CN109929997B - Method for producing germanium concentrate by using N235 extracting agent - Google Patents
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Abstract
The invention relates to the technical field of comprehensive recovery of scattered metals, in particular to a method for producing germanium concentrate by using an N235 extracting agent, which comprises the steps of firstly extracting organic germanic acid from a germanium-containing acidic solution by using the N235 extracting agent to obtain a germanium-loaded organic phase; then washing the loaded organic phase with corresponding organic acid diluent, back-extracting and purifying the organic phase with sodium hydroxide to obtain a germanium-containing alkali back-extraction solution, and circulating the germanium-containing alkali back-extraction solution until the germanium content is more than 20 g/L; then hydrolyzing the strip liquor to precipitate germanium concentrate; causticizing the hydrolysis precipitation filtrate to obtain organic acid calcium precipitate and sodium hydroxide regeneration liquid for returning, and leaching organic acid calcium with sulfuric acid to obtain organic acid leachate for returning. The method not only ensures the organic extraction rate of germanium, but also reduces the consumption of sodium hydroxide, improves the grade of germanium concentrate, regenerates and recovers the sodium hydroxide and the organic complexing agent of germanium, and simultaneously reduces the environmental management cost of waste residue and wastewater.
Description
Technical Field
The invention relates to the technical field of comprehensive recovery of scattered metals, in particular to a method for producing germanium concentrate by using an N235 extracting agent.
Background
Germanium is a rare and rare metal, and mineral resources of germanium are mainly distributed in lead-zinc ores and coal mines. The extraction and separation of germanium from lead-zinc ore is mainly a hydrometallurgical method. The hydrometallurgical recovery of germanium is currently mainly based on tannin precipitation and organic solvent extraction. After tannin organic germanium is obtained by a tannin precipitation method, tannin organic matters must be calcined at the temperature of more than 500 ℃ to obtain 5-20% grade germanium dioxide concentrate. As the grade of the germanium concentrate is improved by 10 percent and the price is increased by more than 200 yuan/kg, tannin can not be recovered after the organic matter is calcined, combustion ash can be generated, and the grade of the germanium concentrate can not reach more than 30 percent.
In order to improve the economic benefit of chlorination distillation of germanium concentrate and reduce the amount of chlorination distillation residues, the tannin method for recycling and producing the germanium concentrate has high cost and low economic benefit. The organic solvent extraction method can overcome the defects of the tannin method, can produce more than 30 percent of germanium concentrate, and is the main development and research direction of the wet extraction of the germanium at present.
The organic solvent extraction method mainly comprises hydroxamic acid (such as LiX63, Klex100, 7815, 8315 and the like) kerosene extraction agent and amines (such as N235, triester and the like)Fatty amine, trioctylamine N263 and the like, N235) kerosene extraction agents are commonly used, the former (hydroxamic acids) can directly extract germanium from acid liquid in a chelating mode, and the back extraction is carried out by adopting a mixture of dilute acid containing fluorine ions or salt containing fluorine ions. The extraction form of the amine extractant, especially the N235 kerosene extractant, is anion-cation association form, so that the extraction compound can be easily back extracted by using sodium hydroxide solution, the operation is simple, the water solubility is small, the loss is small, the price is low, and the industrial production is realized, but the N235 kerosene extractant needs to be firstly acidified, namely, acid radical anions are firstly extracted to form R3N+H2SO4→[R3NH+]HSO4 -Then mixed with a charge having a density lower than HSO4 -The germanium organic complex anion (e.g., organogermanium complex such as germanium pyrocatecholate or germanium tartrate) is exchanged. Because of the low content of germanium in the solution, the N235 loaded organic phase not only contains organic germanium complex anions, but also contains a large amount of HSO4 -And part of impurity anion groups are extracted, and when sodium hydroxide is used for back extraction, a large amount of sodium hydroxide is inevitably consumed, so that the defects of adding an organic complex of germanium and consuming a large amount of sodium hydroxide are mainly caused when the germanium is extracted and recovered from the acidic solution by using the amine extractant. Generally, a person skilled in the art washes before the back extraction process, and if clean water, weak acid and weak base solution are used as a washing agent, although part of impurities and sulfuric acid can be eluted, part of extracted germanium can also be eluted, and the germanium extraction rate is reduced; when the washing with the organic acid solution is carried out, the amount of germanium eluted can be reduced, but the organic reagent is expensive and must be recovered.
Patent No. CN201610339560.9 provides a treatment method for precipitating and recovering germanium from a germanium-containing feed liquid by using a two-stage neutralization hydrolysis method and using a metal oxide as a neutralization precipitant, the method adopts the metal oxide as the neutralization precipitant and uses the two-stage neutralization hydrolysis method to treat a germanium precipitation precursor liquid, the operation is simple, the slag filtering performance is good, the addition amount of auxiliary materials is small, and the grade of the obtained germanium concentrate is about 6-8%.
Patent No. CN201711330085.X provides a method for recovering indium and germanium from chlorination distillation residual liquid containing indium and germanium, which comprises the steps of subjecting distillation residual liquid to the presence of tartaric acid to obtain mixed liquid containing InCl 4-or InCl 63-tartrate anions (Ge (A)32-, A is tartaric acid), simultaneously extracting indium and germanium by adopting an N235-kerosene system extracting agent, reversely extracting indium by adopting dilute sulfuric acid or dilute hydrochloric acid, and reversely extracting germanium by adopting a sodium hydroxide solution. Since washing with any diluent will become a stripping solution for indium, the indium will be dispersed and not be recovered. Meanwhile, the organic acid diluent is adopted for washing or back extraction, and the consumption of metal zinc is increased due to the difficulty of replacing sponge indium by zinc due to the complexation and the masking effect of the organic acid. If the alkali stripping of germanium is carried out first, indium is stripped into the alkali stripping solution, and the indium precipitates together with germanium during the neutralization hydrolysis and cannot be separated. The sectional back extraction of the technology only can be implemented by firstly carrying out acid back extraction on indium and then carrying out alkali back extraction on germanium. Therefore, the technique of this patent cannot be provided with a washing and purifying step of the organic phase loaded. However, if organic acid is not used as the washing exchange solution, not only a large amount of sodium sulfate and impurities enter the stripping solution during the alkali stripping, but also more sodium sulfate is carried during the hydrolysis, and the sodium sulfate component cannot be removed during the calcination, which affects the improvement of the germanium concentrate grade.
Patent No. CN201610545333.1 provides a method for producing high-grade germanium concentrate, which comprises extracting germanium from germanium-containing acidic solution with N235-kerosene system extractant, washing germanium-loaded organic phase with clear water or sodium carbonate diluent or organic and inorganic diluent, back-extracting with sodium hydroxide solution, supplementing back-extraction solution, recycling to make germanium content reach above 15g/L, hydrolyzing, washing, drying, and calcining, wherein if non-corresponding organic acid diluent is used, extracted germanium can be washed and exchanged to obtain extracted impurities and sulfuric acid, and washed germanium can be exchanged to washing solution, and organic germanium anion complex can be formed, but because the washing solution contains more than two organic complexing agents, germanium complexation reaction can be generated to generate competitive extraction, the extraction rate is reduced. Meanwhile, two germanium organic complexing agents also exist in the filtrate after the alkaline back-extraction hydrolysis and germanium precipitation, so that when organic acid is recovered in the subsequent process, the product is not pure and can not be returned for use or sold, and the recovery of the organic complexing agents is worthless.
Disclosure of Invention
The invention provides a method for producing germanium concentrate by using an N235 extracting agent, aiming at solving the problems of high alkali consumption and high energy consumption of a method for producing germanium concentrate by extracting and recovering germanium from an acid solution by using the N235 kerosene extracting agent and realizing the recycling of an organic complexing agent of germanium.
The method is realized by the following technical scheme:
a method of producing germanium concentrate with an N235 extractant, comprising the steps of: 1) adding an organic acid complexing agent of germanium into the acidic solution containing germanium, and extracting the organic acid germanium complex by using an N235 kerosene extraction agent to obtain a loaded organic phase containing the organic acid germanium complex; then washing and purifying the loaded organic phase by using organic acid diluent corresponding to the organic acid germanium complex to obtain a purified loaded organic phase containing the organic acid germanium complex; 2) using sodium hydroxide to back extract the purified loaded organic phase to obtain alkali back extract liquid for multiple times of recycling until the germanium content reaches more than 20 g/L; 3) after the alkali stripping solution hydrolyzes and precipitates the high-grade germanium concentrate, causticizing the hydrolysis and precipitation filtrate by using calcium hydroxide or calcium oxide to obtain organic acid calcium precipitate and sodium hydroxide regeneration solution; 4) the organic acid calcium is leached by sulfuric acid, and the organic acid complexing agent of the germanium is recovered for reuse.
Further, the method comprises the following steps:
(1) adding an organic complexing agent into the germanium-containing acidic solution to enable the mass ratio of the organic complexing agent to germanium to be (3-5):1, and then extracting germanium by using an N235 kerosene extracting agent, wherein the extraction grade is 3-5 grades, so as to obtain a loaded organic phase containing organic complexing germanium;
(2) carrying out 2-3-stage washing on the loaded organic phase containing organic complex germanium by using organic acid diluent which corresponds to the organic germanium complex with the mass fraction of 0.1-5%, and exchanging extracted impurities and sulfuric acid to obtain a purified loaded organic phase;
(3) performing 3-4-stage back extraction on the purified loaded organic phase by using a sodium hydroxide solution with the mass fraction of 20-30%, supplementing sodium hydroxide by using 3-4% of the obtained first-stage germanium-containing back extraction solution, returning to perform back extraction, and recycling until the germanium content of the first-stage back extraction solution reaches more than 20 g/L;
(4) neutralizing alkali stripping solution containing germanium above 20g/L with sulfuric acid to pH 9-11, and hydrolyzing to obtain hydrolysis precipitate containing germanium hydroxide and hydrolysis precipitate filtrate containing sodium salt of organic acid and sodium sulfate;
(5) washing the hydrolysis precipitate for 1-2 times by hot water with the temperature of 60-80 ℃, and calcining and dehydrating at the temperature of 200-300 ℃ to obtain germanium dioxide concentrate with the germanium content of 30-50%; the washing liquid is returned to be used for washing or is combined with the hydrolysis precipitation filtering liquid;
(6) performing causticization reaction on the hydrolysis precipitation filtrate and washing liquid by using calcium hydroxide or calcium oxide at the temperature of 80-90 ℃ and under the condition that the calcium ion/(organic acid + sulfate ion) ((1.1-1.5)/1 molar ratio) for 5-6h to obtain calcium-containing precipitate and sodium hydroxide regeneration liquid;
(7) leaching the calcium-containing precipitate with sulfuric acid to obtain sulfuric acid leachate containing organic acid and calcium sulfate precipitation slag, concentrating and crystallizing the organic acid leachate to recover organic acid complexing agent or directly returning the organic acid complexing agent to be used as germanium complexing agent.
The organic complexing agent is any one of catechol, tartaric acid, citric acid and humic acid; tartaric acid is preferred.
The working principle of the invention is as follows:
the N235 kerosene extractant is weak alkaline anion extractant, firstly extracts sulfuric acid in sulfuric acid solution to form [ R ]3NH+]HSO4 -The ionic associate is exchanged with a complex anion having a low charge density (ion charge density is the number of ions charge/ion group). The charge density of the germanium-forming organic complex anion with the organic complexing agent is very low, for example, the germanium tartrate anion is Ge (C)4O6H4)2-And [ R ]3NH]+Is more matched in hardnessPrepared, and is easy to be extracted by N235 and simultaneously exchanges HSO4 -The extraction reaction equation 2[ R ]3NH]+HSO4 -+H2 +Ge(C4O6H4)2-→[R3NH]2 +Ge(C4O6H4)2-+2H2SO4. While germanium is low in the pickling solution, so that only part of the [ R ] is present3NH]+HSO4 -The sulfuric acid is removed by reaction and exchange with the germanium tartrate anion, and the rest N235 still contains a large amount of sulfuric acid.
The N235 kerosene extraction agent can also be mixed with AsO2 3-、AsO4 3-、SbO2 3-The extracted AsO can be washed and exchanged by using an organic acid diluent corresponding to a complex anion of germanium in the solution as a washing liquid for an organic phase loaded2 3-、AsO4 3-、SbO2 3-Iso-impurities and HSO4 -And purifying the loaded organic phase.
The invention adopts the organic acid corresponding to the extracted germanium as the washing liquid, thereby not only achieving the purification purpose, but also avoiding the loss of the extracted organic germanium. And the organic acid is weak acid, the acidity is greatly reduced after the loaded organic phase is purified, so that the alkali consumption during alkali back extraction is reduced, and the alkali back extraction solution can be returned for recycling for many times after sodium hydroxide is supplemented, so that the germanium content in the back extraction solution is increased, the hydrolysis of germanium is facilitated, and the germanium grade of a hydrolysate is improved. And the calcining process is combined, so that organic matters carried by the hydrolysis precipitate are burnt, and the grade of the germanium is further improved.
The method utilizes the reaction mechanism that organic calcium salt is easy to precipitate and leach by sulfuric acid, and adopts calcium hydroxide or calcium oxide to carry out causticization reaction on organic sodium in hydrolysis precipitation filtrate to obtain organic acid calcium salt and regenerated sodium hydroxide. The organic acid calcium salt is leached by sulfuric acid to obtain organic acid and calcium sulfate precipitate, and the organic complexing agent for recovering germanium is returned for use.
Has the advantages that:
the method ensures the organic extraction rate of the germanium, greatly reduces the consumption of sodium hydroxide, improves the grade of germanium concentrate, regenerates and recovers the organic complexing agent of the sodium hydroxide and the germanium, reduces the environmental management cost of waste residue and wastewater, and has good economic benefit and environmental benefit; the method specifically comprises the following steps: 1) the organic acid diluent adopted in the washing process is consistent with the organic acid used in the complexing reaction, so that the germanium-loaded organic phase is purified, and the extraction rate of germanium is not reduced; 2) the recycling frequency of the alkali stripping solution is increased, so that the consumption of sodium hydroxide is reduced, the content of germanium in the alkali stripping solution is increased, the content of germanium in the sodium germanate hydrolysis precipitate is increased, and high-grade germanium concentrate can be obtained; 3) the organic complexing agent and the sodium hydroxide which recover the germanium are recycled, the using amount of the complexing agent and the using amount of the sodium hydroxide are reduced, the hydrolysis and precipitation of high-grade germanium concentrate from the alkali stripping solution and the causticization recovery of the organic acid complexing agent and the regeneration of the sodium hydroxide from the hydrolysis and precipitation filtrate are facilitated, the environmental treatment cost of waste residue and waste water is reduced, and the economic benefit and the environmental benefit are good.
The invention adopts the technical process of the organic acid diluent corresponding to the organic acid of the complex germanium and the technical process of recovering the organic acid from the solution after the hydrolysis and precipitation of the germanium-containing alkali stripping solution in the washing of the germanium-loaded organic phase, thereby not only reducing the alkali consumption and recovering the organic acid and sodium hydroxide, but also improving the grade of the germanium concentrate obtained by hydrolysis and precipitation and greatly reducing the cost for preparing the germanium concentrate.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
Taking zinc sulfate pickle liquor containing 0.85g/L of germanium and 125g/L of zinc, adding tartaric acid as an organic complexing agent of the germanium according to the ratio of tartaric acid to germanium being 5, and performing 3-level extraction by using 20% of N235 and 80% of kerosene as an organic germanium extracting agent to obtain a first-level organic phase containing organic germanium; then two-stage washing is carried out by using tartaric acid diluent with the pH value of 1.5 and the concentration of 0.5 percent, so as to obtain a first-stage purified organic phase loaded with organic germanium and tartaric acid washing liquid with the pH value of 0.8 and the concentration of 5.3mg/L of germanium; then carrying out three-stage back extraction on the first-stage purified organic phase loaded with the organic germanium by using a 30% sodium hydroxide solution, supplementing 3% sodium hydroxide to the obtained first-stage alkali back extraction solution, returning the first-stage alkali back extraction solution for recycling, and after 8 times of recycling, enabling the first-stage alkali back extraction solution to contain 16.3g/L of germanium; then neutralizing the filtrate with sulfuric acid until the pH value is 10, carrying out hydrolysis precipitation on germanium to obtain hydrolysis precipitate containing 13.8% of germanium, washing the hydrolysis precipitate with hot water, calcining the germanium hydroxide at 200 ℃ to obtain germanium concentrate grade of 31.2%, carrying out causticization treatment on the hydrolysis precipitate filtrate with calcium oxide powder according to the ratio of calcium/(tartaric acid + sulfate radical) of 1.3 at 80 ℃ for 5 hours, wherein the filtrate contains 230mg/L of tartrate radical, trace sulfate radical and 52g/L of sodium hydroxide; the filtered calcium slag is leached by concentrated sulfuric acid to obtain leachate containing 1250mg/L of germanium and 10.2g/L of tartaric acid.
Example 2
Adding catechol into zinc sulfate solution containing 2.28g/L of germanium, 104g/L of zinc and pH 2.5 according to the ratio of catechol/germanium to 3 to serve as a germanium complexing agent, then using 30% of N235 and 70% of kerosene as organic extracting agents to perform three-stage extraction, and using 1% of catechol diluent to perform two-stage washing on a first-stage loaded organic phase, wherein the washing liquid contains trace germanium; carrying out three-stage back extraction on the first-stage purified loaded organic phase by using 25% sodium hydroxide solution, supplementing 4% sodium hydroxide to the first-stage back extraction solution for returning use, recycling the alkali back extraction solution for 12 times, then neutralizing, hydrolyzing and precipitating germanium hydroxide, wherein the pH value of the precipitate is 9, washing the obtained hydrolysis precipitate with hot water, and calcining at 300 ℃ for 1.5 hours to obtain germanium concentrate with the grade of 42.37% germanium; causticizing the hydrolysis precipitation filtrate with calcium hydroxide at 90 ℃ for 6 hours to obtain causticized solution containing 93.5g/L of sodium hydroxide, dissolving and leaching the causticized slag with 30% of sulfuric acid, wherein the leaching solution contains 15.6g/L of catechol.
Example 3
The organic phase loaded with the germanium tartrate in the example 1 is subjected to secondary washing by respectively using clear water and a 5% ammonium bicarbonate dilute solution, and the obtained washing liquid contains 530mg/L and 895mg/L of germanium respectively. The purified loaded organic phase is subjected to three-stage back extraction by using 30-40% of sodium hydroxide, 3% of sodium hydroxide is supplemented into the first-stage back extraction solution, the first-stage back extraction solution is returned for recycling for 5 times, the back extraction solution is thickened, and a large amount of sodium sulfate is crystallized, so that the back extraction is difficult. And (3) testing that the first-stage stripping solution contains 7.3g/L of germanium, washing the hydrolyzed and precipitated germanium hydroxide with hot water, and calcining at 300 ℃ to obtain the germanium concentrate with the grade of 10.5%.
Example 4
Tracking and counting the quality improvement and consumption reduction of germanium concentrate produced by extraction in the embodiments 1, 2 and 3, and comparing the consumption of organic complexing agent and sodium hydroxide for producing 1 kg of germanium; the net amount of the organic complexing agent is the complex germanium amount plus the washing amount minus the recovery amount (80% recovery rate), and the net amount of the sodium hydroxide is the initial amount of the back extraction solution plus the supplement amount minus the recovery amount (50% recovery rate);
example 1: the net amount of tartaric acid complexing agent is 5 kg/kg germanium for complexing, 12 kg/kg germanium for washing, and the effective recovery amount is 15.3 kg/kg germanium and 3.4 kg/kg germanium. The net amount of sodium hydroxide is equal to (300 kg/m)3Initial dosage of 240 kg/m3The supplement dosage is-270 kg/m3Recovery/14.6 kg Ge/m3(the stripping solution is recycled after 8 times, and the stripping solution contains 16.3 g/L-16.3 kg/m germanium3Calculated by 90% hydrolysis precipitation) 18-19 kg/kg germanium
Example 2: the net amount of the catechol complexing agent is 3 kg/kg of germanium, the washing amount is 13.5 kg/kg of germanium, and the effective recovery amount is 13.2 kg/kg of germanium is 3.3 kg/kg of germanium. Sodium hydroxide (250 kg/m)3+480 kg/m3-360 kg/m3) 21.33 kg Ge/m317-18 kg/kg germanium
Example 3: the net amount of tartaric acid complexing agent is 5 kg/kg germanium for complexing, the recovery amount of 2.5 kg/kg germanium (because of containing a large amount of sodium sulfate, the tartaric acid can be recovered to 50 percent at most), and the net amount of tartaric acid complexing agent is 2.5 kg/kg germanium. The net amount of sodium hydroxide is equal to (300 kg/m)3+150 kg/m3-225 kg/m3) 7.3 kg Ge/m334-35 kg/kg ge.
Example 5
The data of example 4 were used to evaluate the calculated economic indicators of examples 1, 2, and 3, calculated according to the current market price of industrial products, 20 yuan/kg tartaric acid, 40 yuan/kg catechol, and 4 yuan/kg sodium hydroxide, then:
example 1: the net cost of tartaric acid is 68 yuan/kg germanium, the net cost of alkali is 72 yuan/kg germanium, and the total cost is 140 yuan/kg germanium;
example 2: the net cost of catechol is 132 yuan/kg germanium, the alkali cost is 68 yuan/kg germanium, and the total cost is 200 yuan/kg germanium;
example 3: the net cost of tartaric acid is 50 yuan/kg germanium, the alkali cost is 140 yuan/kg germanium, and the total cost is 190 yuan/kg germanium. The quality of the obtained germanium concentrate is increased by 150-200 yuan/kg when the quality of the germanium concentrate is increased by 10 percent;
therefore, the economic benefits of example 1 and example 2 are respectively 300-400 yuan/kg germanium and 450-600 yuan/kg germanium compared with example 3; by subtracting the consumption cost of the complexing agent and the alkali, the net economic benefits of the embodiment 1 and the embodiment 2 are 160-260-element/kg germanium and 250-400-element/kg germanium respectively compared with the embodiment 3.
Claims (6)
1. A method of producing germanium concentrate with an N235 extractant, comprising the steps of:
(1) adding an organic complexing agent into the germanium-containing acidic solution, uniformly mixing, adding an N235 kerosene extracting agent for germanium extraction, and obtaining a loaded organic phase containing an organic germanium complex;
(2) washing with organic acid dilute solution, purifying and removing impurities to obtain a purified load organic phase;
(3) adopting sodium hydroxide solution to perform back extraction and purify a loaded organic phase to obtain alkali back extraction liquid, and returning and recycling the alkali back extraction liquid for multiple times until the content of germanium in the alkali back extraction liquid reaches more than 20 g/L;
(4) hydrolyzing an alkali back extraction solution containing more than 20g/L of germanium to obtain a hydrolysis precipitate and a hydrolysis precipitate filtrate; washing the hydrolysis precipitate with hot water, and calcining at the temperature of 200-300 ℃ to obtain high-grade germanium concentrate;
(5) causticizing the hydrolysis precipitation filtrate by using calcium hydroxide or calcium oxide to obtain a calcium-containing precipitate, and returning the sodium hydroxide regenerated liquid to be used for preparing alkali or used as a waste water neutralizer;
(6) dissolving and leaching the calcium-containing precipitate with sulfuric acid to obtain an organic acid leaching solution and calcium sulfate slag; concentrating and crystallizing the organic acid leaching solution to recover the organic acid complexing agent or directly returning the organic acid complexing agent to be used as a germanium complexing agent;
the organic complexing agent is any one of catechol, tartaric acid, citric acid and humic acid;
the organic acid dilute solution is an organic acid dilute solution corresponding to the organic germanium complex.
2. The method for producing germanium concentrate with the N235 extractant as recited in claim 1, wherein the amount of the organic complexing agent is such that the mass ratio of the organic complexing agent to germanium is (3-5): 1.
3. The method of claim 1, wherein the dilute organic acid solution has a concentration of 0.1 to 5% by weight.
4. The method of claim 1, wherein the high quality germanium concentrate is a germanium dioxide concentrate containing 30-50% germanium by mass.
5. The method for producing germanium concentrate with N235 extractant as claimed in claim 1, wherein the causticizing reaction is carried out under the following process conditions: the temperature is 80-90 ℃ and the time is 5-6 h.
6. A method of producing a germanium concentrate with an N235 extractant as claimed in claim 1 wherein the calcium hydroxide or calcium oxide is used in the amount of calcium ions (organic acid + sulphate ions) ═ 1.1-1.5): 1.
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| CN112410584B (en) * | 2020-11-10 | 2022-06-17 | 广东先导稀材股份有限公司 | Method for recovering germanium from zinc leaching residues |
| CN112695212B (en) * | 2020-12-10 | 2023-05-05 | 衢州华友钴新材料有限公司 | Ternary synergistic extraction method for separating germanium from high-iron high-arsenic sulfate solution |
| CN114921665B (en) * | 2022-06-01 | 2023-08-22 | 朝阳金美镓业有限公司 | Method for regenerating germanium and hydrochloric acid from germanium-containing hydrochloric acid solution by extraction method |
| CN115505762A (en) * | 2022-09-22 | 2022-12-23 | 湖南锐异资环科技有限公司 | Indium extraction method of indium-containing multi-metal smelting slag |
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| WO2008003808A1 (en) * | 2006-07-03 | 2008-01-10 | Universidad De Sevilla | Method for the recovery of germanium present in coal ash |
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