CN116555597A - Short-process preparation of high-purity germanium from germanium tetrachloride and tail gas circulation treatment method - Google Patents
Short-process preparation of high-purity germanium from germanium tetrachloride and tail gas circulation treatment method Download PDFInfo
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- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 71
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 40
- 230000009467 reduction Effects 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 8
- 238000004857 zone melting Methods 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- QHGIKMVOLGCZIP-UHFFFAOYSA-N germanium dichloride Chemical compound Cl[Ge]Cl QHGIKMVOLGCZIP-UHFFFAOYSA-N 0.000 claims description 34
- 238000006722 reduction reaction Methods 0.000 claims description 31
- 239000000460 chlorine Substances 0.000 claims description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 14
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 239000006227 byproduct Substances 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000066 reactive distillation Methods 0.000 claims 2
- 238000004821 distillation Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 14
- 238000000926 separation method Methods 0.000 description 9
- 229940119177 germanium dioxide Drugs 0.000 description 7
- 229910000078 germane Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- VXGHASBVNMHGDI-UHFFFAOYSA-N digermane Chemical compound [Ge][Ge] VXGHASBVNMHGDI-UHFFFAOYSA-N 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- ONJMCYREMREKSA-UHFFFAOYSA-N [Cu].[Ge] Chemical compound [Cu].[Ge] ONJMCYREMREKSA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IAGYEMVJHPEPGE-UHFFFAOYSA-N diiodogermanium Chemical compound I[Ge]I IAGYEMVJHPEPGE-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
- C01G17/04—Halides of germanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
- C22B7/002—Dry processes by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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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
Technical Field
The invention relates to the technical field of noble metals, in particular to a method for preparing high-purity germanium by a short-process germanium tetrachloride process and circularly treating tail gas.
Background
Germanium is an important element widely used in the semiconductor and electrical engineering industries, for example, as a material for manufacturing infrared detectors, optical fiber devices, electronic devices, solar cells, and the like. Due to the high refractive index and large absorption coefficient of germanium in the vicinity of wavelength 1.55 μm, the duty cycle for thin germanium films used in photonic and telecommunication applications is steadily increasing. In addition, the application field of germanium is expanding, as it has great application potential in, for example, lithium ion batteries and solar cells. The increasing use of this element in various fields of application has driven the need for high purity germanium.
There are several processes currently used to produce germanium. Conventional methods of depositing germanium on a substrate 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 precursor. Furthermore, in many studies, germanium was obtained by germanium diiodide (GeI 2 ) Disproportionation. The above-described method for preparing germanium has disadvantages in that germane and digermane are toxic and unstable, and iodine is a reactive element.
The smelting method of chlorination-hydrolysis-reduction is realized by germanium tetrachloride hydrolysis (GeCl) 4 ) Formation of germanium dioxide (GeO) 2 ) Reducing GeO with hydrogen 2 And obtaining high-purity germanium through a zone melting purification link. Reduction of germanium metal to GeO in the "chloridizing-hydrolyzing-reducing" process 2 Is prepared by hydrogen reduction, geO is reduced by hydrogen 2 The obtained metal germanium is distributed and reacted, geO 2 Firstly reducing to GeO and then reducing to Ge, wherein 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 ℃, geO is easy to volatilize. Therefore, the reaction temperature is controlled to be 600-650 ℃. However, the hydrolysis process is too long, and the steps of hydrolysis, filtration, cleaning, calcination, grinding, screening and the like are needed, so that the secondary pollution caused by easy introduction of impurities is caused, and the equipment and facilities are excessively input.
In 2015 A.V. Kadomtsiva, copper nano particles are added to modify multi-wall carbon nano tubes for catalysis in the germanium tetrachloride hydrogenation process, and a reaction mechanism of germanium tetrachloride and hydrogen catalytic reduction is proposed. The kinetics of hydrogen reduction of germanium tetrachloride in the presence of pyrolytic tungsten was studied in 2016 a.v. vorotysev, providing activation energy data for the reduction of germanium tetrachloride by hydrogen after the catalyst has been added. The presence of copper germanium was found in comparative analysis of germanium catalyst prepared by reduction of germanium hydrogen tetrachloride by using a hybrid catalyst in 2018 a.v. kadomtsiva. In 2020, kadomtsiva developed a process for catalyzing reduction of germanium tetrachloride by tungsten, which reduces the reaction temperature and the number of steps in the germanium preparation process. However, the above-mentioned findings have the problems of by-product generation and subsequent tail gas treatment. Therefore, a method for preparing germanium by reducing germanium tetrachloride hydrogen in a short process with higher economic benefit needs to be developed in an environment-friendly way.
Disclosure of Invention
In order to solve or partially solve the problems in the related art, the invention provides a method for preparing high-purity germanium by a short process of germanium tetrachloride and circularly treating tail gas, so that the reaction is more stable, the possibility of introducing impurities in the reaction process is smaller, the lengthy step of hydrolyzing the germanium tetrachloride into germanium dichloride is omitted, the investment of equipment cost is reduced, the byproducts can be reused after being treated, the cost is saved, and the economic benefit is improved.
The invention provides a method for circularly treating high-purity germanium and tail gas prepared by a germanium tetrachloride short process, which 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;
specifically, germanium tetrachloride reacts with hydrogen in a reducing furnace as follows:
GeCl 4 +2H 2 =Ge+4HCl
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.
Further, the steam inlet ratio of the high-purity hydrogen to the high-purity germanium tetrachloride is controlled to be 10-30.
Further, the reaction temperature range of the high-purity germanium tetrachloride hydrogen reduction furnace is controlled to be 700-900 ℃.
Further, 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.
Further, after the germanium tetrachloride and the hydrogen in the tail gas are respectively rectified to reach the purity of the germanium tetrachloride and the hydrogen in feeding, the germanium tetrachloride and the hydrogen are conveyed to a germanium tetrachloride hydrogen reduction furnace or respectively conveyed to a germanium tetrachloride gas storage tank and a hydrogen gas storage tank.
Further, 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 to be 1-10, the reaction is carried out, and germanium tetrachloride is generated by chlorination.
Specifically, the following reaction occurs:
GeCl 2 +Cl 2 =GeCl 4
further, the gas after chlorination of the germanium dichloride chlorination system is returned to the reaction rectification system again, germanium tetrachloride in the gas is conveyed into a germanium tetrachloride gas storage tank after the required purity is achieved through repeated rectification, and the incompletely chlorinated germanium dichloride and chlorine are conveyed to the germanium dichloride chlorination system for further treatment.
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 invention as claimed.
The beneficial technical effects of the invention are as follows:
according to the method, only germanium, hydrogen and chlorine ternary elements exist in the elements introduced in the short-process preparation of high-purity germanium by germanium tetrachloride and the tail gas circulation treatment method, and compared with other germanium preparation methods, other impurities are not easy to introduce to cause pollution, so that the purity of the obtained metal germanium is improved.
Compared with the method using the digermane or germane, the method has the advantages that the reaction is more stable, compared with the method of 'chlorination-hydrolysis-reduction', the flow of preparing germanium from germanium tetrachloride is optimized, the lengthy step of hydrolyzing to germanium dichloride is omitted, and the investment of equipment cost is reduced.
The germanium tetrachloride is treated by a chlorination system after separation and rectification to become a reactant germanium tetrachloride. The method can reuse the byproducts, save cost and improve economic benefit.
Drawings
FIG. 1 is a process flow diagram of one embodiment of the present invention.
Detailed Description
Alternative embodiments of the present application will be described in more detail below with reference to the accompanying drawings. While the drawings illustrate alternative embodiments of the present application, it should be understood that the present application may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The terminology used in the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any or all possible combinations of one or more of the associated listed items.
The method for preparing high-purity germanium and circularly treating tail gas by using the short-process germanium tetrachloride in the application of the invention is described in detail below by referring to the accompanying drawings, and is specifically as follows:
for clarity, the following examples are provided in detail.
Example 1
Controlling the flow rate of high-purity hydrogen by controlling a flow meter, bringing the high-purity germanium tetrachloride vapor obtained by repeated rectification on the upstream into a high-purity germanium tetrachloride hydrogen reduction furnace in a ratio of 1:15, controlling the reaction temperature to be 800 ℃, continuously introducing gas for 8 hours by 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; germanium tetrachloride hydrogen which is not completely reacted after the reaction is finished, and hydrogen chloride generated by the reaction is subjected to repeated rectification separation by a reaction tail gas rectification system, wherein the germanium tetrachloride and the hydrogen are sent to a reduction furnace again after the rectification separation; treating hydrogen chloride with pure water; the by-product germanium dichloride is reacted with chlorine through a germanium dichloride chlorination system, the ratio of the chlorine to the germanium dichloride is 2:1, and the germanium tetrachloride is obtained through chlorination. The primary conversion rate of germanium prepared by the short flow path of germanium tetrachloride reduction is 23.82 percent.
Example 2
Controlling the flow rate of high-purity hydrogen by controlling a flow meter, bringing the high-purity germanium tetrachloride vapor obtained by repeated rectification on the upstream into a high-purity germanium tetrachloride hydrogen reduction furnace with the ratio of 1:20, controlling the reaction temperature to 850 ℃, continuously introducing gas for 8 hours by 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; germanium tetrachloride hydrogen which is not completely reacted after the reaction is finished, and hydrogen chloride generated by the reaction is subjected to repeated rectification separation by a reaction tail gas rectification system, wherein the germanium tetrachloride and the hydrogen are sent to a reduction furnace again after the rectification separation; treating hydrogen chloride with pure water; the by-product germanium dichloride is reacted with chlorine through a germanium dichloride chlorination system, the ratio of the chlorine to the germanium dichloride is 1:1, and the germanium tetrachloride is obtained through chlorination. The primary conversion of germanium prepared by the short flow of germanium tetrachloride hydrogen reduction was determined to be 28.32%.
Example 3
Controlling the flow rate of high-purity hydrogen by controlling a flow meter, bringing the high-purity germanium tetrachloride vapor obtained by repeated rectification on the upstream into a high-purity germanium tetrachloride hydrogen reduction furnace in a ratio of 1:20, controlling the reaction temperature to 875 ℃ by a controller, continuously introducing gas for 10 hours, 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; germanium tetrachloride hydrogen which is not completely reacted after the reaction is finished, and hydrogen chloride generated by the reaction is subjected to repeated rectification separation by a reaction tail gas rectification system, wherein the germanium tetrachloride and the hydrogen are sent to a reduction furnace again after the rectification separation; treating hydrogen chloride with pure water; the by-product germanium dichloride is reacted with chlorine through a germanium dichloride chlorination system, the ratio of the chlorine to the germanium dichloride is 2:1, and the germanium tetrachloride is obtained through chlorination. The primary conversion of germanium prepared by the short flow of germanium tetrachloride hydrogen reduction was determined to be 28.44%.
Example 4
Controlling the flow rate of high-purity hydrogen by controlling a flow meter, bringing the high-purity germanium tetrachloride vapor obtained by repeated rectification on the upstream into a high-purity germanium tetrachloride hydrogen reduction furnace in a ratio of 1:25, controlling the reaction temperature to 875 ℃, continuously introducing gas for 10 hours by 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; germanium tetrachloride hydrogen which is not completely reacted after the reaction is finished, and hydrogen chloride generated by the reaction is subjected to repeated rectification separation by a reaction tail gas rectification system, wherein the germanium tetrachloride and the hydrogen are sent to a reduction furnace again after the rectification separation; treating hydrogen chloride with pure water; the by-product germanium dichloride is reacted with chlorine through a germanium dichloride chlorination system, the ratio of the chlorine to the germanium dichloride is 5:1, and the chlorine is chlorinated into germanium tetrachloride. The primary conversion rate of germanium prepared by the short flow of germanium tetrachloride hydrogen reduction is 31.82 percent.
The foregoing description of the embodiments of the present application is illustrative, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the improvement of technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments 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.
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| CN117107357A (en) * | 2023-10-23 | 2023-11-24 | 中铝科学技术研究院有限公司 | Germanium rod for vapor deposition, preparation method thereof and germanium tetrachloride reduction device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117107357A (en) * | 2023-10-23 | 2023-11-24 | 中铝科学技术研究院有限公司 | Germanium rod for vapor deposition, preparation method thereof and germanium tetrachloride reduction device |
| CN117107357B (en) * | 2023-10-23 | 2024-04-19 | 中铝科学技术研究院有限公司 | Germanium rod for vapor deposition, preparation method thereof and germanium tetrachloride reduction device |
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