Flotation separation method for complex refractory high-sulfur copper ore

Abstract

The application provides a flotation separation method for complex and refractory high-sulfur copper ore, and belongs to the field of mineral flotation. The method realizes efficient recovery of valuable elements copper, silver and sulfur under the joint action of inhibitors and synergists by adjusting the ore slurry to a low-alkali environment with lime. The method adopts a low-alkali copper selection process, avoids strong inhibition of copper-sulfur intergrowth and silver-containing minerals in a high-alkali ore slurry environment, introduces regrinding before copper cleaning operation to promote dissociation of copper-sulfur intergrowth, and improves the grade of copper concentrate. In the copper roughing, inhibitors are used to inhibit gangue minerals and pyrite, so as to avoid the formation of a cover on the surface of metallic minerals. Through strong oxidation, electrostatic adsorption and hydroxylated metal point adsorption on the surface of pyrite, selective inhibition of pyrite is generated. The synergist is used to change the surface charge of gangue minerals, prevent the formation of a mucous coating on the surface of chalcopyrite by electrostatic repulsion, and at the same time, the performance of the flotation froth is enhanced, the floating of chalcopyrite is accelerated, and the copper selection effect is optimized.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of flotation, in particular to a flotation separation method for complex and difficult high-sulfur copper ore. BACKGROUND

[0002] As a kind of copper ore resource with high sulfur content, high-sulfur copper ore occupies an important position in China's copper resources, and its main mineral is chalcopyrite, which is often closely associated with pyrite. Its unique chemical properties and mineral composition pose higher requirements on processing technology. With the increasing depletion of mineral resources, improving the recovery rate of high-sulfur copper ore has become a key problem in the industry. At present, although high-alkali flotation process is generally used for copper-sulfur separation, this method often leads to low copper recovery rate, and in a high-alkali environment, associated rare and precious metals such as gold, silver and molybdenum are easily inhibited into sulfur concentrate, causing waste of valuable elements. Therefore, the reasonable selection of beneficiation reagents and the precise adaptation of process flow are crucial for realizing effective separation of copper and sulfur, improving the comprehensive utilization rate of valuable elements, and improving the economic benefit and environmental performance of the entire beneficiation process. SUMMARY

[0003] In view of the technical problems in the background art, the present application provides a flotation separation method for complex and difficult high-sulfur copper ore, which adopts the principle process of preferential copper selection-sulfur selection of copper tailings activation, and can realize effective separation of copper and sulfur in high-sulfur copper ore through high-efficiency inhibitors and synergists.

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

[0005] S1. Lime is added to the raw ore for grinding treatment, and the grinding is carried out to a pulp mass concentration of 60-65%, and the grinding fineness is calculated as the mass percentage of ore particle size less than 0.074mm, and the pulp pH value after grinding is 8-9;

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

[0007] S3. The copper roughing concentrate is added with lime for regrinding to a pulp mass concentration of 60-65%, and the grinding fineness is calculated as the mass percentage of ore particle size less than 0.038mm, and the pulp pH value after grinding is 9-10, and then two copper cleaning is carried out to obtain copper concentrate, and the copper cleaning middlings are returned to the previous operation in turn;

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

[0009] S5. Concentrate and adjust pH of the copper concentrate tailings, then perform sulfur roughing to obtain a sulfur roughing froth and a sulfur roughing underflow;

[0010] S6. Obtain a sulfur concentrate by twice sulfur cleaning of the sulfur roughing froth, and obtain a tailings by twice sulfur scavenging of the sulfur roughing underflow, and the sulfur cleaning middlings and the sulfur scavenging middlings are returned to the previous operation in turn.

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

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

[0013] Further, the depressant is a mixture of sodium silicate, calcium hypochlorite, isoxymethylated polyacrylamide and carboxymethyl hydroxypropyl guar gum in a mass percentage ratio of (50-60%):(20-25%):(8-12%):(6-10%).

[0014] The synergist is a mixture of vinyl acetate-ethylene copolymer emulsion and ethylenediamine tetramethylene phosphonic acid in a mass percentage ratio of (60-70%):(30-40%).

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

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

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

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

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

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

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

[0022] The low-alkali copper selection process avoids the strong inhibition of copper-sulfur intergrowth, silver-containing minerals (silver sulfide, copper-silver intergrowth, silver-gangue intergrowth) in a high-alkali ore pulp environment. Due to the complex copper-sulfur inlay relationship in the raw ore, regrinding is introduced before copper cleaning operation, so that the intergrowth is further dissociated, and the copper concentrate grade is improved.

[0023] Inhibitors are used in copper roughing, mainly to inhibit gangue minerals and pyrite. On the one hand, it disperses and inhibits argillic gangue such as muscovite and chlorite, avoiding the formation of a cover on the surface of metallic minerals. On the other hand, it produces selective inhibition of pyrite through strong oxidation, electrostatic adsorption and hydroxylated metal point adsorption on the surface of pyrite.

[0024] Synergists are used in copper roughing. On the one hand, it changes the surface charge of gangue minerals, preventing argillic gangue from forming a mucous coating on the surface of chalcopyrite by electrostatic repulsion. On the other hand, it appropriately increases the viscosity and uniformity of the flotation froth, improves the froth properties, accelerates the floating rate of chalcopyrite, and improves the copper selection index.

[0025] The above description is only a summary of the technical solutions of the present application. In order to more clearly understand the technical means of the present application, the specific embodiments of the present application can be implemented according to the content of the specification, and in order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the following specific embodiments of the present application are described. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions of the present application, the following will briefly introduce the drawings used in the present application. Obviously, the drawings described below are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creating any creative labor.

[0027] Figure 1 The flotation separation method for complex and refractory high-sulfur copper ore provided for the embodiment 1 of the present application is shown in the figure. DETAILED DESCRIPTION

[0028] The technical solutions of the present application will be described in detail below with reference to the drawings. The following embodiments are only used to more clearly illustrate the technical solutions of the present application, and therefore only serve as examples, but cannot limit the protection scope of the present application.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the present application; the terms "include" and "have" and any variations thereof in the specification and claims of the present application and the above description of drawings are intended to cover non-exclusive inclusion.

[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 "a plurality of" is two or more, unless otherwise explicitly and specifically limited.

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

[0032] At present, high-alkali flotation process is generally used to realize copper-sulfur separation, but 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 ore will be inhibited and enter the sulfur concentrate, so that the valuable elements cannot 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 the process of preferential copper selection-sulfur selection of copper tailings activation, and realizes effective separation of copper and sulfur in high-sulfur copper ore through high-efficiency inhibitor and synergist.

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

[0035] S1. Lime is added to the raw ore for grinding treatment, and the grinding is carried out to a pulp mass concentration of 60-65%, and the grinding fineness is calculated by the mass percentage of ore particle size less than 0.074mm as 75-80%, and the pH value of the ground pulp is 8-9;

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

[0037] S3. The copper roughing concentrate is added with lime for regrinding to a slurry mass concentration of 60-65%, and the grinding fineness is calculated by the mass percentage of ore particles with a size of less than 0.038 mm as 85-90%, and the slurry pH value after grinding is 9-10, and then two copper cleaning is performed to obtain copper concentrate, and the copper cleaning middlings are returned to the previous operation in turn;

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

[0039] S5. The copper tailings are concentrated and the pH value is adjusted, and then sulfur roughing is performed to obtain sulfur roughing froth and sulfur roughing underflow;

[0040] S6. The sulfur roughing froth is subjected to two sulfur cleaning to obtain sulfur concentrate, and the sulfur roughing underflow is subjected to two sulfur scavenging to obtain tailings, and the sulfur cleaning middlings and the sulfur scavenging middlings are returned to the previous operation in turn.

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

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

[0043] In the technical scheme of the embodiments of the present application, the addition of lime can effectively adjust the pH value of the slurry. The appropriate pH value is helpful for 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, which helps to improve the grinding efficiency and makes 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. Under the appropriate pH value, the surface of copper minerals (such as chalcopyrite) is more easily to react with flotation reagents, thereby improving the flotation effect of copper minerals.

[0044] Further, in some embodiments, in step S2, the dosage of the flotation reagent is 1000-1500 g / t of inhibitor, 150-250 g / t of synergist, 10-20 g / t of ethyldithiurea, and 5-15 g / t of butyl xanthate. The inhibitor is a mixture of water glass, calcium hypochlorite, isoxymethylated polyacrylamide, and carboxymethyl hydroxypropyl guar gum in a mass percentage ratio of (50-60%):(20-25%):(8-12%):(6-10%).

[0045] In the technical scheme of the embodiments of the present application, the combination of the inhibitor, the synergist, the ethyldithiurea, and the butyl xanthate can effectively improve the flotation efficiency of copper minerals while inhibiting the flotation of non-target minerals (such as pyrite). The inhibitor prepared by mixing water glass, calcium hypochlorite, isoxymethylated polyacrylamide, and carboxymethyl hydroxypropyl guar gum can effectively inhibit the flotation of gangue and iron sulfide, reducing their entry into the copper concentrate and thus improving the grade of the copper concentrate. The mixed synergist of the vinyl acetate-ethylene copolymer emulsion and the ethylenediamine tetramethylene phosphonic acid can enhance the adsorption capacity of the flotation reagent and improve the floatability of copper minerals. The stirring time after adding the inhibitor is 2-3 min, and the stirring time after adding the synergist is 2-3 min, which ensures sufficient contact and action between the reagent and the minerals and improves the utilization rate of the reagent and the flotation effect. The ethyldithiurea as a collector can effectively collect copper minerals. The butyl xanthate as an auxiliary collector can further improve the recovery rate of copper minerals.

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

[0047] In the technical scheme of the embodiments of the present application, the addition of lime to the copper roughing concentrate for regrinding helps to further adjust the pH value of the slurry, making it more suitable for the flotation of copper minerals. The use of 50-150 g / t of inhibitor as the first copper cleaning reagent can effectively inhibit the flotation of gangue and other unwanted minerals, allowing the copper minerals to be better enriched during the cleaning process. The addition of 200-300 g / t of lime in the second copper cleaning process is to further adjust the pH value or act as a flocculant to help remove fine gangue. At the same time, the use of 25-75 g / t of inhibitor can continue to inhibit unwanted minerals, ensuring the purity of the copper concentrate. Through the use of reagents during the cleaning process, the grade of the copper concentrate can be effectively improved, impurities can be reduced, the flotation efficiency can be improved, the cost of reagents can be reduced, and the production stability can be improved.

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

[0049] In the technical solution of the embodiments 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 reagent uses butyl xanthate at a dosage of 6-10 g / t, which is relatively high, and the purpose is to recover as much copper mineral as possible in the scavenging stage. Butyl xanthate is a commonly used collector that can interact with the surface of copper minerals, enhancing their ability to adhere to bubbles and thus achieving flotation. A higher dosage of reagent helps to improve the recovery rate in the scavenging stage, ensuring that as much copper mineral as possible is captured. In the second copper scavenging stage, the dosage of butyl xanthate is reduced to 2-5 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 reagent can reduce costs and reduce the potential impact on the environment. Excessive reagent can cause unnecessary minerals to also be floated, affecting the quality of the final concentrate.

[0050] By using an appropriate amount of collector in the scavenging stage, the overall recovery rate of the entire flotation process can be improved, ensuring that the copper resources in the ore are fully utilized. By precisely controlling the dosage of reagent, unnecessary reagent consumption can be reduced while ensuring the recovery rate, thereby reducing production costs. An appropriate dosage of reagent helps to reduce the flotation of impurities, thereby improving the quality of the final concentrate.

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

[0052] In the technical solution of the embodiments of the present application, the copper concentrate tailings are concentrated to a concentration of 40-50%, and the purpose of this step is to increase the concentration of solid particles in the ore slurry, facilitating subsequent flotation operations. Concentration can reduce the amount of water in subsequent processing, improving flotation efficiency. Adjusting the pH value of the ore slurry is beneficial to the flotation of sulfur minerals. The addition of sulfuric acid can change the surface charge of the minerals, promoting the interaction between xanthate collectors and the surface of sulfur minerals. The stirring speed is 400-600 r / min, which helps to ensure that the sulfuric acid and the ore slurry are fully mixed, ensuring uniform distribution of the pH value. The settling time is 1-1.5 min, which helps to separate solids and liquids, making the subsequent flotation process more effective.

[0053] The butyl xanthate and isopropyl xanthate are used as the collecting agents for sulfur rough separation, and the combination of the two agents can enhance the collecting ability for sulfur minerals. The pinolene is used as the frother, which helps to form stable bubbles and promote the flotation of sulfur minerals. Through these steps, the sulfur recovery rate can be improved, the flotation effect can be improved, the reagent cost can be reduced, and the concentrate quality can be improved.

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

[0055] In the technical scheme of the embodiments of the present application, different doses of reagents are used in the scavenging stage, which can realize staged collection, and through two times of scavenging, 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 while ensuring the recovery rate, and control the production cost. Through accurate control of the amount of reagent, the flotation of impurities can be reduced, thereby improving the quality of sulfur concentrate.

[0056] Some specific examples are listed below. It should be noted that the examples described below are exemplary and are only used to explain the present application, and cannot be understood as a limitation of the present application. If the specific technology or condition is not specified in the examples, the technology or condition described in the literature in the art or according to the product manual is used. If the reagent or instrument is not specified by the manufacturer, it is a conventional product that can be obtained from the market.

[0057] Example 1

[0058] The ore in the present embodiment is from a high-sulfur copper mine in China, and the copper is mainly chalcopyrite, a small amount of secondary copper sulfide, a trace amount of combined copper and free oxidized copper, and the sulfur is mainly pyrite. The copper, sulfur and silver grades in the ore are 0.72%, 25.46% and 9.12 g / t respectively. The copper-sulfur separation difficulty of the ore is reflected in the following aspects: ① The pyrite content in the raw ore is above 45%, the dissemination characteristics are simple, and the floatability is good; ② The chalcopyrite and pyrite are closely embedded, part of which is associated with magnetite or sphalerite, and a small amount of fine-grained copper is distributed in the gangue minerals, the dissemination characteristics are complex, and the overall floatability is poor. The copper mineral monomer liberation degree of the raw ore ground to a fineness of 80% passing 0.074 mm is 53.46%, and the total amount of the combined copper-sulfur body and copper-gangue associated body is 83.52%, and there is a certain amount of copper-sulfur body and copper-gangue associated body; ③ The content of minerals such as muscovite, chlorite, siderite, goethite, hematite-limonite, quartz-sericite and kaolinite is relatively high, about 29.60%, which is easy to be slimed during the grinding process, and interferes with the copper-sulfur flotation.

[0059] AsFigure 1 The embodiment shown 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 by using a ball mill, the reagent used is lime 5000g / t, the grinding concentration is 60%, the grinding fineness is 75% calculated by the mass percentage of ore particle size less than 0.074mm, and the pH value of the ground ore slurry is 8.5.

[0061] S2. The grinding product is adjusted to a concentration of 30% by adding water, and reagents are added for copper roughing, the reagents used are depressant 1000g / t, synergist 150g / t, ethylene thiourea 15g / t, butyl xanthate 10g / t; wherein the depressant is a mixture of water glass, calcium hypochlorite, isoxymethylated polyacrylamide and carboxymethyl hydroxypropyl guar gum in a mass percentage of 55%:25%:10%:10%, and the synergist is a mixture of vinyl acetate-ethylene copolymer emulsion and ethylenediaminetetramethylene phosphonic acid in a mass percentage of 60%:40%.

[0062] S3. The copper roughing concentrate is re-ground, the reagent used is lime 750g / t, the grinding concentration is 65%, the grinding fineness is 90% calculated by the mass percentage of ore particle size less than 0.038mm, the pH value of the ground ore slurry is 9.0, and the copper concentrate is obtained after two times of cleaning, the cleaning I reagent is depressant 100g / t, and the cleaning II reagent is lime 250g / t and depressant 50g / t; the copper cleaning middlings are returned to the previous operation in turn.

[0063] S4. The copper roughing underflow is cleaned twice to obtain a copper tailing, the cleaning I reagent is butyl xanthate 8g / t, and the cleaning II reagent is butyl xanthate 4g / t; the copper cleaning middlings are returned to the previous operation in turn.

[0064] S5. The copper tailing is poured into a laboratory small-scale concentration device, the slurry is fully stirred, and then settled to remove the supernatant, the underflow is concentrated to a concentration of 45%, and sulfuric acid is added to adjust the pH value of the slurry to 7, wherein the stirring speed is 500r / min, the settling time is 1min, and the sulfuric acid concentration is 20%. The concentrated copper tailing is added with reagents 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 froth is cleaned twice to obtain a sulfur concentrate, and the cleaning I and cleaning II are blank flotation; the sulfur roughing underflow is cleaned twice to obtain a tailing, the cleaning I reagent is butyl xanthate 20g / t and isoamyl xanthate 20g / t, and the cleaning II reagent is butyl xanthate 10g / t and isoamyl xanthate 10g / t, and the middlings obtained from the two cleaning and two cleaning of the sulfur operation are returned to the previous operation in turn.

[0066] In the embodiment, the copper concentrate contains Cu 20.14%, Ag 146.83 g / t, the recovery rate of Cu is 85.48%, the recovery rate of Ag is 52.80%; the sulfur concentrate contains S 46.54%, the recovery rate of S is 78.09%.

[0067] Example 2

[0068] The embodiment provides a flotation separation method for a complex and refractory high-sulfur copper ore, and the difference from the embodiment 1 is that the step S1 adds lime into the mill at a dosage of 6000 g / t, the pH value of the milled ore slurry is 9, and the rest is basically the same as the embodiment 1.

[0069] In the embodiment, the copper concentrate contains Cu 20.26%, Ag 138.51 g / t, the recovery rate of Cu is 83.72%, the recovery rate of Ag is 47.64%; the sulfur concentrate contains S 45.83%, the recovery rate of S is 76.69%.

[0070] Example 3

[0071] The embodiment provides a flotation separation method for a complex and refractory high-sulfur copper ore, and the difference from the embodiment 1 is that the step S2 adds the inhibitor into the ore slurry at a dosage of 1500 g / t in the copper roughing, and the rest is basically the same as the embodiment 1.

[0072] In the embodiment, the copper concentrate contains Cu 21.17%, Ag 147.22 g / t, the recovery rate of Cu is 83.64%, the recovery rate of Ag is 48.32%; the sulfur concentrate contains S 46.11%, the recovery rate of S is 78.38%.

[0073] Example 4

[0074] The embodiment provides a flotation separation method for a complex and refractory high-sulfur copper ore, and the difference from the embodiment 1 is that the step S2 adds the synergist into the ore slurry at a dosage of 250 g / t in the copper roughing, and the rest is basically the same as the embodiment 1.

[0075] In the embodiment, the copper concentrate contains Cu 18.54%, Ag 128.07 g / t, the recovery rate of Cu is 87.04%, the recovery rate of Ag is 53.23%; the sulfur concentrate contains S 45.71%, the recovery rate of S is 75.16%.

[0076] Comparative Example 1

[0077] The comparative example 1 provides a flotation separation method for a complex and refractory high-sulfur copper ore, and the difference from the embodiment 1 is that the copper roughing does not add the inhibitor, and the rest is basically the same as the embodiment 1.

[0078] The copper concentrate obtained in Comparative Example 1 contains Cu 15.38%, Ag 106.23 g / t, the recovery rate of Cu is 77.94%, the recovery rate of Ag is 45.64%; the sulfur concentrate contains S 45.87%, the recovery rate of S is 77.34%.

[0079] Comparative Example 2

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

[0081] The copper concentrate obtained in Comparative Example 2 contains Cu 18.68%, Ag 127.33 g / t, the recovery rate of Cu is 83.50%, the recovery rate of Ag is 49.15%; the sulfur concentrate contains S 45.11%, the recovery rate of S is 77.81%.

[0082] Comparative Example 3

[0083] Comparative Example 3 provides a flotation separation method for a complex and difficult-to-select high-sulfur copper ore, which is different from Example 1 in that the copper roughing concentrate is not re-ground, and the rest is basically the same as Example 1.

[0084] The copper concentrate obtained in Comparative Example 3 contains Cu 18.73%, Ag 132.65 g / t, the recovery rate of Cu is 87.12%, the recovery rate of Ag is 55.08%; the sulfur concentrate contains S 46.04%, the recovery rate of S is 77.40%.

[0085] Comparative Example 4

[0086] Comparative Example 4 provides a flotation separation method for a complex and difficult-to-select high-sulfur copper ore, which is different from Example 1 in that a conventional high-alkali copper selection process is used, 8000 g / t of lime is added to the mill, and the reagents used in copper roughing are butyl xanthate 10 g / t, iso-pentyl xanthate 10 g / t, and butyl ammonium black drug 10 g / t, and the rest is basically the same as Example 1.

[0087] The copper concentrate obtained in Comparative Example 4 contains Cu 19.69%, Ag 134.24 g / t, the recovery rate of Cu is 85.37%, the recovery rate of Ag is 48.26%; the sulfur concentrate contains S 44.36%, the recovery rate of S is 75.28%.

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

[0089]

[0090] As can be seen from Table 1, the grade of copper and the content of silver in the copper concentrate obtained by using the flotation separation method of the present application are generally higher than the corresponding values in the comparative examples, and the recovery rates of copper and silver are also relatively high; for the sulfur concentrate, the grade and recovery rate of sulfur also show good results in the examples, indicating that the process conditions used in the examples of the present application, such as lime adjustment in a low-alkali environment, the use of specific depressants and synergists, are effective in improving the recovery rates of copper and silver and improving the quality of the concentrate. The depressants and synergists more effectively depress gangue and pyrite, reducing the pollution of these minerals to the copper concentrate, and at the same time promoting the flotation of copper minerals. The process of the present application can better promote the dissociation of copper-sulfur intergrowth, so that the copper minerals can be more effectively floated out, thereby improving the grade and recovery rate of the 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 embodiments having substantially the same configuration and playing the same role and effect as the technical idea within the scope of the technical solutions of the present application are all included in the technical scope of the present application. In addition, within the scope of the main idea of the present application, various modifications that can be thought of by those skilled in the art are applied to the embodiments, and other ways constructed by combining part 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-process high-sulfur copper ores, characterized in that, Includes the following steps: S1. Add lime to the raw ore for grinding. Grind until the slurry mass concentration is 60-65%, the grinding fineness is calculated as 75-80% of the ore particle size less than 0.074mm by mass, and the pH value of the slurry after grinding is 8-9. S2. Add water to the grinding product to adjust the slurry mass concentration to 30-35%, add flotation reagents to carry out copper roughing to obtain copper roughing concentrate and copper roughing underflow; The flotation reagents consist of 1000-1500 g / t of inhibitor, 150-250 g / t of synergist, 10-20 g / t of ethionyl amino acid and 5-15 g / t of butyl xanthate; The inhibitor is prepared by mixing water glass, calcium hypochlorite, isohydroxymethylated polyacrylamide and carboxymethyl hydroxypropyl guar gum in a mass percentage ratio of (50~60%):(20~25%):(8~12%):(6~10%). S3. The copper roughing concentrate is added to lime for regrinding until the slurry mass concentration is 60-65%, the grinding fineness is calculated as 85-90% of the ore particle size less than 0.038mm by mass percentage, and the pH value of the slurry after grinding is 9-10. Then, two copper beneficiation processes are performed to obtain copper concentrate. The copper beneficiation middlings are returned to the previous operation in sequence. S4. The copper roughing underflow is subjected to two copper scavenging processes to obtain copper tailings, and the copper scavenged tailings are returned to the previous operation in sequence. S5. The copper tailings are concentrated and the pH value is adjusted, followed by sulfur roughing to obtain sulfur roughing foam and sulfur roughing underflow. S6. The sulfur roughing froth is subjected to two sulfur cleaning processes to obtain sulfur concentrate, and the sulfur roughing underflow is subjected to two sulfur scavenging processes to obtain tailings. The middlings from the sulfur cleaning process and the middlings from the sulfur scavenging process are returned to the previous operation in sequence.

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

3. The flotation separation method for complex and difficult-to-process high-sulfur copper ores according to claim 1, characterized in that, The synergist is a mixture of vinyl acetate-ethylene copolymer emulsion and ethylenediaminetetramethylenephosphonic acid in a mass percentage ratio of (60-70%): (30-40%).

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

5. The flotation separation method for complex and difficult-to-process high-sulfur copper ores according to claim 1, characterized in that, In step S3, the first copper refining agent is an inhibitor of 50-150 g / t, and the second copper refining agent is lime of 200-300 g / t and an inhibitor of 25-75 g / t.

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

7. The flotation separation method for complex and difficult-to-process high-sulfur copper ores 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 of the slurry to 6.5-7.5, the stirring speed is 400-600 r / min, the settling time is 1-1.5 min, and the sulfuric acid concentration is 15-25%; the reagents for sulfur roughing are 60-80 g / t of butyl xanthate, 60-80 g / t of isopropyl xanthate, and 5-15 g / t of pine oil.

8. The flotation separation method for complex and difficult-to-process high-sulfur copper ores according to claim 1, characterized in that, In step S6, the first sulfur scavenging reagent is 15-25 g / t of butyl xanthate and 15-25 g / t of isoamyl xanthate, and the second sulfur scavenging reagent is 8-12 g / t of butyl xanthate and 8-12 g / t of isoamyl xanthate.

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