CN209024654U - A device for preparing pure titanium by electrolysis-chlorination-electrolysis - Google Patents

Abstract

A kind of device of electrolysis-pure titanium of chlorination-electrolytic preparation, including the first electrolytic cell, the second electrolytic cell, chlorination reactor and gas-guide tube；Wherein, the first electrolytic cell (1) and the second electrolytic cell (2) are horizontally disposed, and chlorination reactor (3) is located at the upper position of the first electrolytic cell (1) anode, and porous ceramics partition (4) are arranged in bottom；First gas-guide tube (5) is located at the anode position in the first electrolytic cell (1), and connect with chlorination reactor (3) bottom；Second gas-guide tube (6) one end connects at the top of chlorination reactor (3), and the other end is located at the cathode site in the second electrolytic cell (2)；Third gas-guide tube (7) one end is located at the anode position in the second electrolytic cell (2), and the other end is connect with the first gas-guide tube (5) in the first electrolytic cell (1).The utility model simple process, clean and effective；Simultaneously can be accurate to customize by-product obtained by the first electrolytic cell according to demand, further promote economic benefit.

Description

A device for preparing pure titanium by electrolysis-chlorination-electrolysis

technical field

The utility model relates to a device and a method for preparing pure titanium by electrolysis-chlorination-electrolysis, belonging to the field of electrolytic method for producing metallic titanium.

Background technique

Titanium metal has many excellent physical and chemical properties. It has low density (4.5g/cm ³ ), high melting point (1660°C), corrosion resistance, oxidation resistance, non-toxic and harmless, and good biocompatibility. "Future Metals". It has a wide range of applications in the fields of aerospace, chemical industry, ships and ships, biomedical, civil building materials and sports equipment. On this basis, titanium metal with a titanium content higher than 99.95% or 99.99% (ie 3N5 or 4N) is called high-purity titanium metal. High-purity titanium metal not only has the excellent properties of ordinary titanium metal, but also its excellent elongation (50-60%), section shrinkage (70-80%) and ultra-low content of harmful impurity elements that ordinary titanium cannot. reachable. Therefore, high-purity titanium is favored in high-end fields such as high-end microelectronics, cutting-edge aerospace technology, precision VLSI and display screens.

At present, there are two main methods for the industrial production of high-purity titanium, one is the Kroll method and the other is the molten salt electrolysis method. In the former, TiCl ₄ is obtained by carbon mixing and chlorination with TiO ₂ , TiCl ₄ is obtained by magnesium thermal reduction to obtain titanium metal, and the by-product MgCl ₂ needs to be decomposed by molten salt electrolysis to realize recycling. The whole process is complicated and lengthy, and the yield is limited. In addition, in order to obtain high-purity titanium metal, the used raw materials (TiCl ₄ and magnesium metal) often require higher purity, which increases the preparation cost of high-purity titanium. The latter uses sponge titanium as the anode and titanium-containing halide molten salt as the electrolyte. During the electrolysis process, the anode sponge titanium is dissolved, and the cathode titanium ions are deposited to obtain high-purity titanium metal. Compared with the Kroll method, the process of the method is short, and the oxygen content in the product can be effectively controlled to obtain low-oxygen high-purity titanium metal. However, the preparation of sponge titanium is ultimately inseparable from the Kroll method, so its upstream process is complex and inefficient, which ultimately results in high cost of molten salt electrolytic refining using sponge titanium as the anode.

SUMMARY OF THE INVENTION

In view of the above problems, the utility model proposes a device and method for preparing pure titanium by electrolysis-chlorination-electrolysis. The TiC _x O _y or TiC _x O _y N _z obtained by mixing titanium dioxide and carbonaceous material powder in a certain proportion, briquetting, and carbothermal reduction is used as the raw material. Electrolyzing molten alkali metal chloride, alkaline earth metal chloride, aluminum chloride or their mixture in the first electrolytic cell, the chlorine gas obtained from the anode is passed into the chlorination reactor storing TiC _x O _y or TiC _x O _y N _z raw material , and then chlorinate out _TiCl gas; this gas is passed into the cathode in the second electrolytic cell through the conduit, and utilizes the solubility of _TiCl in the second electrolytic cell to electrolyze high-purity titanium metal; meanwhile, the Cl produced by the anode ₂ is recycled to the first electrolytic cell chlorination reactor to continue to participate in the chlorination of TiC _x O _y or TiC _x O _y N _z . Compared with the Kroll method or the conventional molten salt electrolysis method for preparing high-purity titanium metal, the device and method for preparing pure titanium by electrolysis-chlorination-electrolysis avoids the long and complex batch production characteristics of the Kroll method from the source, and simplifies the entire process flow. , and reduce the production cost of preparing high-purity titanium by Kroll method or conventional molten salt electrolysis method. In addition, the selection of the molten salt composition of the first electrolytic cell can be determined according to market changes or the requirements of alkali metals, alkaline earth metals, aluminum metals or alloys required by customers, thereby increasing the effective value of the by-products.

The utility model provides a device and method for preparing pure titanium by electrolysis-chlorination-electrolysis. Compared with Kroll method or molten salt electrolysis using sponge titanium as raw material to prepare high-purity titanium metal, this method has the characteristics of simple process, low cost, and can prepare high-value by-products.

Accompanying drawing 1 is the schematic diagram of the device for preparing pure titanium by electrolysis-chlorination-electrolysis of the present invention, including a first electrolytic cell, a second electrolytic cell, a chlorination reactor and an air guide;

Wherein, the first electrolytic cell and the second electrolytic cell are arranged horizontally, the chlorination reactor is located at the upper position of the anode of the first electrolytic cell, and the bottom is provided with a porous ceramic separator;

The first air conduit is located at the anode position in the first electrolytic cell and is connected to the bottom of the chlorination reactor; one end of the second air conduit is connected to the top of the chlorination reactor, and the other end is located at the cathode position in the second electrolytic cell; One end of the gas pipe is located at the anode position in the second electrolytic cell, and the other end is connected to the first gas conduit in the first electrolytic cell.

Further, a heating and temperature control system is arranged at the bottom and surrounding of the first electrolytic cell and the second electrolytic cell for controlling the temperature of the material in the chlorination reactor.

Further, the chlorination reactor shell is made of steel, lined with ceramic materials; there is an independent heating and temperature control system outside the chlorination reactor for controlling the temperature of the material inside the chlorination reactor.

Further, the air guide tube is made of steel and is lined with ceramic or polytetrafluoroethylene material.

The method for preparing pure titanium by electrolysis-chlorination-electrolysis using the device of the utility model comprises the following steps:

1) After uniformly mixing titanium dioxide and carbonaceous material powder according to the chemical reaction metering ratio, press molding, and prepare TiC _x O _y under vacuum conditions in the temperature range of 900-1600 ° C or prepare TiC _x O _y under nitrogen atmosphere N _z , loaded into the chlorination reactor;

2) The first electrolytic cell uses molten alkali metal chloride, alkaline earth metal chloride, aluminum chloride or their mixture as the supporting electrolyte, the anode is a carbon material, the cathode is a metal material, the temperature of the electrolytic cell is controlled at 150～1000 ℃, the chlorine The temperature of the chlorination reactor is controlled at 200-600 °C; after the electrolysis starts, Cl ^- migrates to the anode, and the reaction occurs to produce Cl ₂ ; the anode product Cl ₂ enters the chlorination reactor through the porous separator through the first gas pipe, and is mixed with the chlorination reactor. TiC _x O _y or TiC _x O _y N _z in the chlorination reactor reacts to generate TiCl ₄ gas; the gas enters the cathode area of the second electrolytic cell through the second gas conduit;

3) In the second electrolytic cell, molten alkali metal chloride, alkaline earth metal chloride or their mixture is used as the supporting electrolyte, the anode is a carbon material, the cathode is a metal material, and the temperature of the electrolytic cell is controlled at 500～1000 ℃; after the electrolysis starts, The TiCl ₄ gas transported by the second air duct enters the molten salt at the cathode of the second electrolytic cell, and the Ti ⁴⁺ reacts at the cathode to generate low-valent titanium ions, and the low-valent titanium ions continue to react at the cathode to deposit pure titanium. The reaction is as follows :

Ti ⁴⁺ +e=Ti ³⁺

Ti ³⁺ +e=Ti ²⁺

Ti ²⁺ +2e=Ti

Cl ^- migrates to the anode, generates Cl ₂ at the anode, is transported to the first gas pipe through the third gas conduit, mixes with the Cl ₂ generated at the anode of the first electrolytic cell, and enters the chlorination reactor to participate in TiC _x O _y or chlorination of TiC _x O _y N _z ;

4) After one electrolysis cycle is finished, the cathode products in the two electrolytic cells are taken off, and the product high-purity titanium metal is collected from the cathode of the second electrolytic cell through processing steps such as pickling, water washing, drying, etc., from the first electrolytic cell. By-products alkali metals, alkaline earth metals, aluminum metals or alloys are collected on the cathode of the electrolysis cell.

5) After the completion of step 4), the cathode is loaded into two electrolytic cells again, and new TiC _x O _y or TiC _x O _y N _z raw materials are loaded into the chlorination reactor, and a new round of Electrolytic operations for the production of high-purity titanium.

In the step 1), the carbonaceous material powder is one or a combination of graphite, petroleum coke, carbon black, coal, and charcoal.

In the step 1), the number ratio of oxygen atoms in the titanium dioxide to carbon atoms in the carbonaceous material powder is 1.2:1-0.5:1, preferably 1:1-0.667:1.

In the steps 2) and 3), the cathode metal material in the first electrolytic cell and the second electrolytic cell is titanium, carbon steel or nickel.

In the steps 2) and 3), the current densities during electrolysis in the first electrolytic cell and the second electrolytic cell are respectively: anode, 0.01A/cm ² ～2.00A/cm ² ; cathode, 0.01A/cm ² ～ 2.00A/cm ² .

Compared with the prior art, the advantages of the present utility model are:

1), the three parts of chlorine preparation, titanium oxycarbon or titanium oxycarbonitride low-temperature chlorination and titanium tetrachloride electrolysis are completed in the same device, and the process is concise, clean and efficient;

₂ ), avoiding the process of magnesium thermal reduction and the electrolytic decomposition of MgCl involved in the Kroll method production process, thereby greatly shortening the preparation process of high-purity titanium;

3), the application of double electrolytic cells, separate the low-temperature chlorination of titanium oxycarbide or titanium oxycarbonitride and the electrolytic reduction of TiCl ₄ , which is not only conducive to the preparation of high-purity titanium, ensures the purity of titanium, but also separates the Cl produced by the two anodes. ₂ Realize recycling, further reducing pollution and energy consumption;

4) The by-products obtained from the first electrolytic cell can be precisely customized according to market changes or customer needs, thereby improving the utilization value of the by-products.

Description of drawings

Fig. 1 is the device schematic diagram of the electrolysis-chlorination-electrolysis of the utility model to prepare pure titanium;

Symbols: 1. The first electrolytic cell, 2. The second electrolytic cell, 3. The chlorination reactor, 4. The porous ceramic separator, 5. The first air conduit, 6. The second air conduit, 7. The third conduit trachea.

Detailed ways

Example 1

Titanium dioxide and graphite powder were uniformly mixed according to a mass ratio of 40:12, then pressed and formed, and vacuum sintered at 1400 °C for 3 hours to obtain TiC _0.5 O _0.5 and put into a chlorination reactor. The first electrolytic cell uses NaCl-AlCl ₃ eutectic salt as electrolyte, the second electrolytic cell uses NaCl-KCl eutectic salt as electrolyte, and both electrolytic cells are protected by inert gas. During electrolysis, the temperature of the first electrolytic cell was controlled at 150°C, the cathode and anode were both made of graphite, and the current density was 0.5 and 1A/cm ² respectively; the temperature of the second electrolytic cell was controlled at 750°C, the anode was made of graphite, and the cathode was made of Metal nickel plate, the cathode and anode current densities are 1 and 2A/cm ² , respectively. After one electrolysis cycle is over, high-purity titanium metal is collected from the cathode nickel plate of the second electrolytic cell, and high-purity titanium powder or crystal is obtained through pickling, water washing, drying, packaging, etc., from the cathode of the first electrolytic cell. Collection of metal aluminum.

Example 2

Titanium dioxide and graphite powder were uniformly mixed according to a mass ratio of 40:15, then pressed and formed, and vacuum sintered at 1600 °C for 2 hours to obtain TiC _0.25 O _0.75 and put into a chlorination reactor. The first electrolytic cell uses NaCl-MgCl ₂ -AlCl ₃ eutectic salt as electrolyte, the second electrolytic cell uses NaCl-LiCl-KCl eutectic salt as electrolyte, and both electrolytic cells are protected by inert gas. During electrolysis, the temperature of the first electrolytic cell was controlled at 550°C, the cathode and anode were both made of graphite, and the current density was 0.5 and 1.5A/cm ² respectively; the temperature of the second electrolytic cell was controlled at 600°C, the anode was made of graphite, and the cathode was made of graphite Titanium plate was used, and the current densities of cathode and anode were 0.5 and 1A/cm ² , respectively. After one electrolysis cycle is over, high-purity titanium metal is collected from the cathode nickel plate of the second electrolytic cell, and high-purity titanium powder or crystals are obtained through pickling, water washing, drying, packaging, etc., and collected from the cathode of the first electrolytic cell. Magnesium-aluminum alloy.

Example 3

Titanium dioxide and graphite powder were uniformly mixed in a mass ratio of 40:12, then pressed into shape, and sintered at 1300°C in nitrogen atmosphere for 3 hours to obtain TiC _0.2 O _0.2 N _0.6 and put into a chlorination reactor. The first electrolytic cell uses LiCl-KCl eutectic salt as electrolyte, the second electrolytic cell uses NaCl-CaCl eutectic salt as electrolyte, and both electrolytic cells are protected by inert gas. During electrolysis, the temperature of the first electrolytic cell was controlled at 750°C, the cathode and anode were both made of graphite, and the current densities were 0.2 and 1.5A/cm ² respectively; the temperature of the second electrolytic cell was controlled at 800°C, the anode was made of graphite, and the cathode was made of graphite The metal nickel plate was used, and the current densities of the cathode and anode were 0.5 and 1.5 A/cm ² , respectively. After one electrolysis cycle is over, high-purity titanium metal is collected from the cathode nickel plate of the second electrolytic cell, and high-purity titanium powder or crystals are obtained through pickling, water washing, drying, packaging, etc., and collected from the cathode of the first electrolytic cell. Potassium metal.

Of course, the present utility model can also have various embodiments, without departing from the technical essence of the present utility model, those skilled in the art can make various corresponding changes and modifications according to the disclosure of the present utility model, but these Corresponding changes and deformations should belong to the protection scope of the appended claims of the present utility model.

Claims (4)

1. a kind of electrolysis-chlorination-electrolytic preparation pure titanium device, which is characterized in that including the first electrolytic cell, the second electrolytic cell, Chlorination reactor and gas-guide tube；

Wherein, the first electrolytic cell (1) and the second electrolytic cell (2) are horizontally disposed, and chlorination reactor (3) is located at the first electrolytic cell (1) Porous ceramics partition (4) are arranged in the upper position of anode, bottom；

First gas-guide tube (5) is located at the anode position in the first electrolytic cell (1), and connect with chlorination reactor (3) bottom；Second Gas-guide tube (6) one end connects at the top of chlorination reactor (3), and the other end is located at the cathode site in the second electrolytic cell (2)；Third is led Tracheae (7) one end is located at the anode position in the second electrolytic cell (2), the first gas-guide tube in the other end and the first electrolytic cell (1) (5) it connects.

2. electrolysis as described in claim 1-chlorination-electrolytic preparation pure titanium device, which is characterized in that the first electrolytic cell (1) There are heating and temperature control system with the second electrolytic cell (2) bottom and surrounding, for controlling chlorination reactor (3) internal material temperature.

3. electrolysis as described in claim 1-chlorination-electrolytic preparation pure titanium device, which is characterized in that chlorination reactor (3) Shell material is steel, is lined with ceramic material；There are independent heating and temperature control system outside chlorination reactor (3), for controlling Chlorination reactor (3) internal material temperature processed.

4. electrolysis as described in claim 1-chlorination-electrolytic preparation pure titanium device, which is characterized in that gas-guide tube material is steel Material is lined with ceramics or polytetrafluoroethylene material.