Method and device for producing sponge titanium with high oxygen content

Abstract

The invention discloses a method and a device for producing high-oxygen-content titanium sponge, and the method and the device are characterized in that a vanadium oxychloride solution is added into a refined titanium tetrachloride storage tank filled with the refined titanium tetrachloride solution, the vanadium oxychloride solution is used as a reducing agent and is added into a reduction reactor for reaction, and a titanium sponge target product is obtained. According to the method disclosed by the invention, titanium oxychloride can be subjected to decomposition reaction under a high-temperature condition to generate titanium tetrachloride and titanium oxide, and titanium oxychloride has unique properties in the aspects of structure, chemical reactivity, solubility and the like and has relatively good solubility in titanium tetrachloride; according to the method, the titanium oxychloride solution is selected as an oxygen producer to be mixed into the titanium tetrachloride solution, titanium oxide generated by decomposition is uniformly distributed in the sponge titanium, the oxygen element component in the sponge titanium raw material is uniform from the source, and the high-oxygen-content sponge titanium product with the uniform oxygen element component is finally produced; and the quality of raw materials for titanium ingot and titanium alloy smelting is stable and controllable.

Description

Technical Field

[0001] The invention relates to the technical field of titanium alloy preparation, in particular to a method and a device for producing sponge titanium with high oxygen content. Background Art

[0002] Sponge titanium is the raw material for smelting titanium ingots and titanium alloys. In titanium alloys, oxygen is an important interstitial element, which can significantly affect the mechanical and physical properties of the alloy. Titanium ingots or titanium alloys contain a small or trace amount of interstitial elements or impurity elements such as O, C, and N. A large number of studies have shown that the content of interstitial elements and impurity elements has a significant effect on the processability and final performance of the material. The increase in the content of interstitial elements such as O, C, and N will increase the strength of the titanium alloy, but will reduce the plasticity and processability, among which N and C are particularly damaging to the plasticity of the alloy. When the interstitial element O in the alloy is within a certain content range, it can effectively improve the strength of the alloy, and the reduction in plasticity is relatively small. In order to further expand the performance of titanium ingots and titanium alloys and improve the controllability of production, major titanium processing companies have generally added a small amount of oxygen enhancers as additives to the raw material sponge titanium for producing titanium ingots and titanium alloys during production. In order to achieve a specific strength of the material, titanium dioxide (TiO2) is often used as an oxygen enhancer to adjust the oxygen content in the alloy during the smelting process of titanium and titanium alloys. Titanium dioxide and sponge titanium are mixed in a mixer, and electrodes are pressed after the mixture is evenly mixed. Then, the titanium material is oxygenated during the electrode smelting process. However, due to the poor adhesion of powdered titanium dioxide on the surface of sponge titanium, it is easy to locally segregate, resulting in uneven distribution of oxygen content and oxygen segregation in the material, thereby causing local performance degradation of the alloy. This oxide inclusion may also form a crack source in the material, affecting the fatigue performance and toughness of the titanium alloy.

[0003] Chinese patent application CN102978441 discloses a method for adding oxygen and iron to a titanium alloy, in which the oxygen element and the iron element contained in the titanium alloy to be prepared are added in the form of a mixed powder, and the mixed powder is formed by uniformly mixing component A and component B, component A is FeTiO3 powder, and component B is Fe2O3 powder or TiO2 powder. During the smelting process, Fe2O3 powder or TiO2 is used as an oxygenator to adjust the oxygen content in the alloy, and it is mixed with sponge titanium through a mixer, and after the mixing is uniform, an electrode is pressed, and then the titanium material is oxygenated during the electrode smelting process. However, since the powdered oxygenator has poor adhesion to the surface of sponge titanium, it is easy to locally aggregate, resulting in uneven distribution of oxygen content and oxygen segregation in the material.

[0004] Therefore, there is an urgent need for a method for producing high-oxygen sponge titanium, which can attach an oxygen enhancer to the sponge titanium, so as to make the oxygen composition in the sponge titanium raw material uniform from the source, ensure the stable and controllable quality of the titanium material, and improve the quality standard of the titanium material. Summary of the invention

[0005] The purpose of the present invention is to provide a method and device for producing titanium sponge with high oxygen content, which uses titanium dichloride solution as an oxygen enhancer and is mixed with refined titanium tetrachloride solution as a raw material for titanium sponge production, so as to achieve controllable oxygen impurities in titanium sponge and realize the production of titanium sponge with high oxygen content. The method solves the problem that the powder oxygen enhancer commonly used in the prior art has poor adhesion to the surface of titanium sponge and is easy to be locally segregated, resulting in uneven distribution of oxygen content and oxygen segregation in the material.

[0006] In order to achieve the above object, the present invention provides a method for producing high oxygen content titanium sponge, comprising the following steps: Step (1): adding vanadium oxychloride solution to a refined titanium tetrachloride storage tank containing refined titanium tetrachloride solution to obtain a mixed solution; Step (2): stirring the mixed solution in the refined titanium tetrachloride storage tank for 60 to 90 minutes to obtain a mixed solution with a high oxygen content; Step (3): Add the high oxygen content mixed solution into a reduction reactor for reaction to obtain a titanium sponge product.

[0007] The method of the present invention utilizes the decomposition reaction of titanium dichloride under high temperature conditions, and the reaction equation is: 2TiOCl2=TiO2+TiCl4. The decomposition reaction usually occurs above 450°C, and titanium tetrachloride and titanium oxide are decomposed. Because titanium dichloride has unique properties in terms of structure, chemical reactivity, solubility, etc., and has good solubility in titanium tetrachloride, titanium dichloride solution is mixed into titanium tetrachloride solution as an oxygenator, which can meet the uniform distribution of oxygen elements in the raw materials, and the titanium oxide generated by decomposition will be evenly distributed in the titanium sponge, so that the oxygen element composition in the titanium sponge raw material is uniform from the source, and finally a high-oxygen content titanium sponge product with uniform oxygen element composition is produced, which ensures that the quality of raw materials for smelting titanium ingots and titanium alloys is stable and controllable.

[0008] According to the method for producing high oxygen content titanium sponge of the present invention, preferably, in the step (1), the mass of vanadium oxychloride added is M: M=M3 / M1×(M2*(W2-W1) / W3) Where: W1 is the percentage of oxygen element in the production of titanium sponge using only refined titanium tetrachloride solution W2 is the oxygen content of titanium sponge in the titanium alloy composition table for smelting W3 is the average oxygen content of titanium dichloride solution M1 is the mass of titanium tetrachloride added to the single furnace reduction reactor when only refined titanium tetrachloride solution is used to produce titanium sponge. M2 is the mass of titanium sponge produced by a single furnace reduction reactor M3 is the mass of titanium tetrachloride solution in the refined titanium tetrachloride storage tank.

[0009] In the present invention, by controlling the ratio of each component through the above method, a titanium sponge product that meets the requirements of the titanium alloy composition table for smelting can be obtained, thereby further improving the quality of titanium sponge.

[0010] According to the method for producing high-oxygen sponge titanium of the present invention, preferably, in the step (1), W1 is the average oxygen content of the sponge titanium produced by 2-8 reduction reactors when only refined titanium tetrachloride is used to produce sponge titanium.

[0011] According to the method for producing high-oxygen-content titanium sponge of the present invention, preferably, in the step (1), M1 is the average mass of the refined titanium tetrachloride solution added to a single furnace in producing 2-8 furnaces of titanium sponge.

[0012] According to the method for producing high-oxygen content titanium sponge of the present invention, preferably, in step (3), the temperature in the reduction reaction furnace is usually above 450° C. Above 450° C., titanium oxychloride undergoes a decomposition reaction to generate titanium tetrachloride and titanium oxide.

[0013] According to the method for producing high oxygen content titanium sponge of the present invention, preferably, in step (3), the temperature in the reduction reaction furnace is usually above 780°C. The decomposition reaction of titanium dichloride can be carried out at a temperature above 780°C to more quickly decompose titanium tetrachloride and titanium oxide. More preferably, the temperature in the reduction reaction furnace is usually above 780-850°C.

[0014] According to the method for producing high oxygen content sponge titanium of the present invention, preferably, in step (1), the impurity components of the refined titanium tetrachloride solution must meet the TiCl4-01 or TiCl4-02 standard.

[0015] In the present invention, the TiCl4-01 or TiCl4-02 standard is the non-ferrous metal industry standard "Titanium Tetrachloride".

[0016] According to the method for producing high-oxygen content titanium sponge described in the present invention, preferably, in step (1), SiCl4≤0.0050%, FeCl3≤0.0010%, VOCl3≤0.0010%, AlCl3≤0.0050% in the refined titanium tetrachloride solution. By using the above titanium tetrachloride solution, the quality of the generated titanium sponge can be better controlled to meet the requirements.

[0017] According to the method for producing high-oxygen content titanium sponge of the present invention, preferably, in step (1), FeCl3≤0.0010%, VOCl3≤0.001%, and SiCl4≤0.01% in the titanium dichloride solution. By using the titanium dichloride solution, the quality of the generated titanium sponge can be better controlled to meet the requirements.

[0018] In addition, the present invention also provides the above-mentioned device for producing high-oxygen content sponge titanium, comprising a refined titanium tetrachloride storage tank, a vanadium dichloride storage tank and a reduction reaction furnace; wherein, A stirring paddle is provided in the refined titanium tetrachloride storage tank; the vanadium dichloride storage tank is arranged above the refined titanium tetrachloride storage tank, and is connected with the refined titanium tetrachloride storage tank through a first conveying pipeline, a first metering feeder and a first switch valve are provided on the first conveying pipeline, and the first switch valve is provided downstream of the first metering feeder; the refined titanium tetrachloride storage tank is connected with the reduction reaction furnace through a second conveying pipeline, a second metering feeder and a second switch valve are provided on the second conveying pipeline, and the second switch valve is provided downstream of the second metering feeder.

[0019] In the present invention, the first metering feeder and the second metering feeder may be any device in the prior art that can achieve liquid delivery metering, such as a metering pump.

[0020] In the present invention, the first switch valve and the second switch valve may be any valves that can realize the switch function manually or automatically, such as a ball valve, a gate valve, a stop valve, etc.

[0021] The beneficial effects of the present invention are: The present invention provides a method for producing a high-oxygen-content sponge titanium. The method uses titanium dichloride as an oxygen enhancer and decomposes titanium dichloride to generate titanium tetrachloride and titanium oxide at a high temperature. Titanium dichloride has unique properties in terms of structure, chemical reactivity, solubility, etc. It has good solubility in titanium tetrachloride and can meet the requirement of uniform distribution of oxygen in the raw material. The titanium oxide generated by decomposition will be evenly distributed in the titanium sponge, so that the oxygen component in the titanium sponge raw material is uniform from the source, and finally a high-oxygen-content sponge titanium product with uniform oxygen component is produced, thereby ensuring that the quality of raw materials for smelting titanium ingots and titanium alloys is stable and controllable.

[0022] As a more optimal technical solution of the present invention, a titanium oxychloride solution and a refined titanium tetrachloride solution are mixed according to the specific ratio of the present invention to obtain a high-quality and high-oxygen-content sponge titanium product that meets the requirements of smelting special titanium alloys. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For ordinary technicians in this field, other embodiments can be obtained based on these drawings without paying creative work.

[0024] Figure 1 The present invention is a schematic structural diagram of a device for producing high-oxygen content titanium sponge.

[0025] Among them, 1-refined titanium tetrachloride storage tank, 2-vanadium dichloride storage tank, 3-reduction reaction furnace, 4-first metering feeder, 5-second metering feeder, 6-second switch valve, 7-first switch valve, 8-second conveying pipeline, 9-stirring paddle. DETAILED DESCRIPTION

[0026] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the embodiments of the present invention are further described in detail below in combination with specific embodiments and with reference to the accompanying drawings.

[0027] The impurity components of the refined titanium tetrachloride solution used in the present invention must meet the non-ferrous metal industry standard "Titanium Tetrachloride" TiCl4-01 or TiCl4-02 standard, wherein SiCl4≤0.0050%, FeCl3≤0.0010%, VOCl3≤0.0010%, AlCl3≤0.0050%; FeCl3≤0.0010%, VOCl3≤0.0010%, SiCl4≤0.01% in the titanium dichloride solution.

[0028] Example like Figure 1 As shown, this embodiment provides a device for producing high oxygen content sponge titanium, including a refined titanium tetrachloride storage tank 1, a vanadium dichloride storage tank 2 and a reduction reaction furnace 3; wherein, A stirring paddle 9 is provided in the refined titanium tetrachloride storage tank 1, and the vanadium dichloride storage tank 2 is arranged above the refined titanium tetrachloride storage tank 1, and is connected with the refined titanium tetrachloride storage tank 1 through a first conveying pipeline, and a first metering feeder 4 and a first switch valve 7 are provided on the first conveying pipeline, and the first switch valve 7 is arranged downstream of the first metering feeder 4; the refined titanium tetrachloride storage tank 1 is connected with the reduction reaction furnace 3 through a second conveying pipeline 8, and a second metering feeder 5 and a second switch valve 6 are provided on the second conveying pipeline 8, and the second switch valve 6 is arranged downstream of the second metering feeder 5.

[0029] In this embodiment, the first metering feeder 4 and the second metering feeder 5 may be any metering device capable of accurate metering, such as a metering pump.

[0030] The production method of the device of this embodiment comprises the following steps: First, calculate the mass of the vanadium oxychloride solution added to the refined titanium tetrachloride storage tank by the following method: Add the refined titanium tetrachloride solution to the refined titanium tetrachloride storage tank, and only use the refined titanium tetrachloride solution to add to the reduction reaction furnace to produce 5 batches of titanium sponge, and perform oxygen impurity element detection on the titanium sponge products produced in the 5 batches to obtain the average value W1 of the mass percentage of oxygen element and the average mass M1 of titanium tetrachloride added in each batch; From the requirements of the titanium alloy composition table for smelting, the required mass percentage of oxygen element in sponge titanium can be obtained as W2, and the difference between the mass percentage of oxygen element in the currently produced sponge titanium products and the target value as W2-W1 can be calculated based on this; Detect oxygen impurities in titanium oxychloride storage tank 2 and take the average value W3 of the oxygen element mass percentage content; According to the production capacity of the reactor, the mass of titanium sponge produced by a single furnace is set to M2, and the content of oxygen impurity elements to be added to each furnace of titanium lumps is calculated as M2*(W2-W1); The remaining weight of titanium tetrachloride in the refined titanium tetrachloride storage tank is M3, and the content of oxygen impurity elements that need to be added to each batch of titanium lumps is M2*(W2-W1). From this, it can be calculated that the mass of vanadium dichloride solution that needs to be added to the refined titanium tetrachloride storage tank is: M=M3 / M1×(M2*(W2-W1) / W3).

[0031] Then, the following steps are used to produce high oxygen content titanium sponge: Step (1): adding a vanadium oxychloride solution of mass M to a refined titanium tetrachloride storage tank containing a refined titanium tetrachloride solution of mass M3 to obtain a mixed solution; Step (2): stirring the mixed solution in the refined titanium tetrachloride storage tank for 80 minutes to obtain a mixed solution with a high oxygen content; Step (3): Add the high oxygen content mixed liquid into a reduction reactor for reaction at a temperature above 780° C. to obtain a titanium sponge product.

[0032] Titanium dichloride is an important titanium compound, which is widely used in the fields of catalysts, fine chemicals and electronic materials. Through the research of the inventor, it was found that titanium dichloride will undergo a decomposition reaction 2TiOCl2=TiO2+TiCl4 under high temperature conditions, which usually occurs above 450°C, and decomposes to produce titanium tetrachloride and titanium oxide. Because titanium dichloride has unique properties in terms of structure, chemical reactivity, solubility, etc., and has good solubility in titanium tetrachloride, titanium dichloride solution is selected as an oxygenator and mixed into titanium tetrachloride solution to meet the uniform distribution of oxygen elements in the raw materials. During the reduction process, the temperature in the reduction furnace is usually above 780°C, and the titanium dichloride in the mixed solution is very easy to decompose in the reduction reactor 3 to produce titanium tetrachloride. The titanium oxide generated by the decomposition will be evenly distributed in the sponge titanium, which achieves the uniform oxygen element composition in the sponge titanium raw material from the source, and finally produces a high-oxygen content sponge titanium product with uniform oxygen element composition.

[0033] Sponge titanium is the raw material for smelting titanium ingots and titanium alloys, in which the oxygen content is an important indicator. Titanium dioxide (TiO2) is often used as an oxygen enhancer to adjust the oxygen content in the alloy during the smelting process of titanium and titanium alloys at home and abroad. There are problems such as large fluctuations in oxygen impurity elements after smelting during the smelting process, which causes local performance degradation of the alloy. The method of the present invention uses titanium dichloride as an oxygen enhancer, and the oxygen content of the produced sponge titanium is uniform, ensuring that the quality of the subsequent production of titanium ingots and titanium alloys is stable and controllable.

[0034] A person skilled in the art should understand that the discussion of any of the above embodiments is only exemplary and is not intended to imply that the scope of the disclosure of the embodiments of the present invention (including the claims) is limited to these examples; under the concept of the embodiments of the present invention, the technical features in the above embodiments or different embodiments can also be combined, and there are many other changes in different aspects of the embodiments of the present invention as described above, which are not provided in detail for the sake of simplicity. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the embodiments of the present invention should be included in the protection scope of the embodiments of the present invention.

Claims

1. A method for producing high oxygen content titanium sponge, characterized in that: The steps include: Step (1): adding vanadium oxychloride solution to a refined titanium tetrachloride storage tank containing refined titanium tetrachloride solution to obtain a mixed solution; Step (2): stirring the mixed solution in the refined titanium tetrachloride storage tank for 60 to 90 minutes to obtain a mixed solution with a high oxygen content; Step (3): Add the high oxygen content mixed solution into a reduction reactor for reaction to obtain a titanium sponge product.

2. A method for producing high oxygen content titanium sponge according to claim 1, characterized in that: In the step (1), the mass of the added vanadium oxychloride is M: M=M3 / M1×(M2*(W2-W1) / W3) Where: W1 is the percentage of oxygen element in the production of titanium sponge using only refined titanium tetrachloride solution W2 is the oxygen content of titanium sponge in the titanium alloy composition table for smelting W3 is the average oxygen content of titanium dichloride solution M1 is the mass of titanium tetrachloride added to the single furnace reduction reactor when only refined titanium tetrachloride solution is used to produce titanium sponge. M2 is the mass of titanium sponge produced by a single furnace reduction reactor M3 is the mass of titanium tetrachloride solution in the refined titanium tetrachloride storage tank.

3. A method for producing high oxygen content titanium sponge according to claim 2, characterized in that: In the step (1), W1 is the average oxygen content of the titanium sponge produced by 2-8 reduction reactors when only refined titanium tetrachloride is used to produce titanium sponge.

4. A method for producing high oxygen content titanium sponge according to claim 3, characterized in that: In the step (1), M1 is the average mass of the refined titanium tetrachloride solution added to a single furnace in the production of 2-8 furnaces of titanium sponge.

5. A method for producing high oxygen content titanium sponge according to claim 1, characterized in that: In the step (3), the temperature in the reduction reaction furnace is usually above 450°C.

6. A method for producing high oxygen content titanium sponge according to claim 5, characterized in that: In the step (3), the temperature in the reduction reaction furnace is usually above 780°C.

7. A method for producing high oxygen content titanium sponge according to claim 1, characterized in that: In the step (1), the impurity components of the refined titanium tetrachloride solution must meet the TiCl4-01 or TiCl4-02 standards.

8. A method for producing high oxygen content titanium sponge according to claim 7, characterized in that: In the step (1), in the refined titanium tetrachloride solution, SiCl4≤0.0050%, FeCl3≤0.0010%, VOCl3≤0.0010%, and AlCl3≤0.0050%.

9. A method for producing high oxygen content titanium sponge according to claim 1, characterized in that: In step (1), FeCl3≤0.0010%, VOCl3≤0.001%, and SiCl4≤0.01% in the titanium dichloride solution.

10. The device used in the method for producing high oxygen content titanium sponge according to any one of claims 1 to 9, characterized in that: It includes a refined titanium tetrachloride storage tank, a vanadium dichloride storage tank and a reduction reactor; among which, A stirring paddle is provided in the refined titanium tetrachloride storage tank; the vanadium dichloride storage tank is arranged above the refined titanium tetrachloride storage tank, and is connected with the refined titanium tetrachloride storage tank through a first conveying pipeline, a first metering feeder and a first switch valve are arranged on the first conveying pipeline, and the first switch valve is arranged downstream of the first metering feeder; the refined titanium tetrachloride storage tank is connected with the reduction reaction furnace through a second conveying pipeline, a second metering feeder and a second switch valve are arranged on the second conveying pipeline, and the second switch valve is arranged downstream of the second metering feeder.

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