Provided is a method and apparatus for secondary enrichment of germanium from low-grade lignite germanium concentrates in vacuum, and particularly a method and apparatus for secondary enrichment and recovery of germanium from low-grade lignite germanium concentrates with microwave heating in vacuum, which belongs to a germanium extraction method and apparatus in the field of metallurgy.

Provided is a method and apparatus for secondary enrichment of germanium from low-grade lignite germanium concentrates in vacuum, and particularly a method and apparatus for secondary enrichment and recovery of germanium from low-grade lignite germanium concentrates with microwave heating in vacuum, which belongs to a germanium extraction method and apparatus in the field of metallurgy.

A method for extracting germanium based on acid decomposition is provided, including acid decomposition and post-treatment steps, and specifically including: adding an acid to a coal ash for conditioning to obtain a material a; heating the material a to 350 C. to 800 C., and keeping the material a at this temperature for 10 min to 10 h to obtain an acid-decomposed material b; milling the acid-decomposed material b until more than 60% of a milled material has a particle size of less than 200 mesh to obtain a material c; subjecting the material c to distillation to obtain a residual slurry d and a distillation fraction e; and hydrolyzing the distillation fraction e with a dilute hydrochloric acid solution, and then oven-drying to obtain GeO.sub.2.

A method for extracting germanium based on acid decomposition is provided, including acid decomposition and post-treatment steps, and specifically including: adding an acid to a coal ash for conditioning to obtain a material a; heating the material a to 350 C. to 800 C., and keeping the material a at this temperature for 10 min to 10 h to obtain an acid-decomposed material b; milling the acid-decomposed material b until more than 60% of a milled material has a particle size of less than 200 mesh to obtain a material c; subjecting the material c to distillation to obtain a residual slurry d and a distillation fraction e; and hydrolyzing the distillation fraction e with a dilute hydrochloric acid solution, and then oven-drying to obtain GeO.sub.2.

A method of extracting germanium from a germanium deposit using a thermal reduction process is disclosed. The present disclosure relates to a method of extracting germanium, which belongs to the field of metallurgy technologies of nonferrous metal, and particularly relates to a method of extracting germanium from a germanium deposit through thermal reduction, volatilization and concentration using sodium monophosphate as a reducing agent. The method of the present disclosure includes: adding sodium monophosphate to a germanium deposit; isolating from air; increasing the temperature and baking the germanium deposit; and obtaining a germanium concentrate after volatilization and concentration of the germanium deposit. Through baking the germanium deposit at 1,000 C., volatilization and concentration of the germanium deposit, the germanium recycling rate exceeds 96% when sodium monophosphate weighing 2.5% of the germanium depositis added. The present disclosure solves the following problems in the prior arts: existing pyrogenic methods for concentrating and extracting germanium from germanium deposits can hardly achieve a germanium recycling rate of greater than 75%; secondary pyrogenic recycling methods for extracting germanium slag have excessively high production cost and yield low germanium recycling rates; and the cost of hydrometallurgical treatment methods for low-grade germanium concentrates is too high.

A method of extracting germanium from a germanium deposit using a thermal reduction process is disclosed. The present disclosure relates to a method of extracting germanium, which belongs to the field of metallurgy technologies of nonferrous metal, and particularly relates to a method of extracting germanium from a germanium deposit through thermal reduction, volatilization and concentration using sodium monophosphate as a reducing agent. The method of the present disclosure includes: adding sodium monophosphate to a germanium deposit; isolating from air; increasing the temperature and baking the germanium deposit; and obtaining a germanium concentrate after volatilization and concentration of the germanium deposit. Through baking the germanium deposit at 1,000 C., volatilization and concentration of the germanium deposit, the germanium recycling rate exceeds 96% when sodium monophosphate weighing 2.5% of the germanium depositis added. The present disclosure solves the following problems in the prior arts: existing pyrogenic methods for concentrating and extracting germanium from germanium deposits can hardly achieve a germanium recycling rate of greater than 75%; secondary pyrogenic recycling methods for extracting germanium slag have excessively high production cost and yield low germanium recycling rates; and the cost of hydrometallurgical treatment methods for low-grade germanium concentrates is too high.

The invention relates to a method for treating a solution containing zinc sulphate, so that at least one of the rare metals such as indium, gallium and germanium can be separated from it. A portion of the metals to be separated can be precipitated from zinc sulphate solution by neutralizing the acidic solution and at least a portion is cemented by means of metal powder. The solid precipitates that are formed can be combined and treated subsequently in some suitable way to leach out the desired metals.

The invention relates to a method for treating a solution containing zinc sulphate, so that at least one of the rare metals such as indium, gallium and germanium can be separated from it. A portion of the metals to be separated can be precipitated from zinc sulphate solution by neutralizing the acidic solution and at least a portion is cemented by means of metal powder. The solid precipitates that are formed can be combined and treated subsequently in some suitable way to leach out the desired metals.

A method for extracting germanium based on acid decomposition is provided, including acid decomposition and post-treatment steps, and specifically including: adding an acid to a coal ash for conditioning to obtain a material a; heating the material a to 350 C. to 800 C., and keeping the material a at this temperature for 10 min to 10 h to obtain an acid-decomposed material b; milling the acid-decomposed material b until more than 60% of a milled material has a particle size of less than 200 mesh to obtain a material c; subjecting the material c to distillation to obtain a residual slurry d and a distillation fraction e; and hydrolyzing the distillation fraction e with a dilute hydrochloric acid solution, and then oven-drying to obtain GeO.sub.2.

A method for extracting germanium based on acid decomposition is provided, including acid decomposition and post-treatment steps, and specifically including: adding an acid to a coal ash for conditioning to obtain a material a; heating the material a to 350 C. to 800 C., and keeping the material a at this temperature for 10 min to 10 h to obtain an acid-decomposed material b; milling the acid-decomposed material b until more than 60% of a milled material has a particle size of less than 200 mesh to obtain a material c; subjecting the material c to distillation to obtain a residual slurry d and a distillation fraction e; and hydrolyzing the distillation fraction e with a dilute hydrochloric acid solution, and then oven-drying to obtain GeO.sub.2.