A method and apparatus for the synthesis and purification of fiber-optic grade germanium tetrachloride

Abstract

This invention relates to a method and apparatus for the synthesis and purification of fiber-optic grade germanium tetrachloride. Hydrogen chloride and germanium powder react under pressure of 0.1–1 MPa and temperature of 200–400 °C, achieving an effective germanium conversion rate of 60–90%, yielding crude germanium tetrachloride gas. The crude germanium tetrachloride is then subjected to dust removal and deweighting treatment. The deweighting operation pressure is 0.1–0.3 MPa and the operating temperature is 82–123 °C. Non-condensable gases generated during deweighting are treated at -130–-80 °C to recover hydrogen chloride before being discharged. The deweighted material is then purified under pressure of 0.2–0.5 MPa and temperature of 103–143 °C to obtain 8N fiber-optic grade germanium tetrachloride product. The direct reaction of germanium powder and hydrogen chloride avoids the introduction of sulfuric acid and hydrochloric acid, reducing the generation of waste acid and salt, and improving the greenness of the production process. This invention achieves an effective germanium conversion rate of 80–95%, saving energy by ≥40% compared to traditional processes.

Description

Technical Field

[0001] This invention relates to a method and apparatus for the synthesis and purification of fiber-optic grade germanium tetrachloride. Background Technology

[0002] Germanium tetrachloride (GeCl4) is a colorless, fuming liquid commonly used in the production of high-purity germanium dioxide, high-purity germanium, and as a dopant in quartz optical fibers. With the development of modern communications, germanium tetrachloride, as an optical fiber dopant, offers advantages such as high transmission capacity, high refractive index, low dispersion, low loss, strong resistance to nuclear and electromagnetic radiation, and all-weather operation. These advantages significantly improve the performance and quality of optical fibers, leading to a rapid increase in the consumption of germanium in optical fiber manufacturing. In other words, without high-quality germanium tetrachloride, there can be no high-quality quartz optical fiber. The current required standard is the non-ferrous metals industry standard (YS / T13-2007). Based on the product purity and the proportion of metallic impurities, high-purity germanium tetrachloride is divided into three types: GeCl4-08 (impurities ≤2.0 ng / g; purity ≥99.999999%), GeCl4-07 (impurities ≤10 ng / g; purity ≥99.99999%), and GeCl4-05 (impurities ≤500 ng / g; purity ≥99.999%).

[0003] Chinese Patent 200810058153.6 discloses a method for producing germanium tetrachloride for optical fibers. The steps are as follows: adding hydrochloric acid and germanium tetrachloride in a volume ratio of 0.25-2.0:1 to a distillation kettle for distillation, or simultaneously distilling germanium tetrachloride while introducing HCl gas, until the distillation is completed. The distillation temperature is 76-80℃. The distilled solution is separated by a hydrochloric acid separator, and the resulting germanium tetrachloride solution is stored in a storage tank and allowed to stand for 36-72 hours before being discharged into an empty distillation kettle. The temperature of the germanium tetrachloride solution is raised to 70-75℃, and nitrogen gas is continuously introduced for 12-36 hours while being irradiated with an ultraviolet lamp. Finally, a rectification operation is performed at 76-80℃, and the product is transferred out.

[0004] Chinese patent CN 201210466977.3 proposes a production system for germanium tetrachloride for optical fibers, which greatly improves the distillation purity of germanium tetrachloride for optical fibers by setting up multiple distillation units.

[0005] Chinese patent CN2201611028826.4 proposes a process for purifying and preparing high-purity germanium tetrachloride by removing organic impurities. This method involves adding concentrated sulfuric acid to the crude germanium tetrachloride produced by chlorination distillation of germanium concentrate for initial distillation; adding analytical grade hydrochloric acid to the germanium tetrachloride produced by initial distillation and introducing chlorine gas for a first redistillation; redistilling the germanium tetrachloride produced by the first redistillation; adding concentrated sulfuric acid to the germanium tetrachloride produced by the second redistillation for a second digestion and distillation; and transferring the germanium tetrachloride produced by the second digestion and distillation to analytical grade concentrated sulfuric acid for further purification by heating and distillation. This method achieves efficient purification of germanium tetrachloride and further removal of organic impurities, solving the problem of substandard products produced when using conventional production processes to prepare high-purity germanium tetrachloride from germanium-containing lignite.

[0006] The above methods all use crude germanium tetrachloride, produced by the chlorination distillation of germanium concentrate, as raw material. Germanium tetrachloride is obtained through multiple distillations by adding concentrated sulfuric acid, concentrated hydrochloric acid, or by introducing chlorine or hydrogen chloride. The addition of concentrated sulfuric acid and concentrated hydrochloric acid places high demands on equipment materials, significantly increasing production costs and generating large amounts of waste acid, causing environmental pollution. Furthermore, repeated distillations result in high energy consumption.

[0007] To address the challenges in the synthesis and purification of germanium tetrachloride, there is an urgent need to develop a method that can remove hydrogen-containing and metallic impurities in a single step, thereby reducing the material requirements for equipment during the synthesis and purification processes, improving economic efficiency and the greenness of the production process, and simultaneously reducing energy consumption during the purification process. Summary of the Invention

[0008] To address the problems of existing technologies, this invention proposes a method and apparatus for the synthesis and purification of fiber-optic grade germanium tetrachloride. Germanium tetrachloride is prepared by reacting hydrogen chloride and germanium powder as raw materials, followed by dust removal, washing, and purification to obtain the germanium tetrachloride product. This invention avoids the introduction of sulfuric acid and hydrochloric acid, reducing the generation of waste acid and waste salt, and improving the greenness of the production process. It can effectively remove hydrogen-containing impurities and metallic impurities in a single step, avoiding the high energy consumption problem caused by repeated distillation in traditional processes. Furthermore, the use of a double-effect distillation process further saves energy. The single-step effective conversion rate of germanium in this invention is 80-95%, and the purified product is 8N fiber-optic grade germanium tetrachloride, achieving energy savings of ≥40% compared to traditional processes.

[0009] To achieve the above objectives, the present invention employs the following technical solution:

[0010] A method for synthesizing and purifying fiber-optic grade germanium tetrachloride includes the following steps:

[0011] (1) Hydrogen chloride and germanium powder are reacted under a pressure of 0.1-1 MPa and a temperature of 200-400℃ for 2-8 hours to obtain crude germanium tetrachloride gas; the molar ratio of hydrogen chloride to germanium powder is 4-12:1.

[0012] (2) After dust removal, the crude germanium tetrachloride is subjected to deweighting treatment; the deweighting operation pressure is 0.1~0.3MPa and the operation temperature is 82~123℃; the non-condensable gas generated during the deweighting process is discharged after recovering hydrogen chloride under the operation conditions of -130~-80℃, and the recovered hydrogen chloride is reused as raw material.

[0013] (3) The material after deweighting is subjected to pressure of 0.2-0.5 MPa and temperature of 103-143℃ to remove light impurities, and then refined under conditions of 0.1-0.4 MPa and temperature of 82-133℃ to obtain 8N fiber optic grade germanium tetrachloride product.

[0014] The present invention discloses a synthesis and purification apparatus for fiber-optic grade germanium tetrachloride, comprising a reactor R101, a cyclone separator CS101, a bag filter FF101, a spray tower T201, a light component removal tower T301, and a purification tower T401 connected in sequence; each of the spray tower T201, the light component removal tower T301, and the purification tower T401 is equipped with a reboiler; and each of the spray tower T201 and the purification tower T401 is equipped with a condenser at the top.

[0015] The reactor R101 has a raw material inlet at the bottom and a product outlet at the top, with the product outlet connected to a cyclone separator CS101. The cyclone separator CS101 has a material inlet and a material outlet, with the material inlet connected to the reactor R101 and the material outlet connected to a bag filter FF101. The bag filter FF101 has a material inlet and a material outlet, with the material inlet connected to the cyclone separator CS101 and the material outlet connected to a spray tower T201.

[0016] The spray tower T201 has a material inlet in the middle, a top outlet at the top, a reflux port and a spray liquid inlet at the upper part, a reboiler return port at the lower part, and a bottom outlet at the bottom. The material inlet connects to the bag filter FF101, the top outlet connects to the spray tower condenser E201, the reflux port and spray liquid inlet connect to the spray tower condenser E201, and the bottom outlet connects to the spray tower reboiler E202 in one direction and removes heavy impurities in the other. The spray tower condenser E201 has a material inlet, a gas phase outlet, and a liquid outlet. The liquid phase outlet has three branches: two return to the spray tower T201, one connects to the light condenser removal tower T301, and the gas phase outlet connects to the condenser E101. The condenser E101 has a material inlet, a liquid phase material outlet, and a gas phase material outlet. The material inlet connects to the spray tower condenser E201, the gas phase outlet produces non-condensable gas, and the liquid phase outlet produces hydrogen chloride for reuse. The spray tower reboiler E202 has a material inlet and a material outlet, both connected to the spray tower T201.

[0017] The light-light-removal tower T301 has a material inlet in the middle, a tower top outlet at the top, a reflux port at the upper part, a reboiler return port at the lower part, and a tower bottom outlet at the bottom. The material inlet is connected to the spray tower condenser E201, the tower top outlet and reflux port are connected to the reboiler E402 of the refining tower, and the tower bottom outlet is connected to the light-light-removal tower reboiler E301 and the refining tower T401 in one direction. The light-light-removal tower reboiler E301 has a material inlet and a material outlet that are both connected to the light-light-removal tower T301.

[0018] The refining tower T401 has a material inlet in the middle, a top outlet at the top, a reflux port at the upper part, a reboiler return port at the lower part, and a bottom outlet at the bottom. The material inlet is connected to the light component removal tower T301, the top outlet and reflux port are connected to the refining tower condenser E401, and the bottom outlet is connected to the reboiler E402 in one direction and heavy components in the other. The refining tower condenser E401 has a material inlet and a material outlet, both connected to the refining tower T401, and the material outlet is connected to 8N fiber optic grade germanium tetrachloride.

[0019] The reboiler E402 of the refining tower is equipped with a bottom material inlet of refining tower T401, a bottom material outlet of refining tower T401, a top material inlet of light component removal tower T301, and a top material outlet of light component removal tower T301. The bottom material inlet and bottom material outlet of refining tower T401 are both connected to refining tower T401. The top material inlet of light component removal tower T301 is connected to light component removal tower T301. The top material outlet of light component removal tower T301 is divided into two paths, one of which is connected to light component removal tower T301, and the other is used to collect light components.

[0020] Germanium powder is added to reactor R101, and then hydrogen chloride gas is gradually introduced. The hydrogen chloride and germanium powder react fully in reactor R101 to obtain crude germanium tetrachloride gas. The crude gas is collected and passes through cyclone separator CS101 and bag filter FF101 for dust removal before entering spray tower T201 to remove heavy impurities. The reaction pressure in reactor R101 is 0.1-1 MPa, the reaction temperature is 200-400℃, and the reaction time is 2-8 h.

[0021] The material at the top of the spray tower T201 is condensed and cooled by the spray tower condenser E201. Part of it is refluxed, part is returned to the spray tower T201 as spray liquid, and part enters the light impurity removal tower T301. The uncondensed gas phase is collected and enters the partial condenser E101 for deep condensation. Heavy impurities are collected from the bottom of the spray tower T201. The gas phase in the partial condenser E101 is collected as non-condensable gas, and the liquid phase is recycled as HCl raw material. The operating pressure of the spray tower T201 is 0.1~0.3MPa, and the operating temperature is 82~123℃. The operating temperature of the partial condenser E101 is -130~-80℃.

[0022] The operating pressure of the light-light removal tower T301 is 0.2-0.5 MPa, and the operating temperature is 103-143℃; the operating pressure of the refining tower T401 is 0.1-0.4 MPa, and the operating temperature is 82-133℃; the top temperature of the light-light removal tower T301 is ≥10℃ higher than the bottom temperature of the refining tower T401.

[0023] The specific explanation is as follows:

[0024] (1) Add germanium powder to reactor R101, and then gradually introduce hydrogen chloride gas. The hydrogen chloride and germanium powder react fully in reactor R101 to obtain crude germanium tetrachloride gas (containing germanium powder, hydrogen chloride, hydrogen, trichlorogermanium and other impurities). The crude gas is collected and enters spray tower T201 to remove heavy impurities after being removed by cyclone separator CS101 and bag filter FF101.

[0025] The reactor R101 has a reaction pressure of 0.1-1 MPa, a reaction temperature of 200-400℃, and a reaction time of 2-8 h.

[0026] The molar ratio of hydrogen chloride to germanium powder is 4 to 12:1.

[0027] The effective conversion rate of the germanium powder in a single step is 60%-90%.

[0028] (2) After the material at the top of spray tower T201 is condensed and cooled by spray tower condenser E201, part of it is returned to spray tower T201 as spray liquid, and part of it enters light impurity removal tower T301; the uncondensed gas phase is collected and enters the fractional condenser E101 for deep condensation, and heavy impurities are collected from the bottom of spray tower T201. The gas phase in fractional condenser E101 is collected as non-condensable gas (hydrogen chloride, hydrogen, etc.), and the liquid phase is recycled as HCl feedstock. The non-condensable gas generated during the heavy impurity removal process is discharged after recovering hydrogen chloride under operating conditions of -130 to -80℃, and the recovered hydrogen chloride is recycled as feedstock;

[0029] The spray tower T201 operates at a pressure of 0.1–0.3 MPa and a temperature of 82–123°C.

[0030] The operating temperature of the condenser E101 is -130 to -80℃.

[0031] (3) The material after being de-heavy in the spray tower T201 enters the light component removal tower T301; the gas phase at the top of the light component removal tower T301 enters the reboiler E402 of the refining tower for heat exchange, and part of it is used as reflux and part of it is collected as light components. The bottom of the light component removal tower T301 is collected and enters the refining tower T401; 8N fiber optic grade germanium tetrachloride product is collected at the top of the refining tower T401, and the bottom material enters the reboiler E402 of the refining tower for heat exchange and the heavy components are collected.

[0032] The operating pressure of the light-weight removal tower T301 is 0.2-0.5 MPa, and the operating temperature is 103-143℃.

[0033] The refining tower T401 operates at a pressure of 0.1–0.4 MPa and a temperature of 82–133 °C.

[0034] The top temperature of the light-light removal tower T301 is ≥10℃ higher than the bottom temperature of the refining tower T401.

[0035] The beneficial results of this invention are:

[0036] 1. By using germanium powder and hydrogen chloride to react directly, the introduction of sulfuric acid and hydrochloric acid is avoided, the generation of waste acid and waste salt is reduced, and the greenness of the production process is improved.

[0037] 2. It can effectively remove hydrogen-containing impurities and metal impurities in one step, and refine them into 8N fiber-optic grade germanium tetrachloride.

[0038] 3. This method avoids the high energy consumption problem caused by repeated distillation in traditional processes. At the same time, it adopts a double-effect distillation process, in which the top material of the light-light removal tower exchanges heat with the bottom material of the refining tower. Since it is a low-temperature distillation, this method can save energy consumption in both the bottom of the refining tower and the cooling consumption at the top of the light-light removal tower. The effective conversion rate of germanium in one step is 80-95%, and 8N fiber-optic grade germanium tetrachloride is obtained. Compared with traditional processes, it saves energy by ≥40%. Attached Figure Description

[0039] Figure 1 A schematic diagram of a method and apparatus for synthesizing and purifying fiber-optic grade germanium tetrachloride according to the present invention:

[0040] R101: Reactor; CS101: Cyclone Separator; FF101: Bag Filter; E101: Condenser; T201: Spray Tower; E201: Spray Tower Condenser; E202: Spray Tower Reboiler; T301: Light Oxygen Depletion Tower; E301: Light Oxygen Depletion Tower Reboiler; T401: Refining Tower; E401: Refining Tower Condenser; E402: Refining Tower Reboiler Detailed Implementation

[0041] This invention discloses a method and apparatus for synthesizing and refining fiber-optic grade germanium tetrachloride. Germanium tetrachloride is prepared by reacting hydrogen chloride and germanium powder as raw materials, followed by dust removal, washing, and refining to obtain the germanium tetrachloride product. This invention avoids the introduction of sulfuric acid and hydrochloric acid, reducing the generation of waste acid and waste salt, and improving the greenness of the production process. It can effectively remove hydrogen-containing impurities and metallic impurities in a single step, avoiding the high energy consumption problem caused by repeated distillation in traditional processes. Furthermore, the use of a double-effect distillation process further saves energy. The single-step effective conversion rate of germanium in this invention is 80-95%, and the refined product is 8N fiber-optic grade germanium tetrachloride, achieving energy savings of ≥40% compared to traditional processes.

[0042] like Figure 1 As shown, a synthesis and purification apparatus for fiber-optic grade germanium tetrachloride includes a reactor R101, a cyclone separator CS101, a bag filter FF101, a condenser E101, a spray tower T201, a spray tower condenser E201, a spray tower reboiler E202, a light-light-removal tower T301, a light-light-removal tower reboiler E301, a purification tower T401, a purification tower condenser E401, and a purification tower reboiler E402.

[0043] Reactor R101 has a raw material inlet at the bottom and a product outlet at the top, with the product outlet connected to cyclone separator CS101. Cyclone separator CS101 has a material inlet and a material outlet, with the material inlet connected to reactor R101 and the material outlet connected to bag filter FF101. Bag filter FF101 also has a material inlet and a material outlet, with the material inlet connected to cyclone separator CS101 and the material outlet connected to spray tower T201.

[0044] The spray tower T201 has a material inlet in the middle, a top outlet, a reflux port and a spray liquid inlet at the top, a reboiler return port at the bottom, and a bottom outlet. The material inlet connects to the bag filter FF101, the top outlet connects to the spray tower condenser E201, the reflux port and spray liquid inlet connect to the spray tower condenser E201, and the bottom outlet connects to both the spray tower reboiler E202 and heavy impurities. The spray tower condenser E201 has a material inlet, a gas phase outlet, and a liquid phase outlet. The material inlet connects to the spray tower T201, the liquid phase outlet is divided into three paths: two return to the spray tower T201, one connects to the light impurity removal tower T301, and the gas phase outlet connects to the partial condenser E101. The condenser E101 has a material inlet, a liquid material outlet, and a gaseous material outlet. The material inlet is connected to the spray tower condenser E201, the gaseous outlet collects non-condensable gas, and the liquid outlet collects hydrogen chloride for reuse. The spray tower reboiler E202 has a material inlet and a material outlet, both of which are connected to the spray tower T201.

[0045] The light component removal tower T301 has a material inlet in the middle, a top outlet at the top, a reflux port at the upper part, a reboiler return port at the lower part, and a bottom outlet at the bottom. The material inlet connects to the spray tower condenser E201, the top outlet and reflux port connect to the reboiler E402 of the refining tower, and the bottom outlet connects to both the light component removal tower reboiler E301 and the refining tower T401. The light component removal tower reboiler E301 has a material inlet and outlet both connected to the light component removal tower T301. The refining tower T401 has a material inlet in the middle, a top outlet at the top, a reflux port at the upper part, a reboiler return port at the lower part, and a bottom outlet at the bottom. The material inlet connects to the light component removal tower T301, the top outlet and reflux port connect to the refining tower condenser E401, and the bottom outlet connects to both the refining tower reboiler E402 and collects heavy components. The refining tower condenser E401 has a material inlet and a material outlet, both connected to the refining tower T401. One of the material outlets outputs 8N fiber optic grade germanium tetrachloride. The reboiler E402 of the refining tower has a material inlet for the bottom of the refining tower T401, a material outlet for the bottom of the refining tower T401, a material inlet for the top of the light component removal tower T301, and a material outlet for the top of the light component removal tower T301. The material inlet and outlet of the refining tower T401 are both connected to the refining tower T401. The material inlet of the top of the light component removal tower T301 is connected to the light component removal tower T301. The material outlet of the top of the light component removal tower T301 is divided into two paths: one path connects to the light component removal tower T301, and the other path outputs the light component.

[0046] The specific implementation method is as follows:

[0047] (1) Germanium powder is added to reactor R101, and then hydrogen chloride gas is gradually introduced. The hydrogen chloride and germanium powder react fully in reactor R101 to obtain crude germanium tetrachloride gas. The crude gas is collected and enters spray tower T201 to remove heavy impurities after being removed by cyclone separator CS101 and bag filter FF101.

[0048] The reactor R101 has a reaction pressure of 0.1-1 MPa, a reaction temperature of 200-400℃, and a reaction time of 2-8 h.

[0049] The molar ratio of hydrogen chloride to germanium powder is 4 to 12:1.

[0050] The effective conversion rate of the germanium powder in a single step is 60%-90%.

[0051] (2) After the material at the top of spray tower T201 is condensed and cooled by spray tower condenser E201, part of it is returned to spray tower T201, part of it is returned as spray liquid, and part of it enters light impurity removal tower T301; the uncondensed gas phase is collected and enters the partial condenser E101 for deep condensation, and heavy impurities are collected from the bottom of spray tower T201. The gas phase in partial condenser E101 is collected as non-condensable gas, and the liquid phase is recycled as HCl feedstock.

[0052] The spray tower T201 operates at a pressure of 0.1–0.3 MPa and a temperature of 82–123°C.

[0053] The operating temperature of the condenser E101 is -130 to -80℃.

[0054] (3) The material after heavy component removal in spray tower T201 enters light component removal tower T301. The vapor phase from the top of light component removal tower T301 enters the reboiler E402 of the refining tower for heat exchange, and part of it is used as reflux, while part is collected as light components. The bottom product of light component removal tower T301 enters the refining tower T401. 8N fiber optic grade germanium tetrachloride product is collected from the top of refining tower T401. The bottom product of refining tower T401 enters the reboiler E402 of the refining tower for heat exchange, while the other part is collected as heavy components.

[0055] The operating pressure of the light-weight removal tower T301 is 0.2-0.5 MPa, and the operating temperature is 103-143℃.

[0056] The refining tower T401 operates at a pressure of 0.1–0.4 MPa and a temperature of 82–133 °C.

[0057] The top temperature of the light-light removal tower T301 is ≥10℃ higher than the bottom temperature of the refining tower T401.

[0058] Example 1

[0059] The following is in conjunction with the appendix Figure 1 The present invention will be further described in detail below with reference to specific embodiments.

[0060] 1000g of germanium powder was added to reactor R101, and 2011g of high-purity hydrogen chloride was gradually introduced. The reactor pressure was controlled at 0.2MPa, the temperature at 200℃, and the reaction time at 8h, producing 1773g of germanium tetrachloride. The crude germanium tetrachloride product (germanium tetrachloride, germanium trichlorohydrogen, hydrogen, and hydrogen chloride) was collected, and after dust removal by cyclone separator CS101 and bag filter FF101, it entered spray tower T201 to remove heavy impurities. The operating pressure of spray tower T201 was 0.3MPa, and the operating temperature was 123℃. The material at the top of spray tower T201 was condensed and cooled by spray tower condenser E201. Part of the material was refluxed, part was returned to spray tower T201 as spray liquid, and part entered light impurity removal tower T301. The uncondensed gas phase was collected and entered fractional condenser E101 for deep condensation. Heavy impurities were collected from the bottom of spray tower T201. The condenser E101 operates at -80℃. After deep condensation in the condenser E101, the liquid phase is reused as HCl feedstock, and the gas phase is collected as non-condensable gas. The light component removal tower T301 operates at a pressure of 0.5 MPa and a temperature of 143℃. The gas phase from the top of the light component removal tower T301 enters the reboiler E402 of the refining tower for heat exchange; part of it is used as reflux, and part is collected as light components. The bottom product of the light component removal tower T301 enters the refining tower T401. The refining tower T401 operates at a pressure of 0.4 MPa and a temperature of 133℃. Fiber optic grade germanium tetrachloride is collected from the top of the tower, while the bottom product enters the reboiler E402 of the refining tower for heat exchange, and the other part is collected as heavy components.

[0061] The refining process described above can yield 1241g of 8N fiber-grade germanium tetrachloride, which can save 40% energy compared with traditional processes.

[0062] Example 2

[0063] 1000g of germanium powder was added to reactor R101, and 4022g of high-purity hydrogen chloride was gradually introduced. The reactor pressure was controlled at 0.6MPa, the temperature at 300℃, and the reaction time at 4h, producing 2215.9g of germanium tetrachloride. The crude germanium tetrachloride product (germanium tetrachloride, germanium trichlorohydrogen, hydrogen, and hydrogen chloride) was collected, and after dust removal by cyclone separator CS101 and bag filter FF101, it entered spray tower T201 to remove heavy impurities. Spray tower T201 operated at a pressure of 0.1MPa and a temperature of 82℃. The material at the top of spray tower T201 was condensed and cooled by spray tower condenser E201; part of it was refluxed, part was returned to spray tower T201 as spray liquid, and part entered light impurity removal tower T301. The uncondensed gas phase was collected and entered fractional condenser E101 for deep condensation. Heavy impurities were collected from the bottom of spray tower T201. The condenser E101 operates at -130℃. After deep condensation in the condenser E101, the liquid phase is reused as HCl feedstock, and the gas phase is collected as non-condensable gas. The light component removal tower T301 operates at a pressure of 0.2 MPa and a temperature of 103℃. The gas phase from the top of the light component removal tower T301 enters the reboiler E402 of the refining tower for heat exchange; part of it is used as reflux, and part is collected as light components. The bottom product of the light component removal tower T301 enters the refining tower T401. The refining tower T401 operates at a pressure of 0.1 MPa and a temperature of 82℃. Fiber optic grade germanium tetrachloride is collected from the top of the tower, while the bottom product enters the reboiler E402 of the refining tower for heat exchange, and the other part is collected as heavy components.

[0064] The described refining process yields 1883.5g of 8N fiber-grade germanium tetrachloride, achieving 41% energy savings compared to traditional processes.

[0065] Example 3

[0066] 1000g of germanium powder was added to reactor R101, and 6033.1g of high-purity hydrogen chloride was gradually introduced. The reactor pressure was controlled at 1MPa, the temperature at 400℃, and the reaction time at 2h, producing 2659.1g of germanium tetrachloride. The crude germanium tetrachloride product (germanium tetrachloride, germanium trichlorohydrogen, hydrogen, and hydrogen chloride) was collected, and after dust removal by cyclone separator CS101 and bag filter FF101, it entered spray tower T201 to remove heavy impurities. The operating pressure of spray tower T201 was 0.2MPa, and the operating temperature was 106℃. The material at the top of spray tower T201 was condensed and cooled by spray tower condenser E201. Part of the material was refluxed, part was returned to spray tower T201 as spray liquid, and part entered light impurity removal tower T301. The uncondensed gas phase was collected and entered fractional condenser E101 for deep condensation. Heavy impurities were collected from the bottom of spray tower T201. The condenser E101 operates at -100℃. After deep condensation in the condenser E101, the liquid phase is reused as HCl feedstock, and the gas phase is collected as non-condensable gas. The light component removal tower T301 operates at a pressure of 0.35 MPa and a temperature of 127℃. The gas phase from the top of the light component removal tower T301 enters the reboiler E402 of the refining tower for heat exchange; part of it is used as reflux, and part is collected as light components. The bottom product of the light component removal tower T301 enters the refining tower T401. The refining tower T401 operates at a pressure of 0.2 MPa and a temperature of 104℃. Fiber optic grade germanium tetrachloride is collected from the top of the tower, while the bottom product enters the reboiler E402 of the refining tower for heat exchange, and the other part is collected as heavy components.

[0067] The refining process described above can yield 2260.1g of 8N fiber-grade germanium tetrachloride, which can save 41% energy compared with traditional processes.

Claims

1. A method for synthesizing and purifying fiber-optic grade germanium tetrachloride, characterized in that: The steps include the following: (1) Add germanium powder to the reactor, and then gradually introduce hydrogen chloride gas. The hydrogen chloride and germanium powder react fully in the reactor to obtain crude germanium tetrachloride gas. The hydrogen chloride and germanium powder react under the conditions of pressure 0.1-1 MPa and temperature 200-400℃ for 2-8 hours to obtain crude germanium tetrachloride gas. The molar ratio of hydrogen chloride to germanium powder is 4-12:

1. (2) After the crude germanium tetrachloride gas is collected, it is separated by a cyclone separator and a bag filter and then enters a spray tower to remove heavy impurities for de-weighting treatment. The de-weighting operation pressure is 0.1-0.3 MPa and the operation temperature is 82-123℃. The non-condensable gas generated during the de-weighting process is discharged after recovering hydrogen chloride under the operation conditions of -130--80℃. The recovered hydrogen chloride is reused as raw material. (3) The material after deweighting is subjected to pressure of 0.2-0.5 MPa and temperature of 103-143℃ to remove light impurities, and then refined at 0.1-0.4 MPa and temperature of 82-133℃ to obtain the product; (4) 8N fiber-grade germanium tetrachloride product GeCl4-08 was prepared, with impurities ≤2.0 ng / g and purity ≥99.999999%.

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