29results about "Germanium halides" patented technology

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 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 relates to a method for recovering germanium in germanium distillation raffinate and carrying out gradient purification and impurity removal, belongs to the technical field of germanium distillation raffinate resource recovery, and aims at the characteristics that impurity ions in the germanium distillation raffinate are high in concentration, and germanium and impurities are difficult to effectively separate due to similar properties. Short-process efficient and high-purity productization recovery of germanium in the germanium distillation residual liquid is realized by adopting a pretreatment-ion exchange-chlorination distillation technical route, and comprehensive recovery and resource utilization of lead, chlorine, zinc and the like in the germanium distillation residual liquid are realized by adopting an acidification lead precipitation-negative pressure distillation-neutralization impurity removal technical route. According to the method, the high-purity GeCl4 product is directly extracted and produced from the germanium-containing wastewater by adopting chemical modification and ion exchange methods, and compared with the existing process, the method has the technical advantages of high comprehensive utilization rate, short-range high efficiency, greenness, cleanness and the like.

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.

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.

A system and method for preparing germanium tetrafluoride through direct fluorination of fluorine gas comprises an adsorption tank, the bottom of the adsorption tank receives raw material gas, the top of the adsorption tank is connected with the bottom of a buffer tank through a pipeline, the bottom of the buffer tank receives helium gas, the top of the buffer tank is connected with a fluorination reactor through a pipeline, and a stock bin is installed on the fluorination reactor. The fluorination reactor is further connected with a precooler through a pipeline, and a filter is arranged on the connecting pipeline; the precooler, the first-stage condenser, the second-stage condenser, the third-stage condenser, the impurity removal adsorption tank, the flash tower and the finished product tank are sequentially connected end to end; the preparation method comprises a fluorine gas pretreatment process; a fluorination reaction process; and purifying and collecting. According to the method, germanium tetrafluoride in an effective reaction time period is collected to obtain a product with relatively high purity, and the purity of crude germanium tetrafluoride is high.

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 application discloses a method for recovering germanium by means of joule heat chlorination of germanium-containing fly ash, and relates to the technical field of resource recovery, comprising the following steps: mixing germanium-containing fly ash, a solid chlorinating agent and a conductive additive to obtain uniform reaction materials; pressing the reaction materials to form a porous conductive reaction body, and placing the porous conductive reaction body in a joule heat reaction device; making the porous conductive reaction body generate joule heat by electrification, and making the reaction materials generate a chlorination reaction in a chlorine-containing reaction atmosphere and generate gaseous germanium chloride; and setting a temperature gradient regulation zone inside the joule heat reaction device along the gas flow direction, so that the gaseous germanium chloride migrates along the direction of temperature reduction in the temperature gradient regulation zone and maintains a gas phase transport state; by means of the steady-state regulation of the path temperature gradient and the joule heat driving of the porous conductive reaction body, and in combination with the temperature difference induced condensation of the trapping interface, the gaseous germanium chloride is realized to be directionally transported and recovered and enriched without increasing complex gas separation equipment.

The invention belongs to the technical field of gas purification, and particularly relates to a method for reducing hydrogen fluoride in germanium tetrafluoride. The method comprises the steps that S1, a reactor filled with germanium oxide and activated carbon mixed filler is purged with hydrogen, the hydrogen and germanium oxide are subjected to an oxidation-reduction reaction, and germanium oxide is reduced into metal germanium; s2, purging the reduced mixed filler in the reactor with nitrogen, and vacuumizing the reactor; and S3, introducing a hydrogen fluoride-containing germanium tetrafluoride raw material into the mixed filler in the step S2, reacting hydrogen fluoride in the raw material germanium tetrafluoride with germanium, converting into germanium tetrafluoride, and collecting the germanium tetrafluoride. The method is simple in process and capable of realizing large-scale production, realizes efficient removal of HF in germanium tetrafluoride, has high purity, low cost and environmental friendliness, and meets the production requirements of semiconductor-grade GeF4.

The invention relates to a method for recovering germanium and chlorine from germanium deep processing chlorine-containing germanium slag, and belongs to the technical field of chlorine-containing germanium slag treatment.According to the method, the germanium in the chlorine-containing germanium slag is efficiently recovered by adopting a two-section countercurrent alkaline leaching-ion exchange separation and enrichment combined process, the germanium is recovered as a high-quality and high-purity GeCl4 product, the germanium recovery process is greatly simplified, and the production cost is reduced. And the problems of difficulty in recovery and low recovery rate when the germanium in the chlorine-containing germanium slag is converted into another germanium solid enrichment from the chlorine-containing germanium slag in the prior art are solved. Chlorine is produced in the form of hydrochloric acid and used in the process, and the problems of corrosion and pollution of chlorine in the chlorine-containing germanium slag treatment process are solved.

The invention relates to a germanium isotope separation method, device and system. According to the germanium isotope separation method, device and / or system, the problems that in the prior art, a germanium isotope separation method is small in scale, low in production efficiency, incapable of achieving continuous production, not suitable for industrial application and the like are solved through a chemical exchange method.

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 provides a method and a device for removing hydrogen fluoride impurities in a germanium fluorination process. The method comprises the following steps: obtaining fluorine gas containing the hydrogen fluoride impurities; the fluorine gas containing the hydrogen fluoride impurities is subjected to adsorption treatment, part of the hydrogen fluoride impurities are removed, and primarily treated fluorine gas is obtained; reacting the primarily treated fluorine gas with germanium powder to obtain germanium tetrafluoride gas containing hydrogen fluoride impurities; the germanium tetrafluoride gas containing the hydrogen fluoride impurities is sequentially subjected to condensation, flash purification, recondensation and adsorption treatment, purified target germanium tetrafluoride gas is obtained, and the hydrogen fluoride content in the target germanium tetrafluoride gas is lower than a preset value. According to the scheme, the hydrogen fluoride impurity in the germanium tetrafluoride gas can be efficiently removed.

The germanium-containing material pretreatment device comprises a reaction kettle, a material inlet and a tail gas outlet are formed in one side of the top of a kettle body of the reaction kettle, the tail gas outlet is communicated with a vertically upward exhaust pipe, and a strong oxidant inlet is formed in the other side of the top of the kettle body; the treatment kettle is arranged at a position at least 3m away from the reaction kettle, a discharge port at the bottom of the treatment kettle is communicated with a material pipeline and is provided with a material speed control valve, the material pipeline is communicated to a material inlet of the reaction kettle, a camera is arranged beside the material inlet of the reaction kettle, and the camera is connected with a computer or a mobile phone through a wifi signal; the strong oxidant inlet is connected into a strong oxidant pipeline, and the pipeline is provided with a strong oxidant speed control valve and a flowmeter. The device can prevent materials from being pumped away by tail gas, so that the feeding size is more uniform. During operation, a worker does not need to observe the reaction condition in the kettle at a kettle opening, but remotely observes the reaction condition by linking the camera with a mobile phone of the worker, remotely controls the feeding speed of materials and strong oxidants, reduces the material loss and improves the safety.

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.

A method of forming a combinatorial mixed halide perovskite library can include depositing an array of halide perovskite particles on a substrate. The method further includes exposing the array of halide perovskites to a laser to from defects in each of or a selected portion of the halide perovskite particles. The exposure conditions are modified across the array to generate a variation of defect concentration in the halide perovskite particles in the array. The defect containing halide perovskites are then exposed to an ion exchange solution and either anion exchanged or cation exchanged to thereby form a mixed halide perovskite particle.

The invention relates to germanium tetrafluoride mixed gas and application in an ion implantation system, the mixed gas is filled in a fluid supply container, the container outputs the mixed gas containing germanium tetrafluoride and carrier gas in an ion implantation chamber, and the proportion of the carrier gas in the mixed gas is 10-20%. The proportion of the doped gas and each carrier gas is accurately optimized and designed, and the method can reduce the generation of fluoride and hydrogen fluoride when being applied to the ion implantation process, effectively inhibit the side reaction causing corrosion, and protect expensive ion source parts.

The invention relates to a method for generating HGeCl3 from the homogeneous gas phase reaction between GeCl4 and H2 according to (I).

The invention provides a 72GeF4 purification device and a purification process, and belongs to the technical field of 72GeF4 purification. The 72GeF4 purification device comprises a filler rectifying tower, a condensation unit and a storage unit, the filler rectifying tower comprises a tower body, a reboiler, a condenser and filler, the reboiler is located at the bottom of the tower body, the condenser is located at the top of the tower body, the filler is located in the tower body, and the surface of the filler is provided with germanium metal; a gas inlet of the condensing unit is communicated with a discharge hole in the top of the tower body, and the condensing unit is configured to be capable of collecting liquid 72GeF4 and also capable of gasifying the collected liquid 72GeF4; and the storage unit is communicated with a gas outlet of the condensation unit so as to collect and store gaseous 72GeF4. By means of the purification device, high-abundance 72GeF4 can be used as a raw material, and high-abundance and high-purity 72GeF4 can be prepared from the high-abundance 72GeF4.

The utility model discloses a device for improving the germanium deposition rate of residual acid, and belongs to the technical field of germanium tetrachloride production processes. The device comprises a carbon steel lining teflon jacket kettle, the carbon steel lining teflon jacket kettle comprises an inner kettle and a jacket, the inner kettle is arranged in the jacket, a gap is reserved between the outer wall of the inner kettle and the inner wall of the jacket, the top of the inner kettle is sealed through a flange cover, a residual acid inlet, a tail gas outlet and an observation hole are formed in the flange cover, and a residual acid outlet is formed in the middle of the side face of the inner kettle. A material outlet is formed in the bottom of the inner kettle, cooling water outlets are formed in two sides of the jacket, and a cooling water inlet is formed in the bottom of the jacket. The device can prevent high-temperature, volatile and highly corrosive germanium tetrachloride-containing residual acid from volatilizing into a tail gas absorption tower, can also prevent economic loss caused by volatilization of germanium tetrachloride due to corrosion and damage of a container, and can quickly lower the temperature of the residual acid to quickly separate out germanium tetrachloride and improve the re-evaporation recovery rate; and the risk that the germanium tetrachloride-containing residual acid volatilizes in the air to damage the environment and hurt people can be prevented.

The invention discloses a method for directly preparing germanium tetrachloride from germanium tannate, which comprises the following steps: in an inert gas protection atmosphere, carrying out direct chlorination reaction on dried germanium tannate and a chlorinating agent at the reaction temperature of 200-350 DEG C, trapping a gas-phase product, separating and purifying to obtain germanium tetrachloride. According to the method, the traditional calcining step is omitted, the reaction period is greatly shortened, the preparation process is simplified, the equipment investment and the operation cost are reduced, meanwhile, the yield and the purity of germanium tetrachloride are improved, and the purposes of saving energy, reducing consumption, reducing pollution, shortening the process and improving the germanium recovery rate are achieved; the method has the advantages of simple process, high efficiency, economy and easiness in industrial application.

The invention relates to a device for preparing germanium tetrafluoride through direct fluorination of fluorine and a using method, the device comprises a horizontal fluorination reactor, the middle of the horizontal fluorination reactor is connected with a storage bin, and a feeding ball valve is installed below the storage bin; the motor is connected with the horizontal fluorination reactor through a coupler, the motor drives the rotating shaft to rotate, and the shoveling plate is arranged on the rotating shaft; the discharge port is positioned right below the horizontal fluorination reactor; a gas outlet is formed above one side of the horizontal fluorination reactor and is connected with a filter, and a filter element is arranged in the filter. The use method comprises the following steps: S1, opening the feeding ball valve, and adding germanium powder into the horizontal fluorination reactor from the storage bin; s2, fluorine gas enters a horizontal fluorination reactor from a gas inlet and reacts with germanium powder; s3, gas germanium tetrafluoride generated by the reaction is discharged through a gas outlet; and S4, opening the discharge port, and discharging unreacted germanium powder and impurities from the discharge port. The effect of removing impurities and solid materials in the fluorination reactor is achieved.

The invention discloses a device and a method for multi-stage flash evaporation purification of germanium tetrafluoride. The device comprises an impurity removal adsorption tank and a flash evaporation tower, the impurity removal adsorber is connected with a flash tower; the flash tower is connected with a first constant-temperature cold bath device, a second constant-temperature cold bath device and a third constant-temperature cold bath device; the impurity removal adsorption tank and the flash tower are connected with a vacuum pump; the flash tower comprises an upper section, a middle section and a lower end temperature control area; the impurity separation in germanium tetrafluoride is realized by simply setting temperature control interface parameters of the constant-temperature cold bath device and cooperating with the operation of the vacuum pump and the corresponding valve; by independently controlling the temperature of the three sections of the flash tower, impurities such as HF, N2 and O2 are effectively removed, a germanium tetrafluoride product with the purity of 3N is finally obtained, and the problem that germanium tetrafluoride is difficult to separate is solved.

The invention relates to a method for producing HGeCl3 from a homogeneous gas phase reaction between GeCl4 and H2 according to (I). # imgabs0 #

The invention discloses a novel high-purity germanium tetrafluoride synthesis process and a system thereof, and relates to the technical field of inorganic fluoride preparation. The invention discloses a synthesis process for synthesizing germanium tetrafluoride, which comprises the following steps: heating and reacting high-purity fluorine-containing mixed gas and high-purity germanium powder in a reaction kettle to prepare germanium tetrafluoride, and circularly freezing and purifying the prepared germanium tetrafluoride crude product to improve the purity of the product. According to the process, the conversion rate of the germanium powder can reach 99% or above, a germanium tetrafluoride product with the concentration reaching the 4N level is finally obtained, meanwhile, the discharged tail gas reaches the standard through an effective waste gas treatment system, and the environmental protection requirement is met.

The utility model discloses a device for removing hydrogen fluoride impurities in germanium tetrafluoride, and belongs to the technical field of inorganic chemical processes. The device comprises an adsorption tower, a microparticle filter, a pressure gauge, a thermometer and a tripod, the bottom of the adsorption tower is fixedly welded with the tripod, a feed port is formed in the top of the adsorption tower, a discharge port is formed in the bottom of the adsorption tower, and the feed port and the discharge port are connected and sealed through flanges. The microparticle filter bags are mounted on two sides of the adsorption tower through pipelines and are respectively provided with a gas outlet valve and a gas inlet valve; the pressure gauge and the thermometer are mounted on a flange of the feeding hole through pipelines and are respectively provided with a valve, and a probe rod of the thermometer extends to the bottom of the adsorption tower. The device can efficiently, simply, conveniently and safely remove hydrogen fluoride in germanium tetrafluoride, the product quality is improved, strong corrosion of hydrogen fluoride in germanium tetrafluoride to equipment such as detection equipment, valve pipelines and a rectifying tower is avoided, the problem that the pipelines and the valves are blocked is solved, and meanwhile the follow-up rectification purification pressure of germanium tetrafluoride is greatly relieved.

The invention provides a treatment method and device for a germanium-containing material, and the method comprises the following steps: an acid leaching process: carrying out acid leaching treatment on the germanium-containing material by using an acid solution in the presence of an auxiliary agent to obtain a germanium-containing leachate; an adsorption step in which the germanium element-containing leachate is brought into contact with an adsorbent resin for adsorption treatment to obtain a germanium element-loaded adsorbent resin; a desorption process: carrying out desorption treatment on the adsorption resin loaded with the germanium element to obtain a germanium-containing desorption solution; and an evaporation separation process: carrying out distillation treatment and rectification treatment on the germanium-containing desorption solution to obtain germanium tetrachloride. According to the method, the germanium product with relatively high purity can be obtained by simplifying the germanium enrichment process, and the production cost is reduced.

The present invention relates to a manufacturing method for producing HGeCl3 from a homogeneous gas phase reaction between GeCl4 and H2 according to the following equation: JPEG2025540419000007.jpg9170

The invention provides a purification method and device for removing non-condensable gas in germanium tetrafluoride. The purification method comprises the following steps: putting impurity-containing germanium tetrafluoride into a vacuum flash tower; raising the temperature of the flash tower to a first temperature, sublimating the impurity-containing germanium tetrafluoride into gas, and enabling the gas to enter a first condenser to obtain first germanium tetrafluoride; the first condenser is in a vacuum state, and the internal temperature is second temperature; after nitrogen with the preset concentration is used for purging the first condenser according to the preset flow for a first preset time, the first condenser is pumped to be in a preset vacuum state; raising the temperature of the first condenser to a first temperature, sublimating the first germanium tetrafluoride into gas, and enabling the gas to sequentially enter a second condenser and a third condenser to perform the same operation as the first condenser; finally, the germanium tetrafluoride gas enters a collecting tank, and purified germanium tetrafluoride is obtained. And the collection tank contains liquid nitrogen with a preset volume. The purification efficiency, the stability and the economical efficiency of removing the non-condensable gas in the germanium tetrafluoride can be improved.