160 results about "Germanium tetrachloride" patented technology

The invention discloses a method for treating a titanium-containing waste liquid, which belongs to the field of treatment of industrial waste liquids. The method comprises the following process steps of: preparing white lime (Ca(OH)2) and water into lime milk according to a certain proportion in a lime milk storage tank; putting a certain amount of the prepared lime milk into a reactor; and directly adding a certain amount of titanium-containing waste liquid into the reactor, controlling the adding speed of the titanium-containing waste liquid, keeping the reaction temperature below or equal to 90 DEG C, and finally reacting to form solid waste residues TiO2/CaCl2.nH2O. White lime is taken as an alkali neutralizing agent, and the titanium-containing waste liquid directly undergoes a hydrolysis neutralizing reaction with lime milk without a hydrolysis reaction, so that the amount of water needed in the conventional method is saved, and solid waste residues are taken as a final treatment product and are convenient to transport; and moreover, conventional measures such as burning and landfilling can be adopted in a subsequent treatment way, so that the treatment cost is saved.

The invention relates to a method for recovering germanium from flyash by a wet process, belonging to the technical field of wet-process metallurgy. The method comprises the following steps of: (1) crushing flyash to more than 200 meshes by a wet process; (2) carrying out oxidizing leaching twice on wet flyash by using a sulfuric acid solution, sodium chlorate and ammonium fluoride; (3) crushing the flyash to 200-400 meshes for a second time; (4) leaching 3 or 4 times by using the same condition as that of the first leaching; (5) regulating the pH value of the first leached liquid to 2-2.5 by using ammonia water, and then precipitating and leaching out germanium in the liquid by using tannin with a weight percentage content of 80-99 percent; (6) drying and roasting the germanium precipitate to prepare a germanium concentrate; distilling the germanium concentrate with hydrochloric acid by using a conventional method to obtain germanium tetrachloride; and redistilling, rectifying, purifying and hydrolyzing to obtain high-purity germanium dioxide. The invention is used for flyash after recovering germanium by a fire process, sufficiently utilizes rare germanium metal, reduces the pollution of tailings to the environment, and has the advantages of low cost and high recovery rate.

Provided is a process of germanium wet-recovery from chromium-germanium alloy waste. The invention provides a process for recovering germanium aiming at that chromium-germanium alloy contains multiple metallic impurities, and germanium waste material is mixed with a vast amount of organic materials due to the employment of organic solvent in process of mutually wrapping and cutting of the chromium-germanium. A dissolution system of NaOH-H2O2 is employed to destroy organic matters in the waste material, which enables the organic matters to be saponified in NaOH, H2O2 is employed to oxygenize the bare metal germanium in the waste material, which enables the metal germanium to turn into ions which enter solution, then hydrochloric acid is employed to neutralize excessive alkali and distill out dissolved germanium, further hydrochloric acid in hydrochloric acid-MnO2 system is employed to react with chromium and part of metal impurities to enter the solution, the other part of the metal impurities which do not react with the hydrochloric acid is oxidized by chlorine gas to enter the solution, the chlorine gas is generated by the reaction of MnO2 and the hydrochloric acid, germanium wrapped by the impurities is released to react with the chlorine gas to form Ge4+ ions, the Ge4+ ions are combined with chloride ions to form germanium tetrachloride which then escapes after secondary distillation, thereby being separated from the other impurities. The recovery ratio by employing the germanium recovering process reaches above 99%.

The invention provides a method for preparing germanium dioxide (GeO2). According to the embodiment of the invention, the method comprises the following steps: hydrolyzing the germanium tetrachloride(GeCl4) in a fully-closed hydrolysis reactor to obtain the hydrolysis product of the GeCl4, centrifuging and filtering the hydrolysis product of the GeCl4 to obtain the GeO2 and the filtrate, and cleaning the GeO2 by high-purity water to obtain the high-purity GeO2 and the cleaning solution. According to the embodiment of the invention, the GeO2 hydrolyzing, filtrating and washing method and device have the advantages of high degree of automation, high GeO2 hydrolysis yield, good solid-liquid centrifugal separation effect, low production costs, less metal loss and environment friendliness.

The invention provides a preparation purification method of germanium tetrachloride for optical fibers, which adopts germanium concentrate as a raw material; hydrochloric acid, sulfuric acid, and ferric trichloride are added into a chlorination reaction vessel according to a certain proportion for reaction to prepare crude germanium tetrachloride; the crude germanium tetrachloride is fully mixed with hydrochloric acid and manganese dioxide according to a certain proportion in a repeated distillation reaction vessel for distillation and purification to obtain preliminarily purified germanium tetrachloride; the germanium tetrachloride after repeated distillation purification is processed in a quartz rectifying tower in inert atmosphere by controlling a tower bottom temperature to be 75-95 DEG C, a tower column temperature to be 30-95 DEG C, and a reflux ratio of 4:1-14:1, so as to obtain high-purity germanium tetrachloride. The high-purity germanium tetrachloride prepared through three procedures of chlorination distillation, repeated distillation, and rectification purification, has a content of transition metal impurities of less than 3 ppb, a content of hydrogen-containing impurities of less than 1 ppm, and meets the requirements for perform rod germanium tetrachloride for optical fibers.

The invention relates to the field of hydrometallurgy, in particular to a preparation method of low-chloride high-purity germanium dioxide. According to the process, coarse germanium tetrachloride is subject to repeated steaming and rectification to obtain high-purity germanium tetrachloride, and a brand new method is adopted in the hydrolysis section of the high-purity germanium tetrachloride, wherein high-purity nitrogen is adopted for gasifying the high-purity germanium tetrachloride into germanium tetrachloride gas, then the germanium tetrachloride gas is led into a special hydrolysis device, vacuum filtration and germanium dioxide washing are carried out after hydrolysis is finished, then germanium dioxide is dried, the germanium dioxide is dried secondly, and drying is carried out secondly. The low-chloride high-purity germanium dioxide obtained through the process method has the beneficial effects that the purity can reach 99.9999% or above, the chlorine content is lower than 0.0030%, and the germanium dioxide direct recovery rate reaches 92.0% or above.

The invention discloses a preparation method of germane, comprising dripping tetrahydrofuran solution of germanium tetrachloride into sodium hydroxide solution of sodium borohydride to react, and preparing the germane; wherein the molar ratio between the germanium tetrachloride and the sodium borohydride is 1:1-10. The reaction is carried out according to the equation: GeCl4+NaBH4+3NaOH=GeH4+B(OH)3+4NaCl. The method is simple in technique and lower in cost; and the prepared germane has high yield and less impurity content, and is easy to purify.

A method for synthesis of germanium nanoparticles in thin SiO₂ films comprising: preparing a solution comprising silicon esters, germaniumtetrachloride (GeCl₄) or germanium esters, methyl- or higher alcohols, and water; applying the solution to a surface of a substrate; consolidating the solution on the surface of the substrate, thereby obtaining a glass comprising silicon dioxide and germanium dioxide; selectively reducing the germanium dioxide to form germanium nanoparticles.

The invention discloses a method and a device for removing hydrogen-containing impurities from germanium tetrachloride. The method comprises the steps of: using rectified germanium tetrachloride as raw materials, adding germanium tetrachloride with the purity being 4N-5N into a rectifying kettle for rectification, increasing the temperature of the kettle to 75-83 DEG C for rectification, keeping the germanium tetrachloride to be in a sub-boiling state and feeding in nitrogen with the flow rate being 30-40L/h to exhaust HCl gas, wherein exhaust time is no less than 6 hours; after the HCl gas is exhausted, continuously increasing the temperature of the kettle, and when all sieve plates of a rectifying column are in a boiling state, starting to calculate total reflux time, wherein the total reflux time is no less than 3 hours; and after total reflux is completed, turning on a switch of an electromagnetic valve to adjust the reflux ratio to be 8:1 to 12:1, taking products at a front section, detecting the distilled germanium tetrachloride, if the detected products satisfy the production requirement of the germanium tetrachloride for optical fibers, putting the electromagnetic valve on the side with the products being taken, and finally shifting to a filling process after the obtained germanium tetrachloride products are detected as acceptable. The method and the device for removing the hydrogen-containing impurities from the germanium tetrachloride have the advantages that the technological process is simple, the operation is simple, the hydrogen-containing impurities can be well removed from the germanium tetrachloride, and the industrial use value is very high.

The invention relates to a high-precision germanium tetrachloride (GeCl4) supplying method and high-precision germanium tetrachloride supplying equipment for manufacturing a core rod of an optical fiber preform rod. The equipment comprises a programmable logic controller (PLC) of evaporating equipment, a touch screen of the evaporating equipment, a PLC of VAD equipment, a heating tape I, a heating tape II, a heating tape III, a heating tape IV, a temperature sensor I, a temperature sensor II, a temperature sensor III, a temperature sensor IV, a pressure sensor, a liquid level sensor, a control valve I, a control valve II, a control valve III, a mass flow rate controller I, a mass flow rate controller II, an evaporating pot and a power supply, wherein the evaporating pot is provided with a liquid level sensor, the pressure sensor, the temperature sensor I and an electronic scale for monitoring the situation of the evaporating pot, the electronic scale is arranged at the bottom of the evaporating pot for monitoring weight in real time, the heating tape I is arranged outside the evaporating pot, a GeCl4 fluid delivery pipe is arranged on the evaporating pot, the control valve I is arranged on the GeCl4 fluid delivery pipe, an evaporating pot outlet pipeline is arranged on the evaporating pot, and the power supply supplies power to the evaporating equipment.

The invention relates to a process for the purification's of silicon tetrachloride or germanium tetrachloride contaminated with at least one hydrogen-containing compound, in which the silicon tetrachloride or germanium tetrachloride to be purified is treated in a targeted manner by means of a cold plasma and purified silicon tetrachloride or germanium tetrachloride is isolated from the phase which has been treated in this way. The present invention further relates to an apparatus for carrying out the process of the invention, which comprises a stock and vaporization unit for silicon or germanium tetrachloride (4.1 or 5.1) which is connected via a connecting line with the inlet of the reactor (4.3 or 5.3) with control unit (4.4 or 5.4) for producing the dielectrically hindered discharges whose outlet leads via a pipe either directly or indirectly via at least one further reactor (5.5) to a condensation unit (4.5 or 5.11) with downstream collection vessel (4.6 or 5.12) which is connected via an offtake line (4.6.2 or 5.12.1) to a distillation unit (4.8 or 5.13) and, if appropriate, is equipped with a feed line (4.6.1) to the unit (4.1).

A manufacturing method of a rare earth-doped optical fiber preformed rod relates to the field of optical fiber preformed rods, and comprises the following steps: S1, mounting a cylindrical rare earth material preformed target rod at a gas inlet end in a quartz glass substrate tube, mounting the substrate tube on a chemical vapor deposition device; S2, focusing laser on the rare earth material preformed target rod, introducing mixed gas composed of oxygen, chlorine, silicon tetrachloride gas, germanium tetrachloride gas, and carbides of fluorine, performing deposition to form an optical fiber core rod preform; S3, melting the optical fiber core rod preform for contraction at a high temperature to form the transparent optical fiber preformed rod. The method increases the diameter of the optical fiber preformed rod, greatly improves the production manufacturing efficiency and the rare earth ion doping uniformity of the rare earth-doped optical fiber preformed rod, reduces the content of ineffective impurities of the optical fiber preformed rod, also reduces the production cost, and is suitable for popularization of large-scale production.

The invention discloses a method for comprehensively recovering valuable metals from complex alloys containing stibium, tellurium, indium, germanium and silver. The method comprises the following steps of: alkaline roasting and transformation: mechanically and uniformly stirring smashed and ball milled alloy powder and caustic soda flakes according to a weight ratio of 1:2, loading into an automatic control electric roasting furnace and heating to a temperature of 850 DEG C for 10 hours and taking out of the furnace and then smashing for later use; production of germanium: acidizing roasted powder through sulfuric acid, then obtaining germanium tetrachloride through a process for distilling and extracting the germanium and producing high-purity germanium ingots through rectification, hydrolysis, reduction and zone-melting; recovery of tellurium and silver: washing and filter-pressing acid sludge mixed liquor in the kettle after distilling the germanium to obtain residues; recovery of indium and stibium: neutralizing filter-pressed acid liquor by using alkali liquor to have the pH value of 5 to obtain an indium-stibium mine, and leaching by using dilute sulphuric acid, wherein a final pH value is 1.0-1.5, the content of stibium in leached residues is 30 percent; and extracting, replacing, fusion casting, electrolyzing and refining leach liquor through P204 to obtain 4N high-purity indium ingots.

The invention provides a production system of germanium tetrachloride for optical fiber. The production system of germanium tetrachloride for the optical fiber comprises at least two rectification units. The rectification units are connected with each other in series. Each of the rectification units comprises a rectifying still, a rectifying tower, a primary condensing tower, a secondary condensing tower, a discharging head, a primary exhaust gas absorption device, a secondary exhaust gas absorption device and a exhaust gas treatment device. The secondary exhaust gas absorption device is communicated with the primary exhaust gas absorption device. The exhaust gas treatment device is communicated with the secondary exhaust gas absorption device. The production system of germanium tetrachloride for the optical fiber improves the rectifying purity of the germanium tetrachloride for the optical fiber enormously by arranging a plurality of rectification units and improves the reliability of the sealing and maintains the pressure balance in the system by arranging the primary exhaust gas absorption device and the secondary exhaust gas absorption device and can evacuate the exhaust gas finally produced by the production system through the exhaust gas treatment device by arranging the exhaust gas treatment device.

The invention relates to the field of hydrometallurgy, in particular to a technological method for recovering germanium from low-concentration germanium-containing waste liquid. The method comprises the following steps that reacted acid generated through chloridizing distillation of the low-concentration germanium-containing waste liquid and germanium concentrate is combined into a distillation still, the germanium-containing waste liquid is subjected to heating distillation, the temperature of heating distillation is 110-120 DEG C, distilled germanium tetrachloride and hydrogen chloride are cooled firstly and then subjected to reverse absorption through hydrochloric acid, recovered germanium-containing acid liquid is transferred to a germanium concentrate chloridizing distillation working section, and the recovered germanium-containing acid liquid and the newly added hydrochloric acid are used for extracting germanium in the germanium concentrate through chloridizing distillation. By adopting the technological method, 90% of germanium in the germanium-containing waste liquid can be effectively recovered in an energy-saving mode, the using amount of new hydrochloric acid can be reduced by 80% or more by the germanium concentrate chloridizing distillation working section, germanium metal recovered each year can reach 500-1200 kg, and wastewater processing and discharging can be reduced by 90% or more. The efficient recovery of germanium is achieved, and circulation recycling of the hydrochloric acid is also achieved.

The invention discloses a preparation method of germanium dioxide, and relates to the field of rare metal metallurgy. The preparation method sequentially includes the steps of chlorinating and distilling germanium ore, re-steaming the germanium ore, rectifying and purifying the germanium ore to obtain germanium tetrachloride, hydrolyzing the germanium tetrachloride to prepare germanium dioxide andhydrolysis supernatant, precipitating the hydrolysis supernatant to prepare magnesium germanate filter residues, and distilling the magnesium germanate filter residues to obtain the germanium tetrachloride for reutilization. The preparation method has the advantages of high recovery rate, low use cost, less residual liquid, energy conservation and environment protection.

The invention discloses a method for recovering silicon and germanium from germanium-containing optical fiber waste. The method comprises the following steps: 1, the crushed germanium-containing optical fiber waste is screened, and powder is obtained; 2, the powder and water are mixed to be beaten, soluble alkali is added, under the vacuum condition, after microwave heating, the temperature keepsconstant, and leachate containing the silicon and the germanium is obtained; 3, an alkali metal salt is added into the leachate containing the silicon and the germanium, the pH is regulated, stirring,aging and solid-liquid separation are conducted, and a solid and liquid are obtained; 4, the solid is dried, and amorphous silicon dioxide is obtained; 5, a magnesium salt is added into the liquid, stirring for germanium sedimentation, aging and filtering are conducted, and residue and filtrate are obtained; 6, ferric chloride is added into the filtrate, precipitation adsorption reaction, aging and filtering are conducted, and precipitation is obtained; and 7, the residue and the precipitation are mixed with water to be beaten, the mixture is mixed with hydrochloric acid to be distilled, germanium tetrachloride is obtained and hydrolyzed, and germanium dioxide is obtained. According to the method, the silicon and the germanium in the waste can be effectively recovered, and the silicon andthe germanium are separated.

The invention discloses a method for producing germanium tetrachloride for optical fibers, which includes the steps: hydrochloric acid and germanium tetrachloride with a volume ratio of 0.25-2.0: 1 are added into a distiller to be distilled; or while separately distilling the germanium tetrachloride, HCI gas is pumped in until the distilling is finished with the distilling temperature of 76-80 DEG C; after the distilled solution is separated by a hydrochloric separator, the germanium tetrachloride solution is stored in a storage tank to be discharged to an empty tower distiller for 36-72 hours of standing; temperature of the germanium tetrachloride solution is raised to 70-75 DEG C; while continuous pumping nitrogen for 12-36 hours, an ultraviolet lamp is adopted for lighting; finally, distillation operation is carried out at 76-80 DEG C and the product is transferred. The method for producing the germanium tetrachloride for optical fibers has the advantages of simple process course and convenient operation which can remove the impurity containing hydrogen in the germanium tetrachloride with high value for industrial use.

A reactor, a plant, and a continuous, industrial process carried out therein for preparing high-purity silicon tetrachloride or high-purity germanium tetrachloride by treating the silicon tetrachloride or germanium tetrachloride to be purified, which is contaminated by at least one hydrogen-containing compound, by a cold plasma and isolating purified high-purity silicon tetrachloride or germanium tetrachloride from the resulting treated phase by fractional distillation. The treatment is carried out in a plasma reactor in which longitudinal axes of a dielectric, of a high-voltage electrode, and of a grounded, metallic heat exchanger are oriented parallel to one another and at the same time parallel to the force vector of gravity.

The invention relates to a method for extracting germanium from germanium-containing smoke dust, and belongs to the technical field of chemical metallurgy. The method adopts the germanium-containing smoke dust, which is obtained by dry distillation of lignite and has the germanium content of 8.0-30.0wt%, as a raw material to perform extraction, and comprises the following steps: performing leaching distillation on the germanium-containing smoke dust; cooling the obtained gas containing germanium tetrachloride to obtain a crude germanium tetrachloride solution; performing first-time extraction on the crude germanium tetrachloride solution; filtering the germanium tetrachloride solution obtained by the first-time extraction by using a separating column; performing second-time filtration on the obtained germanium tetrachloride solution to obtain a refined germanium tetrachloride solution; and hydrolyzing the obtained refined germanium tetrachloride solution into germanium dioxide, and reducing the germanium dioxide to obtain germanium. According to the method provided by the invention, the technological process is easy to control and strong in operability, the germanium recovery rate is stable, the cost is significantly reduced relative to that of a continuous distillation or continuous extraction process, the purity of germanium can reach more than 99.999%, and the resistivity of germanium is more than 15 ohm cm.

The invention more specifically relates to a regeneration utilization method of germanium in infrared chalcogenide glass waste material. According to the regeneration utilization method of germanium in infrared chalcogenide glass waste material, germanium is extracted from infrared chalcogenide glass waste material, and the method principles are that: the oxidation performance of H2O2 is adopted to destroy Ge-Se, Ge-As, Ge-Sb bonds in infrared chalcogenide glass waste material, germanium is oxidized into GeO, a single GeO layer is formed on the surface, GeO is oxidized into GeO2, GeO2 is dissolved in water to form germanic acid; when an obtained solution contains an alkali, germanic acid is reacted with the alkali to produce sodium germinate, so that germanium dissolving is accelerated; concentrated sulfuric acid is adopted to neutralize excess sodium hydroxide solution and adjust and control the concentration of hydrogen ions in the solution; FeCl3 is adopted to oxidize As<3+> into As<6+>, and sufficienct chloride ions are provided; concentrated hydrochloric acid is adopted for distillation of germanium tetrachloride from the solution, and AsCl6 is left in a distillation raffinate; the germanium tetrachloride obtained through distillation is subjected to traditional technology including secondary distillation, rectification, hydrolysis, reduction, and zone melting so as to obtain high purity zone-refined germanium ingot.

The invention provides a method for producing germanium dioxide by utilizing germanium-containing wastes. The method is characterized by comprising the following steps: directly adding the germanium wastes into a concentrated hydrochloric acid containing ferric trichloride; using chlorine as a shielding gas and adopting a rectifying column for distilling and purifying germanium tetrachloride; preparing germanium dioxide by performing totally closed hydrolysis reaction on the purified germanium tetrachloride; washing the hydrolysate and drying, thereby acquiring dry germanium dioxide; and adding the germanium wastes into a return fluid after completing distillation, thereby continuously producing. The germanium tetrachloride can be continuously produced in the manner of adding the germanium wastes into the concentrated hydrochloric acid containing ferric trichloride, and then adding chlorine for oxidizing, distilling and preparing germanium tetrachloride and adding the germanium wastes after completing the distillation; the usage of acid and hydrogen peroxide can be saved; the distilling return fluid can be repeatedly reused; and no distilling waste acid is generated.

The invention provides a preparation method of germane gas. According to the method, a sodium hydroxide solution of sodium borohydride is prepared; polyether with a volume of 0.5% to 5% of that of the solution is added to the solution; and a tetrahydrofuran solution of germanium tetrachloride is added to the solution for preparing germane gas. Compared to previously disclosed methods, according to the present method, polyether is added to the reaction solution, such that a substantial effect is brought in, generation of yellow precipitate is greatly reduced, and a conversion rate of germane is improved by approximately 7%.

The invention discloses a method for recycling germanium from high-silicon-content optical fiber production waste. The method comprises the following steps that (1) the high-silicon-content and germanium-containing optical fiber production waste is ground till the number of holes is 100 or above,, and then a vulcanizing agent is added and uniformly mixed to prepare particles with the diameters of1-5 mm; (2) sulfidingvolatilization is carried out on the germanium, and the germanium sulfide volatilization smoke dust is collected, or the mixed volatilization smoke dust of the germanium sulfide and germanium dioxide is collected; (3) the obtained germanium-containing smoke dust is subjected to microwave oxidation roasting or oxidation roasting in other forms, or is subjected to sulfuric acidoxidation leaching directly; (4) the high-germanium-content microwave oxidation roasting product is directly subjected to hydrochloric acid chlorination distillation so as to obtain germanium tetrachloride to be subjected to hydrolyzation, and thus a germanium dioxide concentrate is obtained; and (5) sulfuric acid oxidation leaching is carried out on the low-germanium-content materials in the step(2) and the step (3), wherein a leaching solution adopts tannin or an organic solvent to precipitate or extract the enriched germanium and to produce the germanium concentrate. The method can be usedfor extracting and separating the germanium and the silicon from the materials containing 95% or above of the silicon at high efficiency and low cost.