阅读说明：本技术 一种高炉与电解炉联合生产制备钛合金的方法 (Method for preparing titanium alloy by joint production of blast furnace and electrolytic furnace ) 是由 焦树强 焦汉东 王明涌 朱骏 于 2019-10-15 设计创作，主要内容包括：本发明涉及一种高炉与电解炉联合生产制备钛合金的方法,属于冶金工程领域。工艺步骤如下：将钒钛磁铁矿原矿经选矿获得的钒钛磁铁精矿配合焦炭、石灰石等置于高炉中冶炼获得铁水和熔融含钛高炉渣；随后铁水经高炉出铁口与电解炉连接的通道或鱼雷罐车置于电解炉内；熔融含钛高炉渣经过出渣口与电解炉连接的通道或鱼雷罐车置于电解炉内；将石墨置于熔融含钛高炉渣内作为阳极；以铁水作为阴极；采用直流电解工艺进行电解,通过控制电流密度(或槽电压)、电解质内(或阴极铁水内)钛元素(硅元素含量),最终获得液态钛-铁、钛-硅-铁或硅-铁合金产物。相对于传统制备钛合金的方法,该方法具有工艺流程简单、厂地利用率高、能耗低且易实现大规模生产的优点。(The invention relates to a method for preparing titanium alloy by joint production of a blast furnace and an electrolytic furnace, belonging to the field of metallurgical engineering. The process comprises the following steps: putting vanadium-titanium magnetite concentrate obtained by mineral separation of vanadium-titanium magnetite raw ore into a blast furnace together with coke, limestone and the like for smelting to obtain molten iron and molten titanium-containing blast furnace slag; then the molten iron is placed in an electrolytic furnace through a channel or a torpedo tank car which is connected with the electrolytic furnace through a blast furnace taphole; the molten titanium-containing blast furnace slag is placed in the electrolytic furnace through a channel or a torpedo car connected with the electrolytic furnace through a slag hole; placing graphite in molten titanium-containing blast furnace slag as an anode; taking molten iron as a cathode; electrolyzing by adopting a direct current electrolysis process, and finally obtaining a liquid titanium-iron, titanium-silicon-iron or silicon-iron alloy product by controlling the current density (or bath voltage) and the titanium element (silicon element content) in the electrolyte (or cathode molten iron). Compared with the traditional method for preparing the titanium alloy, the method has the advantages of simple process flow, high plant utilization rate, low energy consumption and easy realization of large-scale production.)

1. A method for preparing titanium alloy by jointly producing a blast furnace and an electrolytic furnace is characterized by comprising the following steps:

the method comprises the following steps: putting vanadium-titanium magnetite concentrate obtained by mineral separation of vanadium-titanium magnetite raw ore, coke and limestone into a blast furnace to be smelted to obtain molten iron and molten titanium-containing blast furnace slag;

step two: then the molten iron is placed in an electrolytic furnace through a channel or a torpedo tank car which is connected with the electrolytic furnace through a blast furnace taphole;

step three: the molten titanium-containing blast furnace slag is placed in the electrolytic furnace through a channel or a torpedo car connected with the electrolytic furnace through a slag hole;

step four: placing graphite in molten titanium-containing blast furnace slag as an anode, and taking molten iron as a cathode;

step five: electrolyzing by adopting a direct current electrolysis process, and finally obtaining a liquid titanium-iron, titanium-silicon-iron or silicon-iron alloy product by controlling the current density or bath voltage and the content of titanium element/silicon element in the electrolyte or cathode molten iron.

2. The method for producing titanium alloy by using blast furnace and electrolytic furnace in combination according to claim 1, wherein the raw vanadium titano-magnetite ore in the first step is iron ore resource containing titanium element.

3. The method as claimed in claim 1, wherein the electrolysis furnace in the second step is a direct current arc furnace or other metallurgical furnace heated by a heating element and capable of maintaining 1200-2000 ℃ and is protected by inert gas in the furnace.

4. The method for producing titanium alloy according to claim 1, wherein the channel connecting the taphole of the blast furnace and the electrolytic furnace in the second step is made of inorganic refractory material, the torpedo car is a torpedo type hot metal car commonly used in steel works, and the amount of the hot metal introduced into the electrolytic furnace is determined according to the size of the electrolytic furnace, specifically 2 to 30 percent of the effective volume of the electrolytic furnace.

5. The method for manufacturing titanium alloy according to claim 1, wherein the passage connecting the slag outlet of the blast furnace and the electrolytic furnace in the third step is made of inorganic refractory material, and the amount of the molten slag introduced into the electrolytic furnace is determined according to the amount of the molten iron, and is specifically 1 to 20 times of the volume of the molten iron.

6. The method for producing titanium alloy by using blast furnace and electrolytic furnace in combination as claimed in claim 1, wherein the graphite anode is immersed in the molten titanium-containing blast furnace slag to a depth corresponding to a linear distance from the cathode of the molten iron, i.e. a distance between the cathode and the anode is 5-100 cm.

7. The method for producing titanium alloy in combination with blast furnace and electrolytic furnace as set forth in claim 1, wherein the current density of DC electrolysis in the fifth step is 0.01-10A/cm²The cell voltage is 1-50V; in the electrolysis process, firstly, extracting silicon element in slag to obtain liquid iron-silicon alloy and obtaining an iron-silicon alloy product through an alloy outlet; then injecting new molten iron, electrolyzing and extracting titanium element in the slag to obtain liquid titanium-iron alloy and obtaining an iron-titanium alloy product through an alloy outlet; or directly electrolyzing to obtain a liquid titanium-silicon-iron ternary alloy product.

Technical Field

The invention relates to a method for preparing titanium alloy by combined production of a blast furnace and an electrolytic furnace, belongs to the field of metallurgical engineering, and particularly can realize low-cost, short-flow and large-scale production of titanium-iron, titanium-silicon-iron and silicon-iron alloy.

Background

Titanium alloys represented by titanium-iron and titanium-silicon-iron alloys have a wide industrial application value. For example, because titanium and oxygen have good binding ability, titanium alloy is often used as a deoxidizer in steel-making. Meanwhile, titanium element is added into steel to improve the performance of the steel, so that the titanium alloy is widely applied to alloy additives in steel making. Secondly, titanium alloy is often used as an effective solid hydrogen storage material because of the different binding capacity of titanium with hydrogen at different temperatures.

At present, titanium alloys represented by titanium-iron and titanium-silicon-iron are mainly prepared by a counter-doping method, and the method is mainly formed by mixing and melting pure titanium metal and iron or silicon-iron. However, titanium has special physical and chemical properties, and needs to be prepared by a magnesiothermic reduction method (Kroll method) with long process flow and high cost. This results in high cost of titanium alloys prepared by the counter-doping method, which in turn limits the widespread use of these titanium alloys. Therefore, it is very important to develop a new titanium alloy preparation process which is new, low in cost, short in flow, low in energy consumption and applicable to large-scale application.

On the other hand, the Panzhihua region in Sichuan China stores a large amount of vanadium titano-magnetite which is a composite mineral resource of valuable elements such as titanium, iron and vanadium. At present, the smelting of vanadium titano-magnetite mainly takes 'ironmaking and vanadium extraction'. However, after this procedure, about 50% of the titanium element in vanadium titano-magnetite enters the blast furnace slag. And the titanium content in the titanium-containing blast furnace slag is up to more than 20 percent based on titanium dioxide. In order to effectively utilize the titanium element in the slag, metallurgical researchers have explored various wet, pyrogenic and electrochemical methods for treating the titanium-containing blast furnace slag. However, the titanium element in the titanium-containing blast furnace slag is dispersed in the powder in various mineral phases, so that the wet method and the fire method are limited in effect. In addition, the titanium element is active in chemical property and is easy to combine with gas elements such as oxygen, nitrogen, hydrogen, carbon and the like at high temperature; meanwhile, the titanium has multiple valence states and a complex reduction process, so that the extraction of the titanium element by adopting an electrochemical method is also difficult. At present, the titanium-containing blast furnace slag in the Panzhihua area is mainly stored on two sides of the Jinshajiang river in a stacking mode. The accumulation of a large amount of titanium-containing blast furnace slag not only causes environmental pollution and waste of space, but also causes waste of valuable titanium element.

Disclosure of Invention

The invention provides a method for preparing titanium alloy by joint production of a blast furnace and an electrolytic furnace. Compared with the traditional method for preparing the titanium alloy, the method has the advantages of simple process flow, high plant utilization rate, low energy consumption and easy realization of large-scale production.

In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing titanium alloy by jointly producing a blast furnace and an electrolytic furnace is characterized by comprising the following steps:

the method comprises the following steps: uniformly mixing ilmenite and reducing agent carbon in proportion and then placing the mixture in molten oxide electrolyte;

step two: carrying out carbon thermal reduction on ilmenite in the electrolyte to obtain molten iron;

step three: graphite or an inert electrode is taken as an anode, a graphite rod or an inert metal rod is taken as a cathode conducting rod and inserted into molten iron to be taken as a cathode, and electrolysis is carried out by adopting a constant potential or constant current method;

step four: after electrolysis for a period of time, carrying out electrochemical deposition on cathode molten iron to obtain a ferrotitanium product;

step five: after the contents of iron and titanium in the electrolyte are reduced to a certain value, adding the mixture of ilmenite and reducing agent carbon into the electrolyte again for the next circulation;

step six: when the titanium content in the molten iron is increased to a certain amount or reaches the required ferrotitanium proportion, discharging a liquid ferrotitanium product through an iron outlet at the bottom of the crucible, and continuing the next circulation.

Further, the raw vanadium titano-magnetite ore in the step one is iron ore resources containing titanium in Panzhihua region, Hebei Chengde region or other regions.

Furthermore, the electrolytic furnace in the second step can be a direct current arc furnace, or other metallurgical furnace which is heated by a heating element and can maintain 1200-.

Further, in the second step, a channel for connecting the tap hole of the blast furnace with the electrolytic furnace is made of inorganic refractory materials, the torpedo car is a common torpedo type molten iron car in a steel plant, and the amount of molten iron introduced into the electrolytic furnace is determined according to the size of the electrolytic furnace and is specifically 2-30% of the effective volume of the electrolytic furnace.

Furthermore, a channel connecting the blast furnace slag outlet and the electrolytic furnace in the third step is made of inorganic refractory materials, and the amount of the molten slag introduced into the electrolytic furnace is determined according to the amount of the molten iron, and is specifically 1-20 times of the volume of the molten iron.

Further, in the fourth step, the graphite anode is immersed into the molten titanium-containing blast furnace slag to a depth which is 5-100cm away from the molten iron cathode.

Further, the current density of the direct current electrolysis in the step five is 0.01-10A/cm²The cell voltage is 1-50V; in the electrolysis process, firstly, extracting silicon element in slag to obtain liquid iron-silicon alloy and obtaining an iron-silicon alloy product through an alloy outlet; then injecting new molten iron, electrolyzing and extracting titanium element in the slag to obtain liquid titanium-iron alloy and obtaining an iron-titanium alloy product through an alloy outlet; and the liquid titanium-silicon-iron ternary alloy product can also be obtained by direct electrolysis.

The invention innovatively provides a novel method for preparing titanium alloy by combined production of a blast furnace and an electrolytic furnace. An electrolytic furnace device is constructed near a blast furnace device of an iron-making plant, and the titanium alloy is prepared by in-situ electrolysis by using high-temperature molten iron obtained by reduction of the blast furnace and titanium-containing blast furnace slag as a cathode and electrolyte. Due to the depolarization of the liquid iron cathode, the reduction process of the high-valence titanium element in the slag is simplified, and a liquid titanium alloy product with low oxygen content can be obtained at the cathode. Finally, liquid silicon-iron, titanium-iron or titanium-silicon-iron alloy can be obtained in sequence by controlling the electrolysis time. Compared with the traditional method for preparing the titanium alloy by the counter-doping method, the preparation process of the method is greatly reduced; meanwhile, high-temperature melt raw materials required by electrolysis are provided by relying on blast furnace equipment of an iron-making plant, so that the energy consumption for preparing the alloy can be obviously reduced; the space utilization rate of a factory is effectively improved due to the combined production characteristic of the blast furnace and the electrolytic furnace; the raw material of the electrolytic furnace is directly derived from the liquid phase product of the blast furnace, which is beneficial to the large-scale application of the process and the large-scale preparation of the alloy product.

Compared with the prior art, the invention has the following beneficial effects:

1) electrolyzing high-temperature molten iron obtained by a blast furnace and titanium-containing blast furnace slag serving as raw materials to obtain a titanium alloy product in one step, so that the process flow of alloy preparation is greatly shortened;

2) the high-temperature molten iron and the titanium-containing blast furnace slag do not need secondary heating in the electrolytic furnace, so that the energy consumption in the alloy preparation process is greatly reduced;

3) and the large-scale preparation of the alloy is easy to realize by relying on blast furnace equipment with higher productivity.

Drawings

FIG. 1 is a schematic view of the combined production of a liquid titanium alloy by a blast furnace and an electrolytic furnace of example 1.

Detailed Description

The present invention will be described in more detail below with reference to specific examples, but the scope of the present invention is not limited to these examples.