Germanium-containing material treatment method and device

Abstract

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.

Description

Technical Field

[0001] The present invention relates to the field of germanium-containing material processing, and specifically to a method and device for processing germanium-containing materials. Background Art

[0002] Germanium is widely used in semiconductors, detection, communications, optics, and other fields, making it a critical strategic resource. As competition in the global semiconductor technology sector intensifies, demand for germanium continues to grow. Germanium is difficult to form independently and is often found in sphalerite, arsenic-copper sulfide, silver-lead, iron ore, and coal. The production process for germanium primarily involves three stages: concentrate preparation, extraction, and purification. However, the extraction of germanium from germanium-containing materials suffers from low efficiency and yield. Summary of the Invention

[0003] The present application provides a method and apparatus for processing germanium-containing materials, which can obtain higher-purity germanium products through a simplified germanium enrichment process and reduce production costs.

[0004] In a first aspect, an embodiment of the present application provides a method for processing a germanium-containing material, comprising:

[0005] Acid leaching process, in the presence of an auxiliary agent, using an acidic solution to acid-leach the germanium-containing material to obtain a leachate containing germanium element;

[0006] an adsorption process, wherein the germanium-containing leaching solution is brought into contact with an adsorption resin for adsorption treatment to obtain an adsorption resin loaded with germanium;

[0007] The analytical step is to perform analytical treatment on the adsorption resin loaded with germanium to obtain a germanium-containing analytical solution;

[0008] In the evaporation separation step, the germanium-containing analytical solution is subjected to distillation and rectification to obtain germanium tetrachloride.

[0009] In the treatment method of germanium-containing materials, the additive can be used with Ge 4+ The coordination forms a soluble complex, promoting the leaching of germanium. Furthermore, in this system, the adsorption resin selectively adsorbs the germanium-containing complex, allowing silicon and germanium to be separated during the adsorption process. Since the germanium-containing analytical solution contains relatively low silicon content, a higher-purity germanium product can be obtained through distillation and rectification. This method avoids the complex impurity and germanium separation process, simplifies the germanium enrichment process, and can produce a higher-purity germanium product in a shorter process, thereby reducing the cost of germanium extraction.

[0010] In some embodiments, the process further includes performing an alkaline aging treatment on the germanium-containing material using an alkaline substance and water before the acid leaching process to obtain an aging germanium-containing material. In the above embodiments, the acid leaching process is to perform an acid leaching treatment on the aging germanium-containing material to obtain a leachate containing germanium.

[0011] In some embodiments, the mass ratio of the germanium-containing material, the alkaline substance, and water is 1:(1-2):(0.03-0.3).

[0012] In some embodiments, the alkaline substance includes one or more of sodium hydroxide, potassium hydroxide, and sodium carbonate.

[0013] In some embodiments, the temperature of the alkali aging treatment is 100°C to 200°C.

[0014] In some embodiments, the alkali aging time is 2 hours to 12 hours.

[0015] In some embodiments, the particle size D of the germanium-containing material after aging is 50 ≤30mm.

[0016] In some embodiments, the adjuvant includes a substance that can ionize into carboxylate ions in water.

[0017] In some embodiments, the adjuvant includes one or more of oxalic acid, citric acid, and tartaric acid.

[0018] In some embodiments, the adjuvant includes oxalic acid.

[0019] In some embodiments, the acidic solution includes hydrochloric acid.

[0020] In some embodiments, the acidic solution can provide both oxalate ions and chloride ions.

[0021] In some embodiments, the acid leaching process does not require external heating, and the reaction heat is provided by the residual heat of the matured solids and the heat released by the acid-base neutralization, which helps to reduce energy consumption and production costs.

[0022] In some embodiments, the endpoint pH value of the acid leaching treatment is 0-3.

[0023] In some embodiments, the temperature of the acid leaching treatment is 70°C to 100°C.

[0024] In some embodiments, the leaching rate of germanium is ≥90%.

[0025] In some embodiments, the leaching rate of germanium is ≥90% by combining alkali aging and acid leaching. Alternatively, the leaching rate of germanium is ≥92%. Alternatively, the leaching rate of germanium is 92% to 95%.

[0026] In some embodiments, the adsorption resin comprises an anion exchange resin.

[0027] In some embodiments, the adsorption resin comprises an anion exchange resin containing tertiary amino groups.

[0028] In some embodiments, the adsorption resin comprises IRA-900 resin.

[0029] In some embodiments, the flow rate of the solution for adsorption treatment is 0.5 BV / h to 3 BV / h;

[0030] In some embodiments, the adsorption resin has a separation coefficient of >100 for Ge and Si.

[0031] In some embodiments, the adsorption resin has a separation factor of >20 for Ge and As.

[0032] In some embodiments, the resin has an adsorption rate of greater than 99% for germanium.

[0033] In some embodiments, the germanium-loaded adsorption resin is subjected to desorption treatment using an acidic desorption solution.

[0034] In some embodiments, the acidic analytical solution comprises hydrochloric acid.

[0035] In some embodiments, the concentration of hydrochloric acid in the acidic analytical solution is 6 mol / L to 10 mol / L.

[0036] In some embodiments, the parsing process is performed using a cyclic parsing method, with the number of cycles being 1 to 5.

[0037] In some embodiments, the germanium resolution during the resolution process is greater than 99%.

[0038] In some embodiments, the volume of the solution used in the desorption process is 0.5 BV to 10 BV.

[0039] In some embodiments, the solution flow rates of the adsorption step and the desorption step are independently 0.5 BV / h to 3 BV / h.

[0040] In some embodiments, the process further includes returning the residual liquid produced by the distillation to the distillation process.

[0041] In some embodiments, the process further comprises hydrolyzing, washing and drying germanium tetrachloride to obtain germanium oxide.

[0042] In some embodiments, the process further comprises reducing germanium oxide to obtain metallic germanium.

[0043] In some embodiments, the process further comprises mixing at least one of distillation residue produced by distillation, wastewater produced by hydrolysis, or washing water produced by washing with hydrochloric acid and oxalic acid to prepare an acidic solution.

[0044] In some embodiments, the adsorption liquid generated by the adsorption process is further used to produce a sodium chloride product.

[0045] In a second aspect, an embodiment of the present application provides a device, comprising:

[0046] Leaching equipment, used for acid leaching of germanium-containing materials;

[0047] A filtering device connected to the leaching device is used to filter the solution produced by the leaching device to obtain a leachate containing germanium;

[0048] The adsorption and desorption equipment is connected to the filtration equipment and contains an anion exchange resin for adsorption and desorption of the germanium-containing leachate;

[0049] A distillation device connected to the adsorption and desorption device, used to distill the desorption liquid produced by the adsorption and desorption device;

[0050] The distillation equipment is connected to the distillation equipment and is used to perform distillation treatment on the distillation product output by the distillation equipment.

[0051] In some embodiments, the anion exchange resin is an anion exchange resin containing tertiary amino groups.

[0052] In some embodiments, the anion exchange resin is IRA-900 resin.

[0053] In some embodiments, the apparatus further comprises: an alkali aging device connected to the leaching device for performing alkali aging treatment on the germanium-containing material.

[0054] In some embodiments, the alkali aging apparatus includes a heating component and a stirring component.

[0055] In some embodiments, the apparatus further comprises: a crushing device, wherein the feed port of the crushing device is connected to the alkali ripening device, and the discharge port of the crushing device is connected to the leaching device.

[0056] In some embodiments, the alkali aging equipment is a rake dryer, and the crushing equipment is a double-roll crusher.

[0057] In some embodiments, the vertical distance between the discharge port of the alkali aging device and the ground is greater than the vertical distance between the feed port of the leaching device and the ground.

[0058] In some embodiments, the apparatus further comprises an additive storage device and an acid storage device connected to the leaching device.

[0059] In some embodiments, the apparatus further comprises a hydrolysis device connected to the distillation device, for performing a hydrolysis treatment on the distillation product obtained by the distillation treatment.

[0060] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become obvious from the description below, or will be learned through practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] Figure 1 1 is a schematic diagram of a process flow of a method for treating germanium-containing materials according to an embodiment of the present application. DETAILED DESCRIPTION

[0062] " range " disclosed in the present application is limited in the form of lower limit and upper limit, and given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of special range. The scope limited in this way can be to include end value or not include end value, and can be arbitrarily combined, that is, any lower limit can form a range with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for specific parameters, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range value 1 and 2 are listed, and if the maximum range value 3,4 and 5 are listed, then the following range can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise specified, the numerical range " ab " represents the abbreviation of any real number combination between a and b, wherein a and b are all real numbers. For example, a numerical range of "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is simply an abbreviation for these numerical combinations. Furthermore, when a parameter is expressed as an integer ≥ 2, this is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0063] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0064] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0065] Unless otherwise specified, all steps of the present application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), indicating that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0066] Unless otherwise specified, the terms "include" and "comprising" used in this application may be open-ended or closed-ended. For example, "include" and "comprising" may mean that other components not listed may also be included or that only the listed components are included.

[0067] Unless otherwise specified, the term "or" is used in this application to be inclusive. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, the condition "A or B" is satisfied if any of the following conditions are met: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0068] Unless otherwise specified, in this application, the term "connection" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a direct connection or an indirect connection through an intermediate medium.

[0069] The above summary of the invention of this application is not intended to describe every disclosed embodiment or every implementation in this application. The following description more specifically illustrates exemplary embodiments. In many places throughout the application, guidance is provided by a series of examples, which can be used in various combinations. In each example, the enumeration is intended only as a representative group and should not be construed as exhaustive.

[0070] Herein, the germanium-containing material may also include other impurity elements, such as one or more of silicon, iron, magnesium, etc. For example, the germanium-containing material may be germanium-containing fume generated by smelting laterite nickel ore.

[0071] In the related technologies, germanium is extracted by pyrometallurgy, wet metallurgy and combined pyrometallurgy and wet metallurgy. The wet metallurgy has a long process and consumes a lot of chemical reagents, while the pyrometallurgy enrichment stream is difficult to recover and has a low recovery rate.

[0072] In view of this, the present application provides a method and apparatus for processing germanium-containing materials, aiming to simplify the germanium enrichment process, obtain high-purity germanium products, and reduce production costs.

[0073] In a first aspect, an embodiment of the present application provides a method for processing a germanium-containing material, comprising:

[0074] Acid leaching process, in the presence of an auxiliary agent, using an acidic solution to acid-leach the germanium-containing material to obtain a leachate containing germanium element;

[0075] an adsorption process, wherein the germanium-containing leaching solution is brought into contact with an adsorption resin for adsorption treatment to obtain an adsorption resin loaded with germanium;

[0076] The analytical step is to perform analytical treatment on the adsorption resin loaded with germanium to obtain a germanium-containing analytical solution;

[0077] In the evaporation separation step, the germanium-containing analytical solution is subjected to distillation and rectification to obtain germanium tetrachloride.

[0078] In the method for treating germanium-containing materials provided in the embodiment of the present application, the auxiliary agent can be used with Ge 4+ The coordination forms a soluble complex, which promotes the leaching of the germanium element. Subsequently, an adsorption resin is used as an adsorbent. In the system of the present application, the adsorption resin can achieve highly selective adsorption of germanium and silicon. The adsorption resin can selectively adsorb germanium-containing complexes. The adsorption resin loaded with germanium is subjected to analytical treatment to obtain a germanium-containing analytical solution. The germanium-containing analytical solution has a low content of impurities such as silicon, and a high-purity germanium product can be directly obtained through distillation and rectification. This method reduces the complex silicon and germanium separation process, simplifies the germanium enrichment process, and can obtain a high-purity germanium product through a shorter process, thereby reducing the extraction cost of germanium.

[0079] In some embodiments, the process further includes performing an alkaline aging treatment on the germanium-containing material using an alkaline substance and water before the acid leaching process to obtain an aging germanium-containing material. In this embodiment, the acid leaching process is to perform an acid leaching treatment on the aging germanium-containing material to obtain a leachate containing germanium.

[0080] Alkali aging is combined with acid leaching. The aging process utilizes the localized heat released by alkali dissolution to enhance the aging effect and break down the germanosilicate and germanium-silicon eutectic. The aging germanium-containing material contains alkali. When mixed with acid, the acid and alkali react and release heat, promoting the acid leaching process. This reaction generates heat, reducing process heat consumption and potentially reducing heating equipment investment, further lowering costs.

[0081] In some embodiments, the mass ratio of the germanium-containing material, the alkaline substance and water is 1: (1-2): (0.03-0.3). For example, the mass ratio can be 1: 1: 0.03, 1: 1: 0.06, 1: 1: 0.09, 1: 1.2: 0.03, 1: 1.2: 0.06, 1: 1.2: 0.09, 1: 1.5: 0.03, 1: 1.5: 0.06, 1: 1.5: 0.09, 1: 2: 0.3, or any value or range consisting of any values ​​between 1: (1-2): (0.03-0.3). During the alkali aging process, the addition of alkaline substances such as caustic soda and water can quickly increase the system temperature, improve production efficiency, and shorten the heating aging time. At the same time, the appropriate amount of water and alkaline substance is conducive to further promoting the uniform mixing of the germanium-containing material and the alkaline substance under cost control and improving production efficiency.

[0082] In some embodiments, the alkaline substance includes one or more of sodium hydroxide, potassium hydroxide, and sodium carbonate.

[0083] In some embodiments, the basic substance comprises sodium hydroxide.

[0084] In some embodiments, the temperature of the alkali ripening process is 100-200°C. Exemplarily, the temperature of the alkali ripening process can be 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, or any value or range of values between 100°C and 200°C.

[0085] In some embodiments, the time of the alkali ripening process is 2-12h. Exemplarily, the time of the alkali ripening process can be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, or any value or range of values between 2h and 12h.

[0086] In some embodiments, the particle size of the germanium-containing material after ripening is D 50 ≤30mm. Exemplarily, the particle size of the germanium-containing material after ripening can be 10mm, 12mm, 14mm, 16mm, 18mm, 20mm, 22mm, 24mm, 26mm, 28mm, 30mm, or any value or range of values between D 50 ≤30mm.

[0087] In some embodiments, the auxiliary agent comprises a substance that can ionize carboxylate in water.

[0088] In some embodiments, the auxiliary agent comprises one or more of oxalic acid, citric acid, and tartaric acid.

[0089] In some embodiments, the auxiliary agent comprises oxalic acid.

[0090] In the leaching process, C2O4 2- in the auxiliary agent oxalic acid coordinates with Ge 4+ to form a soluble complex [Ge(C2O 4) ] 2- , promoting the leaching of Ge 4+ and increasing the leaching rate of germanium element, while the ions of nickel, cobalt, calcium, magnesium, zinc, etc. can react with C2O4 2- to form precipitates, so as to simultaneously achieve efficient leaching of germanium element and preliminary separation from impurities. Meanwhile, in the subsequent resin adsorption process, anion resin can selectively adsorb the complex formed by germanium metal and oxalate, thereby increasing the adsorption rate of germanium and further separating germanium from impurities.

[0091] In some embodiments, the acidic solution includes hydrochloric acid. Using hydrochloric acid effectively utilizes residual acid from the distillation and rectification processes, and the system ultimately produces only NaCl wastewater, avoiding the increased costs associated with treating NaCl and Na2SO4 or other mixed salt wastewater, further reducing costs.

[0092] In some embodiments, the acidic solution can provide oxalate ions and chloride ions at the same time. Oxalate ions react with germanium ions to form soluble complexes, promoting the leaching and separation of germanium. On this basis, in the chloride ion system, on the one hand, Cl- as a weak ligand can promote the chelation reaction between germanium and oxalate to form a more stable Ge(C2O4)32-, thereby suppressing the volatilization loss of germanium during the leaching process. On the other hand, it can promote the anion resin to preferentially adsorb the anionic complex formed by the high-valent germanium metal and oxalate, further improving the germanium adsorption rate and the separation efficiency of As and Si.

[0093] In some embodiments, the acid leaching process does not require external heating, and the reaction heat is provided by the residual heat of the matured solids and the exothermic heat of acid-base neutralization. This helps reduce energy consumption, lower production costs, and simplify the operation process.

[0094] In some embodiments, the endpoint pH value of the acid leaching treatment is 0 to 3. For example, the endpoint pH value of the acid leaching treatment can be 0, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, or any value or range consisting of any values ​​between 0 and 3. If the endpoint pH value of the acid leaching treatment is too high, germanium will be precipitated, affecting the leaching of the germanium element; if the pH value is too low, acid will be wasted.

[0095] In some embodiments, the acid leaching temperature is 70° C. to 100° C. For example, the acid leaching temperature can be 70° C., 72° C., 74° C., 76° C., 78° C., 80° C., 82° C., 84° C., 86° C., 88° C., 90° C., 92° C., 94° C., 96° C., 98° C., 100° C., or any value or range of values ​​between 70° C. and 100° C. A suitable acid leaching temperature is beneficial for increasing the reaction rate while reducing material loss.

[0096] In some embodiments, the leaching rate of germanium is ≥90%. The leaching rate refers to the ratio of the amount of target substance leached from the solid raw material into the leachate during the leaching process to the total amount of the target substance in the solid raw material, typically expressed as a percentage. In the embodiments of the present application, it may refer to the ratio of the mass of germanium leached from the germanium-containing material into the leachate during the leaching process to the total mass of germanium in the germanium-containing material, expressed as a percentage.

[0097] By combining alkali aging and acid leaching, the leaching rate of germanium is ≥90%. Optionally, the leaching rate of germanium is ≥92%. Optionally, the leaching rate of germanium is 92% to 95%.

[0098] In some embodiments, the adsorption resin comprises an anion exchange resin.

[0099] In some embodiments, the adsorption resin comprises an anion exchange resin containing tertiary amino groups.

[0100] In some embodiments, the adsorption resin comprises IRA-900 resin.

[0101] Anion exchange resin is selected as the adsorbent. In the chloride ion system, the resin selectively adsorbs the coordination complex formed by germanium metal and oxalate, efficiently adsorbs germanium, and has a highly efficient separation effect on As and Si.

[0102] In some embodiments, the separation coefficient of the adsorption resin for Ge and Si is greater than 100. For example, the separation coefficient of Ge and Si can be 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 120, or 130. In the adsorption process of the present application, especially in systems containing chloride ions and soluble complexes, the adsorption resin has a high separation coefficient for Ge and Si. By selectively adsorbing germanium, the subsequent complex separation processes such as silicon-germanium precipitation and adsorption can be avoided, the subsequent process can be simplified, and a higher purity germanium product can be obtained.

[0103] In some embodiments, the separation coefficient of the adsorption resin for Ge and As is greater than 20. For example, the separation coefficient of Ge and As can be 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 40, 50, or 60.

[0104] In some embodiments, the resin has an adsorption rate of greater than 99% for germanium. Exemplary adsorption rates for germanium may be 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or 100%.

[0105] In some embodiments, the germanium-loaded adsorption resin is subjected to desorption treatment using an acidic desorption solution.

[0106] In some embodiments, the acidic analytical solution comprises hydrochloric acid.

[0107] In some embodiments, the concentration of hydrochloric acid in the acidic elution solution is 6-10 mol / L. For example, the concentration of hydrochloric acid can be 6 mol / L, 6.2 mol / L, 6.4 mol / L, 6.6 mol / L, 6.8 mol / L, 7.0 mol / L, 7.5 mol / L, 8.0 mol / L, 8.5 mol / L, 9.0 mol / L, 9.5 mol / L, 10.0 mol / L, or any value or range of values between 6 mol / L and 10 mol / L. Using the above concentration of hydrochloric acid for elution can directly distill and simplify the production process, thereby reducing the production cost.

[0108] In some embodiments, the elution process is performed by using a cyclic elution method, and the number of cycles is 1-5. For example, the number of cycles can be 1, 2, 3, 4, or 5, or any value or range of values between 1 and 5.

[0109] By adjusting some or all of the process parameters in the above resin adsorption separation and elution process, high germanium adsorption rate and Si and As removal rate can be obtained, such as a germanium adsorption rate of greater than 99.5%, an elution rate of greater than 99.5%, an As removal rate of greater than 92%, and a Si removal rate of greater than 99%. After hydrochloric acid elution, the germanium concentration is enriched by 4-10 times, and the germanium-containing eluate can be directly distilled to further improve the enrichment efficiency of germanium in the germanium-containing material.

[0110] In some embodiments, the elution rate of germanium in the elution process is greater than 99%. For example, the elution rate of germanium can be 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or 100%.

[0111] In some embodiments, the volume of the solution used in the elution process is 0.5-10 BV. For example, the volume of the solution used in the elution process can be 0.5 BV, 1.0 BV, 1.5 BV, 2.0 BV, 2.5 BV / h, 3.0 BV, 4.0 BV, 5.0 BV, 6.0 BV, 7.0 BV, 8.0 BV, 9.0 BV, 10.0 BV, or any value or range of values between 0.5 BV and 10 BV.

[0112] In some embodiments, the solution flow rates of the adsorption process and the desorption process are independently 0.5BV / h to 3BV / h. For example, the solution flow rates of the adsorption and desorption processes can be independently 0.5BV / h, 0.75BV / h, 1.0BV / h, 1.25BV / h, 1.5BV / h, 1.75BV / h, 2.0BV / h, 2.25BV / h, 2.5BV / h, 2.75BV / h, 3.0BV / h, or any value or range between 0.5BV / h and 3BV / h. An appropriate solution flow rate is beneficial for ensuring the germanium adsorption and desorption efficiency while improving the equipment production capacity.

[0113] In some embodiments, the method further comprises distilling and rectifying the germanium-containing analytical solution to obtain germanium tetrachloride. Specifically, the method comprises distilling the germanium-containing analytical solution to obtain a germanium-containing fraction and a distillation residue, and rectifying the germanium-containing fraction to obtain germanium tetrachloride.

[0114] In some embodiments, the process further includes returning the residual liquid produced by the distillation to the distillation process.

[0115] In some embodiments, the process further comprises hydrolyzing, washing and drying germanium tetrachloride to obtain germanium oxide.

[0116] In some embodiments, the process further includes reducing germanium oxide to obtain metallic germanium. The metallic germanium can be obtained by using some conventional germanium reduction methods. For example, the metallic germanium can be obtained by reducing germanium oxide with hydrogen.

[0117] In some embodiments, the process further comprises mixing at least one of distillation residue produced by distillation, wastewater produced by hydrolysis, or washing water produced by washing with hydrochloric acid and oxalic acid to prepare an acidic solution.

[0118] In some embodiments, the adsorption liquid generated by the adsorption process is further used to produce a sodium chloride product.

[0119] In a second aspect, an embodiment of the present application provides a device, comprising:

[0120] Leaching equipment, used for acid leaching of germanium-containing materials;

[0121] A filtering device is connected to the leaching device and is used to filter the solution produced by the leaching device to obtain a leachate containing germanium;

[0122] The adsorption and desorption equipment is connected to the filtration equipment and contains an anion exchange resin for adsorption and desorption of the germanium-containing leachate;

[0123] A distillation device connected to the adsorption and desorption device, used to distill the desorption liquid produced by the adsorption and desorption device;

[0124] The distillation equipment is connected to the distillation equipment and is used to perform distillation treatment on the distillation product output by the distillation equipment.

[0125] The device provided in this embodiment comprises a leaching device, a filtering device, an adsorption and analysis device, a distillation device and a rectification device which are connected in sequence. The leaching device is used to leach the germanium element from the germanium-containing material, and the filtering device can filter the solution produced by the leaching device to remove impurities in the solution, thereby reducing the content of impurities in the germanium-containing leachate. The filtered germanium-containing leachate enters the adsorption and analysis device, and through adsorption and analysis, the separation of germanium and impurities is achieved. The obtained analytical solution can directly enter the distillation device for distillation, and the distillation product (germanium tetrachloride distillate) produced by the distillation enters the rectification device for rectification, and finally a distillation product (refined germanium tetrachloride) is obtained. The device of the present application has a compact structure and a simple process, which can reduce the investment in complex impurity separation equipment and achieve efficient germanium recovery with relatively small equipment investment and relatively small site requirements.

[0126] In some embodiments, the anion exchange resin is an anion exchange resin containing tertiary amino groups.

[0127] In some embodiments, the anion exchange resin is IRA-900 resin.

[0128] The adsorption and desorption equipment contains suitable anion exchange resin, which is conducive to the separation of germanium ions and key impurity ions, such as silicon and arsenic, in the adsorption and desorption equipment, so that the desorption liquid can directly enter the distillation equipment for distillation treatment, reducing the investment in other desorption liquid impurity removal equipment and processes, further reducing costs and achieving efficient germanium recovery.

[0129] In some embodiments, the apparatus further comprises:

[0130] The alkali ripening equipment is connected to the leaching equipment and is used to perform alkali ripening treatment on germanium-containing materials.

[0131] After the alkali aging process, the germanium-containing material is transported to the leaching equipment. The alkali aging process in the alkali aging equipment is followed by acid leaching in the leaching equipment. The combination of the two can further reduce energy consumption, lower the requirements for the heating module of the leaching equipment, and further reduce costs.

[0132] In some embodiments, the alkali aging apparatus includes a heating assembly and a stirring assembly. The heating assembly can be a heating resistor, a heating jacket, or other heating element, and the stirring assembly can be a stirring paddle, stirring rake, or the like. The heating assembly can provide a suitable reaction temperature for the alkali aging process, and the stirring assembly can promote mixing of the materials, thereby shortening the alkali aging process time.

[0133] In some embodiments, the apparatus further comprises: a crushing device, wherein the feed port of the crushing device is connected to the alkali ripening device, and the discharge port of the crushing device is connected to the leaching device.

[0134] In some embodiments, the alkali aging equipment is a rake dryer and the crushing equipment is a roller crusher. The rake dryer and the roller crusher are combined to further integrate the equipment and reduce the equipment space requirements.

[0135] In some embodiments, the vertical distance between the discharge port of the alkali aging device and the ground is greater than the vertical distance between the feed port of the leaching device and the ground. The alkali aging device is located at a high position and can be discharged directly from the high position to the low position by gravity.

[0136] In some embodiments, the apparatus further includes an additive storage device and an acid storage device connected to the leaching device. The additive storage device and the acid storage device can respectively provide the leaching device with the acid and additive required for the leaching reaction. The additive can promote the leaching of the germanium element and the precipitation of impurities. Connecting the leaching device to the filtration device and the additive storage device respectively facilitates the production of a relatively high-purity germanium-containing leachate at a low cost.

[0137] In some embodiments, the apparatus further comprises a hydrolysis device connected to the distillation device for hydrolyzing the distillation product obtained by the distillation process. When processing germanium-containing materials, the distillation product is the refined germanium tetrachloride obtained by the distillation process.

[0138] Example

[0139] The following examples describe the present disclosure in more detail and are intended to be illustrative only, as various modifications and variations within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the following examples are by weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and used directly without further processing, and all instruments used in the examples are commercially available.

[0140] Example 1

[0141] The method of preparing metallic germanium from germanium-containing ash from pyrometallurgical nickel smelting comprises:

[0142] (1) Alkali aging treatment: Take 100g of pyrometallurgical nickel-containing germanium ash, add 100g of flake caustic soda of the same mass, mix well, add 10g of water to form a slightly moist dispersed granular mixture, put it in a 100℃ oven, and age it for 12h, stirring it every 30 minutes during the aging process;

[0143] (2) Acid leaching process: After the aging is completed, the alkali-aged material is crushed and then acid-leached with a mixed solution of hydrochloric acid and oxalic acid. The pH of the acid leaching endpoint is 0.5 and the reaction temperature is 80°C. After solid-liquid separation, a leachate containing germanium and waste residue are obtained. The leaching rate of germanium is calculated to be 92.30%;

[0144] (3) resin adsorption and decomposition treatment, the leachate obtained in step (1) was subjected to anion exchange resin adsorption and decomposition treatment, the anion exchange resin was IRA-900 resin, the resin bed volume was 100 mL, the adsorption and decomposition flow rate was 2 BV / h, 6 mol / L hydrochloric acid was used for decomposition, the decomposition volume was 2 BV, and the decomposition was repeated 5 times to obtain a decomposition solution with a germanium content of 1795 mg / L. After calculation, the germanium adsorption rate was 99.23%, the decomposition rate was 99.12%, the corresponding As removal rate was 92.54%, and the Si removal rate was 99.16%;

[0145] (4) Germanium is distilled, rectified, hydrolyzed and reduced and smelted. The analytical solution obtained in step (3) is distilled and rectified at 85°C for purification, and then hydrolyzed, washed and dried to obtain germanium oxide. The germanium oxide is reduced with hydrogen in a quartz tube of a reduction furnace to obtain metallic germanium. The reduction temperature is 670°C and the reduction time is 24 hours. When the reduction is completed, the temperature is gradually raised to 1050°C to melt the germanium, and then slowly cooled to obtain high-purity metallic germanium;

[0146] (5) treating the adsorbed liquid and waste residue, wherein the waste residue obtained in step (1) enters a pyrometallurgical nickel smelting system to recover nickel; and the adsorbed liquid obtained in step (1) is used to produce industrial sodium chloride;

[0147] (6) Recycling: the distillation residue, the liquid after hydrolysis and washing filtration are returned to the acid leaching to prepare a mixed solution of hydrochloric acid and oxalic acid; the distillation residue is returned to the germanium distillation to further recover germanium.

[0148] Example 2

[0149] The method of preparing metallic germanium from germanium-containing ash from pyrometallurgical nickel smelting comprises:

[0150] (1) Alkali aging treatment: Take 100g of pyrometallurgical nickel-containing germanium ash, add 200g of flake caustic soda, mix well, add 30g of water to form a slightly moist dispersed granular mixture, put it in a 200℃ oven, and age it for 2h. Stir it every 30 minutes during the aging process;

[0151] (2) Acid leaching process: After the aging is completed, the alkali-aged material is crushed and then acid-leached with a mixed solution of hydrochloric acid and oxalic acid. The pH of the acid leaching endpoint is 2.0, the reaction temperature is 95°C, and the solid-liquid separation is performed to obtain a leachate containing germanium and waste residue. The leaching rate of germanium is calculated to be 93.25%;

[0152] (3) resin adsorption treatment and analytical treatment, wherein the leachate obtained in step (1) is subjected to anion exchange resin adsorption and analytical treatment, wherein the anion exchange resin is IRA-900 resin, the resin bed volume is 100 mL, the adsorption and analytical solution flow rate is 0.5 BV / h, 8 mol / L hydrochloric acid is used for analytical analysis, the analytical volume is 2 BV, and the analytical cycle is repeated 3 times to obtain an analytical solution with a germanium content of 1826 mg / L. Calculation shows that the germanium adsorption rate is 99.52%, the analytical rate is 99.53%, the corresponding As removal rate is 92.70%, and the Si removal rate is 99.17%;

[0153] (4) Germanium distillation, rectification, hydrolysis and reduction smelting, wherein the analytical solution obtained in step (3) is distilled and rectified at 85°C for purification, and then hydrolyzed, washed and dried to obtain germanium oxide. The germanium oxide is reduced with hydrogen in a quartz tube of a reduction furnace to obtain metallic germanium. The reduction temperature is 670°C and the reduction time is 24 hours. When the reduction is completed, the temperature is gradually raised to 1050°C to melt the germanium, and then slowly cooled to obtain high-purity metallic germanium;

[0154] (5) treating the adsorbed liquid and waste residue, wherein the waste residue obtained in step (1) enters a pyrometallurgical nickel smelting system to recover nickel; and the adsorbed liquid obtained in step (1) is used to produce industrial sodium chloride;

[0155] (6) Recycling: the distillation residue, the liquid after hydrolysis and washing filtration are returned to the acid leaching to prepare a mixed solution of hydrochloric acid and oxalic acid; the distillation residue is returned to the germanium distillation to further recover germanium.

[0156] Example 3

[0157] This embodiment differs from Example 1 in that an acrylic anion resin is used in the resin adsorption and desorption steps. While the acrylic anion resin in Example 3 can also adsorb Ge, its primary function is to separate Ge from the less volatile impurities of Mg and Fe. However, the acrylic anion resin's selectivity for Ge, As, and Si still does not meet the requirements, resulting in a substandard Si content in the germanium desorption solution. Consequently, the purity of the germanium product obtained directly through distillation and rectification does not meet stringent requirements.

[0158] The above embodiments of the present invention are merely examples for the purpose of clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Those skilled in the art will appreciate that other variations or modifications may be made based on the above description. It is not necessary and impossible to enumerate all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention are intended to be included within the scope of protection of the claims of the present invention.

Claims

1. A method for treating germanium-containing materials, characterized in that: include: Acid leaching process, in the presence of an auxiliary agent, using an acidic solution to acid-leach the germanium-containing material to obtain a leachate containing germanium element; an adsorption step, wherein the germanium-containing leachate is brought into contact with an adsorption resin for adsorption treatment to obtain an adsorption resin loaded with germanium; an analysis step, performing an analysis treatment on the adsorption resin loaded with germanium to obtain a germanium-containing analysis solution; In the evaporation separation step, the germanium-containing analytical solution is subjected to distillation and rectification to obtain germanium tetrachloride.

2. The method for treating germanium-containing materials according to claim 1, wherein: The method further comprises performing an alkali aging treatment on the germanium-containing material using an alkaline substance and water before the acid leaching process to obtain an alkali-aged germanium-containing material.

3. The method for treating germanium-containing materials according to claim 2, wherein: The alkali aging treatment satisfies at least one of the following characteristics: (1) The mass ratio of the germanium-containing material, the alkaline substance and the water is 1:(1-2):(0.03-0.3); (2) The alkaline substance includes one or more of sodium hydroxide, potassium hydroxide, and sodium carbonate; (3) The temperature of the alkali aging treatment is 100° C. to 200° C.; (4) The alkali aging treatment time is 2h to 12h; (5) The particle size D of the aged germanium-containing material 50 ≤30mm.

4. The method for treating germanium-containing materials according to claim 1, wherein: The acid leaching process also meets at least one of the following characteristics: (1) The auxiliary agent includes one or more of oxalic acid, citric acid, and tartaric acid; (2) The auxiliary agent includes oxalic acid; (3) The acidic solution includes hydrochloric acid; (4) Acidic solutions can provide both oxalate ions and chloride ions; (5) The end point pH value of the acid leaching treatment is 0 to 3; (6) The temperature of the acid leaching treatment is 70°C to 100°C.

5. The method for treating germanium-containing materials according to claim 1, characterized in that: The adsorption process also meets at least one of the following characteristics: (1) The adsorption resin includes an anion exchange resin; (2) the adsorption resin comprises an anion exchange resin containing tertiary amino groups; (3) the adsorption resin comprises IRA-900 resin; (4) The flow rate of the solution for the adsorption treatment is 0.5 BV / h to 3 BV / h; (5) The separation coefficient of the adsorption resin for Ge and Si is greater than 100; (6) The separation coefficient of the adsorption resin for Ge and As is greater than 20; (7) The adsorption rate of Ge by the adsorption resin is greater than 99%.

6. The method for treating germanium-containing materials according to claim 1, characterized in that: The analysis process also satisfies at least one of the following characteristics: (1) using an acidic analytical solution to perform analytical treatment on the adsorption resin loaded with germanium; Optionally, the acidic analytical solution includes hydrochloric acid; Optionally, the concentration of hydrochloric acid in the acidic analytical solution is 6 mol / L to 10 mol / L; (2) performing the analysis process using a cyclic analysis method, with the number of cycles being 1 to 5; (3) The resolution rate of germanium in the resolution process is greater than 99%; (4) The volume of the solution used in the analytical treatment is 0.5BV to 10BV; (5) The flow rate of the solution in the analytical treatment is 0.5 BV / h to 3 BV / h.

7. The method for treating germanium-containing materials according to any one of claims 1 to 6, characterized in that: Also includes at least one of the following processes: (1) returning the distillation residue produced by the distillation process to the distillation process; (2) hydrolyzing, washing and drying the germanium tetrachloride to obtain germanium oxide; Optionally, the method further comprises reducing the germanium oxide to obtain metallic germanium; (3) mixing at least one of the distillation residue produced by the distillation treatment, the wastewater produced by the hydrolysis, or the washing water produced by the washing with hydrochloric acid and oxalic acid to prepare an acidic solution.

8. A device, characterized in that: include: Leaching equipment, used for acid leaching of germanium-containing materials; A filtering device connected to the leaching device, used to filter the solution produced by the leaching device to obtain a leachate containing germanium; An adsorption and desorption device is connected to the filtering device and contains an anion exchange resin for adsorbing and desorbing the germanium-containing leachate; a distillation device connected to the adsorption and desorption device, for distilling the desorption liquid produced by the adsorption and desorption device; A distillation device is connected to the distillation device and is used to perform distillation treatment on the distillation product output by the distillation device.

9. The device according to claim 8, characterized in that Also includes at least one of the following features: (1) The anion exchange resin is an anion exchange resin containing tertiary amino groups; (2) the anion exchange resin is IRA-900 resin; (3) The device further comprises: an alkali aging device connected to the leaching device for alkali aging the germanium-containing material; Optionally, the device further comprises: a crushing device, wherein the feed port of the crushing device is connected to the alkali ripening device, and the discharge port of the crushing device is connected to the leaching device; (4) The device further includes an auxiliary agent storage device and an acid storage device connected to the leaching device; (5) The device also includes a hydrolysis device connected to the distillation device, which is used to hydrolyze the distillation product obtained by the distillation treatment.

10. The device according to claim 9, characterized in that Also includes at least one of the following features: (1) The alkali aging equipment includes a heating component and a stirring component; (2) The alkali aging equipment is a rake dryer, and the crushing equipment is a roller crusher; (3) The vertical distance between the discharge port of the alkali aging equipment and the ground is greater than the vertical distance between the feed port of the leaching equipment and the ground.

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