CN116555597A - Short-process preparation of high-purity germanium from germanium tetrachloride and tail gas circulation treatment method - Google Patents

Abstract

The invention discloses a device for preparing high-purity germanium by a germanium tetrachloride short process and a tail gas circulation treatment method. The method comprises the steps of carrying high-purity germanium tetrachloride into a reduction furnace by utilizing high-purity hydrogen, carrying out reaction, depositing germanium metal on a germanium rod, and then carrying out zone melting purification according to the purity requirement; and (3) the gas which is not completely reacted passes through a subsequent rectification and chlorination system to obtain high-purity hydrogen and germanium tetrachloride again, so that tail gas recycling treatment is realized.

Description

A short process for preparing high-purity germanium by germanium tetrachloride and a tail gas circulation treatment method

technical field

The application of the present invention relates to the technical field of precious metals, in particular to a method for preparing high-purity germanium through a short process of germanium tetrachloride and tail gas circulation treatment.

Background technique

Germanium is an important element widely used in the semiconductor and electrical engineering industries, for example, as a material for the manufacture of infrared detectors, optical fiber devices, electronic devices, solar cells, etc. Due to the high refractive index and large absorption coefficient of germanium near the wavelength of 1.55 μm, the use of thin germanium films in photonic and telecom applications has steadily increased. In addition, the field of application of germanium is constantly expanding, due to its great application potential in, for example, lithium-ion batteries and solar cells. The increasing use of this element in various applications is driving the demand for high purity germanium.

Several processes are currently used to produce germanium. Conventional methods of depositing germanium on substrates include chemical vapor deposition (CVD) of digermane or germane and plasma enhanced chemical vapor deposition (13.56 MHz) of germane. In these studies, germane or digermane diluted with hydrogen was used as a precursor. Furthermore, germanium was prepared by disproportionation of germanium diiodide ( _GeI2 ) in many studies. The disadvantages of the above-mentioned method for preparing germanium are that germane and digermane are toxic and unstable, and that iodine is a reactive element.

The "chlorination-hydrolysis-reduction" smelting method generates germanium dioxide (GeO 2 ) through the hydrolysis of germanium tetrachloride (GeCl ₄ ), then reduces _{GeO 2 with} hydrogen and undergoes zone melting purification to obtain high-purity germanium. In the "chlorination-hydrolysis-reduction" method, the reduction production of germanium metal uses _GeO2 as raw material and is prepared by hydrogen reduction. The reduction of _GeO2 with hydrogen gas to obtain metal germanium is a distribution reaction. _GeO2 will be reduced to GeO first, and then reduced For Ge, the reduction reaction is as follows:

GeO ₂ +H ₂ =GeO+H ₂ O

GeO+H ₂ =Ge+H ₂ O

When the temperature reaches 700°C, GeO is volatile. Therefore, the reaction temperature is controlled at 600°C to 650°C. However, because the hydrolysis process is too long, it needs to go through steps such as hydrolysis, filtration, cleaning, calcination, grinding, and screening. There are disadvantages such as easy introduction of impurities to cause secondary pollution, and excessive investment in equipment and facilities.

In 2015, A. V. Kadomtseva studied the addition of copper nanoparticles to modify multi-walled carbon nanotubes for catalysis during the hydrogenation of germanium tetrachloride, and proposed the reaction mechanism of catalytic reduction of germanium tetrachloride and hydrogen. In 2016, A. V. Vorotyntsev studied the hydrogen reduction kinetics of germanium tetrachloride in the presence of pyrolytic tungsten, and provided the reaction activation energy data of the hydrogen reduction of germanium tetrachloride after adding the catalyst. In 2018, A. V. Kadomtseva discovered the existence of copper germanium by using hybrid catalysts in the comparative analysis of germanium tetrachloride hydrogen reduction to prepare germanium catalysts. In 2020, A.V. Kadomtseva developed a process for tungsten-catalyzed hydrogen reduction of germanium tetrachloride, which reduces the reaction temperature and the number of steps in the germanium preparation process. However, in the above-mentioned discovery inventions, there are by-products and the problem of subsequent tail gas treatment is not solved. Therefore, it is necessary to develop a method for preparing germanium in a short process of hydrogen reduction of germanium tetrachloride, which is green and environment-friendly and has higher economic benefits.

Contents of the invention

In order to solve or partially solve the problems existing in the related technology, the application of the present invention provides a short-process preparation of germanium tetrachloride to high-purity germanium and tail gas circulation treatment method, so that the reaction is more stable, and the possibility of introducing impurities in the reaction process is smaller. At the same time, the tedious step of hydrolyzing germanium tetrachloride into germanium dichloride is omitted, which reduces equipment cost investment, and by-products can be reused after treatment, saving costs and improving economic benefits.

The application of the present invention provides a short process for preparing high-purity germanium tetrachloride germanium and tail gas circulation treatment method, including the following steps:

S1. By controlling the flow rate of high-purity hydrogen, the high-purity germanium tetrachloride vapor is brought into the high-purity germanium tetrachloride hydrogen reduction furnace, and the reaction temperature is controlled by the controller to deposit metal germanium particles on the germanium pair rods, and the germanium pairs are collected. Metal germanium particles on the rod and purified by zone melting to obtain high-purity metal germanium;

Specifically, germanium tetrachloride reacts with hydrogen in the reduction furnace as follows:

GeCl ₄ +2H ₂ =Ge+4HCl

S2. The incompletely reacted germanium tetrachloride and hydrogen after the reaction is completed, the hydrogen chloride produced by the reaction and the by-product germanium dichloride are rectified and separated through the reaction tail gas rectification system, wherein the germanium tetrachloride and hydrogen are separated by rectification Sent to the reduction furnace again, the hydrogen chloride is treated with pure water, and the by-product germanium dichloride reacts with the chlorine gas provided by the chlorine gas storage tank through the germanium dichloride chlorination system, and the chlorination is germanium tetrachloride.

Further, the intake ratio of the high-purity hydrogen to the high-purity germanium tetrachloride steam is controlled at 10-30.

Further, the reaction temperature range of the high-purity germanium tetrachloride hydrogen reduction furnace is controlled at 700-900°C.

Further, the germanium tetrachloride, hydrogen, hydrogen chloride and germanium dichloride after the reduction reaction are cooled by the water-cooling system built into the reduction furnace, and then transported to the reaction tail gas rectification system.

Further, germanium tetrachloride and hydrogen in the tail gas are respectively transported to germanium tetrachloride hydrogen reduction furnace or respectively transported to germanium tetrachloride gas storage tank and Hydrogen storage tank.

Further, the germanium dichloride in the tail gas is sent to the germanium dichloride chlorination system after rectification, and the ratio of the chlorine gas provided by the chlorine storage tank to the germanium dichloride intake is controlled between 1 and 10, and the reaction occurs. Chlorination produces germanium tetrachloride.

Specifically, the following reactions occur:

GeCl ₂ +Cl ₂ =GeCl ₄

Further, the gas chlorinated by the germanium dichloride chlorination system returns to the reactive distillation system again, and the germanium tetrachloride is transported to the germanium tetrachloride gas storage tank after repeated rectification to reach the required purity , wherein the incompletely chlorinated germanium dichloride and chlorine are sent to the germanium dichloride chlorination system for further processing.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present application.

Beneficial technical effect of the present invention:

The present invention introduces elements in the short-process preparation of germanium tetrachloride to high-purity germanium and the tail gas circulation treatment method, only germanium, hydrogen, and chlorine are present. Compared with other germanium preparation methods, it is not easy to introduce other impurities to cause pollution, and the obtained product is improved. The purity of germanium metal.

Compared with the method using digermane or germane, the present invention has a more stable reaction, and compared with the "chlorination-hydrolysis-reduction" smelting method, the process of preparing germanium from germanium tetrachloride is optimized, and the hydrolysis into dichloride is omitted. The lengthy steps of germanium reduction reduce the investment in equipment costs.

The by-product germanium dichloride obtained in the process of reacting germanium tetrachloride and hydrogen in the present invention becomes the reactant germanium tetrachloride after separation and rectification through a chlorination system. The method enables by-products to be reused, thereby saving costs and improving economic benefits.

Description of drawings

Figure 1 is a process flow diagram of an embodiment of the present invention.

Detailed ways

Alternative embodiments of the present application will be described in more detail below with reference to the accompanying drawings. Although alternative embodiments of the present application are shown in the drawings, it should be understood that the present application can be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided to make the present application more thorough and complete, and to fully convey the scope of the present application to those skilled in the art.

The terms used in the present application are for the purpose of describing particular embodiments only, and are not intended to limit the present application. As used in this application and the appended claims, the singular forms "a", "the", and "the" are also intended to include the plural forms unless the context clearly dictates otherwise. It should also be understood that the term "and/or" as used herein refers to and includes any and all possible combinations of one or more of the associated listed items.

Below in conjunction with accompanying drawing, the present invention applies for germanium tetrachloride short flow process to prepare high-purity germanium and tail gas circulation treatment method to describe in detail, specifically as follows:

For more clarity, detailed description is given below through the following examples.

Example 1

The flow rate of high-purity hydrogen is controlled by controlling the flowmeter, and the ratio of high-purity germanium tetrachloride vapor and high-purity hydrogen obtained by multiple rectifications upstream is 1:15, and is brought into the high-purity germanium tetrachloride hydrogen reduction furnace. The reaction temperature is controlled at 800°C by the controller, and the gas is continuously fed for 8 hours to deposit metal germanium particles on the germanium rods, collect the metal germanium particles on the germanium rods and purify them by zone melting to obtain high-purity metal germanium; After the reaction is completed, the germanium tetrachloride hydrogen gas that has not completely reacted, the hydrogen chloride produced by the reaction has been separated by rectification for many times through the reaction tail gas rectification system, and the germanium tetrachloride and hydrogen gas are separated by rectification. Sent to the reduction furnace; hydrogen chloride is treated with pure water; the by-product germanium dichloride reacts with chlorine gas through the germanium dichloride chlorination system, the ratio of chlorine gas to germanium dichloride is 2:1, and the chlorination is tetrachloride germanium. It has been determined that the primary conversion rate of germanium prepared by the short process of hydrogen reduction of germanium tetrachloride is 23.82%.

Example 2

The flow rate of high-purity hydrogen is controlled by controlling the flowmeter, and the ratio of high-purity germanium tetrachloride vapor obtained by multiple rectifications upstream to high-purity hydrogen is 1:20, and is brought into the high-purity germanium tetrachloride hydrogen reduction furnace. The reaction temperature is controlled at 850°C by the controller, and the gas is continuously fed for 8 hours to deposit metal germanium particles on the germanium rods, collect the metal germanium particles on the germanium rods and purify them by zone melting to obtain high-purity metal germanium; After the reaction is completed, the germanium tetrachloride hydrogen gas that has not completely reacted, the hydrogen chloride produced by the reaction has been separated by rectification for many times through the reaction tail gas rectification system, and the germanium tetrachloride and hydrogen gas are separated by rectification. Sent to the reduction furnace; hydrogen chloride is treated with pure water; the by-product germanium dichloride reacts with chlorine gas through the germanium dichloride chlorination system, the ratio of chlorine gas to germanium dichloride is 1:1, and the chlorination is tetrachloride germanium. It has been determined that the primary conversion rate of germanium prepared by the short process of hydrogen reduction of germanium tetrachloride is 28.32%.

Example 3

The flow rate of high-purity hydrogen is controlled by controlling the flowmeter, and the ratio of high-purity germanium tetrachloride vapor obtained by multiple rectifications upstream to high-purity hydrogen is 1:20, and is brought into the high-purity germanium tetrachloride hydrogen reduction furnace. The reaction temperature is controlled at 875°C by the controller, and the gas is continuously fed for 10 hours to deposit metal germanium particles on the germanium rods, collect the metal germanium particles on the germanium rods and purify them by zone melting to obtain high-purity metal germanium; After the reaction is completed, the germanium tetrachloride hydrogen gas that has not completely reacted, the hydrogen chloride produced by the reaction has been separated by rectification for many times through the reaction tail gas rectification system, and the germanium tetrachloride and hydrogen gas are separated by rectification. Sent to the reduction furnace; hydrogen chloride is treated with pure water; the by-product germanium dichloride reacts with chlorine gas through the germanium dichloride chlorination system, the ratio of chlorine gas to germanium dichloride is 2:1, and the chlorination is tetrachloride germanium. It has been determined that the primary conversion rate of germanium prepared by the short process of hydrogen reduction of germanium tetrachloride is 28.44%.

Example 4

The flow rate of high-purity hydrogen is controlled by controlling the flowmeter, and the ratio of high-purity germanium tetrachloride vapor obtained by multiple rectifications upstream to high-purity hydrogen is 1:25, and is brought into the high-purity germanium tetrachloride hydrogen reduction furnace. The reaction temperature is controlled at 875°C by the controller, and the gas is continuously fed for 10 hours to deposit metal germanium particles on the germanium rods, collect the metal germanium particles on the germanium rods and purify them by zone melting to obtain high-purity metal germanium; After the reaction is completed, the germanium tetrachloride hydrogen gas that has not completely reacted, the hydrogen chloride produced by the reaction has been separated by the by-product germanium dichloride through the reaction tail gas rectification system, and the germanium tetrachloride and hydrogen gas are separated by rectification and separated again. Sent to the reduction furnace; hydrogen chloride is treated with pure water; the by-product germanium dichloride reacts with chlorine gas through the germanium dichloride chlorination system, the ratio of chlorine gas to germanium dichloride is 5:1, and the chlorination is tetrachloride germanium. It has been determined that the primary conversion rate of germanium prepared by the short process of hydrogen reduction of germanium tetrachloride is 31.82%.

Various embodiments of the present application have been described above, the above description is illustrative, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and alterations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principle of each embodiment, practical application or improvement of technology in the market, or to enable other ordinary skilled in the art to understand each embodiment disclosed herein.

Claims (7)

1. A method for preparing high-purity germanium and circularly treating tail gas by using germanium tetrachloride in a short process is characterized by comprising the following steps of: the method comprises the following steps:

s1, introducing high-purity germanium tetrachloride steam into a high-purity germanium tetrachloride hydrogen reduction furnace by controlling the flow rate of high-purity hydrogen, controlling the reaction temperature by a controller, depositing metal germanium particles on a germanium pair rod, collecting the metal germanium particles on the germanium pair rod, and purifying by zone melting to obtain high-purity metal germanium;

s2, rectifying and separating germanium tetrachloride and hydrogen which are not completely reacted after the reaction is finished, and reacting the generated hydrogen chloride and by-product germanium dichloride through a reaction tail gas rectifying system, wherein the germanium tetrachloride and the hydrogen are sent to a reduction furnace again after being rectified and separated, the hydrogen chloride is treated by pure water, and the by-product germanium dichloride reacts with chlorine provided by a chlorine storage tank through a germanium dichloride chlorination system to be chlorinated into germanium tetrachloride.

2. The method for circularly treating the high-purity germanium and tail gas prepared by the short-process germanium tetrachloride according to claim 1, which is characterized by comprising the following steps of: and the steam inlet ratio of the high-purity hydrogen to the high-purity germanium tetrachloride is controlled to be 10-30.

3. The method for circularly treating the high-purity germanium and tail gas prepared by the short-process germanium tetrachloride according to claim 1, which is characterized by comprising the following steps of: the reaction temperature range of the high-purity germanium tetrachloride hydrogen reduction furnace is controlled to be 700-900 ℃.

4. The method for circularly treating the high-purity germanium and tail gas prepared by the short-process germanium tetrachloride according to claim 1, which is characterized by comprising the following steps of: germanium tetrachloride, hydrogen chloride and germanium dichloride after the reduction reaction are cooled by a water cooling system of a reducing furnace and then conveyed to a reaction tail gas rectifying system.

5. The method for circularly treating the high-purity germanium and tail gas prepared by the short-process germanium tetrachloride according to claim 1, which is characterized by comprising the following steps of: after the germanium tetrachloride and the hydrogen in the tail gas are respectively rectified to reach the purities of the germanium tetrachloride and the hydrogen in feeding, the germanium tetrachloride and the hydrogen are transported to a germanium tetrachloride hydrogen reduction furnace or respectively transported to a germanium tetrachloride gas storage tank and a hydrogen gas storage tank.

6. The method for circularly treating the high-purity germanium and tail gas prepared by the short-process germanium tetrachloride according to claim 1, which is characterized by comprising the following steps of: germanium dichloride in the tail gas is sent to a germanium dichloride chlorination system after rectification, the inlet ratio of chlorine gas provided by a chlorine gas storage tank and germanium dichloride is controlled between 1 and 10, the reaction is carried out, and germanium tetrachloride is generated by chlorination.

7. The method for circularly treating the high-purity germanium and tail gas prepared by the short-process germanium tetrachloride according to claim 1, which is characterized by comprising the following steps of: and (3) returning the gas chlorinated by the germanium dichloride chlorination system to the reactive distillation system again, and conveying the germanium tetrachloride in the reactive distillation system to a germanium tetrachloride gas storage tank after the germanium tetrachloride reaches the required purity through repeated distillation, wherein incompletely chlorinated germanium dichloride and chlorine are conveyed to the germanium dichloride chlorination system for further treatment.