CN107663588B - A kind of method of melting continuously carbide slag - Google Patents

A kind of method of melting continuously carbide slag Download PDF

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Publication number
CN107663588B
CN107663588B CN201710930294.1A CN201710930294A CN107663588B CN 107663588 B CN107663588 B CN 107663588B CN 201710930294 A CN201710930294 A CN 201710930294A CN 107663588 B CN107663588 B CN 107663588B
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slag
electric furnace
furnace
carbide
melting continuously
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CN107663588A (en
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王东生
杨仰军
程晓哲
黄家旭
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Pangang Group Research Institute Co Ltd
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Pangang Group Research Institute Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001Dry processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00Obtaining refractory metals
    • C22B34/10Obtaining titanium, zirconium or hafnium
    • C22B34/12Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1218Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04Working-up slag
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention belongs to field of metallurgy, and in particular to a kind of method of melting continuously carbide slag.Technical problem to be solved by the invention is to provide it is a kind of can melting continuously carbide slag method, this method is divided into heating and reduction phase, and Ti-containing slag heats up melting completely first, is then added in smelting furnace and is restored, up to carbide slag after reduction.The technique avoids carbonization resistant material of electric furnace extremely cold very hot, ensure that the long service life of carbonization resistant material of electric furnace, and can realize closed, continuous, the efficient smelting of large-scale carbonization electric furnace.

Description

A kind of method of melting continuously carbide slag
Technical field
The invention belongs to field of metallurgy, and in particular to a kind of method of melting continuously carbide slag.It is related specifically to blast furnace slag A kind of preparation method of carbide slag during comprehensive utilization.
Background technique
It is abundant to climb western titanium resource, through traditional blast furnace ironmaking-converter steelmaking process, most of titanium is entered in blast furnace slag, high TiO in clinker2Content is that 20%~26%, Cong Pangang founds the factory so far, has stored up more than 6,500 ten thousand tons of blast furnace slag.For blast furnace Slag, domestic many research institutions had once carried out a variety of researchs for mentioning titanium technology path, for example produced silicon titanium composite alloy, production mine Slag microcrystalline glass etc., but processing capacity is limited, cannot fundamentally solve the problem of complex utilization of titanium-containing blast furnace slag.Currently, high " high temperature cabonization-low temperature chlorination produces TiCl to titanium blast furnace slag4" process route be most industrialization prospect technology path, work Skill is divided into three key steps of utilization of high-temperature selective carbonization, cryogenic selective chlorination and chloride residue, place short with process The advantages that reason amount is big, titanium resource comprehensive utilization ratio is high.Wherein, high-temperature selective carbonization technique is by the titanium dioxide in Ti-containing slag Titanium 80~95% is converted into TiC, while other components such as MgO, Al in slag2O3、SiO2, CaO etc. do not reacted with reducing agent then, with This obtains a kind of special carbide slag containing TiC.Wherein, cryogenic selective chloridization process by valuable component TiC in carbide slag with Cl2Preferential reaction is converted into TiCl4, for producing titanium dioxide or Titanium after purified removal of impurities, chlorination process is in fluidized bed furnace Interior progress, chlorine utilization is high, and in no fused salt chlorimation industry the disadvantages of a large amount of residue contaminations, technique is environmentally protective.
Patent CN203498453U provides a kind of hot charging blast furnace slag carbonization electric furnace, and there is water cooling to rotate bell, tilting furnace The structures such as body are a kind of dedicated furnace type structures, and having many advantages, such as can be with hot charging clinker, conveniently slags tap.But the furnace body that fascinates etc. is tied Structure designs the enlargement for being unfavorable for equipment, and electric furnace form limits so that production process interval carries out.
The present invention provides a kind of method of melting continuously carbide slag, the close of large-scale carbonization electric furnace is may be implemented in this method It closes, continuously, efficiently smelt, avoid the extremely cold i.e. enthusiastic condition of carbonization resistant material of electric furnace, ensure that the long service life of carbonization resistant material of electric furnace.
Summary of the invention
For the defect that existing carbide slag cannot continuously, largely be smelted, the present invention provides a kind of melting continuously carbide slags Method.Method includes the following steps:
Step A, Ti-containing slag is added in heating furnace and is warming up to 1550~1650 DEG C;
Step B, carbonaceous reducing agent and step A slag are added in carbonization electric furnace and are restored;Wherein, heating furnace and carbonization Electric furnace is connected to using pipeline.
Specifically, the Ti-containing slag is to contain TiO in the method and step A of above-mentioned melting continuously carbide slag210~ The clinker of 90wt%.It is described be warming up to 1550~1650 DEG C and continue into slag titanium dioxide be converted into the conversion ratio of titanium carbide and be 5~65%, it then adds into carbonization electric furnace.
Specifically, in the method and step B of above-mentioned melting continuously carbide slag, the carbonaceous reducing agent is nut coke, coke powder, thin At least one of coal, anthracite, bituminous coal or lignite.
Further, in the method and step B of above-mentioned melting continuously carbide slag, the reduction temperature is 1600~1750 DEG C, Reduction reaction carries out into slag titanium dioxide and is converted into the conversion ratio of titanium carbide to be 80~95%.
Specifically, the number of the heating furnace is n in the method and step A of above-mentioned melting continuously carbide slag, n is >=1.
Specifically, the heating uses burning carbonaceous reducing agent or day in the method and step A of above-mentioned melting continuously carbide slag Right air lift is for institute's calorific requirement.
Specifically, slag obtained by step A passes through the chute of external heating muff in the method for above-mentioned melting continuously carbide slag Flow into carbonization electric furnace.
The method of the present invention makes carbonization electric furnace closed by the way of pipeline connection, realizes carbonization electric furnace melting continuously, keeps away It is extremely cold very hot to exempt from resistance to material, extends electric furnace service life;The CO concentration in electric furnace flue gas that is carbonized is stablized, and it is high to recycle value;It can be with Realize closed, continuous, the efficient smelting of large-scale carbonization electric furnace.The present invention is a kind of method of melting continuously carbide slag, the method The advantages of be embodied in the following aspects: use molten slag for raw material, clinker charging temperature be 1250~1400 DEG C, can The effective physical thermal for utilizing blast furnace slag;Using combustion heatings such as natural gas, carbon dusts in heating furnace, smelting electricity is further saved Consumption.
Detailed description of the invention
Fig. 1 present invention process equipment connection schematic diagram
Specific embodiment
This field, which routinely smelts Ti-containing slag, to be smelted using the electric furnace of 20t or so, such electric furnace yield is small, into Material mouth unsealing, the air of entrance are easy to have an impact electrode, shorten electrode life, and conventional treatment mode is to tear furnace open, again New furnace is built to be smelted.The defects of such usual manner there are yield small, the discontinuous, cost that wastes raw material, human cost etc.. As directly small yield furnace being changed to big yield furnace, but after need to expanding charging, expand electrode, expand feed inlet will enter it is a large amount of Air, to influence electrode life;If do not expand charging after again there are difficult feeds the problems such as.
In view of the foregoing drawbacks, the present invention provides a kind of methods of melting continuously carbide slag.This method is divided into step A and step In rapid two stages of B, the first stage, (such as volume is 30~55m to use small volume3) heating furnace heat up to raw material, make Raw material melts completely, improves mobility, to be easy to be added in carbonization electric furnace;Part TiO in slag during heating2It is reduced to TiC;Second stage, volume is added in slag obtained by carbonaceous reducing agent and first stage, and larger (such as volume is 120~350m3) It is carbonized in electric furnace and carries out drastic reduction, qualified carbide slag is arrived after reduction reaction;Wherein, heating furnace and carbonization electric furnace It is connected using pipeline, so that it is closed to realize carbonization electric furnace.
Further, multiple heating furnaces can be set around carbonization electric furnace according to the dress quantity of slag of carbonization electric furnace.Such as 1~4 It is a.
Further, the heating furnace provides heat by burning carbonaceous reducing agent or natural gas, and control slag temperature is 1550~1650 DEG C achieve the purpose that improve mobility.A period of time can be kept at such a temperature, such as make titanium dioxide in slag The conversion ratio for being converted into TiC is 5~65%.The carbonaceous reducing agent is in nut coke, coke powder, lean coal, anthracite, bituminous coal or lignite At least one.
Further, the carbonization electric furnace provides carburizing reagent institute calorific requirement by electric heating, and control slag temperature is 1600~1750 DEG C are restored, and being restored to titanium dioxide in slag and being converted into the conversion ratio of TiC is 80~95%.
Preferably, it in order to guarantee that slag loses less as much as possible from the heat that heating furnace is flowed into carbonization electric furnace, uses Slag obtained by step A is flowed into the carbonization electric furnace of step B by the chute of external heating muff.
In the method for the present invention step A, the purpose to heat up in heating furnace is to melt phosphorus bearing slag further, improves clinker Mobility.Be not avoided that in the step temperature-rise period there are part titanium dioxide to be reduced to titanium carbide.
In order to energy saving, it is complete that the reaction gas that heating furnace generates in the method for the present invention step A enters secondary combustion chamber Burning, the high-temperature flue gas for generation of burning can heat waste heat boiler, can also water cooled casing is cooling, gather dust after discharge;In step B The flue gas generated during carbonization electric furnace smelting carbide slag recycles after cooling, dedusting.
Ti-containing slag interruption is added in heating furnace in the method for the present invention step A, opens cinder notch after the completion of heating, slag passes through The chute of external heating muff flows into carbonization electric furnace;The chute is chute commonly used in the art, i.e., external is steel, and inside is built Resistance to material.The continuous power transmission of electric furnace that is carbonized in step B is smelted, and separated cinder notch is slagged tap, and it is residual all to go out net or part for carbide slag when slagging tap It stays.In the method for the present invention, used carbonizing reduction agent be smelt the common reducing agent of carbide slag, as nut coke, coke powder, lean coal, One or more of anthracite, bituminous coal, lignite etc..The dosage of carbonaceous reducing agent used is according to titanium dioxide in Ti-containing slag Content reasonably adjusts, generally TiO in slag2It is completely converted into 1.3~2 times that the reaction of TiC theory needs carbon.
Embodiment 1
Implement the invention in certain factory, a carbonization electric furnace nominal capacity is 65t in operation area, and carbide furnace periphery is southern and northern To two Heating Furnaces of setting, heating furnace nominal capacity is 30t.Full Ti content is 13.60% in molten blast furnace slag, dioxy Changing Ti content is 23.32%, transports through slag ladle and carriage to production operation area, is directly poured into heating furnace after weight broken shell;Heating furnace Using burning heated by natural gas clinker, heating time about 56min, heating end infrared radiation thermometer measures slag surface temperature and is 1582 DEG C, teams and groups' opening is slagged tap, and to measure full Ti content in slag be 13.43%, TiC content to sampling chemical analysis is 5.6%, molten It is 33.36% that titanium dioxide, which is converted into the conversion ratio of TiC, in slag.Melt cinder flows into carbonization electric furnace through chute, and carbonization electric furnace uses stone The heating of electrode ink power transmission, control electric furnace interior reaction temperature are 1600~1700 DEG C, and reducing agent is finely-ground coke, and coke powder 1mm or less is accounted for It than being greater than 80%, is added in electric furnace by carbide furnace top feed opening, coke powder is chemically react theoretical requirement 1.6 with dosage Times;After continuing power transmission 1h50min, CO content is gradually decreased in electric furnace flue gas, and carburizing reagent is slagged tap close to smelting endpoint, opening, Obtain carbide slag.It is 13.72% that measure full Ti content in carbide slag, which be 13.04%, TiC content, and titanium dioxide is converted into TiC's Conversion ratio is 84.17%.During carbonization electric furnace power transmission is smelted, heating furnace continues hot charging slag, temperature-rise period next time, carbon After the completion of change furnace is slagged tap, melt cinder is blended by heating furnace immediately again, continues power transmission and smelt.With this make production process continuously into Row realizes closed, continuous, the efficient smelting of large-scale carbonization electric furnace.

Claims (10)

1. the method for melting continuously carbide slag, it is characterised in that: the following steps are included:
Step A, Ti-containing slag is added in heating furnace to be warming up to 1550~1650 DEG C and continue into slag titanium dioxide and is converted into The conversion ratio of titanium carbide is 5~65%;The heating furnace provides heat by burning carbonaceous reducing agent or natural gas;The carbonaceous Reducing agent is at least one of nut coke, coke powder, lean coal, anthracite, bituminous coal or lignite;
Step B, carbonaceous reducing agent and step A slag are added in carbonization electric furnace and are restored, up to carbide slag after reduction; Wherein, heating furnace is connected to carbonization electric furnace using pipeline.
2. the method for melting continuously carbide slag according to claim 1, it is characterised in that: in step A, the Ti-containing slag To contain TiO2The clinker of 10~90wt%.
3. the method for melting continuously carbide slag according to claim 1, it is characterised in that: in step B, the carbonaceous reduction Agent is at least one of nut coke, coke powder, lean coal, anthracite, bituminous coal or lignite.
4. the method for described in any item melting continuously carbide slags according to claim 1~3, it is characterised in that: in step B, institute Stating reduction temperature is 1600~1750 DEG C, and reduction reaction carries out into slag titanium dioxide and be converted into the conversion ratio of titanium carbide to be 80 ~95%.
5. the method for described in any item melting continuously carbide slags according to claim 1~3, it is characterised in that: in step A, institute The number for stating heating furnace is n, and n is >=1.
6. the method for melting continuously carbide slag according to claim 4, it is characterised in that: in step A, the heating furnace Number is n, and n is >=1.
7. the method for described in any item melting continuously carbide slags according to claim 1~3, it is characterised in that: the step A is molten Slag flows into carbonization electric furnace by the chute of external heating muff.
8. the method for melting continuously carbide slag according to claim 4, it is characterised in that: the step A slag passes through outer The chute for setting heating muff flows into carbonization electric furnace.
9. the method for melting continuously carbide slag according to claim 5, it is characterised in that: the step A slag passes through outer The chute for setting heating muff flows into carbonization electric furnace.
10. the method for melting continuously carbide slag according to claim 6, it is characterised in that: the step A slag passes through outer The chute for setting heating muff flows into carbonization electric furnace.
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Publication number Priority date Publication date Assignee Title
CN109385535A (en) * 2018-10-29 2019-02-26 攀钢集团攀枝花钢铁研究院有限公司 Blast furnace slag high temperature cabonization smelting process
CN110106364A (en) * 2019-06-21 2019-08-09 攀钢集团攀枝花钢铁研究院有限公司 The method for preparing titanium carbide slag with Ti-containing slag

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