WO2018014363A1 - 一种含钛混合熔渣熔融还原回收与调质处理的方法 - Google Patents
一种含钛混合熔渣熔融还原回收与调质处理的方法 Download PDFInfo
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- WO2018014363A1 WO2018014363A1 PCT/CN2016/091699 CN2016091699W WO2018014363A1 WO 2018014363 A1 WO2018014363 A1 WO 2018014363A1 CN 2016091699 W CN2016091699 W CN 2016091699W WO 2018014363 A1 WO2018014363 A1 WO 2018014363A1
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B3/00—General features in the manufacture of pig-iron
- C21B3/04—Recovery of by-products, e.g. slag
- C21B3/06—Treatment of liquid slag
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
- C22B34/1222—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes using a halogen containing agent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
- C22B34/1227—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes using an oxygen containing agent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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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
- Y02P10/20—Recycling
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Definitions
- the invention belongs to the field of non-blast furnace ironmaking and comprehensive utilization of resources, and particularly relates to a method for smelting reduction recovery and quenching and tempering treatment of titanium-containing mixed slag.
- Vanadium-titanium magnetite is a composite ore of symbiotic elements of iron, vanadium, titanium, chromium, phosphorus, copper, nickel, cobalt, lanthanum, cerium, zirconium and hafnium.
- Vanadium-titanium magnetite beneficiation one blast furnace ironmaking-iron-water blowing vanadium slag-converter steelmaking smelting process, vanadium slag one-sodium or calcification roasting process, realizing vanadium-titanium magnetism
- the large-scale utilization of iron ore has produced solid wastes such as titanium-containing blast furnace slag, vanadium-containing titanium steel slag, and vanadium tailings.
- Vanadium-containing titanium waste contains high content of iron, vanadium, titanium, chromium, phosphorus and other valuable elements, which is an important secondary resource.
- the titanium-containing blast furnace slag is produced in the blast furnace ironmaking process of vanadium-titanium magnetite, and has a TiO 2 content of 4 to 30%, a vanadium-containing pig iron content of 4 to 8%, and a vanadium pentoxide content of 0.1 to 0.5%, and contains Titanium blast furnace slag is an important secondary resource; chromium-containing blast furnace slag temperature is higher than or equal to 1300 °C, and a large amount of physical heat is emitted every year. Therefore, titanium is contained. Blast furnace slag is also an important physical thermal resource.
- the vanadium-containing titanium steel slag is produced in the steelmaking process of vanadium-titanium magnetite, and has a TiO 2 content of 0.5 to 10%, a metal iron content of 4 to 12%, an iron oxidation content of 10 to 35%, and a vanadium pentoxide content of 0.5 to 5%, phosphorus pentoxide content is 0.2 to 6%, chromium trioxide content is 0.1 to 5%, and contains a certain amount of free calcium oxide (about 10%).
- Vanadium-containing titanium steel slag is an important secondary resource; the temperature of vanadium-containing titanium molten steel slag is higher than or equal to 1500 ° C, and a large amount of physical heat is discharged every year. Therefore, the vanadium-containing titanium molten steel slag is also an important physical heat resource.
- the titanium-containing blast furnace slag and the vanadium-containing titanium steel slag belong to the same artificial minerals, and the phase containing titanium, vanadium, iron, phosphorus, calcium and the like are finely dispersed, which is difficult to treat, and the comprehensive utilization problem has not been solved efficiently.
- China emits more than 20 million tons of titanium-containing blast furnace slag per year, and has accumulated more than 100 million tons of titanium-containing blast furnace slag, equivalent to more than 15 million tons of TiO 2 , more than 15 million tons of vanadium-containing pig iron, and more than 300,000 tons of vanadium pentoxide. The total value is trillions.
- Titanium-containing blast furnace slag and vanadium-containing titanium steel slag are important metallurgical resources, containing not only valuable components such as iron, vanadium, titanium and chromium, but also a large amount of metallurgical fluxes such as CaO and SiO 2 .
- a lot of researches have been done on the comprehensive utilization of titanium-containing blast furnace slag and vanadium-containing titanium steel slag at home and abroad, and some results have been achieved.
- many methods, although technically feasible, are not economically viable and still cannot be used. For industrial applications and development.
- titanium extraction by alkali method titanium extraction by acid method, preparation of titanium-containing alloy, titanium-containing blast furnace slag carbonitriding titanium, high-temperature modification-precipitation-mineralization separation, and use as building materials.
- the sulfuric acid or hydrochloric acid method extracts and separates the titanium-containing blast furnace slag, and the consumption of acid is large, and a large amount of waste acid and tailings are generated, which seriously pollutes the environment.
- Hydrochloric acid leaching and natural cooling of titanium-containing blast furnace slag is a way to utilize titanium-containing blast furnace slag.
- the leaching residue has no suitable use, that is, a new one is produced after leaching of hydrochloric acid. Waste.
- Titanium-containing blast furnace slag carbonitriding titanium is a way to utilize titanium-containing blast furnace slag, and there are some obvious shortcomings.
- the key problem of excessive carbonization power consumption of electric furnace is not solved, and electricity costs account for 70-80 of the total cost of carbonized slag. Above 5%, a large amount of chlorinated residue is generated, which causes serious secondary pollution.
- problems such as the bottom of the furnace and some smelting furnaces have serious problems such as foam slag, and production is difficult to continue.
- cement raw materials require TiO 2 ⁇ 10wt% in slag, if TiO 2 > 10wt%, it will not be used as cement raw material. Used as cast stone, slag cotton, etc., with a small amount of treatment.
- the method in the above two patents can only realize the effective utilization of a kind of slag, that is, titanium-containing blast furnace slag, low chemical activity, low temperature, high treatment cost, and poor effect of migration, enrichment and growth of iron and titanium components. The recovery rate is low, only the iron and titanium groups can be recycled and utilized, and the effective enrichment of valuable elements is not realized; 2.
- the method in the above two patents can only utilize one kind of slag, namely titanium-containing blast furnace slag, single slag- Titanium-containing blast furnace slag slag temperature is low, need to compensate a large amount of heat, high cost, complicated operation; 3. Can not handle cold titanium-containing blast furnace slag; 4.
- Both of the above two patents need to add SiO 2 , CaO, CaF 2 and other additives
- the temperature of the slag is rapidly decreased, and a part of the heat in the slag is wasted. Therefore, it is necessary to compensate the heat, waste energy, increase the cost, and increase the complexity of the treatment process; 5.
- the above two inventions The separation methods used in the process are all combined with flotation and hydrometallurgical methods. Flotation separation and hydrometallurgical separation process are likely to cause environmental pollution.
- the titanium-containing steel slag mainly adopts the water quenching process and the steel slag “squeaky tank” treatment process, and magnetically recovers the metal iron in the slag, but the recovery rate is low, and the residual metal iron content in the slag is as high as 5%, and the process only considers the metal in the recovered slag. Iron, iron oxides containing up to 30% or more of the recovered slag are not considered.
- the water quenching process and the steel slag “squeaky tank” treatment process consume a large amount of water resources, generate corrosive hot steam, heat cannot be recycled, water resources cannot be recycled, and a large amount of heat resources are difficult to be utilized.
- the free CaO and MgO in the slag reduce the stability of the steel slag volume, and the higher content of iron oxide increases the difficulty of grinding and limits the application of steel slag.
- the comprehensive utilization of vanadium components in vanadium-containing titanium steel slag is still in the research stage, and there is no recycling of titanium. Therefore, the vanadium-containing titanium steel slag is accumulated in a large amount, which pollutes the environment and wastes resources.
- the blast furnace liquid molten titanium-containing blast furnace slag and vanadium-containing molten steel slag contain abundant thermal energy resources, contain a large amount of hot metallurgical flux, and contain high content of iron, vanadium, titanium, chromium, phosphorus, calcium and other valuables. Elements are important secondary resources.
- the liquid molten titanium-containing blast furnace slag is a reducing slag, and the vanadium-containing molten steel slag is an oxidizing slag, and both are slag systems excellent in physical and chemical properties.
- the method for separating iron titanium vanadium calcium from slag (containing titanium blast furnace slag and vanadium-containing titanium molten steel slag), the invention has the following advantages: (1) the raw material is liquid molten titanium-containing blast furnace slag ( ⁇ 1300 ° C) flowing out from the slag outlet And steel slag ( ⁇ 1500 °C), with high temperature, high heat characteristics, make full use of slag physical heat resources, and save energy efficiently; (2) due to high content of free calcium oxide in liquid molten titanium blast furnace slag, liquid The molten converter steel slag has a high content of low-valent titanium oxide, has high chemical activity under high temperature conditions, and easily realizes migration and enrichment of vanadium, titanium, iron and calcium components, and can simultaneously recover titanium components in the mixed slag, Iron component, vanadium component and free calcium oxide component, achieve high-efficiency comprehensive recovery of secondary resources, recycle and utilize physical heat resources of titanium-containing blast furnace slag and vanadium-containing titanium molten steel slag; (3)
- the present invention provides a method for smelting reduction recovery and quenching and tempering treatment of titanium-containing mixed slag.
- the method is a method for recovering vanadium-containing pig iron or vanadium-containing steel, titanium-rich phase, vanadium-rich phase, phosphorus-rich phase and slag by containing titanium mixed slag; the method has short reaction time and high metal recovery rate
- the invention has the advantages of low production cost, strong raw material adaptability, large processing capacity, environmental friendliness and high economic benefit, and can effectively solve the problem of efficient recycling of metallurgical resources and thermal energy; the method of the invention is a new smelting reduction oxidation process.
- the method for smelting reduction recovery and quenching and tempering treatment of the titanium-containing mixed slag of the invention fully utilizes the physical heat resource of the titanium-containing blast furnace slag and the vanadium-containing titanium molten steel slag and the hot metallurgical flux, and the reducing property of the titanium-containing blast furnace slag
- the oxidizing property of the vanadium-containing titanium molten steel slag is achieved by mixing two kinds of slags and spraying an oxidizing gas to achieve smelting reduction and oxidation: 1 the titanium component in the mixed slag is sufficiently oxidized under an oxidizing atmosphere, the iron oxide It is fully reduced to metal iron; 2 the vanadium-containing metal iron component in the mixed slag is aggregated, grown and settled; 3 the titanium and calcium components in the mixed slag migrate, enrich in the perovskite phase, and achieve long Large and sedimentation; the vanadium components in the mixed slag migrate and concentrate in the metallic iron phase and the vanadium-rich phase
- Step 1 slag mixing:
- the titanium-containing blast furnace slag: vanadium-containing titanium molten steel slag 100: (1 ⁇ 1000) ingredients, added to the heat preservation device, the pourable smelting reaction device or the fixed smelting reaction device to form the titanium-containing mixed slag a smelting reduction reaction occurs; the temperature of the titanium-containing mixed slag is controlled within a set temperature range;
- the set temperature range is 1400 ⁇ 1600 ° C;
- the temperature range of the titanium-containing mixed slag is set to 1400 to 1600 ° C;
- the temperature range of the titanium-containing mixed slag is set to 1450 ⁇ 1600 ° C;
- the method for controlling the temperature of the titanium-containing mixed slag in the set temperature range is:
- the fuel or the vanadium-containing titanium molten steel slag is added to the titanium-containing mixed slag by the heating function of the reaction device itself, or the titanium-containing mixed slag is added.
- the temperature reaches the set temperature range;
- the temperature of the titanium-containing mixed slag is higher than the upper limit of the set temperature range, one or more of the vanadium-containing titanium material, the iron-containing material, the fluorine-containing material or the titanium-containing blast furnace slag are added to the titanium-containing mixed slag, Bringing the temperature of the titanium-containing mixed slag to a set temperature range;
- Injecting gas a preheating oxidizing gas is sprayed into the titanium-containing mixed slag; wherein the preheating temperature of the oxidizing gas is 0 to 1200 ° C, and the relationship between the oxidizing gas time and the flow rate is 1 to 105L/(min ⁇ kg);
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the control method is:
- step 1 The method for controlling the temperature of the titanium-containing mixed slag in the set temperature range in step 1;
- a reducing agent is added to the titanium-containing mixed slag to reduce the iron oxide to metal iron in the titanium-containing mixed slag;
- vanadium-containing metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out; the vanadium-containing metal iron layer in the remaining slow slag is crushed to a particle size of 20-400 ⁇ m, ground and magnetically separated. Remaining vanadium containing metal iron;
- tailings recycling There are two kinds of tailings recycling: 1 as cement raw materials, building materials, instead of crushed stone as aggregate, road material or phosphate fertilizer; 2 using hydrometallurgy, beneficiation method or beneficiation-hydrometallurgical joint method The phosphorus-containing components in the tailings are separated;
- the temperature of the mixed slag after reduction and oxidation is lowered to 1150 to 1250 ° C, and the mixed slag after reduction and oxidation in the middle and upper portions is poured out, and then air-cooled or water-quenched, and used as a cement raw material or a building material;
- reaction device uses a pourable smelting reaction device or a stationary smelting reaction device, method D is employed:
- the external slag treatment adopts Method D-1 or Method D-2:
- Method D-1 When the mass fraction of the vanadium-containing titanium slag TiO 2 after reduction and oxidation is ⁇ 10%, the reduced-oxidized vanadium-containing titanium slag is directly poured out, air-cooled or water-quenched, and used as a cement raw material or Building materials;
- Method D-2 Pour the vanadium-containing titanium slag after reduction and oxidation into a heat preservation device, perform smelting reduction and oxidation according to the method in Step 2, and separate and recycle Method A, Method B or Method C.
- the temperature of the titanium-containing blast furnace slag is ⁇ 1300 ° C
- the temperature of the vanadium-containing titanium molten steel slag is ⁇ 1500 ° C.
- the titanium-containing blast furnace slag is obtained from the blast furnace slag outlet;
- the vanadium-containing titanium molten steel slag is obtained from the steel slag slag outlet;
- the titanium-containing blast furnace slag contains TiO 2 in a mass fraction of 4 to 30%; the vanadium-containing titanium molten steel slag contains TiO 2 in a mass fraction of 0.3 to 6%, and contains V 2 O 5 mass.
- the score is 0.3 to 5%.
- the vanadium-containing titanium molten steel slag is a vanadium-containing titanium molten steel slag or an electric furnace containing vanadium-titanium molten oxidized steel slag.
- the heat preservation device is a pourable heat preservation device or a non-pourable heat preservation device; the non-pourable heat preservation device is a heat preservation pit; and the method for raising the temperature is to add fuel.
- the pourable holding device is a pourable insulated slag pot; the method of raising the temperature is to add fuel.
- the pourable smelting reaction device is a pourable converter, a pourable smelting reaction slag or an induction furnace.
- the fixed smelting reaction device is a reaction device with a slag port or an iron port at the bottom; the fixed reaction device is a plasma furnace, a direct current arc furnace, an alternating current arc furnace, a submerged arc furnace, a blast furnace or a reverberatory furnace.
- the inner layer of the heat preservation device, the pourable smelting reaction device or the fixed smelting reaction device is a carbon-containing thermal insulation mold release refractory material;
- the carbon-containing thermal insulation mold release refractory material is a carbon-containing composite refractory material, specifically carbon It is one or several of carbon, graphite, petroleum pitch coke, metallurgical coke, asphalt, anthracite, bituminous coal or lignite.
- the refractory material is siliceous, semi-silica, clay, high alumina, magnesia, dolomite.
- the carbon-containing thermal insulation mold release refractory material has two functions: (1) protecting the heat preservation device to improve its life, and (2) allowing the cooled slow cooling slag to be easily removed from the heat preservation device.
- the fuel and the vanadium-containing titanium molten steel slag are simultaneously added to the titanium-containing mixed slag, the fuel and the vanadium-containing titanium molten steel slag are in an arbitrary ratio.
- the method for controlling the temperature of the titanium-containing mixed slag in the set temperature range is that the preheating temperature of the fuel is 0 to 1200 ° C, and the temperature of the vanadium-containing titanium molten steel slag is ⁇ 1500 ° C.
- the fuel is added to the titanium-containing mixed slag by blowing.
- the blowing method is to insert the slag into the slag by using a refractory lance or to put the fuel into the upper part or the side of the slag.
- the method for controlling the temperature of the titanium-containing mixed slag in a set temperature range is that the fuel is pulverized coal.
- the fuel and the vanadium-containing titanium molten steel slag are simultaneously added to the mixed slag, the fuel and the vanadium-containing titanium molten steel slag are in an arbitrary ratio.
- the vanadium-containing titanium material is titanium-containing blast furnace slag, vanadium-containing titanium steel slag, vanadium-bearing tailings, titanium-selective tailings, low-grade vanadium-titanium magnetic Iron ore, vanadium-titanium magnetite concentrate, vanadium-titanium magnetite direct reduced iron, vanadium-titanium magnetite concentrate metallized pellet, vanadium-titanium magnetite concentrate carbon-containing pre-reduction pellet, vanadium-titanium magnetite concentrate ore, vanadium-titanium One or more of the magnet concentrate pellets; the iron-containing material is ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate sintered ore, ordinary iron concentrate pellet, ordinary iron concentrate Metallized pellets, ordinary iron concentrates containing carbon prereducing pellets, ordinary steel slag, blast furnace gas ash, blast furnace soot
- the method for controlling the temperature of the titanium-containing mixed slag in a set temperature range, the vanadium-containing titanium material, the iron-containing material and the Fluorine materials are pellets or powdery materials; wherein, the granular material has a particle size of ⁇ 150 ⁇ m, and the powdery material is sprayed into the titanium-containing mixed slag, and the loading gas is air, argon, nitrogen-air mixture. , nitrogen-oxygen gas mixture or air-argon gas mixture.
- the blowing method is that the slag is inserted into the slag by using a refractory spray gun or placed on the upper part or the side of the slag to blow the powdery material.
- the method for controlling the temperature of the titanium-containing mixed slag in the set temperature range when the temperature of the titanium-containing mixed slag is > the upper limit of the set temperature, adding the vanadium-containing titanium material, the iron-containing material, the fluorine-containing material or the One or more of titanium blast furnace slag, the purpose is to avoid excessive temperature, protect carbon-containing thermal insulation mold release refractory material, inhibit vanadium-containing pig iron in titanium-containing blast furnace slag, vanadium-containing iron in vanadium-containing titanium molten steel slag and The oxidation of the reduced metal iron increases the recovery rate of the metal iron.
- the method for controlling the temperature of the titanium-containing mixed slag in the set temperature range adding one or more of the cold vanadium-containing titanium material, the iron-containing material, the fluorine-containing material, and the titanium-containing blast furnace slag
- the remaining low-priced titanium Ti 2+ , Ti 3+
- high-priced titanium Ti 4+
- metallic iron Fe metallic iron
- the low-valent titanium (Ti 2+ , Ti 3+ ) in the reducing titanium-containing blast furnace slag is oxidized to high-priced titanium during the mixing process of the reducing titanium-containing blast furnace slag and the oxidizing vanadium-containing titanium molten steel slag.
- Ti 4+ oxidized vanadium-containing titanium molten steel slag
- Fe 3+ , Fe 2+ is reduced to Fe and Fe 2+ .
- the oxidizing gas is one of air, oxygen, oxygen-enriched air, nitrogen-oxygen mixed gas, nitrogen-air mixed gas, oxygen-argon mixed gas or air-argon mixed gas.
- the preheating temperature of the oxidizing gas varies depending on the gas.
- the oxidizing gas is inserted into the slag by using a refractory lance or placed on the upper side or side of the slag to blow an oxidizing gas.
- the oxidizing gas injection time and flow rate are determined according to the slag quality, temperature, and degree of reduction oxidation.
- the reducing agent is one of coal powder, coke powder, bituminous coal or anthracite.
- step 2 (2) when the reduction property of the titanium-containing mixed slag is insufficient in accordance with (b), the reductant is injected into the slag.
- the parameter (b) is guaranteed to have sufficient reducing property in the titanium-containing mixed slag, and in actual production, one is judged by the mass percentage of iron oxide in the titanium-containing mixed slag. Whether the reducing property in the titanium-containing mixed slag is sufficient.
- the remaining low-valent titanium (Ti 2+ , Ti 3+ ) in the titanium-containing mixed slag is sufficiently oxidized to high-priced titanium (Ti 4+ ) to ensure the titanium-containing mixed slag.
- the remaining high-valent iron (Fe 3+ , Fe 2+ ) is sufficiently reduced to metallic iron Fe to ensure that the metal iron particles in the titanium-containing mixed slag are not oxidized, and the smelting reduction and oxidation + blowing gas process include
- the vanadium-containing pig iron in the slag of the titanium blast furnace, the vanadium-containing iron in the vanadium-containing titanium molten steel slag and the reduced metal iron realize aggregation, growth and settlement.
- the cooling method is natural cooling or rotary cooling.
- the specific operation of the rotary cooling is: the heat preservation device equipped with the mixed slag after the redox is placed on the rotating platform, and rotates according to a certain speed, and the rotation speed depends on the slag quality.
- the rotation time depends on the slag quality and the slag solidification; the heat preservation device containing the redox mixed slag is placed on the rotating platform for the purpose of accelerating the metal iron and calcium. Aggregation, growth and sedimentation of titanium ore-rich phase, vanadium-rich phase, shorten settlement time, improve sedimentation effect, and improve production efficiency.
- step 3 in the method A(1), during the cooling process, most of the vanadium-containing metal iron, the titanium-containing group and the vanadium-containing component settle to the bottom due to the difference in density and the mineral size.
- the upper, middle and lower portions of the slow cooling slag from which the iron slag and the vanadium-containing metal iron layer are removed are separated by gravity separation method to obtain titanium concentrate and vanadium-rich fine.
- the titanium and calcium components in the mixed slag after reduction and oxidation continue to migrate and enrich in the perovskite phase, and realize growth and sedimentation;
- the vanadium components in the slag continue to migrate, enrich in the metal iron phase and vanadium-rich oxide phase, and achieve growth and sedimentation;
- the phosphorus component in the mixed slag after reduction oxidation continues to migrate and is enriched in Ca 2 SiO 4 -Ca 3 (PO 4 ) 2 phase, distributed at the phase interface between the two phases of perovskite and other mineral phases; iron oxide, free calcium oxide and free magnesium oxide disappeared in the mixed slag after redox, slag Realize tempering.
- the gravity sorting method is a shaker sorting, a chute sorting or a combination of the two.
- the hydrometallurgy is a dilute acid leaching method, wherein the dilute acid leaching method is one of inorganic acid leaching and organic acid leaching.
- the inorganic acid is selected from one or more of sulfuric acid, hydrochloric acid and phosphoric acid
- the organic acid is one or more selected from the group consisting of oxalic acid, acetic acid and citric acid.
- the metal iron recovery rate is 90-97%, and the mass fraction of the TiO 2 in the titanium concentrate having the main phase is perovskite is 35 to 52%, and the recovery of the titanium is performed.
- the ratio is 60-80%; in the method B, the metal iron recovery rate is 90-95%, and the mass fraction of the TiO 2 in the titanium concentrate with the main phase is perovskite is 35-52%, titanium The recovery rate is 58 to 76%.
- the method for smelting reduction and recovery and quenching and tempering treatment of the titanium-containing mixed slag, the quenching and tempering process is continued from the mixing of the raw materials until the separation and recovery process, the free calcium oxide and the free magnesium oxide in the slag disappear, and the iron oxide is oxidized. The metal and metal iron disappear or almost disappear, and the slag is tempered.
- the method for recovering and quenching and tempering the titanium-containing mixed slag of the invention has high recovery rate of metal iron, which is a gas containing titanium mixed slag, which not only contains vanadium-containing pig iron in the slag containing titanium blast furnace and molten steel slag containing vanadium and titanium
- metal iron which is a gas containing titanium mixed slag, which not only contains vanadium-containing pig iron in the slag containing titanium blast furnace and molten steel slag containing vanadium and titanium
- the vanadium iron aggregates, grows and settles, and the iron oxides (FeO, Fe 2 O 3 ) in the molten mixed slag are sufficiently reduced to metal iron to achieve aggregation, growth and sedimentation.
- the method for smelting reduction recovery and quenching and tempering treatment of the titanium-containing mixed slag of the present invention increases the mineral grindability.
- the phase interface between the two phases of the perovskite and other mineral phases is beneficial to the mineral dissociation of the perovskite phase, which is favorable for beneficiation Separate
- the invention fully utilizes the physical heat resources of the titanium-containing blast furnace slag and the vanadium-containing titanium molten steel slag, the thermal metallurgical flux in the slag, and the reduction and oxidation of the titanium-containing blast furnace slag and the vanadium-containing titanium molten steel slag.
- the molten slag is mixed with an oxidizing gas to achieve smelting reduction and oxidation, controlling the oxygen potential, and the iron oxide is sufficiently reduced to metallic iron, and the titanium component in the slag is sufficiently oxidized; it is a new method of smelting reduction;
- the titanium and calcium components in the mixed slag migrate and enrich in the perovskite phase, and grow and settle, the elemental vanadium component migrates and is concentrated in the metallic iron phase, and the low-valent vanadium oxide Enriched in the vanadium-rich oxide phase, and achieve growth and sedimentation, phosphorus component migration, enrichment in the Ca 2 SiO 4 -Ca 3 (PO 4 ) 2 phase, occurring at the interface of the perovskite phase;
- the slow cooling slag is separated from the settled iron ingot to recover the vanadium-containing metal iron, and the vanadium-containing metal iron remaining at the bottom of the slag is magnetically separated to realize the pig iron and vanadium-containing titanium in the titanium-containing blast furnace slag.
- the phosphorus-rich phase at the interface of the perovskite phase contributes to the dissociation and beneficiation of the perovskite phase;
- the process of the invention can be carried out continuously or discontinuously to meet the needs of industrial production.
- the inner layer of the reaction device of the present invention uses a carbon-containing thermal insulation mold release refractory material, which not only protects the heat preservation device, but also facilitates the removal of the cooled slow cooling slag from the heat preservation device;
- the raw material of the present invention is a liquid molten titanium-containing blast furnace slag ( ⁇ 1300 ° C) and a vanadium-containing titanium molten steel slag ( ⁇ 1500 ° C) flowing out of the slag outlet, and contains abundant heat energy resources, and has high temperature and high heat.
- the characteristics make full use of the slag physical heat resources and save energy efficiently; the liquid molten titanium-containing blast furnace slag and the vanadium-containing titanium molten steel slag contain a large amount of hot metallurgical flux, which are slag systems with excellent physical and chemical properties, realizing metallurgical resources.
- liquid molten titanium-containing blast furnace slag is reducing slag
- vanadium-containing titanium molten steel slag is oxidative slag, which fully utilizes the characteristics of high responsive chemical activity of the two kinds of slag
- the present invention realizes smelting reduction and oxidation by mixing two kinds of slag, spraying oxidizing gas, controlling oxygen potential, and not only collecting iron in the slag containing titanium blast furnace and vanadium-containing iron in the molten steel slag containing vanadium and titanium, Growing up and sedimentation, and fully reducing iron oxides (FeO, Fe 2 O 3 ) in the titanium-containing molten steel slag into metallic iron to achieve aggregation, growth and sedimentation;
- adding cold material and hot-melting titanium-containing blast furnace slag avoids excessive slag temperature, protects carbon-containing thermal insulation mold release refractory material, improves the life of the heat preservation device, and suppresses pig iron in the titanium-containing blast furnace slag.
- the two kinds of slag mixing of the invention realizes smelting reduction and oxidation, spraying oxidizing gas, controlling oxygen potential, oxidizing low-priced titanium into high-priced titanium, and migrating titanium and calcium components in mixed slag and enriching in calcium Titanium ore phase, and realize growth and sedimentation; vanadium oxide is fully reduced to elemental vanadium and low-valent vanadium, migrated and enriched in metal iron phase and vanadium-rich oxide phase, and grows up and settles, not only achieves melting Recovery of elemental vanadium in the slag, and enrichment, growth and sedimentation of vanadium oxide in the slag;
- the iron component, the titanium component, the vanadium component and the phosphorus component in the slag are separately transported and concentrated in the vanadium-containing metal iron, the titanium-rich phase, the vanadium-rich phase, and the phosphorus-rich phase.
- the heat preservation device equipped with slag is rotated on the rotating platform to accelerate the accumulation, growth and settlement of the vanadium-containing metal iron, titanium-rich phase, vanadium-rich phase and phosphorus-rich phase, and shorten Settling time, improve sedimentation effect, improve production efficiency;
- the addition of fluorine-containing materials accelerates the aggregation, growth and settlement of vanadium-containing metal iron, titanium-rich phase, vanadium-rich phase and phosphorus-rich phase, shortens settlement time and improves sedimentation effect;
- the phosphorus component in the mixed slag of the method of the present invention migrates and is concentrated in the Ca 2 SiO 4 -Ca 3 (PO 4 ) 2 phase, and is distributed in the phase interface between the two phases of the perovskite and other mineral phases, Conducive to beneficiation separation; free calcium oxide and free magnesium oxide disappear, metal iron and iron oxide almost disappear, free calcium oxide and magnesium oxide disappeared in the slag, mineral grindability increased, slag to achieve quenching and tempering;
- the method of the invention adopts a method of manual sorting, magnetic separation and reselection, separating vanadium-containing metal iron, vanadium-rich oxide phase and perovskite phase deposited at the bottom to realize titanium component in the mixed slag, High-efficiency recovery of iron component, vanadium component, phosphorus component and free calcium oxide component; since titanium-rich phase, vanadium-containing metal iron and vanadium-rich phase settle at the bottom, the amount of slag to be sorted is small, and the mineral can be ground.
- tailings recycling 1 as cement raw materials, building materials, instead of crushed stone as aggregate, road material or phosphate fertilizer; 2 using hydrometallurgy, beneficiation method or beneficiation-hydrometallurgical combination method Separation of phosphorus-containing components ; tailings use value is large, a wide range of applications;
- the invention fully utilizes the slag physical heat resource, the oxidative and reducing properties of the hot metallurgical flux and the slag in the slag, realizes the smelting reduction and oxidation, the iron component, the titanium component and the vanadium group in the slag
- the phosphorus component is separately migrated and enriched in the Vanadium metal iron, titanium-rich phase, vanadium-rich phase, phosphorus-rich phase, and achieve aggregation, growth and sedimentation, to achieve titanium, iron, vanadium, phosphorus and free calcium oxide in mixed slag
- High-efficiency recycling and can process cold vanadium, titanium and iron materials, and realize slag quenching and tempering treatment to achieve efficient and comprehensive utilization of secondary resources.
- the method has the advantages of short reaction time, high metal recovery rate, low production cost, strong adaptability of raw materials, large processing capacity, environmental friendliness and high economic benefit, and can effectively solve the problem of efficient recycling of metallurgical resources and thermal energy.
- FIG. 1 is a process flow diagram of a method for smelting reduction recovery and quenching and tempering treatment of a titanium-containing mixed slag according to an embodiment of the present invention.
- the solid-liquid ratio referred to in the following examples refers to the mass ratio of tailings to the leachate in units of g:L.
- a method for smelting reduction recovery and quenching and tempering treatment of titanium-containing mixed slag specifically comprising the following steps:
- Step 1 slag mixing:
- the 410kg liquid molten titanium-containing blast furnace slag and 40kg converter vanadium-containing titanium molten steel slag flowing out of the slag outlet are poured into a pourable insulating slag tank with graphite-dolomite composite thermal insulation mold release refractory material, and fully mixed to form titanium-containing slag Mixing slag, smelting reduction reaction occurs;
- the slag temperature is 1394 ° C, which is lower than the set temperature of 1400-1600 ° C in the titanium-containing mixed slag; the refractory spray gun is inserted into the mixed slag and blown into the coal powder 2 kg, so that the temperature of the mixed slag is raised to 1426 °C;
- the vanadium-containing titanium molten steel slag contains components and mass percentages thereof: 3.26 wt% V 2 O 5 , TFe 20.68 wt%, 40.89 wt% CaO, 12.36 wt% SiO 2 , 3.62 wt% TiO 2 , 2.47 wt% MgO, 1.22 wt. %MnO, 1.64wt% Al 2 O 3 , the balance is other impurities;
- Injecting gas In the titanium-containing mixed slag, oxygen is pre-heated and a total of 18 minutes of oxygen is sprayed; wherein the preheating temperature of oxygen is 30 ° C, and the relationship between oxygen time and flow rate is 1 L/(min). ⁇ kg); the mode of oxygen injection is to insert oxygen into the titanium-containing mixed slag by using a refractory spray gun.
- the temperature of the titanium-containing mixed slag is between 1400 and 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the reduction and oxidation process measured the mixed slag temperature of 1456 ⁇ 1466 ° C, within the set range;
- the remaining low-cost titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- vanadium-containing metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out; the vanadium-containing metal iron layer in the remaining slow slag is crushed to a particle size of 20-400 ⁇ m, ground and magnetically separated.
- the remaining vanadium-containing metal iron; the metal iron recovery rate is 92%, and the total iron in the tailings slag in this step is 0.792% by weight;
- the lower slow cooling slag of the slow cooling slag from the iron slag and the vanadium containing metal iron layer is selected by the chute once, the shaker is selected once, the two sweeps are selected, and the upper and middle passes through the chute are coarsely selected and shaken.
- the bed is selected once, once sweeped, and the titanium-containing component is separated from the gangue to obtain a titanium concentrate with a main phase of perovskite phase, a vanadium-containing magnesium-aluminum spinel medium ore and tailings, and a titanium concentrate.
- the mass fraction of medium TiO 2 is 48.41%
- the mass fraction of V 2 O 5 in the vanadium-containing magnesium-aluminum spinel is 8.71%
- the mass fraction of P 2 O 5 in the phosphorus-rich phase is 28%.
- tailings are separated by 2% dilute sulfuric acid at a solid-liquid ratio of 1:2, and the phosphorus recovery rate is 80%.
- a method for recovering and quenching and tempering a titanium-containing mixed slag comprises the following steps:
- Step 1 slag mixing:
- the liquid molten 100kg titanium-containing blast furnace slag and the 1000kg converter vanadium-containing titanium molten steel slag which are discharged from the slag outlet are poured into the thermal insulation pit with the carbon-magnesium composite thermal insulation mold release refractory material, and fully mixed to form the titanium-containing mixed slag.
- the smelting reduction reaction occurs; the slag temperature after mixing is 1570 ° C, and the temperature of the titanium-containing mixed slag is set in the range of 1400 to 1600 ° C;
- Vanadium-containing titanium molten steel slag containing components and mass percentage thereof 2.29 wt% V 2 O 5 , TFe 18.79 wt%, 41.64 wt% CaO, 11.36 wt% SiO 2 , 3.92 wt% TiO 2 , 3.54 wt% MgO, 1.43 wt% MnO, 1.37wt% Al 2 O 3 , the balance is other impurities;
- (1) Injecting gas The preheated air is sprayed into the titanium-containing mixed slag for a total of 5 minutes; wherein the preheating temperature of the air is 900 ° C, and the relationship between the air time and the flow rate is 105 L / (min). ⁇ kg); the air is sprayed by means of a refractory spray gun placed in the upper part of the mixed slag;
- the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the redox process measured the temperature of the mixed slag as high as 1620 ° C; because the temperature is higher than the set value, adding 2 kg of titanium-containing blast furnace slag at normal temperature to the titanium-containing mixed slag, 1 kg of ordinary iron concentrate carbon-containing pre-reduction pellets and 2kg of vanadium-titanium steel slag, the temperature of the titanium-containing mixed slag is reduced to 1550 ⁇ 1560 ° C, within the set range;
- the reducing property in the titanium-containing mixed slag is insufficient, and 3 kg of coke powder is added to the titanium-containing mixed slag, so that the remaining low-valent titanium is oxidized into high-priced titanium in the titanium-containing mixed slag, and the remaining iron oxide is reduced.
- Metal iron
- the reduced oxidized mixed slag is rotated and cooled to room temperature to obtain slow cooling slag; wherein, the specific operation of the rotary cooling is: the heat preservation device containing the mixed slag after redox is placed on the rotating platform, according to Rotation at a certain speed, the rotation speed depends on the quality of the slag and the height or depth of the insulation device, and the rotation time depends on the quality of the slag and the solidification of the slag;
- vanadium-containing metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out; the vanadium-containing metal iron layer in the remaining slow slag is crushed to a particle size of 20-400 ⁇ m, ground and magnetically separated.
- the remaining vanadium-containing metal iron; the metal iron recovery rate is 93%, and the total iron in the tailings slag is 0.463wt%;
- Tailings are used as phosphate fertilizer.
- a method for recovering and quenching and tempering a titanium-containing mixed slag comprises the following steps:
- Step 1 slag mixing:
- the liquid molten 400kg titanium-containing blast furnace slag and 45kg converter vanadium-containing titanium molten steel slag flowing out of the slag outlet are poured into the inner layer of the thermal insulation pit with metallurgical coke-high alumina composite thermal insulation mold release refractory material, fully mixed to form titanium-containing mixed melting Slag, smelting reduction reaction; slag temperature after mixing is 1420 ° C; temperature control range of titanium-containing mixed slag is 1400 ⁇ 1600 ° C;
- Vanadium-containing titanium molten steel slag containing components and mass percentage thereof 1.79 wt% V 2 O 5 , TFe 18.76 wt%, 43.84 wt% CaO, 12.92 wt% SiO 2 , 3.94 wt% TiO 2 , 3.78 wt% MgO, 1.21 wt %MnO, 1.26wt% Al 2 O 3 , the balance is other impurities;
- Injecting gas In the titanium-containing mixed slag, the preheated oxygen is sprayed and a total of 5 minutes of oxygen is sprayed; wherein the preheating temperature of oxygen is 1200 ° C, and the relationship between oxygen time and flow rate is 40 L/(min). ⁇ kg); the oxygen is sprayed by means of a refractory spray gun placed on the side of the mixed slag.
- the temperature of the titanium-containing mixed slag is set within 1400 to 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- measuring the mixed slag temperature is 1462 ⁇ 1467 ° C, within the set temperature range;
- vanadium-containing metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out; the vanadium-containing metal iron layer in the remaining slow slag is crushed to a particle size of 20-400 ⁇ m, ground and magnetically separated. Remaining vanadium-containing metal iron; metal iron recovery rate of 91%, total iron in the tailings slag of this step is 0.872wt%;
- the mass fraction of TiO 2 in the titanium concentrate is 44.27%, and the mass fraction of V 2 O 5 in the vanadium-bearing magnesia-alumina spinel is 8.89%.
- the mass fraction of P 2 O 5 is 28%;
- Tailings are used as phosphate fertilizer.
- a method for recovering and quenching and tempering a titanium-containing mixed slag comprises the following steps:
- Step 1 slag mixing:
- the liquid molten 400kg titanium-containing blast furnace slag and 65kg converter vanadium-containing titanium molten steel slag flowing out of the slag outlet are poured into a pourable insulating slag tank with an asphalt-semi-silica composite thermal insulation mold release refractory material, and fully mixed to form titanium-containing slag
- the molten slag is mixed to cause a smelting reduction reaction; the slag temperature after mixing is 1440 ° C; and the temperature of the titanium-containing mixed slag is set in the range of 1400 to 1600 ° C; wherein:
- Vanadium-containing titanium molten steel slag containing components and mass percentage 3.12 wt% V 2 O 5 , TFe 20.51 wt%, 41.19 wt% CaO, 9.34 wt% SiO 2 , 5.79 wt% TiO 2 , 1.24 wt% MgO, 2.31 wt% MnO, 1.30wt% Al 2 O 3 , the balance is other impurities;
- Injecting gas The preheated air is sprayed into the titanium-containing mixed slag for a total of 4 minutes; wherein the air preheating temperature is 1000 ° C, and the relationship between the air time and the flow rate is 87 L/(min ⁇ Kg); the air is blown by inserting a mixed slag into the refractory spray gun;
- the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- measuring the mixed slag temperature is 1500 ⁇ 1510 ° C, in the set temperature range;
- vanadium-containing metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out; the vanadium-containing metal iron layer in the remaining slow slag is crushed to a particle size of 20-400 ⁇ m, ground and magnetically separated.
- the remaining vanadium-containing metal iron; the metal iron recovery rate is 93%, and the total iron content in the tailings slag in this step is 0.502wt%;
- the mass fraction of TiO 2 in the titanium concentrate is 49.31%, and the mass fraction of V 2 O 5 in the vanadium-containing magnesium-aluminum spinel is 8.98%, and the P 2 in the phosphorus-rich phase
- the mass fraction of O 5 is 27%, re-separation separation, and the phosphorus recovery rate is 60%;
- Tailings are used as building materials.
- a method for recovering and quenching and tempering a titanium-containing mixed slag comprises the following steps:
- Step 1 slag mixing:
- the liquid molten 400kg titanium-containing blast furnace slag and 80kg converter vanadium-containing titanium molten steel slag flowing out of the slag outlet are poured into the pourable thermal insulation slag tank with the bituminous coal-spinel composite thermal insulation mold release refractory material, and fully mixed to form
- the titanium mixed slag is subjected to a smelting reduction reaction; the slag temperature after mixing is 1450 ° C; and the temperature of the titanium-containing mixed slag is set in the range of 1400 to 1600 ° C; wherein:
- Vanadium-containing titanium molten steel slag containing components and mass percentage thereof 0.62 wt% V 2 O 5 , TFe 18.74 wt%, 41.32 wt% CaO, 12.74 wt% SiO 2 , 4.78 wt% TiO 2 , 3.14 wt% MgO, 1.29 wt %MnO, 1.87wt% Al 2 O 3 , the balance is other impurities;
- Injecting gas The preheated air is sprayed into the titanium-containing mixed slag for a total of 4 minutes; wherein the air preheating temperature is 0 ° C, and the relationship between the air time and the flow rate is 23 L/(min ⁇ Kg); the air is blown by inserting a mixed slag into the refractory spray gun;
- the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the measured mixed slag temperature is 1468 ⁇ 1476 ° C, within the set range;
- vanadium-containing metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out; the vanadium-containing metal iron layer in the remaining slow slag is crushed to a particle size of 20-400 ⁇ m, ground and magnetically separated.
- the remaining vanadium-containing metal iron; the metal iron recovery rate is 91%, and the total iron content in the slag is 0.519wt%;
- the titanium-containing component is separated from the gangue to obtain a titanium concentrate with a main phase of perovskite phase, including In the vanadium-magnesium-aluminum spinel mine and tailings, the mass fraction of TiO 2 in the titanium concentrate is 42.87%, and the mass fraction of V 2 O 5 in the vanadium-bearing magnesium-aluminum spinel is 8.71%. The mass fraction of P 2 O 5 is 28%;
- tailings are separated by 2% dilute sulfuric acid, and the phosphorus pentoxide is separated by a solid-liquid ratio of 1:2, and the phosphorus recovery rate is 75%.
- a method for recovering and quenching and tempering a titanium-containing mixed slag comprises the following steps:
- Step 1 slag mixing:
- the liquid molten 400kg titanium-containing blast furnace slag and 50kg electric furnace vanadium-containing titanium molten oxidized steel slag flowing out of the slag outlet are poured into the thermal insulation pit with carbon-clay composite thermal insulation mold release refractory material, and fully mixed to form titanium-containing mixed slag.
- Smelting reduction Reaction; the slag temperature after mixing is 1430 ° C; the temperature of the titanium-containing mixed slag is set in the range of 1400 ⁇ 1600 ° C;
- Vanadium-containing titanium molten steel slag containing components and mass percentage thereof 2.32 wt% V 2 O 5 , TFe 18.76 wt%, 42.25 wt% CaO, 11.96 wt% SiO 2 , 4.89 wt% TiO 2 , 3.26 wt% MgO, 1.45 wt %MnO, 1.69wt% Al 2 O 3 , the balance is other impurities;
- Injecting gas In the titanium-containing mixed slag, the preheated oxygen is sprayed and a total of 7 minutes of oxygen is sprayed; wherein the oxygen preheating temperature is 900 ° C, and the relationship between the oxygen time and the flow rate is 9 L/(min ⁇ Kg); the oxygen is injected by means of a refractory spray gun inserted into the mixed slag;
- the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the mixed slag temperature is 1483 ⁇ 1491 ° C, within the set range;
- vanadium-containing metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out; the vanadium-containing metal iron layer in the remaining slow slag is crushed to a particle size of 20-400 ⁇ m, ground and magnetically separated.
- the remaining vanadium-containing metal iron; the metal iron recovery rate is 92%, and the total iron content in the tailings slag in this step is 0.741wt%;
- the lower slow cooling slag is once coarsely selected, the shaker is selected once, and the sweeping is performed twice.
- the upper and middle sections are firstly selected by a chute, the shaker is selected once, and the sweeping is performed once, and the titanium-containing component is separated from the gangue to obtain a titanium concentrate having a main phase of a perovskite phase, a vanadium-containing magnesium-aluminum tip.
- the mass fraction of TiO 2 in the titanium concentrate is 36.39%, and the mass fraction of V 2 O 5 in the vanadium-containing magnesium-aluminum spinel is 8.07%, and the P 2 O 5 in the phosphorus-rich phase.
- the quality score is 26%;
- Tailings are used as phosphate fertilizer.
- a method for recovering and quenching and tempering a titanium-containing mixed slag comprises the following steps:
- Step 1 slag mixing:
- the liquid molten 40kg titanium-containing blast furnace slag and 400kg electric furnace vanadium-containing titanium fused oxide steel slag flowing out of the slag outlet are poured into the inner layer.
- slag temperature after mixing is 1580 ° C;
- temperature is set at 1400 of titanium-containing mixed slag ⁇ 1600°C; among them;
- Vanadium-containing titanium molten steel slag containing components and mass percentage thereof 1.34 wt% V 2 O 5 , TFe 18.72 wt%, 41.19 wt% CaO, 12.37 wt% SiO 2 , 4.96 wt% TiO 2 , 3.19 wt% MgO, 1.89 wt %MnO, 1.29wt% Al 2 O 3 , the balance is other impurities;
- Injecting gas In the titanium-containing mixed slag, oxygen is pre-heated and a total of 14 minutes of oxygen is sprayed; wherein the oxygen preheating temperature is 180 ° C, and the relationship between oxygen time and flow rate is 1.8 L/(min). ⁇ kg); the way of blowing oxygen is to insert a mixed slag into the refractory spray gun;
- the temperature of the titanium-containing mixed slag is within the set temperature of 1400 to 1600 ° C
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the reduction oxidation process measured the mixed slag temperature as high as 1618 ° C, because the temperature is higher than the set value, adding 2 kg of vanadium-containing titanium steel slag to the titanium-containing mixed slag, so that the temperature of the titanium-containing mixed slag is 1520 ⁇ 1525 ° C, in the set temperature range;
- vanadium-containing metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out; the vanadium-containing metal iron layer in the remaining slow slag is crushed to a particle size of 20-400 ⁇ m, ground and magnetically separated.
- the remaining vanadium-containing metal iron; the metal iron recovery rate is 93%, and the total iron content in the tailings slag in this step is 0.879wt%;
- Tailings are used as phosphate fertilizer.
- a method for recovering and quenching and tempering a titanium-containing mixed slag comprises the following steps:
- Step 1 slag mixing:
- the liquid molten 200kg titanium-containing blast furnace slag and the 200kg electric furnace vanadium-containing titanium molten oxidized steel slag which are discharged from the slag outlet are poured into the thermal insulation pit of the carbon-olivine composite thermal insulation mold release refractory material, and fully mixed to form mixed slag.
- a smelting reduction reaction occurs; the slag temperature after mixing is 1440 ° C; and the temperature of the titanium-containing mixed slag is set in the range of 1400 to 1600 ° C;
- Vanadium-containing titanium molten steel slag containing components and mass percentage thereof 0.39 wt% V 2 O 5 , TFe 18.72 wt%, 42.26 wt% CaO, 12.17 wt% SiO 2 , 4.96 wt% TiO 2 , 3.15 wt% MgO, 1.57 wt %MnO, 1.91wt% Al 2 O 3 , the balance is other impurities;
- Injecting gas In the titanium-containing mixed slag, the preheated oxygen is sprayed and the oxygen is sprayed for 2 minutes; wherein the oxygen preheating temperature is 1050 ° C, and the relationship between the oxygen time and the flow rate is 20 L/(min ⁇ Kg); the oxygen is injected by means of a refractory spray gun inserted into the mixed slag;
- the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the mixed slag temperature measured during the reduction process is 1470 ⁇ 1480 ° C, within the set range;
- vanadium-containing metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out; the vanadium-containing metal iron layer in the remaining slow slag is crushed to a particle size of 20-400 ⁇ m, ground and magnetically separated.
- the remaining vanadium-containing metal iron; the metal iron recovery rate is 92%, and the total iron content in the tailings slag in this step is 0.879wt%;
- the lower slow-cooling slag is coarsely selected through the chute, and the shaker is selected once, which will contain
- the titanium component is separated from the gangue to obtain a titanium concentrate with a main phase of perovskite phase, a mineral containing vanadium-magnesium-aluminum spinel and a tailings.
- the mass fraction of TiO 2 in the titanium concentrate is 32.19%, including
- the mass fraction of V 2 O 5 in the vanadium-magnesium-aluminum spinel is 8.20%, and the mass fraction of P 2 O 5 in the phosphorus-rich phase is 27%;
- Tailings are used as phosphate fertilizer.
- a method for recovering and quenching and tempering a titanium-containing mixed slag comprises the following steps:
- Step 1 slag mixing:
- the liquid molten 100kg titanium-containing blast furnace slag and the 500kg electric furnace vanadium-containing titanium molten oxidized steel slag which are discharged from the slag outlet are poured into the thermal insulation pit of the graphite-vanadium-containing titanium steel slag composite thermal insulation mold release refractory material, and fully mixed to form mixed slag.
- a smelting reduction reaction occurs; the slag temperature after mixing is 1470 ° C; and the temperature of the titanium-containing mixed slag is set in the range of 1400 to 1600 ° C;
- Vanadium-containing titanium molten steel slag containing components and mass percentage thereof 2.14 wt% V 2 O 5 , TFe 16.71 wt%, 43.26 wt% CaO, 12.38 wt% SiO 2 , 0.53 wt% TiO 2 , 2.96 wt% MgO, 1.85 wt %MnO, 1.79wt% Al 2 O 3 , the balance is other impurities;
- Injecting gas In the titanium-containing mixed slag, oxygen is pre-heated and a total of 4 minutes of oxygen is sprayed; wherein the oxygen preheating temperature is 280 ° C, and the relationship between oxygen time and flow rate is 10 L/(min ⁇ Kg); the oxygen is injected by means of a refractory spray gun inserted into the mixed slag;
- the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the mixed slag temperature is 1520 ⁇ 1530 ° C, within the set temperature range;
- a method for recovering and quenching and tempering a titanium-containing mixed slag comprises the following steps:
- Step 1 slag mixing:
- the liquid molten 400kg titanium-containing blast furnace slag and the 360kg electric furnace vanadium-containing titanium molten oxidized steel slag flowing out of the slag outlet are poured into the pourable slag pot with the petroleum pitch-titanium blast furnace slag composite thermal insulation mold release refractory material, and fully mixed.
- Vanadium-containing titanium molten steel slag containing components and mass percentage thereof 2.24 wt% V 2 O 5 , TFe 16.94 wt%, 42.86 wt% CaO, 11.29 wt% SiO 2 , 4.86 wt% TiO 2 , 2.98 wt% MgO, 1.94 wt %MnO, 1.78wt% Al 2 O 3 , the balance is other impurities;
- Injecting gas In the titanium-containing mixed slag, the preheated oxygen is sprayed and a total of 7 minutes of oxygen is sprayed; wherein the oxygen preheating temperature is 300 ° C, and the relationship between the oxygen time and the flow rate is 50 L/(min ⁇ Kg); the oxygen is injected by means of a refractory spray gun inserted into the mixed slag;
- the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the reduction oxidation process measures the mixed slag temperature of 1470 ⁇ 1478 ° C, within the set range;
- vanadium-containing metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out; the vanadium-containing metal iron layer in the remaining slow slag is crushed to a particle size of 20-400 ⁇ m, ground and magnetically separated.
- the remaining vanadium-containing metal iron; the metal iron recovery rate is 92%, and the total iron content in the tailings slag in this step is 0.778 wt%;
- a titanium concentrate with a main phase of perovskite phase, a vanadium-bearing magnesium-aluminum spinel ore and tailings, and the mass fraction of TiO 2 in the titanium concentrate is 38.28%, the mass fraction of V 2 O 5 in the vanadium-bearing magnesium-aluminum spinel is 8.51%, and the mass fraction of P 2 O 5 in the phosphorus-rich phase is 27%;
- tailings were separated by 2% hydrochloric acid, and the phosphorus pentoxide was separated by a solid-liquid ratio of 1:2, and the phosphorus recovery rate was 70%.
- a method for recovering and quenching and tempering a titanium-containing mixed slag comprises the following steps:
- Step 1 slag mixing:
- the liquid molten 40kg titanium-containing blast furnace slag flowing out from the slag outlet and the 400kg electric furnace vanadium-containing titanium molten oxidized steel slag are poured into the pourable smelting reaction slag tank with metallurgical coke-spinel composite thermal insulation release refractory material, fully Mixing to form a titanium-containing mixed slag, and a smelting reduction reaction occurs; after mixing, the slag temperature is 1610 ° C;
- Vanadium-containing titanium molten steel slag containing components and mass percentage thereof 0.3 wt% V 2 O 5 , TFe 16.94 wt%, 45.32 wt% CaO, 10.36 wt% SiO 2 , 3.54 wt% TiO 2 , 2.67 wt% MgO, 1.85 wt %MnO, 1.64wt% Al 2 O 3 , the balance is other impurities;
- Injecting gas In the titanium-containing mixed slag, preheating oxygen-enriched air is sprayed, and oxygen-enriched air is sprayed for 5 minutes; wherein the volume percentage of oxygen in the oxygen-enriched air is 22%, and the oxygen-enriched air is pre-charged.
- the heat temperature is 1200 ° C
- the relationship between the time of oxygen-enriched air and the flow rate is 60 L / (min ⁇ kg)
- the method of blowing oxygen-enriched air is to insert the refractory spray gun into the side of the slag;
- the temperature of the titanium-containing mixed slag is in the range of the set temperature of 1450 to 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the redox process measures the mixed slag temperature up to 1655 ° C; because the temperature is higher than the set value, 3 kg of vanadium-titanium magnetite concentrate metallized pellets are blown into the titanium-containing mixed slag to make the titanium-containing mixture The temperature of the slag is lowered to 1560 ⁇ 1570 ° C, within the set range;
- the temperature of the mixed slag after reduction and oxidation is lowered to 1250 ° C, and the mixed slag after reduction and oxidation in the middle and upper portions is water quenched and used as a cement raw material or a building material;
- the lower reduced oxidized mixed slag is spin-cooled to room temperature to obtain slow cooling slag;
- the rotary cooling operation is: the heat preservation device containing the mixed slag after redox is placed on the rotating platform at a certain speed Rotation, the rotation speed depends on the quality of the slag and the height or depth of the insulation device, and the rotation time depends on the quality of the slag and the solidification of the slag;
- the vanadium-containing metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out; the vanadium-containing metal iron layer in the remaining slow slag is crushed to a particle size of 20-400 ⁇ m, and the remaining vanadium is separated by magnetic separation.
- the upper, middle and lower parts of the slow-cooling slag for removing iron slag and vanadium-containing metal iron layer are separated by gravity separation method; the lower slow cooling slag is coarsely selected through the chute, the shaker is selected once, and the sweeping is performed twice.
- the titanium-containing component is separated from the gangue to obtain a titanium concentrate with a main phase of perovskite phase, a vanadium-bearing magnesium-aluminum spinel ore and tailings, and the mass fraction of TiO 2 in the titanium concentrate is 35.00%.
- the mass fraction of V 2 O 5 in the vanadium-containing magnesium-aluminum spinel is 9.21%; the mass fraction of P 2 O 5 in the phosphorus-rich phase is 26%;
- the tailings were separated by 2% hydrochloric acid, and the ratio of solid to liquid was 1:2, and the phosphorus recovery was 60%.
- a method for recovering and quenching and tempering a titanium-containing mixed slag comprises the following steps:
- Step 1 slag mixing:
- the liquid molten 150kg titanium-containing blast furnace slag flowing out from the slag outlet and the 500kg electric furnace vanadium-containing titanium molten oxidized steel slag are poured into a converter with a graphite-magnesium composite thermal insulation mold release refractory, and fully mixed to form a titanium-containing mixed slag, which occurs. Smelting reduction reaction; the slag temperature after mixing is 1610 ° C;
- Vanadium-containing titanium molten steel slag containing components and mass percentage thereof 5.00 wt% V 2 O 5 , TFe 15.49 wt%, 41.78 wt% CaO, 15.11 wt% SiO 2 , 2.54 wt% TiO 2 , 1.86 wt% MgO, 1.79 wt %MnO, 1.62wt% Al 2 O 3 , the balance is other impurities;
- Injecting gas a preheated nitrogen-air mixture is sprayed into the titanium-containing mixed slag, and a nitrogen-air mixture is blown for 10 minutes; wherein the volume percentage of nitrogen in the nitrogen-air mixture is 40%. %, nitrogen-air mixture preheating temperature is 500 °C, nitrogen-air mixture time and flow rate relationship is 40L / (min ⁇ kg); nitrogen-air mixture injection method is to use refractory spray gun placed in mixed slag Blow in the upper part;
- the temperature of the titanium-containing mixed slag is in the range of the set temperature of 1450 to 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the redox process measures the temperature of the mixed slag as high as 1618 ° C; because the temperature is higher than the set value, 1 kg of the titanium magnet concentrate concentrate containing carbon pre-reduction pellets is blown into the titanium-containing mixed slag to make titanium The temperature of the mixed slag is lowered to 1575 ⁇ 1582 ° C, within the set range;
- the vanadium-containing titanium slag after reduction and oxidation is subjected to slag treatment outside the furnace, and the mass fraction of the vanadium-containing titanium slag TiO 2 after reduction oxidation is determined to be 8.9% ⁇ 10% by method D-1.
- the oxidized vanadium-containing titanium slag is directly cooled and used as a cement raw material or building material;
- a method for recovering and quenching and tempering a titanium-containing mixed slag comprises the following steps:
- Step 1 slag mixing:
- the liquid molten 420kg titanium-containing blast furnace slag and 380kg electric furnace vanadium-containing titanium fused oxide steel slag flowing out of the slag outlet are poured into a DC arc furnace with an asphalt-olivine composite thermal insulation mold release refractory material, and fully mixed to form a titanium-containing mixed melting furnace.
- Slag, smelting reduction reaction; slag temperature after mixing is 1380 ° C;
- Vanadium-containing titanium molten steel slag containing components and mass percentage thereof 2.56 wt% V 2 O 5 , TFe 15.36 wt%, 40.25 wt% CaO, 11.39 wt% SiO 2 , 5.35 wt% TiO 2 , 2.64 wt% MgO, 1.92 wt %MnO, 1.59wt% Al 2 O 3 , the balance is other impurities;
- the refractory spray gun is inserted into the mixed slag to be blown;
- the temperature of the titanium-containing mixed slag is in the range of the set temperature of 1450 to 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the reduced-oxidized vanadium-containing titanium slag is directly quenched and used as a cement raw material or a building material;
- a method for recovering and quenching and tempering a titanium-containing mixed slag comprises the following steps:
- Step 1 slag mixing:
- the liquid molten 400kg titanium-containing blast furnace slag and 100kg converter vanadium-containing titanium molten steel slag flowing out of the slag outlet are poured into an inner layer of an anthracite-clay composite thermal insulation mold release refractory, and fully mixed to form a titanium-containing mixed slag. a smelting reduction reaction occurs; the slag temperature after mixing is 1389 ° C;
- Vanadium-containing titanium molten steel slag containing components and mass percentage thereof 5.21 wt% V 2 O 5 , TFe 15.68 wt%, 40.01 wt% CaO, 12.12 wt% SiO 2 , 4.86 wt% TiO 2 , 2.66 wt% MgO, 1.90 wt %MnO, 1.71wt% Al 2 O 3 , the balance is other impurities;
- Injecting gas a pre-heated nitrogen-oxygen mixed gas is sprayed into the titanium-containing mixed slag, and a nitrogen-oxygen mixed gas is sprayed for 8 minutes; wherein the volume percentage of nitrogen in the nitrogen-oxygen mixed gas is 60%. %, the preheating temperature of the nitrogen-oxygen mixture is 480 ° C, the relationship between the time of the nitrogen-oxygen mixture and the flow rate is 10 L / (min ⁇ kg); the blowing method of the nitrogen - oxygen mixture is to insert the mixed slag with the refractory spray gun Blow in
- the temperature of the titanium-containing mixed slag is in the range of the set temperature of 1450 to 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the reduction oxidation process measures the mixed slag temperature of 1480 ⁇ 1488 ° C, within the set range;
- method D-2 is adopted for the treatment of slag outside the furnace:
- the reduced oxidation-containing vanadium-containing titanium slag is poured into the thermal insulation pit of the bituminous coal-high alumina composite thermal insulation mold release refractory material, and then the following operations are performed:
- the preheated nitrogen-oxygen mixed gas is sprayed, and a nitrogen-oxygen mixed gas is sprayed for 2 minutes; wherein the volume percentage of nitrogen in the nitrogen-oxygen mixture is 60%.
- the preheating temperature of the nitrogen-oxygen mixture is 500 °C, the relationship between the time of the nitrogen-oxygen mixture and the flow rate is 12 L/(min ⁇ kg); the blowing method of the nitrogen-oxygen mixture is to insert the mixed slag into the refractory spray gun. ;
- the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the reduction oxidation process measured the mixed slag temperature to be 1422 ⁇ 1429 ° C, within the set range;
- the remaining low-priced titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the oxidized slag is reduced and naturally cooled to room temperature to obtain a slow cooling slag
- the vanadium-containing metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out; the vanadium-containing metal iron layer in the remaining slow slag is crushed to a particle size of 20-400 ⁇ m, and the remaining vanadium is separated by magnetic separation.
- the upper, middle and lower parts of the slow-cooling slag for removing iron slag and vanadium-containing metal iron layer are separated by gravity separation method; the lower slow cooling slag is coarsely selected through the chute, the shaker is selected once, and the sweeping is performed twice.
- the titanium-containing component is separated from the gangue to obtain a titanium concentrate with a main phase of perovskite phase, a vanadium-bearing magnesium-aluminum spinel medium ore and tailings, and the mass fraction of TiO 2 in the titanium concentrate is 48.96%.
- the mass fraction of V 2 O 5 in the vanadium-containing magnesium-aluminum spinel is 9.65%
- the mass fraction of P 2 O 5 in the phosphorus-rich phase is 30%;
- the tailings were treated with 2% hydrochloric acid, and the phosphorus pentoxide was separated by a solid-liquid ratio of 1:2, and the phosphorus recovery rate was 80%.
- a method for recovering and quenching and tempering a titanium-containing mixed slag comprises the following steps:
- Step 1 slag mixing:
- the liquid molten 380kg titanium-containing blast furnace slag and 480kg converter vanadium-containing titanium molten steel slag flowing out of the slag outlet are poured into a converter with petroleum pitch coke-silice composite thermal insulation mold release refractory, and fully mixed to form titanium-containing mixed slag. a smelting reduction reaction occurs; the slag temperature after mixing is 1632 ° C;
- Vanadium-containing titanium molten steel slag containing components and mass percentage thereof 1.32 wt% V 2 O 5 , TFe 16.59 wt%, 43.12 wt% CaO, 13.33 wt% SiO 2 , 5.06 wt% TiO 2 , 3.68 wt% MgO, 2.67 wt %MnO, 2.00wt% Al 2 O 3 , the balance is other impurities;
- Injecting gas In the titanium-containing mixed slag, the preheated oxygen is sprayed and a total of 6 minutes of oxygen is sprayed; wherein the oxygen preheating temperature is 1000 ° C, and the relationship between the oxygen time and the flow rate is 45 L/(min ⁇ Kg); the air is blown by inserting a mixed slag into the refractory spray gun;
- the temperature of the titanium-containing mixed slag is in the range of the set temperature of 1450 to 1600 ° C;
- the temperature of the mixed slag measured by the redox process is as high as 1612 ° C; since the temperature is higher than the set value, 1 kg of ordinary iron concentrate metallized pellets is added to the titanium-containing mixed slag to make the titanium-containing mixed slag The temperature is lowered to 1580 ⁇ 1585 ° C, within the set range;
- the preheated oxygen is sprayed and a total of 3 minutes of oxygen is sprayed; wherein the preheating temperature of the oxygen mixed gas is 960 ° C, and the relationship between the time and flow rate of the oxygen mixed gas is 40 L/(min). ⁇ kg); the oxygen mixed gas is injected by means of a refractory spray gun inserted into the mixed slag;
- the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;
- the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the reduction oxidation process measures the mixed slag temperature of 1570 ⁇ 1576 ° C, within the set range;
- the remaining low-priced titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;
- the mixed slag after reduction and oxidation is separated, and the precipitated slag-gold is separated to obtain vanadium-containing molten iron and reduced-oxidized vanadium-containing titanium slag;
- the mass fraction of the vanadium-containing titanium slag TiO 2 after reduction and oxidation is 8.5% ⁇ 10%
- the reduced-oxidized vanadium-containing titanium slag is directly quenched and used as a cement raw material or a building material.
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Abstract
一种含钛混合熔渣熔融还原回收与调质处理的方法,包括:1)含钛高炉熔渣和含钒钛熔融钢渣混合形成含钛混合熔渣,将含钛混合熔渣的温度控制在设定温度范围;2)喷吹氧化性气体,进行熔融还原与氧化,过程中保证含钛混合熔渣的温度在设定温度范围内,且含钛混合熔渣中,低价钛氧化成高价钛,铁氧化物还原成金属铁;3)根据反应装置不同进行分离回收。该方法实现混合熔渣中钛组分、铁组分、钒组分、磷组分与自由氧化钙组分的高效回收,可处理冷态含钒、钛、铁物料,实现熔渣调质处理,资源高效综合利用,且反应时间短、金属回收率高、生产成本低、原料适应性强、处理量大、环境友好、经济收益高、可有效解决冶金资源与热能高效回收利用问题。
Description
本发明属于非高炉炼铁与资源综合利用领域,具体涉及一种含钛混合熔渣熔融还原回收与调质处理的方法。
我国是钛资源大国,拥有丰富的钒钛磁铁矿资源,主要分布在攀西与承德地区。钒钛磁铁矿是铁、钒、钛、铬、磷、铜、镍、钴、钪、铌、锆、钇等多种有价元素共生的复合矿。经过多年多年技术攻关,我国采用“钒钛磁铁矿选矿一高炉炼铁一铁水吹钒渣一转炉炼钢”选冶工艺流程,钒渣一钠化或钙化焙烧工艺流程,实现了钒钛磁铁矿的大规模利用,并产生了含钛高炉渣、含钒钛钢渣、提钒尾渣等固体废弃物。含钒钛废弃物中含有较高含量的铁、钒、钛、铬、磷等多种有价元素,是重要的二次资源。
含钛高炉渣产生于钒钛磁铁矿的高炉炼铁过程,其TiO2含量为4~30%,含钒生铁含量为4~8%,五氧化二钒含量为0.1~0.5%,并含有铬、镓、钪等有价元素,含钛高炉渣是一种重要的二次资源;由高炉放出的含钛高炉熔渣温度高于等于1300℃,每年排放大量的物理热,因此,含钛高炉熔渣也是重要的物理热资源。
含钒钛钢渣产生于钒钛磁铁矿的炼钢过程,其TiO2含量为0.5~10%,金属铁含量为4~12%,铁氧化含量为10~35%,五氧化二钒含量为0.5~5%,五氧化二磷含量为0.2~6%,三氧化二铬含量为0.1~5%,并含有一定的自由氧化钙(10%左右)。含钒钛钢渣是一种重要的二次资源;含钒钛熔融钢渣温度高于等于1500℃,每年排放大量的物理热,因此,含钒钛熔融钢渣也是重要的物理热资源。
含钛高炉渣和含钒钛钢渣同属人造矿,含钛、钒、铁、磷、钙等物相分散细小,属难处理矿,其综合利用问题尚未得到高效解决。我国每年排放2000万吨以上含钛高炉渣,堆积已超过上亿吨含钛高炉渣,相当于堆积1500万吨以上的TiO2,含钒生铁1500万吨以上,五氧化二钒30万吨以上,总价值上万亿。同时,每年排放700万吨以上含钒钢渣,堆积已超过2000万吨以上,相当于堆积60万吨以上的TiO2,金属铁400万吨以上,五氧化二钒60万吨以上,五氧化二磷15万吨以上,自由氧化钙200万吨以上,总价值上千亿。大量含钛渣(含钛高炉渣与含钒钛钢渣)大量堆积,既浪费资源,又污染环境。
含钛高炉渣与含钒钛钢渣是重要的冶金资源,不仅含有铁、钒、钛、铬等有价组分,还含有大量的CaO、SiO2等冶金熔剂。国内外对含钛高炉渣与含钒钛钢渣的综合利用作了大量的研究,取得了一定成果,然而,很多方法尽管在技术上可行,但由于经济上,环境上不可
行,至今尚不能用于工业应用和开发。
目前,科研工作者们对含钛高炉渣与含钒钛钢渣与提钒弃渣的综合利用研究如下:
一.含钛高炉渣的综合利用
包括碱法提钛、酸法提钛、制备含钛合金、含钛高炉渣碳氮化提钛、高温改性-析出-选矿分离、用作建筑材料等方法。
碱法提取钛碱耗量大,考虑回收钠盐将大大增加成本和全套工艺的复杂程度,钛的富集效果也并不十分理想,贫钛相中钛含量仍然较高、处理不当可能产生新的污染,同时高温下用碱处理高炉渣会产生较严重的空气污染和巨大的能耗等问题。
硫酸或盐酸法提取分离含钛高炉渣,酸的消耗量大,产生大量废酸和尾渣,严重污染环境。盐酸浸取自然冷却含钛高炉渣是一种利用含钛高炉渣的途径,然而,盐酸浸出后会产生大量浸出残渣,浸出残渣没有合适的用途,也就是说,盐酸浸出后又会产生新的废弃物。
由于同时需要钛和硅作为合金化剂的钢种很少,钛硅合金的应用范围窄,用量小,无法解决攀钢高炉渣数量大的问题,这是该技术方案难以实现产业化的关键所在。此外,还原残渣虽然具有潜在的水硬性,残钛量仍然较高,需要进一步降低其含量,但又可能造成成本太高。
含钛高炉渣碳氮化提钛是一种利用含钛高炉渣的途径,亦存在一些明显缺点,如电炉碳化电耗过高这一关键问题没有解决,电费占碳化渣总成本的70~80%以上,产生大量的氯化残渣,带来严重的二次污染,此外,还暴露出炉底以及某些冶炼炉有较严重的泡沫渣等问题,生产难以连续。
直接水淬,用作水泥原料,或用作建筑材料,但水泥原料要求渣中TiO2≤10wt%,如果TiO2>10wt%,将不能用作水泥原料。用作铸石、矿渣棉等,处理量小。
针对含钛高炉渣利用的以上种种问题,本发明人曾在专利号为200610134260.3的“从含钛高炉渣中分离生产富钛料的方法”及专利号为201110072575.0的“一种用含钛高炉渣生产人造金红石的方法”中提出了两种利用含钛高炉渣的方法,尽管以上两种方法具有处理量大的特点,但是仍然存在如下缺点:
1.以上两个专利中的方法只能实现一种炉渣即含钛高炉熔渣的有效利用,化学活性低,温度低,处理成本高,铁、钛组分迁移、富集与长大效果差,回收率低,仅能实现铁、钛组回收利用,没有实现有价元素的有效富集;2.以上两个专利中的方法只能利用一种炉渣即含钛高炉熔渣,单一炉渣-含钛高炉渣熔渣温度低,需要补偿大量热,成本高,操作复杂;3.不能处理冷态含钛高炉渣;4.以上两个专利中均需要加入SiO2、CaO、CaF2等添加剂,在添加剂加入的过程中会使熔渣温度迅速下降,浪费了熔渣中的一部分热量,因此,需要补偿热量,浪费能源,增加成本,加大处理过程的复杂性;5.以上两种发明中采用的分离方法均为
重选与浮选及湿法冶金的方式相结合的方法,浮选分离及湿法冶金分离过程容易造成环境污染。
二.含钒钛钢渣的综合利用
目前,含钛钢渣主要采用水淬工艺、钢渣“闷罐”处理工艺,磁选回收渣中金属铁,但回收率低,渣中剩余金属铁含量高达5%,该工艺仅考虑回收渣中金属铁,没有考虑回收渣中含量高达30%以上的铁氧化物。水淬工艺、钢渣“闷罐”处理工艺消耗大量水资源,产生腐蚀性热蒸汽、热量不能回收、水资源不能循环,大量热资源很难得到利用。同时,渣中游离CaO和MgO降低了钢渣体积的稳定,较高含量的铁氧化物增加了磨矿的难度,限制了钢渣的应用。含钒钛钢渣中钒组分的综合利用,还处在研究阶段,尚未有关于对于钛的回收利用。因此,含钒钛钢渣大量堆积,既污染环境,又浪费资源。
高炉液态熔融含钛高炉渣和含钒熔融钢渣,蕴含着丰富的热能资源,含有大量的热态冶金熔剂,而且含有较高含量的铁、钒、钛、铬、磷、钙等多种有价元素,是重要的二次资源。液态熔融含钛高炉渣为还原性熔渣,含钒熔融钢渣为氧化性熔渣,都是物理化学性质优良的熔渣体系。
基于此,针对现有技术存在的问题,本发明人曾在专利号为ZL201310290767.8“一种从含钛混合熔渣中分离铁钛钒钙的方法”中,提供一种从含钛混合熔渣(含钛高炉熔渣与含钒钛熔融钢渣)中分离铁钛钒钙的方法,该发明具有如下优点:(1)原料是出渣口中流出的液态熔融含钛高炉渣(≥1300℃)和钢渣(≥1500℃),具有高温度、高热量的特点,充分利用了熔渣物理热资源,高效节约能源;(2)由于液态熔融含钛高炉渣中具有高含量的自由氧化钙,液态熔融转炉钢渣中具有高含量的低价钛氧化物,在高温条件下具有高化学活性,容易实现钒、钛、铁、钙组分迁移与富集,可以同时回收混合熔渣中钛组分、铁组分、钒组分与自由氧化钙组分,达到二次资源高效综合回收,回收利用含钛高炉熔渣与含钒钛熔融钢渣物理热资源;(3)在后续的分离过程采用物理选矿(磁选或重选),分离的介质为水,水在选矿过程中可以循环,因而分离过程中不会产生环境污染,使得整个含钛混合熔渣工艺具有流程短、操作简单、铁、钒、钛、钙回收率高、无废水产生,具有高效、清洁、环保的特点;(4)重选分离获得的尾矿可作为生产高标号水泥的优质原料,整个处理过程无固体废弃物产生;(5)整个过程无需加入任何添加剂,无需任何热补偿,可操作性强,生产成本低。
尽管以上方法具有明显的特点,但是仍然存在如下缺点:(1)只能处理热态熔渣(含钛高炉熔渣与含钒钛熔融钢渣),不能处理冷态含钒钛物料;(2)含钛混合熔渣(含钛高炉熔渣与含钒钛熔融钢渣)中还原态物质氧化放热,熔渣温度过高,容易损坏保温脱模炉衬材料及罐体,使其寿命减少;(3)含钛混合熔渣(含钛高炉熔渣与含钒钛熔融钢渣)中还原态物质氧化放热,
熔渣温度过高,混合熔渣中金属铁加速氧化为铁氧化物,金属铁的沉降减少,金属铁的回收率下降;(4)含钛混合熔渣还原态物质氧化放热,熔渣温度过高,造成大量热资源浪费;(5)金属铁回收率低,仅回收了混合熔渣中金属铁,没有考虑混合熔渣中铁氧化物的还原与回收;(6)没有充分利用含钛高炉熔渣的还原性与还原性;(7)仅考虑了熔渣中单质钒的回收,没有回收熔渣中含钒氧化物;(8)没有控制熔渣氧势,混合熔渣中铁氧化物部分还原,部分还原铁重新氧化,因此,渣中铁氧化物含量较高,难以磨矿;(9)富钛相-钙钛矿相没有沉降,炉渣量大,磨矿成本、磁选成本与重选成本高;(10)没有回收磷组分;(11)熔渣没有进行调质处理,尾矿利用受到限制。
发明内容
针对现有技术存在的问题,本发明提供一种含钛混合熔渣熔融还原回收与调质处理的方法。该方法是一种由含钛混合熔渣回收含钒生铁或含钒钢、富钛相、富钒相、富磷相与熔渣调质处理的方法;该方法反应时间短、金属回收率高、生产成本低、原料适应性强、处理量大、环境友好、经济收益高、可有效解决冶金资源与热能高效回收利用问题;本发明方法是一种新的熔融还原氧化工艺。
本发明的含钛混合熔渣熔融还原回收与调质处理的方法,充分利用含钛高炉熔渣与含钒钛熔融钢渣物理热资源和热态冶金熔剂,及含钛高炉熔渣的还原性与含钒钛熔融钢渣的氧化性,通过两种熔渣混合,及喷吹氧化性气体,实现了熔融还原与氧化:①混合熔渣中的钛组分在氧化气氛下得到充分氧化,铁氧化物得到充分还原为金属铁;②混合熔渣中的含钒金属铁组分聚集、长大与沉降;③混合熔渣中的钛与钙组分迁移、富集于钙钛矿相,并实现长大与沉降;④混合熔渣中的钒组分分别迁移、富集于金属铁相与富钒相,并实现长大与沉降;⑤混合熔渣中的磷组分迁移、富集于Ca2SiO4-Ca3(PO4)2相,分布于钙钛矿相界面;⑥混合熔渣中的自由氧化钙与氧化镁消失,铁氧化物还原成金属铁,混合熔渣实现调质;采用人工分拣、磁选与重选结合的方法,分离沉降在底部的含钒金属铁、富钒氧化物相、钙钛矿相,实现混合熔渣中钛组分、铁组分、钒组分、磷组分与自由氧化钙组分的高效回收;可以处理固态含钒、钛、铁物料,同时实现熔渣调质处理,达到资源高效综合利用;
具体包括以下步骤:
步骤1,熔渣混合:
按质量比,含钛高炉熔渣∶含钒钛熔融钢渣=100∶(1~1000)配料,加入保温装置、可倾倒的熔炼反应装置或固定式的熔炼反应装置中,形成含钛混合熔渣,发生熔融还原反应;将含钛混合熔渣的温度控制在设定温度范围内;
其中:
设定温度范围为1400~1600℃;
当反应装置采用保温装置时,含钛混合熔渣的温度范围设定为1400~1600℃;
当反应装置采用可倾倒的熔炼反应装置或固定式的熔炼反应装置时,含钛混合熔渣的温度范围设定为1450~1600℃;
控制含钛混合熔渣的温度在设定温度范围的方法为:
当含钛混合熔渣的温度<设定温度范围下限时,通过反应装置自身的加热功能,或向含钛混合熔渣中加入燃料和/或含钒钛熔融钢渣,使含钛混合熔渣的温度达到设定温度范围内;
当含钛混合熔渣的温度>设定温度范围上限时,向含钛混合熔渣中加入含钒钛物料、含铁物料、含氟物料或含钛高炉熔渣中的一种或几种,使含钛混合熔渣的温度达到设定温度范围内;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后氧化性气体;其中,氧化性气体的预热温度为0~1200℃,氧化性气体时间与流量的关系为1~105L/(min·kg);
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
调控方法为:
对应(a):
采用步骤1中的控制含钛混合熔渣的温度在设定温度范围的方法;
对应(b):
当含钛混合熔渣中还原性不足时,向含钛混合熔渣中加入还原剂,使含钛混合熔渣中,铁氧化物还原成金属铁;
步骤3,分离回收:
采用以下方法中的一种:
一.当反应装置采用保温装置时,采用方法A、方法B或方法C:
当反应装置采用不可倾倒的保温装置或可倾倒的保温装置时,采用方法A:
(1)将还原氧化后的混合熔渣,冷却至室温,获得缓冷渣;
(2)含钒金属铁沉降到反应装置的底部,形成铁坨,人工取出铁坨;将剩余缓冷渣中含钒金属铁层,破碎至粒度为20~400μm,磨矿,磁选分离出剩余含钒金属铁;
(3)对去除铁坨和含钒金属铁层的缓冷渣,采用重力分选法进行分离,获得钛精矿、富钒精矿和尾矿;
(4)尾矿的回收利用有2种:①作为水泥原料、建筑材料、代替碎石作骨料、路材或磷肥使用;②采用湿法冶金、选矿方法或选矿-湿法冶金联合法将尾矿中含磷组分分离出来;
仅当反应装置采用可倾倒的保温装置时,采用方法B或方法C:
方法B:
(1)将还原氧化后的混合熔渣的温度降温至1150~1250℃,将中部和上部的还原氧化后的混合熔渣倒出后,空冷或水淬,用作水泥原料或建筑材料;
(2)将下部的还原氧化后的混合熔渣,仍在可倾倒的保温装置中,作为方法A还原氧化后的混合熔渣进行处理;
方法C:
(1)将还原氧化后的混合熔渣,沉降渣-金分离,获得含钒铁水与还原氧化后的含钒钛熔渣;
(2)当还原氧化后的含钒钛熔渣TiO2的质量分数≤10%时,直接将还原氧化后的含钒钛熔渣倒出后,空冷或水淬,用作水泥原料或建筑材料;
(3)将含钒铁水送往转炉炼钢;
二.当反应装置采用可倾倒的熔炼反应装置或固定式的熔炼反应装置时,采用方法D:
(1)将还原氧化后的混合熔渣,沉降渣-金分离,获得含钒铁水与还原氧化后的含钒钛熔渣;
(2)将还原氧化后的含钒钛熔渣,进行炉外熔渣处理;
(3)将含钒铁水送往转炉炼钢;
其中,炉外熔渣处理采用方法D-1或方法D-2:
方法D-1:当还原氧化后的含钒钛熔渣TiO2的质量分数≤10%时,直接将还原氧化后的含钒钛熔渣倒出后,空冷或水淬,用作水泥原料或建筑材料;
方法D-2:将还原氧化后的含钒钛熔渣倒入保温装置,按照步骤2中的方法进行熔融还原与氧化,分离回收采用方法A、方法B或方法C。
所述的步骤1中,含钛高炉熔渣的温度≥1300℃,含钒钛熔融钢渣的温度≥1500℃。
所述的步骤1中,含钛高炉熔渣由高炉出渣口获得;含钒钛熔融钢渣由钢渣出渣口获得;
所述的步骤1中,含钛高炉熔渣,含有TiO2的质量分数为4~30%;含钒钛熔融钢渣,含有TiO2的质量分数为0.3~6%,含有V2O5的质量分数为0.3~5%。
所述的含钒钛熔融钢渣,为转炉含钒钛熔融钢渣或电炉含钒钛熔融氧化钢渣。
所述的保温装置为可倾倒的保温装置或不可倾倒的保温装置;不可倾倒的保温装置为保温地坑;其升高温度方法均为加入燃料。可倾倒的保温装置为可倾倒的保温渣罐;其升高温度方法为加入燃料。
所述的可倾倒的熔炼反应装置为可倾倒的转炉、可倾倒的熔炼反应渣灌或感应炉。
所述的固定式熔炼反应装置为底部带有渣口或铁口的反应装置;所述的固定式反应装置为等离子炉、直流电弧炉、交流电弧炉、矿热炉、鼓风炉或反射炉。
所述的保温装置、可倾倒的熔炼反应装置或固定式的熔炼反应装置内层为含碳保温脱模耐火材料;所述的含碳保温脱模耐火材料是含碳复合耐火材料,具体为碳是碳素、石墨、石油沥青焦、冶金焦、沥青、无烟煤、烟煤或褐煤中的一种或几种,耐火材料是硅质、半硅质、粘土质、高铝质、镁质、白云石质、橄榄石质、尖晶石质、冷态含钛高炉渣或冷态含钒钛钢渣中的一种或几种。所述的含碳保温脱模耐火材料的作用有两个:(1)保护保温装置,提高其寿命,(2)使冷却好的缓冷渣易于从保温装置中脱除。
所述的控制含钛混合熔渣的温度在设定温度范围的方法中,向含钛混合熔渣中同时加入燃料和含钒钛熔融钢渣时,燃料和含钒钛熔融钢渣为任意比。
所述的控制含钛混合熔渣的温度在设定温度范围的方法中,燃料的预热温度为0~1200℃,含钒钛熔融钢渣的温度≥1500℃。
所述的控制含钛混合熔渣的温度在设定温度范围的方法中,燃料采用喷吹的方式加入含钛混合熔渣。所述的喷吹方式为采用耐火喷枪***熔渣或置于熔渣上部或侧面吹入燃料。
所述的控制含钛混合熔渣的温度在设定温度范围的方法中,燃料为煤粉。
所述的控制混合熔渣的温度在设定温度范围的方法中,当同时向混合熔渣中加入燃料和含钒钛熔融钢渣时,燃料和含钒钛熔融钢渣为任意比。
所述的控制含钛混合熔渣的温度在设定温度范围的方法中,当含钛混合熔渣的温度<设定温度范围下限时,向含钛混合熔渣中加入燃料和/或含钒钛熔融钢渣,进行热量补偿。
所述的控制含钛混合熔渣的温度在设定温度范围的方法中,含钒钛物料是含钛高炉渣、含钒钛钢渣、提钒尾渣、选钛尾矿、低品位钒钛磁铁矿、钒钛磁铁精矿、钒钛磁铁矿直接还原铁,钒钛磁铁精矿金属化球团、钒钛磁铁精矿含碳预还原球团、钒钛磁铁精矿烧结矿、钒钛磁铁精矿球团矿中的一种或几种;含铁物料是普通铁精矿、普通铁精矿直接还原铁,普通铁精矿烧结矿、普通铁精矿球团矿、普通铁精矿金属化球团、普通铁精矿含碳预还原球团、普通钢渣、高炉瓦斯灰、高炉烟尘、转炉烟尘、氧化铁皮、湿法炼锌过程的锌浸出渣、氧化铝生产过程产生的赤泥、煤粉灰、硫酸烧渣中的一种或几种;含氟物料是萤石和/或CaF2。
所述的控制含钛混合熔渣的温度在设定温度范围的方法中,含钒钛物料、含铁物料和含
氟物料均为球团或粉状物料;其中,粉状物料的粒度≤150μm,粉状物料以喷吹的方式加入含钛混合熔渣,载入气体为空气、氩气、氮气-空气混合气、氮气-氧气混合气或空气-氩气混合气。所述的喷吹方式为采用耐火喷枪***熔渣或置于熔渣上部或侧面吹入粉状物料。
所述的控制含钛混合熔渣的温度在设定温度范围的方法中,当含钛混合熔渣的温度>设定温度上限时,加入含钒钛物料、含铁物料、含氟物料或含钛高炉熔渣中的一种或几种,目的是避免温度过高,保护含碳保温脱模耐火材料,抑制含钛高炉熔渣中含钒生铁、含钒钛熔融钢渣中含钒粒铁及被还原的金属铁的氧化,提高金属铁的回收率。
所述的控制含钛混合熔渣的温度在设定温度范围的方法中,当含钛混合熔渣的温度>设定温度上限时,加入含氟物料的另一个作用是降低粘度,加速熔渣中含钒金属铁、富钛相、富钒相、富磷相的聚集、长大与沉降。
所述的控制含钛混合熔渣的温度在设定温度范围的方法中,加入冷态含钒钛物料、含铁物料、含氟物料、含钛高炉熔渣中的一种或几种,降低温度,在喷出气体过程中保证剩余低价钛(Ti2+,Ti3+)充分氧化为高价钛(Ti4+),保证混合熔渣中剩余高价铁(Fe3+,Fe2+)被充分还原为金属铁Fe,保证熔渣中金属铁颗粒不被氧化。
所述的步骤1中,还原性含钛高炉熔渣与氧化性含钒钛熔融钢渣混合过程中,还原性含钛高炉熔渣中低价钛(Ti2+,Ti3+)氧化为高价钛(Ti4+),氧化性含钒钛熔融钢渣中(Fe3+,Fe2+)被还原为Fe与Fe2+。
所述的氧化性气体是空气、氧气、富氧空气、氮气-氧气混合气、氮气-空气混合气、氧气-氩气混合气或空气-氩气混合气中的一种。所述氧化性气体的预热温度因气体不同而异。
所述的氧化性气体采用耐火喷枪***熔渣或置于熔渣上部或侧面吹入氧化性气体。
所述的氧化性气体喷吹时间与流量依熔渣质量、温度及还原氧化程度来确定。
所述的步骤2和步骤3中,还原剂均为煤粉、焦粉、烟煤或无烟煤中的一种。
所述的步骤2(2)中,对应(b),含钛混合熔渣还原性不足时,向熔渣中喷吹补充还原剂。
所述的步骤2(2)中,保证参数(b)体现了含钛混合熔渣中有充分的还原性,在实际生产中,一股以含钛混合熔渣中铁氧化物的质量百分比来判断含钛混合熔渣中还原性是否充足。
所述的步骤2熔融还原与氧化过程中,保证含钛混合熔渣中剩余低价钛(Ti2+,Ti3+)充分氧化为高价钛(Ti4+),保证含钛混合熔渣中剩余高价铁(Fe3+,Fe2+)被充分还原为金属铁Fe,保证含钛混合熔渣中金属铁颗粒不被氧化,所述的熔融还原与氧化+喷吹气体的过程中,含钛高炉熔渣中含钒生铁、含钒钛熔融钢渣中含钒粒铁及被还原的金属铁实现聚集、长大与沉降。
所述的步骤3,方法A(1)中,冷却方式为自然冷却或旋转冷却。
所述的步骤3,方法A(1)中,旋转冷却的具体操作为:装有氧化还原后的混合熔渣的保温装置置于旋转平台上,按照一定速度进行旋转,旋转速度依熔渣质量与保温装置高度或深度而定,旋转时间依熔渣质量与熔渣凝固情况而定;将装有氧化还原后的混合熔渣的保温装置置于旋转平台上旋转,目的是加速金属铁、钙钛矿相、富钒相的聚集、长大与沉降,缩短沉降时间,改善沉降效果,提高生产效率。
所述的步骤3,方法A(1)中,冷却过程中,由于密度不同与矿物大小不同,大部分含钒金属铁、含钛组和含钒组分沉降于底部。
所述的步骤3,方法A(3)中,对去除铁坨和含钒金属铁层的缓冷渣上、中、下部,分别采用重力分选法进行分离,获得钛精矿、富钒精矿和尾矿;
所述的步骤3,方法A(1)中,还原氧化后的混合熔渣中钛与钙组分继续迁移、富集于钙钛矿相,并实现长大与沉降;还原氧化后的混合熔渣中钒组分分别继续迁移、富集于金属铁相与富钒氧化物相,并实现长大与沉降;还原氧化后的混合熔渣中磷组分继续迁移、富集于Ca2SiO4-Ca3(PO4)2相,分布于钙钛矿与其它矿物相的两相之间的相界面;氧化还原后的混合熔渣中铁氧化物、自由氧化钙与自由氧化镁消失,熔渣实现调质。
所述的步骤3,方法A(3)中,重力分选法是摇床分选、溜槽分选或者二者相结合。
所述的步骤3,方法A(4)中,湿法冶金是稀酸浸出法,其中稀酸浸出法是无机酸浸、有机酸浸中的一种。所述的无机酸选用硫酸、盐酸、磷酸的一种或多种,有机酸选用草酸、乙酸、柠檬酸中的一种或多种。
所述的步骤3,所述的方法A中,金属铁回收率为90~97%,主要物相为钙钛矿的钛精矿中TiO2的质量分数均为35~52%,钛的回收率为60~80%;所述的方法B中,金属铁回收率为90~95%,主要物相为钙钛矿的钛精矿中TiO2的质量分数均为35~52%,钛的回收率为58~76%。
所述的含钛混合熔渣熔融还原回收与调质处理的方法,调质过程是从原料混合开始直至分离回收过程一直在持续发生,熔渣中的自由氧化钙和自由氧化镁消失,铁氧化物与金属铁消失或几乎消失,熔渣实现调质。
本发明的含钛混合熔渣回收与调质处理的方法,金属铁回收率高是含钛混合熔渣喷出气体,不仅使含钛高炉熔渣中含钒生铁与含钒钛熔融钢渣中含钒粒铁聚集、长大与沉降,而且使熔混合渣中铁氧化物(FeO、Fe2O3)充分还原为金属铁,实现聚集、长大与沉降。
本发明的含钛混合熔渣熔融还原回收与调质处理的方法,矿物可磨性增加。
本发明的含钛混合熔渣回收与调质处理的方法,富磷相分布于钙钛矿与其它矿物相的两相之间的相界面是有利于钙钛矿相的矿物解离,利于选矿分离;
本发明的含钛混合熔渣熔融还原回收与调质处理的方法,与现有技术相比,本发明的特点是:
本发明充分利用了含钛高炉熔渣与含钒钛熔融钢渣物理热资源、熔渣中的热态冶金熔剂及含钛高炉熔渣与含钒钛熔融钢渣的还原性与氧化性,通过两种熔渣混合喷吹氧化性气体,实现了熔融还原与氧化,控制氧势,铁氧化物得到充分还原为金属铁,熔渣中钛组分得到充分氧化;是一种新的熔融还原的方法;
同时含钛高炉熔渣中生铁、含钒钛熔融钢渣中含钒铁及被还原的金属铁开始聚集、长大,当接近一定尺寸后;开始沉降,大部分沉降到渣坨底部,形成整块铁锭;
喷吹气体结束后,混合熔渣中钛与钙组分迁移、富集于钙钛矿相,并实现长大与沉降,单质钒组分迁移、富集于金属铁相,低价钒氧化物富集于富钒氧化物相,并实现长大与沉降,磷组分迁移、富集于Ca2SiO4-Ca3(PO4)2相,赋存于钙钛矿相界面;
熔渣冷却后,将缓冷渣与沉降的铁锭分离,回收含钒金属铁,同时采用磁选分离渣坨底部剩余的含钒金属铁,实现了含钛高炉熔渣中生铁、含钒钛熔融钢渣中含钒粒铁及铁氧化物中铁的高效回收,金属铁回收率高;
由于富钛相(钙钛矿相)、富钒相(富钒氧化物相)沉降在下部,因此,需分选炉渣量小,磨矿、磁选与重选成本低,同时,赋存于钙钛矿相界面的富磷相有助于钙钛矿相解离与选矿;
不仅实现了渣中单质钒的回收,而且实现了含钒氧化物的富集、长大、沉降与分离;
自由氧化钙与自由氧化镁消失,金属铁与铁氧化物几乎消失,熔渣实现调质,尾矿利用限制因素消失,可作为水泥原料或建筑材料或代替碎石作骨料和路材或磷肥或采用湿法冶金方法将含磷组分分离出来,尾矿利用价值大,应用范围广。
本发明方法可连续或间断的进行,满足了工业生产的需要。
本发明的有益效果是:
(1)本发明的反应装置内层使用含碳保温脱模耐火材料,不仅保护了保温装置,而且使冷却后的缓冷渣易于从保温装置中脱除;
(2)本发明的原料是出渣口中流出的液态熔融含钛高炉渣(≥1300℃)和含钒钛熔融钢渣(≥1500℃),蕴含着丰富的热能资源,具有高温度、高热量的特点,充分利用了熔渣物理热资源,高效节约能源;液态熔融含钛高炉渣与含钒钛熔融钢渣含有大量的热态冶金熔剂,都是物理化学性质优良的熔渣体系,实现了冶金资源与热资源的高效利用;液态熔融含钛高炉渣为还原性熔渣,含钒钛熔融钢渣为氧化性熔渣,充分利用了两种熔渣高反应化学活性的特点;
(3)本发明通过两种熔渣混合实现了熔融还原与氧化,喷吹氧化性气体,控制氧势,不
仅使含钛高炉熔渣中生铁与含钒钛熔融钢渣中含钒粒铁聚集、长大与沉降,而且使含钛熔融钢渣中铁氧化物(FeO、Fe2O3)充分还原为金属铁,实现聚集、长大与沉降;
(4)本发明方法中,加入冷态物料与热熔融含钛高炉渣避免了熔渣温度过高,保护含碳保温脱模耐火材料,提高保温装置的寿命;抑制含钛高炉熔渣中生铁、含钒钛熔融钢渣中含钒粒铁及被还原的金属铁的氧化,提高金属铁的回收率;加入冷态物料与热熔融含钛高炉渣提高了原料处理量,不仅可以处理液态熔渣,而且可以处理少量冷态物料,原料适应性强;加入冷态物料实现了熔渣氧化反应释放的化学热与熔渣物理热的高效利用;
(5)本发明两种熔渣混合实现了熔融还原与氧化,喷吹氧化性气体,控制氧势,低价钛氧化为高价钛,混合熔渣中钛与钙组分迁移、富集于钙钛矿相,并实现长大与沉降;钒氧化物充分还原为单质钒与低价钒,迁移、富集于金属铁相与富钒氧化物相,并长大与沉降,不仅实现了了熔渣中单质钒的回收,而且熔渣中含钒氧化物的富集、长大与沉降;
(6)本发明方法自然冷却过程中,熔渣中铁组分、钛组分、钒组分与磷组分分别迁移、富集于含钒金属铁、富钛相、富钒相、富磷相,并实现聚集、长大与沉降;装有熔渣的保温装置置于旋转平台上旋转,加速含钒金属铁、富钛相、富钒相、富磷相的聚集、长大与沉降,缩短沉降时间,改善沉降效果,提高生产效率;含氟物料的加入,加速含钒金属铁、富钛相、富钒相、富磷相的聚集、长大与沉降,缩短沉降时间,改善沉降效果;
(7)本发明方法混合熔渣中磷组分迁移、富集于Ca2SiO4-Ca3(PO4)2相,分布于钙钛矿与其它矿物相的两相之间的相界面,利于选矿分离;自由氧化钙与自由氧化镁消失,金属铁与铁氧化物几乎消失,熔渣中游离氧化钙与氧化镁消失,矿物可磨性增加,熔渣实现调质;
(8)本发明方法采用人工分拣、磁选与重选结合的方法,分离沉降在底部的含钒金属铁、富钒氧化物相、钙钛矿相,实现混合熔渣中钛组分、铁组分、钒组分、磷组分与自由氧化钙组分的高效回收;由于富钛相、含钒金属铁、富钒相沉降在底部,因此,需分选炉渣量小,矿物可磨性增加,磨矿、磁选与重选成本低;后续的分离过程采用物理选矿(磁选或重选),分离的介质为水,水在选矿过程中可以循环,因而分离过程中不会产生环境污染,使得整个含钛混合熔渣工艺具有流程短、操作简单、铁、钒、钛、钙回收率高、无废水产生,具有高效、清洁、环保的特点;由于熔渣经过调质处理,尾矿的回收利用有2种:①作为水泥原料、建筑材料、代替碎石作骨料、路材或磷肥使用;②采用湿法冶金、选矿方法或选矿-湿法冶金联合法将尾矿中含磷组分分离出来;,尾矿利用价值大,应用范围广;
(9)本发明方法整个过程无需热补偿或需少量热补偿,可操作性强,生产成本低;
(10)本发明充分利用了熔渣物理热资源、熔渣中热态冶金熔剂及熔渣的氧化性与还原性,实现了熔融还原与氧化,熔渣中铁组分、钛组分、钒组分与磷组分分别迁移、富集于含
钒金属铁、富钛相、富钒相、富磷相,并实现聚集、长大与沉降,实现混合熔渣中钛组分、铁组分、钒组分、磷组分与自由氧化钙组分的高效回收,而且可以处理冷态含钒、钛、铁物料,同时实现熔渣调质处理,达到二次资源高效综合利用。该方法反应时间短、金属回收率高、生产成本低、原料适应性强、处理量大、环境友好、经济收益高、可有效解决冶金资源与热能高效回收利用问题。
图1本发明实施例的含钛混合熔渣熔融还原回收与调质处理的方法的工艺流程图。
以下实施例的含钛混合熔渣熔融还原回收与调质处理的方法的工艺流程图如图1所示。
以下实施例中涉及到的固液比,是指尾矿的质量与浸出液的体积比,单位为g:L。
实施例1
一种含钛混合熔渣熔融还原回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的410kg液态熔融含钛高炉渣和40kg转炉含钒钛熔融钢渣倒入内层有石墨-白云石质复合保温脱模耐火材料的可倾倒的保温渣罐,充分混合形成含钛混合熔渣,发生熔融还原反应;
混合后熔渣温度为1394℃,低于在含钛混合熔渣的设定温度1400~1600℃范围;将耐火喷枪***混合熔渣吹入煤粉2kg,使混合熔渣的温度升高到1426℃;其中:
含钛高炉熔渣,含有成分及其质量百分比为:20.34wt%TiO2、22.26wt%CaO、8.12wt%MgO、10.89wt%Al2O3、2.96wt%FeO和20.46wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣含有成分及其质量百分比为:3.26wt%V2O5、TFe20.68wt%、40.89wt%CaO、12.36wt%SiO2、3.62wt%TiO2、2.47wt%MgO、1.22wt%MnO、1.64wt%Al2O3,余量为其他杂质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后氧气,共喷吹氧气18min;其中,氧气的预热温度为30℃,氧气时间与流量的关系为1L/(min·kg);氧气的喷吹方式为采用耐火喷枪***含钛混合熔渣吹入氧气。
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在1400~1600℃;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a),还原与氧化过程测得混合熔渣温度为1456~1466℃,在设定范围内;
对应(b),还原与氧化过程,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法A:
(1)将还原氧化后的混合熔渣,自然冷却至室温,获得缓冷渣;
(2)含钒金属铁沉降到反应装置的底部,形成铁坨,人工取出铁坨;将剩余缓冷渣中含钒金属铁层,破碎至粒度为20~400μm,磨矿,磁选分离出剩余含钒金属铁;金属铁回收率92%,本步骤尾矿渣中全铁为0.792wt%;
(3)对去除铁坨和含钒金属铁层的缓冷渣的下部缓冷渣,经溜槽一次粗选,摇床一次精选,两次扫选,上、中部经溜槽一次粗选,摇床一次精选,一次扫选,将含钛组分与脉石相分离,得到主要物相为钙钛矿相的钛精矿、含钒镁铝尖晶石中矿和尾矿,钛精矿中TiO2的质量分数为48.41%,含钒镁铝尖晶石中矿中V2O5的质量分数为8.71%,富磷相中P2O5的质量分数为28%,
(4)尾矿采用2%稀硫酸,按固液比1∶2,将五氧化二磷分离出来,磷回收率为80%。
实施例2
一种含钛混合熔渣回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的液态熔融100kg含钛高炉渣和1000kg转炉含钒钛熔融钢渣倒入内层有碳-镁质复合保温脱模耐火材料的保温地坑,充分混合形成含钛混合熔渣,发生熔融还原反应;混合后熔渣温度为1570℃,在含钛混合熔渣的温度设定1400~1600℃范围内;其中:
含钛高炉熔渣,含有成分及其质量百分比为:22.65wt%TiO2、19.79wt%CaO、9.31wt%MgO、11.96wt%Al2O3、3.26wt%FeO、和19.48wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣含有成分及其质量百分比:2.29wt%V2O5、TFe18.79wt%、41.64wt%CaO、11.36wt%SiO2、3.92wt%TiO2、3.54wt%MgO、1.43wt%MnO、1.37wt%Al2O3,余量为其他杂质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后空气,共喷吹空气5min;其中,空气的预热温度为900℃,空气时间与流量的关系为105L/(min·kg);空气的喷吹方式为采用耐火喷枪置于混合熔渣上部吹入;
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1400~1600℃范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):
氧化还原过程测得混合熔渣温度高达1620℃;由于温度高出设定值,向含钛混合熔渣中加入常温的含钛高炉渣2kg、普通铁精矿含碳预还原球团1kg和含钒钛钢渣2kg,使含钛混合熔渣的温度降低至1550~1560℃,在设定范围内;
对应(b):
氧化还原过程中,表现含钛混合熔渣中还原性不足,向含钛混合熔渣中加入焦粉3kg,使含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法A:
(1)将还原氧化后的混合熔渣,旋转冷却至室温,获得缓冷渣;其中,旋转冷却的具体操作为:装有氧化还原后的混合熔渣的保温装置置于旋转平台上,按照一定速度进行旋转,旋转速度依熔渣质量与保温装置高度或深度而定,旋转时间依熔渣质量与熔渣凝固情况而定;
(2)含钒金属铁沉降到反应装置的底部,形成铁坨,人工取出铁坨;将剩余缓冷渣中含钒金属铁层,破碎至粒度为20~400μm,磨矿,磁选分离出剩余含钒金属铁;金属铁回收率93%,本步骤尾矿渣中全铁为0.463wt%;
(3)对去除铁坨和含钒金属铁层的缓冷渣下部,经溜槽一次粗选,摇床一次精选,两次扫选,将含钛组分与脉石相分离,得到主要物相为钙钛矿相的钛精矿、含钒镁铝尖晶石中矿和尾矿,钛精矿中TiO2的质量分数为38.31%,含钒镁铝尖晶石中矿中V2O5的质量分数为9.58%,富磷相中P2O5的质量分数为29%;
(4)尾矿作为磷肥使用。
实施例3
一种含钛混合熔渣回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的液态熔融400kg含钛高炉渣和45kg转炉含钒钛熔融钢渣倒入内层有冶金焦-高铝质复合保温脱模耐火材料的保温地坑,充分混合形成含钛混合熔渣,发生熔融还原反应;混合后熔渣温度为1420℃;在含钛混合熔渣的温度控制范围1400~1600℃;其中:
含钛高炉熔渣,含有成分及其质量百分比为:21.96wt%TiO2、20.37wt%CaO、8.75wt%MgO、11.62wt%Al2O3、4.4.46wt%FeO、和19.28wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣,含有成分及其质量百分比:1.79wt%V2O5、TFe18.76wt%、43.84wt%CaO、12.92wt%SiO2、3.94wt%TiO2、3.78wt%MgO、1.21wt%MnO、1.26wt%Al2O3,余量为其他杂质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后氧气,共喷吹氧气5min;其中,氧气的预热温度为1200℃,氧气时间与流量的关系为40L/(min·kg);氧气的喷吹方式为采用耐火喷枪置于混合熔渣侧面吹入。
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定1400~1600℃内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):还原氧化过程,测得混合熔渣温度为1462~1467℃,在设定温度范围内;
对应(b):还原氧化过程,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法A:
(1)将还原氧化后的混合熔渣,自然冷却至室温,获得缓冷渣;其中,旋转冷却方法同实施例2;
(2)含钒金属铁沉降到反应装置的底部,形成铁坨,人工取出铁坨;将剩余缓冷渣中含钒金属铁层,破碎至粒度为20~400μm,磨矿,磁选分离出剩余含钒金属铁;金属铁回收率91%,本步骤尾矿渣中全铁0.872wt%;
(3)对去除铁坨和含钒金属铁层的缓冷渣上、中、下部,分别采用重力分选法进行分离,下部缓冷渣经溜槽两次粗选,摇床一次精选,两次扫选,上、中部经溜槽两次粗选,摇床两次精选,一次扫选,将含钛组分与脉石相分离,得到主要物相为钙钛矿相的钛精矿、含钒镁铝尖晶石中矿和尾矿,钛精矿中TiO2的质量分数为44.27%,含钒镁铝尖晶石中矿中V2O5的质量分数为8.89%,富磷相中P2O5的质量分数为28%;
(4)尾矿作为磷肥使用。
实施例4
一种含钛混合熔渣回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的液态熔融400kg含钛高炉渣和65kg转炉含钒钛熔融钢渣倒入内层有沥青-半硅质复合保温脱模耐火材料的可倾倒的保温渣罐,充分混合形成含钛混合熔渣,发生熔融还原反应;混合后熔渣温度为1440℃;在含钛混合熔渣的温度设定1400~1600℃范围内;其中:
含钛高炉熔渣,含有成分及其质量百分比为:18.69wt%TiO2、21.32wt%CaO、9.26wt%MgO、12.31wt%Al2O3、4.49wt%FeO、和20.14wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣,含有成分及质量百分比:3.12wt%V2O5、TFe20.51wt%、41.19wt%CaO、9.34wt%SiO2、5.79wt%TiO2、1.24wt%MgO、2.31wt%MnO、1.30wt%Al2O3,余量为其他杂质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后空气,共喷吹空气4min;其中,空气预热温度为1000℃,空气时间与流量的关系为87L/(min·kg);空气的喷吹方式为采用耐火喷枪***混合熔渣吹入;
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1400~1600℃范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):还原氧化过程,测得混合熔渣温度为1500~1510℃,在设定温度范围;
对应(b):还原氧化过程,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法A:
(1)将还原氧化后的混合熔渣,旋转冷却至室温,获得缓冷渣;其中,旋转冷却方法同实施例2;
(2)含钒金属铁沉降到反应装置的底部,形成铁坨,人工取出铁坨;将剩余缓冷渣中含钒金属铁层,破碎至粒度为20~400μm,磨矿,磁选分离出剩余含钒金属铁;金属铁回收率93%,本步骤尾矿渣中全铁含量0.502wt%;
(3)对去除铁坨和含钒金属铁层的缓冷渣上、中、下部,分别采用重力分选法进行分离,下部缓冷渣经溜槽一次粗选,摇床一次精选,两次扫选,上、中部经溜槽一次粗选,摇床一次精选,一次扫选,将含钛组分与脉石相分离,得到主要物相为钙钛矿相的钛精矿、含钒镁铝尖晶石中矿和尾矿,钛精矿中TiO2的质量分数为49.31%,含钒镁铝尖晶石中矿中V2O5的质量分数为8.98%,富磷相中P2O5的质量分数为27%,重选分离,磷回收率为60%;
(4)尾矿作为建筑材料使用。
实施例5
一种含钛混合熔渣回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的液态熔融400kg含钛高炉渣和80kg转炉含钒钛熔融钢渣倒入内层有烟煤-尖晶石质复合保温脱模耐火材料的可倾倒的保温渣罐,充分混合形成含钛混合熔渣,发生熔融还原反应;混合后熔渣温度为1450℃;在含钛混合熔渣的温度设定1400~1600℃范围内;其中:
含钛高炉熔渣,含有成分及其质量百分比为:19.31wt%TiO2、19.69wt%CaO、9.84wt%MgO、13.28wt%Al2O3、4.47wt%FeO、和20.26wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣,含有成分及其质量百分比:0.62wt%V2O5、TFe18.74wt%、41.32wt%CaO、12.74wt%SiO2、4.78wt%TiO2、3.14wt%MgO、1.29wt%MnO、1.87wt%Al2O3,余量为其他杂质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后空气,共喷吹空气4min;其中,空气预热温度为0℃,空气时间与流量的关系为23L/(min·kg);空气的喷吹方式为采用耐火喷枪***混合熔渣吹入;
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1400~1600℃范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):还原氧化过程,测得混合熔渣温度为1468~1476℃,在设定范围内;
对应(b):还原氧化过程,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法A:
(1)将还原氧化后的混合熔渣,自然冷却至室温,获得缓冷渣;
(2)含钒金属铁沉降到反应装置的底部,形成铁坨,人工取出铁坨;将剩余缓冷渣中含钒金属铁层,破碎至粒度为20~400μm,磨矿,磁选分离出剩余含钒金属铁;金属铁回收率91%,渣中全铁含量0.519wt%;
(3)对去除铁坨和含钒金属铁层的缓冷渣上、中、下部,分别采用重力分选法进行分离,下部缓冷渣,经溜槽两次粗选,摇床一次精选,两次扫选,上、中部经溜槽一次粗选,摇床一次精选,一次扫选,将含钛组分与脉石相分离,得到主要物相为钙钛矿相的钛精矿、含钒镁铝尖晶石中矿和尾矿,钛精矿中TiO2的质量分数为42.87%,含钒镁铝尖晶石中矿中V2O5的质量分数为8.71%,富磷相中P2O5的质量分数为28%;
(4)尾矿采用2%稀硫酸,按固液比1∶2将五氧化二磷分离出来,磷回收率为75%。
实施例6
一种含钛混合熔渣回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的液态熔融400kg含钛高炉渣和50kg电炉含钒钛熔融氧化钢渣倒入内层有碳-粘土质复合保温脱模耐火材料的保温地坑,充分混合形成含钛混合熔渣,发生熔融还原
反应;混合后熔渣温度为1430℃;在含钛混合熔渣的温度设定1400~1600℃范围内;其中;
含钛高炉熔渣,含有成分及其质量百分比:12.46wt%TiO2、21.37wt%CaO、11.26wt%MgO、16.14wt%Al2O3、5.09wt%FeO、和19.48wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣,含有成分及其质量百分比:2.32wt%V2O5、TFe18.76wt%、42.25wt%CaO、11.96wt%SiO2、4.89wt%TiO2、3.26wt%MgO、1.45wt%MnO、1.69wt%Al2O3,余量为其他杂质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后氧气,共喷吹氧气7min;其中,氧气预热温度为900℃,氧气时间与流量的关系为9L/(min·kg);氧气的喷吹方式为采用耐火喷枪***混合熔渣吹入;
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1400~1600℃范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):还原氧化过程测,得混合熔渣温度为1483~1491℃,在设定范围内;
对应(b):还原氧化过程测,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法A:
(1)将还原氧化后的混合熔渣,自然冷却至室温,获得缓冷渣;
(2)含钒金属铁沉降到反应装置的底部,形成铁坨,人工取出铁坨;将剩余缓冷渣中含钒金属铁层,破碎至粒度为20~400μm,磨矿,磁选分离出剩余含钒金属铁;金属铁回收率92%,本步骤尾矿渣中全铁含量0.741wt%;
(3)对去除铁坨和含钒金属铁层的缓冷渣上、中、下部,分别采用重力分选法进行分离,下部缓冷渣一次粗选,摇床一次精选,两次扫选,上、中部经溜槽一次粗选,摇床一次精选,一次扫选,将含钛组分与脉石相分离,得到主要物相为钙钛矿相的钛精矿、含钒镁铝尖晶石中矿和尾矿,钛精矿中TiO2的质量分数为36.39%,含钒镁铝尖晶石中矿中V2O5的质量分数为8.07%,富磷相中P2O5的质量分数为26%;
(4)尾矿作为磷肥使用。
实施例7
一种含钛混合熔渣回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的液态熔融40kg含钛高炉渣和400kg电炉含钒钛熔融氧化钢渣倒入内层
有碳-尖晶石质复合保温脱模耐火材料的保温地坑,充分混合形成混合熔渣,发生熔融还原反应;混合后熔渣温度为1580℃;在含钛混合熔渣的温度设定1400~1600℃范围内;其中;
含钛高炉熔渣,含有成分及其质量百分比为:29.48wt%TiO2、19.67wt%CaO、5.38wt%MgO、12.27wt%Al2O3、2.47wt%FeO、和17.74wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣,含有成分及其质量百分比:1.34wt%V2O5、TFe18.72wt%、41.19wt%CaO、12.37wt%SiO2、4.96wt%TiO2、3.19wt%MgO、1.89wt%MnO、1.29wt%Al2O3,余量为其他杂质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后氧气,共喷吹氧气14min;其中,氧气预热温度为180℃,氧气时间与流量的关系为1.8L/(min·kg);氧气的喷吹方式为采用耐火喷枪***混合熔渣吹入;
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1400~1600℃范围内
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):还原氧化过程测得混合熔渣温度高达1618℃,由于温度高出设定值,向含钛混合熔渣中加入含钒钛钢渣2kg,使含钛混合熔渣的温度为1520~1525℃,在设定温度范围;
对应(b):氧化还原过程中,表现含钛混合熔渣中还原性不足,向含钛混合熔渣中加入焦粉2kg,使含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法A:
(1)将还原氧化后的混合熔渣,旋转冷却至室温,获得缓冷渣;其中,旋转冷却方法同实施例2;
(2)含钒金属铁沉降到反应装置的底部,形成铁坨,人工取出铁坨;将剩余缓冷渣中含钒金属铁层,破碎至粒度为20~400μm,磨矿,磁选分离出剩余含钒金属铁;金属铁回收率93%,本步骤尾矿渣中全铁含量0.879wt%;
(3)对去除铁坨和含钒金属铁层的缓冷渣上、中、下部,分别采用重力分选法进行分离,下部缓冷渣经溜槽一次粗选,摇床一次精选,两次扫选,将含钛组分与脉石相分离,得到主要物相为钙钛矿相的钛精矿、含钒镁铝尖晶石中矿和尾矿,钛精矿中TiO2的质量分数为37.28%,含钒镁铝尖晶石中矿中V2O5的质量分数为9.18%;富磷相中P2O5的质量分数为29%;
(4)尾矿作为磷肥使用。
实施例8
一种含钛混合熔渣回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的液态熔融200kg含钛高炉渣和200kg电炉含钒钛熔融氧化钢渣倒入内层有碳素-橄榄石质复合保温脱模耐火材料的保温地坑,充分混合形成混合熔渣,发生熔融还原反应;混合后熔渣温度为1440℃;在含钛混合熔渣的温度设定1400~1600℃范围内;其中:
含钛高炉熔渣,含有成分及其质量百分比为:4.37wt%TiO2、256.28wt%CaO、9.77wt%MgO、16.14wt%Al2O3、2.89wt%FeO、和22.98wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣,含有成分及其质量百分比:0.39wt%V2O5、TFe18.72wt%、42.26wt%CaO、12.17wt%SiO2、4.96wt%TiO2、3.15wt%MgO、1.57wt%MnO、1.91wt%Al2O3,余量为其他杂质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后氧气,共喷吹氧气2min;其中,氧气预热温度为1050℃,氧气时间与流量的关系为20L/(min·kg);氧气的喷吹方式为采用耐火喷枪***混合熔渣吹入;
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1400~1600℃范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):还原过程测得混合熔渣温度为1470~1480℃,在设定范围内;
对应(b):氧化还原过程中,表现含钛混合熔渣中还原性不足,向含钛混合熔渣中加入焦粉1kg,使含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法A:
(1)将还原氧化后的混合熔渣,旋转冷却至室温,获得缓冷渣;其中,旋转冷却方法同实施例2;
(2)含钒金属铁沉降到反应装置的底部,形成铁坨,人工取出铁坨;将剩余缓冷渣中含钒金属铁层,破碎至粒度为20~400μm,磨矿,磁选分离出剩余含钒金属铁;金属铁回收率为92%,本步骤尾矿渣中全铁含量0.879wt%;
(3)对去除铁坨和含钒金属铁层的缓冷渣上、中、下部,分别采用重力分选法进行分离,下部缓冷渣经溜槽一次粗选,摇床一次精选,将含钛组分与脉石相分离,得到主要物相为钙钛矿相的钛精矿、含钒镁铝尖晶石中矿和尾矿,钛精矿中TiO2的质量分数为32.19%,含钒镁铝尖晶石中矿中V2O5的质量分数为8.20%,富磷相中P2O5的质量分数为27%;
(4)尾矿作为磷肥使用。
实施例9
一种含钛混合熔渣回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的液态熔融100kg含钛高炉渣和500kg电炉含钒钛熔融氧化钢渣倒入内层有石墨-含钒钛钢渣复合保温脱模耐火材料的保温地坑,充分混合形成混合熔渣,发生熔融还原反应;混合后熔渣温度为1470℃;在含钛混合熔渣的温度设定1400~1600℃范围内;其中;
含钛高炉熔渣,含有成分及其质量百分比为:29.97wt%TiO2、19.17wt%CaO、5.69wt%MgO、11.98wt%Al2O3、2.47wt%FeO、和16.26wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣,含有成分及其质量百分比:2.14wt%V2O5、TFe16.71wt%、43.26wt%CaO、12.38wt%SiO2、0.53wt%TiO2、2.96wt%MgO、1.85wt%MnO、1.79wt%Al2O3,余量为其他杂质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后氧气,共喷吹氧气4min;其中,氧气预热温度为280℃,氧气时间与流量的关系为10L/(min·kg);氧气的喷吹方式为采用耐火喷枪***混合熔渣吹入;
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1400~1600℃范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):还原氧化过程测,得混合熔渣温度为1520~1530℃,在设定温度范围内;
对应(b):氧化还原过程中,表现含钛混合熔渣中还原性不足,向含钛混合熔渣中加入焦粉2kg,使含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法A:
(1)将还原氧化后的混合熔渣,自然冷却至室温,获得缓冷渣;
(2)含钒金属铁沉降到反应装置的底部,形成铁坨,人工取出铁坨;将剩余缓冷渣中含钒金属铁层,破碎至粒度为20~400μm,磨矿,磁选分离出剩余含钒金属铁;金属铁回收率为93%,本步骤尾矿渣全铁含量0.794wt%;
(3)对去除铁坨和含钒金属铁层的缓冷渣上、中、下部,分别采用重力分选法进行分离,下部缓冷渣经溜槽一次粗选,摇床一次精选,两次扫选,将含钛组分与脉石相分离,得到主
要物相为钙钛矿相的钛精矿、含钒镁铝尖晶石中矿和尾矿,钛精矿中TiO2的质量分数37.38%,含钒镁铝尖晶石中矿中V2O5的质量分数为9.15%,富磷相中P2O5的质量分数为28%;
(4)尾矿采用2%柠檬酸,固液比1∶2将五氧化二磷分离出来,磷回收率为70%。
实施例10
一种含钛混合熔渣回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的液态熔融400kg含钛高炉渣和360kg电炉含钒钛熔融氧化钢渣倒入内层有石油沥青-含钛高炉渣复合保温脱模耐火材料的可倾倒的保温渣罐,充分混合形成含钛混合熔渣,发生熔融还原反应;混合后熔渣温度为1430℃;在含钛混合熔渣的温度设定1400~1600℃范围内;其中;
含钛高炉熔渣,含有成分及其质量百分比为:13.41wt%TiO2、21.49wt%CaO、9.87wt%MgO、15.37wt%Al2O3、4.43wt%FeO、和20.28wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣,含有成分及其质量百分比:2.24wt%V2O5、TFe16.94wt%、42.86wt%CaO、11.29wt%SiO2、4.86wt%TiO2、2.98wt%MgO、1.94wt%MnO、1.78wt%Al2O3,余量为其他杂质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后氧气,共喷吹氧气7min;其中,氧气预热温度为300℃,氧气时间与流量的关系为50L/(min·kg);氧气的喷吹方式为采用耐火喷枪***混合熔渣吹入;
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1400~1600℃范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):还原氧化过程测得混合熔渣温度为1470~1478℃,在设定范围内;
对应(b):氧化还原过程中,表现含钛混合熔渣中还原性不足,向含钛混合熔渣中加入煤粉1kg,使含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法A:
(1)将还原氧化后的混合熔渣,自然冷却至室温,获得缓冷渣;
(2)含钒金属铁沉降到反应装置的底部,形成铁坨,人工取出铁坨;将剩余缓冷渣中含钒金属铁层,破碎至粒度为20~400μm,磨矿,磁选分离出剩余含钒金属铁;金属铁回收率为92%,本步骤尾矿渣中全铁含量0.778wt%;
(3)对去除铁坨和含钒金属铁层的缓冷渣上、中、下部,分别采用重力分选法进行分离;下部缓冷渣经溜槽一次粗选,摇床一次精选,两次扫选,将含钛组分与脉石相分离,得到主要物相为钙钛矿相的钛精矿、含钒镁铝尖晶石中矿和尾矿,钛精矿中TiO2质量分数为38.28%,含钒镁铝尖晶石中矿中V2O5的质量分数为8.51%,富磷相中P2O5的质量分数为27%;
(4)尾矿采用2%盐酸,按固液比1∶2将五氧化二磷分离出来,磷回收率为70%。
实施例11
一种含钛混合熔渣回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的液态熔融40kg含钛高炉渣和400kg电炉含钒钛熔融氧化钢渣倒入内层有冶金焦-尖晶石质复合保温脱模耐火材料的可倾倒的熔炼反应渣罐,充分混合形成含钛混合熔渣,发生熔融还原反应;混合后熔渣温度为1610℃;
高于在含钛混合熔渣的温度设定1450~1600℃范围;采用耐火喷枪以喷吹的方式,加入平均粒度为140μm的转炉烟尘粉状物料4kg,载入气体为空气,使含钛混合熔渣的温度降低至1580℃;其中:
含钛高炉熔渣,含有成分及其质量百分比为:4wt%TiO2、25.49wt%CaO、1.06wt%MgO、14.35wt%Al2O3、4.56wt%FeO、和21.03wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣,含有成分及其质量百分比:0.3wt%V2O5、TFe16.94wt%、45.32wt%CaO、10.36wt%SiO2、3.54wt%TiO2、2.67wt%MgO、1.85wt%MnO、1.64wt%Al2O3,余量为其他杂质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后富氧空气,共喷吹富氧空气5min;其中,富氧空气中氧气的体积百分比为22%,富氧空气预热温度为1200℃,富氧空气时间与流量的关系为60L/(min·kg);富氧空气的喷吹方式为采用耐火喷枪***置于熔渣侧面吹入;
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1450~1600℃范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):氧化还原过程测得混合熔渣温度高达1655℃;由于温度高出设定值,向含钛混合熔渣中吹入钒钛磁铁精矿金属化球团3kg,使含钛混合熔渣的温度降低至1560~1570℃,在设定范围内;
对应(b):氧化还原过程中,表现含钛混合熔渣中还原性不足,向含钛混合熔渣中加入烟
煤2kg,使含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法B:
(1)将还原氧化后的混合熔渣的温度降温至1250℃,将中部和上部的还原氧化后的混合熔渣水淬,用作水泥原料或建筑材料;
(2)将下部的还原氧化后的混合熔渣,仍在内层有冶金焦-尖晶石质复合保温脱模耐火材料的熔炼反应渣罐中,进行如下操作:
将下部的还原氧化后的混合熔渣,旋转冷却至室温,获得缓冷渣;其中,旋转冷却的操作为:装有氧化还原后的混合熔渣的保温装置置于旋转平台上,按照一定速度进行旋转,旋转速度依熔渣质量与保温装置高度或深度而定,旋转时间依熔渣质量与熔渣凝固情况而定;
含钒金属铁沉降到反应装置的底部,形成铁坨,人工取出铁坨;将剩余缓冷渣中含钒金属铁层,破碎至粒度为20~400μm,磨矿,磁选分离出剩余含钒金属铁;金属铁的回收率为91%,本步骤尾矿渣中全铁含量0.652wt%;
对去除铁坨和含钒金属铁层的缓冷渣上、中、下部,分别采用重力分选法进行分离;下部缓冷渣经溜槽一次粗选,摇床一次精选,两次扫选,将含钛组分与脉石相分离,得到主要物相为钙钛矿相的钛精矿、含钒镁铝尖晶石中矿和尾矿,钛精矿中TiO2的质量分数为35.00%,含钒镁铝尖晶石中矿中V2O5的质量分数为9.21%;富磷相中P2O5的质量分数为26%;
尾矿采用2%盐酸,固液比1∶2将五氧化二磷分离出来,磷回收率为60%。
实施例12
一种含钛混合熔渣回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的液态熔融150kg含钛高炉渣和500kg电炉含钒钛熔融氧化钢渣倒入内层有石墨-镁质复合保温脱模耐火材料的转炉,充分混合形成含钛混合熔渣,发生熔融还原反应;混合后熔渣温度为1610℃;
高于在含钛混合熔渣的温度设定1450~1600℃范围;向混合熔渣加入钒钛磁铁精矿含碳预还原球团2kg和萤石1kg,使含钛混合熔渣的温度降低至1570℃;其中:
含钛高炉熔渣,含有成分及其质量百分比为:30wt%TiO2、15.64wt%CaO、8.32wt%MgO、10.79wt%Al2O3、3.54wt%FeO、和18.45wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣,含有成分及其质量百分比:5.00wt%V2O5、TFe15.49wt%、41.78wt%CaO、15.11wt%SiO2、2.54wt%TiO2、1.86wt%MgO、1.79wt%MnO、1.62wt%Al2O3,余量为其他杂质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后氮气-空气混合气,共喷吹氮气-空气混合气10min;其中,氮气-空气混合气中氮气的体积百分比为40%,氮气-空气混合气预热温度为500℃,氮气-空气混合气时间与流量的关系为40L/(min·kg);氮气-空气混合气喷吹方式为采用耐火喷枪置于混合熔渣上部吹入;
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1450~1600℃范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):氧化还原过程测得混合熔渣温度高达1618℃;由于温度高出设定值,向含钛混合熔渣中吹入钛磁铁精矿含碳预还原球团1kg,使含钛混合熔渣的温度降低至1575~1582℃,在设定范围内;
对应(b):氧化还原过程中,表现含钛混合熔渣中还原性不足,向含钛混合熔渣中加入无烟煤2.5kg,使含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法D:
(1)将还原氧化后的混合熔渣,沉降渣-金分离,得含钒铁水与还原氧化后的含钒钛熔渣;
(2)将还原氧化后的含钒钛熔渣,进行炉外熔渣处理,采用方法D-1:测得还原氧化后的含钒钛熔渣TiO2的质量分数为8.9%≤10%,直接将还原氧化后的含钒钛熔渣空冷,用作水泥原料或建筑材料;
(3)将含钒铁水送往转炉炼钢。
实施例13
一种含钛混合熔渣回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的液态熔融420kg含钛高炉渣和380kg电炉含钒钛熔融氧化钢渣倒入内层有沥青-橄榄石质复合保温脱模耐火材料的直流电弧炉,充分混合形成含钛混合熔渣,发生熔融还原反应;混合后熔渣温度为1380℃;
低于在含钛混合熔渣的温度设定1450~1600℃范围;通过直流电弧炉自身加热功能,使含钛混合熔渣的温度升高至1450℃;其中:
含钛高炉熔渣,含有成分及其质量百分比为:15.64wt%TiO2、20.64wt%CaO、9.98wt%MgO、16.31wt%Al2O3、5.01wt%FeO、和21.61wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣,含有成分及其质量百分比:2.56wt%V2O5、TFe15.36wt%、40.25wt%CaO、11.39wt%SiO2、5.35wt%TiO2、2.64wt%MgO、1.92wt%MnO、1.59wt%Al2O3,余量为其他杂
质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后氧气-氩气混合气,共喷吹氧气-氩气混合气6min;其中,氧气-氩气混合气中氧气的体积百分比为50%,氧气-氩气混合气预热温度为800℃,氧气-氩气混合气时间与流量的关系为80L/(min·kg);氧气-氩气混合气的喷吹方式为采用耐火喷枪***混合熔渣吹入;
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1450~1600℃范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):还原氧化过程测得混合熔渣温度为1470~1475℃,在设定范围内;
对应(b):氧化还原过程中,表现含钛混合熔渣中还原性不足,向含钛混合熔渣中加入烟煤2.0kg,使含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法D:
(1)将还原氧化后的混合熔渣,沉降渣-金分离,获得含钒铁水与还原氧化后的含钒钛熔渣;
(2)将还原氧化后的含钒钛熔渣,进行炉外熔渣处理,采用方法D-1:
测得还原氧化后的含钒钛熔渣TiO2的质量分数=9.8≤10%时,直接将还原氧化后的含钒钛熔渣水淬,用作水泥原料或建筑材料;
(3)将含钒铁水送往转炉炼钢。
实施例14
一种含钛混合熔渣回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的液态熔融400kg含钛高炉渣和100kg转炉含钒钛熔融钢渣倒入内层有无烟煤-粘土质复合保温脱模耐火材料的矿热炉,充分混合形成含钛混合熔渣,发生熔融还原反应;混合后熔渣温度为1389℃;
低于在含钛混合熔渣的温度设定1450~1600℃范围;通过矿热炉自身加热功能,使含钛混合熔渣的温度升高至1462℃;其中;
含钛高炉熔渣,含有成分及其质量百分比为:10.65wt%TiO2、22.68wt%CaO、9.08wt%MgO、17.62wt%Al2O3、5.05wt%FeO、和21.03wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣,含有成分及其质量百分比:5.21wt%V2O5、TFe15.68wt%、40.01wt%CaO、
12.12wt%SiO2、4.86wt%TiO2、2.66wt%MgO、1.90wt%MnO、1.71wt%Al2O3,余量为其他杂质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后氮气-氧气混合气,共喷吹氮气-氧气混合气8min;其中,氮气-氧气混合气中氮气的体积百分比为60%,氮气-氧气混合气预热温度为480℃,氮气-氧气混合气时间与流量的关系为10L/(min·kg);氮气-氧气混合气的喷吹方式为采用耐火喷枪***混合熔渣吹入;
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1450~1600℃范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):还原氧化过程测得混合熔渣温度为1480~1488℃,在设定范围内;
对应(b):氧化还原过程中,表现含钛混合熔渣中还原性不足,向含钛混合熔渣中加入无烟煤1.8kg,使含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法D:
(1)将还原氧化后的混合熔渣,沉降渣-金分离,获得含钒铁水与还原氧化后的含钒钛熔渣;
(2)将还原氧化后的含钒钛熔渣,进行炉外熔渣处理:
(3)将含钒铁水送往转炉炼钢;
其中,炉外熔渣处理采用方法D-2:
将还原氧化后的含钒钛熔渣倒入烟煤-高铝质复合保温脱模耐火材料的保温地坑,然后进行如下操作:
①向还原氧化后的含钒钛熔渣中,喷吹预热后氮气-氧气混合气,共喷吹氮气-氧气混合气2min;其中,氮气-氧气混合气中氮气的体积百分比为60%,氮气-氧气混合气预热温度为500℃,氮气-氧气混合气时间与流量的关系为12L/(min·kg);氮气-氧气混合气的喷吹方式为采用耐火喷枪***混合熔渣吹入;
②控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1400~1600℃范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):还原氧化过程测得混合熔渣温度为1422~1429℃,在设定范围内;
对应(b):剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
③分离回收采用方法A:
将还原氧化后的熔渣,自然冷却至室温,获得缓冷渣;
含钒金属铁沉降到反应装置的底部,形成铁坨,人工取出铁坨;将剩余缓冷渣中含钒金属铁层,破碎至粒度为20~400μm,磨矿,磁选分离出剩余含钒金属铁;金属铁回收率95%,本步骤尾矿渣中全铁为0.665wt%;
对去除铁坨和含钒金属铁层的缓冷渣上、中、下部,分别采用重力分选法进行分离;下部缓冷渣经溜槽一次粗选,摇床一次精选,两次扫选,将含钛组分与脉石相分离,得到主要物相为钙钛矿相的钛精矿、含钒镁铝尖晶石中矿和尾矿,钛精矿中TiO2的质量分数为48.96%,含钒镁铝尖晶石中矿中V2O5的质量分数为9.65%;富磷相中P2O5的质量分数为30%;
尾矿采用2%盐酸,按固液比1∶2将五氧化二磷分离出来,磷回收率为80%。
实施例15
一种含钛混合熔渣回收与调质处理的方法,具体包括以下步骤:
步骤1,熔渣混合:
将出渣口中流出的液态熔融380kg含钛高炉渣和480kg转炉含钒钛熔融钢渣倒入内层有石油沥青焦-硅质复合保温脱模耐火材料的转炉,充分混合形成含钛混合熔渣,发生熔融还原反应;混合后熔渣温度为1632℃;
高于在含钛混合熔渣的温度设定1450~1600℃范围;向混合熔渣加入普通铁精矿金属化球团1.5kg,使含钛混合熔渣的温度降低至1560℃;其中:
含钛高炉熔渣,含有成分及其质量百分比为:10.94wt%TiO2、21.49wt%CaO、9.95wt%MgO、14.39wt%Al2O3、6.66wt%FeO、和22.61wt%SiO2,余量为其他杂质;
含钒钛熔融钢渣,含有成分及其质量百分比:1.32wt%V2O5、TFe16.59wt%、43.12wt%CaO、13.33wt%SiO2、5.06wt%TiO2、3.68wt%MgO、2.67wt%MnO、2.00wt%Al2O3,余量为其他杂质;
步骤2,熔融还原与氧化:
(1)喷吹气体:向含钛混合熔渣中,喷吹预热后氧气,共喷吹氧气6min;其中,氧气预热温度为1000℃,氧气时间与流量的关系为45L/(min·kg);空气的喷吹方式为采用耐火喷枪***混合熔渣吹入;
(2)控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1450~1600℃范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;随着反应的进行,熔渣还原性不足,加入煤粉1kg,使铁氧化物还原成金属铁;
对应(a):氧化还原过程测得混合熔渣温度高达1612℃;由于温度高出设定值,向含钛混合熔渣中加入普通铁精矿金属化球团1kg,使含钛混合熔渣的温度降低至1580~1585℃,在设定范围内;
对应(b):氧化还原过程中,表现含钛混合熔渣中还原性不足,向含钛混合熔渣中加入煤粉2kg,使含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
步骤3,分离回收采用方法D:
(1)将还原氧化后的混合熔渣,沉降渣-金分离,获得含钒铁水与还原氧化后的含钒钛熔渣;
(2)将还原氧化后的含钒钛熔渣,进行炉外熔渣处理:
(3)将含钒铁水送往转炉炼钢;
其中,炉外熔渣处理的采用方法D-2:
①将还原氧化后的含钒钛熔渣倒入石油沥青焦-尖晶石质复合保温脱模耐火材料的保温渣灌,然后进行如下操作:
向还原氧化后的含钒钛熔渣中,喷吹预热后氧气,共喷吹氧气3min;其中,氧气混合气体预热温度为960℃,氧气混合气体时间与流量的关系为40L/(min·kg);氧气混合气体的喷吹方式为采用耐火喷枪***混合熔渣吹入;
②控制还原与氧化过程:
在喷吹过程中,通过调控同时保证(a)和(b)两个参数:
(a)含钛混合熔渣的温度在设定温度1400~1600℃范围内;
(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
对应(a):还原氧化过程测得混合熔渣温度为1570~1576℃,在设定范围内;
对应(b):剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;
③分离回收采用方法C:
将还原氧化后的混合熔渣,沉降渣-金分离,获得含钒铁水与还原氧化后的含钒钛熔渣;
当还原氧化后的含钒钛熔渣TiO2的质量分数=8.5%≤10%时,直接将还原氧化后的含钒钛熔渣水淬,用作水泥原料或建筑材料。
Claims (12)
- 一种含钛混合熔渣熔融还原回收与调质处理的方法,其特征在于,包括以下步骤:步骤1,熔渣混合:按质量比,含钛高炉熔渣∶含钒钛熔融钢渣=100∶(1~1000)配料,加入保温装置、可倾倒的熔炼反应装置或固定式的熔炼反应装置中,形成含钛混合熔渣,发生熔融还原反应;将含钛混合熔渣的温度控制在设定温度范围内;其中:设定温度范围为1400~1600℃;当反应装置采用保温装置时,含钛混合熔渣的温度范围设定为1400~1600℃;当反应装置采用可倾倒的熔炼反应装置或固定式的熔炼反应装置时,含钛混合熔渣的温度范围设定为1450~1600℃;控制含钛混合熔渣的温度在设定温度范围的方法为:当含钛混合熔渣的温度<设定温度范围下限时,通过反应装置自身的加热功能,或向含钛混合熔渣中加入燃料和/或含钒钛熔融钢渣,使含钛混合熔渣的温度达到设定温度范围内;当含钛混合熔渣的温度>设定温度范围上限时,向含钛混合熔渣中加入含钒钛物料、含铁物料、含氟物料或含钛高炉熔渣中的一种或几种,使含钛混合熔渣的温度达到设定温度范围内;步骤2,熔融还原与氧化:(1)喷吹气体:向含钛混合熔渣中,喷吹预热后氧化性气体;其中,氧化性气体的预热温度为0~1200℃,氧化性气体时间与流量的关系为1~105L/(min·kg);(2)控制还原与氧化过程:在喷吹过程中,通过调控同时保证(a)和(b)两个参数:(a)含钛混合熔渣的温度在设定温度范围内;(b)含钛混合熔渣中,剩余低价钛氧化成高价钛,剩余铁氧化物还原成金属铁;调控方法为:对应(a):采用步骤1中的控制含钛混合熔渣的温度在设定温度范围的方法;对应(b):当含钛混合熔渣中还原性不足时,向含钛混合熔渣中加入还原剂,使含钛混合熔渣中,铁氧化物还原成金属铁;步骤3,分离回收:采用以下方法中的一种:一.当反应装置采用保温装置时,采用方法A、方法B或方法C:当反应装置采用不可倾倒的保温装置或可倾倒的保温装置时,采用方法A:(1)将还原氧化后的混合熔渣,冷却至室温,获得的缓冷渣;(2)含钒金属铁沉降到反应装置的底部,形成铁坨,人工取出铁坨;将剩余缓冷渣中含钒金属铁层,破碎至粒度为20~400μm,磨矿,磁选分离出剩余含钒金属铁;(3)对去除铁坨和含钒金属铁层的缓冷渣,采用重力分选法进行分离,获得钛精矿、富钒精矿和尾矿;(4)尾矿的回收利用有2种:①作为水泥原料、建筑材料、代替碎石作骨料、路材或磷肥使用;②采用湿法冶金、选矿方法或选矿-湿法冶金联合法将尾矿中含磷组分分离出来;仅当反应装置采用可倾倒的保温装置时,采用方法B或方法C:方法B:(1)将还原氧化后的混合熔渣的温度降温至1150~1250℃,将中部和上部的还原氧化后的混合熔渣倒出后,空冷或水淬,用作水泥原料或建筑材料;(2)将下部的还原氧化后的混合熔渣,仍在可倾倒的保温装置中,作为方法A还原氧化后的混合熔渣进行处理;方法C:(1)将还原氧化后的混合熔渣,沉降渣-金分离,获得含钒铁水与还原氧化后的含钒钛熔渣;(2)当还原氧化后的含钒钛熔渣TiO2的质量分数≤10%时,直接将还原氧化后的含钒钛熔渣倒出后,空冷或水淬,用作水泥原料或建筑材料;(3)将含钒铁水送往转炉炼钢;二.当反应装置采用可倾倒的熔炼反应装置或固定式的熔炼反应装置时,采用方法D:(1)将还原氧化后的混合熔渣,沉降渣-金分离,获得含钒铁水与还原氧化后的含钒钛熔渣;(2)将还原氧化后的含钒钛熔渣,进行炉外熔渣处理;(3)将含钒铁水送往转炉炼钢;其中,炉外熔渣处理采用方法D-1或方法D-2:方法D-1:当还原氧化后的含钒钛熔渣TiO2的质量分数≤10%时,直接将还原氧化后的含钒钛熔渣倒出后,空冷或水淬,用作水泥原料或建筑材料;方法D-2:将还原氧化后的含钒钛熔渣倒入保温装置,按照步骤2中的方法进行熔融还原与氧化,,分离回收采用方法A、方法B或方法C。
- 根据权利要求1所述的含钛混合熔渣熔融还原回收与调质处理的方法,其特征在于,所述的步骤1中,含钛高炉熔渣由高炉出渣口获得,含钛高炉熔渣的温度≥1300℃,所述的含钛高炉熔渣,含有TiO2的质量分数为4~30%;含钒钛熔融钢渣由钢渣出渣口获得,含钒钛熔融钢渣的温度≥1500℃,所述的含钒钛熔融钢渣,含有TiO2的质量分数为0.3~6%,含有V2O5的质量分数为0.3~5%。
- 根据权利要求2所述的含钛混合熔渣熔融还原回收与调质处理的方法,其特征在于,所述的含钒钛熔融钢渣,为转炉含钒钛熔融钢渣或电炉含钒钛熔融氧化钢渣。
- 根据权利要求1所述的含钛混合熔渣熔融还原回收与调质处理的方法,其特征在于,所述的保温装置为可倾倒的保温装置或不可倾倒的保温装置;所述的不可倾倒的保温装置为保温地坑;所述的可倾倒的保温装置为可倾倒的保温渣罐;所述的可倾倒的熔炼反应装置为可倾倒的转炉、可倾倒的熔炼反应渣灌或感应炉;固定式熔炼反应装置为底部带有渣口或铁口的反应装置;所述的固定式反应装置为等离子炉、直流电弧炉、交流电弧炉、矿热炉、鼓风炉或反射炉。
- 根据权利要求1所述的含钛混合熔渣熔融还原回收与调质处理的方法,其特征在于,所述的保温装置、可倾倒的熔炼反应装置或固定式的熔炼反应装置内层为含碳保温脱模耐火材料;所述的含碳保温脱模耐火材料是含碳复合耐火材料,具体为碳是碳素、石墨、石油沥青焦、冶金焦、沥青、无烟煤、烟煤或褐煤中的一种或几种,耐火材料是硅质、半硅质、粘土质、高铝质、镁质、白云石质、橄榄石质、尖晶石质、冷态含钛高炉渣或冷态含钒钛钢渣中的一种或几种。
- 根据权利要求1所述的含钛混合熔渣熔融还原回收与调质处理的方法,其特征在于,所述的控制含钛混合熔渣的温度在设定温度范围的方法中,向混合熔渣中加入燃料和/或含钒钛熔融钢渣时,燃料的预热温度为0~1200℃,含钒钛熔融钢渣的温度≥1500℃;燃料采用采用耐火喷枪***熔渣或置于熔渣上部或侧面吹入燃料;当同时向混合熔渣中加入燃料和含钒钛熔融钢渣时,燃料和含钒钛熔融钢渣为任意比;所述的含钒钛物料是含钛高炉渣、含钒钛钢渣、提钒尾渣、选钛尾矿、低品位钒钛磁铁矿、钒钛磁铁精矿、钒钛磁铁矿直接还原铁,钒钛磁铁精矿金属化球团、钒钛磁铁精矿含碳预还原球团、钒钛磁铁精矿烧结矿、钒钛磁铁精矿球团矿中的一种或几种;含铁物料是普通铁精矿、普通铁精矿直接还原铁,普通铁精矿烧结矿、普通铁精矿球团矿、普通铁精矿金属化球团、普通铁精矿含碳预还原球团、普通钢渣、高炉瓦斯灰、高炉烟尘、转炉烟尘、氧化铁皮、湿法炼锌过程的锌浸出渣、氧化铝生产过程产生的赤泥、煤粉灰、硫酸烧渣中的一种或几种;含氟物料是萤石和/或CaF2。
- 根据权利要求6所述的含钛混合熔渣熔融还原回收与调质处理的方法,其特征在于,燃料为煤粉。
- 根据权利要求6所述的含钛混合熔渣熔融还原回收与调质处理的方法,其特征在于,含钒钛物料、含铁物料和含氟物料为均球团或粉状物料;其中,粉状物料的粒度≤150μm,粉状物料以喷吹的方式加入含钛混合熔渣,载入气体为空气、氩气、氮气-空气混合气、氮气-氧气混合气或空气-氩气混合气;喷吹方式为采用耐火喷枪***熔渣或置于熔渣上部或侧面吹入粉状物料。
- 根据权利要求1所述的含钛混合熔渣熔融还原回收与调质处理的方法,其特征在于,所述的氧化性气体是空气、氧气、富氧空气、氮气-氧气混合气、氮气-空气混合气、氧气-氩气混合气或空气-氩气混合气中的一种;氧化性气体的喷吹方式为采用耐火喷枪***熔渣或置于熔渣上部或侧面吹入氧化性气体。
- 根据权利要求1所述的含钛混合熔渣熔融还原回收与调质处理的方法,其特征在于,所述的步骤2和步骤3中,还原剂均为煤粉、焦粉、烟煤或无烟煤中的一种。
- 根据权利要求1所述的含钛混合熔渣熔融还原回收与调质处理的方法,其特征在于,所述的步骤3,方法A(1)中,冷却方式为自然冷却或旋转冷却;所述的旋转冷却的具体操作为:装有氧化还原后的混合熔渣的保温装置置于旋转平台上,按照一定速度进行旋转,旋转速度依熔渣质量与保温装置高度或深度而定,旋转时间依熔渣质量与熔渣凝固情况而定;方法A(3)中,重力分选法是摇床分选、溜槽分选或者二者相结合;方法A(4)中,湿法冶金是稀酸浸出法,其中稀酸浸出法是无机酸浸、有机酸浸中的一种;所述的无机酸选用硫酸、盐酸、磷酸的一种或多种,有机酸选用草酸、乙酸、柠檬酸中的一种或多种。
- 根据权利要求1所述的含钛混合熔渣熔融还原回收与调质处理的方法,其特征在于,所述的步骤3,方法A中,金属铁回收率为90~97%,主要物相为钙钛矿的钛精矿中TiO2的质量分数均为35~52%,钛的回收率为60~80%;方法B中,金属铁回收率为90~95%,主要物相为钙钛矿的钛精矿中TiO2的质量分数均为35~52%,钛的回收率为58~76%。
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