Flotation separation method for complex refractory high-sulfur copper ore

Abstract

The invention provides a flotation separation method for complex and difficult-to-separate high-sulfur copper ore, and belongs to the field of mineral flotation, lime is adopted to adjust ore pulp to a low-alkali environment, and efficient recovery of valuable elements of copper, silver and sulfur is achieved under the combined action of an inhibitor and a synergist. A low-alkali copper separation process is adopted, copper-sulfur intergrowth and silver-containing minerals are prevented from being strongly inhibited in a high-alkali ore pulp environment, regrinding is introduced before copper concentration operation to promote dissociation of the copper-sulfur intergrowth, and the grade of copper concentrate is improved. During copper roughing, gangue minerals and pyrite are inhibited by adopting an inhibitor to prevent the gangue minerals and the pyrite from forming a cover on the surface of metal minerals, and selective inhibition on the pyrite is generated in the forms of strong oxidation, electrostatic adsorption, hydroxylated metal point adsorption and the like on the surface of the pyrite; the synergist is adopted to change the surface charge of gangue minerals, the argillaceous gangue is prevented from forming a mucus coating on the surface of the chalcopyrite by means of electrostatic repulsion, meanwhile, the flotation froth performance is enhanced, floating of the chalcopyrite is accelerated, and the copper separation effect is optimized.

Description

Technical Field

[0001] The invention relates to the field of flotation technology, and in particular to a flotation separation method for complex and difficult-to-separate high-sulfur copper ore. Background Art

[0002] High-sulfur copper ore, as a copper ore resource with a high sulfur content, occupies an important position in my country's copper resources. Its main mineral is chalcopyrite, which is often closely associated with pyrite. Its unique chemical properties and mineral composition put forward higher requirements for processing technology. With the increasing depletion of mineral resources, improving the recovery rate of high-sulfur copper ore has become a key issue in the industry. At present, although the high-alkali flotation process is widely used for copper-sulfur separation, this method often leads to a low copper recovery rate, and in a high-alkali environment, associated rare and precious metals such as gold, silver, and molybdenum are easily suppressed from entering the sulfur concentrate, resulting in a waste of valuable elements. Therefore, the reasonable selection of mineral processing agents and the precise adaptation of the process flow are crucial to achieve effective separation of copper and sulfur, improve the comprehensive utilization rate of valuable elements, and enhance the economic benefits and environmental performance of the entire mineral processing process. Summary of the invention

[0003] In view of the technical problems existing in the background technology, the present invention provides a flotation separation method for complex and difficult-to-select high-sulfur copper ores, which adopts the principle process of preferential copper selection-copper tailings activation and sulfur selection, and can achieve effective separation of copper and sulfur in high-sulfur copper ores through high-efficiency inhibitors and enhancers.

[0004] The present invention provides a flotation separation method for complex and difficult to select high-sulfur copper ore, comprising the following steps:

[0005] S1. Add lime to the raw ore for grinding, grind to a pulp mass concentration of 60-65%, grind fineness calculated as the mass percentage of ore particles less than 0.074 mm to 75-80%, and grind pulp pH value to 8-9;

[0006] S2. The grinding product is added with water to adjust the pulp mass concentration to 30-35%, and a flotation agent is added to perform copper roughing to obtain a copper roughing concentrate and a copper roughing underflow;

[0007] S3. adding lime to the copper rougher concentrate for regrinding, grinding to a pulp mass concentration of 60-65%, a grinding fineness of 85-90% calculated as the mass percentage of ore particles less than 0.038 mm, a pulp pH value of 9-10 after grinding, and then performing two copper concentrations to obtain a copper concentrate, and the copper concentration middlings are returned to the previous operation in sequence;

[0008] S4. The copper roughing underflow is subjected to two copper scavenging operations to obtain copper tailings, and the copper scavenging tailings are returned to the previous operation in sequence;

[0009] S5. concentrating the copper tailings and adjusting the pH value, and then performing sulfur roughing to obtain sulfur roughing foam and sulfur roughing underflow;

[0010] S6. The sulfur roughing foam is subjected to two sulfur concentrations to obtain sulfur concentrate, the sulfur roughing underflow is subjected to two sulfur scavengings to obtain tailings, and the sulfur concentration middlings and sulfur scavenging middlings are returned to the previous operation in sequence.

[0011] As a further improvement of the present invention, in step S1, the amount of lime used is 5000-6000 g / t.

[0012] As a further improvement of the present invention, in step S2, the flotation reagents are 1000-1500 g / t of inhibitor, 150-250 g / t of synergist, 10-20 g / t of ethionamide and 5-15 g / t of butyl xanthate.

[0013] Furthermore, the inhibitor is prepared by mixing water glass, calcium hypochlorite, isomethylolated polyacrylamide and carboxymethyl hydroxypropyl guar gum in the mass percentages of (50-60%): (20-25%): (8-12%): (6-10%).

[0014] The synergist is prepared by mixing vinyl acetate-ethylene copolymer emulsion and ethylenediaminetetramethylenephosphonic acid in the mass percentage of (60-70%):(30-40%).

[0015] As a further improvement of the present invention, in step S3, the amount of lime used is 600-900 g / t.

[0016] Furthermore, the first copper concentration reagent is 50-150 g / t of inhibitor, and the second copper concentration reagent is 200-300 g / t of lime and 25-75 g / t of inhibitor.

[0017] As a further improvement of the present invention, in step S4, the first copper scavenging agent is 6-10 g / t of butyl xanthate, and the second copper scavenging agent is 2-5 g / t of butyl xanthate.

[0018] As a further improvement of the present invention, in step S5, the copper tailings are concentrated to a concentration of 40-50%, sulfuric acid is added to adjust the pH value of the slurry to 6.5-7.5, the stirring speed is 400-600 r / min, the sedimentation time is 1-1.5 min, and the sulfuric acid concentration is 15-25%; the sulfur roughing agent is 60-80 g / t of butyl xanthate, 60-80 g / t of isopropyl xanthate, and 5-15 g / t of pine oil.

[0019] As a further improvement of the present invention, in step S6, the first sulfur sweep reagent is 15-25 g / t of butyl xanthate and 15-25 g / t of isopentyl xanthate, and the second sulfur sweep reagent is 8-12 g / t of butyl xanthate and 8-12 g / t of isopentyl xanthate.

[0020] The beneficial effects of the present invention are:

[0021] The present invention provides a flotation separation method for complex and difficult-to-select high-sulfur copper ores, which uses lime to adjust the ore pulp to a low-alkali environment, and under the joint action of green and efficient inhibitors and synergists, realizes efficient recovery of valuable elements copper, silver and sulfur.

[0022] The low-alkali copper selection process is adopted to avoid the strong inhibition of copper-sulfur intergrowths and silver-containing minerals (silver sulfide, copper-silver intergrowths, silver-gangue intergrowths) in the high-alkali slurry environment. Due to the complex copper-sulfur mosaic relationship in the original ore, regrinding is introduced before the copper selection operation to further dissociate the intergrowths and improve the grade of copper concentrate.

[0023] Inhibitors are used in copper roughing to inhibit gangue minerals and pyrite. On the one hand, they disperse and inhibit muddy gangue minerals such as muscovite and chlorite to prevent them from forming a cover on the surface of metal minerals; on the other hand, selective inhibition of pyrite is achieved through strong oxidation, electrostatic adsorption and hydroxylated metal point adsorption on the pyrite surface.

[0024] The use of enhancers in copper roughing can, on the one hand, change the surface charge of gangue minerals and prevent the formation of a slime coating on the surface of chalcopyrite by means of electrostatic repulsion; on the other hand, it can appropriately increase the viscosity and uniformity of flotation foam, improve the properties of foam, accelerate the floating rate of chalcopyrite, and improve copper selection indicators.

[0025] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the technical solution of the present application, the following is a brief introduction to the drawings used in the present application. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0027] Figure 1 Schematic diagram of the flotation separation method for complex and difficult-to-separate high-sulfur copper ore provided in Example 1 of the present application. DETAILED DESCRIPTION

[0028] The following embodiments of the technical solution of the present application are described in detail in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present application.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" in the specification and claims of this application and the above-mentioned figure descriptions and any variations thereof are intended to cover non-exclusive inclusions.

[0030] In the description of the embodiments of the present application, the technical terms "first", "second", etc. are only used to distinguish different objects, and cannot be understood as indicating or implying relative importance or implicitly indicating the number, specific order or primary and secondary relationship of the indicated technical features. In the description of the embodiments of the present application, the meaning of "multiple" is more than two, unless otherwise clearly and specifically defined.

[0031] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0032] At present, high-alkali flotation process is commonly used to separate copper and sulfur. However, the high-alkali environment not only makes the copper recovery rate low, but also a large amount of rare and precious metals such as gold, silver, and molybdenum associated with copper sulfide ores will be suppressed and enter the sulfur concentrate, making it impossible for the valuable elements to be fully utilized.

[0033] In order to solve the technical problems of low copper recovery rate and limited recovery of rare and precious metals in high-sulfur copper ore, the present application provides a flotation separation method for complex and difficult-to-select high-sulfur copper ore, which adopts a process of preferential copper selection-copper tailings activation and sulfur selection, and realizes effective separation of copper and sulfur in high-sulfur copper ore through high-efficiency inhibitors and enhancers.

[0034] The present application provides a flotation separation method for complex and difficult to select high-sulfur copper ore, comprising the following steps:

[0035] S1. Add lime to the raw ore for grinding, grind to a pulp mass concentration of 60-65%, grind fineness calculated as the mass percentage of ore particles less than 0.074 mm to 75-80%, and grind pulp pH value to 8-9;

[0036] S2. The grinding product is added with water to adjust the pulp mass concentration to 30-35%, and a flotation agent is added to perform copper roughing to obtain a copper roughing concentrate and a copper roughing underflow;

[0037] S3. adding lime to the copper rougher concentrate for regrinding, grinding to a pulp mass concentration of 60-65%, a grinding fineness of 85-90% calculated as the mass percentage of ore particles less than 0.038 mm, a pulp pH value of 9-10 after grinding, and then performing two copper concentrations to obtain a copper concentrate, and the copper concentration middlings are returned to the previous operation in sequence;

[0038] S4. The copper roughing underflow is subjected to two copper scavenging operations to obtain copper tailings, and the copper scavenging tailings are returned to the previous operation in sequence;

[0039] S5. concentrating the copper tailings and adjusting the pH value, and then performing sulfur roughing to obtain sulfur roughing foam and sulfur roughing underflow;

[0040] S6. The sulfur roughing foam is subjected to two sulfur concentrations to obtain sulfur concentrate, the sulfur roughing underflow is subjected to two sulfur scavengings to obtain tailings, and the sulfur concentration middlings and sulfur scavenging middlings are returned to the previous operation in sequence.

[0041] Through fine grinding treatment and optimization of flotation reagent system, the recovery rate of copper can be effectively improved, thereby improving the utilization efficiency of copper resources. By adjusting the pH value of the pulp and the grinding fineness, it is possible to effectively separate copper and sulfur, reduce the sulfur content in the copper concentrate, and improve the quality of the copper concentrate. In the flotation process, through reasonable reagent selection and process design, the loss of rare and precious metals such as gold, silver, and molybdenum in the sulfur concentrate is reduced, and the comprehensive recovery rate of these valuable elements is improved. Through effective reagent use and process control, the generation of pollutants such as wastewater and waste residue is reduced, and environmental pollution is reduced.

[0042] Furthermore, in some embodiments, in step S1, the amount of lime used is 5000-6000 g / t.

[0043] In the technical solution of the embodiment of the present application, the addition of lime can effectively adjust the pH value of the slurry. The appropriate pH value is conducive to the adsorption of subsequent flotation reagents and the selective flocculation of mineral particles. The addition of lime can improve the chemical environment of the slurry, help improve the grinding efficiency, and make the ore easier to be ground to the required particle size. In the flotation of high-sulfur copper ore, an appropriate amount of lime can inhibit the flotation of sulfide minerals (such as pyrite), thereby reducing the sulfur content in the copper concentrate and improving the grade of the copper concentrate. At a suitable pH value, the surface of copper minerals (such as chalcopyrite) is more likely to react with flotation reagents, thereby improving the flotation effect of copper minerals.

[0044] Further, in some embodiments, in step S2, the flotation reagents and dosages are 1000-1500 g / t of inhibitor, 150-250 g / t of synergist, 10-20 g / t of ethiocarbamate, and 5-15 g / t of butyl xanthate. The inhibitor is prepared by mixing water glass, calcium hypochlorite, isomethylolated polyacrylamide, and carboxymethyl hydroxypropyl guar gum in the mass percentages of (50-60%): (20-25%): (8-12%): (6-10%). The synergist is prepared by mixing vinyl acetate-ethylene copolymer emulsion and ethylenediaminetetramethylenephosphonic acid in the mass percentages of (60-70%): (30-40%).

[0045] In the technical scheme of the embodiment of the present application, by using a combination of inhibitors, synergists, ethiocarbamate and butyl xanthate, the flotation efficiency of copper minerals can be effectively improved, while suppressing the flotation of non-target minerals (such as pyrite). The inhibitor prepared by mixing water glass, calcium hypochlorite, isomethylolated polyacrylamide and carboxymethyl hydroxypropyl guar gum can effectively suppress the flotation of gangue and iron sulfide, reduce their entry into copper concentrate, and thus improve the grade of copper concentrate. The mixed synergist of vinyl acetate-ethylene copolymer emulsion and ethylenediaminetetramethylenephosphonic acid can enhance the adsorption capacity of flotation reagents and improve the floatability of copper minerals. The stirring time after the inhibitor is added is 2 to 3 minutes, and the stirring time after the synergist is added is 2 to 3 minutes, ensuring that the reagent is fully in contact and action with the mineral, and improving the utilization rate and flotation effect of the reagent. Ethiocarbamate can effectively capture copper minerals as a collector. Butyl xanthate can further improve the recovery rate of copper minerals as an auxiliary collector.

[0046] Furthermore, in some embodiments, in step S3, the amount of lime used in the regrinding process is 600-900 g / t. The first copper concentration reagent is 50-150 g / t of inhibitor, and the second copper concentration reagent is 200-300 g / t of lime and 25-75 g / t of inhibitor.

[0047] In the technical solution of the embodiment of the present application, the copper roughing concentrate is re-grinded with lime, which helps to further adjust the pH value of the slurry and make it more suitable for the flotation of copper minerals. The first copper concentration reagent uses 50-150g / t of inhibitors, which can effectively inhibit the flotation of gangue and other unwanted minerals, so that the copper minerals are better enriched during the concentration process. In the second copper concentration, 200-300g / t of lime is added to further adjust the pH value, or as a flocculant to help remove fine-grained gangue. At the same time, the use of 25-75g / t of inhibitors can continue to inhibit unwanted minerals and ensure the purity of the copper concentrate. Through the use of reagents in the concentration process, the grade of copper concentrate can be effectively improved, impurities can be reduced, flotation efficiency can be improved, reagent costs can be reduced, and production stability can be improved.

[0048] Furthermore, in some embodiments, in step S4, the first copper scavenging agent is 6-10 g / t of butyl xanthate, and the second copper scavenging agent is 2-5 g / t of butyl xanthate.

[0049] In the technical solution of the embodiment of the present application, butyl xanthate is used as a collector to further recover copper minerals that were not captured in the previous flotation process. The first copper scavenging agent uses 6 to 10 g / t of butyl xanthate, which is a relatively high amount. The purpose is to recover as many copper minerals as possible in the scavenging stage. Butyl xanthate is a commonly used collector that can react with the surface of copper minerals to enhance its adhesion to bubbles, thereby achieving flotation. A higher dosage of reagent helps to improve the recovery rate in the scavenging stage and ensure that as many copper minerals as possible are captured. In the second copper scavenging stage, the dosage of butyl xanthate is reduced to 2 to 5 g / t. After the first scavenging, most of the floatable copper minerals have been recovered, and the remaining copper mineral content is relatively low. Reducing the dosage of reagents can reduce costs and reduce potential impacts on the environment. Excessive reagents may cause unnecessary minerals to be floated up, affecting the quality of the final concentrate.

[0050] By using an appropriate amount of collector in the scavenging stage, the total recovery rate of the entire flotation process can be improved, ensuring that the copper resources in the ore are fully utilized. By accurately controlling the amount of reagents, it is possible to reduce unnecessary reagent consumption and production costs while ensuring the recovery rate. The appropriate amount of reagents helps to reduce the flotation of impurities, thereby improving the quality of the final concentrate.

[0051] Furthermore, in some embodiments, in step S5, the copper tailings are concentrated to a concentration of 40-50%, sulfuric acid is added to adjust the pH value of the slurry to 6.5-7.5, the stirring speed is 400-600 r / min, the sedimentation time is 1-1.5 min, and the sulfuric acid concentration is 15-25%; the sulfur roughing agent is 60-80 g / t of butyl xanthate, 60-80 g / t of isopropyl xanthate, and 5-15 g / t of pine oil.

[0052] In the technical solution of the embodiment of the present application, the copper tailings are concentrated to a concentration of 40-50%. The purpose of this step is to increase the concentration of solid particles in the slurry to facilitate subsequent flotation operations. Concentration can reduce the amount of water for subsequent treatment and improve flotation efficiency. Adjusting the pH value of the slurry is beneficial to the flotation of sulfur minerals. The addition of sulfuric acid can change the surface charge of the mineral and promote the interaction between the xanthate collector and the surface of the sulfur mineral. The stirring speed is 400-600r / min. Such a stirring speed helps to fully mix the sulfuric acid with the slurry and ensure a uniform distribution of the pH value. The sedimentation time is 1-1.5min. This step helps to separate the solid and liquid, making the subsequent flotation process more effective.

[0053] The sulfur roughing agents butyl xanthate and isopropyl xanthate are used as collectors. The combination of these two agents can enhance the collection capacity of sulfur minerals. Pine alcohol oil is used as a frother, which helps to form stable bubbles and promote the flotation of sulfur minerals. Through these steps, the sulfur recovery rate can be increased, the flotation effect can be improved, the reagent cost can be reduced, and the concentrate quality can be improved.

[0054] Furthermore, in some embodiments, in step S6, the two sulfur concentrations are blank flotation, the first sulfur scavenging reagent is 15-25 g / t of butyl xanthate and 15-25 g / t of isopentyl xanthate, and the second sulfur scavenging reagent is 8-12 g / t of butyl xanthate and 8-12 g / t of isopentyl xanthate.

[0055] In the technical solution of the embodiment of the present application, by using different dosages of reagents in the scavenging stage, graded collection can be achieved. By two scavengings, the total recovery rate of sulfur minerals can be maximized and the loss of sulfur minerals in tailings can be reduced. Reasonable allocation of reagent dosage can reduce reagent consumption and control production costs while ensuring the recovery rate. By accurately controlling the dosage of reagents, the flotation of impurities can be reduced, thereby improving the quality of sulfur concentrate.

[0056] Some specific embodiments are listed below. It should be noted that the embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. If specific techniques or conditions are not specified in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. The reagents or instruments used without specifying the manufacturer are all conventional products that can be obtained commercially.

[0057] Example 1

[0058] In terms of mass percentage, the ore of this embodiment comes from a high-sulfur copper mine in China. The copper is mainly chalcopyrite, a small amount of secondary copper sulfide, trace amounts of combined copper and free-oxidized copper, and the sulfur is mainly pyrite. The grades of copper, sulfur and silver in the ore are 0.72%, 25.46% and 9.12 g / t, respectively. The difficulty of separating copper and sulfur from ore is reflected in the following aspects: ① The pyrite content in the original ore is above 45%, with simple intergrowth characteristics and good floatability; ② Chalcopyrite is closely intergrowthed with pyrite, and some of them are intergrowthed with minerals such as pyrrhotite or sphalerite. A small amount of fine copper is impregnated and distributed in the gangue minerals, with complex intergrowth characteristics and poor overall floatability. The dissociation degree of copper mineral monomers under the fineness of -0.074mm and 80% of the original ore is 53.46%, and the total is 83.52% including rich intergrowths. There are a certain amount of copper-sulfur intergrowths and copper-gangue intergrowths; ③ The content of minerals such as muscovite, chlorite, siderite, goethite, hematite-limonite, quartz-sericite and kaolinite is relatively high, about 29.60%, which are easy to become muddy during the grinding process, interfering with the flotation of copper and sulfur.

[0059] like Figure 1 As shown, this embodiment provides a flotation separation method for complex and difficult to select high-sulfur copper ore, and the specific steps are as follows:

[0060] S1. The raw ore is ground using a ball mill. The reagent used is 5000 g / t of lime. The grinding concentration is 60%. The grinding fineness is 75% calculated based on the mass percentage of ore particles less than 0.074 mm. The pH value of the slurry after grinding is 8.5.

[0061] S2. Add water to the grinding product to adjust the concentration to 30%, and add reagents thereto for rough copper selection. The reagents used are 1000g / t of inhibitor, 150g / t of synergist, 15g / t of ethiocarbamate, and 10g / t of butyl xanthate; the inhibitor is a mixture of water glass, calcium hypochlorite, isomethylolated polyacrylamide, and carboxymethyl hydroxypropyl guar gum in the mass percentage of 55%:25%:10%:10%, and the synergist is a mixture of vinyl acetate-ethylene copolymer emulsion and ethylenediaminetetramethylenephosphonic acid in the mass percentage of 60%:40%.

[0062] S3. The copper rough concentrate is regrinded, and the reagent used is lime 750g / t, the grinding concentration is 65%, the grinding fineness is 90% calculated as the mass percentage of ore particles less than 0.038mm, and the pH value of the slurry after grinding is 9.0. After two concentrations, copper concentrate is obtained. The reagent for concentration I is 100g / t of inhibitor, and the reagent for concentration II is 250g / t of lime and 50g / t of inhibitor; the copper concentrated middlings are returned to the previous operation in sequence.

[0063] S4. The copper roughing bottom flow is scavenged twice to obtain copper tailings. The scavenging agent I is 8g / t butyl xanthate, and the scavenging agent II is 4g / t butyl xanthate. The copper scavenging tailings are returned to the previous operation in sequence.

[0064] S5. Pour the copper tailings into the laboratory small concentration equipment, stir the pulp fully, let it settle to remove the supernatant, concentrate the underflow to a concentration of 45%, add sulfuric acid to adjust the pulp pH to 7, wherein the stirring speed is 500r / min, the settling time is 1min, and the sulfuric acid concentration is 20%. Add reagents to the concentrated copper tailings for sulfur roughing, the reagents used are butyl xanthate 70g / t, isopropyl xanthate 70g / t, and pine oil 10g / t.

[0065] S6. The sulfur roughing foam is subjected to two concentrations to obtain sulfur concentrate, and concentrations I and II are blank flotation. The sulfur roughing underflow is subjected to two scavengings to obtain tailings, and the reagents for scavenging I are 20g / t butyl xanthate and 20g / t isopentyl xanthate, and the reagents for scavenging II are 10g / t butyl xanthate and 10g / t isopentyl xanthate. The middlings obtained from the two concentrations and two scavengings of the sulfur selection operation are returned to the previous operation in sequence.

[0066] The copper concentrate obtained in this embodiment contains 20.14% Cu and 146.83g / t Ag, with a Cu recovery rate of 85.48% and an Ag recovery rate of 52.80%; the sulfur concentrate contains 46.54% S and a S recovery rate of 78.09%.

[0067] Example 2

[0068] This embodiment provides a flotation separation method for complex and difficult-to-select high-sulfur copper ore. Compared with Example 1, the difference is that the amount of lime added to the mill in step S1 is 6000 g / t, the pH value of the slurry after grinding is 9, and the rest is basically the same as Example 1.

[0069] The copper concentrate obtained in this embodiment contains 20.26% Cu and 138.51 g / t Ag, with a Cu recovery rate of 83.72% and an Ag recovery rate of 47.64%. The sulfur concentrate contains 45.83% S and a S recovery rate of 76.69%.

[0070] Example 3

[0071] This embodiment provides a flotation separation method for complex and difficult-to-select high-sulfur copper ore. Compared with Example 1, the difference is that the amount of inhibitor added to the ore pulp in step S2 copper roughing is 1500 g / t, and the rest is basically the same as Example 1.

[0072] The copper concentrate obtained in this embodiment contains 21.17% Cu and 147.22g / t Ag, with a Cu recovery rate of 83.64% and an Ag recovery rate of 48.32%; the sulfur concentrate contains 46.11% S and a S recovery rate of 78.38%.

[0073] Example 4

[0074] This embodiment provides a flotation separation method for complex and difficult-to-select high-sulfur copper ore. Compared with Example 1, the difference is that the amount of enhancer added to the ore pulp in step S2 copper roughing is 250 g / t, and the rest is basically the same as Example 1.

[0075] The copper concentrate obtained in this embodiment contains 18.54% Cu and 128.07 g / t Ag, with a Cu recovery rate of 87.04% and an Ag recovery rate of 53.23%; the sulfur concentrate contains 45.71% S and a S recovery rate of 75.16%.

[0076] Comparative Example 1

[0077] Comparative Example 1 provides a flotation separation method for complex and difficult-to-select high-sulfur copper ore. Compared with Example 1, the difference is that no inhibitor is added in the copper roughing, and the rest is basically the same as Example 1.

[0078] The copper concentrate obtained in Comparative Example 1 contained 15.38% Cu and 106.23 g / t Ag, with a Cu recovery rate of 77.94% and an Ag recovery rate of 45.64%. The sulfur concentrate contained 45.87% S and a S recovery rate of 77.34%.

[0079] Comparative Example 2

[0080] Comparative Example 2 provides a flotation separation method for complex and difficult-to-select high-sulfur copper ores. Compared with Example 1, the difference is that no synergist is added in the copper roughing, and the rest is basically the same as Example 1.

[0081] The copper concentrate obtained in Comparative Example 2 contained 18.68% Cu and 127.33 g / t Ag, with a Cu recovery rate of 83.50% and an Ag recovery rate of 49.15%. The sulfur concentrate contained 45.11% S and a S recovery rate of 77.81%.

[0082] Comparative Example 3

[0083] Comparative Example 3 provides a flotation separation method for complex and difficult-to-select high-sulfur copper ore. Compared with Example 1, the difference is that the copper rougher concentrate is not regrinded, and the rest is basically the same as Example 1.

[0084] The copper concentrate obtained in Comparative Example 3 contained 18.73% Cu and 132.65 g / t Ag, with a Cu recovery rate of 87.12% and an Ag recovery rate of 55.08%. The sulfur concentrate contained 46.04% S and a S recovery rate of 77.40%.

[0085] Comparative Example 4

[0086] Comparative Example 4 provides a flotation separation method for complex and difficult-to-select high-sulfur copper ore. Compared with Example 1, the difference is that a conventional high-alkali copper selection process is adopted, the amount of lime added to the mill is 8000g / t, and the reagents used for copper rough selection are 10g / t of butyl xanthate, 10g / t of isopentyl xanthate, and 10g / t of butylammonium black medicine. The rest is basically the same as Example 1.

[0087] The copper concentrate obtained in Comparative Example 4 contained 19.69% Cu and 134.24 g / t Ag, with a Cu recovery rate of 85.37% and an Ag recovery rate of 48.26%. The sulfur concentrate contained 44.36% S and a S recovery rate of 75.28%.

[0088] Table 1 Flotation separation results of examples and comparative examples

[0089]

[0090] As can be seen from Table 1, the copper grade and silver content in the copper concentrate obtained by the flotation separation method of the present application are generally higher than the corresponding values ​​in the comparative example, and the recovery rates of copper and silver are also relatively high; for sulfur concentrate, the grade and recovery rate of sulfur also show good results in the examples, indicating that the process conditions adopted in the examples of the present application, such as lime adjustment in a low-alkali environment, the use of specific inhibitors and synergists, are effective in improving the recovery rates of copper and silver and improving the quality of the concentrate. Inhibitors and synergists more effectively inhibit gangue and pyrite, reduce the pollution of these minerals to copper concentrate, and promote the flotation of copper minerals. The process of the present application can better promote the dissociation of copper-sulfur conjoined bodies, so that copper minerals can be floated out more effectively, thereby improving the grade and recovery rate of copper concentrate.

[0091] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and the embodiments having the same structure as the technical idea and exerting the same effect within the scope of the technical solution of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the main purpose of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of combining some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. A flotation separation method for complex and difficult to select high-sulfur copper ore, characterized in that: The following steps are involved: S1. Add lime to the raw ore for grinding, grind to a pulp mass concentration of 60-65%, grind fineness calculated as the mass percentage of ore particles less than 0.074 mm to 75-80%, and grind pulp pH value to 8-9; S2. The grinding product is added with water to adjust the pulp mass concentration to 30-35%, and a flotation agent is added to perform copper roughing to obtain a copper roughing concentrate and a copper roughing underflow; S3. adding lime to the copper rougher concentrate for regrinding, grinding to a pulp mass concentration of 60-65%, a grinding fineness of 85-90% calculated as the mass percentage of ore particles less than 0.038 mm, a pulp pH value of 9-10 after grinding, and then performing two copper concentrations to obtain a copper concentrate, and the copper concentration middlings are returned to the previous operation in sequence; S4. The copper roughing underflow is subjected to two copper scavenging operations to obtain copper tailings, and the copper scavenging underflow is returned to the previous operation in sequence; S5. concentrating the copper tailings and adjusting the pH value, and then performing sulfur roughing to obtain sulfur roughing foam and sulfur roughing underflow; S6. The sulfur roughing foam is subjected to two sulfur concentrations to obtain sulfur concentrate, the sulfur roughing underflow is subjected to two sulfur scavengings to obtain tailings, and the sulfur concentration middlings and sulfur scavenging middlings are returned to the previous operation in sequence.

2. The flotation separation method for complex and difficult to select high-sulfur copper ore according to claim 1, characterized in that: In step S1, the amount of lime used is 5000-6000 g / t.

3. The flotation separation method for complex and difficult to select high-sulfur copper ore according to claim 1, characterized in that: In step S2, the flotation reagents are 1000-1500 g / t of inhibitor, 150-250 g / t of synergist, 10-20 g / t of ethionamide and 5-15 g / t of butyl xanthate.

4. The flotation separation method for complex and difficult to select high-sulfur copper ore according to claim 3, characterized in that: The inhibitor is prepared by mixing water glass, calcium hypochlorite, isomethylolated polyacrylamide and carboxymethyl hydroxypropyl guar gum in the mass percentages of (50-60%): (20-25%): (8-12%): (6-10%).

5. The flotation separation method for complex and difficult to select high-sulfur copper ore according to claim 3, characterized in that: The synergist is prepared by mixing vinyl acetate-ethylene copolymer emulsion and ethylenediaminetetramethylenephosphonic acid in the mass percentage of (60-70%):(30-40%).

6. The flotation separation method for complex and difficult to select high-sulfur copper ore according to claim 1, characterized in that: In step S3, the amount of lime used is 600-900 g / t.

7. The flotation separation method for complex and difficult to select high-sulfur copper ore according to claim 1, characterized in that: In step S3, the first copper concentration reagent is 50-150 g / t of inhibitor, and the second copper concentration reagent is 200-300 g / t of lime and 25-75 g / t of inhibitor.

8. The flotation separation method for complex and difficult to select high-sulfur copper ore according to claim 1, characterized in that: In step S4, the first copper scavenging agent is 6-10 g / t of butyl xanthate, and the second copper scavenging agent is 2-5 g / t of butyl xanthate.

9. The flotation separation method for complex and difficult to select high-sulfur copper ore according to claim 1, characterized in that: In step S5, the copper tailings are concentrated to a concentration of 40-50%, sulfuric acid is added to adjust the pH value of the slurry to 6.5-7.5, the stirring speed is 400-600 r / min, the sedimentation time is 1-1.5 min, and the sulfuric acid concentration is 15-25%; the sulfur roughing agent is 60-80 g / t of butyl xanthate, 60-80 g / t of isopropyl xanthate, and 5-15 g / t of pine oil.

10. The flotation separation method for complex and difficult to select high-sulfur copper ore according to claim 1, characterized in that: In step S6, the first sulfur sweep reagent is 15-25 g / t of butyl xanthate and 15-25 g / t of isopentyl xanthate, and the second sulfur sweep reagent is 8-12 g / t of butyl xanthate and 8-12 g / t of isopentyl xanthate.

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