A high-efficiency recovery method of copper in chalcocite type copper concentrate sulfuric acid roasting acid leaching residue

Abstract

The application provides a high-efficiency recovery method for copper in chalcocite-type copper concentrate sulfuric acid roasting and acid leaching residue, and belongs to the technical field of mineral processing.The application recovers sulfide copper minerals and intergrowth of the sulfide copper minerals and cupric ferrite in chalcocite-type copper concentrate sulfuric acid roasting and acid leaching residue through flotation, then recovers cupric ferrite and intergrowth of the cupric ferrite and the sulfide copper minerals in middlings and tailings in the flotation through magnetic separation, and finally recovers superfine cupric ferrite and copper mineral particles completely wrapped by gangue minerals in the tailings in the magnetic separation through chemical dissociation.The application uses the method of combination of flotation, magnetic separation and chemical dissociation, strengthens recovery of the copper in chalcocite-type copper concentrate sulfuric acid roasting and acid leaching residue, and the comprehensive recovery rate can reach 91.18%.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral processing, and in particular relates to a method for efficiently recovering copper from sulphate-roasting and acid-leaching residues of chalcocite-type copper concentrate. Background Art

[0002] Copper slag is a solid waste produced by pyrometallurgical copper smelting or hydrometallurgical copper smelting. Pyrometallurgical copper smelting is usually used to process copper sulfide ores, while hydrometallurgical copper smelting usually processes copper oxide ores. The copper slag produced by pyrometallurgical copper smelting is mainly due to the complex physical and chemical reactions of copper ore in a high-temperature oxidizing environment. Copper is not only enriched in the copper matte, but also enriched together with associated gangue such as iron oxides, thus forming copper slag. The copper slag produced by hydrometallurgical copper smelting is mainly leaching residue that has not been leached, separated and recovered after leaching. Copper is a sulfur-loving element, and copper ores are mostly copper sulfide ores. Therefore, currently more than 80% of copper ores are processed by pyrometallurgy, and less than 20% of copper ores are processed by hydrometallurgy.

[0003] Copper slag has a complex composition and often contains valuable elements such as copper and iron. Therefore, it is a mineral resource with development and utilization value. In the case of severe shortage of existing resources in my country, the development of resource-based comprehensive utilization technology of copper-containing slag has important strategic and practical significance for promoting circular economy, sustainable development and environmental protection.

[0004] Due to the different components and properties of copper slag, the methods for recovering copper elements are also different. At present, the methods for recovering copper elements in copper slag mainly include three types: pyrometallurgical depletion, flotation method and wet leaching. In pyrometallurgical depletion, a large amount of Fe3O4 is produced in the process of copper smelting, which increases the viscosity of copper slag and makes the slag and matte unable to be effectively separated. However, pyrometallurgical depletion is to add a reducing agent to the copper slag at a high furnace temperature, so as to reduce Fe3O4 in the copper slag to FeO, so that the copper matte is gathered and settled, thereby reducing the copper content of the copper slag. For example, the patent with publication number CN 114150157 A records that a tilted pipe smelting device is added between the copper smelting device and the storage pool, reducing and oxidizing gases are blown in from the bottom end, a gas burner and a powder spraying device are added at the top end, and the reduction conditions of copper in the copper slag are optimized by blowing in carbon powder to realize continuous depletion of the copper slag. However, this method is only suitable for the process of producing copper slag and cannot recover copper in the already produced copper slag. Flotation method is to use appropriate flotation reagents to enrich copper-containing minerals according to the difference in hydrophilicity of the surface of mineral particles in copper slag, and after stirring and aeration, copper concentrate foam is formed in the form of bubbles, while gangue minerals are deposited at the bottom of the ore pulp to form tailings, so as to realize the separation and recovery of copper in copper slag. For example, the patent with publication number CN 117299347 A records that during the grinding and screening process, natural copper that produces ductile deformation during the grinding process is preferentially recovered, high-concentration flotation is then performed to recover copper sulfide and natural copper, and finally, sulfurizing agent is used to recover the remaining copper oxide minerals. However, this method is only suitable for copper slag in which copper elements are mainly distributed in elemental copper, and the applicability is poor. Wet leaching is that the leaching agent reacts with the copper slag under specific conditions, and the soluble reaction products are separated from the insoluble leaching residue, and the valuable metals in the copper slag are extracted through extraction separation and other operations. According to the different leaching methods and media, the wet leaching of copper slag mainly includes chemical leaching and biological leaching. Among them, chemical leaching mainly uses sulfuric acid, ammonia and other chemical reagents as leaching agents. For example, the patent with publication number CN 115449640 A records that water, sulfuric acid and a solubility aid are added to the copper slag for leaching, the leaching residue and leaching solution are obtained after solid-liquid separation, a reactive metal is added to the leaching solution for reaction, and sponge copper and cobalt sulfate solution are obtained after solid-liquid separation again. However, this method has a slow leaching process and needs to perform solid-liquid separation twice, so the efficiency is low.

[0005] It can be seen that the research on the recycling of copper slag is in-depth and comprehensive, but the technology for recycling the waste generated in the process of copper slag utilization is rarely reported. The content of the -10 mu particle size in the acid leaching slag produced by using sulfuric acid to leach the chalcocite type flotation copper concentrate after sulfuric acid roasting is 80%, and the distribution rate of copper metal is 90%. Copper mainly exists in the form of combined copper oxide, accounting for 91.10%. Copper elements are mainly distributed in copper ferrite (CuFe2O4, a kind of "artificial mineral", hereinafter referred to as copper ferrite) and copper sulfide minerals. The copper-containing minerals and gangue minerals are wrapped in each other, and the embedded relationship is complex and diverse, forming a large number of intergrowths and inclusions. The high combination rate of copper oxide is a recognized extremely difficult mineral to be separated. Although the current flotation technology can separate the combined copper oxide, the flotation recovery rate is low. The main reason is that a part of the high combination rate of copper oxide may be in the form of intergrowth combined with gangue, which may be in the form of physical way to become a very fine copper mineral inclusion in the gangue, and may be in the form of chemical way to become isomorphism. Moreover, the grinding has limited effect on improving the dissociation degree of the embedded ultra-fine copper mineral particles. Therefore, the present application provides a high-efficiency recovery method for copper in chalcocite type copper concentrate sulfuric acid roasting acid leaching slag. SUMMARY

[0006] To solve the above technical problems, the present application provides a high-efficiency recovery method for copper in chalcocite type copper concentrate sulfuric acid roasting acid leaching slag.

[0007] To achieve the above purpose, the present application provides the following technical solutions:

[0008] One of the technical solutions of the present application is:

[0009] A high-efficiency recovery method for copper in chalcocite type copper concentrate sulfuric acid roasting acid leaching slag, which recovers the copper sulfide minerals and their intergrowths in the chalcocite type copper concentrate sulfuric acid roasting acid leaching slag by flotation method, and then recovers the copper ferrite and its intergrowths with copper sulfide minerals in the middlings and tailings of flotation by magnetic separation method, and finally recovers the ultra-fine copper ferrite and copper mineral particles completely wrapped in gangue minerals in the tailings of magnetic separation by chemical dissociation.

[0010] Further, a high-efficiency recovery method for copper in chalcocite type copper concentrate sulfuric acid roasting acid leaching slag includes the following steps:

[0011] (1) Grinding the chalcocite type copper concentrate sulfuric acid roasting acid leaching slag to obtain a slurry, then adding a dispersing agent, a sulfidizing agent, a combined collector and a frother into the slurry in sequence and stirring to obtain a mixed slurry, and then performing flotation roughing treatment on the mixed slurry to obtain a flotation rough concentrate and a flotation tailings, and then performing flotation cleaning treatment on the flotation rough concentrate to obtain a flotation concentrate and a flotation middlings;

[0012] (2) the middling and the tailings are combined and subjected to magnetic separation to obtain a magnetic concentrate and a magnetic tailings;

[0013] (3) the magnetic tailings are thickened and subjected to chemical dissociation to obtain a dissociation liquid and a dissociation residue;

[0014] (4) the flotation concentrate, the magnetic concentrate and the dissociation liquid are recovered to realize the recovery of copper from the acid leaching residue.

[0015] Further, in step (1), the copper grade of the chalcocite type copper concentrate sulfuric acid roasting acid leaching residue is 10-11%, the content of the -10 μm particle size is 80%, the distribution rate of copper in the -10 μm particle size is 90%, and the copper exists in the form of combined oxidized copper, accounting for 91.10%, and the copper element is mainly distributed in the copper ferrite and copper sulfide minerals.

[0016] Further, in step (1), the chalcocite type copper concentrate sulfuric acid roasting acid leaching residue is ground to 90% of -38 μm, and the pulp concentration is adjusted to 30-40 wt% by adding water to obtain a pulp.

[0017] Further, in step (1), the dispersing agent is sodium carbonate, and the addition amount is 100-600 g / t;

[0018] The sulfidizing agent is sodium sulfide, and the addition amount is 500-2000 g / t;

[0019] The combined collector includes xanthate and / or black drug, and the addition amount is 100-1000 g / t;

[0020] The frother is methyl isobutyl carbinol (MIBC), and the addition amount is 20-80 g / t.

[0021] Further, the xanthate includes one or more of ethyl xanthate, butyl xanthate, amyl xanthate and secondary octyl xanthate, and the black drug includes one or more of butylamine black drug, butyl sodium black drug and aniline black drug.

[0022] Further, in step (1), the stirring time is 2-3 min.

[0023] Further, in step (1), the flotation cleaning treatment refers to a process of not adding drugs for the flotation concentrate obtained by the flotation roughing treatment.

[0024] Further, in step (2), the number of magnetic separation is 2, the magnetic field strength of the magnetic separation is 0.1-0.2 T, preferably 0.12-0.16 T, and more preferably 0.14 T.

[0025] Further, in step (3), the chemical dissociation is adding sulfuric acid to the magnetic tailings.

[0026] Further, the amount of sulfuric acid (concentration of 98%) is 300-1200 kg / t, the temperature of chemical dissociation is 80-120℃, the time is 0.5-4 h, and the liquid-solid ratio is 3:1-6:1 (L:kg), wherein the liquid-solid ratio refers to the ratio of the volume of liquid phase (sulfuric acid and water) to the mass of solid phase (ore) in the chemical dissociation process.

[0027] The present application recovers sulfide copper minerals and part of the intergrowth of sulfide copper minerals and cupric ferrite in the sulfuric acid roasting and acid leaching residue of chalcocite type copper concentrate through a flotation process. In the flotation process, sodium carbonate is used as a dispersant to improve the flotation effect in view of the high content of fine particles in the copper residue; sodium sulfide is used as an activator in view of the high oxidation rate of the acid leaching residue; at the same time, a combined collector is used to improve the recovery rate in view of the difficulty in separation of the acid leaching residue due to the presence of "artificial minerals"; then a magnetic separation method is used to recover cupric ferrite and its intergrowth with sulfide copper minerals in the middlings and tailings of flotation; finally, a chemical dissociation technique is used to recover ultra-fine cupric ferrite and copper mineral particles completely wrapped by gangue minerals in the tailings of magnetic separation. The specific steps are as follows:

[0028] (1) The sulfuric acid roasting and acid leaching residue of chalcocite type copper concentrate is ground to a particle size of -38 μm, accounting for 90%, and water is added to obtain a pulp I with a concentration of 30-40 wt%; sodium carbonate is added as a dispersant to the pulp I at a dosage of 100-600 g / t and stirred for 2-3 min to obtain a pulp II; sodium sulfide is added as a sulfidizing agent to the pulp II at a dosage of 500-2000 g / t and stirred for 2-3 min to obtain a pulp III; a combined collector is added to the pulp III at a dosage of 100-1000 g / t and stirred for 2-3 min to obtain a pulp IV; MIBC is added as a frother to the pulp IV at a dosage of 20-80 g / t and stirred for 2-3 min to obtain a pulp V; the pulp V is subjected to rough flotation to obtain a rough flotation concentrate and a flotation tailings; the rough flotation concentrate is subjected to 1-4 times of cleaning flotation to obtain a flotation concentrate and a plurality of flotation middlings;

[0029] (2) The plurality of flotation middlings and the flotation tailings are combined and subjected to 2 times of magnetic separation at a magnetic field strength of 0.1-0.2 T to obtain a magnetic separation concentrate I, a magnetic separation concentrate II, and a magnetic separation tailings; the magnetic separation concentrate I and the magnetic separation concentrate II are combined to obtain a magnetic separation concentrate;

[0030] (3) The magnetic separation tailings are thickened and sulfuric acid is added for chemical dissociation, wherein the amount of sulfuric acid (concentration of 98%) is 300-1200 kg / t, the temperature of chemical dissociation is 80-120℃, the time is 0.5-4 h, and the liquid-solid ratio is 3:1-6:1 (L:kg) to obtain a dissociation liquid and a dissociation residue;

[0031] (4) The final products include flotation concentrate, magnetic separation concentrate, dissociation liquid and dissociation residue, the copper-rich products include flotation concentrate, magnetic separation concentrate and dissociation liquid, the flotation concentrate, the magnetic separation concentrate and the dissociation liquid are recovered, and the recovery of copper in the acid leaching residue is realized.

[0032] Technical principles of the present application:

[0033] (1) The present application uses the characteristics that copper sulfide is easily collected by xanthate and the surface of cupric ferrite can be sulfidized, adopts the sulfidized xanthate method to float and recover copper sulfide minerals and their intergrowths with cupric ferrite, uses sodium carbonate as a dispersing agent to improve the flotation effect in the flotation process according to the characteristics of the ultra-fine particle size of the copper residue, uses sodium sulfide as an activator according to the characteristics of the high oxidation rate of the acid leaching residue, and uses a combined collector to improve the recovery rate to solve the problem that the acid leaching residue is difficult to separate due to the presence of artificial minerals.

[0034] (2) The present application uses the characteristics that cupric ferrite has strong magnetism and is closely intergrown with copper sulfide minerals, and uses two weak magnetic separations to fully recover cupric ferrite and its intergrowth with copper sulfide minerals in the middlings and tailings of flotation.

[0035] (3) The present application uses the characteristics that the copper in the magnetic separation tailings mainly exists in ultra-fine particle size cupric ferrite and copper-containing minerals wrapped by gangue minerals, and recovers the remaining cupric ferrite with ultra-fine particle size and copper mineral particles completely wrapped by gangue minerals in the magnetic separation tailings through a chemical dissociation process.

[0036] Compared with the prior art, the present application has the following advantages and technical effects:

[0037] 1. According to the properties of the sulfuric acid roasting and acid leaching residue of chalcocite type copper concentrate, such as fine particle size, high proportion of oxidized copper, high combination rate, and complex and diverse intergrowth relationship between copper minerals and gangue minerals, the present application uses a targeted beneficiation method to realize the intensified recovery of copper, specifically, the flotation process is used to separate copper sulfide minerals and intergrowth of copper sulfide minerals and cupric ferrite, the magnetic separation process is used to separate cupric ferrite with strong magnetism and intergrowth of cupric ferrite and copper sulfide minerals, and the chemical dissociation process is used to separate cupric ferrite with ultra-fine particle size and copper mineral particles completely wrapped by gangue minerals.

[0038] 2. According to the proportion of copper sulfide and oxidized copper in the sulfuric acid roasting and acid leaching residue of chalcocite type copper concentrate, the physical and chemical properties of artificial minerals in oxidized copper, and the intergrowth relationship of copper-containing minerals, the present application adjusts the reagent system of flotation, the number of cleaning, the magnetic field strength of magnetic separation and the conditions of chemical dissociation to realize the intensified recovery of copper in the ore.

[0039] 3. The present application uses the combination of flotation, magnetic separation and chemical dissociation to intensively recover the copper in the sulfuric acid roasting and acid leaching residue of chalcocite type copper concentrate, and the comprehensive recovery rate can reach 91.18%. BRIEF DESCRIPTION OF DRAWINGS

[0040] The accompanying drawings, which constitute part of the present invention, are provided to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are provided to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0041] Figure 1 This is a process flow chart of Example 1 of the present invention. DETAILED DESCRIPTION

[0042] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0043] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any intermediate value within a stated value or stated range and any other stated value or intermediate value within the stated range is also encompassed by the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0044] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0045] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be illustrative only.

[0046] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0047] The embodiment of the present invention provides a highly efficient method for recovering copper from slag of sulfuric acid roasting and acid leaching of chalcocite-type copper concentrate. The method comprises the following steps: recovering copper sulfide minerals and their intergrowths with copper ferrite from the slag of sulfuric acid roasting and acid leaching of chalcocite-type copper concentrate by flotation; recovering copper ferrite and its intergrowths with copper sulfide minerals from flotation ore and tailings by magnetic separation; and finally recovering copper ferrite and copper mineral particles completely encapsulated by gangue minerals from the magnetic separation tailings by chemical dissociation. The method comprises the following steps:

[0048] (1) grinding the sulfuric acid roasting and acid leaching residue of chalcocite-type copper concentrate and adding water to obtain a pulp, then sequentially adding a dispersant, a sulfiding agent, a combined collector and a frother to the pulp, stirring to obtain a mixed pulp, subjecting the mixed pulp to a flotation roughing treatment to obtain a flotation rough concentrate and a flotation tailing, and subjecting the flotation rough concentrate to a flotation concentration treatment to obtain a flotation concentrate and a flotation tailing;

[0049] (2) combining the flotation ore and the flotation tailings and performing magnetic separation to obtain magnetic concentrate and magnetic tailings;

[0050] (3) thickening the magnetically separated tailings and performing chemical dissociation to obtain a dissociation liquid and a dissociation slag;

[0051] (4) recovering the flotation concentrate, magnetic separation concentrate and dissociation liquid to achieve copper recovery in the acid leaching residue.

[0052] In step (1) of the preferred embodiment of the present invention, the copper grade of the chalcocite-type copper concentrate sulfated roasted acid leaching residue is 10-11%, the content of the -10 μm particle size is 80%, the metal distribution rate of copper in the -10 μm particle size is 90%, copper exists in the form of combined copper oxide, accounting for 91.10%, and the copper element is mainly distributed in copper ferrite and copper sulfide minerals.

[0053] In step (1) of the preferred embodiment of the present invention, the sulphate roasting and acid leaching residue of chalcocite copper concentrate is ground to -38 μm with a proportion of 90%, and water is added to adjust the pulp concentration to 30-40 wt% to obtain pulp.

[0054] In step (1) of the preferred embodiment of the present invention, the dispersant is sodium carbonate, and the addition amount is 100-600 g / t; the vulcanizing agent is sodium sulfide, and the addition amount is 500-2000 g / t; the combined collector includes xanthate and / or black medicine, and the addition amount is 100-1000 g / t, and the xanthate is selected from one or more of ethyl xanthate, butyl xanthate, amyl xanthate and sec-octyl xanthate, and the black medicine is selected from one or more of butyl ammonium black medicine, butyl sodium black medicine and aniline black medicine;

[0055] The foaming agent is methyl isobutyl carbinol (MIBC), and the added amount is 20-80 g / t.

[0056] In step (1) of the preferred embodiment of the present invention, the stirring time is 2 to 3 minutes.

[0057] In step (1) of the preferred embodiment of the present invention, the flotation concentration treatment refers to the process of performing a non-drug-adding flotation treatment on the flotation concentrate obtained by the flotation roughing treatment.

[0058] In step (2) of a preferred embodiment of the present invention, the number of magnetic separations is 2 times, and the magnetic field strength of the magnetic separation is 0.1 to 0.2 T, preferably 0.12 to 0.16 T, and more preferably 0.14 T.

[0059] In step (3) of the preferred embodiment of the present invention, the chemical dissociation is to add sulfuric acid to the magnetic separation tailings, the amount of sulfuric acid (concentration of 98%) is 300-1200 kg / t, the temperature of the chemical dissociation is 80-120° C., the time is 0.5-4 h, and the liquid-solid ratio is 3:1-6:1 (L:kg).

[0060] In step (3) of the preferred embodiment of the present invention, thickening the tailings with magnetic separation refers to the process of concentrating the tailings slurry by equipment such as a thickener.

[0061] The equipment used for flotation, magnetic separation, thickening and chemical dissociation in the embodiments of the present invention are all commonly used equipment in the field, and there is no special limitation on their models.

[0062] All raw materials used in the embodiments of the present invention are commercially available. The copper grade in the sulfuric acid roasting and acid leaching residue of the chalcocite-type copper concentrate used is 10.53%, the -10 μm particle size distribution is 80%, and the distribution rate of Cu in the -10 μm particle size is 90%. Copper mainly exists in the form of bound copper oxide, accounting for 91.10%. Copper is distributed in a variety of minerals, mainly in copper ferrite and copper sulfide minerals.

[0063] The technical solution of the present invention is further illustrated by the following examples.

[0064] Example 1

[0065] A highly efficient method for recovering copper from sulphate roasting and acid leaching residues of chalcocite type copper concentrate. Figure 1 , specifically including the following steps:

[0066] (1) grinding the chalcocite-type copper concentrate to a particle size of -38 μm of sulfated roasted acid leaching residue accounting for 90%, adding water to obtain a slurry I with a concentration of 30 wt%, adding 300 g / t of sodium carbonate as a dispersant to the slurry I and stirring for 2 min to obtain slurry II, adding 1500 g / t of sodium sulfide as a sulfiding agent to the slurry II and stirring for 2 min to obtain slurry III, adding 350 g / t of amyl xanthate as a combined collector and 100 g / t of butyl ammonium black powder to the slurry III and stirring for 2 min to obtain slurry IV, adding 40 g / t of MIBC as a foaming agent to the slurry IV and stirring for 2 min to obtain slurry V, subjecting the slurry V to a flotation roughing treatment to obtain a flotation rough concentrate and a flotation tailing, and subjecting the flotation rough concentrate to two flotation cleaning treatments to obtain a flotation concentrate and two different flotation tailings;

[0067] (2) combining all flotation ore and flotation tailings and performing magnetic separation twice with a magnetic field intensity of 0.14 T to obtain magnetic concentrate I, magnetic concentrate II and magnetic tailings, and combining magnetic concentrate I and magnetic concentrate II to obtain magnetic concentrate;

[0068] (3) thickening the magnetically separated tailings and adding sulfuric acid (98%) for chemical dissociation, wherein the amount of sulfuric acid is 600 kg / t, the chemical dissociation temperature is 95°C, the time is 2 h, and the liquid-solid ratio is 4:1 (L:kg), to obtain a dissociation liquid and a dissociation slag;

[0069] (4) The final products include flotation concentrate, magnetic concentrate, dissociation liquid and dissociation slag. The copper-rich products include flotation concentrate, magnetic concentrate and dissociation liquid. The flotation concentrate, magnetic concentrate and dissociation liquid are recovered to achieve the recovery of copper in the acid leaching slag.

[0070] In order to reduce the relative error in the test process, according to the above process method, multiple tests were carried out and the average value was taken (the same below). The recovery results of copper in Example 1 are shown in Table 1.

[0071] Table 1 Copper recovery results

[0072]

[0073] As shown in Table 1, the comprehensive recovery rate of copper is 91.18%. After the acid leaching residue is treated by the process of Example 1 of the present invention, efficient recovery of copper in copper metallurgical leaching residue is achieved.

[0074] Comparative Example 1

[0075] The same as Example 1, except that the magnetic separation and chemical dissociation steps in steps (2) and (3) are omitted. The specific steps are as follows:

[0076] (1) The particle size of the sulfuric acid roasted acid leaching residue of chalcocite type copper concentrate is -38 μm by grinding, and water is added to obtain a slurry I with a concentration of 30 wt%. 300 g / t of sodium carbonate as a dispersant is added to the slurry I and stirred for 2 min to obtain slurry II. 1500 g / t of sodium sulfide as a sulfiding agent is added to the slurry II and stirred for 2 min to obtain slurry III. 350 g / t of amyl xanthate as a combined collector and 100 g / t of butyl ammonium black powder are added to the slurry III and stirred for 2 min to obtain slurry IV. 40 g / t of MIBC as a foaming agent is added to the slurry IV and stirred for 2 min to obtain slurry V. Slurry V is subjected to flotation roughing treatment to obtain flotation rough concentrate and flotation tailings. The flotation rough concentrate is subjected to two flotation treatments to obtain flotation concentrate and two different flotation tailings.

[0077] (2) The final products include flotation concentrate, flotation ore and flotation tailings.

[0078] The recovery results of copper in Comparative Example 1 are shown in Table 2.

[0079] Table 2 Copper recovery results

[0080] Product Name Yield / % Cu grade / % Cu recovery rate / % Flotation concentrate 4.27 26.47 10.73 Flotation ore extraction (2 times) 44.96 11.88 50.72 Flotation tailings 50.77 7.99 38.55

[0081] Comparative Example 2

[0082] Same as Example 1, except that step (1) flotation and step (3) chemical dissociation are omitted:

[0083] (1) subjecting the sulphate-refined, roasted and acid-leached residue of chalcocite-type copper concentrate to magnetic separation twice at a magnetic field strength of 0.14 T to obtain magnetic concentrate I, magnetic concentrate II and magnetic tailings, and combining magnetic concentrate I and magnetic concentrate II to obtain magnetic concentrate;

[0084] (2) The final products include magnetic concentrate and magnetic tailings.

[0085] The recovery results of copper in Comparative Example 2 are shown in Table 3.

[0086] Table 3 Copper recovery results

[0087] Product Name Yield / % Cu grade / % Cu recovery rate / % Magnetic concentrate 34.25 18.06 58.72 Magnetic separation tailings 65.75 6.61 41.28

[0088] As shown in Table 2 of Comparative Example 1, when flotation alone was performed, the Cu grade of the flotation concentrate was 26.47% and the recovery rate was 10.73%. As shown in Table 3 of Comparative Example 2, when magnetic separation alone was performed, the Cu grade of the magnetic separation concentrate was 18.06% and the recovery rate was 58.72%. Neither of the above two solutions achieved effective enrichment of copper-containing minerals in copper metallurgical leaching residues, resulting in serious waste of resources.

[0089] Example 2

[0090] Same as Example 1, except that the magnetic field strength in step (2) is 0.1T.

[0091] The recovery results of copper in Example 2 are shown in Table 4.

[0092] Table 4 Copper recovery results

[0093]

[0094] Example 3

[0095] Same as Example 1, except that the magnetic field strength in step (2) is 0.2T.

[0096] The recovery results of copper in Example 3 are shown in Table 5.

[0097] Table 5 Copper recovery results

[0098]

[0099] It can be seen from the copper recovery results in Examples 1 to 3 that the field strength of the magnetic separation is closely related to the Cu grade and recovery rate of the concentrate. When the magnetic separation field strength is 0.1T, the Cu grade in the magnetic separation concentrate can reach 18.53%, but its yield is too low, the Cu recovery rate in the magnetic separation concentrate is reduced to 38.20%, and the comprehensive recovery rate is 87.28%. When the magnetic separation field strength is 0.2T, the selectivity in the magnetic separation process decreases, and the Cu recovery rate in the magnetic separation concentrate is 49.25%, which is almost not improved compared with the magnetic separation concentrate in Example 1. The comprehensive recovery rate is 90.48%, which is lower than the comprehensive recovery rate of Example 1.

[0100] Example 4

[0101] A method for efficiently recovering copper from sulphate roasting and acid leaching residues of chalcocite-type copper concentrate comprises the following steps:

[0102] (1) grinding the chalcocite-type copper concentrate to a particle size of -38 μm of sulfated roasted acid leaching residue, and adding water to obtain a 30 wt% slurry I, adding 100 g / t of sodium carbonate as a dispersant to the slurry I and stirring for 3 min to obtain slurry II, adding 2000 g / t of sodium sulfide as a sulfiding agent to the slurry II and stirring for 3 min to obtain slurry III, adding 50 g / t of amyl xanthate as a combined collector and 50 g / t of butyl ammonium black powder to the slurry III and stirring for 3 min to obtain slurry IV, adding 20 g / t of MIBC as a foaming agent to the slurry IV and stirring for 3 min to obtain slurry V, subjecting the slurry V to a flotation roughing treatment to obtain a flotation rough concentrate and a flotation tailing, and subjecting the flotation rough concentrate to two flotation cleaning treatments to obtain a flotation concentrate and two different flotation tailings;

[0103] (2) combining all flotation ore and flotation tailings and performing magnetic separation twice with a magnetic field intensity of 0.12 T to obtain magnetic concentrate I, magnetic concentrate II and magnetic tailings, and combining magnetic concentrate I and magnetic concentrate II to obtain magnetic concentrate;

[0104] (3) densely magnetically separated tailings and chemically dissociated by adding sulfuric acid, wherein the amount of sulfuric acid (concentration of 98%) is 300 kg / t, the chemical dissociation temperature is 120° C., the time is 4 h, and the liquid-solid ratio is 6:1 (L:kg), to obtain dissociation liquid and dissociation slag;

[0105] (4) The final products include flotation concentrate, magnetic concentrate, dissociation liquid and dissociation slag. The copper-rich products include flotation concentrate, magnetic concentrate and dissociation liquid. The flotation concentrate, magnetic concentrate and dissociation liquid are recovered to achieve the recovery of copper in the acid leaching slag.

[0106] The recovery results of copper in Example 4 are shown in Table 6.

[0107] Table 6 Copper recovery results

[0108]

[0109]

[0110] Example 5

[0111] A method for efficiently recovering copper from sulphate roasting and acid leaching residues of chalcocite-type copper concentrate comprises the following steps:

[0112] (1) grinding the chalcocite-type copper concentrate to obtain a sulfated roasted acid leaching residue of -38 μm with a particle size of 90%, adding water to obtain a slurry I with a concentration of 40 wt%, adding 600 g / t of sodium carbonate as a dispersant to the slurry I and stirring for 3 min to obtain a slurry II, adding 500 g / t of sodium sulfide as a sulfiding agent to the slurry II and stirring for 3 min to obtain a slurry III, adding 500 g / t of amyl xanthate as a combined collector and 500 g / t of butyl ammonium black powder to the slurry III and stirring for 3 min to obtain a slurry IV, adding 80 g / t of MIBC as a foaming agent to the slurry IV and stirring for 3 min to obtain a slurry V, subjecting the slurry V to a flotation roughing treatment to obtain a flotation rough concentrate and a flotation tailing, and subjecting the flotation rough concentrate to two flotation cleaning treatments to obtain a flotation concentrate and two different flotation tailings;

[0113] (2) combining all flotation ore and flotation tailings and performing magnetic separation twice with a magnetic field intensity of 0.16 T to obtain magnetic concentrate I, magnetic concentrate II and magnetic tailings, and combining magnetic concentrate I and magnetic concentrate II to obtain magnetic concentrate;

[0114] (3) thickening the tailings through magnetic separation and adding them into a sulfuric acid machine for chemical dissociation, wherein the amount of sulfuric acid is 1200 kg / t, the temperature of chemical dissociation is 80 ° C, the time is 0.5 h, and the liquid-solid ratio is 6:1 (L:kg), to obtain dissociation liquid and dissociation slag;

[0115] (4) The final products include flotation concentrate, magnetic concentrate, dissociation liquid and dissociation slag. The copper-rich products include flotation concentrate, magnetic concentrate and dissociation liquid. The flotation concentrate, magnetic concentrate and dissociation liquid are recovered to achieve the recovery of copper in the acid leaching slag.

[0116] The recovery results of copper in Example 5 are shown in Table 7.

[0117] Table 7 Copper recovery results

[0118]

[0119] Combined with the copper recovery results of Examples 1-5, it can be seen that the present invention adjusts the flotation reagent system, the number of cleaning times, the magnetic separation field strength, and the chemical dissociation conditions according to the ratio of copper sulfide and copper oxide in the sulfuric acid roasting and acid leaching residue of chalcocite-type copper concentrate, the physicochemical properties of the artificial minerals in the copper oxide, and the intercalation relationship of the copper-containing minerals to achieve enhanced recovery of copper from the ore. The present invention uses a method combining flotation, magnetic separation, and chemical dissociation to enhance the recovery of copper from the sulfuric acid roasting and acid leaching residue of chalcocite-type copper concentrate, with an overall recovery rate of up to 91.18%.

[0120] In summary, the above technical effects can only be achieved in the technical solution defined in the present invention, and any changes in the process flow or parameters will have an adverse effect on the technical effects.

[0121] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A method for efficiently recovering copper from sulphate roasting and acid leaching residues of chalcocite-type copper concentrate, characterized in that: The method comprises the following steps: recovering copper sulfide minerals and their intergrowths with copper ferrite from the sulphate roasting and acid leaching residue of chalcocite-type copper concentrate by flotation, recovering copper ferrite and its intergrowths with copper sulfide minerals from the flotation ore and tailings by magnetic separation, and finally recovering ultrafine copper ferrite and copper mineral particles completely wrapped by gangue minerals from the magnetic tailings by chemical dissociation; and (1) grinding the sulfuric acid roasting and acid leaching residue of chalcocite-type copper concentrate and adding water to obtain a pulp, then sequentially adding a dispersant, a sulfiding agent, a combined collector and a frother to the pulp, and stirring to obtain a mixed pulp; performing a flotation roughing treatment on the mixed pulp to obtain a flotation rough concentrate and a flotation tailing; and performing a flotation concentration treatment on the flotation rough concentrate to obtain a flotation concentrate and a flotation tailing; (2) combining the flotation ore and the flotation tailings and performing magnetic separation to obtain magnetic concentrate and magnetic tailings; (3) thickening the magnetically separated tailings and performing chemical dissociation to obtain a dissociation liquid and a dissociation slag; (4) recovering the flotation coarse concentrate, magnetic separation concentrate and dissociation liquid to achieve copper recovery in the acid leaching residue.

2. The method for efficiently recovering copper from sulphate-roasted acid leaching residues of chalcocite-type copper concentrate according to claim 1, characterized in that: In step (1), the copper grade of the slag from the sulfuric acid roasting and acid leaching of the chalcocite-type copper concentrate is 10-11%, the content of the -10 μm particle size is 80%, and the metal distribution rate of copper in the -10 μm particle size is 90%.

3. The method for efficiently recovering copper from sulphate-roasted acid leaching residues of chalcocite-type copper concentrate according to claim 1, characterized in that: In step (1), the sulphate roasting and acid leaching residue of chalcocite copper concentrate is ground to -38 μm with a proportion of 90%, and water is added to adjust the pulp concentration to 30-40 wt% to obtain pulp.

4. The method for efficiently recovering copper from sulphate-roasted acid leaching residues of chalcocite-type copper concentrate according to claim 1, characterized in that: In step (1), the dispersant is sodium carbonate, and the addition amount is 100-600 g / t; The vulcanizing agent is sodium sulfide, and the addition amount is 500-2000g / t; The combined collector includes xanthate and / or black medicine, and the addition amount is 100-1000 g / t; The foaming agent is methyl isobutyl carbinol, and the added amount is 20-80 g / t.

5. The method for efficiently recovering copper from sulphate-roasted acid leaching residues of chalcocite-type copper concentrate according to claim 4, characterized in that: The xanthate is selected from one or more of ethyl xanthate, butyl xanthate, amyl xanthate and sec-octyl xanthate, and the black drug is selected from one or more of butyl ammonium black drug, butyl sodium black drug and aniline black drug.

6. The method for efficiently recovering copper from sulphate-roasted acid leaching residues of chalcocite-type copper concentrate according to claim 1, characterized in that: In step (1), the stirring time is 2 to 3 minutes.

7. The method for efficiently recovering copper from sulphate-roasted acid leaching residues of chalcocite-type copper concentrate according to claim 1, characterized in that: In step (2), the number of magnetic separations is 2 times, and the magnetic field intensity of the magnetic separation is 0.1 to 0.2 T.

8. The method for efficiently recovering copper from sulphate-roasted acid leaching residues of chalcocite-type copper concentrate according to claim 1, characterized in that: In step (3), the reagent used in the chemical dissociation process is sulfuric acid.

9. The method for efficiently recovering copper from sulphate-roasted acid leaching residues of chalcocite-type copper concentrate according to claim 8, characterized in that: The amount of sulfuric acid used is 300-1200 kg / t, the temperature of the chemical dissociation is 80-120° C., the time is 0.5-4 hours, and the liquid-to-solid ratio is 3:1-6:1.

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