32 results about "Germanium tetrachloride" patented technology

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 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 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 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.

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 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 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.

The invention relates to the technical field of metallurgy, in particular to a method for recovering zinc and germanium from germanium-containing zinc concentrate. The specific technical scheme is as follows: after pulpifying and grinding the zinc concentrate, directly carrying out leaching reaction under the conditions of high temperature and high pressure, carrying out settling separation on the reacted slurry, adding zinc and germanium in supernate, adding zinc oxide powder into the supernate for neutralization reaction, filtering to obtain neutralization liquid, adding zinc powder into the neutralization liquid for replacing germanium, and finally adding the zinc powder into the neutralization liquid for replacing germanium. And filtering to obtain germanium precipitation slag and a solution containing zinc and iron. Drying the germanium precipitation slag, performing chlorination distillation treatment to obtain germanium tetrachloride, and performing hydrolysis, filtration, drying and hydrogen high-temperature reduction on the germanium tetrachloride to obtain a metal germanium ingot; the zinc and iron-containing solution is subjected to iron removal, zinc powder replacement, electrolysis and casting to obtain a zinc ingot. According to the method, zinc and scattered metal can be directly leached into the solution to the maximum extent through oxygen pressure leaching, the leaching rate of zinc and germanium is high, the germanium recovery process of the whole process is short, and the recovery rate is high.

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.

To provide an apparatus for manufacturing an optical fiber porous preform without corroding the inside of the apparatus even when using a halogen based compound raw material as the raw material of glass fine particles.SOLUTION: In an apparatus for manufacturing an optical fiber porous preform, capable of depositing the optical fiber porous preform by hydrolyzing a halogen compound raw material, an internal structural material including a chamber housing or a part of a drive mechanism is constituted using valve single metal except aluminum and zinc or alloy using the valve metal except aluminum and zinc as a main body. The halogen compound raw material may be one or more selected from a group of silicon tetrachloride, trichlorosilane and germanium tetrachloride.SELECTED DRAWING: Figure 1

The utility model discloses a device for recovering crude germanium tetrachloride from germanium distillation residues, and relates to the technical field of germanium extraction. The device comprises a distillation kettle, a heating assembly is arranged in the distillation kettle, and a feeding assembly is further arranged at the top of the distillation kettle; the heating assembly comprises a steam box fixedly connected to the front end of the distillation still, rotating pipes are rotationally connected to the upper portion and the lower portion of the rear end of the steam box through rotating joints, and the rear ends of the rotating pipes rotationally penetrate through the rear end face of the steam box and fixedly communicate with the same connecting pipe through the rotating joints. The hollow plate is driven by the rotating pipe to rotate in the distillation kettle, and steam is provided for the interior of the hollow plate through the steam box, so that a mixture of germanium distillation residues and concentrated hydrochloric acid in the distillation kettle is heated and stirred, and the problem that the existing heating effect is not ideal is solved; and meanwhile, the germanium distillation residues are crushed through the rotation of the rotary drum and the crushing sleeve on the mounting rod, so that the problem that the germanium distillation residues are inconvenient to pretreat at present is solved.

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 utility model discloses a steam heating coil device and belongs to the technical field of processes for producing crude germanium tetrachloride by distilling germanium raw materials. The device comprises a flange joint, PVDF straight pipes, PVDF elbows and a fixing ring, a plurality of PVDF straight pipes and PVDF elbows are connected at intervals to form an annular U-shaped coil pipe, the fixing ring is in an annular cylinder shape and is provided with inserting holes matched with the PVDF straight pipes in number and diameter, each PVDF straight pipe is inserted into the corresponding inserting hole to enable the U-shaped coil pipe to be fixed in the fixing ring, and the PVDF straight pipes and the PVDF elbows are connected at intervals to form the annular U-shaped coil pipe. PVDF straight pipes are connected to the two ends of the U-shaped coil pipe in a hot melting mode to form an air inlet pipe and a water outlet pipe, and the ends of the air inlet pipe and the water outlet pipe are connected with a steam inlet and a cooling water outlet through flange connectors respectively. The device can be produced and maintained by itself, the production cost is reduced, direct hot melting connection is facilitated, and maintenance is convenient.

To provide a rutile-type germanium dioxide free-standing substrate and a method for producing the same, a rutile-type germanium dioxide template and a method for producing the same, a rutile-type germanium dioxide device wafer and a method for producing the same, a method for producing a germanium tetrachloride gas which can grow a rutile-type germanium dioxide crystal, a method for producing a rutile-type germanium dioxide monocrystal which can grow a rutile-type germanium dioxide crystal, and a device for producing a rutile-type germanium dioxide monocrystal which can grow a rutile-type germanium dioxide crystal.SOLUTION: A rutile-type germanium dioxide free-standing substrate comprises a rutile-type germanium dioxide monocrystal. In the germanium dioxide free-standing substrate, the planar density of macro defects appearing on the surface is 5000 / cm2 or less in at least a part of the plane.SELECTED DRAWING: None

The invention provides a germanium tetrachloride hydrolysis-germanium dioxide drying and calcining integrated device, and relates to germanium tetrachloride, the germanium tetrachloride hydrolysis-germanium dioxide drying and calcining integrated device comprises a hydrolysis reaction part, a sedimentation washing part and a drying and calcining part, and the hydrolysis reaction part, the sedimentation washing part and the drying and calcining part are sequentially connected from top to bottom to jointly form an integrated tower body; a mixing reaction cavity is formed in the hydrolysis reaction part, the top of the hydrolysis reaction part is connected with a gas input pipe and a liquid input pipe, and a stirring and mixing unit is arranged below the gas input pipe and the liquid input pipe. The core of the hydrolysis reaction part is provided with a composite stirring and mixing unit comprising a turbulent flow filter screen cylinder, a hollow self-suction turbine stirring piece and an outer turbulent flow stirring piece. In the working process, the hollow self-suction type turbine stirring piece rotates at a high speed, liquid can be sheared violently, germanium tetrachloride liquid can be sucked from the position above the liquid level and dispersed into fine bubbles, and the contact area of the gas phase and the liquid phase is greatly increased.

Embodiments of the present disclosure generally relate to the field of semiconductor manufacturing processes, more particularly, to precursor chemistries and methods of depositing silicon-containing films for forming semiconductor devices. In one or more embodiments, a method includes co-flowing a silicon-containing precursor with a dopant precursor into a processing chamber at a temperature of 600 °C or less to deposit an epitaxial layer over a substrate disposed within the processing chamber. The silicon-containing precursor is selected from a list consisting of silane (SiH4), disilane (Si2H6), trisilane(Si3H8), tetrasilane (Si4H10), monochlorotrisilane (Si3H7CI), diiodosilane (SiH2l2), and dibromosilane (SiH2Br2). The dopant precursor selected from a list consisting of phosphine (PH3), phosphorus trichloride (PCI3), phosphorus tribromide (PBr3), tert-butylphosphine (TBP), tri-tert-butylborane ((tBu)3B), tert-butylarsine (TBAs), arsenic trichloride (AsCI3), trisilylphosphine (TSP), triisopropylborane (iPr)3B, tert-butylsilane ((tBu)SiH3), isopropylsilane ((iPr)SiH3), tetrakis(tert-butyl)tin ((tBu)4Sn), tetrakis(isopropyl)tin ((iPr)4Sn), tetrakis(tert-butyl)germane ((tBu)4Ge), tetrakis(isopropyl)germane ((iPr)4Ge), germanium tetrachloride (GeCI4), carbon tetrachloride (CCI4), and hexachlorodisilane (Si2CI6).

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 invention provides a method for recycling germanium and tin from germanium-tin alloy waste and a special chlorination separation device. The method comprises the steps that S1, low-concentration alkali liquor selectively corrodes the waste, and high-purity water is used for washing and drying; s2, the dried waste is fed into a chlorination separation device, chlorine is introduced, gradient temperature control is carried out, gaseous chloride is generated from germanium and tin, and grading separation, germanium tetrachloride condensation and collection, tin tetrachloride reflux and collection and chlorine compliance treatment are carried out through an intermediate-temperature chamber and a separation tower; and S3, residual chlorine is purged by inert gas, and discharging is performed after cooling. Wherein the chlorination separation device comprises a high-temperature chamber, an intermediate-temperature chamber and the like, the separation tower is provided with multiple layers of sieve plates, and the material is adaptive to high-temperature corrosion working conditions. According to the method, high-efficiency and high-purity separation and all-component recovery of germanium and tin are realized, various pain points of a traditional process are solved, and the method has the advantages of safety, convenience, economy and environmental protection and is suitable for industrial continuous production.