WO2018014363A1 - Method for smelting reduction, recycling and tempering of titaniferous mixed slag - Google Patents

Abstract

Disclosed is a method for smelting reduction, recycling and tempering of a titaniferous mixed slag, comprising: (1) mixing titaniferous blast furnace slag with vanadium-titanium-containing molten steel slag to form a titaniferous mixed slag, and controlling the temperature of the titaniferous mixed slag within a set temperature range; (2) injecting an oxidizing gas for smelting reduction and oxidization, and during the process, the temperature of the titaniferous mixed slag is ensured to be within the set temperature range, and in the titaniferous mixed slag, low-valence titanium is oxidized into high-valence titanium, and the iron oxide is reduced into metal iron; and (3) carrying out separation and recycling according to different reaction devices. According to the invention, efficient recycling of the titanium component, iron component, vanadium component, phosphorus component and free calcium oxide component in the mixed slag is realized, and a cold-state vanadium-titanium-iron-containing material can be treated to realize the tempering of the slag and efficient and comprehensive utilization of the resources; the method has a short reaction time, a high metal recovery rate, a low production cost, a high raw material adaptability, a large handling capacity, is environmentally friendly and has a high economic benefit, and the problems during efficient recycling of the metallurgy resource and thermal energy can be effectively solved.

Description

Method for smelting reduction recovery and quenching and tempering treatment of titanium-containing mixed slag Technical field

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.

Background technique

China is a large country with large titanium resources and rich in vanadium-titanium magnetite resources, mainly distributed in Panxi and Chengde. Vanadium-titanium magnetite is a composite ore of symbiotic elements of iron, vanadium, titanium, chromium, phosphorus, copper, nickel, cobalt, lanthanum, cerium, zirconium and hafnium. After many years of technical research, China has adopted the “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. At the same time, the annual discharge of more than 7 million tons of vanadium-containing steel slag, the accumulation has exceeded 20 million tons, equivalent to more than 600,000 tons of TiO ₂ , more than 4 million tons of metal iron, more than 600,000 tons of vanadium pentoxide, pentoxide More than 150,000 tons of phosphorus, more than 2 million tons of free calcium oxide, the total value of hundreds of billions. A large amount of titanium-containing slag (containing titanium blast furnace slag and vanadium-containing titanium steel slag) is piled up in large quantities, which wastes resources and pollutes the environment.

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. However, many methods, although technically feasible, are not economically viable and still cannot be used. For industrial applications and development.

At present, the researcher's comprehensive utilization of titanium-containing blast furnace slag and vanadium-containing titanium steel slag and vanadium-bearing waste slag is as follows:

1. Comprehensive utilization of titanium-containing blast furnace slag

Including 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.

Alkali extraction of titanium alkali consumption is large, considering the recovery of sodium salt will greatly increase the cost and complexity of the complete process, titanium enrichment effect is not very satisfactory, titanium content in the titanium-poor phase is still high, improper treatment may produce new The pollution, while treating the blast furnace slag with alkali at high temperatures, can cause serious air pollution and huge energy consumption.

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. However, after leaching of hydrochloric acid, a large amount of leaching residue is generated, and the leaching residue has no suitable use, that is, a new one is produced after leaching of hydrochloric acid. Waste.

Since there are few steels that require titanium and silicon as alloying agents at the same time, the application range of titanium-silicon alloy is narrow and the amount is small, which cannot solve the problem of large number of blast furnace slag in Panzhihua Iron and Steel Co., Ltd., which is the key to the industrialization of this technical solution. . In addition, although the reducing residue has potential hydraulic properties, the amount of residual titanium is still high, and the content thereof needs to be further reduced, but the cost may be too high.

Titanium-containing blast furnace slag carbonitriding titanium is a way to utilize titanium-containing blast furnace slag, and there are some obvious shortcomings. For example, 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. In addition, 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.

Direct water quenching, used as cement raw material, or used as building materials, but 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.

In view of the above various problems in the utilization of titanium-containing blast furnace slag, the inventors have previously described in the patent No. 200610134260.3 "Method for separating and producing titanium-rich material from titanium-containing blast furnace slag" and Patent No. 201110072575.0 "a titanium-containing blast furnace slag" Two methods for utilizing titanium-containing blast furnace slag are proposed in the method for producing artificial rutile. Although the above two methods have the characteristics of large processing capacity, the following disadvantages still exist:

1. 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 In the process of adding the additive, 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.

2. Comprehensive utilization of vanadium-containing titanium steel slag

At present, 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. At the same time, 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.

Based on this, in view of the problems existing in the prior art, the inventors have provided a kind of mixed melting from titanium containing in the patent No. ZL201310290767.8 "a method for separating iron titanium vanadium calcium from titanium-containing mixed slag". 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) physical beneficiation in subsequent separation process (magnetic separation or heavy Optional), the separated medium is water, and the water can be circulated during the beneficiation process, so that no environmental pollution occurs during the separation process, so that the entire titanium-containing mixed slag process has a short process, simple operation, and recovery of iron, vanadium, titanium, and calcium. High rate, no waste water, high efficiency, clean and environmentally friendly; (4) tailings obtained by re-separation can be used as high-quality raw materials for producing high-grade cement, no solid waste is produced during the whole process; (5) whole process No need to add any additives, no thermal compensation, high operability and low production cost.

Although the above method has obvious characteristics, it still has the following disadvantages: (1) can only deal with hot slag (containing titanium blast furnace slag and vanadium-containing titanium molten steel slag), and can not handle cold vanadium-containing titanium materials; (2) The titanium-containing mixed slag (containing titanium blast furnace slag and vanadium-containing titanium molten steel slag) is oxidized and exothermic, and the slag temperature is too high, which easily damages the insulation release liner material and the tank body, thereby reducing the service life; TiO2 mixed slag (containing titanium blast furnace slag and vanadium-containing titanium molten steel slag) in the oxidative heat release of reduced substances, If the slag temperature is too high, the metal iron in the mixed slag is accelerated to iron oxide, the settlement of the metal iron is reduced, and the recovery rate of the metal iron is decreased; (4) the titanium-containing mixed slag is reduced in oxidation state, and the slag temperature is lowered. Too high, causing a large amount of waste of heat resources; (5) low recovery rate of metal iron, only recovering metal iron in mixed slag, not considering reduction and recovery of iron oxide in mixed slag; (6) not fully utilizing titanium-containing blast furnace Reducing and reducing of slag; (7) only considering the recovery of elemental vanadium in the slag, not recovering vanadium oxide in the slag; (8) not controlling the slag oxygen potential, mixing the iron oxide part of the slag Reduction, partial reduction of iron reoxidation, therefore, the content of iron oxide in the slag is high, it is difficult to grind; (9) Titanium-rich phase-perovskite phase does not settle, the amount of slag is large, grinding cost, magnetic separation cost and re-election The cost is high; (10) no phosphorus component is recovered; (11) the slag is not subjected to quenching and tempering, and tailings utilization is limited.

Summary of the invention

In view of the problems existing in the prior art, 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, respectively, and achieve growth and sedimentation; 5 the phosphorus component in the mixed slag migrates and is enriched in Ca ₂ SiO ₄ -Ca ₃ (PO ₄ ) ₂ phase, distributed at the perovskite phase interface; 6 free calcium oxide and magnesium oxide in the mixed slag disappear, iron oxide reduced to metal iron, mixed slag to achieve quenching and tempering; Method of combining manual sorting, magnetic separation and re-election The vanadium-containing metal iron, vanadium-rich oxide phase and perovskite phase settled at the bottom, thereby achieving efficient recovery of the titanium component, the iron component, the vanadium component, the phosphorus component and the free calcium oxide component in the mixed slag; It can process solid vanadium, titanium and iron materials, and at the same time realize slag quenching and tempering treatment to achieve efficient and comprehensive utilization of resources;

Specifically, the following steps are included:

Step 1, slag mixing:

According to the mass ratio, 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;

among them:

The set temperature range is 1400 ~ 1600 ° C;

When the reaction device adopts the heat preservation device, the temperature range of the titanium-containing mixed slag is set to 1400 to 1600 ° C;

When the reaction device uses a pourable smelting reaction device or a stationary smelting reaction device, 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:

When the temperature of the titanium-containing mixed slag is lower than the set temperature range, 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;

When 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;

Step 2, smelting reduction and oxidation:

(1) 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);

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is within a set temperature range;

(b) in the titanium-containing mixed slag, 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:

Corresponding to (a):

The method for controlling the temperature of the titanium-containing mixed slag in the set temperature range in step 1;

Corresponding to (b):

When the reducing property in the titanium-containing mixed slag is insufficient, 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;

Step 3, separate and recycle:

Use one of the following methods:

1. When the reaction device is insulated, use Method A, Method B or Method C:

When the reaction device uses a non-dumpable insulation device or a pourable insulation device, Method A is used:

(1) reducing the oxidized mixed slag, cooling to room temperature, to obtain a slow cooling slag;

(2) 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 μm, ground and magnetically separated. Remaining vanadium containing metal iron;

(3) Separating the slow-cooling slag of iron slag and vanadium-containing metal iron layer by gravity separation method to obtain titanium concentrate, vanadium-rich concentrate and tailings;

(4) 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;

Use Method B or Method C only if the reaction unit uses a pourable insulation unit:

Method B:

(1) 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;

(2) the lower reduced oxidized mixed slag is still in the pourable heat preservation device, and is treated as the method A to reduce the oxidized mixed slag;

Method C:

(1) separating the oxidized mixed slag and separating the slag-gold to obtain vanadium-containing molten iron and the reduced-oxidized vanadium-containing titanium slag;

(2) 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, and then air-cooled or water-quenched, used as a cement raw material or building material. ;

(3) sending vanadium-bearing molten iron to converter steelmaking;

2. When the reaction device uses a pourable smelting reaction device or a stationary smelting reaction device, method D is employed:

(1) separating the oxidized mixed slag and separating the slag-gold to obtain vanadium-containing molten iron and the reduced-oxidized vanadium-containing titanium slag;

(2) reducing the oxidized vanadium-containing titanium slag and performing slag treatment outside the furnace;

(3) sending vanadium-bearing molten iron to converter steelmaking;

Among them, 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.

In the step 1, the temperature of the titanium-containing blast furnace slag is ≥ 1300 ° C, and the temperature of the vanadium-containing titanium molten steel slag is ≥ 1500 ° C.

In the step 1, 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;

In the step 1, 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. One or more of a quality, olivine, spinel, cold titanium-containing blast furnace slag or cold vanadium-containing titanium steel slag. 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.

In the method of controlling the temperature of the titanium-containing mixed slag in a set temperature range, when 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.

In the method of controlling the temperature of the titanium-containing mixed slag in a set temperature range, 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.

In the method of controlling the temperature of the mixed slag in the set temperature range, when 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 method for controlling the temperature of the titanium-containing mixed slag in a set temperature range, when the temperature of the titanium-containing mixed slag is lower than the lower limit of the set temperature range, adding fuel and/or vanadium to the titanium-containing mixed slag Titanium molten steel slag for heat compensation.

The method for controlling the temperature of the titanium-containing mixed slag in a set temperature range, 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, converter soot, iron oxide scale, zinc leaching residue in wet zinc smelting process, red mud produced in alumina production process One or more of coal powder ash and sulfuric acid slag; the fluorine-containing material is fluorite and/or CaF ₂ .

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 ≤150μm, 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.

In 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, another function of adding the fluorine-containing material is to lower the viscosity and accelerate the slag. Aggregation, growth and sedimentation of vanadium-containing metallic iron, titanium-rich phase, vanadium-rich phase, and phosphorus-rich phase.

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 At the temperature, during the process of ejecting gas, the remaining low-priced titanium (Ti ²⁺ , Ti ³⁺ ) is sufficiently oxidized to high-priced titanium (Ti ⁴⁺ ) to ensure the remaining high-valent iron (Fe ³⁺ , Fe ²⁺ ) in the mixed slag. It is sufficiently reduced to metallic iron Fe to ensure that the metal iron particles in the slag are not oxidized.

In the step 1, 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.

In the step 2 and the step 3, the reducing agent is one of coal powder, coke powder, bituminous coal or anthracite.

In the above 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.

In the step 2 (2), 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.

In the step 2, the smelting reduction and oxidation process, 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.

In the step 3, in the method A(1), the cooling method is natural cooling or rotary cooling.

In the step 3, in the method A(1), 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. Depending on the height or depth of the insulation device, 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.

In the above 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.

In the step 3, in the method A (3), 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. Mine and tailings;

In the step 3, in the method A(1), 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.

In the step 3, in the method A (3), the gravity sorting method is a shaker sorting, a chute sorting or a combination of the two.

In the step 3, in the method A (4), 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, and the organic acid is one or more selected from the group consisting of oxalic acid, acetic acid and citric acid.

In the step 3, in the method A, 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 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 method for recovering and quenching and tempering the titanium-containing mixed slag according to the present invention, 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 method for smelting reduction recovery and quenching and tempering treatment of the titanium-containing mixed slag of the present invention has the following features in comparison with the prior art:

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;

At the same time, in the titanium-containing blast furnace slag, the ferrite-containing and vanadium-containing titanium in the molten steel slag containing vanadium and the reduced metal iron began to aggregate and grow up, and when they approach a certain size, the sedimentation begins, and most of the sedimentation falls to the bottom of the dross to form a monolith. Iron ingots;

After the end of the blowing gas, 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;

After the slag is cooled, 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. High-efficiency recovery of iron in vanadium-bearing iron and iron oxide in molten steel slag, high recovery rate of metal iron;

Since the titanium-rich phase (perovskite phase) and the vanadium-rich phase (vanadium-rich oxide phase) settle in the lower part, the amount of slag to be sorted is small, the cost of grinding, magnetic separation and re-election is low, and at the same time, The phosphorus-rich phase at the interface of the perovskite phase contributes to the dissociation and beneficiation of the perovskite phase;

It not only realizes the recovery of elemental vanadium in the slag, but also realizes the enrichment, growth, sedimentation and separation of vanadium-containing oxides;

Free calcium oxide and free magnesium oxide disappear, metal iron and iron oxide almost disappear, slag realizes quenching and tempering, tailings use limiting factors disappear, can be used as cement raw materials or building materials or instead of crushed stone as aggregate and road material or phosphate fertilizer Or the hydrometallurgical method is used to separate the phosphorus-containing components, and the tailings have large utilization value and wide application range.

The process of the invention can be carried out continuously or discontinuously to meet the needs of industrial production.

The beneficial effects of the invention are:

(1) 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;

(2) 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. High-efficiency utilization of thermal resources; liquid molten titanium-containing blast furnace slag is reducing slag, and 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;

(3) 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;

(4) In the method of the present invention, 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. Oxidation of vanadium-containing iron and reduced metal iron in vanadium-containing titanium molten steel slag to increase the recovery rate of metal iron; adding cold material and hot-melting titanium-containing blast furnace slag improves the processing amount of raw materials, and can not only treat liquid slag Moreover, a small amount of cold material can be processed, and the raw material is highly adaptable; the addition of the cold material realizes the efficient use of the chemical heat released by the slag oxidation reaction and the physical heat of the slag;

(5) 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;

(6) In the natural cooling process of the method of the present invention, 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. And realize the aggregation, growth and settlement; 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;

(7) 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;

(8) 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. Increased in nature, low cost of grinding, magnetic separation and re-election; subsequent separation process uses physical beneficiation (magnetic separation or re-election), the separated medium is water, and water can be circulated during the beneficiation process, so no separation occurs during the separation process. The environmental pollution makes the whole titanium-containing mixed slag process have the advantages of short process, simple operation, high recovery rate of iron, vanadium, titanium and calcium, no waste water generation, high efficiency, cleanness and environmental protection; since the slag is subjected to quenching and tempering treatment, 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 combination method Separation of phosphorus-containing components ; tailings use value is large, a wide range of applications;

(9) The whole process of the method of the invention does not require thermal compensation or requires a small amount of thermal compensation, and has high operability and low production cost;

(10) 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.

DRAWINGS

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.

detailed description

The process flow chart of the method for the smelting reduction recovery and quenching and tempering treatment of the titanium-containing mixed slag in the following examples is shown in FIG.

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.

Example 1

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;

After mixing, 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; where:

Titanium-containing blast furnace slag containing components and mass percentages thereof: 20.34 wt% TiO ₂ , 22.26 wt% CaO, 8.12 wt% MgO, 10.89 wt% Al ₂ O ₃ , 2.96 wt% FeO, and 20.46 wt% SiO ₂ , The amount is other impurities;

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;

Step 2, smelting reduction and oxidation:

(1) 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.

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is between 1400 and 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a), the reduction and oxidation process measured the mixed slag temperature of 1456 ~ 1466 ° C, within the set range;

Corresponding to (b), reduction and oxidation process, the remaining low-cost titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Step 3, separation and recovery using method A:

(1) reducing the oxidized mixed slag, and naturally cooling to room temperature to obtain a slow cooling slag;

(2) 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 μm, 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;

(3) 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%, and the mass fraction of P ₂ O ₅ in the phosphorus-rich phase is 28%.

(4) The tailings are separated by 2% dilute sulfuric acid at a solid-liquid ratio of 1:2, and the phosphorus recovery rate is 80%.

Example 2

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;

Titanium-containing blast furnace slag containing components and mass percentages thereof: 22.65 wt% TiO ₂ , 19.79 wt% CaO, 9.31 wt% MgO, 11.96 wt% Al ₂ O ₃ , 3.26 wt% FeO, and 19.48 wt% SiO ₂ , The balance is other impurities;

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;

Step 2, smelting reduction and oxidation:

(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;

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a):

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;

Corresponding to (b):

In the redox process, 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

Step 3, separation and recovery using method A:

(1) 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;

(2) 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 μm, 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%;

(3) The lower part of the slow cooling slag for removing the iron slag and the vanadium-containing metal iron layer is once selected by the chute, the shaker is selected once, and the sweeping is performed twice, and the titanium-containing component is separated from the gangue to obtain the main material. Titanium concentrate with perovskite phase, ore and tailings containing vanadium-magnesium-magnesium-aluminum spinel, mass fraction of TiO ₂ in titanium concentrate is 38.31%, V ₂ O in ore containing vanadium-magnesium-aluminum-doped spinel The mass fraction of ₅ is 9.58%, and the mass fraction of P ₂ O ₅ in the phosphorus-rich phase is 29%;

(4) Tailings are used as phosphate fertilizer.

Example 3

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;

Titanium-containing blast furnace slag containing components and mass percentages thereof: 21.96 wt% TiO ₂ , 20.37 wt% CaO, 8.75 wt% MgO, 11.62 wt% Al ₂ O ₃ , 4.4.46 wt% FeO, and 19.28 wt% SiO ₂ The balance is other impurities;

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;

Step 2, smelting reduction and oxidation:

(1) 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.

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) The temperature of the titanium-containing mixed slag is set within 1400 to 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a): reducing oxidation process, measuring the mixed slag temperature is 1462 ~ 1467 ° C, within the set temperature range;

Corresponding to (b): reduction oxidation process, the remaining low-cost titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Step 3, separation and recovery using method A:

(1) the reduced oxidized mixed slag, naturally cooled to room temperature, to obtain slow cooling slag; wherein, the rotary cooling method is the same as in Example 2;

(2) 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 μm, 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%;

(3) 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, and the lower slow slag is coarsely selected twice through the chute, and the shaker is selected once, two After the second sweep, the upper and middle sections are roughly selected by the chute twice, the shaker is selected twice, and the sweeping is performed to separate the titanium-containing component from the gangue to obtain the titanium concentrate with the main phase being the perovskite phase. In the vanadium-bearing magnesia-alumina spinel mine and tailings, 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%;

(4) Tailings are used as phosphate fertilizer.

Example 4

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:

Titanium-containing blast furnace slag containing components and mass percentages thereof: 18.69 wt% TiO ₂ , 21.32 wt% CaO, 9.26 wt% MgO, 12.31 wt% Al ₂ O ₃ , 4.49 wt% FeO, and 20.14 wt% SiO ₂ , The balance is other impurities;

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;

Step 2, smelting reduction and oxidation:

(1) 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;

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a): reduction oxidation process, measuring the mixed slag temperature is 1500 ~ 1510 ° C, in the set temperature range;

Corresponding to (b): reduction oxidation process, the remaining low-cost titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Step 3, separation and recovery using method A:

(1) the reduced oxidized mixed slag, rotary cooling to room temperature, to obtain slow cooling slag; wherein, the rotary cooling method is the same as in Example 2;

(2) 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 μm, 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%;

(3) 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, and the lower slow slag is coarsely selected through the chute, and the shaker is selected once and twice. Sweeping, the upper and middle sections are selected by the chute once, the shaker is selected once, and the sweeping is performed once, and the titanium-containing component is separated from the gangue to obtain the titanium concentrate with the main phase being the perovskite phase, and the vanadium-containing magnesium. In the aluminum spinel mine and tailings, 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%;

(4) Tailings are used as building materials.

Example 5

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:

Titanium-containing blast furnace slag containing components and mass percentages thereof: 19.31 wt% TiO ₂ , 19.69 wt% CaO, 9.84 wt% MgO, 13.28 wt% Al ₂ O ₃ , 4.47 wt% FeO, and 20.26 wt% SiO ₂ , The balance is other impurities;

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;

Step 2, smelting reduction and oxidation:

(1) 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;

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a): reduction oxidation process, the measured mixed slag temperature is 1468 ~ 1476 ° C, within the set range;

Corresponding to (b): reduction oxidation process, the remaining low-cost titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Step 3, separation and recovery using method A:

(1) reducing the oxidized mixed slag, and naturally cooling to room temperature to obtain a slow cooling slag;

(2) 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 μm, 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%;

(3) 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, and the lower part of the slow-cooling slag is coarsely selected twice through the chute, and the shaker is selected once. Two sweeps, the upper and middle sections are selected by a chute, the shaker is selected once, and the sweeping is performed. 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%;

(4) The 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%.

Example 6

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;

Titanium-containing blast furnace slag containing components and mass percentage thereof: 12.46 wt% TiO ₂ , 21.37 wt% CaO, 11.26 wt% MgO, 16.14 wt% Al ₂ O ₃ , 5.09 wt% FeO, and 19.48 wt% SiO ₂ , The amount is other impurities;

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;

Step 2, smelting reduction and oxidation:

(1) 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;

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a): reduction oxidation process, the mixed slag temperature is 1483 ~ 1491 ° C, within the set range;

Corresponding to (b): reduction oxidation process, the remaining low-cost titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Step 3, separation and recovery using method A:

(1) reducing the oxidized mixed slag, and naturally cooling to room temperature to obtain a slow cooling slag;

(2) 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 μm, 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%;

(3) Separating the upper, middle and lower parts of the slow-cooling slag and the vanadium-containing metal iron layer by gravity separation method, 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. In the spar mine and tailings, 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%;

(4) Tailings are used as phosphate fertilizer.

Example 7

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. Insulation pit with carbon-spinel composite thermal insulation release refractory material, fully mixed to form mixed slag, and smelting reduction reaction occurs; slag temperature after mixing is 1580 ° C; temperature is set at 1400 of titanium-containing mixed slag ～1600°C; among them;

Titanium-containing blast furnace slag containing components and mass percentages thereof: 29.48 wt% TiO ₂ , 19.67 wt% CaO, 5.38 wt% MgO, 12.27 wt% Al ₂ O ₃ , 2.47 wt% FeO, and 17.74 wt% SiO ₂ , The balance is other impurities;

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;

Step 2, smelting reduction and oxidation:

(1) 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;

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) The temperature of the titanium-containing mixed slag is within the set temperature of 1400 to 1600 ° C

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a): 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;

Corresponding (b): During the redox process, the reduction of reducing property in the titanium-containing mixed slag is insufficient, and 2 kg of coke powder is added to the titanium-containing mixed slag to oxidize the remaining low-valent titanium into high-priced titanium in the titanium-containing mixed slag. Reducing iron oxide to metal iron;

Step 3, separation and recovery using method A:

(1) the reduced oxidized mixed slag, rotary cooling to room temperature, to obtain slow cooling slag; wherein, the rotary cooling method is the same as in Example 2;

(2) 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 μm, 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%;

(3) 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, and the lower slow slag is coarsely selected through the chute, and the shaker is selected once and twice. Sweeping, separating the titanium-containing component from the gangue to obtain the titanium concentrate with the main phase as the perovskite phase, the ore and tailings of the vanadium-bearing magnesium-aluminum spinel, and the mass fraction of TiO ₂ in the titanium concentrate. 37.28%, the mass fraction of V ₂ O ₅ in the vanadium-bearing magnesium-aluminum spinel is 9.18%; the mass fraction of P ₂ O ₅ in the phosphorus-rich phase is 29%;

(4) Tailings are used as phosphate fertilizer.

Example 8

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;

Titanium-containing blast furnace slag containing components and mass percentages thereof: 4.37 wt% TiO ₂ , 256.28 wt% CaO, 9.77 wt% MgO, 16.14 wt% Al ₂ O ₃ , 2.89 wt% FeO, and 22.98 wt% SiO ₂ , The balance is other impurities;

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;

Step 2, smelting reduction and oxidation:

(1) 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;

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a): the mixed slag temperature measured during the reduction process is 1470 ~ 1480 ° C, within the set range;

Corresponding (b): During the redox process, the reduction of reducing property in the titanium-containing mixed slag is insufficient, and 1 kg of coke powder is added to the titanium-containing mixed slag to oxidize the remaining low-valent titanium into high-priced titanium in the titanium-containing mixed slag. Reducing iron oxide to metal iron;

Step 3, separation and recovery using method A:

(1) the reduced oxidized mixed slag, rotary cooling to room temperature, to obtain slow cooling slag; wherein, the rotary cooling method is the same as in Example 2;

(2) 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 μm, 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%;

(3) Separating the upper, middle and lower parts of the slow-cooling slag and the vanadium-containing metal iron layer by gravity separation method, 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%;

(4) Tailings are used as phosphate fertilizer.

Example 9

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;

Titanium-containing blast furnace slag containing components and mass percentages thereof: 29.97 wt% TiO ₂ , 19.17 wt% CaO, 5.69 wt% MgO, 11.98 wt% Al ₂ O ₃ , 2.47 wt% FeO, and 16.26 wt% SiO ₂ , The balance is other impurities;

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;

Step 2, smelting reduction and oxidation:

(1) 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;

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a): reduction oxidation process, the mixed slag temperature is 1520 ~ 1530 ° C, within the set temperature range;

Corresponding (b): During the redox process, the reduction of reducing property in the titanium-containing mixed slag is insufficient, and 2 kg of coke powder is added to the titanium-containing mixed slag to oxidize the remaining low-valent titanium into high-priced titanium in the titanium-containing mixed slag. Reducing iron oxide to metal iron;

Step 3, separation and recovery using method A:

(1) reducing the oxidized mixed slag, and naturally cooling to room temperature to obtain a slow cooling slag;

(2) 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 μm, ground and magnetically separated. The remaining vanadium-containing metal iron; the metal iron recovery rate is 93%, and the total iron content of the tailings slag in this step is 0.794% by weight;

(3) 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, and the lower slow slag is coarsely selected through the chute, and the shaker is selected once and twice. Sweeping, separating the titanium-containing component from the gangue to obtain the titanium concentrate with the main phase as the perovskite phase, the ore and tailings of the vanadium-bearing magnesium-aluminum spinel, and the mass fraction of TiO ₂ in the titanium concentrate. 37.38%, the mass fraction of V ₂ O ₅ in the vanadium-bearing magnesium-aluminum spinel is 9.15%, and the mass fraction of P ₂ O ₅ in the phosphorus-rich phase is 28%;

(4) The tailings were separated by 2% citric acid, and the ratio of solid to liquid was 1:2, and the phosphorus recovery was 70%.

Example 10

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. Forming a titanium-containing mixed slag to cause a smelting reduction reaction; the slag temperature after mixing is 1430 ° C; and the temperature of the titanium-containing mixed slag is set within a range of 1400 to 1600 ° C; wherein;

Titanium-containing blast furnace slag containing components and mass percentages thereof: 13.41 wt% TiO ₂ , 21.49 wt% CaO, 9.87 wt% MgO, 15.37 wt% Al ₂ O ₃ , 4.43 wt% FeO, and 20.28 wt% SiO ₂ , The balance is other impurities;

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;

Step 2, smelting reduction and oxidation:

(1) 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;

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a): the reduction oxidation process measures the mixed slag temperature of 1470 ~ 1478 ° C, within the set range;

Corresponding (b): During the redox process, the reduction of reducing property in the titanium-containing mixed slag is insufficient, and 1 kg of coal powder is added to the titanium-containing mixed slag to oxidize the remaining low-valent titanium into high-priced titanium. Reducing iron oxide to metal iron;

Step 3, separation and recovery using method A:

(1) reducing the oxidized mixed slag, and naturally cooling to room temperature to obtain a slow cooling slag;

(2) 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 μm, 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%;

(3) 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 slag is coarsely selected by the chute, and the shaker is selected once and twice. Sweeping, separating the titanium-containing component 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 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%;

(4) The 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%.

Example 11

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;

It is higher than the temperature set in the titanium-containing mixed slag from 1450 to 1600 °C; 4kg of converter dusty material with an average particle size of 140μm is added by means of a refractory spray gun, and the gas is filled into air to mix the titanium. The temperature of the slag is reduced to 1580 ° C; where:

Titanium-containing blast furnace slag containing components and mass percentages thereof: 4 wt% TiO ₂ , 25.49 wt% CaO, 1.06 wt% MgO, 14.35 wt% Al ₂ O ₃ , 4.56 wt% FeO, and 21.03 wt% SiO ₂ , The amount is other impurities;

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;

Step 2, smelting reduction and oxidation:

(1) 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;

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is in the range of the set temperature of 1450 to 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a): 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;

Corresponding (b): In the redox process, the reduction of reducing property in the titanium-containing mixed slag is indicated, and the smoke is added to the titanium-containing mixed slag. 2kg of coal, in the titanium-containing mixed slag, the remaining low-cost titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Step 3, separation and recovery using method B:

(1) 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;

(2) The lower oxidized mixed slag is still in the smelting reaction slag tank of the metallurgical coke-spinel composite thermal insulation mold release refractory in the inner layer, and the following operations are performed:

The lower reduced oxidized mixed slag is spin-cooled to room temperature to obtain slow cooling slag; wherein, 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 μm, and the remaining vanadium is separated by magnetic separation. Metal iron; the recovery rate of metallic iron is 91%, and the total iron content in the tailings slag of this step is 0.652wt%;

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%.

Example 12

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;

Higher than the temperature in the titanium-containing mixed slag set 1450 ~ 1600 ° C; to the mixed slag added vanadium-titanium magnetite concentrate carbon-containing pre-reduction pellets 2kg and fluorite 1kg, so that the temperature of the titanium-containing mixed slag is reduced to 1570 ° C; where:

Titanium-containing blast furnace slag containing components and mass percentages thereof: 30 wt% TiO ₂ , 15.64 wt% CaO, 8.32 wt% MgO, 10.79 wt% Al ₂ O ₃ , 3.54 wt% FeO, and 18.45 wt% SiO ₂ , The amount is other impurities;

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;

Step 2, smelting reduction and oxidation:

(1) 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;

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is in the range of the set temperature of 1450 to 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a): 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;

Corresponding (b): During the redox process, the reduction of reducing property in the titanium-containing mixed slag is insufficient, and 2.5 kg of anthracite is added to the titanium-containing mixed slag to oxidize the remaining low-valent titanium into high-priced titanium. Reducing iron oxide to metal iron;

Step 3, separation and recovery using method D:

(1) separating the oxidized mixed slag and separating the slag-gold to obtain vanadium-containing molten iron and the reduced-oxidized vanadium-containing titanium slag;

(2) 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;

(3) Send vanadium-bearing molten iron to converter steelmaking.

Example 13

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;

Lower than the temperature in the titanium-containing mixed slag set 1450 ~ 1600 ° C; through the DC arc furnace self-heating function, the temperature of the titanium-containing mixed slag is raised to 1450 ° C;

Titanium-containing blast furnace slag containing components and mass percentages thereof: 15.64 wt% TiO ₂ , 20.64 wt% CaO, 9.98 wt% MgO, 16.31 wt% Al ₂ O ₃ , 5.01 wt% FeO, and 21.61 wt% SiO ₂ , The balance is other impurities;

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;

Step 2, smelting reduction and oxidation:

(1) Injecting gas: into the titanium-containing mixed slag, pre-heating the oxygen-argon gas mixture, and blowing a mixture of oxygen and argon gas for 6 minutes; wherein, the volume of oxygen in the oxygen-argon mixture The percentage is 50%, the preheating temperature of the oxygen-argon mixture is 800 °C, the relationship between the oxygen-argon mixture time and the flow rate is 80 L/(min·kg); the injection mode of the oxygen-argon mixture is adopted. The refractory spray gun is inserted into the mixed slag to be blown;

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is in the range of the set temperature of 1450 to 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a): reduction oxidation process measured mixed slag temperature of 1470 ~ 1475 ° C, within the set range;

Corresponding (b): During the redox process, the reduction of reducing property in the titanium-containing mixed slag is insufficient, and 2.0 kg of bituminous coal is added to the titanium-containing mixed slag to oxidize the remaining low-valent titanium into high-priced titanium in the titanium-containing mixed slag. Reducing iron oxide to metal iron;

Step 3, separation and recovery using method D:

(1) separating the oxidized mixed slag and separating the slag-gold to obtain vanadium-containing molten iron and the reduced-oxidized vanadium-containing titanium slag;

(2) The vanadium-containing titanium slag after reduction and oxidation is subjected to slag treatment outside the furnace, and method D-1 is adopted:

After measuring the mass fraction of the vanadium-containing titanium slag TiO ₂ after reduction oxidation = 9.8 ≤ 10%, the reduced-oxidized vanadium-containing titanium slag is directly quenched and used as a cement raw material or a building material;

(3) Send vanadium-bearing molten iron to converter steelmaking.

Example 14

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;

Lower than the temperature in the titanium-containing mixed slag set 1450 ~ 1600 ° C; through the submerged furnace self-heating function, the temperature of the titanium-containing mixed slag is raised to 1462 ° C;

Titanium-containing blast furnace slag containing components and mass percentages thereof: 10.65 wt% TiO ₂ , 22.68 wt% CaO, 9.08 wt% MgO, 17.62 wt% Al ₂ O ₃ , 5.05 wt% FeO, and 21.03 wt% SiO ₂ , The balance is other impurities;

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;

Step 2, smelting reduction and oxidation:

(1) 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

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is in the range of the set temperature of 1450 to 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a): the reduction oxidation process measures the mixed slag temperature of 1480 ~ 1488 ° C, within the set range;

Corresponding (b): During the redox process, the reduction of reducing property in the titanium-containing mixed slag is insufficient, and 1.8 kg of anthracite is added to the titanium-containing mixed slag to oxidize the remaining low-valent titanium into high-priced titanium. Reducing iron oxide to metal iron;

Step 3, separation and recovery using method D:

(1) separating the oxidized mixed slag and separating the slag-gold to obtain vanadium-containing molten iron and the reduced-oxidized vanadium-containing titanium slag;

(2) The oxidized vanadium-containing titanium slag will be reduced and treated outside the furnace:

(3) sending vanadium-bearing molten iron to converter steelmaking;

Among them, 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:

1 to the vanadium-containing titanium slag after reduction and oxidation, 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. ;

2 Control the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a): the reduction oxidation process measured the mixed slag temperature to be 1422 ~ 1429 ° C, within the set range;

Corresponding to (b): the remaining low-priced titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

3 separation and recovery using method A:

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 μm, and the remaining vanadium is separated by magnetic separation. Metal iron; metal iron recovery rate of 95%, total iron in the tailings slag of this step is 0.665wt%;

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%.

Example 15

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;

Higher than the temperature in the titanium-containing mixed slag set 1450 ~ 1600 ° C; adding 1.5 kg of ordinary iron concentrate metallized pellets to the mixed slag, the temperature of the titanium-containing mixed slag is reduced to 1560 ° C;

Titanium-containing blast furnace slag containing components and mass percentages thereof: 10.94 wt% TiO ₂ , 21.49 wt% CaO, 9.95 wt% MgO, 14.39 wt% Al ₂ O ₃ , 6.66 wt% FeO, and 22.61 wt% SiO ₂ , The balance is other impurities;

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;

Step 2, smelting reduction and oxidation:

(1) 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;

(2) Controlling the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is in the range of the set temperature of 1450 to 1600 ° C;

(b) In the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron; as the reaction proceeds, the slag is less reductive, and 1 kg of pulverized coal is added to reduce the iron oxide. Metal iron

Corresponding to (a): 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;

Corresponding (b): During the redox process, the reduction of reducing property in the titanium-containing mixed slag is insufficient, and 2 kg of coal powder is added to the titanium-containing mixed slag to oxidize the remaining low-valent titanium into high-priced titanium in the titanium-containing mixed slag. Reducing iron oxide to metal iron;

Step 3, separation and recovery using method D:

(1) separating the oxidized mixed slag and separating the slag-gold to obtain vanadium-containing molten iron and the reduced-oxidized vanadium-containing titanium slag;

(2) The oxidized vanadium-containing titanium slag will be reduced and treated outside the furnace:

(3) sending vanadium-bearing molten iron to converter steelmaking;

Among them, the method of using slag treatment outside the furnace D-2:

1 Pour the reduced oxidation-containing vanadium-containing titanium slag into the thermal slag of the petroleum pitch coke-spinel composite thermal insulation mold release refractory, and then perform the following operations:

To the vanadium-containing titanium slag after reduction and oxidation, 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;

2 Control the reduction and oxidation process:

During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

(a) the temperature of the titanium-containing mixed slag is in the range of a set temperature of 1400 to 1600 ° C;

(b) in the titanium-containing mixed slag, the remaining low-valent titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

Corresponding to (a): the reduction oxidation process measures the mixed slag temperature of 1570 ~ 1576 ° C, within the set range;

Corresponding to (b): the remaining low-priced titanium is oxidized to high-priced titanium, and the remaining iron oxide is reduced to metallic iron;

3 separation and recovery method C:

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;

When 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.

Claims (12)

1. A method for smelting reduction recovery and quenching and tempering treatment of titanium-containing mixed slag, comprising the steps of:

   Step 1, slag mixing:

   According to the mass ratio, 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;

   among them:

   The set temperature range is 1400 ~ 1600 ° C;

   When the reaction device adopts the heat preservation device, the temperature range of the titanium-containing mixed slag is set to 1400 to 1600 ° C;

   When the reaction device uses a pourable smelting reaction device or a stationary smelting reaction device, 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:

   When the temperature of the titanium-containing mixed slag is lower than the set temperature range, 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;

   When 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;

   Step 2, smelting reduction and oxidation:

   (1) 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);

   (2) Controlling the reduction and oxidation process:

   During the blowing process, two parameters (a) and (b) are guaranteed by regulation:

   (a) the temperature of the titanium-containing mixed slag is within a set temperature range;

   (b) in the titanium-containing mixed slag, 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:

   Corresponding to (a):

   The method for controlling the temperature of the titanium-containing mixed slag in the set temperature range in step 1;

   Corresponding to (b):

   When the reducing property in the titanium-containing mixed slag is insufficient, 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;

   Step 3, separate and recycle:

   Use one of the following methods:

   1. When the reaction device is insulated, use Method A, Method B or Method C:

   When the reaction device uses a non-dumpable insulation device or a pourable insulation device, Method A is used:

   (1) a slow cooling slag obtained by reducing the oxidized mixed slag and cooling to room temperature;

   (2) 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 μm, ground and magnetically separated. Remaining vanadium containing metal iron;

   (3) Separating the slow-cooling slag of iron slag and vanadium-containing metal iron layer by gravity separation method to obtain titanium concentrate, vanadium-rich concentrate and tailings;

   (4) 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;

   Use Method B or Method C only if the reaction unit uses a pourable insulation unit:

   Method B:

   (1) 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;

   (2) the lower reduced oxidized mixed slag is still in the pourable heat preservation device, and is treated as the method A to reduce the oxidized mixed slag;

   Method C:

   (1) separating the oxidized mixed slag and separating the slag-gold to obtain vanadium-containing molten iron and the reduced-oxidized vanadium-containing titanium slag;

   (2) 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, and then air-cooled or water-quenched, used as a cement raw material or building material. ;

   (3) sending vanadium-bearing molten iron to converter steelmaking;

   2. When the reaction device uses a pourable smelting reaction device or a stationary smelting reaction device, method D is employed:

   (1) separating the oxidized mixed slag and separating the slag-gold to obtain vanadium-containing molten iron and the reduced-oxidized vanadium-containing titanium slag;

   (2) reducing the oxidized vanadium-containing titanium slag and performing slag treatment outside the furnace;

   (3) sending vanadium-bearing molten iron to converter steelmaking;

   Among them, 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.
2. The method for smelting reduction recovery and quenching and tempering treatment of a titanium-containing mixed slag according to claim 1, wherein in the step 1, the titanium-containing blast furnace slag is obtained from a blast furnace slag outlet, and the titanium-containing blast furnace slag is obtained. The temperature of the titanium-containing blast furnace slag containing TiO ₂ is 4-30%; the vanadium-containing titanium molten steel slag is obtained from the steel slag slag outlet, and the temperature of the vanadium-containing titanium molten steel slag is ≥1500 ° C, The vanadium-containing titanium molten steel slag contains TiO _{2 in} a mass fraction of 0.3 to 6% and a V ₂ O ₅ mass fraction of 0.3 to 5%.
3. The method for smelting reduction recovery and quenching and tempering treatment of titanium-containing mixed slag according to claim 2, wherein 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 .
4. The method for smelting reduction recovery and quenching and tempering treatment of a titanium-containing mixed slag according to claim 1, wherein the heat insulating device is a pourable heat insulating device or a non-dumpable heat insulating device; the non-pourable The heat preservation device is a heat preservation pit; the pourable heat preservation device is a pourable heat preservation slag tank; the pourable smelting reaction device is a pourable converter, a pourable smelting reaction slag irrigation or an induction furnace; The 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.
5. The method for smelting reduction recovery and quenching and tempering treatment of a titanium-containing mixed slag according to claim 1, wherein the inner layer of the heat preservation device, the pourable smelting reaction device or the stationary smelting reaction device is carbonaceous The mold-containing refractory material is a carbon-containing composite refractory material, specifically carbon is carbon, graphite, petroleum pitch coke, metallurgical coke, asphalt, anthracite, bituminous coal or lignite Or several, the refractory material is siliceous, semi-silica, clay, high alumina, magnesia, dolomite, olivine, spinel, cold titanium-containing blast furnace slag or cold vanadium-containing titanium steel slag One or several of them.
6. The method for smelting reduction recovery and quenching and tempering treatment of a titanium-containing mixed slag according to claim 1, wherein the method for controlling the temperature of the titanium-containing mixed slag in a set temperature range is to mix slag When adding fuel and/or vanadium-containing titanium molten steel slag, the preheating temperature of the fuel is 0-1200 ° C, and the temperature of the vanadium-containing titanium molten steel slag is ≥1500 ° C; the fuel is inserted into the slag by using a refractory spray gun or placed on the upper part of the slag or The fuel is blown into the side; when 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 any 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 magnetite, vanadium-titanium magnetite concentrate, vanadium-titanium magnetite direct reduced iron , one or more of vanadium-titanium magnetite concentrate metallized pellets, vanadium-titanium magnetite concentrate carbon-containing pre-reduction pellets, vanadium-titanium magnetite concentrate ore, vanadium-titanium magnet concentrate pellets; iron-containing materials It is ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate ore, ordinary iron concentrate pellet, ordinary iron concentrate metallized pellet, ordinary iron concentrate carbon pre-reduction pellet, common One or more of steel slag, blast furnace gas ash, blast furnace dust, converter dust, iron oxide scale, zinc leaching slag in wet zinc smelting process, red mud produced in alumina production process, coal dust ash, sulfuric acid slag; The fluorine material is fluorite and/or CaF ₂ .
7. The method according to claim 6, wherein the fuel is pulverized coal.
8. The method for smelting reduction recovery and quenching and tempering treatment of a titanium-containing mixed slag according to claim 6, wherein the vanadium-containing titanium material, the iron-containing material and the fluorine-containing material are uniform pellets or powdery materials; The granular material has a particle size of ≤150μm, and the powdery material is sprayed into the titanium-containing mixed slag, and the loading gas is air, argon, nitrogen-air mixture gas, nitrogen-oxygen gas mixture or air-argon gas mixture; The blowing method is to insert the slag into the slag by using a refractory spray gun or to blow the powdery material on the upper part or the side of the slag.
9. The method according to claim 1, wherein the oxidizing gas is air, oxygen, oxygen-enriched air, nitrogen-oxygen gas mixture, nitrogen-air One of a mixed gas, an oxygen-argon mixed gas or an air-argon mixed gas; the oxidizing gas is blown by inserting a slag into a slag or by placing an oxidizing gas on the upper side or the side of the slag.
10. The method for smelting reduction recovery and quenching and tempering treatment of titanium-containing mixed slag according to claim 1, wherein in the step 2 and the step 3, the reducing agent is pulverized coal, coke breeze, bituminous coal or anthracite. One kind.
11. The method for smelting reduction recovery and quenching and tempering treatment of a titanium-containing mixed slag according to claim 1, wherein in the step 3, in the method A (1), the cooling mode is natural cooling or spin cooling; The specific operation of the rotary cooling is as follows: the heat preservation device containing the mixed slag after redox is placed on the rotating platform and rotated according to a certain speed, and the rotation speed depends on the quality of the slag and the height or depth of the heat preservation device, and the rotation time depends on The quality of the slag depends on the solidification of the slag; in the method A (3), the gravity separation method is a shaker sorting, a chute sorting or a combination of the two; in the method A (4), the hydrometallurgy is a dilute acid The 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, and the organic acid is selected from oxalic acid, acetic acid and citric acid. One or more.
12. The method for smelting reduction recovery and quenching and tempering treatment of a titanium-containing mixed slag according to claim 1, wherein in the step 3, in the method A, the metal iron recovery rate is 90 to 97%, and the main phase is The mass fraction of TiO ₂ in perovskite titanium concentrate is 35-52%, the recovery of titanium is 60-80%; in method B, the recovery rate of metallic iron is 90-95%, and the main phase is calcium-titanium. The mass fraction of TiO ₂ in the ore-concentrated titanium concentrate is 35-52%, and the recovery of titanium is 58-76%.

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