Beneficiation method for high-sulfur copper ore containing mud and pyrrhotite

Abstract

The invention provides a beneficiation method for high-sulfur copper ore containing mud and pyrrhotite, and belongs to the technical field of ore separation processes. According to the method, the mineral processing technology of copper rapid flotation, enhanced flotation, copper rough concentrate differential regrinding, step-by-step concentration, copper tail sulfur flotation and sulfur tail magnetic separation and a CD-ND + CD-SD combined inhibitor are adopted for synchronously inhibiting argillaceous gangue and pyrite, ethionine ester, isopropyl xanthate and ethionine xanthate collect copper minerals step by step, interference of the argillaceous gangue to the preferential copper flotation process is reduced, and the copper flotation efficiency is improved. The effective inhibition on sulfur is realized under the condition of relatively low pH. The copper and sulfur separation technical scheme combining low-alkali-acid-free flotation and magnetic flotation is constructed, interference of argillaceous gangue on the sulfide ore flotation process is reasonably and effectively controlled, the technological process is short and stable, the copper and sulfur separation index is excellent, the copper and sulfur ore separation recovery rate and grade index are improved, and the method is suitable for industrial production. The method effectively solves the problem of clean and efficient beneficiation and recovery of high-sulfur copper ore containing mud pyrrhotite, and provides a new effective method for clean and efficient recovery of similar copper and sulfur resources.

Description

Technical Field

[0001] The present invention relates to the technical field of ore separation technology, and in particular to a beneficiation method for high-sulfur copper ore containing mud and pyrrhotite. Background Art

[0002] High-sulfur copper ores containing muddy pyrrhotite are a type of complex and difficult-to-separate copper-sulfur resource, and their clean and efficient mineral processing and recovery are common problems in the industry. The raw ore contains a certain amount of calcium, magnesium, and aluminum-containing floating or muddy gangue minerals such as chlorite, actinolite, white / sericite, calcite, and dolomite. These minerals interfere with the copper-sulfur separation process by absorbing and consuming reagents, carrying them up, and covering the surface of the target minerals. The high sulfur (pyrite and pyrrhotite) and low copper (chalcopyrite, etc.) content make efficient separation of copper and sulfur difficult. The high pyrrhotite content and easy oxidation consume the active oxygen in the solution that is beneficial to the flotation of sulfide ores, which is not conducive to the effective interaction between copper minerals and collectors, and has an adverse effect on copper flotation. There are many types of copper minerals, and the floatability of primary and secondary copper sulfides spans a wide range, exists and is prone to fluctuation, which places higher requirements on the adaptability of the copper flotation reagent system and process flow.

[0003] At present, the more mature technical solutions are mainly: "high alkali sulfur inhibition, preferential copper flotation - copper tails with large amounts of sulfuric acid activation for sulfur selection", but there are problems such as sticky foam, large circulation volume of middlings, large fluctuations in copper selection indicators, low copper concentrate grade and low recovery rate, difficulty in de-inhibiting and activating sulfur, large fluctuations in sulfur selection indicators, large acid and alkali consumption, and high safety and environmental risks, which greatly limit the clean and efficient recovery of this type of copper and sulfur resources.

[0004] Some researchers have adopted the principle of "pre-magnetic separation-copper flotation-sulfur flotation" and used magnetic separation to remove pyrrhotite before copper flotation to reduce the impact on copper flotation. However, the magnetic properties of pyrrhotite with different crystal structures vary greatly, making it difficult to be effectively removed. This method has certain defects. Another method uses persulfate and sodium iron chlorophyllin to selectively inhibit pyrite and achieve low-alkalinity copper-sulfur separation, but there are problems such as the actual application of oxidants being more dangerous and the poor stability of the agent effect. Summary of the Invention

[0005] In view of the technical problems existing in the background technology, the present application provides a beneficiation method for high-sulfur copper ores containing mud and pyrrhotite, aiming to solve the problems of difficulty in beneficiation of existing high-sulfur copper ores containing mud and pyrrhotite, low recovery rate, environmentally unfriendly reagents and poor stability.

[0006] The present invention provides a method for beneficiating high-sulfur copper ore containing mud and pyrrhotite, comprising the following steps:

[0007] S1. The ore is crushed, and then a sulfur inhibitor and a regulator are added, followed by a first grinding to obtain a ground sample, water is added to the ground sample, and the mixture is stirred to obtain a flotation ore pulp;

[0008] S2. The flotation ore pulp is subjected to rapid copper flotation to obtain a rapid copper flotation concentrate and a rapid copper flotation tailings;

[0009] S3. The copper rapid flotation tailings are sequentially subjected to copper roughing and copper scavenging to obtain a copper roughing concentrate and copper scavenging tailings 2;

[0010] S4. The copper rougher concentrate is subjected to a second grinding, and then copper concentration and copper scavenging are performed in sequence to obtain a copper concentrate and a copper scavenging tailing; wherein the copper scavenging tailings are returned to the copper rougher;

[0011] S5. The copper scavenging tailings 2 are sequentially subjected to sulfur roughing and sulfur concentration to obtain a floating sulfur concentrate and sulfur roughing tailings;

[0012] S6. The sulfur roughing tailings are sequentially subjected to sulfur scavenging, magnetic roughing and magnetic concentration to obtain magnetic sulfur concentrate and magnetic roughing tailings;

[0013] S7. Perform magnetic scavenging on the magnetic rougher tailings to obtain magnetic scavenging concentrate and tailings, wherein the magnetic scavenging concentrate is returned to the magnetic rougher.

[0014] In the technical solution of the embodiment of the present application, a beneficiation process of copper rapid flotation + enhanced flotation - differentiated regrinding of copper rough concentrate + step-by-step selection - copper tail flotation sulfur - sulfur tail magnetic separation is used. According to the differences in floatability and particle size between copper minerals, and the differences in floatability and magnetism between pyrite and some pyrrhotite, a copper-sulfur beneficiation and recovery process is rationally and efficiently designed. Copper minerals with good floatability and sufficient dissociation are preferentially floated to obtain high-quality copper rough concentrate, and through copper concentrate operation, rapid and efficient recovery of floatable copper is achieved; copper minerals with poor floatability and copper-sulfur conjoined bodies are then enhanced to obtain relatively low-quality copper rough concentrate, and after regrinding, further dissociation is carried out to improve the dissociation degree and achieve enhanced copper recovery; sulfur is first floated on the copper tail, and then the remaining sulfur is magnetically separated; the problem of insufficient and effective recovery of copper due to uneven copper flotation rate and dissociation degree is effectively solved, and the problem of insufficient and effective recovery of pyrrhotite by flotation is effectively solved.

[0015] In some embodiments, in step S1, the crushed particle size is -2 mm, the fineness of the first grinding is -0.074 mm, accounting for 70-75%, the concentration of the slurry is 31-35%, the first sulfur inhibitor is lime, and the amount of the first sulfur inhibitor added is 3500-4500 g / t, the adjusting agent is sodium humate and sodium sulfide, and the amount of sodium humate and sodium sulfide added is 50-200 g / t and 100-300 g / t, respectively; the pH value of the slurry is 8.5-9. It should be noted that the amount of all reagents used in this application refers to the amount relative to the original ore, that is, the mass of the reagent required to be added per ton of original ore, which will not be repeated below.

[0016] In this embodiment, the raw ore is crushed and ground to obtain raw ore pulp for mineral processing; the first sulfur inhibitor and the regulator are added during the grinding process to effectively complex the surface of the copper mineral and dissolve the Cu 2+ , preventing it from having a continuous flotation activation effect on pyrite, and appropriately forming a sulfide film similar to sulfide ore on the surface of slightly oxidized copper minerals, thereby improving the overall floatability of copper minerals.

[0017] In some embodiments, in step S2, the reagent for rapid copper flotation includes a gangue inhibitor, a first sulfur-assisted inhibitor, a first copper collector, and a first frother. The gangue inhibitor is CD-ND, and the gangue inhibitor CD-ND includes: carboxypropyl starch, dioctyl adipate, methyl amyl alcohol, and aluminum sulfate in a mass ratio of 0.1-0.2: 0.2-0.4: 0.3-0.5: 0.05-0.1. The addition amount of the gangue inhibitor is 50-200 g / t. The first sulfur-assisted inhibitor is The preparation is CD-SD, the first sulfur auxiliary inhibitor CD-SD includes: fulvic acid, pyrogallic acid and sodium carboxymethyl dithiocarbonate, and the mass ratio thereof is 0.2-0.3:0.3-0.5:0.3-0.4. The addition amount of the first sulfur auxiliary inhibitor is 100-300 g / t, the first copper collector is ethylthiocarbamate, and the addition amount of the first copper collector is 20-40 g / t. The first foaming agent is MIBC, and the addition amount of the first foaming agent is 10-30 g / t.

[0018] In this embodiment, by adding a gangue inhibitor CD-ND, a first sulfur auxiliary inhibitor CD-SD, a first copper collector ethiocarbamate, and a first frother MIBC during the rapid copper flotation process, CD-ND enhances the inhibition of muddy gangue, and CD-SD is combined with lime to achieve effective inhibition of sulfur at a relatively low pulp alkalinity, thereby facilitating the preferential flotation recovery of copper minerals and reducing the difficulty of subsequent de-inhibition and activation of sulfur.

[0019] In some embodiments, in step S3, the copper roughing agent includes a second sulfur auxiliary inhibitor, a second copper collector and a second foaming agent, the second sulfur auxiliary inhibitor is CD-SD, and the second sulfur auxiliary inhibitor CD-SD includes: fulvic acid, pyrogallic acid and sodium carboxymethyl dithiocarbonate, and the mass ratio thereof is 0.2-0.3:0.3-0.5:0.3-0.4, the addition amount of the second sulfur auxiliary inhibitor is 50-200 g / t, the second copper collector is isopropyl xanthate, the addition amount of the second copper collector is 10-30 g / t, the second foaming agent is MIBC, and the addition amount of the second foaming agent is 5-15 g / t.

[0020] In this embodiment, by adding the second sulfur auxiliary depressant CD-SD and the second copper collector isopropyl xanthate in the copper roughing process, the copper mineral is further floated to further separate the copper and pyrite in the ore.

[0021] In some embodiments, in step S3, the copper scavenging is performed twice, and the reagents for the two copper scavengings include a third copper collector, which is isopropyl xanthate. In the two copper scavengings, the dosage of the third copper collector is 5-10 g / t.

[0022] In this embodiment, copper minerals are fully and effectively recovered through two copper scavenging operations.

[0023] In some embodiments, in step S4, the fineness of the second grinding is -0.037 mm, accounting for 80-85%; the number of copper concentrations is three times, and the reagents for the three copper concentrations include a second sulfur inhibitor and a third sulfur auxiliary inhibitor, the second sulfur inhibitor is lime, and the third sulfur auxiliary inhibitor is CD-SD, and the third sulfur auxiliary inhibitor CD-SD includes: fulvic acid, pyrogallic acid and sodium carboxymethyl dithiocarbonate, and the mass ratio thereof is 0.2-0.3:0.3-0.5:0.3-0.4. In the three copper concentrations, the amount of disulfide inhibitor added is 200-500 g / t, and the amount of the third sulfur auxiliary inhibitor added is 20-50 g / t.

[0024] In this embodiment, the copper coarse concentrate is regrinded to achieve further dissociation of the copper minerals and then subjected to three copper concentrations. At the same time, the second sulfur inhibitor lime and the third sulfur auxiliary inhibitor CD-SD are added to strengthen the effective inhibition of pyrite. The copper rapid flotation concentrate is fed into the second copper concentration, effectively achieving the "early recovery" of copper metal.

[0025] In some embodiments, in step S5, the sulfur roughing agent includes a sulfur activator, a first sulfur collector and a third foaming agent, the sulfur selection is blank selection, the sulfur activator is copper sulfate, the first sulfur collector is butyl xanthate, and the third foaming agent is 2# Oil, in the crude sulfur selection, the amount of the sulfur activator is 150-250 g / t, the amount of the first sulfur collector is 150-300 g / t, and the amount of the third foaming agent is 20-40 g / t.

[0026] In this embodiment, sulfur roughing and then sulfur blank selection are carried out to "lightly press and moderately activate" the sulfur, effectively reducing the difficulty of de-inhibiting the activation of the floatable pyrite flotation.

[0027] In some embodiments, in step S6, the sulfur sweep is performed three times, and the reagents used in the three sulfur sweeps include a second sulfur collector, which is butyl xanthate. In the three sulfur sweeps, the amount of the second sulfur collector used is 50-100 g / t.

[0028] In this embodiment, the floatable pyrite is fully recovered through three sulfur sweeps.

[0029] In some embodiments, in step S6, the magnetic field strength of the rough magnetic separation is 1400-1800 Oe; the magnetic field strength of the fine magnetic separation is 700-1100 Oe.

[0030] In this embodiment, pyrrhotite and gangue minerals are effectively separated through magnetic roughing and magnetic concentration to obtain magnetic sulfide concentrate of qualified quality.

[0031] In some embodiments, in step S7, the magnetic field strength of the magnetic scanning is 2300-2700 Oe.

[0032] In this embodiment, pyrrhotite and gangue minerals are further separated by magnetic sweeping, so that pyrrhotite can be fully recovered.

[0033] 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

[0034] To more clearly illustrate the technical solution of this application, the following is a brief introduction to the drawings used in this application. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be derived from these drawings without inventive effort.

[0035] Figure 1 This is a flow chart of the beneficiation method for high-sulfur copper ore containing mud and pyrrhotite in Example 1 of the present application. DETAILED DESCRIPTION

[0036] The following embodiments of the technical solution of the present application will be described in detail with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application and are therefore only examples and are not intended to limit the scope of protection of the present application.

[0037] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art 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" and any variations thereof in the specification and claims of this application and the above-mentioned figure descriptions are intended to cover non-exclusive inclusions.

[0038] In the description of the embodiments of this application, the technical terms "first" and "second" are used only to distinguish different objects and should not be understood to indicate or imply relative importance or implicitly specify the quantity, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, the meaning of "plurality" is more than two, unless otherwise clearly and specifically defined.

[0039] References herein to "embodiments" mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0040] In the description of the embodiments of this application, the term "and / or" is simply a description of the association relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can represent the following three situations: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " in this document generally indicates that the associated objects are in an "or" relationship.

[0041] In order to solve the problems of existing high-sulfur copper ores containing muddy pyrrhotite, such as difficulty in beneficiation, low recovery rate, environmentally unfriendly reagents and poor stability, the present application provides a beneficiation method for high-sulfur copper ores containing mud and pyrrhotite. The present application adopts a beneficiation process of copper rapid flotation + enhanced flotation - differentiated regrinding of copper rough concentrate + step-by-step concentration - copper tail flotation sulfur - sulfur tail magnetic separation. According to the differences in floatability and particle size between copper minerals, and the differences in floatability and magnetic properties between pyrite and some pyrrhotite, a rational and efficient copper-sulfur beneficiation and recovery process is designed. Prioritize the flotation of copper minerals with good floatability and relatively complete dissociation to obtain high-quality copper concentrate, and through copper concentrate operation, realize the rapid and efficient recovery of floatable copper; then strengthen the flotation of copper minerals with poor floatability and copper-sulfur conglomerates to obtain relatively low-quality copper concentrate, and through regrinding, further dissociate and improve the dissociation degree to realize enhanced copper recovery; first float sulfur from the copper tail, and then magnetically separate the remaining sulfur; effectively solve the problem of insufficient and effective recovery of copper caused by uneven copper flotation rate and dissociation degree, and effectively solve the problem of insufficient effective recovery of pyrrhotite by flotation; in addition, CD-ND+CD-SD combined inhibitor is used to simultaneously suppress muddy gangue and sulfur-containing ores, ethylthiocarbamate, isopropyl xanthate, and ethyl xanthate capture copper minerals in steps, reduce the interference of muddy gangue on the preferential copper flotation process, and realize effective inhibition of sulfur under lower pH conditions. The present application has constructed a copper-sulfur separation technology scheme of "low alkali-acid-free" flotation and "magnetic flotation combined", which reasonably and effectively controls the interference of muddy gangue on the flotation process of sulfide ore. The process flow is short and stable, the copper-sulfur separation indicators are excellent, and the copper and sulfur beneficiation recovery rates and grade indicators are improved. It effectively solves the problem of clean and efficient beneficiation and recovery of high-sulfur copper ores containing muddy pyrrhotite, and provides a new and effective method for the clean and efficient recovery of similar copper and sulfur resources.

[0042] The present invention provides a method for beneficiating high-sulfur copper ore containing mud and pyrrhotite, comprising the following steps:

[0043] S1. The ore is crushed, and then a sulfur inhibitor and a regulator are added, followed by a first grinding to obtain a ground sample, water is added to the ground sample, and the mixture is stirred to obtain a flotation ore pulp;

[0044] S2. The flotation ore pulp is subjected to rapid copper flotation to obtain a rapid copper flotation concentrate and a rapid copper flotation tailings;

[0045] S3. The copper rapid flotation tailings are sequentially subjected to copper roughing and copper scavenging to obtain a copper roughing concentrate and copper scavenging tailings 2;

[0046] S4. The copper rougher concentrate is subjected to a second grinding, and then copper concentration and copper scavenging are performed in sequence to obtain a copper concentrate and a copper scavenging tailing; wherein the copper scavenging tailings are returned to the copper rougher;

[0047] S5. The copper scavenging tailings 2 are sequentially subjected to sulfur roughing and sulfur concentration to obtain a floating sulfur concentrate and sulfur roughing tailings;

[0048] S6. The sulfur roughing tailings are sequentially subjected to sulfur scavenging, magnetic roughing and magnetic concentration to obtain magnetic sulfur concentrate and magnetic roughing tailings;

[0049] S7. Perform magnetic scavenging on the magnetic rougher tailings to obtain magnetic scavenging concentrate and tailings, wherein the magnetic scavenging concentrate is returned to the magnetic rougher.

[0050] In the technical solution of the embodiment of the present application, a beneficiation process of copper rapid flotation + enhanced flotation - differentiated regrinding of copper rough concentrate + step-by-step selection - copper tail flotation sulfur - sulfur tail magnetic separation is used. According to the differences in floatability and particle size between copper minerals, and the differences in floatability and magnetism between pyrite and some pyrrhotite, a copper-sulfur beneficiation and recovery process is rationally and efficiently designed. Copper minerals with good floatability and sufficient dissociation are preferentially floated to obtain high-quality copper rough concentrate, and through copper concentrate operation, rapid and efficient recovery of floatable copper is achieved; copper minerals with poor floatability and copper-sulfur conjoined bodies are then enhanced to obtain relatively low-quality copper rough concentrate, and after regrinding, further dissociation is carried out to improve the dissociation degree and achieve enhanced copper recovery; sulfur is first floated on the copper tail, and then the remaining sulfur is magnetically separated; the problem of insufficient and effective recovery of copper due to uneven copper flotation rate and dissociation degree is effectively solved, and the problem of insufficient and effective recovery of pyrrhotite by flotation is effectively solved.

[0051] Furthermore, in some embodiments, in step S1, the crushed particle size is -2 mm, the fineness of the first grinding is -0.074 mm, accounting for 70-75%, the concentration of the slurry is 31-35%, the first sulfur inhibitor is lime, and the addition amount of the first sulfur inhibitor is 3500-4500 g / t, the adjusting agents are sodium humate and sodium sulfide, and the addition amounts of sodium humate and sodium sulfide are 50-200 g / t and 100-300 g / t, respectively; the pH value of the slurry is 8.5-9.

[0052] In the technical solution of the embodiment of the present application, the raw ore is crushed and ground to obtain raw ore pulp for mineral processing; the first sulfur inhibitor and the regulator are added during the grinding process to effectively complex the surface of the copper mineral and dissolve the Cu 2+ , preventing it from having a continuous flotation activation effect on pyrite, and appropriately forming a sulfide film similar to sulfide ore on the surface of slightly oxidized copper minerals, thereby improving the overall floatability of copper minerals.

[0053] Furthermore, in some embodiments, in step S2, the reagent for rapid copper flotation includes a gangue inhibitor, a first sulfur auxiliary inhibitor, a first copper collector and a first frother, the gangue inhibitor is CD-ND, and the gangue inhibitor CD-ND includes: carboxypropyl starch, dioctyl adipate, methyl amyl alcohol and aluminum sulfate, and the mass ratio thereof is 0.1-0.2:0.2-0.4:0.3-0.5:0.05-0.1, and the addition amount of the gangue inhibitor is 80-120 g / t, the first sulfur auxiliary inhibitor is 0.1-0.2:0.2-0.4:0.3-0.5:0.05-0.1, and the addition amount of the gangue inhibitor is 80-120 g / t. The auxiliary inhibitor is CD-SD, and the first sulfur auxiliary inhibitor CD-SD includes: fulvic acid, pyrogallic acid and sodium carboxymethyl dithiocarbonate, and the mass ratio thereof is 0.2-0.3:0.3-0.5:0.3-0.4. The addition amount of the first sulfur auxiliary inhibitor is 100-300 g / t, the first copper collector is ethylthiocarbamate, and the addition amount of the first copper collector is 20-40 g / t. The first foaming agent is MIBC, and the addition amount of the first foaming agent is 10-30 g / t.

[0054] In the technical solution of the embodiment of the present application, by adding a gangue inhibitor CD-ND, a first sulfur auxiliary inhibitor CD-SD, a first copper collector ethiocarbamate and a first foaming agent MIBC during the rapid flotation process of copper, CD-ND strengthens the inhibition of muddy gangue, and CD-SD is combined with lime to achieve effective inhibition of sulfur at a lower pulp alkalinity, providing convenient conditions for the preferential flotation recovery of copper minerals and reducing the difficulty of subsequent sulfur deinhibition and activation.

[0055] Furthermore, in some embodiments, in step S3, the copper roughing agent includes a second sulfur auxiliary inhibitor, a second copper collector and a second foaming agent, the second sulfur auxiliary inhibitor is CD-SD, and the second sulfur auxiliary inhibitor CD-SD includes: fulvic acid, pyrogallic acid and sodium carboxymethyl dithiocarbonate, and the mass ratio thereof is 0.2-0.3:0.3-0.5:0.3-0.4, the addition amount of the second sulfur auxiliary inhibitor is 50-200 g / t, the second copper collector is isopropyl xanthate, the addition amount of the second copper collector is 10-30 g / t, the second foaming agent is MIBC, and the addition amount of the second foaming agent is 5-15 g / t.

[0056] In the technical solution of the embodiment of the present application, by adding the second sulfur auxiliary depressant CD-SD and the second copper collector isopropyl xanthate in the copper roughing operation, the copper mineral is further floated and the copper and pyrite in the ore are further separated.

[0057] Furthermore, in some embodiments, in step S3, the copper scanning includes two copper scannings, and the specific steps are as follows:

[0058] 1. Add 5-10 g / t isopropyl xanthate to the copper rougher tailings to perform a first copper scavenging to obtain a copper scavenging concentrate 1 and a copper scavenging tailing 1, wherein the copper scavenging concentrate 1 is returned to the copper rougher;

[0059] 2. Add 5-10 g / t isopropyl xanthate to the copper scavenging tailings 1 to carry out a second copper scavenging to obtain a copper scavenging concentrate 2 and a copper scavenging tailings 2, wherein the copper scavenging concentrate 2 is returned to the first copper scavenging.

[0060] In the technical solution of the embodiment of the present application, copper minerals are fully and effectively recovered through two copper sweeps.

[0061] Furthermore, in some embodiments, in step S4, the fineness of the second grinding is -0.037 mm, accounting for 80-85%.

[0062] In the technical solution of the embodiment of the present application, the copper rough concentrate is regrinded to achieve further and sufficient dissociation of the copper minerals, which facilitates subsequent mineral processing.

[0063] Furthermore, in some embodiments, in step S4, the copper concentrating includes three copper concentrating steps, and the specific steps are as follows:

[0064] 1. Add water to the reground ore sample until the concentration of the reground slurry is 30-40%.

[0065] 2. Adding 200-500 g / t of lime and 20-50 g / t of CD-SD to the reground slurry to perform the first copper concentration to obtain copper concentrate 1 and copper concentrated tailings 1;

[0066] 3. The copper concentrate 1 is combined with the copper rapid flotation concentrate, and 200-500 g / t of lime and 20-50 g / t of CD-SD are added to perform a second copper concentration to obtain a copper concentrate 2 and a copper concentration tailing 2, wherein the copper concentration tailing 2 is returned to the previous copper concentration operation;

[0067] 4. Add 200-500 g / t of lime and 20-50 g / t of CD-SD to the copper concentrate 2 to perform a third copper concentration to obtain a copper concentrate 3 and a copper concentrated tailing 3; wherein the copper concentrated tailing 3 is returned to the previous copper concentration operation.

[0068] The CD-SD comprises fulvic acid, pyrogallic acid and sodium carboxymethyl dithiocarbonate, and the mass ratio thereof is 0.2-0.3:0.3-0.5:0.3-0.4.

[0069] In the technical solution of the embodiment of the present application, the regrinded minerals are subjected to three copper concentrations, and the second sulfur inhibitor lime and the third sulfur auxiliary inhibitor CD-SD are added at the same time to strengthen the effective inhibition of pyrite, and the copper rapid flotation concentrate is fed into the second copper concentration to achieve "early recovery" of copper metal.

[0070] Furthermore, in some embodiments, in step S5, the sulfur roughing agent includes a sulfur activator, a first sulfur collector and a third foaming agent, the sulfur selection is blank selection, the sulfur activator is copper sulfate, the first sulfur collector is butyl xanthate, and the third foaming agent is 2 # In the crude sulfur selection, the amount of the sulfur activator is 150-250 g / t, the amount of the first sulfur collector is 150-300 g / t, and the amount of the third foaming agent is 20-40 g / t.

[0071] In the technical solution of the embodiment of the present application, sulfur roughing is followed by sulfur blank selection, and sulfur is “lightly pressed and moderately activated”, effectively reducing the difficulty of de-inhibiting activation of floatable pyrite flotation.

[0072] Furthermore, in some embodiments, in step S6, the sulfur sweep includes three sulfur sweeps, and the specific steps are as follows:

[0073] 50-100 g / t of butyl xanthate is added to the sulfur roughing tailings, and a first sulfur scavenging is carried out to obtain a sulfur scavenging concentrate 1 and a sulfur scavenging tailing 1; 50-100 g / t of butyl xanthate is added to the sulfur scavenging tailings 1, and a second sulfur scavenging is carried out to obtain a sulfur scavenging concentrate 2 and a sulfur scavenging tailing 2; 50-100 g / t of butyl xanthate is added to the sulfur scavenging tailings 2, and a third sulfur scavenging is carried out to obtain a sulfur scavenging concentrate 3 and a sulfur scavenging tailing 3, wherein the sulfur scavenging concentrate 1 is returned to the sulfur roughing, and the sulfur scavenging concentrate 2 and the sulfur scavenging concentrate 3 are sequentially returned to the previous sulfur scavenging.

[0074] In the technical solution of the embodiment of the present application, the floatable pyrite can be fully recovered through three sulfur sweeps.

[0075] Furthermore, in some embodiments, in step S6, the magnetic field strength of the rough magnetic separation is 1400-1800 Oe; and the magnetic field strength of the fine magnetic separation is 700-1100 Oe.

[0076] In the technical solution of the embodiment of the present application, pyrrhotite and gangue minerals are effectively separated through magnetic roughing and magnetic concentration to obtain magnetic sulfide concentrate of qualified quality.

[0077] Furthermore, in some embodiments, in step S7, the magnetic field strength of the magnetic scanning is 2300-2700 Oe.

[0078] In the technical solution of the embodiment of the present application, pyrrhotite and gangue minerals are further separated by magnetic sweeping, so that pyrrhotite can be fully recovered.

[0079] 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 should not be construed as limiting the present application. Where specific techniques or conditions are not specified in the examples, the techniques or conditions described in the literature in this area or the product specifications are used. Reagents or instruments used without manufacturer's indication are all commercially available conventional products.

[0080] Example 1

[0081] This embodiment provides a high-sulfur copper ore beneficiation method containing mud and pyrrhotite. The beneficiation flow chart is as follows: Figure 1 As shown, the specific steps include:

[0082] (1) Weigh 500 g of ore sample, crush it to -2 mm, then add 4000 g / t of sulfur inhibitor lime, 100 g / t of adjusting agent sodium humate, and 200 g / t of adjusting agent sodium sulfide, grind it to a fineness of -0.074 mm, accounting for 75%, add clean water to the pulp concentration of 33%, stir and mix, and obtain a flotation ore pulp with a pH value of 8.5;

[0083] (2) adding 100 g / t of gangue inhibitor CD-ND, 200 g / t of sulfur auxiliary inhibitor CD-SD, 30 g / t of copper collector ethiocarbamate, and 20 g / t of frother MIBC to the slurry to perform copper rapid flotation to obtain copper rapid flotation concentrate and copper rapid flotation tailings;

[0084] (3) 100 g / t of sulfur auxiliary depressant CD-SD, 20 g / t of copper collector isopropyl xanthate, and 10 g / t of frother MIBC were added to the copper rapid flotation tailings to perform copper roughing to obtain copper roughing concentrate and copper roughing tailings.

[0085] (4) adding 10 g / t isopropyl xanthate to the copper roughing tailings and performing the first copper scavenging to obtain copper scavenging concentrate 1 and copper scavenging tailings 1, wherein the copper scavenging concentrate 1 is returned to the copper roughing; adding 10 g / t isopropyl xanthate to the copper scavenging tailings 1 and performing the second copper scavenging to obtain copper scavenging concentrate 2 and copper scavenging tailings 2, wherein the copper scavenging concentrate 2 is returned to the first copper scavenging.

[0086] (5) The copper rougher concentrate is regrinded to a fineness of -0.037 mm, accounting for 85%, and then water is added to the regrinding pulp until the concentration is 35%. 300 g / t of lime and 30 g / t of CD-SD are added to the regrinding pulp to perform the first copper concentration, obtaining copper concentrate 1 and copper concentration tailings 1; copper concentrate 1 is combined with the copper rapid flotation concentrate, and 300 g / t of lime and 30 g / t of CD-SD are added to perform the second copper concentration, obtaining copper concentrate 2 and copper concentration tailings 2; 300 g / t of lime and 30 g / t of CD-SD are added to copper concentrate 2 to perform the third copper concentration, obtaining copper concentrate 3 and copper concentration tailings 3; wherein, copper concentration tailings 2 and copper concentration tailings 3 are sequentially returned to the previous copper concentration operation.

[0087] (6) Add 10 g / t of copper collector ethyl xanthate to the copper concentrate tailings 1 to carry out copper scavenging to obtain copper scavenging concentrate and copper scavenging tailings, wherein the copper scavenging concentrate is returned to the first copper concentration, and the copper scavenging tailings are returned to the copper roughing.

[0088] (7) Add 200 g / t of sulfur activator copper sulfate, 200 g / t of sulfur collector butyl xanthate, and 30 g / t of foaming agent 2# oil to the copper scavenging tailings 2, and perform sulfur roughing and sulfur blank selection to obtain sulfur roughing tailings and floating sulfur tailings, wherein the floating sulfur tailings are returned to the sulfur roughing.

[0089] (8) 80 g / t of butyl xanthate is added to the sulfur roughing tailings to carry out the first sulfur scavenging to obtain sulfur scavenging concentrate 1 and sulfur scavenging tailings 1; 80 g / t of butyl xanthate is added to the sulfur scavenging tailings 1 to carry out the second sulfur scavenging to obtain sulfur scavenging concentrate 2 and sulfur scavenging tailings 2; 80 g / t of butyl xanthate is added to the sulfur scavenging tailings 2 to carry out the third sulfur scavenging to obtain sulfur scavenging concentrate 3 and sulfur scavenging tailings 3, wherein the sulfur scavenging concentrate 1 is returned to the sulfur roughing, and the sulfur scavenging concentrate 2 and the sulfur scavenging concentrate 3 are returned to the previous sulfur scavenging in sequence.

[0090] (9) The sulfur roughing tailings are subjected to magnetic roughing and magnetic concentration in magnetic drums with magnetic field strengths of 1600 Oe and 900 Oe, respectively, to obtain magnetic sulfur concentrate and magnetic roughing tailings.

[0091] (10) The magnetic roughing tailings are magnetically swept in a magnetic drum with a magnetic field strength of 2500 Oe to obtain magnetic sweep concentrate and tailings, wherein the magnetic sweep concentrate is returned to the magnetic roughing.

[0092] The source and performance parameters of the ore sample are as follows: the raw ore Cu grade is 0.42-0.56% (mainly chalcopyrite, with a small amount of bornite), the S grade is 15-18% (mainly pyrite and pyrrhotite), and the Fe grade is 18-22% (mainly pyrrhotite and iron-bearing gangue); the raw ore contains 3-6% chlorite, 2-5% actinolite, 5-15% white / sericite, 2-5% calcite, and 2-5% dolomite; the raw ore contains 10-15% pyrrhotite;

[0093] CD-ND is composed of carboxypropyl starch, dioctyl adipate, methyl amyl alcohol and aluminum sulfate in a mass ratio of 0.2:0.3:0.45:0.05;

[0094] CD-SD is composed of fulvic acid, pyrogallic acid and sodium carboxymethyldithiocarbonate in a mass ratio of 0.25:0.45:0.3.

[0095] The test results of the separation index of high-sulfur copper ore containing muddy pyrrhotite in this embodiment are shown in Table 1.

[0096] Table 1 Separation index of high sulfur copper ore containing muddy pyrrhotite in Example 1

[0097]

[0098] Example 2

[0099] Example 2 provides a beneficiation method for high-sulfur copper ore containing mud and pyrrhotite. Compared with Example 1, the difference is that the amount of sodium sulfide added as the adjusting agent is different, the amount of sodium sulfide added is 300 g / t, and the pH value of the final flotation ore pulp is 9. The other steps are roughly the same as those in Example 1 and are not repeated here.

[0100] The test results of the separation index of the high-sulfur copper ore containing muddy pyrrhotite in Example 2 are shown in Table 2.

[0101] Table 2 Separation index of high sulfur copper ore containing muddy pyrrhotite in Example 2

[0102]

[0103] It can be seen from the test results of Examples 1 and 2 in Tables 1 and 2 that the beneficiation method for high-sulfur copper ore containing muddy pyrrhotite of the present invention is used, and the beneficiation reagent is combined with the slurry pH value in the range of 8.5 to 9 to achieve effective suppression of sulfur in high-sulfur copper ore containing muddy pyrrhotite.

[0104] Comparative Example 1

[0105] This comparative example provides a beneficiation method for high-sulfur copper ore containing mud and pyrrhotite. Compared with Example 1, the difference is that the reagents CD-ND and CD-SD are replaced with conventional reagent water glass. The other steps are roughly the same as those in Example 1 and will not be repeated here.

[0106] Comparative Example 2

[0107] This comparative example provides a beneficiation method for high-sulfur copper ore containing mud and pyrrhotite. Compared with Example 1, the difference is that the flotation process of "copper roughing-coarse concentrate regrinding-sulfur magnetic separation-copper tail activation sulfur selection" is adopted. The other steps are roughly the same as those in Example 1 and are not repeated here.

[0108] The test results of separation index of high-sulfur copper ore containing muddy pyrrhotite in Comparative Examples 1 and 2 are shown in Table 3.

[0109] Table 3 Separation index of high sulfur copper ore containing muddy pyrrhotite in comparative examples 1 to 2

[0110]

[0111] It can be seen from the test results of Comparative Example 1 in Table 3 that, compared with Example 1, when the reagents CD-ND and CD-SD are replaced with the conventional reagent water glass, the Cu grade and recovery rate of the copper concentrate are significantly reduced, and the comprehensive sulfur concentrate recovery rate is also reduced due to the non-selective inhibitory effect of water glass; it can be seen from the test results of Comparative Example 2 that, compared with Example 1, when the mineral processing steps are changed to the "copper roughing-rough concentrate regrinding-sulfur magnetic separation-copper tail activation sulfur selection" process, the copper and sulfur concentrate grades are reduced, and the comprehensive sulfur concentrate sulfur recovery rate is significantly reduced, mainly because the magnetic separation-flotation sulfur process makes it difficult for some pyrite to be effectively activated and flotated for recovery.

[0112] In summary, the present application provides a beneficiation method for high-sulfur copper ores containing mud and pyrrhotite. The method first adopts a beneficiation process of copper rapid flotation + enhanced flotation - differentiated regrinding of copper rough concentrate + step-by-step selection - copper tail flotation sulfur - sulfur tail magnetic separation. According to the differences in floatability and particle size between copper minerals, and the differences in floatability and magnetism between pyrite and some pyrrhotite, a copper-sulfur beneficiation recovery process is rationally and efficiently designed. Prioritize the flotation of copper minerals with good floatability and relatively complete dissociation to obtain high-quality copper concentrate, and through copper concentrate operation, realize the rapid and efficient recovery of floatable copper; then strengthen the flotation of copper minerals with poor floatability and copper-sulfur conglomerates to obtain relatively low-quality copper concentrate, and through regrinding, further dissociate and improve the dissociation degree to realize enhanced copper recovery; first float sulfur from the copper tail, and then magnetically separate the remaining sulfur; effectively solve the problem of insufficient and effective recovery of copper caused by uneven copper flotation rate and dissociation degree, and effectively solve the problem of insufficient effective recovery of pyrrhotite by flotation; in addition, CD-ND+CD-SD combined inhibitor is used to simultaneously suppress muddy gangue and sulfur-containing ores, ethylthiocarbamate, isopropyl xanthate, and ethyl xanthate capture copper minerals in steps, reduce the interference of muddy gangue on the preferential copper flotation process, and realize effective inhibition of sulfur under lower pH conditions. The present application has constructed a copper-sulfur separation technology scheme of "low alkali-acid-free" flotation and "magnetic flotation combined", which reasonably and effectively controls the interference of muddy gangue on the flotation process of sulfide ore. The process flow is short and stable, the copper-sulfur separation indicators are excellent, and the copper and sulfur beneficiation recovery rates and grade indicators are improved. It effectively solves the problem of clean and efficient beneficiation and recovery of high-sulfur copper ores containing muddy pyrrhotite, and provides a new and effective method for the clean and efficient recovery of similar copper and sulfur resources.

[0113] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any embodiments having substantially the same structure and effect as the technical concept within the scope of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the present application, any other embodiments that can be conceived by those skilled in the art and that combine some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. A beneficiation method for high-sulfur copper ore containing mud and pyrrhotite, characterized in that: The steps include: S1. The ore is crushed, and then a sulfur inhibitor and a regulator are added, followed by a first grinding to obtain a ground sample, water is added to the ground sample, and the mixture is stirred to obtain a flotation ore pulp; S2. The flotation ore pulp is subjected to rapid copper flotation to obtain a rapid copper flotation concentrate and a rapid copper flotation tailings; S3. The copper rapid flotation tailings are sequentially subjected to copper roughing and copper scavenging to obtain a copper roughing concentrate and copper scavenging tailings 2; S4. The copper rougher concentrate is subjected to a second grinding, and then copper concentration and copper scavenging are performed in sequence to obtain a copper concentrate and a copper scavenging tailing; wherein the copper scavenging tailings are returned to the copper rougher; S5. The copper scavenging tailings 2 are sequentially subjected to sulfur roughing and sulfur concentration to obtain a floating sulfur concentrate and sulfur roughing tailings; S6. The sulfur roughing tailings are sequentially subjected to sulfur scavenging, magnetic roughing and magnetic concentration to obtain magnetic sulfur concentrate and magnetic roughing tailings; S7. Perform magnetic scavenging on the magnetic rougher tailings to obtain magnetic scavenging concentrate and tailings, wherein the magnetic scavenging concentrate is returned to the magnetic rougher.

2. The beneficiation method for high-sulfur copper ore containing mud and pyrrhotite according to claim 1, characterized in that: In step S1, the crushed particle size is -2 mm, the fineness of the first grinding is -0.074 mm, accounting for 70-75%, the concentration of the slurry is 31-35%, the first sulfur inhibitor is lime, and the addition amount of the first sulfur inhibitor is 3500-4500 g / t, the adjusting agents are sodium humate and sodium sulfide, and the addition amounts of sodium humate and sodium sulfide are 50-200 g / t and 100-300 g / t, respectively; the pH value of the slurry is 8.5-9.

3. The beneficiation method for high-sulfur copper ore containing mud and pyrrhotite according to claim 1, characterized in that: In step S2, the reagents for rapid copper flotation include a gangue inhibitor, a first sulfur auxiliary inhibitor, a first copper collector and a first frother. The gangue inhibitor is CD-ND, which includes: carboxypropyl starch, dioctyl adipate, methyl amyl alcohol and aluminum sulfate in a mass ratio of 0.1-0.2:0.2-0.4:0.3-0.5:0.05-0.

1. The addition amount of the gangue inhibitor is 50-200 g / t. The first sulfur auxiliary inhibitor is C D-SD, the first sulfur auxiliary inhibitor CD-SD includes: fulvic acid, pyrogallic acid and sodium carboxymethyl dithiocarbonate, and the mass ratio thereof is 0.2-0.3:0.3-0.5:0.3-0.

4. The addition amount of the first sulfur auxiliary inhibitor is 100-300 g / t, the first copper collector is ethylthiocarbamate, and the addition amount of the first copper collector is 20-40 g / t. The first foaming agent is MIBC, and the addition amount of the first foaming agent is 10-30 g / t.

4. The beneficiation method for high-sulfur copper ore containing mud and pyrrhotite according to claim 1, characterized in that: In step S3, the copper roughing agent includes a second sulfur auxiliary inhibitor, a second copper collector and a second foaming agent, the second sulfur auxiliary inhibitor is CD-SD, and the second sulfur auxiliary inhibitor CD-SD includes: fulvic acid, pyrogallic acid and sodium carboxymethyl dithiocarbonate, and the mass ratio thereof is 0.2-0.3:0.3-0.5:0.3-0.

4. The addition amount of the second sulfur auxiliary inhibitor is 50-200 g / t, the second copper collector is isopropyl xanthate, and the addition amount of the second copper collector is 10-30 g / t. The second foaming agent is MIBC, and the addition amount of the second foaming agent is 5-15 g / t.

5. The beneficiation method for high-sulfur copper ore containing mud and pyrrhotite according to claim 1, characterized in that: In step S3, the copper scavenging is performed twice. The reagents used in the two copper scavenging processes include a third copper collector, which is isopropyl xanthate. In the two copper scavenging processes, the dosage of the third copper collector is 5-10 g / t.

6. The beneficiation method for high-sulfur copper ore containing mud and pyrrhotite according to claim 1, characterized in that: In step S4, the fineness of the second grinding is -0.037 mm, accounting for 80-85%; the number of copper concentrations is three times, and the reagents for the three copper concentrations include a second sulfur inhibitor and a third sulfur auxiliary inhibitor, the second sulfur inhibitor is lime, and the third sulfur auxiliary inhibitor is CD-SD, and the third sulfur auxiliary inhibitor CD-SD includes: fulvic acid, pyrogallic acid and sodium carboxymethyl dithiocarbonate, and the mass ratio thereof is 0.2-0.3:0.3-0.5:0.3-0.

4. In the three copper concentrations, the addition amount of the second sulfur inhibitor is 200-500 g / t, and the addition amount of the third sulfur auxiliary inhibitor is 20-50 g / t.

7. The beneficiation method for high-sulfur copper ore containing mud and pyrrhotite according to claim 1, characterized in that: In step S5, the sulfur roughing agent includes a sulfur activator, a first sulfur collector and a third foaming agent, the sulfur selection is blank selection, the sulfur activator is copper sulfate, the first sulfur collector is butyl xanthate, and the third foaming agent is 2 # Oil, in the crude sulfur selection, the amount of the sulfur activator is 150-250 g / t, the amount of the first sulfur collector is 150-300 g / t, and the amount of the third foaming agent is 20-40 g / t.

8. The beneficiation method for high-sulfur copper ore containing mud and pyrrhotite according to claim 1, characterized in that: In step S6, the sulfur sweep is performed three times. The reagents used in the three sulfur sweeps include a second sulfur collector, which is butyl xanthate. In the three sulfur sweeps, the amount of the second sulfur collector used is 50-100 g / t.

9. The beneficiation method for high-sulfur copper ore containing mud and pyrrhotite according to claim 1, characterized in that: In step S6, the magnetic field strength of the rough magnetic separation is 1400 to 1800 Oe; the magnetic field strength of the fine magnetic separation is 700 to 1100 Oe.

10. The beneficiation method for high-sulfur copper ore containing mud and pyrrhotite according to claim 1, characterized in that: In step S7, the magnetic field strength of the magnetic scanning is 2300-2700 Oe.

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