45 results about "Germanium tetrachloride" patented technology

The invention provides a gradient recycling method for germanium, lead, zinc and iron in hard zinc slag, and belongs to the technical field of extraction of valuable elements in lead-zinc smelting waste. The method comprises the eight working procedures of reduction smelting, fuming volatilization, acid making, leaching, reduction germanium precipitation, two-stage pyrolysis, chlorination distillation and rectification, lead in the hard zinc slag can be recycled in the form of metal lead through reduction smelting, zinc and germanium are enriched in the form of smoke through fuming volatilization, iron is enriched in water-quenched slag, zinc and germanium are leached in a solution, then tannin is used for germanium precipitation, and after the tannin is used for germanium precipitation, the two-stage pyrolysis is carried out. According to the method, germanium can be completely enriched in tannin germanium residues, tannin germanium is pyrolyzed to obtain different products, a pyrolysis product washing is subjected to chlorination distillation to obtain crude germanium tetrachloride, and the crude germanium tetrachloride is rectified to obtain refined GeCl4. According to the method, the direct recovery rate of lead can reach 98%, the direct recovery rate of zinc can reach 96.92%, the recycling rate of iron can reach 99%, and the direct recovery rate of germanium can reach 95.04%.

The invention provides a preparation method of small-particle-size high-purity germanium dioxide, and relates to the technical field of new material preparation, and the preparation method comprises the following steps: S1, preparation of a hydrolysis solution, S2, spraying hydrolysis of germanium tetrachloride, S3, low-temperature aging, S4, solid-liquid separation and washing, and S5, high-temperature drying. The germanium dioxide production process is simple, low in cost and efficient, and the product is small in particle size and good in uniformity.

The invention discloses a method for preparing superfine high-purity germanium dioxide from germanium tetrachloride. The method comprises the following steps: step 1, preparing a reactor; step 2, preparing hydrolysis mother liquor; step 3, hydrolysis; step 4, suction filtration and washing; step 5, drying; and step 6, screening. According to the method for preparing the superfine high-purity germanium dioxide, the production efficiency of the superfine high-purity germanium dioxide can be effectively improved, and the superfine high-purity germanium dioxide is efficiently prepared by controlling the hydrolysis ratio, the acidity of hydrolysate, the germanium content, the temperature of the whole hydrolysis process, the hydrolysis rate and the stirring power.

The present invention belongs to the technical field of preparation of high-purity rare metal materials, and specifically relates to a method for preparing nano-scale high-purity germanium dioxide. High-purity germanium tetrachloride, polyvinyl alcohol solution and water are prepared, mixed and stirred to form a mixed solution, and then germanium dioxide is extracted through a hydrolysis reaction. The generated high-purity germanium dioxide is then strengthened by ultrasonic waves to prepare nano-scale germanium dioxide, thereby obtaining high-purity germanium dioxide with smaller particle size.

The invention relates to the technical field of preparation of germanium dioxide, in particular to a preparation method of ultra-pure germanium dioxide, which comprises the following steps: grinding a germanium ingot to obtain germanium powder; transferring the germanium powder into a closed reactor, introducing high-purity chlorine into the closed reactor, and fully reacting to obtain germanium tetrachloride; distilling and purifying germanium tetrachloride; adding ultrapure water into the purified germanium tetrachloride, fully stirring, standing, and filtering to obtain germanium dioxide precipitate; and cleaning, drying and calcining the germanium dioxide precipitate to obtain the ultra-high-purity germanium dioxide with the purity of 7N or above. Germanium dioxide obtained by the preparation method of ultra-pure germanium dioxide is high in purity and high in yield, the chlorine content is lower than 0.003%, and the preparation requirements of BGO crystals are met.

The invention provides a method for recycling valuable metal from germanium-antimony-tellurium alloy waste. The method comprises the three steps of surface treatment, chlorine reaction and compartment condensation and discharging. Oxidation films on the surfaces of the waste materials are removed through surface treatment, and the subsequent chlorine reaction efficiency is improved; then a self-made chlorination-step condensation integrated device is utilized, germanium, antimony and tellurium react with chlorine at the high temperature to generate gaseous chloride, step-by-step condensation separation is achieved through partition temperature control based on the boiling point difference of tellurium tetrachloride, antimony pentachloride and germanium tetrachloride, and target products are collected respectively; and finally, introducing inert gas to purge residual chlorine, and discharging safely. The method has the advantages of short process flow, no need of complex wet process steps and low equipment investment; metal chlorides are efficiently separated through the integrated device, and recovery is thorough; and the pyrogenic process is mainly adopted, no wastewater is generated, only tail gas is treated in a compliance manner, and the method is environment-friendly. Compared with a traditional wet process, the method has the remarkable advantages of high efficiency, low cost, environment friendliness and the like.

The present application belongs to the technical field of rare metal metallurgy, and particularly relates to a method and device for removing arsenic in germanium tetrachloride by hydrogen peroxide oxidation. The arsenic removal device comprises GeCl4, H2O2 and HCl storage containers, the storage containers are connected with a first reactor and a second reactor through pipelines, fourth, fifth, sixth, seventh and eighth valves are arranged on the pipelines, a first constant temperature heater is arranged at the lower part of the first reactor, a first mechanical stirrer is arranged at the top of the first reactor, a first residual liquid collector is connected with the bottom of the first reactor through a pipeline, and ninth and eleventh valves are arranged between the first reactor and the first residual liquid collector. Compared with the traditional chlorine arsenic removal method, the present application uses hydrogen peroxide to remove arsenic in germanium tetrachloride, is more environmentally friendly, safe, low-cost and does not bring new impurity elements, and the arsenic removal effect is very significant.

The invention provides a preparation method of high-purity germanium dioxide, and relates to the field of preparation and research of detectors, and the method comprises the following steps: S1, carrying out a hydrolysis reaction on germanium tetrafluoride gas, and adding dilute sulfuric acid into the generated germanium tetrafluoride hydrolysate to generate a germanium sulfate solution; s2, adding a sodium hydroxide solution into the germanium sulfate solution, and stirring to generate a sodium germanate solution; and S3, adding concentrated hydrochloric acid into the sodium germanate solution, carrying out chlorination distillation, stopping distillation when the distillation temperature of a fraction is greater than or equal to 110 DEG C to obtain a germanium tetrachloride fraction, cooling, hydrolyzing, filtering and drying to obtain the high-purity germanium dioxide. According to the preparation method disclosed by the invention, the hydrolysis loss of the germanium tetrachloride is effectively reduced, the distillation yield of the germanium tetrachloride is improved, so that the yield of the germanium dioxide is improved, other volatile substances are not introduced in the reaction process, other impurities are not introduced during distillation of the germanium tetrachloride, and the purity of the germanium dioxide product is effectively improved.

The invention provides a novel method for purifying crude germanium tetrachloride, which comprises the processes of first-stage low-temperature evaporation, second-stage medium-temperature evaporation, third-stage negative-pressure evaporation, recovery of germanium tetrachloride tailings and the like. In the staged evaporation process of first-stage low-temperature evaporation, second-stage medium-temperature evaporation and third-stage negative-pressure evaporation, low-boiling-point impurities (such as chlorine and other volatile impurities) in germanium tetrachloride can be effectively removed, germanium tetrachloride is separated and purified in different stages by gradually increasing the temperature and adjusting the pressure, and the purity of germanium tetrachloride is improved. Finally, germanium tetrachloride with the purity of 99.9% or above is obtained. According to the method, the introduction of chemical materials such as concentrated hydrochloric acid, chlorine and the like is avoided while the coarse germanium tetrachloride is fully and preliminarily purified, so that the safety and environmental risks are reduced; and the method has the remarkable advantages of good purification effect, environmental friendliness and the like.

The invention relates to a method for recovering germanium and regenerating mixed acid from zone-melting germanium ingot mixed acid cleaning fluid. The method comprises the following steps: (1) adding concentrated sulfuric acid with the concentration of 98% into germanium-containing fluorine-containing waste acid, and distilling to obtain germanium-containing concentrated liquor and regenerated mixed acid; new acid is added into the regenerated mixed acid, the ratio of hydrofluoric acid to nitric acid in the new acid is 1: 3, and the new acid is used for cleaning the zone-melting germanium ingot; (2) when F <-> in the germanium-containing concentrated liquor is greater than or equal to 0.5 g / L, returning to the step (1), continuously adding concentrated sulfuric acid with the concentration of 98%, and then distilling until F <-> in the germanium-containing concentrated liquor is less than 0.5 g / L; and (3) when F <-> in the germanium-containing concentrated liquor is less than 0.5 g / L, adding industrial hydrochloric acid into the germanium-containing concentrated liquor, and distilling to obtain a germanium tetrachloride product. According to the scheme provided by the invention, the germanium in the germanium-containing fluorine-containing waste acid is recovered, the process is short, the operation is simple and convenient, and the acid can be recycled.

The invention relates to a method for preparing high-purity germanium through reduction of hydrogen and germanium tetrachloride, and belongs to the technical field of high-purity metal material preparation. The method comprises the following steps: introducing vaporized germanium tetrachloride and preheated hydrogen from the top of a vertical quartz reaction tube, and mixing; the mixed gas downwards passes through a reaction zone, a concentric quartz ring tube bundle is arranged in the reaction zone, and the reaction zone is divided into an upper high-temperature reaction zone (1000-1150 DEG C), a middle medium-temperature deposition zone (600-850 DEG C) and a lower high-temperature melting zone (940-1000 DEG C) in the gas flow direction; gaseous germanium is condensed in the ring tube bundle in the middle deposition area to form solid germanium, and the solid germanium grows downwards to the lower melting area to be melted into liquid to drop and be collected; and treating the tail gas to recover germanium tetrachloride and hydrogen for recycling. Through the design of the annular tube bundle carrier and the temperature field, the deposition-melting dynamic process is achieved, reaction balance is broken, and the conversion per pass of germanium tetrachloride is increased to 70% or above.

The present invention discloses a short-process method for preparing high-purity germanium from germanium tetrachloride and treating tail gas in a cycle. The device for preparing high-purity germanium by short-process hydrogen reduction of germanium tetrachloride according to the present invention includes a gas storage tank, a high-purity germanium tetrachloride hydrogen reduction furnace, a reaction tail gas rectification system, and a germanium dichloride chlorination system. The method of the present invention is to use high-purity hydrogen to carry high-purity germanium tetrachloride into the reduction furnace for reaction to deposit germanium metal on germanium rods, and then perform zone melting purification according to purity requirements; the unreacted gas passes through the subsequent rectification and chlorination systems to obtain high-purity hydrogen and germanium tetrachloride again, realizing the treatment of tail gas in a cycle.

The invention provides a preparation method of germanium dioxide. The invention relates to a preparation method of germanium dioxide, which comprises the following steps: preparing a concentrated hydrochloric acid solution of germanium tetrachloride, and enabling the germanium tetrachloride in the mixed solution not to generate hydrolysis reaction; the mixed solution is electrolyzed, chlorine is generated by an anode, hydrogen is generated by a cathode, and the concentration of hydrochloric acid in the mixed solution is reduced; and when the concentration of the hydrochloric acid is reduced to a threshold value for promoting the germanium tetrachloride and the water to generate hydrolysis reaction, continuously reacting to enable the germanium tetrachloride and the water to react to generate germanium dioxide precipitate, and separating out the germanium dioxide precipitate after the reaction is finished. The concentration of the germanium tetrachloride is 0.76 mol / L. According to the method for preparing germanium dioxide by promoting germanium tetrachloride hydrolysis through electrolysis of concentrated hydrochloric acid, the situation that extra alkali is used for adjusting the reaction is avoided, the production cost and environmental pollution are reduced, and meanwhile the product purity and the production efficiency are improved.

The invention discloses a method for simultaneously extracting germanium and indium from a zinc sulfate solution containing germanium and indium, which comprises the following steps of: firstly, adding tartaric acid complexing germanium into a zinc sulfate leaching solution containing germanium and indium to obtain germanium tartrate, and then simultaneously extracting germanium and indium by using a kerosene mixed extracting agent of N235 and P204, then hydrochloric acid larger than 6N or a mixed solution of hydrochloric acid and chlorine salt is used for conducting reverse extraction on germanium and indium at the same time, after germanium and indium in reverse extraction liquid are enriched, chlorination of the reverse extraction liquid is conducted, germanium tetrachloride is distilled, hydrochloric acid is used for absorbing germanium tetrachloride, or purified water or dilute alkali liquor is used for absorbing and hydrolyzing germanium tetrachloride into germanium hydroxide or Ge02, and germanium is recycled through precipitation; the sponge indium in the distillation residual liquid is replaced by metal zinc or aluminum, so that the purposes of simplifying the process flow and improving the economic benefit are achieved.

The invention relates to a method for synchronously recovering germanium tetrachloride from a metal-state regenerated germanium raw material through oxychlorination, and belongs to the technical field of germanium extraction metallurgy. The method comprises the following steps: mixing a metal-state regenerated germanium raw material with hydrochloric acid in a chlorination distillation kettle, dropwise adding a hydrogen peroxide solution in sections to react with hydrochloric acid to generate a high-activity chlorine species, and directly oxidizing and chlorinating metal germanium to generate germanium tetrachloride. In the process, the reaction is a strong exothermic reaction, a product is distilled out by using heat released by the reaction, and the reaction temperature is controlled at 82-84 DEG C through a cooling medium. And after the reaction is basically completed, carrying out deep distillation through a heating medium, and finally condensing and collecting to obtain a germanium tetrachloride product. According to the method, a traditional multi-step process is integrated into one step, the process is short, alkali liquor does not need to be added, reaction heat is fully utilized, the energy-saving effect is remarkable, the germanium direct recovery rate is high, and the problems that a traditional method is long in process, high in energy consumption, large in auxiliary material consumption and low in direct recovery rate are effectively solved.

A control device for a germanium tetrachloride rectification reflux valve body comprises a horizontal bottom plate, a vertical fixing rod and a vertical supporting rod are fixed to the two sides of the bottom plate respectively, a wire coil is arranged at the top of the supporting rod and driven by a direct current motor to rotate, and a polytetrafluoroethylene traction belt is wound in the wire coil; spring hanging holes with different heights are formed in the upper parts of the fixing rods; two symmetrical bearings are arranged at the joint of the fixing rod and the bottom plate and connected with a cantilever arm, and the cantilever arm is connected with any spring hanging hole through a spring. The teflon traction belt is tied to the other end of the cantilever arm, and a permanent magnet is fixed to the middle of the cantilever arm. Input power required by the direct current motor is reduced, current during stalling is reduced, heat is reduced, coils are not easy to burn out, long-term stalling is realized without burning the direct current motor, the smaller the magnetic force of the coils in the direct current motor is, the demagnetization of the permanent magnets in the direct current motor is, and the system becomes reliable.

The invention discloses a method and device for extracting germanium from germanium tetrafluoride production tail gas absorption liquid, and belongs to the technical field of semiconductor germanium material production processes. The device comprises a concentration and distillation reaction kettle, a stirrer, a heater, a condenser, a multi-stage absorber, an air draft system and a spray tower. The device is used for stirring, concentrating and distilling for three times to extract germanium, the rotating speed of a stirrer for the first time is 60 r / min-200 r / min, the heating and distilling temperature is 90-100 DEG C, boric acid is added for the second time, the heating and distilling temperature is raised to 100-115 DEG C, industrial hydrochloric acid is added for the third time, and the distilling temperature is 100-120 DEG C. After concentration and distillation are completed, a concentrated solution is collected and sampled, the fluorine content and the germanium content in the concentrated solution are analyzed, and the result shows that the recovery rate of germanium in the method reaches 98% or above, and the fluorine content in germanium tetrachloride obtained through distillation is lower than 0.3% and does not exceed the requirement of the germanium tetrachloride product standard. And the method can be used for producing a high-purity germanium tetrachloride product in the next step of rectification and purification.

The invention discloses a preparation method of metal germanium. The preparation method comprises the following steps: primary crushing of raw materials; a germanium-containing material is selected and put into a ball mill to be smashed; adding alkali and leaching; adding alkali into the crushed germanium-containing material for leaching; roasting is performed; the germanium-containing material obtained after leaching is put into a roasting furnace to be roasted till the germanium-containing material becomes yellow; performing secondary crushing; taking out the roasted germanium-containing material, and further crushing in a Raymond mill; performing chlorination distillation; putting the crushed germanium-containing material into a closed reaction kettle, introducing chlorine, and distilling to obtain germanium tetrachloride; performing secondary distillation; putting germanium tetrachloride obtained by distillation into a closed reaction kettle, and adding 2N hydrochloric acid for secondary distillation; performing hydrolysis; putting the germanium tetrachloride subjected to secondary distillation into a reaction kettle, adding pure water, hydrolyzing, filtering and drying to obtain germanium dioxide; performing reduction; putting germanium dioxide into a closed quartz boat, heating to 1100 DEG C, and adding hydrogen and oxygen for reduction to obtain a germanium ingot; melting into a strip shape; performing ultrasonic detection to obtain a finished product.

The application discloses a method for directly preparing germanium tetrachloride from tannin germanium, which comprises the following steps: under the protection of an inert gas atmosphere, directly chlorinating dry tannin germanium with a chlorinating agent at a reaction temperature of 200-350 DEG C, capturing a gas phase product and separating and purifying the gas phase product to obtain germanium tetrachloride. The application omits a traditional calcination step, greatly shortens a reaction period, simplifies a preparation process, reduces equipment investment and operation cost, improves the yield and purity of germanium tetrachloride, realizes the goals of energy saving and consumption reduction, pollution reduction, process shortening and improved germanium recovery rate, and has the advantages of simple process, high efficiency and economy and easy industrial application.

The large rectifying tower comprises a tower kettle, a tower rod and a tower head which are sequentially connected from bottom to top, the top of the tower kettle is provided with a connector connected with the tower rod, the bottom of the tower kettle is provided with a liquid outlet, and the tower head is provided with an exhaust port and a product outlet. The tower kettle is an enamel kettle which has the capacity of 1000L and is provided with a heating temperature control device, and a feeding hole and a temperature sensor A are arranged at the top of the tower kettle; the tower pole is formed by connecting a plurality of temperature compensators in series; and a temperature sensor B is mounted at the bottom of the tower head. According to the utility model, the purification space is enlarged, the rectifying tower is enlarged, meanwhile, the large-scale and continuous production of germanium tetrachloride is realized by adopting the large-scale tower kettle capable of accurately controlling the heating temperature, and the tower pole is replaced by the temperature compensator consisting of the steel lining polytetrafluoroethylene and the polytetrafluoroethylene sieve plate, so that the temperature change in the tower pole is stabilized after the tower pole is heightened.

The present invention proposes a stepwise resource recovery method for germanium, lead, zinc and iron in hard zinc slag, and belongs to the technical field of valuable element extraction in lead and zinc smelting waste. The method of the present invention includes 8 steps of reduction smelting, fuming volatilization, acid production, leaching, reduction precipitation of germanium, two-stage pyrolysis, chlorination distillation and rectification. The reduction smelting can recover the lead in the hard zinc slag in the form of metallic lead, the fuming volatilization can enrich zinc and germanium in the form of smoke dust, the iron is enriched in the water-quenched slag, the zinc and germanium are leached into the solution, and then tannin is used to precipitate germanium, which can enrich all the germanium in the tannin germanium slag, the tannin germanium is pyrolyzed to obtain different products, the washing of the pyrolysis product is subjected to chlorination distillation to obtain crude germanium tetrachloride, and the crude germanium tetrachloride is rectified to obtain refined GeCl 4 In the present invention, the lead direct recovery rate can reach 98%, the zinc direct recovery rate can reach 96.92%, the iron resource utilization rate can reach 99%, and the germanium direct recovery rate can reach 95.04%.

The present invention discloses a method for efficiently enriching germanium by treating vortex furnace dust. The method comprises the following steps: (1) uniformly mixing vortex furnace dust containing germanium with a vulcanization accelerator to obtain a germanium-containing material; (2) volatilizing the germanium-containing material under a protective atmosphere at a temperature of 1000°C to 1200°C for 2 to 8 hours, collecting dust to obtain germanium-arsenic-rich dust and a volatilized residue; (3) subjecting the germanium-arsenic-rich dust to oxygen pressure leaching treatment, and performing liquid-solid separation to obtain a germanium-rich solution and a leaching residue; (4) adding concentrated hydrochloric acid to the germanium-rich solution to adjust the hydrochloric acid concentration to 8 to 10 mol / L, and distilling to obtain germanium tetrachloride and a distillation residue; (5) diluting the distillation residue to a hydrochloric acid solution concentration of 1 to 2 mol / L, and then returning the distillation residue to the oxygen pressure leaching process. The present invention successfully separates germanium and arsenic from vortex furnace dust by using an oxygen pressure leaching method, and converts arsenic into ferric arsenate. The hydrochloric acid consumption in the subsequent chlorination distillation process is greatly reduced through the above-mentioned pretreatment process, and the arsenic and ferric arsenate are returned to the oxygen pressure leaching arsenic and iron separation process to realize the closed-loop recycling of the chlorination distillation residue.

This invention discloses a method for recovering germanium and hydrochloric acid from germanium tetrachloride hydrolysis mother liquor, comprising the following steps: (1) Acidification: sulfuric acid is added to the hydrolysis mother liquor to increase its acidity, which is beneficial for the distillation of germanium tetrachloride; (2) Distillation: a negative pressure segmented distillation technique is adopted, with an operating pressure of -0.007 to -0.06 MPa and a time of 7 to 8 hours. Since the boiling point of germanium tetrachloride is 83.1℃ and the boiling point of hydrochloric acid is higher, germanium tetrachloride is preferentially distilled out during the distillation process, followed by concentrated hydrochloric acid, and finally dilute hydrochloric acid; (3) Wastewater treatment: the dilute hydrochloric acid is discharged into a wastewater treatment plant for wastewater treatment. This method for recovering germanium and hydrochloric acid from germanium tetrachloride hydrolysis mother liquor has high purity of distilled germanium tetrachloride and a comprehensive recovery rate of germanium greater than 99.5%. The entire process is simple to operate, requires less equipment investment, has low energy consumption, and causes less environmental pollution, making it suitable for large-scale production.

The invention discloses a method for efficiently removing arsenic from a crude germanium tetrachloride solution based on arsenic hydride reduction, and belongs to the technical field of rare and noble metal metallurgy. According to the method, arsenic hydride gas is introduced into a crude germanium tetrachloride solution containing arsenic impurities under the protection of inert atmosphere and under the mild condition of 20-80 DEG C; the arsenic hydride and arsenic compounds such as arsenic trichloride, arsenious acid and arsenic acid in the solution are subjected to selective reduction reaction to generate simple substance arsenic solid precipitate. Then a germanium tetrachloride solution subjected to deep arsenic removal can be obtained through simple solid-liquid separation operation, obtained arsenic-containing solids are washed and dried, and resource recycling of crude arsenic products is synchronously achieved. The method provided by the invention initiates a new arsenic removal path of reduction-precipitation, has the outstanding advantages of high arsenic removal efficiency, good selectivity, short process flow, no secondary pollution and capability of realizing arsenic resource utilization, and provides a brand new solution for green and efficient preparation of high-purity germanium tetrachloride.

This invention provides a method for recovering valuable metals from germanium-antimony-tellurium alloy waste, comprising three steps: surface treatment, chlorine reaction and compartment condensation, and discharge. Surface treatment removes the oxide film from the waste surface, improving the efficiency of the subsequent chlorine reaction. A self-made integrated chlorination-step condensation device is then used to react germanium-antimony-tellurium with chlorine at high temperature to generate gaseous chlorides. Based on the boiling point differences of tellurium tetrachloride, antimony pentachloride, and germanium tetrachloride, step-by-step condensation and separation are achieved through compartment temperature control, and the target products are collected separately. Finally, inert gas is introduced to purge residual chlorine, and the material is safely discharged. This invention features a short process flow, eliminates the need for complex wet processing steps, and requires low equipment investment. The integrated device efficiently separates metal chlorides, ensuring thorough recovery. Furthermore, it primarily uses pyrometallurgical methods, generating no wastewater and only requiring compliant tail gas treatment, making it environmentally friendly. Compared to traditional wet processes, it offers significant advantages such as high efficiency, low cost, and environmental friendliness.

The invention relates to a special storage device for high-purity germanium tetrachloride for optical fibers, which comprises a refrigeration temperature control device, an outer tank body, an inner tank body and a tank cover, a nitrogen cylinder cavity is arranged outside the inner tank body, and a nitrogen cylinder is arranged in the nitrogen cylinder cavity; a tank opening is formed in the top of the inner tank body; an air channel is formed in the outer top, close to the tank opening, of the inner tank body, an air hole communicated with the air channel and the interior of the inner tank body is formed in the inner tank body below the tank opening, and the air channel is communicated to a nitrogen cylinder in the nitrogen cylinder cavity through an air pipe; the inner tank body is arranged in the outer tank body and forms an interlayer, the refrigeration temperature control device is arranged in the refrigeration temperature control device cavity, and an evaporator copper pipe of the refrigeration temperature control device is arranged in the interlayer; and a product can be prevented from being in contact with the outside during taking and sampling.

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.

The invention relates to a method for recovering HCl and zinc sulfate from zinc and germanium-containing concentrate chlorination distillation residual liquid, which comprises the following steps: filtering distillation residues from the residual liquid, placing the residual liquid in a distillation kettle, adding concentrated sulfuric acid with the mass of more than or equal to 95% at the speed of 10-30mL / min, heating to 100 + / -10 DEG C, and carrying out a reaction of replacing hydrochloric acid with sulfuric acid to enable HCl gas and GeCl4 gas to escape, generating mixed replacement residual liquid containing sulfuric acid and zinc sulfate and calcium sulfate replacement residues; cooling escaped gas through a two-stage water-cooled snakelike coil pipe, obtaining hydrochloric acid of about 6N and GeCl4 liquid at the bottom at the first-stage cooling temperature of 60 + / -10 DEG C, obtaining hydrochloric acid of more than 7N at the second-stage cooling temperature of 30 + / -10 DEG C, leaching waste gas through clear water or dilute alkali liquor, and emptying; and filtering the sulfuric acid replacement hydrochloric acid residual liquid, feeding the obtained sulfuric acid and zinc sulfate mixed solution to a zinc hydrometallurgy system to recover sulfuric acid and zinc sulfate, and washing and drying calcium sulfate filter residues to obtain a gypsum product. According to the method, efficient recovery of HCl, zinc sulfate, gypsum and germanium tetrachloride is achieved, and zero discharge of waste liquid is achieved.

The utility model discloses a germanium tetrachloride tail gas treatment device which comprises a base, a support is installed at the top of the base, a first reaction bin is installed at the top of the support, and a guide assembly used for guiding tail gas to improve the contact effect of the tail gas and an alkaline solution is arranged in the first reaction bin. Spraying assemblies for spraying an alkaline solution into the first reaction bin are mounted on two sides of the first reaction bin; tail gas enters from the gas inlet pipe and then is exhausted from the first pipe body, the flow path of the gas in the first reaction bin is increased through the first partition plate and the second partition plate, an alkaline solution is sprayed to the gap between the first partition plate and the second partition plate, and the gap between the first partition plate and the second partition plate is an inevitable way for tail gas circulation. Therefore, the spraying liquid can be in uniform and sufficient contact with the tail gas, and the purification efficiency of the germanium tetrachloride tail gas is improved.

The invention relates to a use method of a storage device special for high-purity germanium tetrachloride for optical fibers. The use method comprises the following steps that S1, all parts of the device are cleaned and dried; s2, the device is assembled; comprising the following steps that B1, a refrigeration temperature control device is assembled and fixed in an outer tank body; b2, the upper outer tank body and the inner tank body are assembled and fixed; b3, assembling the inner tank body and the outer tank body; b4, filler is injected, and the tank body is fixed; and S3, the assembled tank body is verified, and final cleaning is conducted. The method comprises the following steps that C1, electrical connection is conducted; step C2, manual verification of inflation is carried out; step C3, automatically verifying inflation; step C4, verifying a gas wall; step C5, refrigeration temperature control verification; step C6, cleaning before filling; the method is combined with the storage device for use, and sealing and storage failures of the device can be avoided as much as possible.