阅读说明：本技术 提钛尾渣的回收利用方法 (Recycling method of titanium extraction tailings ) 是由 刘娟 叶恩东 王建鑫 王东生 于 2020-06-29 设计创作，主要内容包括：本发明涉及提钛尾渣的回收利用方法,属于钛资源利用领域。本发明提供了提钛尾渣的回收利用方法,包括如下步骤：取提钛尾渣,水洗,磁选,将所得磁选精料干燥,沸腾氯化处理,即得四氯化钛；其中,所述的提钛尾渣含有如下质量百分比的成分：TiC 2％～3.5％、TTi 11％～14％、TFe 1.2％～1.7％、SiO<Sub>2</Sub>20～28％、FeO 1％～2％、MgCl<Sub>2</Sub>0.1％～1％、CaCl<Sub>2</Sub>2％～4％。采用本发明方法对提钛尾渣进行处理后,尾渣中TiC降低至1.0％以下,整个工艺流程的Ti的回收率大于80％,对于提高尾渣中Ti的利用率具有重要意义。(The invention relates to a recycling method of titanium extraction tailings, belonging to the field of titanium resource utilization. The invention provides a recycling method of titanium extraction tailings, which comprises the following steps: taking and extracting titanium tailings, washing with water, carrying out magnetic separation, drying the obtained magnetic separation concentrate, and carrying out boiling chlorination treatment to obtain titanium tetrachloride; wherein the titanium extraction tailings comprise the following components in percentage by mass: TiC 2% -3.5%, TTi 11% -14%, TFe 1.2% -1.7%, SiO 2 20～28％、FeO 1％～2％、MgCl 2 0.1％～1％、CaCl 2 2 to 4 percent. After the method is adopted to treat the tailings of extracting the titanium, the TiC in the tailings is reduced to be less than 1.0 percent, the recovery rate of the Ti in the whole process flow is more than 80 percent, and the method has important significance for improving the utilization rate of the Ti in the tailings.)

1. The recycling method of the titanium extraction tailings is characterized by comprising the following steps: the method comprises the following steps: taking and extracting titanium tailings, washing with water, carrying out magnetic separation, drying the obtained magnetic separation concentrate, and carrying out boiling chlorination treatment to obtain titanium tetrachloride; wherein the titanium extraction tailings comprise the following components in percentage by mass: TiC 2% -3.5%, TTi 11% -14%, TFe 1.2% -1.7%, SiO₂20～28％、FeO 1％～2％、MgCl₂0.1％～1％、CaCl₂2％～4％。

2. The recycling method according to claim 1, wherein: the titanium extraction tailings are residues generated after chlorination of carbonized blast furnace slag; preferably, the TiO in the blast furnace slag₂The content is 20-25%.

3. The recycling method according to claim 1, wherein: washing with water to obtain MgCl in the titanium extraction tailings₂The content of CaCl is less than 0.03 percent₂The content is less than 0.03%.

4. The recycling method according to claim 1, wherein: the magnetic separation satisfies at least one of the following conditions: wet magnetic separation is adopted; the magnetic field intensity is 0.6-0.9T.

5. The recycling method according to claim 1, wherein: respectively collecting magnetic separation concentrate and magnetic separation tailings after magnetic separation, wherein the concentrate comprises the following components: the mass ratio of tailings is (0.5-0.68): (0.82-1).

6. The recycling method according to claim 1, wherein: the drying adopts flue gas generated in the boiling chlorination process to dry the magnetic separation concentrate.

7. The recycling method according to claim 1, wherein: the boiling chlorination treatment uses a mixed gas of nitrogen and chlorine as a chlorination gas, wherein the ratio of nitrogen: the volume ratio of the chlorine gas is 2: 1-3: 1.

8. The recycling method according to claim 1 or 7, wherein: the gas flow rate of the boiling chlorination treatment is 2.0-3.0L/min.

9. The recycling method according to claim 1, wherein: the chlorination temperature is 450-500 ℃.

10. The recycling method according to claim 1, wherein: the average residence time of the magnetic separation concentrate in the fluidized bed chlorination furnace is 3-5 min.

Technical Field

The invention relates to a recycling method of titanium extraction tailings, belonging to the field of titanium resource utilization.

Background

Titanium tetrachloride is an important raw material for preparing titanium sponge and titanium dioxide, and one of the production methods is to adopt TiO₂Blast furnace slag with 20-25% of contentAnd (2) adding carbon at the temperature for smelting to obtain carbide slag with the TiC content of about 12-15%, and carrying out chlorination reaction on the TiC and chlorine at the low temperature of 450-500 ℃, so as to extract and utilize titanium in the blast furnace slag. In the whole low-temperature chlorination reaction process, even if TiC is fully consumed, residues after the chlorination reaction, the total weight of which is 80-85%, still remain. Calculated by the yield of titanium tetrachloride produced in the prior steel climbing production, the yield of titanium extraction tailings is about 2-3 ten thousand tons every year, the TiC content in the titanium extraction tailings is about 2-3.5%, and chloride ions in the titanium extraction tailings are generally removed and then used in the building material industry at present, so that the great waste of titanium resources is caused. Therefore, how to treat and efficiently utilize the titanium extraction tailings has great significance for improving the comprehensive utilization rate of titanium resources.

Disclosure of Invention

The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention aims to provide a method for recycling titanium tailings.

The invention provides a recycling method of titanium extraction tailings, which comprises the following steps: taking and extracting titanium tailings, washing with water, carrying out magnetic separation, drying the obtained magnetic separation concentrate, and carrying out boiling chlorination treatment to obtain titanium tetrachloride; wherein the titanium extraction tailings comprise the following components in percentage by mass: TiC 2% -3.5%, TTi 11% -14%, TFe1.2% -1.7%, SiO₂20～28％、FeO1％～2％、MgCl₂0.1％～1％、CaCl₂2％～4％。

Further, the titanium extraction tailings are residues generated after chlorination of carbonized blast furnace slag.

Preferably, the TiO in the blast furnace slag₂The content is 20-25%.

Further washing the titanium extraction tailings with water to obtain MgCl₂The content of CaCl is less than 0.03 percent₂The content is less than 0.03%.

Further, the magnetic separation satisfies at least one of the following conditions:

wet magnetic separation is adopted;

the magnetic field intensity is 0.6-0.9T.

Further, magnetic separation concentrate and magnetic separation tailings are collected respectively after magnetic separation, wherein the concentrate: the mass ratio of tailings is (0.5-0.68): (0.82-1).

Further, the flue gas generated in the boiling chlorination process is used for drying the magnetic separation concentrate in the drying process.

Further, the boiling chlorination treatment uses a mixed gas of nitrogen and chlorine as a chlorination gas, wherein the ratio of nitrogen: the volume ratio of the chlorine gas is 2: 1-3: 1.

Furthermore, the flow rate of the gas for the boiling chlorination treatment is 2.0-3.0L/min.

Further, the chlorination temperature is 450-500 ℃.

Further, the average residence time of the magnetic separation concentrate in the fluidized bed chlorination furnace is 3-5 min.

Reducing the steel-climbing blast furnace slag by carbon at high temperature to ensure that TiO in the slag₂Converted to TiC and the corresponding slag is called carbide slag. The carbonized slag is subjected to low-temperature selective chlorination at the temperature of below 700 ℃, and titanium in the blast furnace slag is treated with TiCl₄Is extracted, which is a process for extracting titanium from low-grade and complex titanium raw materials such as the Panzhi steel blast furnace slag. Wherein, the residue generated after the chlorination reaction is the titanium extraction tailings.

According to some embodiments of the invention, the apparatus used for the boiling chlorination treatment is a phi 50mm batch low-temperature boiling chlorination furnace. Preferably, the feed amount for the boiling chlorination is 200 g. According to the requirement, the fluidized reactor can be enlarged by boiling chlorination treatment, and the treatment capacity of the titanium extraction tailings is improved.

The invention provides a recycling method of titanium extraction tailings, which is used for treating the titanium extraction tailings, the TiC in the tailings is reduced to be less than 1.0%, the recovery rate of Ti in the whole process flow is more than 80%, and the recycling method has important significance for improving the utilization rate of Ti in the tailings. In addition, the titanium extraction tailings treatment process provided by the invention is initiated at home and abroad, the process flow is simple, and the used equipment is common equipment, so that the titanium extraction tailings treatment process has a good popularization and application prospect.

Drawings

FIG. 1 is a schematic view of a typical process flow of titanium tailing treatment in the example.

Detailed Description

The invention provides a recycling method of titanium extraction tailings, which comprises the following steps: taking and extracting titanium tailings, washing with water, carrying out magnetic separation, drying the obtained magnetic separation concentrate, and carrying out boiling chlorination treatment to obtain titanium tetrachloride; wherein the titanium extraction tailings comprise the following components in percentage by mass: TiC 2% -3.5%, TTi 11% -14%, TFe1.2% -1.7%, SiO₂20～28％、FeO1％～2％、MgCl₂0.1％～1％、CaCl₂2％～4％。

The present invention has been completed based on the following findings of the inventors: 2 to 3.5 percent of TiC remains in the titanium extraction tailings, which indicates that the chlorination reaction is not completely carried out. Although it is theoretically possible to extend the chlorination reaction time continuously to obtain higher conversion rate, in practice, as the reaction time is prolonged, it is found that some substances in a molten state are more and more accumulated in the bed layer, so that particles are bonded, the fluidization furnace condition is worsened, and even the sieve plate holes are blocked, and the chlorination operation cannot be normally carried out. The inventor analyzes the chemical compositions of the titanium extraction tailings and the molten state substances to obtain the byproduct CaCl mainly caused by chlorination reaction₂And MgCl₂Causing the above-described situation. Therefore, the invention proposes that CaCl in the titanium extraction tailings is removed by water washing₂And MgCl₂Provides possibility for further chlorination of the tailings. And (3) carrying out magnetic separation after washing, wherein TiC and Fe are combined together, so that TiC particles in the slag can be separated, the TiC content is increased from 2.5-3.5% to 5.5-6.5%, and the particle size is slightly increased. And then the magnetic separation tailing can be used for preparing building materials, the magnetic separation concentrate can be dried by utilizing smoke generated in the boiling chlorination process of carbide slag, the dried magnetic separation concentrate returns to a chlorination furnace for boiling chlorination again, titanium resources in the titanium separation concentrate are extracted to prepare crude titanium tetrachloride, and raw material support is provided for titanium sponge and titanium dioxide. The process realizes the recycling of valuable components in the titanium tailings and improves the comprehensive utilization rate of titanium resources.

In the recycling method, the titanium extraction tailings are washed by water to remove water-soluble chloride CaCl₂And MgCl₂Reducing the amount of molten material produced, facilitating boilingThe fluidization state goes forward during chlorination. The TiC content in the titanium extraction tailings can be increased by magnetic separation treatment from 2.5% -3.5% to 5.5% -6.5%, the particle size of coarse particles is increased from 60-240 meshes to 90% to 60-150 meshes to 90%, and the fluidization state is better during boiling chlorination. By reasonably controlling chlorination parameters, the TiC content in the tailings after chlorination is reduced to below 1.0%. In the whole process flow, the tailings after titanium extraction from the carbide slag are subjected to series treatment and then returned to the boiling chlorination furnace for low-temperature chlorination treatment, so that the fluidization state is good, the chlorination rate reaches over 75 percent, and the recovery rate of Ti is over 80 percent.

The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.