CN104334749B - The manufacture method of the mixture of reduced iron and slag - Google Patents

The manufacture method of the mixture of reduced iron and slag Download PDF

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Publication number
CN104334749B
CN104334749B CN201380027484.2A CN201380027484A CN104334749B CN 104334749 B CN104334749 B CN 104334749B CN 201380027484 A CN201380027484 A CN 201380027484A CN 104334749 B CN104334749 B CN 104334749B
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agglomerate
amount
iron
slag
melting
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CN104334749A (en
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日野光兀
杉山健
田中英年
小林勋
浦上昭
根上卓也
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Kobe Steel Ltd
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Kobe Steel Ltd
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B11/00—Making pig-iron other than in blast furnaces
    • C21B11/08—Making pig-iron other than in blast furnaces in hearth-type furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/10—Making spongy iron or liquid steel, by direct processes in hearth-type furnaces
    • C21B13/105—Rotary hearth-type 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • C22B1/244—Binding; Briquetting ; Granulating with binders organic
    • 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
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen

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

Abstract

Provide in the mixture of a kind of reduced iron obtaining under the semi-molten state of whole agglomerate incomplete fusions and slag, improve the technology separatory of reduced iron and slag. A manufacture method for the mixture of reduced iron and slag, it comprises following operation successively: in the material that contains iron oxide and titanium oxide and carbon material, then concoct fusing point conditioning agent, the raw mixture obtaining is thus become to the operation of piece; The agglomerate that obtains of heating and make a part of melting, reduces the operation of contained iron oxide in this agglomerate.

Description

The manufacture method of the mixture of reduced iron and slag
Technical field
The present invention relates to the agglomerate of material that heat packs contains iron oxide and titanium oxide and carbon material and manufacture reduced iron andThe method of the mixture of slag.
Background technology
As by iron ore etc. manufacture the iron-refining process of reduced iron containing iron oxide material, known have following (1)～(3)Method.
(1) pelletizing that burns till that has carried out sintering taking iron ore as main material is heated to about 1000 DEG C in shaft furnace, byThe method of contained iron oxide in reducing gas reductive firing pelletizing.
(2) by compound iron ore with carbon material (solid reduction material) and become the agglomerate of piece to be supplied to moving hearth stove (converter),With approximately 1300 DEG C of heating, reduce the method for contained iron oxide in this agglomerate.
(3) by compound iron ore with carbon material and become the agglomerate of piece to be supplied to moving hearth stove, be heated to about 1450 DEG C andMake reduced iron melting, at this moment utilize capillary difference of the slag that metallic iron and by-product go out etc., be separated into reduced iron and slagMethod.
About the manufacture method of such reduced iron, for example, the known technology that has patent documentation 1～4.
About the method for above-mentioned (1), for example, the known technology that has patent documentation 1. In patent documentation 1, describe, directly alsoFormer pulverizing iron ore, after iron is separated with gangue, then pulverizes both, therefrom reclaims respectively iron. Describe as reducing gas, canUse CO gas and H2Gas, heating-up temperature is 700～1200 DEG C, pulverizing can be used the rolls that metallic iron can be flattened to slabbingDeng, iron and gangue separate be by the separation that utilizes 20 mesh sieve (mesh 0.83mm) to carry out separate with magnetic separation combined intoOK.
About the method for above-mentioned (2), for example, the known technology that has patent documentation 2. In patent documentation 2, be to contain ironThe mixture of raw material and coal carries out heat reduction processing under high-temperature atmosphere, the reduced iron that pulverization process obtains, then, to adviseFixed particle diameter is that boundary carries out grading. Specifically, separate/be classified into average grain diameter with grading machine and be greater than 100 μ m'sParticle and the average grain diameter particle below 100 μ m. Then, utilize magnetic force, by the reduction abrasive grit below average grain diameter 100 μ mSon, is separated into and contains in a large number hard magnetization thing particle and the iron that iron divides and divide few weakly magnetization thing particle, will be through grading superReduced iron particle and the above-mentioned hard magnetization thing particle of crossing afore mentioned rules particle diameter use as reduced iron. On the other hand, in weakly magnetizationIn thing particle, few because iron divides, contain in a large number slag composition, so directly as cement and pitch recycling. Therefore above-mentionedIn patent documentation 2, separate slag about dividing from iron few weakly magnetization thing particle, reclaim the problem that iron divides and utilize as source of ironDo not give consideration completely.
About the method for above-mentioned (3), for example, the known technology that has patent documentation 3,4.
Wherein, in patent documentation 3, described a kind of method of being manufactured high-grade reduced iron by ironmaking dust, it is to pass throughManufacture the carbonaceous pelletizing that is made up of multiple dust and carbon material, calcining furnace to it by rotation siege formula, with 1250～1350 DEG CTemperature is reduced processing, and thus, the dust of pelletizing inside is reduced by carbon material, moves and the metallic iron of aggegation by intragranular materialParticle, the slag part of the low melting point that contains FeO generating from gangue by dust, utilizes the effect of natural separation and extractsMetal iron particles, produces high-grade granular reduced iron.
In patent documentation 4, describe and have a kind of method, it is to manufacture the carbonaceous pelletizing being made up of iron ore and carbon material, by itWith the calcining furnace of rotation siege formula, after reducing with the temperature of 1250～1350 DEG C, then make temperature rise to 1400 in stove～1500 DEG C make it melting, make metallic iron aggegation, thereby obtain highly purified granulated metal iron.
, in above-mentioned iron ore, except iron oxide, also contain the useful non-ferrous metal oxidation of titanium oxide etc.Thing. In patent documentation 5, describe the manufacture method that has a kind of titanium oxide to contain slag, it is to contain titanium oxide, iron oxide, carbonThe raw mixture of matter reducing agent heats in revolving burner pool furnace, obtains reduced iron after the iron oxide reducing in this mixture,Then again it heated and make this reduced iron melting, making it from separating containing titanium oxide slag, by the obtained oxidation that containsTitanium slag is discharged to stove outward and is reclaimed.
But in above-mentioned patent documentation 3～5, be by making the complete melting of reduced iron, thus by reduced iron and by-productSlag separates, and the mixture of the reduced iron obtaining under the state that there is no complete melting about agglomerate and slag is separatoryImprove and do not give consideration completely.
Prior art document
Patent documentation
Patent documentation 1: No. 6048382nd, U.S. Patent bulletin
Patent documentation 2: TOHKEMY 2002-363624 communique
Patent documentation 3: Japanese kokai publication hei 10-147806 communique
Patent documentation 4: TOHKEMY 2009-91664 communique
Patent documentation 5: No. 4153281 communique of Japan Patent
Summary of the invention
The present invention is conceived to above-mentioned such situation and completes, and its object is, provides a kind of completely not molten at agglomerateIn the reduced iron obtaining under the semi-molten state melting and the mixture of slag, can improve the separatory of reduced iron and slagTechnology. In addition, another object of the present invention is to, provide a kind of by reclaiming titanium oxide as slag, thus can be by oxygenChange titanium concentration high be used in the method for Titanium raw material containing titanium oxide slag.
Can solve the manufacture method of the reduced iron of the present invention of above-mentioned problem and the mixture of slag, comprise successively asIn lower operation this point, there is main idea: by further blending fusing point adjusting in the material that contains iron oxide and titanium oxide and carbon materialAgent and the raw mixture that obtains becomes the operation of piece; Mode according to a part of melting that makes obtained agglomerate addsHeat, reduces the operation of contained iron oxide in this agglomerate.
In addition, above-mentioned problem by comprise successively in following operation this point, have main idea, reduced iron and slagThe manufacture method of mixture also can be reached: will in the material that contains iron oxide and titanium oxide and carbon material, further concoct fusing pointConditioning agent and the raw mixture that obtains becomes the operation of piece; The temperature of the part generation melting of obtained agglomerate withUpper and lower than the temperature of melting completely, heat described agglomerate, reduce thus the operation of contained iron oxide in this agglomerate.
In the present invention, described fusing point conditioning agent at least contains CaO supplies with material, about being blended in described agglomerateCaO supplies with amount of substance, preferably by CaO amount and SiO by this agglomerate2Basicity (the CaO/SiO of the slag that amount is tried to achieve2) controlIn 0.2～0.9 scope. Supply with material as described CaO, for example, preferably blending is from CaO, Ca (OH)2And CaCO3FormAt least one that select in group.
In the present invention, preferably adjust the blending amount of described fusing point conditioning agent, the maximum temperature while making to heat described agglomerateThe melting amount that deducts gangue contained in this agglomerate at the temperature of 100 DEG C is more than 55 quality %. The described of described gangue meltedThe amount of melting, CaO, SiO based on comprising in described agglomerate2、Al2O3, MgO and TiO2The amount of these five kinds of compositions determines. Described groupThe heating of piece, preferably at the contained CaO-SiO of this agglomerate2-Al2O3-MgO-TiO2Five yuan is the melting amount of oxide, reaches thisFive yuan is that more than 55 quality % of oxide amount temperature adds at the temperature of 100 DEG C and carries out.
As the material that contains described iron oxide and titanium oxide, for example, the Fe's that preferably use contains 40～60 quality %Iron ore, also preferably uses the TiO that contains 7～20 quality %2Iron ore. Contained fixed carbon amount in described carbon material, preferablyMake it with respect to can reduce the iron oxide that comprises in described agglomerate fixed carbon amount and be ± 5 quality %, so described in blendingCarbon material. The heating of described agglomerate, for example, preferably carries out with 1200～1500 DEG C.
The present invention also comprises the separation method of reduced iron and slag, and the method comprises following operation successively: will be according to above-mentionedThe reduced iron that obtains of manufacture method and the mixture of slag be crushed to the operation of diameter 8mm following (containing 0mm); For gainedTo the crushed material operation of carrying out magnetic separation separation.
In addition, in the present invention, also comprise the unmagnetized thing and the magnetization thing that have carried out screening with above-mentioned separation method, this is non-Magnetization thing, for example, contain TiO more than 40 quality %2; This magnetization thing, for example SiO2Be suppressed in 8 quality % following (not containing 0 matterAmount %).
The effect of invention
According to the present invention, adjust by being produced in the material that contains iron oxide and titanium oxide and carbon material further blending fusing pointThe agglomerate that saves agent (except the material that the fusing point of iron is exerted an influence) and obtain, heats this agglomerate, makes one partial melting, and makesIncomplete fusion, can manufacture thus the mixture that mixing under the state that reduced iron separates with slag (following, be called reductionPelletizing). The mixture obtaining, for example, can easily be separated into reduced iron and slag by pulverizing, magnetic separation, respectively canBe used in the purposes of expectation. At this moment reduced iron is mainly split into magnetization thing side, and titanium oxide is split into unmagnetized as slagThing side, therefore according to the present invention, separating reducing iron and titanium oxide easily. That is, according to the present invention, except reduced iron withAs useful nonferrous metal oxides, can also carry out the separation of titanium oxide and reclaim outward.
In addition, also known in the present invention, (a) considering on the basis of heating-up temperature, make the molten of the contained gangue of agglomerateThe amount of melting reaches ormal weight above and the blending amount of adjustment fusing point conditioning agent, or (b) is considering the contained CaO-SiO of agglomerate2-Al2O3-MgO-TiO2Five yuan is that the melting amount of oxide is on basis, by the heating-up temperature of selected agglomerate, even use notBe common iron ore that adopt, that contain iron oxide and titanium oxide always, also can manufacture reduced iron.
Brief description of the drawings
Fig. 1 is the plot that represents the relation of heating-up temperature T and unmagnetized rate.
Fig. 2 is the C representing from the temperature (T-100 DEG C) of 100 DEG C of heating-up temperature T reductionsaO-SiO2-Al2O3-MgO-TiO2Five yuan is the melting amount of oxide, with the plot of the relation of unmagnetized rate.
Detailed description of the invention
The present inventors, (are called the material that contains iron oxide and titanium oxide always being used hardly containing oxygen below,Change the material of iron etc.) use as raw material, heat packs, containing this material containing iron oxide etc. and the agglomerate of carbon material, makes its partMelting, and make it all meltings, for the mixture of the reduced iron obtaining thus and slag (gangue content), in order to improve pointSeparation property when becoming reduced iron and slag and studying with keen determination. It found that, at material and carbon material containing iron oxide etc.Mixture in, if further concoct fusing point conditioning agent, can improve the reducting pellet that obtains of heating agglomerate is separatedSeparation property while becoming reduced iron and slag, thus the present invention completed.
In addition, the present inventors find, for separating reducing iron and slag more well, and following (a), the means of (b)Effectively.
(a), when in heating, heating-up temperature T when agglomerate has determined, the maximum temperature when making to heat this agglomerate deductsThe melting amount of the contained gangue content of this agglomerate at the temperature of 100 DEG C is mode more than 55 quality %, adjusts above-mentioned moltenThe blending amount of some conditioning agent (for example, CaO supplies with material etc.).
(b) when the heating-up temperature T in the time of heating agglomerate is not determined, with CaO-SiO contained in this agglomerate2-Al2O3-MgO-TiO2Five yuan is the melting amount of oxide, and reaching these five yuan is that more than 55 quality % of oxide amount temperature adds 100DEG C temperature, heat above-mentioned agglomerate.
In addition, the present inventors are about said mixture being separated into reduced iron and slag, manufacture as electric furnace refining etc.Raw material use reduced iron also repeatedly study. It found that, by by comprising containing the material of iron oxide etc., carbon material andThe agglomerate of fusing point conditioning agent carries out heat reduction under the state of partial melting, although reduced iron and slag (gangue content) are mixedAssorted, but it is the reducting pellet that can easily be separated into the state of reduced iron and slag, and this reducting pellet is through pulverizing, magnetic separation etc.Processing can be separated into reduced iron and slag. Below, be at length illustrated for the present invention.
While manufacturing in the present invention the mixture of reduced iron and slag, importantly comprise successively following operation: to containingThe material of iron oxide etc. with in carbon material further blending fusing point conditioning agent and the raw mixture that obtains become piece operation (withUnder, be called into piece operation); Mode with a part of melting of the agglomerate that obtained heats, and reduces to comprise in this agglomerateThe operation (following, to be called heating process) of iron oxide. This heating process, it is a part of melting of the agglomerate to be obtainedTemperature above and heat described agglomerate lower than the temperature of melting completely again, reduce contained iron oxide in this agglomerate.
(becoming piece operation)
In one-tenth piece operation of the present invention, at the material that contains iron oxide and titanium oxide (containing the material of iron oxide etc.) and carbonIn material, further concoct fusing point conditioning agent, use as raw mixture using gained material. Above-mentioned fusing point conditioning agent, the meaning isExcept material (for example, carbon etc.) that the fusing point of iron is exerted an influence in addition, to the composition (spy beyond the iron oxide comprising in agglomerateNot gangue) the material that exerts an influence of fusing point. That is, by concocting fusing point conditioning agent as above-mentioned raw materials mixture, thus rightThe fusing point of the composition (particularly gangue) beyond the iron oxide comprising in agglomerate exerts an influence, for example, can make under its fusing pointFall. Thus, the melting of gangue is promoted, and forms molten slag. At this moment a part for iron oxide melts in molten slag, moltenIn melting slag, be reduced and become metallic iron. The metallic iron generating in molten slag, by with the state of solid under be reducedMetallic iron contact, as the reduced iron generation aggegation of solid. So in the present invention, can obtain the mixed of reduced iron and slagCompound.
As above-mentioned fusing point conditioning agent, preferably use at least contains the fusing point conditioning agent of CaO supply material. As above-mentionedCaO supplies with material, and for example, preferably blending is from CaO (quick lime), Ca (OH)2(calcium hydroxide), CaCO3(lime stone) and CaMg(CO3)2At least one that select in the group that (dolomite) forms.
As above-mentioned fusing point conditioning agent, can only use above-mentioned CaO to supply with material, and except above-mentioned CaO supply with material itFor example, can also use MgO to supply with material, Al outward,2O3Supply with material, SiO2Supply with material etc. MgO, Al2O3And SiO2Also withAbove-mentioned CaO is same, is the material that the fusing point of the composition (particularly gangue) beyond iron oxide to comprising in agglomerate exerts an influence.
Supply with material as above-mentioned MgO, for example, preferably blending is from MgO powder, by what extract natural crystal and seawater etc.Containing Mg material, MgCO3At least one that select in the group who forms. As above-mentioned Al2O3Supply with material, for example, preferably blendingAl2O3Powder, alumina, boehmite, gibbsite, diaspore etc. As above-mentioned SiO2Supply with material, for example, can use SiO2Powder and silica sand etc.
In the present invention, preferably adjust the CaO concocting in above-mentioned agglomerate and supply with amount of substance, according to making according to above-mentioned agglomerateIn CaO amount (quality %) and SiO2Basicity (the CaO/SiO of the slag that amount (quality %) is tried to achieve2) be 0.2～0.9 scope andAdjust. By the basicity of above-mentioned slag is controlled to this scope, can make gangue contained in above-mentioned agglomerate (particularlyCaO-SiO2-Al2O3-MgO-TiO2Five yuan is oxide) melting point depression. Therefore under lower temperature, also can make gangue melting,Can increase the melting amount in agglomerate. The basicity of above-mentioned slag, more preferably more than 0.3, more preferably more than 0.35. SeparatelyOutward, the basicity of above-mentioned slag, more preferably below 0.8, more preferably below 0.7.
The above-mentioned material containing iron oxide etc. is the material that contains iron oxide and titanium oxide. As the material containing iron oxide etc.,For example, can use iron ore (for example, titanomagnetite ore etc.), iron ore, ironmaking dust, non-iron refining residues, ironmaking uselessGurry etc. As the above-mentioned material containing iron oxide etc., for example, can use the iron ore of the Fe that contains 40～60 quality %. SeparatelyAs the above-mentioned material containing iron oxide etc., for example, can use the TiO that contains 7～20 quality % outward,2Iron ore.
In the present invention, become piece by containing containing material, carbon material and the raw mixture of fusing point conditioning agent of iron oxide etc. andManufacture agglomerate. Then heat this agglomerate, reach the semi-molten state of a part of melting of this agglomerate, can utilize thus in carbon materialAsh content and fusing point conditioning agent as flux, generate molten slag inner point of agglomerate, realize the aggegation of reduced iron, can be withShort time is manufactured reduced iron. , as the present invention heating containing the material of iron oxide etc. and the agglomerate of carbon material and fusing point conditioning agentTime, even if generate FeO-SiO in agglomerate2Be molten slag, the carbon comprising in the carbon material of FeO and neighborhood also can react,Manufacture rapidly reduced iron. Therefore in agglomerate, reduced iron and SiO2Deng gangue separate and generate, so even reduced iron with moltenSlag mixes, and by being pulverized, gangue also can be broken easily, and can be separated into reduced iron and slag. At this moment titanium oxideBe recovered as slag, therefore can separate with reduced iron easily. On the other hand, do not have for existing with reducibility gasIn having, join in the method for above-mentioned (1) that the pelletizing of carbon material reduces, concocted fusing point conditioning agent in above-mentioned agglomerate after, because ofFor not being heated to semi-molten state, so the reduced iron comprising in the above-mentioned material containing iron oxide etc. is tired with separating of titanium oxideDifficult. Therefore, the above-mentioned material containing iron oxide etc., cannot serve as commercial iron ore and use, but according to the present invention, can be by like thisThe material containing iron oxide etc. use as source of iron.
,, as the method for above-mentioned (1), by the shaft furnace of about 1000 DEG C, utilize reducing gas reduction to containThe method of burning till pelletizing of iron ore, also can manufacture reduced iron, but in the method, if to exceed the high temperature of 1200 DEG C by alsoRaw-gas is reduced, mutually bonding and become bulk between the pelletizing being reduced, and cannot decline, or discharge tired in shaftDifficult. Therefore heating-up temperature need to 1200 DEG C with under heat. If but heat below at 1200 DEG C, even if prolongThe long heat time, the aggegationization of reduced iron is also insufficient, therefore the pulverizing separation difficulty of reduced iron and gangue.
As carbon material used in the present invention, for example, can use Coal and coke etc. As long as containing, carbon material can reduceState the fixed carbon of the amount of the iron oxide comprising in agglomerate. The fixed carbon amount that above-mentioned carbon material is contained, specifically, with respect to energyEnough reduce the fixed carbon amount of the iron oxide comprising in above-mentioned agglomerate, in ± 5% scope.
In above-mentioned agglomerate, as the composition beyond material, carbon material and fusing point conditioning agent containing iron oxide etc., can also concoctAdhesive etc. As adhesive, for example, can use polysaccharide (for example, starch of cornstarch and wheat flour etc. etc.) etc.
Above-mentioned material, carbon material and fusing point conditioning agent containing iron oxide etc. are preferably pulverized in advance before mixing. Specifically,The above-mentioned material containing iron oxide etc., for example recommending to be crushed in advance average grain diameter is 10～60 μ m; Above-mentioned carbon material, for example, recommend pre-First being crushed to average grain diameter is 10～60 μ m; Above-mentioned fusing point conditioning agent, for example recommending to be crushed in advance average grain diameter is 5～90 μm。
The method of pulverizing the above-mentioned material containing iron oxide etc. etc. is not particularly limited, and can adopt known method, for example, makesWith vibrating mill, rolls and ball mill etc.
As the mixer that mixes above-mentioned raw materials mixture, for example, can use rotary container shape mixer and fixed containerShape mixer. As above-mentioned rotary container shape mixer, for example, can use the mixed of rotational circle tubular, dual cone shape, V-arrangement etc.Close machine. As above-mentioned fixed container shape mixer, for example, can use and in mixing channel, be provided with rotating vane (for example ploughing sheet etc.)Mixer.
As making above-mentioned raw materials mixture become the one-tenth piece machine of piece, for example can use granulating disc (dish type comminutor),Rotary drum shape comminutor (cylindrical shape comminutor) and two roll shape briquetting forming machines etc.
The shape of above-mentioned agglomerate is not particularly limited, and for example block, granular, brick-shaped, pelletizing shape, bar-shaped etc. are excellentElect pelletizing shape and brick-shaped as.
(heating process)
In heating process of the present invention, importantly, so that a part for the agglomerate obtaining in above-mentioned one-tenth piece operationThe mode of melting heats, and reduces the iron oxide comprising in this agglomerate. That is, importantly, in the temperature of a part of melting of agglomerateAbove and to heat above-mentioned agglomerate lower than the temperature of melting completely. Specifically, supply with above-mentioned agglomerate to heating furnace, for example,The temperature field heating of 1200～1500 DEG C, manufacture reduced iron with contained iron oxide in carbon material reduction agglomerate. This temperatureIn degree territory, although some composition melting in agglomerate, fused solution oozes out few, is the shape that keeps agglomerate, and agglomerate can notIntegrally fused temperature. By in the heating of this temperature field, can obtain slag that reduced iron and gangue cause etc. and mix in insideReducting pellet.
In the present invention, the heating of above-mentioned agglomerate, preferably carries out with following temperature, that is, and and contained CaO-in this agglomerateSiO2-Al2O3-MgO-TiO2Five yuan is the melting amount (melting liquid measure) of oxide, and reaching these five yuan is 55 matter of oxide amountTemperature more than amount % is added the temperature of 100 DEG C. , the one-tenth of above-mentioned agglomerate is grouped into while decision, tries to achieve this by calculatingContained CaO-SiO in agglomerate2-Al2O3-MgO-TiO2Five yuan is that to reach these five yuan be oxide amount for the melting amount of oxideTemperature t more than 55 quality %, to add that in this temperature t the temperature more than temperature (t+100 DEG C) of 100 DEG C carries out above-mentioned groupThe heating of piece. By heating with t+100 DEG C of above temperature, can make the abundant melting of gangue contained in agglomerate,The gangue aggegation of melting, is promoted with separating of reduced iron. Therefore the reduced iron that obtained and the mixture of slag, reduced ironGood with the separation property of slag.
Above-mentioned five yuan is the melting amount of oxide, can use thermodynamic data library software to calculate. Use in the present inventionFactSage6.2 (ThermfactandGTT-Technologies system) and thermodynamic data storehouse FAST53, FToxid.
As above-mentioned heating furnace, use known stove, for example, use moving hearth formula heating furnace. What is called is movedMoving siege formula heating furnace, is exactly the heating furnace that siege moves as ribbon conveyer in stove, specifically, can illustrate and revolveConverter pool furnace. About revolving burner pool furnace, so that the Origin And Destination of siege is in identical position mode, by the outward appearance shape of siegeShape is designed to circle (circular), heated reduction during being supplied to agglomerate on siege and turning around in stove and generate reductionIron. Therefore, in revolving burner pool furnace, be provided with agglomerate is supplied to the charge mechanism in stove at the upstream side of direction of rotation,The downstream of direction of rotation (because be rotary configured, so in fact the positive upstream side in charge mechanism) is provided with discharge machineStructure.
As the present invention, in the reducting pellet obtaining with semi-molten state heating agglomerate in stove, comprising average grain diameter is 1The reduced iron particle of μ m～3mm degree. On the other hand, as the method for above-mentioned (2) and (3), in stove, make the complete melting of agglomerate andThe average grain diameter of the granulated metal iron obtaining is more than 8mm left and right.
The reducting pellet (mixture of reduced iron and slag) obtaining in above-mentioned heating process, be crushed to diameter 8mm withUnder after (containing 0mm), obtained crushed material is carried out to magnetic separation and separates. By reducting pellet is crushed to diameter 8mm withAfter lower, carry out magnetic separation separation, want to reclaim reduced iron as magnetization owner, want to reclaim slag as unmagnetized owner.And according to the present invention, as this slag because can reclaim above-mentioned titanium oxide, so can carry out reduced iron and titanium oxideSeparation. But if the size while pulverizing reducting pellet exceedes diameter 8mm,, in the time that magnetic separation separates, slag can be blended into magnetizationThing side, or reduced iron is blended into unmagnetized thing side, the separation property variation of reduced iron and slag. While therefore, pulverizing reducting pelletSize, is preferably below diameter 8mm.
As pulverizing the method for above-mentioned reducting pellet, can adopt known method, for example, use vibrating mill, roller brokenMachine, ball mill, roller mill etc. As the method for carrying out magnetic separation separation for above-mentioned crushed material, can adopt known method.
According to the present invention, the contained SiO of magnetization thing2Amount is below 8 quality %, the TiO that unmagnetized thing is contained2Amount is 40 matterMore than amount %.
(optimal way)
In the present invention, in above-mentioned heating process, establish the maximum temperature of heating when above-mentioned agglomerate and be T (DEG C) time, preferablyMake the melting amount that deducts gangue contained in this agglomerate the temperature of 100 DEG C from this temperature T reach 55 matter of this gangue amountMore than amount %, so adjust the blending amount of above-mentioned fusing point conditioning agent. ,, when the heating-up temperature T of above-mentioned agglomerate determines, preferably make to addThe many modes of melting quantitative change when heat, are used fusing point conditioning agent in advance the fusing point of composition contained in agglomerate to be adjusted. Then,Heating when agglomerate, makes the 55 quality % positively melting above of gangue contained in this agglomerate, so the highest when from heatingThe melting amount that temperature T deducts the gangue at the temperature of 100 DEG C is benchmark, concocts above-mentioned fusing point conditioning agent and carries out the composition of agglomerateAdjust.
The above-mentioned melting amount of above-mentioned gangue, among the contained gangue of above-mentioned agglomerate, especially based on CaO, SiO2、Al2O3, MgO and TiO2Fifty percent point amount determine.
The Japan patent application of the application based on application on May 30th, 2012 advocated priority No. 2012-123745Interests. The full content of the description that No. 2012-123745th, this Japan's patent application, in this application for reference alsoQuote.
Below, enumerate embodiment and be described more specifically the present invention, but the present invention is not limited by following embodiment certainly, at energyEnough meet in the scope of the forward and backward aim of stating and can certainly suitably be changed enforcement, these are all included in skill of the present inventionIn the scope of art.
[embodiment]
(experimental example 1)
Become piece by containing iron ore, carbon material and the raw mixture of fusing point conditioning agent that the one-tenth shown in following table 1 is grouped into,With the agglomerate that heating by electric cooker was obtained, manufacture the mixture (reducting pellet) of reduced iron and slag. In following table 1, T.Fe meaningThink of is total iron amount.
As above-mentioned carbon material, with respect to as the contained iron oxide of above-mentioned iron ore and the molal quantity of the oxygen amount of combination, adjustClose the carbon material of the have ± fixed carbon of 2 % by mole (, with respect to reducing the fixed carbon of the contained iron oxide of above-mentioned agglomerateAmount, the contained fixed carbon amount of carbon material is ± 2 quality %). Blending lime stone (CaCO3) and silica as above-mentioned fusing point conditioning agent.
In the raw mixture that contains iron ore, carbon material and fusing point conditioning agent that the one-tenth shown in following table 1 is grouped into, thenMixed adhesive, is a granulated into piece and is manufactured the agglomerate of φ 19mm by rotation. Blending wheat flour is as above-mentioned adhesive.
In following table 2, show that the one-tenth of dried agglomerate is grouped into. Agglomerate a shown in following table 2 is by adjustingBasicity (the CaO/SiO of this agglomerate2), when while making to heat, iron oxide is reduced, the fusing point of the slag of by-product reaches minimum and has adjustedThe example that becomes to be grouped into. Agglomerate b shown in following table 2 is the CaO-SiO that makes this agglomerate contained2-Al2O3-MgO-TiO2Five yuanThe fusing point that is oxide reaches minimum and has carried out the example that composition is adjusted.
Further, in following table 2, T.C represents total carbon, CaO/SiO2Represent basicity. In addition, CaO+SiO2+Al2O3+The MgO meaning is gangue amount. In addition, [TiO2/(CaO+SiO2+Al2O3+MgO+TiO2)] × 100, the meaning is the oxygen in slag compositionChange titanium (TiO2) concentration.
Then, pack the agglomerate obtaining into electric furnace, heat 18 minutes and reduce contained iron oxide in agglomerate. In electric furnaceHeating-up temperature T is made as 1300 DEG C, 1350 DEG C or 1400 DEG C, and the atmosphere in electric furnace is adjusted into N2Gas atmosphere. In the reduction of iron oxideTime, by-product goes out slag, and can obtain the mixture (reducting pellet) of reduced iron and slag.
Molten condition during with each heating-up temperature T heating is presented at following table 3. In following table 3, so-called " without melting ",The meaning is the state that does not generate fused solution in agglomerate, so-called " having melting ", and the meaning is the shape that fused solution has occurred in agglomerateState, represents a part of melting of agglomerate.
Pulverize the reducting pellet being obtained with vibrating mill, make it diameter reach 3mm following after, use magnet, magnetic separation dividesFrom becoming magnetization thing and unmagnetized thing. During magnetic separation separates, use 2000 Gausses' magnet, by the magnetic force of test portion position from 200 GaussesAdjust to 500 Gausses, remagnetization operation and carry out magnetic separation separation. Separate the magnetization thing that obtains and unmagnetized thing by magnetic separationBecome to be grouped into and be presented in following table 3. Further, M.Fe represents metallic iron amount.
In addition, in following table 3, show and separate by magnetic separation the magnetization thing and unmagnetized thing ratio, the metal separately that obtainRate (MetFe), CaO+SiO2+Al2O3The total amount of+MgO, the Ti rate of recovery. Degree of metalization (MetFe) is calculated by following formula.
MetFe (%)=[metallic iron amount (M.Fe)]/[Quan Tieliang (T.Fe)] × 100
As the Ti rate of recovery of magnetization thing, and as the Ti rate of recovery of unmagnetized thing, calculated by following formula.
As the Ti rate of recovery (%)=(the contained Ti amount of Ti amount/agglomerate that magnetization thing is contained) × 100 of magnetization thing
As the Ti rate of recovery (%)=(the contained Ti amount of Ti amount/agglomerate that unmagnetized thing is contained) × 100 of unmagnetized thing
Based on following table 3, can investigate as follows. No.3 shown in following table 3,5, the 6th, make it-part of heating agglomerateThe example of melting, can be separated into the crushed material magnetic separation of reducting pellet magnetization thing and unmagnetized thing. On the other hand, No.1,2,4Be the example of the state heating not generate fused solution in agglomerate, can not carry out magnetic separation separation. In addition, from following table 3, makeHeating-up temperature T is higher, as unmagnetized thing and the Ti of separated recovery amount is more.
[table 1]
[table 2]
[table 3]
(experimental example 2)
In experimental example 2, contained CaO-SiO in investigation agglomerate2-Al2O3-MgO-TiO2Five yuan is the melting of oxideThe heating-up temperature T of amount and electric furnace, the impact that the result that magnetic separation is separated causes.
In the raw mixture that contains iron ore, carbon material and fusing point conditioning agent using in above-mentioned experimental example 1, then mixAdhesive, and add CaO, SiO2, same with above-mentioned experimental example 1, be a granulated into piece by rotation, manufacture the gangue amount of φ 19mmDifferent agglomerate c, d. As above-mentioned carbon material, with respect to as the contained iron oxide of above-mentioned iron ore and the oxygen amount of combination moleNumber, the carbon material of the have ± fixed carbon of 2 % by mole of blending is (, with respect to reducing the consolidating of the contained iron oxide of above-mentioned agglomerateDetermine carbon amount, the contained fixed carbon amount of carbon material is ± 2 quality %). As above-mentioned fusing point conditioning agent, same with above-mentioned experimental example 1, adjustClose lime stone (CaCO3) and silica. As above-mentioned adhesive, same with above-mentioned experimental example 1, blending wheat flour.
Based on dried agglomerate contained CaO amount and SiO2Amount, calculates basicity (CaO/SiO2) and be presented at following table 4In.
In addition, the CaO based on contained in dried agglomerate, SiO2、Al2O3、MgO、TiO2Amount, uses thermodynamic dataLibrary software " FactSage ", calculates contained CaO-SiO in agglomerate2-Al2O3-MgO-TiO2Five yuan is the melt temperature of oxideL.T, is presented in following table 4 in the lump.
In addition the CaO based on contained in dried agglomerate, SiO,2、Al2O3、MgO、TiO2Amount, uses above-mentioned" FactSage ", calculates melting amount (fused solution growing amount) and reaches the temperature [LT55 (DEG C)] of 55 quality %, and its result is aobvious in the lumpBe shown in following table 4.
Then, pack obtained agglomerate into electric furnace, heat 18 minutes, contained iron oxide in reduction agglomerate, also manufacturesThe mixture (reducting pellet) of former iron and slag. Heating-up temperature T in electric furnace is 1300 DEG C, 1350 DEG C or 1400 DEG C. In electric furnaceAtmosphere be N2Gas atmosphere (N2Gas 100 volume %).
In addition, calculating deducts CaO-SiO from the heating-up temperature T in electric furnace2-Al2O3-MgO-TiO2Five yuan is oxideThe value (T-L.T) of melt temperature L.T, is presented at following table 4 in the lump. When T-L.T is negative value, mean with lower than CaO-SiO2-Al2O3-MgO-TiO2Five yuan is the temperature heating of the melt temperature L.T of oxide.
In addition, use above-mentioned " FactSage ", calculate from the temperature (T-100 DEG C) of 100 DEG C of heating-up temperature T declinesCaO-SiO2-Al2O3-MgO-TiO2Five yuan is the melting amount of oxide. Result is presented in following table 4 in the lump. Further, followingIn table 4, as with reference to value, calculate the CaO-SiO from the temperature (T-50 DEG C) of 50 DEG C of heating-up temperature T declines2-Al2O3-MgO-TiO2Five yuan is the melting amount of oxide, and its result also shows in the lump.
Next, same with above-mentioned experimental example 1, with ball mill and vibrating mill, obtained reducting pellet is pulverized, makeDiameter reach 3mm following after, use magnet to carry out magnetic separation separation. In following table 4, show and separate by magnetic separation the unmagnetized obtainingThe ratio (unmagnetized rate) of thing.
[table 4]
Then, represent the relation of heating-up temperature T and unmagnetized rate at Fig. 1. In Fig. 1, ◆ represent the result of No.7～9,Represents the result of No.10～12.
From above-mentioned table 4 and Fig. 1, reach the temperature of 55 quality % by being heated to melting amount (fused solution growing amount)More than [LT55 (DEG C)] adds the temperature (that is, being 1400 DEG C in No.7～9, is 1350 DEG C in No.10～12) of 100 DEG C, reductionIron starts to separate with slag, and unmagnetized rate uprises (No.9,11,12).
Secondly, in Fig. 2, represent the CaO-SiO from the temperature (T-100 DEG C) of 100 DEG C of heating-up temperature T declines2-Al2O3-MgO-TiO2Five yuan be the melting amount of oxide, with the relation of unmagnetized rate. In Fig. 2, the result of No.7～9 by ◆ represent,The result of No.10～12 is represented by.
From above-mentioned table 4 and Fig. 2, if more than melting amount (fused solution growing amount) reaches 55 quality %, metallic iron withSlag starts to separate, the rising of heat tracing temperature T, and unmagnetized rate uprises.
As more than, according to the present invention, by heating agglomerate make one partial melting, the separation property of reduced iron and slag is carriedHeight, can separate expeditiously and reclaim reduced iron and titanium oxide. In addition, according to the present invention, can reclaim expeditiously reduced iron.

Claims (13)

1. a manufacture method for the mixture of reduced iron and slag, is characterized in that, comprises successively following operation:
In the material that contains iron oxide and titanium oxide and carbon material, further concoct fusing point conditioning agent, by the raw material obtaining thusMixture becomes the operation of piece; And
So that the mode of a part of melting of the agglomerate obtaining heats, reduce the work of contained iron oxide in this agglomerateOrder,
Wherein, adjust the blending amount of described fusing point conditioning agent, make the maximum temperature when heating described agglomerate deduct the temperature of 100 DEG CIn this agglomerate under degree, the melting amount of contained gangue is more than 55 quality %.
2. a manufacture method for the mixture of reduced iron and slag, is characterized in that, comprises successively following operation:
In the material that contains iron oxide and titanium oxide and carbon material, further concoct fusing point conditioning agent, by the raw material obtaining thusMixture becomes the operation of piece; And
More than the temperature of a part of melting of obtained agglomerate and lower than the temperature of melting completely, heat described agglomerate, byThis reduces the operation of contained iron oxide in this agglomerate,
Wherein, adjust the blending amount of described fusing point conditioning agent, make the maximum temperature when heating described agglomerate deduct the temperature of 100 DEG CIn this agglomerate under degree, the melting amount of contained gangue is more than 55 quality %.
3. manufacture method according to claim 1 and 2, wherein, described fusing point conditioning agent at least contains CaO supplies with material,And according to CaO amount and SiO by this agglomerate2The basicity of the slag that amount is tried to achieve is CaO/SiO2Be that 0.2～0.9 mode is adjustedThe CaO concocting in described agglomerate supplies with amount of substance.
4. manufacture method according to claim 3, wherein, supplies with material as described CaO, and blending is from CaO, Ca (OH)2WithCaCO3At least one that select in the group who forms.
5. manufacture method according to claim 1, wherein, the described melting amount of described gangue, based on institute in described agglomerateThe CaO, the SiO that contain2、Al2O3, MgO and TiO2The amount of these five kinds of compositions decides.
6. manufacture method according to claim 1 and 2, wherein, the heating of described agglomerate is carried out at following temperature, described inTemperature is the CaO-SiO contained with this agglomerate2－Al2O3－MgO－TiO2Five yuan is that the melting amount of oxide reaches these five yuanBe that more than 55 quality % of oxide amount temperature adds 100 DEG C.
7. manufacture method according to claim 1 and 2, wherein, is used the iron ore masonry of the Fe that contains 40～60 quality %For containing the material of described iron oxide and titanium oxide.
8. manufacture method according to claim 1 and 2, wherein, is used the TiO that contains 7～20 quality %2Iron ore masonryFor containing the material of described iron oxide and titanium oxide.
9. manufacture method according to claim 1 and 2, wherein, according to make the contained fixed carbon amount of described carbon material with respect toThe fixed carbon amount of the contained iron oxide of described agglomerate of can reducing is concocted described carbon material for the mode of ± 5 quality %.
10. manufacture method according to claim 1 and 2, wherein, the heating of described agglomerate is carried out at 1200～1500 DEG C.
The separation method of 11. 1 kinds of reduced irons and slag, is characterized in that, comprises successively following operation:
By the mixture of the reduced iron being obtained by the manufacture method described in claim 1 or 2 and slag to be crushed to diameter be 8mm withLower but not containing the operation of 0mm; And
Carry out the operation of magnetic separation separation for obtained crushed material.
12. 1 kinds of unmagnetized things, is characterized in that, are the unmagnetized things by the separation method screening described in claim 11, shouldUnmagnetized thing contains TiO more than 40 quality %2。
13. 1 kinds of magnetization things, is characterized in that, are by the magnetization thing of the separation method screening described in claim 11, contain 8 matterAmount % is following but not containing the SiO of 0 quality %2。
CN201380027484.2A 2012-05-30 2013-05-21 The manufacture method of the mixture of reduced iron and slag Expired - Fee Related CN104334749B (en)

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