Synchronous separation and efficient recovery process for arsenic and indium in copper smelting smoke dust

Abstract

The invention discloses a synchronous separation and efficient recovery process for arsenic and indium in copper smelting smoke dust, and belongs to the technical field of hydrometallurgy. The method comprises the following steps: uniformly mixing smelting smoke dust and water according to a solid-to-liquid ratio of 1: (2-4), adding 70-100g / L concentrated sulfuric acid, heating to 70-85 DEG C, adding 10-20g / L arsenic removal agent, reacting at constant temperature for 1.5-2.5 hours, and filtering to obtain indium-containing leachate and arsenic-containing leaching residues. Mixing the leaching solution and the indium extraction organic phase according to the ratio of O to A being 1: (8-10), extracting at room temperature, mixing the indium-loaded organic phase and a stripping agent according to the ratio of O to A being (4-6): 1 after phase splitting, adding a displacer which is 1.5-2.5 times of the molar mass of indium in the stripping solution after extracting at room temperature and phase splitting, reacting at room temperature for 20-40 minutes, and filtering to obtain sponge indium. The arsenic removal agent is added in the indium leaching process, efficient indium leaching is achieved, arsenic inhibition is synchronously achieved, dispersion and influence of arsenic in the indium extraction process are avoided, and generation of highly toxic arsenic hydride gas is avoided. And the leaching liquid does not contain arsenic, and the indium raffinate does not contain arsenic, so that the indium raffinate can be returned to the leaching process for recycling, the enrichment of arsenic in the solution is avoided, and the open-circuit treatment cost of the wastewater is reduced. The technological process is short and efficient, and industrialization is easy to achieve.

Description

Technical Field

[0001] This invention belongs to the field of hydrometallurgical technology, specifically relating to a process for the simultaneous separation and efficient recovery of arsenic and indium from copper smelting flue dust. Background Technology

[0002] Copper smelting fumes typically contain a certain amount of indium. Indium is usually leached into a solution using a sulfuric acid system for further recovery. However, during the leaching process, a large amount of arsenic from the fumes is also leached into the solution, causing arsenic to disperse throughout the indium extraction process. Furthermore, the displacement process can generate highly toxic arsine gas. Therefore, it is necessary to propose a process for the simultaneous separation and efficient recovery of arsenic and indium from copper smelting fumes, avoiding the dispersion of arsenic in various processes, while simultaneously shortening the process flow, reducing energy consumption, improving recovery rate and product purity, and meeting the requirements of electrolytic refining. Summary of the Invention

[0003] The purpose of this invention is to provide a process for the simultaneous separation and efficient recovery of arsenic and indium from copper smelting flue dust.

[0004] The objective of this invention is achieved as follows: the process for simultaneous separation and efficient recovery of arsenic and indium from copper smelting flue dust includes the following steps: Mix copper smelting fumes with water at a solid-liquid ratio of S:L=1:2~4, add concentrated sulfuric acid at a concentration of 70~100g / L, and heat to 70~85℃. After reaching the reaction temperature, add 10~20g / L of arsenic removal agent to the solution, stir the reaction at a constant temperature for 1.5~2.5h, filter, and the obtained filtrate is the indium-containing leachate, and the obtained filter residue is the arsenic-containing leachate residue. After mixing the indium-containing leachate with the indium-extracting organic phase at a ratio of O:A = 1:8~10, the mixture was extracted by shaking at room temperature. After standing and phase separation, the indium-loaded organic phase was mixed with the back-extractant at a ratio of O:A = 4~6:1. The mixture was extracted by shaking at room temperature. After standing and phase separation, the indium-containing back-extractant was obtained. Add a displacement agent at 1.5 to 2.5 times the molar mass of indium in the indium-containing back-extraction solution, stir the reaction at room temperature for 20 to 40 minutes, and then filter to obtain sponge indium.

[0005] The technical solution described in this invention has the following advantages compared with the prior art: (1) Adding an arsenic removal agent during the indium leaching process can not only achieve efficient indium leaching, but also simultaneously inhibit arsenic, so that indium enters the leaching solution and arsenic enters the leaching residue, thus avoiding the dispersion and influence of arsenic in the subsequent indium extraction process.

[0006] (2) This process avoids the generation of highly toxic arsine gas during the indium replacement process.

[0007] (3) The leaching process removes arsenic. The leaching solution does not contain arsenic, and the indium extraction residue does not contain arsenic. It can be returned to the leaching process for repeated recycling, which will not cause arsenic enrichment in the solution, reduce the amount of water used in the system, and reduce the cost of open-loop wastewater treatment.

[0008] (4) Indium-containing leachate can be used to prepare sponge indium products with a purity of >90% through extraction-back-extraction-displacement process, thus realizing the recycling of resources.

[0009] (5) The process is simple, efficient, and produces no toxic or harmful gases or wastewater, making it easy to industrialize. Attached Figure Description

[0010] Figure 1 This is a process flow diagram of the technical solution described in this invention. Detailed Implementation

[0011] The present invention will be further described below, but this is not intended to limit the invention in any way. Any modifications or substitutions made based on the teachings of the present invention shall fall within the scope of protection of the present invention.

[0012] The process for simultaneous separation and efficient recovery of arsenic and indium from copper smelting dust described in this invention includes the following steps: Mix copper smelting fumes with water at a solid-liquid ratio of S:L=1:2~4, add concentrated sulfuric acid at a concentration of 70~100g / L, and heat to 70~85℃. After reaching the reaction temperature, add 10~20g / L of arsenic removal agent to the solution, stir the reaction at a constant temperature for 1.5~2.5h, filter, and the obtained filtrate is the indium-containing leachate, and the obtained filter residue is the arsenic-containing leachate residue. After mixing the indium-containing leachate with the indium-extracting organic phase at a ratio of O:A = 1:8~10, the mixture was extracted by shaking at room temperature. After standing and phase separation, the indium-loaded organic phase was mixed with the back-extractant at a ratio of O:A = 4~6:1. The mixture was extracted by shaking at room temperature. After standing and phase separation, the indium-containing back-extractant was obtained. Add a displacement agent at 1.5 to 2.5 times the molar mass of indium in the indium-containing back-extraction solution, stir the reaction at room temperature for 20 to 40 minutes, and then filter to obtain sponge indium.

[0013] The preferred solid-liquid ratio of copper smelting flue dust to water is S:L=1:3.

[0014] The concentrated sulfuric acid mentioned is 98% sulfuric acid.

[0015] The arsenic removal agent is either sodium sulfide (Na2S) or ferrous sulfate (FeSO4).

[0016] The preferred arsenic removal reaction time is 2 hours.

[0017] The arsenic-containing leaching residue can be reheated system.

[0018] The preferred ratio of the indium-containing leachate to the indium-extracting organic phase is O:A = 1:9.

[0019] The indium extraction organic phase is P204 extractant.

[0020] The raffinate after extraction can be returned to the controlled arsenic leaching process.

[0021] The preferred ratio of the supported indium organic phase to the stripping agent is O:A = 5:1.

[0022] The stripping agent is 6M hydrochloric acid.

[0023] The organic phase after back-extraction can be regenerated and returned to the extraction process.

[0024] The preferred extraction time is 5 minutes.

[0025] The preferred settling time for phase separation is 5 minutes.

[0026] The stirring speed is 100~200 r / min.

[0027] The displacement agent is either zinc powder or aluminum powder.

[0028] The amount of the displacement agent added is preferably twice the molar mass of indium in the indium-containing stripping solution.

[0029] The preferred displacement reaction time is 30 min.

[0030] The purity of the sponge indium is >90%.

[0031] Example 1

[0032] Mix copper smelting fumes with water at a solid-liquid ratio of S:L=1:3, add 98% concentrated sulfuric acid at a concentration of 85g / L, and heat to 78℃.

[0033] After reaching the reaction temperature, 15 g / L of sodium sulfide was added to the solution, and the mixture was stirred at a constant temperature for 2 hours. After filtration and washing, the filtrate (i.e., indium-containing leachate) and filter residue (i.e., arsenic-containing leachate residue) were obtained.

[0034] The indium-containing leaching solution was mixed with P204 extractant at a ratio of O:A=1:9, and extracted with shaking at room temperature for 5 min. After standing for 5 min, the phases were separated. The indium-loaded organic phase was then mixed with 6M hydrochloric acid at a ratio of O:A=5:1, and extracted with shaking at room temperature for 5 min. After standing for 5 min, the phases were separated to obtain a high-concentration indium-containing back-extraction solution.

[0035] Zinc powder was slowly added at twice the molar mass of indium in the indium-containing back-extraction solution. The mixture was stirred at 150 r / min for 30 min at room temperature, and then filtered to obtain sponge indium.

[0036] The leaching data in this embodiment are shown in Table 1, the extraction data in Table 2, and the displacement data in Table 3; the detection method is calculated according to the conventional calculation method in the paper. (1) Leaching rate detection and calculation: Definition: Leaching rate is an important standard in the leaching process of various metals, used to indicate the degree to which a certain substance is leached.

[0037] Significance: A higher leaching rate indicates a better metal extraction rate, which means better economic benefits for industrial and mining enterprises.

[0038] Calculation method: The leaching rate is obtained by measuring the mass of metal in the leached solution and comparing it with the total mass of metal in the raw material, then multiplying by 100%. This value directly reflects the efficiency of the leaching process. That is, leaching rate (%) = (soluble leaching amount / solute mass in raw material) × 100%; (2) Extraction rate detection and calculation: The extraction rate is calculated using the formula E% = [D / (D + F)] * 100%, where E% represents the extraction rate, D represents the content of the target substance in the extract, and F represents the content of the target substance in the raw material. Extraction rate usually refers to extraction efficiency, which is an indicator of the efficiency of solute A's partitioning between aqueous solution and organic solvent.

[0039] Table 1 Leaching data for Example 1

[0040] Table 2 Extraction data from Example 1 Table 3. Permutation data for Example 1

[0041] Example 2 Mix copper smelting fumes with water at a solid-liquid ratio of S:L=1:4, add 98% concentrated sulfuric acid at a concentration of 100g / L, and heat to 70℃.

[0042] After reaching the reaction temperature, 20 g / L of ferrous sulfate was added to the solution, and the mixture was stirred at a constant temperature for 2.5 h. After filtration and washing, the filtrate (i.e., indium-containing leaching solution) and filter residue (i.e., arsenic-containing leaching residue) were obtained.

[0043] The indium-containing leaching solution was mixed with P204 extractant at a ratio of O:A=1:10, and extracted with shaking at room temperature for 5 min. After standing for 5 min, the phases were separated. The indium-loaded organic phase was then mixed with 6M hydrochloric acid at a ratio of O:A=6:1, and extracted with shaking at room temperature for 5 min. After standing for 5 min, the phases were separated to obtain a high-concentration indium-containing back-extraction solution.

[0044] Aluminum powder was slowly added at 2.5 times the molar mass of indium in the indium-containing back-extraction solution. The mixture was stirred at 200 r / min for 40 min at room temperature, and then filtered to obtain sponge indium.

[0045] Example 3

[0046] Mix copper smelting fumes with water at a solid-liquid ratio of S:L=1:2, add 98% concentrated sulfuric acid at a concentration of 70g / L, and heat to 85℃.

[0047] After reaching the reaction temperature, 10 g / L of sodium sulfide was added to the solution, and the mixture was stirred at a constant temperature for 1.5 h. After filtration and washing, the filtrate (i.e., indium-containing leaching solution) and filter residue (i.e., arsenic-containing leaching residue) were obtained.

[0048] The indium-containing leaching solution was mixed with P204 extractant at a ratio of O:A=1:8, and extracted with shaking at room temperature for 5 min. After standing for 5 min, the phases were separated. The indium-loaded organic phase was then mixed with 6M hydrochloric acid at a ratio of O:A=4:1, and extracted with shaking at room temperature for 5 min. After standing for 5 min, the phases were separated to obtain a high-concentration indium-containing back-extraction solution.

[0049] Zinc powder was slowly added at 1.5 times the molar mass of indium in the indium-containing back-extraction solution. The mixture was stirred at 100 r / min for 20 min at room temperature, and then filtered to obtain sponge indium.

Claims

1. A process for simultaneous separation and efficient recovery of arsenic and indium from copper smelting dust, characterized in that, The method comprises the following steps: The copper smelting dust is mixed with water in a solid-liquid ratio S:L = 1:2~4, and concentrated sulfuric acid is added in an amount of 70~100g / L, and the temperature is raised to 70~85℃; After the reaction temperature is reached, 10~20g / L of a dearsenification agent is added to the solution, and constant temperature stirring is carried out for 1.5~2.5h, then filtration is carried out, and the obtained filtrate is an indium-containing leaching solution, and the obtained filter residue is an arsenic-containing leaching residue; The indium-containing leaching solution and an indium extraction organic phase are mixed in a phase ratio O:A = 1:8~10, and then oscillation extraction is carried out at room temperature, and after phase separation, the indium-loaded organic phase is mixed with a stripping agent in a phase ratio O:A = 4~6:1, and then oscillation extraction is carried out at room temperature, and after phase separation, an indium-containing stripping solution is obtained; A displacement agent is added in an amount of 1.5~2.5 times the molar mass of indium in the indium-containing stripping solution, and stirring is carried out at room temperature for 20~40min, and then filtration is carried out, and sponge indium is obtained.

2. The process for simultaneous separation and efficient recovery of arsenic and indium from copper smelting dust according to claim 1, characterized in that, The solid-liquid ratio S:L of the copper smelting dust and water is 1:

3.

3. The process for simultaneous separation and efficient recovery of arsenic and indium from copper smelting dust according to claim 1, characterized in that, The dearsenification agent is any one of sodium sulfide and ferrous sulfate.

4. The process for simultaneous separation and efficient recovery of arsenic and indium from copper smelting dust according to claim 1, characterized in that, The dearsenification reaction time is 2h.

5. The process for simultaneous separation and efficient recovery of arsenic and indium from copper smelting dust according to claim 1, characterized in that, The phase ratio O:A of the indium-containing leaching solution and the indium extraction organic phase is 1:

9.

6. The process for simultaneous separation and efficient recovery of arsenic and indium from copper smelting dust according to any one of claims 1 or 5, characterized in that, The indium extraction organic phase is a P204 extraction agent.

7. The process for simultaneous separation and efficient recovery of arsenic and indium from copper smelting dust according to claim 1, characterized in that, The phase ratio O:A of the indium-loaded organic phase and the stripping agent is 5:

1.

8. The process for simultaneous separation and efficient recovery of arsenic and indium from copper smelting dust according to any one of claims 1 or 7, characterized in that, The stripping agent is 6M hydrochloric acid.

9. The process for simultaneous separation and efficient recovery of arsenic and indium from copper smelting dust according to claim 1, characterized in that, The displacement agent is any one of zinc powder and aluminum powder.

10. The process for simultaneous separation and efficient recovery of arsenic and indium from copper smelting dust according to claim 1, characterized in that, The displacement reaction time is 30min.

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