阅读说明：本技术 一种制备含钒海绵钛的方法 (Method for preparing vanadium-containing titanium sponge ) 是由 张美杰 和奔流 刘峰 王丽艳 张军丽 杨倩 张建林 张燕平 赵冠杰 杨德 陈建立 于 2021-08-25 设计创作，主要内容包括：本发明公开了一种制备含钒海绵钛的方法,属于钛冶金技术领域,解决了传统技术中海绵钛制备成本高、易出现钒元素偏析现象,导致合金成分难以控制的问题,其包括以下步骤：步骤A：回收蒸馏釜中的VOCl2；步骤B：将步骤A中的VOCl2进行还原处理,转化为钒的氯化物；步骤C：将步骤C中的钒的氯化物加入精四氯化钛中,钒的氯化物在四氯化钛中充分溶解后,加入还原炉中；步骤D：钒的氯化物与四氯化钛在还原炉中进行同步还原反应,生成含钒海绵钛；步骤E：将海绵钛进行蒸馏破碎,并筛分成合适的粒径,实现了降低在海绵钛制备中的钒元素的成本,且钒元素含量可控的技术效果。(The invention discloses a method for preparing vanadium-containing titanium sponge, belongs to the technical field of titanium metallurgy, and solves the problems that in the prior art, the titanium sponge has high preparation cost and is easy to cause vanadium element segregation, so that the alloy components are difficult to control, and the method comprises the following steps: step A: recovering VOCl2 in the distillation kettle; and B: reducing the VOCl2 in the step A to convert the VOCl2 into vanadium chloride; and C: c, adding the vanadium chloride in the step C into fine titanium tetrachloride, and adding the vanadium chloride into a reduction furnace after the vanadium chloride is fully dissolved in the titanium tetrachloride; step D: performing synchronous reduction reaction on the vanadium chloride and titanium tetrachloride in a reduction furnace to generate vanadium-containing titanium sponge; step E: the titanium sponge is distilled and crushed, and is screened into proper particle size, so that the technical effects of reducing the cost of vanadium in the preparation of the titanium sponge and controlling the content of the vanadium are achieved.)

1. The method for preparing vanadium-containing titanium sponge is characterized by comprising the following steps:

step A: VOCl in recovery distillation still₂；

And B: the VOCl in the step A₂Carrying out reduction treatment to convert the vanadium into vanadium chloride;

and C: c, adding the vanadium chloride in the step C into fine titanium tetrachloride, and adding the vanadium chloride into a reduction furnace after the vanadium chloride is fully dissolved in the titanium tetrachloride;

step D: performing synchronous reduction reaction on the vanadium chloride and titanium tetrachloride in a reduction furnace to generate vanadium-containing titanium sponge;

step E: the titanium sponge is crushed by distillation and sieved to a suitable particle size.

2. The method for preparing vanadium-containing titanium sponge according to claim 1, wherein the chloride of vanadium in step B is VCl₂、VCl₃Or VCl₄And mixtures thereof.

3. The method for preparing titanium sponge containing vanadium according to claim 1, wherein the content of vanadium in the titanium tetrachloride solution in the step C is between 0.01% and 50%.

4. The method for preparing vanadium-containing titanium sponge according to claim 1, wherein the reduction reaction in step D is:

VOCl₃+C→VCl₃+CO↑；

VOCl₃+C→VCl₂+CO↑。

5. the method for preparing vanadium-containing titanium sponge according to claim 1, wherein the VOCl2 in step A is a still bottom deposited in a primary still.

Technical Field

The invention belongs to the technical field of titanium metallurgy, and particularly relates to a method for preparing vanadium-containing titanium sponge.

Background

The titanium alloy has the advantages that due to the diversity of alloy elements, the strength, the heat resistance, the corrosion resistance and the like of the titanium alloy are improved compared with pure titanium, and the titanium alloy has wider application in high-tech fields such as aviation, aerospace, ships, nuclear energy, military industry and the like. For example, the TC4 titanium alloy which is the most widely used at present contains 6% of Al and 4% of V, and can be widely applied to various beams, bulkheads, slide rails, fans of aircraft engines and the like in aircraft structures. The titanium alloy is produced by casting granular titanium sponge and alloy elements in a certain proportion into titanium ingots, and then processing the titanium ingots into materials by forging, rolling, extruding and other processing methods. The vanadium-titanium-containing alloy is generally prepared by preparing high-purity titanium sponge and vanadium-aluminum alloy, properly adding aluminum beans, and then casting ingots and processing into various sections. However, in the processing process, high-purity vanadium with high price needs to be additionally added, but in the process of casting and ingot making, the segregation of vanadium elements is caused, and the alloy components are difficult to control. Patent CN 109306411 describes that refined titanium tetrachloride containing 0.4% of vanadium is prepared by omitting the vanadium removal process in the titanium tetrachloride refining process, and the prepared titanium sponge has low vanadium content and can introduce oxygen element, and simultaneously the vanadium content is not adjustable.

Therefore, it is necessary to develop a new method for smelting titanium alloy, which can reduce the cost of vanadium element, avoid the segregation phenomenon of vanadium element and control the content of vanadium element.

Disclosure of Invention

Aiming at the problems that sponge titanium in the prior art is high in preparation cost and easy to cause vanadium element segregation phenomenon, so that alloy components are difficult to control, the invention provides a method for preparing vanadium-containing sponge titanium, which aims to solve the problems that: the cost of vanadium element in the preparation of the titanium sponge is reduced, and the content of the vanadium element is controllable.

The technical scheme adopted by the invention is as follows:

the method for preparing vanadium-containing titanium sponge is characterized by comprising the following steps:

step A: VOCl in recovery distillation still₂；

And B: the VOCl in the step A₂Carrying out reduction treatment to convert the vanadium into vanadium chloride;

and C: c, adding the vanadium chloride in the step C into fine titanium tetrachloride, and adding the vanadium chloride into a reduction furnace after the vanadium chloride is fully dissolved in the titanium tetrachloride;

step D: performing synchronous reduction reaction on the vanadium chloride and titanium tetrachloride in a reduction furnace to generate vanadium-containing titanium sponge;

step E: the titanium sponge is crushed by distillation and sieved to a suitable particle size.

By adopting the scheme, the vanadium-containing material at the bottom of the distillation kettle is recycled, so that the cost of vanadium in the titanium sponge preparation process is reduced, the resource is recycled, the cost performance of the titanium alloy is improved, and in the step C, the vanadium chloride is dissolved into the refined titanium tetrachloride, so that the vanadium element and the titanium element can be synchronously reduced, the vanadium element is distributed in the titanium sponge more uniformly, and the vanadium segregation phenomenon is avoided.

The chloride of vanadium in the step B is VCl₂、VCl₃Or VCl₄And mixtures thereof.

The content of vanadium in the titanium tetrachloride solution in the step C is between 0.01 and 50 percent.

By adopting the scheme, the vanadium content of the vanadium-titanium alloy is diversified, and the proportion of the vanadium chloride dissolved into the refined titanium tetrachloride is adjustable, so that the smelting requirements of most vanadium-titanium-containing alloys are met.

The reduction reaction in the step D is as follows:

VOCl₃+C→VCl₃+CO↑；

VOCl₃+C→VCl₂+CO↑。

the VOCl2 of step a is the still bottoms deposited in the primary still.

In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:

1. and in the step C, the chloride of vanadium is dissolved into the refined titanium tetrachloride, and the vanadium element and the titanium element can be synchronously reduced, so that the vanadium element is more uniformly distributed in the titanium sponge, and the phenomenon of vanadium segregation is avoided.

2. Because the vanadium content of the vanadium-titanium alloy is diversified, the proportion of the vanadium chloride dissolved into the refined titanium tetrachloride is adjustable, and the smelting requirements of most vanadium-titanium-containing alloys are met.

Drawings

The invention will now be described, by way of example, with reference to the accompanying drawings, in which:

FIG. 1 is a flow chart of the preparation of one embodiment of the present invention.

Detailed Description

All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.

The present invention will be described in detail with reference to fig. 1.

The first embodiment is as follows:

the method for preparing vanadium-containing titanium sponge is characterized by comprising the following steps:

step A: VOCl in recovery distillation still₂；

And B: the VOCl in the step A₂Carrying out reduction treatment to convert the vanadium into vanadium chloride;

and C: c, adding the vanadium chloride in the step C into fine titanium tetrachloride, and adding the vanadium chloride into a reduction furnace after the vanadium chloride is fully dissolved in the titanium tetrachloride;

step D: performing synchronous reduction reaction on the vanadium chloride and titanium tetrachloride in a reduction furnace to generate vanadium-containing titanium sponge;

step E: the titanium sponge is crushed by distillation and sieved to a suitable particle size.

By adopting the scheme, the vanadium-containing material at the bottom of the distillation kettle is recycled, so that the cost of vanadium in the titanium sponge preparation process is reduced, the resource is recycled, the cost performance of the titanium alloy is improved, and in the step C, the vanadium chloride is dissolved into the refined titanium tetrachloride, so that the vanadium element and the titanium element can be synchronously reduced, the vanadium element is distributed in the titanium sponge more uniformly, and the vanadium segregation phenomenon is avoided.

The chloride of vanadium in the step B is VCl₂、VCl₃Or VCl₄And mixtures thereof.

The content of vanadium in the titanium tetrachloride solution in the step C is between 0.01 and 50 percent.

By adopting the scheme, the vanadium content of the vanadium-titanium alloy is diversified, and the proportion of the vanadium chloride dissolved into the refined titanium tetrachloride is adjustable, so that the smelting requirements of most vanadium-titanium-containing alloys are met.

The reduction reaction in the step D is as follows:

VOCl₃+C→VCl₃+CO↑；

VOCl₃+C→VCl₂+CO↑。

the VOCl2 of step a is the still bottoms deposited in the primary still.

In the embodiment, the method is used for preparing titanium sponge products with different vanadium contents, the kettle substrate in the primary kettle is used as a raw material, vanadium elements in the raw material are recovered, vanadium chlorides are prepared, the vanadium chlorides are dissolved into fine Sijunhuatai in different proportions, a vanadium-containing titanium tetrachloride solution is added into a reduction furnace, the vanadium elements and the titanium elements are synchronously reduced, and finally vanadium-containing titanium sponge is obtained, wherein the final vanadium content in the vanadium-containing titanium sponge can be adjusted according to requirements by adjusting the addition amount of a green ring of vanadium;

wherein the reduction reaction in the step D, the distillation crushing in the step E and the screening process are carried out according to the titanium sponge production process in the prior art, and the description is not repeated.

In this example, the following embodiments are provided:

firstly, adding a chlorinating agent into a kettle substrate of a primary kettle, and adding VOCl₂Chlorination to VOCl₃Distilling to obtain TiCl₄And VOCl₃Adding excess carbon to the mixed solution, and adding VOCl₃Reduction to VCl₃And VCl₄And (2) waiting for vanadium chloride, dissolving the vanadium chloride into the refined titanium tetrachloride according to the proportion of 6 percent, adding the mixed solution into a reduction furnace according to a reduction feeding system to synchronously reduce the vanadium-titanium chloride into elemental sponge metal, removing magnesium and magnesium chloride in the vanadium-containing sponge titanium through a distillation process, and crushing and screening to obtain a commercial product of the vanadium-containing sponge titanium.

The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.