-containing material are equal pelletizing or granular material；Wherein, granularity≤150 μm of granular material, powder Shape material adds titaniferous mixing slag in a manner of being blown, and loading gas is air, argon gas, nitrogen-air Mixture, nitrogen- Oxygen mixture or Air-Argon gaseous mixture；Injection method is to be inserted into slag using refractory lance or be placed in slag top or side Face is blown into granular material.
9. the method for titaniferous mixing slag melting and reducing recycling according to claim 1 and modifier treatment, it is characterised in that The oxidizing gas is air, oxygen, oxygen-enriched air, nitrogen-oxygen mixture, nitrogen-air Mixture, oxygen-argon One kind in gas gaseous mixture or Air-Argon gaseous mixture；The injection method of oxidizing gas is to be inserted into slag using refractory lance Or it is placed in slag top or side is blown into oxidizing gas.
10. the method for titaniferous mixing slag melting and reducing recycling according to claim 1 and modifier treatment, its feature exist In in the step 2 and step 3, reducing agent is one kind in coal dust, coke powder, bituminous coal or anthracite.
11. the method for titaniferous mixing slag melting and reducing recycling according to claim 1 and modifier treatment, its feature exist In, the step 3, method A (1), the type of cooling is natural cooling or rotation cooling；The specific behaviour of the rotation cooling As：Attemperator equipped with the mixing slag after redox is placed on rotating platform, is rotated according to certain speed, rotation Rotary speed according to slag quality and attemperator height or depth depending on, rotational time according to slag quality and slag solidification situation and It is fixed；In method A (3), gravity separation method be separation by shaking table, sluicing or the two be combined；In method A (4), hydrometallurgy It is diluted acid leaching method, wherein diluted acid leaching method is one kind in inorganic acidleach, organic acidleach；The inorganic acid select sulfuric acid, The one or more of hydrochloric acid, phosphoric acid, organic acid select the one or more in oxalic acid, acetic acid, citric acid.
12. the method for titaniferous mixing slag melting and reducing recycling according to claim 1 and modifier treatment, its feature exist In, the step 3, method A, metal iron recovery is 90~97%, and main thing is mutually TiO in the ilmenite concentrate of perovskite2 Mass fraction be 35~52%, the rate of recovery of titanium is 60~80%；In method B, metal iron recovery is 90~95%, main It is mutually TiO in the ilmenite concentrate of perovskite to want thing2Mass fraction be 35~52%, the rate of recovery of titanium is 58~76%.
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