Extraction device and indium extraction method

Abstract

The invention discloses an extraction device and an extraction method for indium, and the extraction device comprises a first reaction device which is used for containing an indium-containing solution; the gas supply device is provided with a gas outlet communicated with the first reaction device, and the gas supply device is used for providing sulfur dioxide gas into the first reaction device through the gas outlet so as to extract a solution in the first reaction device; the second reaction device is arranged on the downstream side of the first reaction device and is used for accommodating the extracted solution; the liquid supply device is communicated with the second reaction device and is used for introducing sulfuric acid into the second reaction device and carrying out reverse extraction. According to the extraction device, sulfur dioxide gas is conveyed into the first reaction device through the gas supply device, so that counter-current extraction is carried out on an indium-containing solution and an organic phase, iron ions in the solution are eliminated, and the extraction rate of indium is increased.

Description

Technical Field

[0001] The invention relates to the technical field of hydrometallurgy, and in particular to an extraction device and an extraction method for indium. Background Art

[0002] In the related art, the mainstream process for producing indium is leaching-extraction-electrolysis, that is, the target metal indium and other impurity metals in the raw material are first transferred to the solution in the form of ions, and then the indium is extracted through the extraction and stripping stages to achieve the purpose of enrichment and recovery, and finally the product indium is obtained by electrolysis. In the extraction process of indium, accompanied by the co-extraction of impurity iron ions, problems such as poisoning and aging of the organic phase are caused, and the organic phase cannot be recycled in the end, resulting in increased extraction costs and waste of resources. Therefore, how to optimize the extraction process of indium and avoid the influence of iron ions on the extraction process has become a problem to be solved in this field. Summary of the invention

[0003] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, one object of the present invention is to provide an extraction device. The extraction device of the present invention delivers sulfur dioxide gas to a first reaction device through a gas supply device to perform countercurrent extraction on an indium-containing solution and an organic phase, eliminate iron ions in the solution, and improve the extraction rate of indium.

[0004] The invention also provides a method for extracting indium.

[0005] The extraction device according to the present invention includes: a first reaction device, in which an indium-containing solution is arranged; a gas supply device, which is provided with a gas outlet connected to the first reaction device, and the gas supply device is used to provide sulfur dioxide gas to the first reaction device through the gas outlet to extract the solution in the first reaction device; a second reaction device, which is arranged on the downstream side of the first reaction device and is used to accommodate the extracted solution; and a liquid supply device, which is connected to the second reaction device and is used to introduce sulfuric acid into the second reaction device for stripping.

[0006] According to the extraction device of the present invention, sulfur dioxide gas is introduced into the mixed solution of the indium-containing solution and the organic phase in the first reaction device through the gas supply device for countercurrent extraction. The sulfur dioxide gas reduces the iron ions in the solution to ferrous ions that are difficult to extract, thereby improving the indium extraction rate and avoiding the co-extraction of iron, thereby preventing the aging of the organic phase and extending the service life. Through countercurrent extraction and replacement reaction, indium can be efficiently extracted and recovered.

[0007] According to some embodiments of the present invention, the extraction device further comprises: a replacement device, which is disposed on the downstream side of the second reaction device and is used to accommodate the solution after stripping, and the replacement device is suitable for replacing the solution after stripping.

[0008] According to some embodiments of the present invention, the replacement device includes: a third reaction device, which is arranged on the downstream side of the second reaction device and is selectively connected to the second reaction device; and a metal delivery device, which is used to deliver metal into the third reaction device.

[0009] According to some embodiments of the present invention, the extraction device further comprises: a preheating device, which is disposed on the upstream side of the first reaction device and is used to heat the indium-containing solution entering the first reaction device.

[0010] The extraction method for indium according to the present invention is briefly described below.

[0011] The indium extraction method according to the present invention comprises: mixing a preheated indium-containing solution with an organic phase, and then introducing sulfur dioxide gas for countercurrent extraction to obtain an indium-loaded organic phase; mixing the indium-loaded organic phase with dilute sulfuric acid to form a stripping solution; and reacting a metal sheet with the stripping solution to obtain sponge indium.

[0012] According to some embodiments of the present invention, the organic phase is an organic phase composed of di(2-ethylhexyl) phosphate, trialkyl phosphine oxide and sulfonated kerosene, or an organic phase composed of di(2-ethylhexyl) phosphate, trioctyl phosphine oxide and sulfonated kerosene.

[0013] According to some embodiments of the present invention, the indium-containing solution is an In-H2SO4-H2O system, the indium ion concentration is 0.72 to 10 g / L, and the acidity of the solution is 40 to 90 g / L.

[0014] According to some embodiments of the present invention, the metal sheet is an aluminum sheet.

[0015] Additional aspects and advantages of the present invention will be given in part in the following description and in part will be obvious from the following description, or will be learned through practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The above and / or additional aspects and advantages of the present invention will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0017] Figure 1 is a schematic diagram of the extraction device according to some embodiments of the present invention;

[0018] Figure 2is a flow chart of an extraction method for indium according to some embodiments of the present invention.

[0019] Reference numerals:

[0020] Extraction device 1;

[0021] The first reaction device 11;

[0022] The second reaction device 12;

[0023] Replacement device 13, third reaction device 131, metal delivery device 132;

[0024] Gas supply device 14; liquid supply device 15, preheating device 16. DETAILED DESCRIPTION

[0025] Embodiments of the present invention are described in detail below, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and cannot be understood as limiting the present invention.

[0026] In the related art, the mainstream process for producing indium is leaching-extraction-electrolysis, that is, the target metal indium and other impurity metals in the raw material are first transferred to the solution in the form of ions, and then the indium is extracted through the extraction and stripping stages to achieve the purpose of enrichment and recovery, and finally the product indium is obtained by electrolysis. In the extraction process of indium, accompanied by the co-extraction of impurity iron ions, problems such as poisoning and aging of the organic phase are caused, and the organic phase cannot be recycled in the end, resulting in increased extraction costs and waste of resources. Therefore, how to optimize the extraction process of indium and avoid the influence of iron ions on the extraction process has become a problem to be solved in this field.

[0027] Reference below Figure 1 An extraction device according to an embodiment of the present invention is described.

[0028] The extraction device 1 according to the present invention comprises: a first reaction device 11, in which an indium-containing solution is arranged; a gas supply device 14, in which a gas outlet is provided which is connected to the first reaction device 11, and the gas supply device 14 is used to supply sulfur dioxide gas to the first reaction device 11 through the gas outlet to extract the solution in the first reaction device 11; a second reaction device 12, in which the second reaction device 12 is arranged on the downstream side of the first reaction device 11 and is used to accommodate the extracted solution; a liquid supply device 15, in which the liquid supply device 15 is connected to the second reaction device 12 and is used to introduce sulfuric acid into the second reaction device 12 and perform stripping.

[0029] Specifically, the first reaction device 11 can be constructed as an autoclave, an indium-containing solution is added into the autoclave, an organic solvent is added into the indium-containing solution, the indium-containing solution is mixed with the organic phase, sulfur dioxide gas is provided into the first reaction device 11 through the gas supply device 14 to extract the indium-containing solution in the first reaction device 11, the sulfur dioxide gas will react with the trivalent iron ions in the indium-containing solution, and the iron ions are reduced to ferrous ions that are not easily extracted, thereby improving the indium extraction rate and avoiding the co-extraction of iron, wherein the reaction formula is SO2+2H2O+2Fe3+=2Fe2++SO42-+4H+, sulfur dioxide reacts with water and iron ions to generate sulfate and ferrous ions, after the reaction is completed, the phases are allowed to stand and separate to obtain an indium-loaded organic phase and a raffinate, the second reaction device 12 is used to accommodate the indium-loaded organic phase, sulfuric acid is introduced into the second reaction device 12 through the liquid supply device 15, sulfuric acid reacts with the indium-loaded organic phase to obtain an indium-rich stripping solution, and the indium-rich stripping solution can be subjected to a replacement reaction with an active metal, thereby extracting indium from the stripping solution.

[0030] According to the extraction device 1 of the present invention, sulfur dioxide gas is introduced into the mixed solution of the indium-containing solution and the organic phase in the first reaction device 11 through the gas supply device 14 for countercurrent extraction. The sulfur dioxide gas reduces the iron ions in the solution to ferrous ions that are difficult to extract, thereby improving the indium extraction rate and avoiding the co-extraction of iron, thereby preventing the aging of the organic phase and extending the service life. Through countercurrent extraction and replacement reaction, indium can be efficiently extracted and recovered.

[0031] According to some embodiments of the present invention, the extraction device 1 further comprises: a replacement device 13, which is disposed at the downstream side of the second reaction device 12 and is used to receive the stripping solution, and the replacement device 13 is suitable for replacing the stripping solution.

[0032] Specifically, the replacement device 13 is arranged on the downstream side of the second reaction device 12. The replacement device 13 is used to accommodate the indium-rich stripping solution obtained after stripping. By adding active metals such as aluminum or zinc into the replacement device 13, it can react with the indium ions in the stripping solution to extract indium from the stripping solution, thereby improving the indium extraction rate.

[0033] According to some embodiments of the present invention, the replacement device 13 includes: a third reaction device 131, which is arranged on the downstream side of the second reaction device 12 and is selectively connected to the second reaction device 12; and a metal delivery device 132, which is used to deliver metal into the third reaction device 131.

[0034] Specifically, the replacement device 13 includes a third reaction device 131. After the stripping solution flows out of the second reaction device 12, it can selectively enter the third reaction device 131. In the third reaction device 131, the metal introduced by the metal introduction device 132 undergoes a replacement reaction with the ions in the solution. The metal structure is an active metal such as aluminum or zinc. After the replacement reaction, the generated metal or metal compound is collected through appropriate separation and purification steps to improve the purification of indium and improve the extraction rate of indium.

[0035] According to some embodiments of the present invention, the extraction device 1 further includes: a preheating device 16 , which is disposed at the upstream side of the first reaction device 11 and is used to heat the indium-containing solution entering the first reaction device 11 .

[0036] Specifically, the main function of the preheating device 16 is to heat the indium-containing solution entering the first reaction device 11. Heating can increase the reaction activity of the solution and help the chemical reaction in the extraction process to proceed more smoothly. The heating method can be electric heating, steam heating or heat exchange, etc. A temperature control system can be provided in the preheating device 16 to ensure that the solution reaches a predetermined heating temperature, which helps to maintain the stability of the extraction process and improve the extraction efficiency.

[0037] The extraction method for indium according to the present invention is briefly described below.

[0038] The indium extraction method according to the present invention comprises: mixing a preheated indium-containing solution with an organic phase and then introducing sulfur dioxide gas for countercurrent extraction to obtain an indium-loaded organic phase; mixing the indium-loaded organic phase with dilute sulfuric acid to form a stripping solution; and reacting a metal sheet with the stripping solution to obtain sponge indium.

[0039] Specifically, the extraction method for indium of the present invention first preheats the indium-containing solution. Preheating can improve the reaction activity of the solution and help the subsequent extraction process. The preheated indium-containing solution is mixed with an organic phase, and then sulfur dioxide gas is introduced for countercurrent extraction. Sulfur dioxide reacts with indium ions in the solution to generate indium compounds soluble in the organic phase, thereby obtaining an indium-carrying organic phase. Sulfur dioxide reacts with iron ions in water to generate ferrous ions that are not easily extracted, avoiding the co-extraction of iron ions, preventing the aging of the organic phase, and extending the service life of the organic phase. The indium-carrying organic phase is mixed with dilute sulfuric acid. Under acidic conditions, the indium compound is transferred from the organic phase to the aqueous phase to form a stripping solution, which realizes the transfer of indium from the organic phase to the aqueous phase and prepares for the subsequent replacement reaction. A metal sheet (such as a zinc sheet, an aluminum sheet, etc.) is reacted with the stripping solution. The metal sheet undergoes a replacement reaction with the indium ions in the stripping solution to generate sponge indium, which is a porous metal form that is easy to separate from the solution. The extraction method of the present invention can efficiently extract and recover indium through countercurrent extraction and displacement reaction, and can achieve precise control of the extraction process by adjusting parameters such as preheating temperature, extractant concentration, sulfur dioxide flow rate and dilute sulfuric acid concentration.

[0040] According to some embodiments of the present invention, the organic phase is an organic phase composed of di(2-ethylhexyl)phosphate, trialkylphosphine oxide and sulfonated kerosene, or an organic phase composed of di(2-ethylhexyl)phosphate, trioctylphosphine oxide and sulfonated kerosene.

[0041] Specifically, the organic phase is an organic phase composed of di(2-ethylhexyl) phosphate, trialkyl phosphine oxide and sulfonated kerosene, or an organic phase composed of di(2-ethylhexyl) phosphate, trioctyl phosphine oxide and sulfonated kerosene. Di(2-ethylhexyl) phosphate is a commonly used extractant with good extraction performance for indium ions; trialkyl phosphine oxide or trioctyl phosphine oxide is used as an auxiliary extractant to enhance the extraction effect; sulfonated kerosene is used as a diluent to adjust the viscosity and extraction performance of the organic phase. By using the above organic phase composition, indium ions in an indium-containing solution can be effectively extracted to achieve efficient indium extraction. The organic phase has good stability during the extraction process and is not prone to decomposition or deterioration, thereby ensuring the stability and reliability of the extraction process.

[0042] According to some embodiments of the present invention, the indium-containing solution is an In-H2SO4-H2O system, the indium ion concentration is 0.72-10 g / L, and the acidity of the solution is 40-90 g / L.

[0043] Specifically, the indium-containing solution is an In-H2SO4-H2O system, that is, a solution system composed of indium ions, sulfuric acid and water. The concentration range of indium ions is 0.72 to 10 g / L, which is a relatively wide concentration range and is suitable for the extraction of indium-containing raw materials of different sources and concentrations. The acidity of the solution (in terms of sulfuric acid) is 40 to 90 g / L. This acidity range helps the extractant to effectively extract indium ions, and also helps the subsequent stripping and replacement reactions. Appropriate indium ion concentration and solution acidity can significantly improve the extraction efficiency, so that more indium ions can be effectively extracted into the organic phase. By controlling the acidity of the solution and the indium ion concentration, the selectivity of the extraction process can be optimized, the interference of other impurities can be reduced, and the purity of indium can be improved. Within the above-mentioned concentration and acidity range, the extraction process can be guaranteed to be more stable, which helps to ensure the continuity and stability of the extraction process, thereby helping to optimize the extraction process, improve the extraction efficiency and purity of indium, and reduce production costs.

[0044] The preheated indium-containing solution and the organic phase are added to the autoclave at a volume ratio of 2:1 between the organic phase and the aqueous phase, and then sulfur dioxide gas is introduced for three-stage countercurrent extraction. The sulfur dioxide pressure is maintained at 0.15 MPa and the temperature is 25°C. The extraction is stirred for 5 minutes and the phases are allowed to stand for 5 minutes to separate. An indium-containing organic phase with an indium content of 2.12 g / L and an iron content of less than 0.01 g / L is obtained. The indium extraction rate is 99% and the iron co-extraction rate is less than 0.1%; the organic phase is di(2-ethylhexyl) phosphate, trialkyl Phosphorus oxide and sulfonated kerosene are composed in a volume ratio of 10:2:88, the indium-containing solution is an In-H2SO4-H2O system, the indium ion concentration in the solution is 0.72 g / L, and the total acid concentration is 30 g / L; the indium-loaded organic phase is subjected to a first-stage countercurrent stripping with 3 mol / L sulfuric acid, the volume ratio of the organic phase to the aqueous phase is controlled to be 6:1, the temperature is 25°C, after stirring for stripping for 30 minutes, the stripping solution containing 12.6 g / L indium is obtained after standing for phase separation for 10 minutes, and the stripping rate of indium is 99.1%.

[0045] The preheated leaching solution and the organic phase are added to the autoclave in a volume ratio of 1:1 between the organic phase and the aqueous phase, and then sulfur dioxide gas is introduced for three-stage countercurrent extraction. The pressure in the sulfur dioxide is maintained at 0.2 MPa and the temperature is 25°C. The extraction is stirred for 5 minutes, and the phases are allowed to stand for 5 minutes to separate. An indium-loaded organic phase containing 2.8 g / L indium and less than 0.01 g / L iron is obtained. The extraction rate of indium is 99.5%, and the co-extraction rate of iron is less than 0.01%. The organic phase is di(2-ethylhexyl) phosphate, trialkyl oxide Phosphorus and sulfonated kerosene are composed in a volume ratio of 10:4:88; the indium-containing solution is an In-H2SO4-H2O system, the indium ion concentration in the solution is 0.72 g / L, and the total acid concentration is 30 g / L; the obtained indium-loaded organic phase is subjected to two-stage countercurrent stripping with 3 mol / L sulfuric acid, the volume ratio of the organic phase to the aqueous phase is controlled to be 6:1, the temperature is 25°C, after stirring for stripping for 30 minutes, the stripping solution containing 16.7 g / L indium is obtained after standing for phase separation for 10 minutes, and the stripping rate of indium is 99.4%.

[0046] The preheated leaching solution and the organic phase are added to the autoclave at a volume ratio of 2:1 between the organic phase and the aqueous phase, and then sulfur dioxide gas is introduced for 4-stage countercurrent extraction. The pressure in the mixing tank is maintained at 0.2 MPa and the temperature is 25°C. The extraction is stirred for 8 minutes, and the phases are allowed to stand for 10 minutes to separate. An indium-loaded organic phase containing 7.5 g / L indium and less than 0.01 g / L iron is obtained. The extraction rate of indium is 99.5%, and the co-extraction rate of iron is less than 0.1%. The organic phase is di(2-ethylhexyl) phosphate, trioctylphosphine oxide, sulfonic acid The sulfonated kerosene is added after being mixed in a volume ratio of 10:1:89; the indium-containing solution is an In-H2SO4-H2O system, the indium ion concentration in the solution is 0.72 g / L, and the total acid concentration is 30 g / L; the indium-loaded organic phase is subjected to three-stage countercurrent stripping with 4 mol / L sulfuric acid, the volume ratio of the organic phase to the aqueous phase is controlled to be 2:1, the temperature is 25°C, after stirring for stripping for 30 minutes, the stripping solution containing 29.15 g / L indium is allowed to stand for phase separation for 10 minutes, and the indium stripping rate is 99.7%.

[0047] The preheated leaching solution and the organic phase are added to the autoclave in a volume ratio of 1:1 between the organic phase and the aqueous phase, and then sulfur dioxide gas is introduced for 4-stage countercurrent extraction. The sulfur dioxide pressure is maintained at 0.3 MPa and the temperature is 25°C. The extraction is stirred for 6 minutes, and the phases are allowed to stand for 10 minutes to separate. An indium-loaded organic phase containing 12.4 g / L indium and less than 0.01 g / L iron is obtained. The extraction rate of indium is 98.9%, and the co-extraction rate of iron is less than 0.1%. The organic phase is di(2-ethylhexyl) phosphate, trialkyl oxide Phosphine and sulfonated kerosene are composed in a volume ratio of 10:4:86; the indium-containing solution is an In-H2SO4-H2O system, the indium ion concentration in the solution is 3.72 g / L, and the total acid concentration is 30 g / L; the indium-loaded organic phase is subjected to two-stage countercurrent stripping with 4.5 mol / L sulfuric acid, the volume ratio of the organic phase to the aqueous phase is controlled to be 2:1, the temperature is 25°C, after stirring for stripping for 15 minutes, the stripping solution containing 29.15 g / L indium is obtained after standing for phase separation for 10 minutes, and the indium stripping rate is 99.7%.

[0048] According to some embodiments of the present invention, the metal sheet is an aluminum sheet.

[0049] Specifically, aluminum is an active metal that can easily undergo a replacement reaction with indium ions in a solution to generate sponge indium, thereby increasing the extraction rate of indium. Aluminum is a relatively cheap metal, and using aluminum sheets as a replacement agent can reduce production costs, is easy to recycle and reuse, and reduces environmental pollution.

[0050] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as limiting the present invention.

[0051] In the description of the present invention, "first feature" or "second feature" may include one or more of the features.

[0052] In the description of the present invention, "plurality" means two or more.

[0053] In the description of the present invention, a first feature being “on” or “under” a second feature may include that the first and second features are directly in contact with each other, or may include that the first and second features are not in direct contact with each other but are in contact with each other via another feature therebetween.

[0054] In the description of the present invention, "above", "over" and "on" a first feature includes the first feature being directly above and obliquely above the second feature, or simply means that the first feature is horizontally higher than the second feature.

[0055] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "illustrative embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0056] Although the embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the claims and their equivalents.

Claims

1. An extraction device, characterized in that: include: A first reaction device (11), wherein the first reaction device (11) is used to place an indium-containing solution; a gas supply device (14), the gas supply device (14) being provided with a gas outlet connected to the first reaction device (11), the gas supply device (14) being used for supplying sulfur dioxide gas to the first reaction device (11) through the gas outlet so as to extract the solution in the first reaction device (11); A second reaction device (12), the second reaction device (12) is arranged at the downstream side of the first reaction device (11) and is used to receive the extracted solution; A liquid supply device (15), the liquid supply device (15) is connected to the second reaction device (12) and is used to introduce sulfuric acid into the second reaction device (12) for stripping.

2. The extraction device according to claim 1, characterized in that Also includes: A replacement device (13), wherein the replacement device (13) is arranged at the downstream side of the second reaction device (12) and is used to accommodate the solution after stripping, and the replacement device (13) is suitable for replacing the solution after stripping.

3. The extraction device according to claim 2, characterized in that: The replacement device (13) comprises: a third reaction device (131), the third reaction device (131) being disposed at a downstream side of the second reaction device (12) and selectively connected to the second reaction device (12); A metal delivery device (132), wherein the metal delivery device (132) is used to deliver metal into the third reaction device (131).

4. The extraction device according to claim 1, characterized in that: It also includes: a preheating device (16), which is arranged on the upstream side of the first reaction device (11), and the preheating device (16) is used to heat the indium-containing solution entering the first reaction device (11).

5. A method for extracting indium, characterized in that: include: The preheated indium-containing solution is mixed with the organic phase, and then sulfur dioxide gas is introduced into the mixture for countercurrent extraction to obtain an indium-loaded organic phase; The indium-loaded organic phase is mixed with dilute sulfuric acid to form a stripping solution; The metal sheet is reacted with the stripping solution to obtain sponge indium.

6. The method for extracting indium according to claim 5, characterized in that: The organic phase is an organic phase composed of di(2-ethylhexyl) phosphate, trialkyl phosphorus oxide and sulfonated kerosene, or an organic phase composed of di(2-ethylhexyl) phosphate, trioctyl phosphorus oxide and sulfonated kerosene.

7. The method for extracting indium according to claim 5, characterized in that: The indium-containing solution is an In-H2SO4-H2O system, the indium ion concentration is 0.72-10 g / L, and the acidity of the solution is 40-90 g / L.

8. The method for extracting indium according to claim 5, characterized in that: The metal sheet is an aluminum sheet.

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