Process for recovering copper in bismuth matte by full-wet method

Abstract

The invention discloses a process for recovering copper in bismuth matte by a full-wet method. According to the process, a process condition for selectively leaching the copper in the bismuth copper matte through an acid solution under the condition of an oxidizing agent is provided, so that the copper in the bismuth copper matte enters the acid solution, and other valuable elements such as gold, silver, lead, bismuth and antimony in the bismuth copper matte are basically not leached out. The obtained copper-containing leachate can be directly subjected to electrodeposition without purification and impurity removal to prepare an electrolytic copper product meeting the national standard A level; the leaching residues containing gold, silver, lead, bismuth, antimony and other valuable metals can be returned to a lead anode mud pyrometallurgy system to be recycled. According to the process, the recovery rate of gold, silver, lead, bismuth, antimony and other valuable metals in the bismuth matte is high, acid consumption is low, three wastes are not generated in the process, and green recovery of the valuable metals in the bismuth matte can be achieved.

Description

Technical Field

[0001] The invention belongs to the field of nonferrous metal hydrometallurgy, and in particular relates to a process for fully hydrometallurgically recovering copper from bismuth matte. Background Art

[0002] Bismuth matte is the product of bismuth fire refining process, containing a large amount of copper, lead, antimony and sulfur. The chemical composition of bismuth matte used in this experiment is mainly: Cu 20-40%, Fe 0.5-10%, S 5-15%, Pb 8-40%, Sb 0.5-15%, Ag 2-8%, Bi 0.5-7%, As 0.1-2.0%. Among them, copper mainly exists in the form of sulfides such as Cu2S, CuS, Cu2Sb, Cu9S5, etc. It is necessary to add a suitable oxidant to fully oxidize the copper-containing sulfide ore before the copper can be further efficiently leached into the acidic leachate.

[0003] At present, the processes for processing copper matte mainly include pyrometallurgy, pyrometallurgy-hydrometallurgy combined and all-hydrometallurgy processes. For example, patent CN116574920A discloses a pyrometallurgy process for producing blister copper by converting high-grade copper matte into blister copper by adding copper matte and cold materials in batches and adding flux in small amounts multiple times. However, the process has the disadvantages of long process, low metal recovery rate and environmental pollution. Moreover, the process is not suitable for bismuth copper matte with low copper grade because the sulfur content is low and the low concentration of SO2 produced cannot be effectively recycled. The pyrometallurgy-hydrometallurgy combined process mainly involves oxidizing and roasting the copper matte first, then leaching the roasting slag with sulfuric acid to obtain a copper sulfate solution and a leaching slag rich in lead sulfate, and finally recovering the copper in the copper sulfate solution (paper "Solvent Extraction of Copper from the Acid Leaching Solution of Oxidative Roasting Product of Lead Copper Matte, Hydrometallurgy, 2017, (5), 388-390"). The roasting stage of this process also has the problem that low-concentration SO2 is difficult to recycle, and its process flow is long and energy consumption is high. The full wet process mainly includes pressurized leaching and normal pressure leaching. For example, the methods disclosed in patents CN114934182A, CN101225476B and CN104789783B all add appropriate oxidants to the ground copper matte material for acidic pressurized oxidation leaching; patents CN102586600B and CN102230083B pressurized oxidation leaching of copper matte in an alkaline system to effectively separate the valuable elements in the raw materials. However, pressurized leaching not only has high requirements on equipment but also has some operational problems. The risk of certain damage is high; Patent CN105543479B uses concentrated sulfuric acid and dilute sulfuric acid to carry out two-stage atmospheric pressure oxidation leaching of matte, and the leachate is subjected to copper electrodeposition treatment after purification. Since concentrated sulfuric acid is used for leaching in one stage, the leachate contains more metal impurities such as Bi and Fe, which increases the purification process; Patent CN102051478B uses sulfuric acid and sodium chloride to oxidatively leach lead matte, and uses iron filings to reduce the copper-containing leachate to obtain sponge copper. This process will introduce a large amount of Cl ions into the replacement tail liquid, increasing the burden of wastewater treatment. Summary of the invention

[0004] The invention discloses a process for recovering copper from bismuth matte by a fully wet method, so as to solve any of the above and other potential problems in the prior art.

[0005] In order to achieve the above object, the technical solution of the present invention is: a process for recovering copper from bismuth matte by a fully wet method, the process specifically comprising the following steps:

[0006] S1) crushing and grinding the blocky bismuth matte to a certain particle size to obtain bismuth matte powder;

[0007] S2) mixing the bismuth matte powder obtained in S1) with an acidic solvent in a certain ratio, stirring continuously at a certain rate, heating to a certain temperature, keeping the temperature for a certain time, and filtering to obtain leaching residue and copper-containing acidic leaching solution after leaching is completed;

[0008] S3) adding a certain amount of additives to the copper-containing acidic leaching solution obtained in S2) and directly performing electrowinning at an appropriate current density to obtain electrowinning copper.

[0009] Furthermore, more than 80% of the particle size in S1) is less than 200 mesh.

[0010] Furthermore, the solid-liquid ratio of bismuth matte to acidic solvent in S2) is 1kg:6.0L~10L, the stirring speed is above 100r / min, the oxidant is continuously added during the leaching process, the pressure is normal pressure, the reaction temperature is 70℃~95℃, and the insulation time is 6h~15h.

[0011] Furthermore, the sulfuric acid concentration in the acidic solvent is 1.6 mol / L to 2.3 mol / L; the copper ion concentration is 5-25 g / L; the bismuth ion concentration is 0.5-3 g / L; the iron ion concentration is 0-3 g / L; and the antimony ion concentration is 0-0.3 g / L.

[0012] Further, the oxidant is H2O2 and oxygen;

[0013] The amount of H2O2 added is 0.1 to 0.5 times the weight of the bismuth matte; oxygen is added at a flow rate of 1 to 10 L / min per kilogram of bismuth matte powder.

[0014] Further, the amount of the additive in S3) is 20-400 g / t copper; the current density is controlled at 150 A / m 2 ~300A / m 2 .

[0015] Furthermore, the additive is one or a combination of bone glue, gelatin, guar gum, casein, thiourea, polyethylene glycol, chloride ion, cobalt sulfate, and abiraterone.

[0016] Furthermore, the anode of the electrolytic cell in the electrolytic process is a lead alloy plate, and the cathode is a stainless steel plate, and the electrolytic waste liquid can be returned to the acidic solvent for recycling.

[0017] Furthermore, the copper leaching rate of the process is not less than 94%, the leaching rates of bismuth and antimony are close to 0, and the purity of the electrolytic copper obtained after electrowinning of the copper sulfate leaching solution is 99.995%.

[0018] An electrolytic copper is prepared by adopting the above process.

[0019] The present invention has the following advantages:

[0020] 1) The separation effect of copper and other valuable metals is good. No less than 94% of the copper in bismuth matte can be selectively leached and separated, and valuable metals such as gold, silver, lead, bismuth and antimony are basically enriched in the slag.

[0021] 2) The production process is short, and the copper in the bismuth matte can be better separated through a one-step atmospheric pressure oxidation leaching.

[0022] 3) The consumption of sulfuric acid is low, and the electrodeposition lean solution can be used again to prepare the acidic leaching agent to leach bismuth matte.

[0023] 4) All reactions are carried out under normal pressure, with low requirements on equipment materials and small equipment investment.

[0024] 5) The reaction raw materials have strong adaptability, low energy consumption, no three wastes are generated, and it is environmentally friendly. It can economically and efficiently comprehensively recover the various valuable metals in bismuth matte and achieve zero discharge of waste slag and wastewater from lead smelting enterprises.

[0025] 6) This method has low requirements on leaching conditions, low requirements on equipment, short process flow, and is easy to operate. The obtained leaching solution can be directly electrolytically deposited without purification to generate electrolytic copper products that meet national standard A level. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The present invention is a process flow chart of fully wet method for recovering copper from bismuth matte. DETAILED DESCRIPTION

[0027] The following specific examples illustrate the implementation methods of the present invention. People familiar with this technology can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. Obviously, the described embodiments are part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] like Figure 1 As shown, the present invention provides a process for recovering copper from bismuth matte by a fully wet method, and the process specifically comprises the following steps:

[0029] S1) crushing and grinding the blocky bismuth matte to a certain particle size to obtain bismuth matte powder;

[0030] S2) mixing the bismuth matte powder obtained in S1) with an acidic solvent in a certain ratio, stirring continuously at a certain rate, heating to a certain temperature, keeping the temperature for a certain time, and filtering to obtain leaching residue and copper-containing acidic leaching solution after leaching is completed;

[0031] S3) adding a certain amount of additives to the copper-containing acidic leaching solution obtained in S2) and directly performing electrowinning at an appropriate current density to obtain electrowinning copper.

[0032] Furthermore, more than 80% of the particle size in S1) is less than 200 mesh.

[0033] Furthermore, the solid-liquid ratio of bismuth matte to acidic solvent in S2) is 1kg:6.0L~10L, the stirring speed is above 100r / min, the oxidant is continuously added during the leaching process, the pressure is normal pressure, the reaction temperature is 70℃~95℃, and the insulation time is 6h~15h.

[0034] Furthermore, the sulfuric acid concentration in the acidic solvent is 1.6 mol / L to 2.3 mol / L; the copper ion concentration is 5-25 g / L; the bismuth ion concentration is 0.5-3 g / L; the iron ion concentration is 0-3 g / L; and the antimony ion concentration is 0-0.3 g / L.

[0035] Further, the oxidant is H2O2 and oxygen;

[0036] The amount of H2O2 added is 0.1 to 0.5 times the weight of the bismuth matte; oxygen is added at a flow rate of 1 to 10 L / min per kilogram of bismuth matte powder.

[0037] Further, the amount of the additive in S3) is 20-400 g / t copper; the current density is controlled at 150 A / m 2 ~300A / m 2 .

[0038] Furthermore, the additive is one or a combination of bone glue, gelatin, guar gum, casein, thiourea, polyethylene glycol, chloride ion, cobalt sulfate, and abiraterone.

[0039] Furthermore, the anode of the electrolytic cell in the electrolytic process is a lead alloy plate, and the cathode is a stainless steel plate, and the electrolytic waste liquid can be returned to the acidic solvent for recycling.

[0040] Furthermore, the copper leaching rate of the process is not less than 94%, the leaching rates of bismuth and antimony are close to 0, and the purity of the electrolytic copper obtained after electrowinning of the copper sulfate leaching solution is 99.995%.

[0041] An electrolytic copper is prepared by adopting the above process.

[0042] Example 1

[0043] This embodiment provides a method for recovering copper by oxidative acid leaching of bismuth matte, and its process flow is as follows: Figure 1 The method comprises the following steps:

[0044] (1) crushing bismuth matte (Cu: 25%, Fe: 1.29%, S: 8.92%, Pb: 35.6%, Sb: 13.1%, Ag: 2.36%, Bi: 2.7%, As: 1.75%) blocks to a particle size of less than 200 meshes as a bismuth matte leaching raw material;

[0045] (2) an acidic solvent containing a copper ion concentration of 5 g / L, a bismuth ion concentration of 3 g / L, an iron ion concentration of 1.5 g / L, an antimony ion concentration of 0.3 g / L and a sulfuric acid concentration of 1.6 mol / L is placed in a 1 L beaker, 100 g of bismuth matte powder is added, the reaction temperature is 85° C., the liquid-to-solid ratio is 10:1 (mL / g), 18 ml of hydrogen peroxide is evenly added dropwise over a period of about 1 hour, then the addition of hydrogen peroxide is stopped, and pure O2 is introduced into the bottom of the leachate at a flow rate of 0.3 L / min. The reaction time is 10 hours. After the leaching is completed, the copper sulfate leachate and the leachate residue are obtained by filtration and separation, and the leachate is used as a raw material solution for electrolytic copper.

[0046] (3) The copper sulfate leaching solution is directly electrolytically processed at a current density of 300 A / m 2 After 6 hours of electrolysis, the cathode copper was taken out for analysis.

[0047] (4) The results of laboratory analysis show that after leaching bismuth matte with an acidic solvent, the copper leaching rate is 94%, the leaching rates of bismuth and antimony are close to 0, and the purity of the electrolytic copper obtained after electrolysis of copper sulfate leaching solution is 99.995%, which meets the national standard for grade A electrolytic copper, and the current efficiency is 94.7%.

[0048] Example 2

[0049] This embodiment provides a method for recovering copper by oxidative acid leaching of bismuth matte, and its process flow is as follows: Figure 1 The method comprises the following steps:

[0050] (1) crushing bismuth matte (Cu: 45.3%, Fe: 0.34%, S: 11.3%, Pb: 30.9%, Sb: 0.72%, Ag: 4.58%, Bi: 1.62%, As: 0.093%) blocks to a particle size of less than 200 meshes as a bismuth matte leaching raw material;

[0051] (2) placing an acidic solvent containing a copper ion concentration of 25 g / L, a bismuth ion concentration of 3 g / L, an iron ion concentration of 1.5 g / L, an antimony ion concentration of 0.3 g / L and a sulfuric acid concentration of 2.3 mol / L into a 1 L beaker, adding 100 g of bismuth matte powder, the reaction temperature being 80° C., the liquid-solid ratio being 8:1 (mL / g), first evenly adding 45 ml of hydrogen peroxide dropwise over a period of about 1 hour, then stopping the addition of hydrogen peroxide, and introducing pure O2 to the bottom of the leachate at a flow rate of 0.5 L / min, the reaction time being 12 hours, filtering and separating after the leaching is completed, and obtaining a copper sulfate leachate and a leach residue, the copper sulfate leachate being used as a raw material solution for electrolytic copper;

[0052] (3) The copper sulfate leaching solution is directly electrolytically processed at a current density of 250 A / m 2 After 7 h of electrolysis, the cathode copper was taken out for analysis.

[0053] (4) The results of laboratory analysis show that after leaching bismuth matte with an acidic solvent, the copper leaching rate is 94.5%, and the leaching rates of bismuth and antimony are close to 0. The purity of the electrolytic copper obtained after electrowinning of the copper sulfate leaching solution is 99.993%, which meets the national standard for grade A electrolytic copper, and the current efficiency is 94.2%.

[0054] Example 3

[0055] This embodiment provides a method for recovering copper by oxidative acid leaching of bismuth matte, and its process flow is as follows: Figure 1 The method comprises the following steps:

[0056] (1) crushing bismuth matte (Cu: 49.3%, Fe: 2.67%, S: 12.2%, Pb: 12.7%, Sb: 4.0%, Ag: 2.83%, Bi: 1.82%, As: 1.3%) blocks to a particle size of less than 200 meshes as a bismuth matte leaching raw material;

[0057] (2) placing an acidic solvent containing a copper ion concentration of 25 g / L, a bismuth ion concentration of 3 g / L, an iron ion concentration of 1.5 g / L, an antimony ion concentration of 0.3 g / L and a sulfuric acid concentration of 2.3 mol / L into a 1 L beaker, adding 100 g of bismuth matte powder, the reaction temperature being 80° C., the liquid-solid ratio being 6:1 (mL / g), first evenly adding 45 ml of hydrogen peroxide dropwise over a period of about 1 hour, then stopping the addition of hydrogen peroxide, and introducing pure O2 to the bottom of the leachate at a flow rate of 1 L / min, the reaction time being 15 hours, filtering and separating after the leaching is completed, obtaining a copper sulfate leachate and a leach residue, and the copper sulfate leachate is used as a raw material solution for electrolytic copper;

[0058] (3) The copper sulfate leaching solution is directly electrolytically processed at a current density of 300 A / m 2 After 5 h of electrolysis, the cathode copper was taken out for analysis.

[0059] (4) The results of laboratory analysis show that after leaching bismuth matte with an acidic solvent, the copper leaching rate is 93.5%, the leaching rates of bismuth and antimony are close to 0, and the purity of the electrolytic copper obtained after electrolysis of the copper sulfate leaching solution is 99.993%, which meets the national standard for grade A electrolytic copper, and the current efficiency is 93.8%.

[0060] The invention can efficiently leach and separate the copper element in bismuth matte and further enrich and recover the gold, silver, lead, bismuth, antimony and other elements therein, and has obvious advantages in environmental protection and resource recycling.

[0061] The above is a detailed introduction to a fully wet process for recovering copper from bismuth matte provided in the embodiment of the present application. The description of the above embodiment is only used to help understand the method and core idea of ​​the present application; at the same time, for those skilled in the art, according to the idea of ​​the present application, there will be changes in the specific implementation method and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

[0062] For example, certain words are used in the specification and claims to refer to specific components. Those skilled in the art should understand that hardware manufacturers may use different nouns to refer to the same component. This specification and claims do not use differences in names as a way to distinguish components, but use differences in the functions of components as the criteria for distinction. As mentioned throughout the specification and claims, "including" and "comprising" are open-ended terms, so they should be interpreted as "including / including but not limited to". "Approximately" means that within an acceptable error range, those skilled in the art can solve the technical problem within a certain error range and basically achieve the technical effect. The subsequent description of the specification is a preferred embodiment of the present application, but the description is for the purpose of illustrating the general principles of the present application, and is not used to limit the scope of the present application. The scope of protection of the present application shall be determined by the definition of the attached claims.

[0063] It should also be noted that the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a product or system including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such a product or system. In the absence of more restrictions, the elements defined by the sentence "comprises a ..." do not exclude the existence of other identical elements in the product or system including the elements.

[0064] It should be understood that the term "and / or" used in this article is only a description of the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0065] The above description shows and describes several preferred embodiments of the present application, but as mentioned above, it should be understood that the present application is not limited to the form disclosed herein, and should not be regarded as excluding other embodiments, but can be used in various other combinations, modifications and environments, and can be modified within the scope of the application concept described herein through the above teachings or the technology or knowledge of the relevant field. The changes and modifications made by those skilled in the art do not deviate from the spirit and scope of the present application, and should be within the scope of protection of the claims attached to the present application.

Claims

1. A process for recovering copper from bismuth matte by a fully wet method, characterized in that: The process specifically comprises the following steps: S1) crushing and grinding the blocky bismuth matte to a certain particle size to obtain bismuth matte powder; S2) mixing the bismuth matte powder obtained in S1) with an acidic solvent in a certain ratio, stirring continuously at a certain rate, heating to a certain temperature, keeping the temperature for a certain time, and filtering to obtain leaching residue and copper-containing acidic leaching solution after leaching is completed; S3) adding a certain amount of additives to the copper-containing acidic leaching solution obtained in S2) and directly performing electrowinning at an appropriate current density to obtain electrowinning copper.

2. The process according to claim 1, characterized in that The particle size in S1) is more than 80% smaller than 200 mesh.

3. The process according to claim 1, characterized in that The solid-liquid ratio of bismuth matte to acidic solvent in S2) is 1kg:6.0L~10L, the stirring speed is above 100r / min, the oxidant is continuously added during the leaching process, the pressure is normal pressure, the reaction temperature is 70℃~95℃, and the insulation time is 6h~15h.

4. The process according to claim 3, characterized in that The acidic solvent has a sulfuric acid concentration of 1.6 mol / L to 2.3 mol / L, a copper ion concentration of 5-25 g / L, a bismuth ion concentration of 0.5-3 g / L, a iron ion concentration of 0-3 g / L and an antimony ion concentration of 0-0.3 g / L.

5. The process according to claim 3, characterized in that The oxidant is H2O2 and oxygen; The amount of H2O2 added is 0.1 to 0.5 times the weight of the bismuth matte; oxygen is added at a flow rate of 1 to 10 L / min per kilogram of bismuth matte powder.

6. The process according to claim 1, characterized in that The amount of the additive in S3) is 20-400 g / t copper; the current density is controlled at 150 A / m 2 ~300A / m 2 .

7. The process according to claim 6, characterized in that The additive is one or a combination of bone glue, gelatin, guar gum, casein, thiourea, polyethylene glycol, chloride ion, cobalt sulfate and abiraterone.

8. The process according to claim 1, characterized in that The anode of the electrolytic cell in the electrolytic process is a lead alloy plate, and the cathode is a stainless steel plate. The electrolytic waste liquid can be returned to the acidic solvent for recycling.

9. The process according to claim 1, characterized in that The copper leaching rate of the process is not less than 94%, the leaching rates of bismuth and antimony are close to 0, and the purity of the electrolytic copper obtained after electrowinning of the copper sulfate leaching solution is 99.995%.

10. An electrolytic copper deposition method, characterized in that: The electrolytic copper is prepared by the process described in any one of claims 1 to 9.

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