16 results about "Germanium tetrachloride" patented technology

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 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.

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 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 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.

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 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.

This invention discloses a method for efficiently recovering germanium from germanium-containing waste from zone-melted germanium ingots, comprising the following steps: grinding the germanium-containing waste to obtain germanium-containing waste powder from zone-melted germanium ingots; adding the ground germanium-containing waste powder into an assembled chlorination reaction vessel, adding industrial hydrochloric acid, introducing chlorine gas, opening the condensate valve, setting the reaction pressure and stirrer speed, and starting the chlorination reaction; distilling the solution containing hydrochloric acid and germanium tetrachloride after the chlorination reaction to obtain germanium tetrachloride with a purity of 2N to 3N, recovering the residual acid from the distillation to a residual acid tank, and sending the tail gas to a tail gas treatment station. This method for efficiently recovering germanium from germanium-containing waste from zone-melted germanium ingots offers several advantages: high efficiency conversion: directly converting sparingly soluble germanium into germanium tetrachloride, which can then be further distilled and hydrolyzed to obtain high-purity germanium products, significantly improving recovery efficiency; cost reduction: hydrochloric acid can be recycled for the distillation process, reducing reagent costs; and the chlorination reaction is exothermic, requiring only cooling water for temperature control, reducing energy costs.