Comprehensive recovery method for valuable metals in smelting waste acid
By selectively separating copper and rhenium with sulfur and sulfur-containing compounds, combined with leaching, extraction and evaporation of crystallization, the problem of separation of rhenium and arsenic in smelting acids is solved, which improves the recovery rate of rhenium and reduces production costs.
Patent Information
- Application Number
- CN202510758957.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-09
- Publication Date
- 2025-08-26
AI Technical Summary
The prior art has problems in the recycling process of rhenium in smelting polluted acids, which are difficult to separate rhenium from arsenic, have low recovery rate and high production costs.
Sulfur and sulfur-containing compounds are used instead of traditional precipitants such as sodium sulfide and sodium hydrosulfide. Copper and rhenium are selectively separated by heating and mixing and passing sulfur-containing compounds, and then leaching, extraction and evaporation and crystallization are carried out to achieve selective separation and recovery of copper rhenium and arsenic.
The precipitation rate of rhenium is improved, the effective separation of copper rhenium and arsenic is achieved, the production cost is reduced, and the economic benefits of the enterprise are improved.
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Abstract
Description
Technical Field
[0001] The present application relates to the technical field of hydrometallurgy, and in particular to a comprehensive recovery method for valuable metals in waste smelting acid. Background Art
[0002] Rhenium is a strategically important rare earth metal with a high melting point, high mechanical strength, good plasticity, and mechanical stability. It is widely used in aerospace and other fields, primarily in high-temperature alloy components for aircraft jet engines. Rhenium occurs naturally at a relatively low grade, often associated with copper and molybdenum. It is recovered during the copper and molybdenum smelting processes. During copper smelting, rhenium is primarily concentrated in waste acid, from which it is recovered. However, the low elemental content, high solution acidity, large processing volumes, and complex composition of the solution pose challenges to its recovery.
[0003] The main methods for recovering rhenium from smelting waste acid include extraction, ion exchange, chemical precipitation, and adsorption. The extraction method requires a large solution treatment volume, has high organic losses, and high production costs. The ion exchange method produces a large amount of wastewater, has low resin decomposition efficiency, and is prone to failure. Currently, both chemical precipitation and ion exchange methods are used in industrial production. A domestic company uses sodium sulfide precipitation to treat waste acid. All copper and arsenic are precipitated into the slag. The arsenic sulfide slag is pressurized and oxidized to produce arsenic trioxide. The arsenic crystallization mother liquor is extracted to recover rhenium, but the overall rhenium recovery rate is low. To increase the precipitation rate of rhenium, studies have shown that both sodium thiosulfate and N12 can increase the precipitation rate of rhenium, achieve the separation of rhenium and arsenic, and improve the grade of rhenium in the slag. However, compared with sodium sulfide, sodium thiosulfate requires a large amount and is expensive, resulting in increased production costs for the company.
[0004] Therefore, it is of great significance to develop new precipitants to achieve effective separation of rhenium and arsenic, improve the grade of rhenium slag, reduce material processing volume, and reduce enterprise production costs. Summary of the Invention
[0005] The purpose of this application is to provide a comprehensive recovery method for valuable metals in smelting waste acid to solve the above problems.
[0006] To achieve the above objectives, this application adopts the following technical solutions:
[0007] The present application provides a comprehensive recovery method for valuable metals in smelting waste acid, the method comprising:
[0008] Heating the waste smelting acid and mixing it with a sulfur-containing substance, and introducing the sulfur-containing compound to selectively separate copper and rhenium from the waste smelting acid to obtain copper-rhenium-rich slag and copper-rhenium precipitation liquid;
[0009] The copper-rhenium-rich slag is leached to obtain a leachate; the leachate is extracted to obtain a loaded organic phase and a raffinate; the loaded organic phase is stripped to obtain ammonium rhenate; and the raffinate is evaporated and crystallized to obtain copper sulfate.
[0010] Optionally, the smelting waste acid includes an acidic solution produced after purification and filtration of sulfur dioxide-containing flue gas produced during concentrate smelting or roasting; the smelting waste acid includes: H2SO4 30-150g / L, Cu 0.2-2g / L, Re 2-70mg / L, and As 1-15g / L.
[0011] Optionally, the heating temperature is 50-120°C.
[0012] Optionally, the reaction temperature of the selective separation is 50-120° C., and the time is 1-5 h.
[0013] Optionally, the sulfur-containing substance includes at least one of elemental sulfur and sulfur-containing slag produced in a smelting or chemical process; the sulfur content of the sulfur-containing substance is not less than 15%.
[0014] Optionally, the sulfur-containing substance is added in an amount of 1 mol of copper ions for every 0.5-5 mol of sulfur element.
[0015] Optionally, the sulfur-containing compound is added in an amount with a molar ratio of 1-5:1 to the sulfur-containing substance.
[0016] Optionally, the sulfur-containing compound includes at least one of gaseous sulfur dioxide, liquid sulfur dioxide, flue gas containing sulfur dioxide, sodium sulfite, and sodium metabisulfite.
[0017] Optionally, the added amount of the sulfur-containing compound is no less than 1.5 mol of the sulfur-containing compound for every 1 mol of sulfur element in the sulfur-containing substance.
[0018] Optionally, the leaching is oxygen-enriched leaching, and the leaching reagent of the oxygen-enriched leaching includes at least one of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid.
[0019] Optionally, the temperature of the oxygen-enriched leaching is 80-150° C., and the time is 1-5 hours.
[0020] Optionally, the comprehensive recovery method further comprises: mixing the copper-rhenium precipitation liquid with an arsenic precipitation material to perform sulfide precipitation of arsenic to obtain arsenic sulfide slag and arsenic precipitation liquid;
[0021] The arsenic precipitating substance includes at least one of sodium sulfide, sodium hydrosulfide, and hydrogen sulfide.
[0022] Compared with the prior art, the advantages of this application include:
[0023] The present application adopts sulfur and sulfur-containing compounds to replace traditional precipitants such as sodium sulfide, sodium hydrosulfide, and sodium thiosulfate. Compared with sodium sulfide and sodium hydrosulfide, the precipitation rate of rhenium can be increased, and the selective separation of copper rhenium and arsenic in waste acid can be achieved. Compared with sodium thiosulfate, the reagent cost is reduced, and the sulfur dioxide-containing flue gas and sulfur-containing smelting slag in the production can be fully utilized, thereby reducing the production cost of the enterprise and improving the economic benefits of the enterprise. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following is a brief introduction to the drawings required for use in the embodiments. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope of the present application.
[0025] Figure 1 This is a schematic diagram of the process flow of the comprehensive recovery method of valuable metals in smelting waste acid provided in the embodiment. DETAILED DESCRIPTION
[0026] As used herein:
[0027] "Prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variations thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
[0028] The conjunction "consisting of" excludes any unspecified element, step, or component. If used in a claim, this phrase renders the claim closed, excluding materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause of the body of a claim, rather than immediately following the subject matter, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.
[0029] When an amount, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed alone. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted as including the range "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described herein, unless otherwise stated, the range is intended to include its end values and all integers and fractions within the range.
[0030] In these examples, parts and percentages are by mass unless otherwise indicated.
[0031] "Parts by mass" refers to the basic unit of measurement used to express the mass ratio of multiple components. One part can represent any unit of mass, such as 1g or 2.689g. If we say that the mass of component A is a parts and the mass of component B is b parts, this means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, we could say that the mass of component A is aK and the mass of component B is bK (K is an arbitrary number representing a multiplication factor). It's important to note that, unlike parts by mass, the sum of the mass of all components is not limited to 100 parts.
[0032] "And / or" is used to indicate that one or both of the stated situations may occur, for example, A and / or B includes (A and B) and (A or B).
[0033] In order to better explain the technical solution of the present application, an overall statement of the technical solution of the present application is first made before the specific implementation method.
[0034] The method includes:
[0035] The smelting waste acid is heated and then mixed with a sulfur-containing substance, and the sulfur-containing compound is introduced to selectively separate copper and rhenium from the smelting waste acid to obtain copper-rhenium-rich slag and copper-rhenium precipitation liquid;
[0036] The copper-rhenium-rich slag is leached to obtain a leachate; the leachate is extracted to obtain a loaded organic phase and a raffinate; the loaded organic phase is stripped to obtain ammonium rhenate; and the raffinate is evaporated and crystallized to obtain copper sulfate.
[0037] The smelting waste acid includes an acidic solution produced after purification and filtration of sulfur dioxide-containing flue gas produced during concentrate smelting or roasting; the smelting waste acid includes: H2SO4 30-150g / L, Cu 0.2-2g / L, Re 2-70mg / L, and As 1-15g / L.
[0038] Optionally, in the smelting waste acid: the content of H2SO4 can be 30g / L, 40g / L, 50g / L, 60g / L, 70g / L, 80g / L, 90g / L, 100g / L, 110g / L, 120g / L, 130g / L, 140g / L, 150g / L, or any value between 30-150g / L; the content of Cu can be 0.2g / L, 0.4g / L, 0.6g / L, 0.8g / L, 1g / L, 1.2g / L, 1.4g / L, 1.6g / L, 1.8g / L, 2g / L, or any value between 0.2-2g / L; the content of Re can be 2 The content of As may be selected from the group consisting of: 1 g / L, 2 g / L, 3 g / L, 4 g / L, 5 g / L, 6 g / L, 7 g / L, 8 g / L, 9 g / L, 10 g / L, 11 g / L, 12 g / L, 13 g / L, 14 g / L, 15 g / L, or any value between 1 and 15 g / L.
[0039] In an optional embodiment, the heating temperature is 50-120°C.
[0040] Optionally, the heating temperature can be 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, or any value between 50-120°C.
[0041] In an optional embodiment, the reaction temperature of the selective separation is 50-120° C., and the time is 1-5 h.
[0042] Optionally, the reaction temperature of the selective separation can be 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, or any value between 50-120°C; the heating time can be 1h, 2h, 3h, 4h, 5h, or any value between 1-5h.
[0043] In an optional embodiment, the sulfur-containing substance includes at least one of elemental sulfur and sulfur-containing slag produced in a smelting or chemical process; the sulfur content of the sulfur-containing substance is not less than 15%.
[0044] Optionally, the sulfur content of the sulfur-containing substance can be 15%, 16%, 17%, 18%, 19%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, or any value not less than 15%.
[0045] In an optional embodiment, the sulfur-containing substance is added in an amount of 1 mol of copper ions for every 0.5-5 mol of sulfur element.
[0046] Optionally, the amount of the sulfur-containing substance added can be 0.5 mol of elemental sulfur per 1 mol of copper ions, 1 mol of elemental sulfur per 1 mol of copper ions, 2 mol of elemental sulfur per 1 mol of copper ions, 3 mol of elemental sulfur per 1 mol of copper ions, 4 mol of elemental sulfur per 1 mol of copper ions, 5 mol of elemental sulfur per 1 mol of copper ions, or any value between 0.5-5 mol of elemental sulfur per 1 mol of copper ions.
[0047] In an optional embodiment, the sulfur-containing compound is added in an amount with a molar ratio of 1-5:1 to the sulfur-containing substance.
[0048] Optionally, the molar ratio of the added amount of the sulfur-containing compound to the sulfur-containing substance can be 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, or any value between 1-5:1.
[0049] In an optional embodiment, the sulfur-containing compound includes at least one of gaseous sulfur dioxide, liquid sulfur dioxide, flue gas containing sulfur dioxide, sodium sulfite, and sodium metabisulfite.
[0050] In an optional embodiment, the amount of the sulfur-containing compound added is no less than 1.5 mol of the sulfur-containing compound for every 1 mol of sulfur element in the sulfur-containing substance.
[0051] Optionally, the amount of the sulfur-containing compound added can be 1.5 mol of the sulfur-containing compound for every 1 mol of sulfur element in the sulfur-containing substance, 2 mol of the sulfur-containing compound for every 1 mol of sulfur element in the sulfur-containing substance, 2.5 mol of the sulfur-containing compound for every 1 mol of sulfur element in the sulfur-containing substance, 3 mol of the sulfur-containing compound for every 1 mol of sulfur element in the sulfur-containing substance, 3.5 mol of the sulfur-containing compound for every 1 mol of sulfur element in the sulfur-containing substance, 4 mol of the sulfur-containing compound for every 1 mol of sulfur element in the sulfur-containing substance, or the amount of the sulfur-containing compound added can be any value of not less than 1.5 mol of the sulfur-containing compound for every 1 mol of sulfur element in the sulfur-containing substance.
[0052] In an optional embodiment, the leaching is oxygen-enriched leaching, and the leaching reagent of the oxygen-enriched leaching includes at least one of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid.
[0053] In an optional embodiment, the temperature of the oxygen-enriched leaching is 80-150° C., and the time is 1-5 hours.
[0054] In an optional embodiment, the temperature of the oxygen-enriched leaching can be 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, or any value between 80-150°C.
[0055] In an optional embodiment, the comprehensive recovery method further comprises: mixing the copper-rhenium precipitation solution with an arsenic precipitation material to perform sulfide precipitation of arsenic to obtain arsenic sulfide slag and arsenic precipitation solution;
[0056] The arsenic precipitating substance includes at least one of sodium sulfide, sodium hydrosulfide, and hydrogen sulfide.
[0057] The embodiments of the present application will be described in detail below in conjunction with specific examples, but it will be understood by those skilled in the art that the following examples are merely illustrative of the present application and should not be considered as limiting the scope of the present application. In the examples, if specific conditions are not specified, the conditions are carried out according to conventional conditions or manufacturer recommendations. The reagents or instruments used are not specified by the manufacturer and are conventional products that can be purchased commercially.
[0058] Example 1
[0059] This embodiment provides a comprehensive recovery method for valuable metals in smelting waste acid, the process is as follows Figure 1 The specific steps are as follows:
[0060] The main components of the smelting waste acid used in this embodiment include Cu 0.28g / L, Re 0.013g / L, As 5.03g / L, and H2SO4 50g / L.
[0061] Weigh 1m3 of smelting waste acid 3 , heated to 90°C, added 0.2g of sulfur, and continuously introduced sulfur dioxide gas, controlling the flow rate of the sulfur dioxide gas to 5L / min, and the reaction time to 2h, to obtain copper-rich rhenium slag and copper-rhenium precipitation liquid; the copper-rhenium precipitation liquid contained 2.86mg / L of Cu ions and 2.18mg / L of Re; among them, the copper precipitation rate was 98.98%, the rhenium precipitation rate was 83.23%, and the arsenic precipitation rate was 5.53%.
[0062] Copper-rhenium-rich slag is slurried in a sulfuric acid solution and subjected to oxygen-enriched leaching at 110°C for 2 hours. Sulfuric acid is used as the leaching agent, with an initial concentration of 140 g / L, and the reaction time is 2 hours. A leachate is obtained. The leachate is extracted with nitrogen-235 to extract rhenium, yielding a loaded organic phase and a raffinate. The loaded organic phase is stripped to yield ammonium rhenate, and the raffinate is evaporated and crystallized to yield copper sulfate.
[0063] Sodium hydrosulfide is added to the post-copper-rhenium precipitation solution to precipitate arsenic, thereby obtaining arsenic sulfide slag and post-arsenic precipitation solution.
[0064] Example 2
[0065] This embodiment provides a comprehensive recovery method for valuable metals in smelting waste acid, the process is as follows Figure 1 The specific steps are as follows:
[0066] The main components of the smelting waste acid used in this embodiment include Cu 536 mg / L, Re 6.15 mg / L, As 9540 mg / L, and H2SO4 140 g / L.
[0067] Weigh 1m3 of smelting waste acid 3 , add 0.3g of sulfur, heat to 95℃ in a sealed container, and introduce sulfur dioxide gas. Control the sulfur dioxide gas pressure at 0.1MPa. The reaction time is 1h to obtain copper-rich rhenium slag and copper-rhenium precipitation liquid. The copper precipitation rate is 98.74%, the rhenium precipitation rate is 97.72%, and the arsenic precipitation rate is 11.82%.
[0068] The copper-rhenium-rich slag is slurried and then leached in oxygen-rich water at 110°C for 2 hours. The leaching agent used is sulfuric acid with an initial concentration of 150g / L to obtain a copper-rhenium-rich leachate. The leachate is used to extract and separate rhenium, and the raffinate is evaporated and crystallized to produce copper sulfate.
[0069] Sodium sulfide or sodium hydrosulfide is added to the copper-rhenium precipitation solution to precipitate arsenic, thereby obtaining arsenic sulfide slag and arsenic precipitation solution.
[0070] Example 3
[0071] This embodiment provides a comprehensive recovery method for valuable metals in smelting waste acid, the process is as follows Figure 1The specific steps are as follows:
[0072] The main components of the smelting waste acid used in this embodiment include Cu 536 mg / L, Re 6.15 mg / L, As 9540 mg / L, and H2SO4 140 g / L.
[0073] Weigh 1m3 of smelting waste acid 3 , heat to 95°C, add 0.5g of sulfur, and slowly add 10g of sodium sulfite. The reaction time is 3h to obtain copper-rich rhenium slag and copper-rhenium precipitation liquid. The copper precipitation rate is 97.13%, the rhenium precipitation rate is 70.57%, and the arsenic precipitation rate is 9.23%.
[0074] The copper-rhenium-rich slag is slurried and then leached in oxygen-rich water at 110°C for 2 hours. The leaching agent used is sulfuric acid with an initial concentration of 150g / L to obtain a copper-rhenium-rich leachate. The leachate is used to extract and separate rhenium, and the raffinate is evaporated and crystallized to produce copper sulfate.
[0075] Sodium sulfide or sodium hydrosulfide is added to the copper-rhenium precipitation solution to precipitate arsenic, thereby obtaining arsenic sulfide slag and arsenic precipitation solution.
[0076] Comparative Example 1
[0077] This comparative example provides a method for recovering valuable metals in waste acid using sodium thiosulfate, and the specific steps are as follows:
[0078] The main components of the smelting waste acid used in this embodiment include Cu 536 mg / L, Re 6.15 mg / L, As 9540 mg / L, and H2SO4 140 g / L.
[0079] Weigh 1m3 of smelting waste acid 3 The reaction mixture was heated to 60°C, 15g of sodium thiosulfate was added, and the reaction time was 1 hour. A copper-rhenium-rich slag and a copper-rhenium precipitation solution were obtained. The copper precipitation rate was 98.13%, the rhenium precipitation rate was 82.48%, and the arsenic precipitation rate was 12.26%. Sodium thiosulfate can achieve selective separation of copper and rhenium, but the dosage is relatively high.
[0080] Comparative Example 2
[0081] This comparative example provides a method for recovering valuable metals in waste acid using an ion exchange method, and the specific steps are as follows:
[0082] The main components of the smelting waste acid used in this example include Cu 536mg / L, Re 6.15mg / L, As 9540mg / L, and H2SO4 140g / L. After ion exchange adsorption, the rhenium content of the solution can be reduced to 0.34mg / L, with a rhenium adsorption rate of 94.47% and a resolution of 87.64%.
[0083] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some or all of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
[0084] Furthermore, those skilled in the art will appreciate that although some embodiments herein include certain features included in other embodiments but not others, combinations of features from different embodiments are intended to be within the scope of this application and to form distinct embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is intended solely to enhance understanding of the overall background of this application and should not be construed as an admission or any implication that such information constitutes prior art known to those skilled in the art.
Claims
1. A comprehensive recovery method for valuable metals in smelting waste acid, characterized in that: include: Heating the waste smelting acid and mixing it with a sulfur-containing substance, and introducing the sulfur-containing compound to selectively separate copper and rhenium from the waste smelting acid to obtain copper-rhenium-rich slag and copper-rhenium precipitation liquid; The copper-rhenium-rich slag is leached to obtain a leachate; the leachate is extracted to obtain a loaded organic phase and a raffinate; the loaded organic phase is stripped to obtain ammonium rhenate; and the raffinate is evaporated and crystallized to obtain copper sulfate.
2. The comprehensive recovery method of valuable metals in smelting waste acid according to claim 1, characterized in that: The smelting waste acid includes an acidic solution produced after purification and filtration of sulfur dioxide-containing flue gas produced during concentrate smelting or roasting; the smelting waste acid includes: H2SO4 30-150g / L, Cu ion 0.2-2g / L, Re 2-70mg / L, and As 1-15g / L.
3. The comprehensive recovery method of valuable metals in smelting waste acid according to claim 1, characterized in that: At least one of the following conditions is met: a. The heating temperature is 50-120 ℃; b. The reaction temperature of the selective separation is 50-120°C and the time is 1-5h.
4. The comprehensive recovery method of valuable metals in smelting waste acid according to claim 1, characterized in that: The sulfur-containing substance includes at least one of elemental sulfur and sulfur-containing slag produced in a smelting or chemical process; the sulfur content of the sulfur-containing substance is not less than 15%.
5. The comprehensive recovery method of valuable metals in smelting waste acid according to claim 4, characterized in that: The amount of the sulfur-containing substance added is 1 mol of copper ions for every 0.5-5 mol of sulfur element; The sulfur-containing compound is added in an amount with a molar ratio of 1-5:1 to the sulfur-containing substance.
6. The comprehensive recovery method of valuable metals in smelting waste acid according to claim 1, characterized in that: The sulfur-containing compound includes at least one of gaseous sulfur dioxide, liquid sulfur dioxide, flue gas containing sulfur dioxide, sodium sulfite, and sodium metabisulfite.
7. The comprehensive recovery method of valuable metals in smelting waste acid according to claim 6, characterized in that: The amount of the sulfur-containing compound added is no less than 1.5 mol of the sulfur-containing compound for every 1 mol of sulfur element in the sulfur-containing substance.
8. The comprehensive recovery method of valuable metals in smelting waste acid according to claim 1, characterized in that: The leaching is oxygen-enriched leaching, and the leaching reagent of the oxygen-enriched leaching includes at least one of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid.
9. The comprehensive recovery method of valuable metals in smelting waste acid according to claim 8, characterized in that: The temperature of the oxygen-enriched leaching is 80-150° C., and the time is 1-5 hours.
10. The comprehensive recovery method of valuable metals in smelting waste acid according to any one of claims 1 to 9, characterized in that: The comprehensive recovery method further comprises: mixing the copper-rhenium precipitation liquid with an arsenic precipitation material to perform sulfide precipitation of arsenic to obtain arsenic sulfide slag and arsenic precipitation liquid; The arsenic precipitating substance includes at least one of sodium sulfide, sodium hydrosulfide, and hydrogen sulfide.