CN104334749A - Method for manufacturing mixture of reduce iron and slag - Google Patents
Method for manufacturing mixture of reduce iron and slag Download PDFInfo
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- CN104334749A CN104334749A CN201380027484.2A CN201380027484A CN104334749A CN 104334749 A CN104334749 A CN 104334749A CN 201380027484 A CN201380027484 A CN 201380027484A CN 104334749 A CN104334749 A CN 104334749A
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- agglomerate
- slag
- cao
- melting
- manufacture method
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Classifications
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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
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- 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
Abstract
A technique for enhancing the separability of reduced ion and slag in a mixture of reduced iron and slag obtained in a semi-molten state in which the entire agglomerate is not completely melted. A method for manufacturing a mixture of reduced iron and slag, comprising, in the following order: a step for agglomerating a substance containing iron oxide and titanium oxide, and a raw material mixture in which a melting point regulator has been furthermore added to a carbon material; and a step for heating the resulting agglomerate so as to melt a portion of the resulting agglomerate to reduce the iron oxide contained in the agglomerate.
Description
Technical field
The present invention relates to heat packs manufactures the mixture of reduced iron and slag method containing containing ferric oxide and the material of titanium oxide and the agglomerate of carbon material.
Background technology
As the iron smelting method manufacturing reduced iron containing iron oxide material by iron ore etc., there will be a known the method for following (1) ~ (3).
(1) will be that the pelletizing that burns till that main raw material sinters is heated to about 1000 DEG C in shaft furnace with iron ore, by the method for ferric oxide contained in reducing gas reductive firing pelletizing.
(2) become the agglomerate of block to be supplied to moving hearth stove (converter) with carbon material (solid reduction material) compound iron ore, with about 1300 DEG C of heating, reduce the method for ferric oxide contained in this agglomerate.
(3) become the agglomerate of block to be supplied to moving hearth stove with carbon material compound iron ore, be heated to about 1450 DEG C and make reduced iron melting, the capillary difference etc. of the slag at this moment utilizing metallic iron and by-product to go out, be separated into the method for reduced iron and slag.
About the manufacture method of such reduced iron, such as, there will be a known the technology of patent documentation 1 ~ 4.
About the method for above-mentioned (1), such as, there will be a known the technology of patent documentation 1.Describe in patent documentation 1, direct-reduction pulverizes iron ore, after being separated by iron, then both pulverizing, therefrom reclaims iron respectively with gangue.Describe as reducing gas, CO gas and H can be used
2gas, Heating temperature is 700 ~ 1200 DEG C, and pulverize and can use the crushing rolls etc. that metallic iron can be flattened slabbing, iron is the separation utilizing 20 mesh sieve (mesh 0.83mm) to carry out be separated to be combined with magnetic separation to carry out with being separated of gangue.
About the method for above-mentioned (2), such as, there will be a known the technology of patent documentation 2.In patent documentation 2, be the mixture containing iron material and coal is carried out heat reduction process under high-temperature atmosphere, the reduced iron that pulverization process obtains, then, with the particle diameter specified for boundary carries out size classification.Specifically, be separated/be classified into size classification machine particle and the particle of median size below 100 μm that median size is greater than 100 μm.Then, utilize magnetic force, by the reduced iron particle of median size less than 100 μm, be separated into a large amount of hard magnetization thing particle of dividing containing iron and iron divides few weakly magnetization thing particle, use through the reduced iron particle exceeding afore mentioned rules particle diameter of size classification and above-mentioned hard magnetization thing particle as reduced iron.On the other hand, in weakly magnetization thing particle, because iron divides few, in a large number containing slag composition, so directly as cement and pitch recycling.Therefore in above-mentioned patent documentation 2, being separated slag about dividing from iron in few weakly magnetization thing particle, reclaiming iron and divide and do not give consideration completely as the problem that source of iron utilizes.
About the method for above-mentioned (3), such as, there will be a known the technology of patent documentation 3,4.
Wherein in patent documentation 3, describe a kind of method being manufactured higher-grade reduced iron by ironmaking dust, it is by manufacturing the carbonaceous pelletizing be made up of multiple dust and carbon material, it is used to the calcining furnace of rotary oven bed, reduction treatment is carried out with the temperature of 1250 ~ 1350 DEG C, thus, the dust of pelletizing inside is reduced by carbon material, move and the metal iron particles of aggegation by intragranular material, from the slag part of the low melting point containing FeO that the gangue by dust generates, utilize the effect of natural separation and extract metal iron particles, producing higher-grade granular reduced iron.
Describe in patent documentation 4 and have a kind of method, it manufactures the carbonaceous pelletizing be made up of iron ore and carbon material, used the calcining furnace of rotary oven bed, after reducing with the temperature of 1250 ~ 1350 DEG C, make in-furnace temperature rise to 1400 ~ 1500 DEG C again and make it melting, make metallic iron aggegation, thus obtain highly purified granulated metal iron.
, in above-mentioned iron ore, except ferric oxide, the useful nonferrous metal oxides also containing titanium oxide etc.Describing in patent documentation 5 has a kind of titanium oxide to contain the manufacture method of slag, it is by the raw mixture containing titanium oxide, ferric oxide, carbonaceous reducing agent, heat in rotary oven pool furnace, reduced iron is obtained after the ferric oxide reduced in this mixture, then again it heated and make this reduced iron melting, make it to be separated from containing titanium oxide slag, by obtained being discharged to containing titanium oxide slag, stove is outer also to be reclaimed.
But in above-mentioned patent documentation 3 ~ 5, by making the complete melting of reduced iron, be separated with the slag of by-product by reduced iron thus, the raising separatory of the reduced iron obtained under the state not having complete melting about agglomerate and the mixture of slag does not then give consideration completely.
Prior art document
Patent documentation
Patent documentation 1: No. 6048382nd, U.S. Patent bulletin
Patent documentation 2: Japanese Unexamined Patent Publication 2002-363624 publication
Patent documentation 3: Japanese Unexamined Patent Publication 10-147806 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2009-91664 publication
Patent documentation 5: Japanese Patent No. 4153281 publication
Summary of the invention
The present invention is conceived to above-mentioned such situation and completes, and its object is to, and in the reduced iron obtained and the mixture of slag, can improve the technology separatory of reduced iron and slag under providing a kind of semi-melting state not having complete melting at agglomerate.In addition, another object of the present invention is to, providing a kind of by reclaiming titanium oxide as slag, thus can by the method being used in metal titanium raw material containing titanium oxide slag high for titanium oxide concentration.
The manufacture method of the reduced iron of the present invention of above-mentioned problem and the mixture of slag can be solved, there is main idea comprising successively in following operation this point: by the material containing ferric oxide and titanium oxide with concoct fusing point conditioning agent further in carbon material and the raw mixture that obtains carries out into the operation of block; Heat according to the mode of a part of melting making obtained agglomerate, reduce the operation of ferric oxide contained in this agglomerate.
In addition, above-mentioned problem by comprise successively following operation this point has main idea, reduced iron also can reach with the manufacture method of the mixture of slag: concoct fusing point conditioning agent and the raw mixture that obtains carries out into the operation of block by the material containing ferric oxide and titanium oxide with further in carbon material; More than the temperature of the part generation melting of obtained agglomerate, lower than the temperature of complete melting, heat described agglomerate, reduce the operation of ferric oxide contained in this agglomerate thus.
In the present invention, described fusing point conditioning agent at least supplies material containing CaO, supplies amount of substance about the CaO be blended in described agglomerate, preferably measures by the CaO in this agglomerate and SiO
2measure the basicity (CaO/SiO of the slag of trying to achieve
2) control 0.2 ~ 0.9 scope.Supply material as described CaO, such as, preferably blending is from CaO, Ca (OH)
2and CaCO
3select in the group formed at least one.
In the present invention, the preferably blending amount of the described fusing point conditioning agent of adjustment, the melting amount of gangue contained in this agglomerate under making top temperature during the described agglomerate of heating deduct the temperature of 100 DEG C is more than 55 quality %.The described melting amount of described gangue, based on CaO, SiO of comprising in described agglomerate
2, Al
2o
3, MgO and TiO
2the amount of these five kinds of compositions determines.The heating of described agglomerate, the CaO-SiO preferably contained by this agglomerate
2-Al
2o
3-MgO-TiO
2five yuan is the melting amount of oxide compound, and reaching these five yuan is carry out under the temperature of more than the 55 quality % of oxide amount adds the temperature of 100 DEG C.
As the material containing described ferric oxide and titanium oxide, such as, preferably use the iron ore of the Fe containing 40 ~ 60 quality %, also preferably use the TiO containing 7 ~ 20 quality %
2iron ore.Fixing carbon amounts contained in described carbon material, preferably make it relative to can reduce the ferric oxide comprised in described agglomerate fixing carbon amounts and be ± 5 quality %, so described carbon material of blending.The heating of described agglomerate, such as, 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: the operation mixture of the reduced iron obtained according to above-mentioned manufacture method and slag being crushed to below diameter 8mm (not containing 0mm); Obtained crushed material is carried out to the operation of magnetic separation separation.
In addition, in the present invention, also comprise the non-magnetic compound and magnetization thing of screening with above-mentioned separation method, this non-magnetic compound, such as, TiO containing more than 40 quality %
2; This magnetization thing, such as SiO
2be suppressed in below 8 quality % (not containing 0 quality %).
The effect of invention
According to the present invention, fusing point conditioning agent (material except having an impact to the fusing point of iron) is concocted further in material containing ferric oxide and titanium oxide and carbon material and the agglomerate that obtains by being produced on, heat this agglomerate, make one partial melting, and make it incomplete fusion, the mixture (hereinafter referred to as reducting pellet) mixed under can manufacturing the state that reduced iron is separated with slag thus.The mixture obtained, such as by pulverizing, magnetic separation and easily can be separated into reduced iron and slag, the purposes of expectation can be used in respectively.At this moment reduced iron is mainly split into magnetization thing side, and titanium oxide is split into non-magnetic compound side as slag, therefore according to the present invention, and can separating reducing iron and titanium oxide easily.That is, according to the present invention, except reduced iron, as useful nonferrous metal oxides, the Separation and Recovery of titanium oxide can also be carried out.
In addition, also known in the present invention, (a), on the basis considering Heating temperature, makes the melting amount of the gangue contained by agglomerate reach more than specified amount and adjust the blending amount of fusing point conditioning agent, or (b) is considering the CaO-SiO contained by agglomerate
2-Al
2o
3-MgO-TiO
2five yuan be the melting amount of oxide compound on basis, by the Heating temperature of selected agglomerate, even use be not always usually adopt, iron ore containing ferric oxide and titanium oxide, also can manufacture reduced iron.
Accompanying drawing explanation
Fig. 1 is the graph of the relation representing Heating temperature T and non-magnetic rate.
Fig. 2 represents the C reduced from Heating temperature T the temperature (T-100 DEG C) of 100 DEG C
ao-SiO
2-Al
2o
3-MgO-TiO
2five yuan is the melting amount of oxide compound, with the graph of the relation of non-magnetic rate.
Embodiment
The present inventors, by always (following by the material containing ferric oxide and titanium oxide used hardly, be called the material containing ferric oxide etc.) use as starting material, heat packs is containing this material containing ferric oxide etc. and the agglomerate of carbon material, make one partial melting, and make it all meltings, for the mixture of the reduced iron obtained thus and slag (gangue content), study with keen determination in order to the separation property improved when being separated into reduced iron and slag.It found that, containing in the material of ferric oxide etc. and the mixture of carbon material, if blending fusing point conditioning agent further, then can improve the separation property when reducting pellet that heating agglomerate obtains being separated into reduced iron and slag, thus complete the present invention.
In addition, the present inventors find, in order to separating reducing iron and slag more well, the means of following (a), (b) are effective.
When () Heating temperature T when heating agglomerate determines a, the melting amount deducting the gangue content contained by this agglomerate at the temperature of 100 DEG C according to top temperature when making this agglomerate of heating is the mode of more than 55 quality %, adjust the blending amount of above-mentioned fusing point conditioning agent (such as, CaO supplies material etc.).
When () Heating temperature T when heating agglomerate is not by decision b, with CaO-SiO contained in this agglomerate
2-Al
2o
3-MgO-TiO
2five yuan is the melting amount of oxide compound, reaches these the five yuan temperature being the temperature of more than the 55 quality % of oxide amount and adding 100 DEG C, heats above-mentioned agglomerate.
In addition, the present inventors are separated into reduced iron and slag about by said mixture, manufacture the reduced iron that the raw material as electric furnace refining etc. uses and also repeatedly study.It found that, by the agglomerate comprised containing the material of ferric oxide etc., carbon material and fusing point conditioning agent is carried out heat reduction under the state of partial melting, although reduced iron and slag (gangue content) mix, but it is the reducting pellet that easily can be separated into the state of reduced iron and slag, this reducting pellet can be separated into reduced iron and slag through the process of pulverizing, magnetic separation etc.Below, the present invention is illustrated in detail.
When manufacturing the mixture of reduced iron and slag in the present invention, importantly comprise following operation successively: blending fusing point conditioning agent and the raw mixture that obtains become the operation (hereinafter referred to as one-tenth block operation) of block further in containing material and the carbon material of ferric oxide etc.; Heat in the mode of a part of melting of obtained agglomerate, reduce the operation (hereinafter referred to as heating process) of the ferric oxide comprised in this agglomerate.This heating process, its carry out be with more than the temperature of a part of melting of obtained agglomerate and again lower than complete melting heating temperatures described in agglomerate, reduce ferric oxide contained in this agglomerate.
(becoming block operation)
In one-tenth block operation of the present invention, in the material (material containing ferric oxide etc.) containing ferric oxide and titanium oxide with carbon material, blending fusing point conditioning agent, uses using gained material as raw mixture further.Above-mentioned fusing point conditioning agent, is meant to beyond the material (such as, carbon etc.) except having an impact to the fusing point of iron, to the material that the fusing point of the composition (particularly gangue) beyond the ferric oxide comprised in agglomerate has an impact.That is, by concocting fusing point conditioning agent as above-mentioned raw materials mixture, thus the fusing point of the composition (particularly gangue) beyond the ferric oxide comprised in agglomerate is had an impact, such as, its fusing point can be made to decline.Thus, the melting of gangue is promoted, and forms molten slag.At this moment a part for ferric oxide melts in molten slag, is reduced and becomes metallic iron in molten slag.The metallic iron generated in molten slag, by contacting with the metallic iron be reduced under the state of solid, as the reduced iron generation aggegation of solid.So in the present invention, the mixture of reduced iron and slag can be obtained.
As above-mentioned fusing point conditioning agent, preferably use the fusing point conditioning agent at least supplying material containing CaO.Supply material as above-mentioned CaO, such as, preferably blending is from CaO (unslaked lime), Ca (OH)
2(slaked lime), CaCO
3(Wingdale) and CaMg (CO
3)
2select in the group that (rhombspar) is formed at least one.
As above-mentioned fusing point conditioning agent, above-mentioned CaO only can be used to supply material, and except above-mentioned CaO supplies material, such as, MgO can also be used to supply material, Al
2o
3supply material, SiO
2supply material etc.MgO, Al
2o
3and SiO
2also same with above-mentioned CaO, be to the ferric oxide comprised in agglomerate beyond the material that has an impact of the fusing point of composition (particularly gangue).
Supply material as above-mentioned MgO, such as, preferably blending contains Mg material, MgCO from MgO powder, by what extract natural crystal and seawater etc.
3select in the group formed at least one.As above-mentioned Al
2o
3supply material, such as, preferably concocts Al
2o
3powder, alumina, boehmite, gibbsite, diasporite etc.As above-mentioned SiO
2supply material, such as, can use SiO
2powder and silica sand etc.
In the present invention, the CaO preferably concocted in the above-mentioned agglomerate of adjustment supplies amount of substance, according to making to measure (quality %) and SiO according to the CaO in above-mentioned agglomerate
2basicity (the CaO/SiO of the slag that amount (quality %) is tried to achieve
2) be 0.2 ~ 0.9 scope adjust.By controlling in this scope by the basicity of above-mentioned slag, gangue (particularly CaO-SiO contained in above-mentioned agglomerate can be made
2-Al
2o
3-MgO-TiO
2five yuan is oxide compound) fusing point reduce.Therefore under comparatively low temperature, also can make gangue melting, the melting amount in agglomerate can be increased.The basicity of above-mentioned slag, is more preferably more than 0.3, and more preferably more than 0.35.In addition, the basicity of above-mentioned slag, is more preferably less than 0.8, and more preferably less than 0.7.
The above-mentioned material containing ferric oxide etc. is the material containing ferric oxide and titanium oxide.As the material containing ferric oxide etc., such as, iron ore (such as, titanomagnetite ore etc.), iron sand, ironmaking dust, non-ferric refining residues, ironmaking waste etc. can be used.As the above-mentioned material containing ferric oxide etc., such as, the iron ore of the Fe containing 40 ~ 60 quality % can be used.In addition, as the above-mentioned material containing ferric oxide etc., such as, the TiO containing 7 ~ 20 quality % can be used
2iron ore.
In the present invention, become block with the raw mixture of fusing point conditioning agent by containing containing the material of ferric oxide etc., carbon material and manufacture agglomerate.Then this agglomerate is heated, reach the semi-melting state of a part of melting of this agglomerate, ash content in carbon material and fusing point conditioning agent can be utilized thus as flux, generate molten slag in agglomerate inside point, realize the aggegation of reduced iron, reduced iron can be manufactured with the short period of time.That is, when heating the agglomerate containing the material of ferric oxide etc. and carbon material and fusing point conditioning agent as the present invention, even if generate FeO-SiO in agglomerate
2be molten slag, the carbon comprised in the carbon material of FeO and neighborhood also can react, and manufactures reduced iron rapidly.Therefore in agglomerate, reduced iron and SiO
2deng gangue be separated and generate, even if so reduced iron and slag mix, by being pulverized, gangue also can fragmentation easily, and can be separated into reduced iron and slag.At this moment titanium oxide is recovered as slag, therefore, it is possible to be separated with reduced iron easily.On the other hand, with reducing gas for existing do not have in join carbon material pelletizing carry out in the method for above-mentioned (1) of reducing, concocted fusing point conditioning agent in above-mentioned agglomerate after, because be not heated to semi-melting state, so the separation difficulty of the reduced iron comprised in the above-mentioned material containing ferric oxide etc. and titanium oxide.Therefore, the above-mentioned material containing ferric oxide etc., cannot use as the iron ore of commercialization, but according to the present invention, such material containing ferric oxide etc. can be used as source of iron.
Namely, as the method for above-mentioned (1), by in the shaft furnace of about 1000 DEG C, the method of burning till pelletizing utilizing reducing gas to reduce containing iron ore, also can manufacture reduced iron, but in the method, if to be reduced by reducing gas more than the high temperature of 1200 DEG C, mutually bond between the pelletizing be then reduced and become bulk, cannot decline in shaft, or discharging difficulty.Therefore Heating temperature needs to heat below 1200 DEG C.If but heat below 1200 DEG C, even if then extend heat-up 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, such as, Coal and coke etc. can be used.As long as carbon material is containing reducing the fixed carbon of amount of the ferric oxide comprised in above-mentioned agglomerate.Fixing carbon amounts contained by above-mentioned carbon material, specifically, relative to reducing the fixing carbon amounts of the ferric oxide comprised in above-mentioned agglomerate, in the scope of ± 5%.
In above-mentioned agglomerate, as the composition beyond material, carbon material and the fusing point conditioning agent containing ferric oxide etc., tackiness agent etc. can also be concocted.As tackiness agent, such as, can use polyose (such as, the starch etc. of W-Gum and wheat-flour etc.) etc.
Above-mentioned material, carbon material and fusing point conditioning agent containing ferric oxide etc., preferably pulverize before combination in advance.Specifically, the above-mentioned material containing ferric oxide etc., such as recommending to be crushed to median size is in advance 10 ~ 60 μm; Above-mentioned carbon material, such as recommending to be crushed to median size is in advance 10 ~ 60 μm; Above-mentioned fusing point conditioning agent, such as recommending to be crushed to median size is in advance 5 ~ 90 μm.
The method pulverizing the above-mentioned material containing ferric oxide etc. etc. is not particularly limited, and can adopt known method, such as, uses vibrating mill, crushing rolls and ball mill etc.
As the mixing machine of mixing above-mentioned raw materials mixture, such as, can use rotary container shape mixing machine and fixed container shape mixing machine.As above-mentioned rotary container shape mixing machine, such as, can use the mixing machine of rotational circle tubular, dual cone shape, V-arrangement etc.As above-mentioned fixed container shape mixing machine, such as, the mixing machine being provided with rotating paddle (such as blades etc.) can be used in tempering tank.
As the one-tenth block machine making above-mentioned raw materials mixture become block, such as, can use granulating disc (process type pelletizer), rotary drum shape tablets press (round shape tablets press) and two roll shape briquetting forming machines etc.
The shape of above-mentioned agglomerate is not particularly limited, such as block, granular, brick-shaped, pelletizing shape, bar-shaped etc., is preferably pelletizing shape and brick-shaped.
(heating process)
In heating process of the present invention, importantly, heat in the mode of a part of melting making the agglomerate obtained in above-mentioned one-tenth block operation, reduce the ferric oxide comprised in this agglomerate.That is, importantly, more than the temperature of a part of melting of agglomerate and with the above-mentioned agglomerate of heating temperatures lower than melting completely.Specifically, supply above-mentioned agglomerate to process furnace, such as, the temperature field heating of 1200 ~ 1500 DEG C, manufacture reduced iron with contained ferric oxide in carbon material reduction agglomerate.In this temperature field, although in agglomerate some components fuse, fused solution oozes out few, is the shape keeping agglomerate, the temperature that agglomerate can not be integrally fused.By heating at this temperature field, the reducting pellet that slag etc. that reduced iron and gangue cause mixes in inside can be obtained.
In the present invention, the heating of above-mentioned agglomerate, preferably carries out with following temperature, that is, contained in this agglomerate CaO-SiO
2-Al
2o
3-MgO-TiO
2five yuan is the melting amount (melting liquid measure) of oxide compound, reaches these the five yuan temperature being the temperature of more than the 55 quality % of oxide amount and adding 100 DEG C.That is, when the one-tenth of above-mentioned agglomerate is grouped into and determines, CaO-SiO contained in this agglomerate is tried to achieve by calculating
2-Al
2o
3-MgO-TiO
2five yuan is that the melting amount of oxide compound reaches the temperature t that these five yuan are more than the 55 quality % of oxide amount, carries out the heating of above-mentioned agglomerate with the temperature more than temperature (t+100 DEG C) adding 100 DEG C on this temperature t.By heating with the temperature of more than t+100 DEG C, can make the abundant melting of gangue contained in agglomerate, the gangue aggegation of melting, is promoted with being separated of reduced iron.Therefore obtained reduced iron and the mixture of slag, the separation property of reduced iron and slag is good.
Above-mentioned five yuan is the melting amount of oxide compound, and thermodynamic data library software can be used to calculate.Use Fact Sage 6.2 (Thermfact and GTT-Technologies system) and thermodynamic data storehouse FAST53, FToxid in the present invention.
As above-mentioned process furnace, use known stove, such as, use moving hearth formula process furnace.So-called moving hearth formula process furnace, is exactly the process furnace of siege movement in stove as endless belt conveyor, specifically, can illustrates rotary oven pool furnace.About rotary oven pool furnace, to make the Origin And Destination of siege be in identical position mode, the face shaping of siege is designed to circle (circular), during the agglomerate be supplied on siege turns around in stove, is generated reduced iron by heat reduction.Therefore, in rotary oven pool furnace, be provided with the charging mechanism be supplied to by agglomerate in stove in the side, most upstream of sense of rotation, be provided with output mechanism in the most downstream side (because be rotary configured, so be in fact in the positive upstream side of charging mechanism) of sense of rotation.
As the present invention, in the reducting pellet obtained with semi-melting state heating agglomerate in stove, comprise the reduced iron particle that median size is 1 μm ~ 3mm degree.On the other hand, as the method for above-mentioned (2) and (3), in stove, make the complete melting of agglomerate and the median size of the granulated metal iron obtained is more than about 8mm.
The reducting pellet (mixture of reduced iron and slag) obtained in above-mentioned heating process, after being crushed to below diameter 8mm (not containing 0mm), carrying out magnetic separation by obtained crushed material and is separated.After reducting pellet being crushed to below diameter 8mm, carrying out magnetic separation separation, wanting to reclaim reduced iron as magnetization owner, want to reclaim slag as unmagnetized owner.And according to the present invention, as this slag because above-mentioned titanium oxide can be reclaimed, so being separated of reduced iron and titanium oxide can be carried out.But if size when pulverizing reducting pellet exceedes diameter 8mm, then when magnetic separation is separated, slag can be mixed into magnetization thing side, or reduced iron is mixed into non-magnetic compound side, and the separation property of reduced iron and slag is deteriorated.Therefore, pulverize size during reducting pellet, be preferably below diameter 8mm.
As the method pulverizing above-mentioned reducting pellet, known method can be adopted, such as, use vibrating mill, crushing rolls, ball mill, roller mill etc.As the method for above-mentioned crushed material being carried out to magnetic separation separation, known method can be adopted.
According to the present invention, the SiO of magnetization contained by thing
2amount is below 8 quality %, the TiO contained by non-magnetic compound
2amount is more than 40 quality %.
(optimal way)
In the present invention, in above-mentioned heating process, if when top temperature when heating above-mentioned agglomerate is T (DEG C), the melting amount preferably making to deduct from this temperature T gangue contained in this agglomerate the temperature of 100 DEG C reaches more than the 55 quality % of this gangue amount, so the blending amount of the above-mentioned fusing point conditioning agent of adjustment.That is, when the Heating temperature T of above-mentioned agglomerate determines, the mode that when preferably making heating, melting quantitative change is many, uses fusing point conditioning agent to adjust the fusing point of composition contained in agglomerate in advance.Then, during heating agglomerate, to make in this agglomerate more than the 55 quality % positively melting of contained gangue, so to deduct the melting amount of the gangue at the temperature of 100 DEG C for benchmark from top temperature T during heating, concoct above-mentioned fusing point conditioning agent and carry out the composition adjustment of agglomerate.
The above-mentioned melting amount of above-mentioned gangue, among the gangue contained by above-mentioned agglomerate, especially based on CaO, SiO
2, Al
2o
3, MgO and TiO
2the amount of fifty percent point determine.
The application is based on the interests of the Japan patent application 2012-123745 CLAIM OF PRIORITY applied on May 30th, 2012.The full content of the specification sheets of No. 2012-123745th, this Japan's patent application, in this application for reference to and quote.
Below, enumerate embodiment and further illustrate the present invention, but the present invention does not limit by following embodiment certainly, suitably can certainly be changed enforcement in the scope that can meet the forward and backward aim stated, these are all included in the scope of technology of the present invention.
[embodiment]
(experimental example 1)
The iron ore be grouped into containing the one-tenth shown in following table 1, carbon material are become block with the raw mixture of fusing point conditioning agent, the agglomerate obtained with heating by electric cooker, manufacture the mixture (reducting pellet) of reduced iron and slag.In following table 1, T.Fe is meant to total iron.
As above-mentioned carbon material, relative to the mole number of the oxygen amount combined as the ferric oxide contained by above-mentioned iron ore, blending has ± the carbon material of the fixed carbon of 2 % by mole (namely, relative to the fixing carbon amounts of the ferric oxide that can reduce contained by above-mentioned agglomerate, the fixing carbon amounts contained by carbon material is ± 2 quality %).Blending Wingdale (CaCO
3) and silica as above-mentioned fusing point conditioning agent.
In the raw mixture of the iron ore be grouped into containing the one-tenth shown in following table 1, carbon material and fusing point conditioning agent, remix tackiness agent, is a granulated into block by rotation and manufactures the agglomerate of φ 19mm.Tempered wheats powder is as above-mentioned tackiness agent.
In following table 2, the one-tenth showing dried agglomerate is grouped into.Agglomerate a shown in following table 2 is the basicity (CaO/SiO by adjusting this agglomerate
2), when when making heating, ferric oxide is reduced, the fusing point of the slag of by-product reaches minimum and have adjusted into the example be grouped into.Agglomerate b shown in following table 2 makes the CaO-SiO contained by this agglomerate
2-Al
2o
3-MgO-TiO
2five yuan is that the fusing point of oxide compound reaches minimum and carried out the example of composition adjustment.
Further, in following table 2, T.C represents total carbon, CaO/SiO
2represent basicity.In addition, CaO+SiO
2+ Al
2o
3+ MgO is meant to gangue amount.In addition, [TiO
2/ (CaO+SiO
2+ Al
2o
3+ MgO+TiO
2)] × 100, be meant to the titanium oxide (TiO in slag composition
2) concentration.
Then, the agglomerate that obtains is loaded electric furnace, heat 18 minutes and ferric oxide contained by reducing in agglomerate.Heating temperature T in electric furnace is set to 1300 DEG C, 1350 DEG C or 1400 DEG C, and the atmosphere in electric furnace is adjusted to N
2gas atmosphere.When the reduction of ferric oxide, by-product goes out slag, and can obtain the mixture (reducting pellet) of reduced iron and slag.
Following table 3 is presented at molten state during each Heating temperature T heating.In following table 3, so-called " without melting ", is meant to the state not generating fused solution in agglomerate, and so-called " having melting ", is meant to the state that there occurs fused solution in agglomerate, represents a part of melting of agglomerate.
Pulverize the reducting pellet obtained with vibrating mill, make it after diameter reaches below 3mm, use magnet, magnetic separation is separated into magnetization thing and non-magnetic compound.Magnetic separation uses the magnet of 2000 Gausses, the magnetic force of test portion position is adjusted to 500 Gausses from 200 Gausses in being separated, and remagnetization operates and carries out magnetic separation separation.Becoming to be grouped into and being presented in following table 3 of the magnetization thing that obtains and non-magnetic compound is separated by magnetic separation.Further, M.Fe represents metal iron.
In addition, in following table 3, show and be separated by magnetic separation the magnetization thing and non-magnetic compound ratio separately, degree of metalization (MetFe), CaO+SiO that obtain
2+ Al
2o
3the total amount of+MgO, the Ti rate of recovery.Degree of metalization (MetFe) is calculated by following formula.
MetFe (%)=[metal iron (M.Fe)]/[Total iron content (T.Fe)] × 100
As the Ti rate of recovery of magnetization thing, and as the Ti rate of recovery of non-magnetic compound, calculated by following formula.
As the Ti rate of recovery (%)=(the Ti amount contained by the Ti amount/agglomerate contained by magnetization thing) × 100 of magnetization thing
As the Ti rate of recovery (%)=(the Ti amount contained by the Ti amount/agglomerate contained by non-magnetic compound) × 100 of non-magnetic compound
Based on following table 3, can investigate as follows.No.3 shown in following table 3,5,6 is that heating agglomerate makes it the-example of partial melting, the crushed material magnetic separation of reducting pellet can be separated into magnetization thing and non-magnetic compound.On the other hand, No.1,2,4 is with the example of the state not generating fused solution in agglomerate heating, can not carry out magnetic separation separation.In addition, from following table 3, make Heating temperature T higher, as non-magnetic compound, the Ti of separated recovery measures more.
[table 1]
[table 2]
[table 3]
(experimental example 2)
In experimental example 2, CaO-SiO contained in investigation agglomerate
2-Al
2o
3-MgO-TiO
2five yuan is the melting amount of oxide compound and the Heating temperature T of electric furnace, on the impact that the result of magnetic separation separation causes.
What use in above-mentioned experimental example 1 contains in the raw mixture of iron ore, carbon material and fusing point conditioning agent, remix tackiness agent, and adds CaO, SiO
2, same with above-mentioned experimental example 1, being a granulated into block by rotating, manufacturing agglomerate c, d that the gangue amount of φ 19mm is different.As above-mentioned carbon material, relative to the mole number of the oxygen amount combined as the ferric oxide contained by above-mentioned iron ore, blending has ± the carbon material of the fixed carbon of 2 % by mole (namely, relative to the fixing carbon amounts of the ferric oxide that can reduce contained by above-mentioned agglomerate, the fixing carbon amounts contained by carbon material is ± 2 quality %).As above-mentioned fusing point conditioning agent, same with above-mentioned experimental example 1, blending Wingdale (CaCO
3) and silica.As above-mentioned tackiness agent, same with above-mentioned experimental example 1, tempered wheats powder.
Based on the CaO amount contained by dried agglomerate and SiO
2amount, calculates basicity (CaO/SiO
2) and be presented in following table 4.
In addition, based on CaO, SiO contained in dried agglomerate
2, Al
2o
3, MgO, TiO
2amount, uses thermodynamic data library software " FactSage ", calculates CaO-SiO contained in agglomerate
2-Al
2o
3-MgO-TiO
2five yuan is the melt temperature L.T of oxide compound, is presented in the lump in following table 4.
In addition, based on CaO, SiO contained in dried agglomerate
2, Al
2o
3, MgO, TiO
2amount, uses above-mentioned " FactSage ", and calculate the temperature [LT55 (DEG C)] that melting amount (fused solution growing amount) reaches 55 quality %, its result is presented in following table 4 in the lump.
Then, obtained agglomerate is loaded electric furnace, heats 18 minutes, ferric oxide contained in reduction agglomerate, manufactures the mixture (reducting pellet) of reduced iron and slag.Heating temperature T in electric furnace is 1300 DEG C, 1350 DEG C or 1400 DEG C.Atmosphere in electric furnace is N
2gas atmosphere (N
2gas 100 volume %).
In addition, calculate and deduct CaO-SiO from the Heating temperature T in electric furnace
2-Al
2o
3-MgO-TiO
2five yuan is the value (T-L.T) of the melt temperature L.T of oxide compound, is presented at following table 4 in the lump.When T-L.T is negative value, mean with lower than CaO-SiO
2-Al
2o
3-MgO-TiO
2five yuan is the heating temperatures of the melt temperature L.T of oxide compound.
In addition, use above-mentioned " FactSage ", calculate from the CaO-SiO Heating temperature T declines the temperature (T-100 DEG C) of 100 DEG C
2-Al
2o
3-MgO-TiO
2five yuan is the melting amount of oxide compound.Result is presented in following table 4 in the lump.Further, in following table 4, as with reference to value, calculate from the CaO-SiO Heating temperature T declines the temperature (T-50 DEG C) of 50 DEG C
2-Al
2o
3-MgO-TiO
2five yuan is the melting amount of oxide compound, 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, make it after diameter reaches below 3mm, to use magnet to carry out magnetic separation separation.The ratio (non-magnetic rate) being separated the non-magnetic compound obtained by magnetic separation is shown in following table 4.
[table 4]
Then, the relation of Heating temperature T and non-magnetic rate is represented at Fig. 1.In FIG, ◆ represent the result of No.7 ~ 9, represents the result of No.10 ~ 12.
From above-mentioned table 4 and Fig. 1, (namely the temperature [LT55 (DEG C)] reaching 55 quality % by being heated to melting amount (fused solution growing amount) adds the temperature of 100 DEG C, in No.7 ~ 9 be 1400 DEG C, in No.10 ~ 12 be 1350 DEG C) more than, reduced iron and slag start to be separated, and non-magnetic rate uprises (No.9,11,12).
Secondly, represent in fig. 2 from the CaO-SiO Heating temperature T declines the temperature (T-100 DEG C) of 100 DEG C
2-Al
2o
3-MgO-TiO
2five yuan is the melting amount of oxide compound, the relation with non-magnetic rate.In fig. 2, No.7 ~ 9 result by ◆ represent, the result of No.10 ~ 12 is represented by.
From above-mentioned table 4 and Fig. 2, if melting amount (fused solution growing amount) reaches more than 55 quality %, then metallic iron and slag start to be separated, the rising of heat tracing temperature T, and non-magnetic rate uprises.
As more than, according to the present invention, make one partial melting by heating agglomerate, the separation property of reduced iron and slag improves, can Separation and Recovery reduced iron and titanium oxide expeditiously.In addition, according to the present invention, reduced iron can be reclaimed expeditiously.
Claims (14)
1. a manufacture method for the mixture of reduced iron and slag, is characterized in that, comprises following operation successively:
In the material containing ferric oxide and titanium oxide and carbon material, blending fusing point conditioning agent, carries out into the operation of block by the raw mixture obtained thus further; And
Heat in the mode of a part of melting making obtained agglomerate, reduce the operation of ferric oxide contained in this agglomerate.
2. a manufacture method for the mixture of reduced iron and slag, is characterized in that, comprises following operation successively:
In the material containing ferric oxide and titanium oxide and carbon material, blending fusing point conditioning agent, carries out into the operation of block by the raw mixture obtained thus further; And
More than the temperature of a part of melting of obtained agglomerate and lower than complete melting heating temperatures described in agglomerate, reduce the operation of ferric oxide contained in this agglomerate thus.
3. the manufacture method according to claim l or 2, wherein, described fusing point conditioning agent at least supplies material containing CaO, and measures and SiO according to by the CaO in this agglomerate
2measure basicity and the CaO/SiO of the slag of trying to achieve
2be 0.2 ~ 0.9 mode adjust the CaO that concocts in described agglomerate and supply amount of substance.
4. manufacture method according to claim 3, wherein, supplies material as described CaO, concocts from CaO, Ca (OH)
2and CaCO
3select in the group formed at least one.
5. manufacture method according to claim 1 and 2, wherein, adjusts the blending amount of described fusing point conditioning agent, makes the melting amount deducting gangue contained in this agglomerate the temperature of 100 DEG C from top temperature during the described agglomerate of heating be more than 55 quality %.
6. manufacture method according to claim 5, wherein, the described melting amount of described gangue, based on CaO, SiO contained in described agglomerate
2, Al
2o
3, MgO and TiO
2the amount of these five kinds of compositions decides.
7. manufacture method according to claim 1 and 2, wherein, the heating of described agglomerate is carried out at following temperature, and described temperature is for the CaO-SiO contained by this agglomerate
2-Al
2o
3-MgO-TiO
2five yuan is that to reach these five yuan be that the temperature of more than the 55 quality % of oxide amount adds 100 DEG C for the melting amount of oxide compound.
8. manufacture method according to claim 1 and 2, wherein, uses the iron ore of the Fe containing 40 ~ 60 quality % as the material containing described ferric oxide and titanium oxide.
9. manufacture method according to claim 1 and 2, wherein, uses the TiO containing 7 ~ 20 quality %
2iron ore as the material containing described ferric oxide and titanium oxide.
10. manufacture method according to claim 1 and 2, wherein, the mode being ± 5 quality % according to the fixing carbon amounts making the fixing carbon amounts contained by described carbon material relative to the ferric oxide that can reduce contained by described agglomerate concocts described carbon material.
11. 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 12. 1 kinds of reduced irons and slag, is characterized in that, comprises following operation successively:
The mixture of the reduced iron obtained by the manufacture method described in claim 1 or 2 and slag is crushed to diameter and is below 8mm but not containing the operation of 0mm; And
Obtained crushed material is carried out to the operation of magnetic separation separation.
13. 1 kinds of non-magnetic compounds, is characterized in that, be the non-magnetic compound of being screened by separation method according to claim 12, this non-magnetic compound contains the TiO of more than 40 quality %
2.
14. 1 kinds of magnetization things, it is characterized in that, be the magnetization thing screened by separation method according to claim 12, containing below 8 quality % but not containing the SiO of 0 quality %
2.
Applications Claiming Priority (3)
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|---|---|---|---|
| JP2012123745A JP2013249496A (en) | 2012-05-30 | 2012-05-30 | Method for manufacturing mixture of reduced iron and slag |
| JP2012-123745 | 2012-05-30 | ||
| PCT/JP2013/064033 WO2013179942A1 (en) | 2012-05-30 | 2013-05-21 | Method for manufacturing mixture of reduce iron and slag |
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| CN (1) | CN104334749B (en) |
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| CN105907968A (en) * | 2016-05-05 | 2016-08-31 | 朱鸿民 | Method of extracting iron and titanium with ferrotitanium compound minerals as raw material and filtering equipment |
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| JP6303901B2 (en) * | 2014-08-01 | 2018-04-04 | 住友金属鉱山株式会社 | Nickel oxide ore smelting method |
| KR101635936B1 (en) * | 2014-11-11 | 2016-07-04 | 주식회사 포스코 | Processing method for raw material |
| CA2980471A1 (en) * | 2015-03-31 | 2016-10-06 | Hazer Group Limited | A process for producing hydrogen and graphitic carbon from hydrocarbons |
| CN115820947A (en) * | 2022-11-25 | 2023-03-21 | 钢城集团凉山瑞海实业有限公司 | Multicomponent slagging agent for titanium-containing blast furnace slag |
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| JP2004131753A (en) * | 2002-10-08 | 2004-04-30 | Kobe Steel Ltd | Method for producing slag containing titanium oxide |
| CN1623003A (en) * | 2000-08-09 | 2005-06-01 | 株式会社神户制钢所 | Method for producing metallic iron |
| CN101990581A (en) * | 2008-04-10 | 2011-03-23 | 株式会社神户制钢所 | Titanium oxide-containing agglomerate for producing granular metallic iron |
| JP2011179090A (en) * | 2010-03-03 | 2011-09-15 | Jfe Steel Corp | Method for producing granulated iron |
| WO2011118738A1 (en) * | 2010-03-25 | 2011-09-29 | 株式会社神戸製鋼所 | Carbon-material-containing iron oxide briquette composition, method for producing same, and method for producing reduced iron using same |
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| JP2659807B2 (en) * | 1989-01-26 | 1997-09-30 | 万鎔工業株式会社 | Direct smelting method |
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2012
- 2012-05-30 JP JP2012123745A patent/JP2013249496A/en active Pending
-
2013
- 2013-05-21 WO PCT/JP2013/064033 patent/WO2013179942A1/en active Application Filing
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1623003A (en) * | 2000-08-09 | 2005-06-01 | 株式会社神户制钢所 | Method for producing metallic iron |
| JP2004131753A (en) * | 2002-10-08 | 2004-04-30 | Kobe Steel Ltd | Method for producing slag containing titanium oxide |
| CN101990581A (en) * | 2008-04-10 | 2011-03-23 | 株式会社神户制钢所 | Titanium oxide-containing agglomerate for producing granular metallic iron |
| JP2011179090A (en) * | 2010-03-03 | 2011-09-15 | Jfe Steel Corp | Method for producing granulated iron |
| WO2011118738A1 (en) * | 2010-03-25 | 2011-09-29 | 株式会社神戸製鋼所 | Carbon-material-containing iron oxide briquette composition, method for producing same, and method for producing reduced iron using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105907968A (en) * | 2016-05-05 | 2016-08-31 | 朱鸿民 | Method of extracting iron and titanium with ferrotitanium compound minerals as raw material and filtering equipment |
| CN105907968B (en) * | 2016-05-05 | 2017-12-12 | 朱鸿民 | A kind of method and filter plant that iron, titanium are extracted using ferrotianium grandidierite as raw material |
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| JP2013249496A (en) | 2013-12-12 |
| UA110687C2 (en) | 2016-01-25 |
| WO2013179942A1 (en) | 2013-12-05 |
| RU2014152621A (en) | 2016-07-20 |
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