Sorting method of arsenopyrite-containing copper sulphide ore

Abstract

The invention relates to the technical field of mineral separation, in particular to a sorting method of arsenopyrite-containing copper sulphide ore, which comprises the following steps: after grinding raw ore, carrying out slurry mixing, regulation and control of a composite inhibitor, powerful collection of a high-efficiency collecting agent and combined sorting of reagent removal-magnetic separation, and adopting a flow of'one-time roughing, two-time scavenging and four-time concentration 'and sequential returning of middling ore, so as to obtain the arsenopyrite-containing copper sulphide ore. And high-quality copper concentrate and tailings are obtained, so that efficient separation of the arsenopyrite-containing copper sulphide ore is realized. According to the compound inhibitor disclosed by the invention, the hydrophilicity of the surface of the arsenopyrite can be remarkably enhanced through the combined action of chelating modification; the efficient collecting agent can obviously enhance the hydrophobicity of the copper sulfide ore. Refined separation of copper sulfide minerals and arsenopyrite can be achieved through reagent removal-magnetic separation, and high-quality copper concentrate with the arsenic content smaller than 0.3% and the copper grade larger than 26% can be obtained. The application method is simple and easy for industrial production.

Description

Technical Field

[0001] The invention relates to the technical field of ore dressing, and in particular to a method for separating arsenopyrite-containing copper sulfide ore. Background Art

[0002] Copper sulfide ore is the main raw material for obtaining copper concentrate, and the main copper sulfides are chalcopyrite, chalcocite, bornite, covellite, etc. Arsenopyrite is the most widely distributed arsenic-containing mineral in metal deposits, and is often associated with copper sulfides. Copper sulfide ore containing arsenopyrite is a difficult point in the field of mineral processing. Since the physical and chemical properties of arsenopyrite and copper sulfide minerals are similar, the floatability is similar, and it is inevitable that copper ions have a good activation effect on arsenopyrite, so that the conventional mineral processing reagent system and flotation method will cause the simultaneous enrichment of arsenic-containing minerals and copper minerals, and ultimately cause the arsenic content of copper concentrate to exceed the standard. The high arsenic content in the flotation concentrate will not only cause great pollution to the environment during the smelting process, but also greatly increase the processing cost. Therefore, the research and development of separation technology for copper sulfide ore containing arsenopyrite is of great practical significance for improving product quality and improving the smelting environment.

[0003] The separation process of arsenic-containing copper sulfide ores faces the problem of separating copper and arsenic. Copper-arsenic flotation separation usually uses the technology of adding humic acid, sodium sulfite and oxidant to the high-alkalinity pulp to inhibit arsenopyrite. The main disadvantages of this process are: large amount of lime, large amount of inhibitor, unsatisfactory effect of single inhibitor, and difficulty in treating ore dressing wastewater. There have been relevant reports on the processing technology of arsenic-containing copper sulfide ore resources. The invention patent of Chinese patent document 202210410663.5 discloses "a flotation inhibitor of arsenopyrite, its application, and a flotation separation method of arsenopyrite and chalcopyrite". By using hexamethylenediaminetetramethylenephosphonic acid or its aqueous solution as an inhibitor of arsenopyrite, efficient flotation separation of pure minerals of arsenopyrite and chalcopyrite is achieved. The inhibitor provided by this method is simple to prepare and environmentally friendly, but the sorting effect on actual arsenic-containing copper sulfide ores remains to be investigated. Chinese patent document 202111364385.6 discloses "a method for preparing a copper-arsenic flotation separation inhibitor for mixed copper ore and its application". The inhibitor in this method uses starch, sulfuric acid and thiourea as the main raw materials, which can inhibit arsenopyrite in the flotation of copper sulfide ores in secondary copper mines under medium alkalinity conditions, but the method requires starch to react with sulfuric acid at 80°C for 2 hours to produce dextrin, which is then mixed with thiourea and stirred for 1 hour. The energy consumption of the entire preparation process is as high as 120kWh / t, and the preparation process of the inhibitor is relatively complicated and has high energy consumption. Therefore, flotation is a conventional technology for processing copper sulfide ores, but there are still many challenges to achieve the selective separation of copper sulfide minerals and arsenic-containing sulfide ores.

[0004] Based on the above status quo, the sorting process and technology of arsenic-containing copper sulfide ore need to be improved. The present invention proposes a sorting method for arsenopyrite-containing copper sulfide ore. High-quality copper concentrate and tailings are obtained through slurry adjustment, regulation of composite inhibitors, strong collection of high-efficiency collectors, and a combined sorting process of stirring deagent-magnetic separation, thereby achieving efficient sorting of arsenopyrite-containing copper sulfide ore. Summary of the invention

[0005] The purpose of the present invention is to provide a method for separating copper sulfide ore containing arsenopyrite, which is accomplished through a combined process of "flotation-strong magnetic separation" and a technical route of "composite inhibitor regulation-strong collection by high-efficiency collector-drug removal-fine separation by strong magnetic separation".

[0006] In order to achieve the above technical objectives and the above technical effects, the present invention is implemented through the following technical solutions:

[0007] A method for separating copper sulfide ore containing arsenopyrite comprises the following steps:

[0008] S1: Grind the raw ore, add pH adjuster, composite inhibitor, high-efficiency collector and frother into the slurry in sequence, and perform roughing after the action of the agents to obtain roughing concentrate and roughing tailings;

[0009] S2: adding composite inhibitors to the roughing concentrate described in step S1 in sequence, and after the agent acts, performing the first concentration to obtain the first concentrated concentrate and the first concentrated tailings; adding composite inhibitors to the first concentrated concentrate, and after the agent acts, performing the second concentration to obtain the second concentrated concentrate and the second concentrated tailings, wherein the second concentrated tailings are returned to the first concentration operation; adding composite inhibitors and high-efficiency collectors to the second concentrated concentrate, and after the agent acts, performing the third concentration to obtain the third concentrated concentrate and the third concentrated tailings, wherein the third concentrated tailings are returned to the second concentration operation;

[0010] Adding 600-800 g / t of composite depressant to the rougher concentrate;

[0011] Adding 300-400 g / t of the composite inhibitor to the first concentrate;

[0012] Adding 150-200 g / t of the composite inhibitor to the second concentrate;

[0013] Adding 5 to 10 g / t of the combined collector to the second concentrate;

[0014] S3: adding sodium sulfide and ethylenediaminetetraacetic acid to the third concentrated concentrate in step S2 to perform a stirring and drug removal operation;

[0015] S4: performing a fourth strong magnetic concentration on the dedoped concentrate in step S3 to obtain high-quality copper concentrate and magnetically separated tailings, wherein the magnetically separated tailings are returned to the third concentration operation;

[0016] S5: adding a high-efficiency collector to the roughing tailings described in step S1, and after the action of the agent, performing a first scavenging to obtain a first scavenging concentrate and a first scavenging tailings, wherein the first scavenging concentrate is combined with the first concentrated tailings described in step S2 and returned to the roughing action; adding a composite inhibitor and a high-efficiency collector to the first scavenging tailings, and after the action of the agent, performing a second scavenging to obtain a second scavenging concentrate and a second scavenging tailings, wherein the second scavenging concentrate is returned to the first scavenging operation.

[0017] Adding 10-20 g / t of high-efficiency collector to the first sweep;

[0018] Adding 150-200 g / t of composite inhibitor to the second sweep;

[0019] Adding 5-10 g / t of high-efficiency collector to the second sweep;

[0020] Furthermore, the particle size of -0.074 mm in the ore pulp of step S1 accounts for 85-95 wt %;

[0021] Furthermore, in step S1, the pH adjusting agent is NaOH, and the amount of NaOH added is 900-1200 g / t (measured according to the original ore, the same below);

[0022] Furthermore, in steps S1, S2 and S5, the composite inhibitor is a mixture of polyaspartic acid and pyrogallic acid, and the mass ratio of polyaspartic acid to pyrogallic acid is 1:2-4; the high-efficiency collector is sodium diisobutyl dithiophosphinate;

[0023] Furthermore, in step S1, the amount of the composite inhibitor added to the ore pulp is 1200-1600 g / t;

[0024] Furthermore, in step S1, the amount of the high-efficiency collector added to the slurry is 20-40 g / t;

[0025] Furthermore, in step S1, the foaming agent is pine oil, and the addition amount of pine oil is 10-20 g / t;

[0026] Furthermore, in steps S1, S2 and S5, the interval between sequentially adding the drugs is 3 to 5 minutes, and the drug action time is 3 to 5 minutes.

[0027] Further, in step S3, the stirring comprises a stirring speed of 400 to 800 rpm and a stirring time of 5 to 10 min;

[0028] Furthermore, in step S3, the addition amounts of sodium sulfide and ethylenediaminetetraacetic acid are 300-500 g / t and 200-400 g / t respectively;

[0029] Furthermore, in step S4, the strong magnetic concentration conditions are as follows: the magnetic induction intensity is 0.5-1.0 T, the stroke is 10-20 mm, and the stroke frequency is 10-30 times / minute.

[0030] Beneficial effects of the present invention:

[0031] The present invention adopts a combined process of "flotation-strong magnetic separation" and realizes efficient separation of copper sulfide ore containing arsenopyrite by scientifically optimizing the synergistic effect of flotation and magnetic separation. In the flotation stage, NaOH is used to adjust the pH value of the slurry in view of the fact that the -0.074mm particle size accounts for as high as 85%-95% of the slurry, thereby optimizing the acid-base environment on the surface of the mineral and improving the selectivity of the composite inhibitor and collector. When the mineral is selectively inhibited by the composite inhibitor, the collector such as sodium diisobutyl dithiophosphinate can be effectively adsorbed to the surface of the target copper sulfide mineral under higher pH conditions to form a stable collection complex, enhance the hydrophobicity of the mineral, and significantly improve the recovery efficiency of copper. Subsequently, through the strong magnetic separation process, the magnetic induction intensity is 0.5-1.0T, combined with the reasonably set stroke and number of strokes, harmful impurities such as arsenic are further removed, ensuring the high purity of the copper concentrate.

[0032] The present invention uses a composite inhibitor composed of polyaspartic acid and pyrogallic acid. The polyaspartic acid molecule contains a -COOH functional group, which can effectively alleviate the activation effect of copper ions on arsenopyrite through complexation and precipitation. 2, which has a strong chelating ability for the As sites on the mineral surface. Pyrogallic acid is rich in -OH functional groups and can be effectively adsorbed on the surface of arsenopyrite, hindering the adsorption of collectors. The composite inhibitor can achieve selective inhibition of arsenopyrite through the combined action of the above-mentioned chelating modifications. This synergistic effect not only improves the inhibition effect, but also effectively avoids excessive inhibition of copper sulfide minerals, ensuring a good recovery rate of copper. This inhibition mechanism effectively balances the selectivity and recovery efficiency in the flotation process. The combined use of polyaspartic acid and pyrogallic acid will produce obvious co-adsorption synergistic effects on the surface of arsenopyrite. The functional groups in different inhibitors will act through hydrogen bonds, making the adsorption configuration of a single inhibitor more compact and firm. At the same time, under the action of the composite inhibitor, the disorder of the system increases, the entropy change increases, and the Gibbs free energy of inhibitor adsorption is further reduced, which promotes the adsorption of a single inhibitor on the surface of arsenopyrite minerals. Through the simulation of Materials Studio software, it was found that when the mass ratio was 1:3, the -NH 2 The group and the pyrogallol structure of pyrogallol can form a π-π conjugated system, which reduces the adsorption energy of the composite inhibitor on the surface of arsenopyrite to -58.3 kJ / mol (the single component is only -32.6 kJ / mol); comparative experiments show that when the mass ratio is <1:2, excessive pyrogallol will cause the contact angle on the copper mineral surface to decrease by more than 5°; when >1:4, excessive polyaspartic acid will reduce the arsenic inhibition rate by 12.6%).

[0033] The sodium diisobutyl dithiophosphinate of the present invention can react with copper sulfide minerals as a collector to form a stable complex, thereby giving the minerals excellent hydrophobicity. This process is achieved by forming a strong coordination bond between the dithio group of the collector molecule and the metal ions on the surface of the copper mineral, making it easier for the mineral to combine with bubbles and float during the flotation process. The solid-affinity group (SPS) in the sodium diisobutyl dithiophosphinate has a significant affinity for the copper component on the surface of the copper sulfide ore, can form a stable adsorption layer on the mineral surface, enhance the hydrophobicity of the copper sulfide mineral, and improve the efficiency of mineral flotation. At the same time, it has a weak ability to capture arsenopyrite and pyrite. The accidental capture of other minerals is reduced, ensuring the selectivity and stability of the flotation system.

[0034] After the third concentration, the present invention implements a drug removal process, by adding sodium sulfide and ethylenediaminetetraacetic acid and performing efficient stirring to remove the drug, and remove the residual agent on the surface of the mineral. This process not only improves the physical and chemical properties of the mineral surface, but also its subsequent strong magnetic separation step effectively utilizes the mineral separation characteristics enhanced by the drug removal effect. During the magnetic separation process, by adjusting the magnetic field strength and the slurry flow rate, the deep separation of arsenides is achieved, and the purity and recovery efficiency of the copper concentrate are significantly improved. This combined operation is particularly suitable for the treatment of high-arsenic content ores, reflecting the effectiveness and innovation of the process design.

[0035] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0037] Figure 1 The present invention is a process flow chart of a method for separating copper sulfide ore containing arsenopyrite. DETAILED DESCRIPTION

[0038] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0039] Example 1

[0040] The ore comes from an arsenic-containing copper mine in Tibet. The Cu grade in the original ore is 0.6%, and the As content is 0.45%. The copper minerals in the ore mainly exist in the form of chalcopyrite and chalcocite, and the arsenic-containing minerals are mainly arsenopyrite. The gangue minerals mainly include calcite, quartz, feldspar, etc.

[0041] A method for separating copper sulfide ore containing arsenopyrite comprises the following steps:

[0042] S1: Grind the raw ore to a particle size of -0.074 mm, accounting for 85%. Then, add 900 g / t of NaOH (measured according to the raw ore, the same below), 1200 g / t of composite inhibitor (the mass ratio of polyaspartic acid and pyrogallic acid is 1:2), 30 g / t of sodium diisobutyl dithiophosphinate and 15 g / t of pine oil to the slurry in sequence. The dosing interval is 3 minutes. After the reagents act for 3 minutes, aerate and float to obtain rougher concentrate and rougher tailings.

[0043] S2: adding 600 g / t of a composite inhibitor (the mass ratio of polyaspartic acid to pyrogallic acid is 1:2) to the rougher concentrate described in step S1, and after the agent acts for 3 minutes, performing the first concentration to obtain the first concentrate and the first concentrated tailings;

[0044] S3: adding 300 g / t of a composite inhibitor (the mass ratio of polyaspartic acid to pyrogallic acid is 1:2) to the first concentrate described in step S2, and after the agent acts for 3 minutes, performing a second concentration to obtain a second concentrate and a second concentrated tailings, wherein the second concentrated tailings are returned to the first concentration operation;

[0045] S4: adding 150 g / t of composite inhibitor (the mass ratio of polyaspartic acid and pyrogallic acid is 1:2) and 7.5 g / t of sodium diisobutyl dithiophosphinate to the second concentrate in step S3 in sequence, with an interval of 3 min for adding the inhibitors. After the reagents act for 3 min, a third concentration is performed to obtain a third copper concentrate and a third concentrated tailings, wherein the third concentrated tailings are returned to the second concentration operation;

[0046] S5: adding 300 g / t of sodium sulfide and 200 g / t of ethylenediaminetetraacetic acid to the third concentrated ore in step S4, and removing the drug at a stirring speed of 400 rpm and a stirring time of 5 min;

[0047] S6: The dedoped concentrate in step S5 is subjected to a fourth strong magnetic concentration at a magnetic induction intensity of 0.5 T, a stroke of 10 mm, and a stroke frequency of 10 times / minute to obtain high-quality copper concentrate and magnetically separated tailings, wherein the magnetically separated tailings are returned to the third concentration operation;

[0048] S7: adding 15 g / t of sodium diisobutyl dithiophosphinate to the roughing tailings in step S1, and after the agent acts for 3 minutes, performing the first scavenging to obtain the first scavenging concentrate and the first scavenging tailings, wherein the first scavenging concentrate is combined with the first concentrating tailings in step S2 and then returned to the roughing action;

[0049] S8: 150 g / t of composite inhibitor (the mass ratio of polyaspartic acid and pyrogallic acid is 1:2) and 7.5 g / t of sodium diisobutyl dithiophosphinate are added to the first sweep tailings ore described in step S7 in sequence, with an interval of 3 minutes for dosing. After the reagents act for 3 minutes, aeration flotation is performed to obtain a second sweep concentrate and a second sweep tailings, wherein the second sweep concentrate is returned to the first sweep operation.

[0050] The final copper concentrate has a copper grade of 27.35%, an arsenic content of 0.18%, and a copper recovery rate of 91.16%.

[0051] Comparative Example 1

[0052] The ore was sorted using a conventional flotation reagent system, lime (1200 g / t) and calcium hypochlorite (800 g / t) were used to replace the composite inhibitor and pH adjuster (NaOH) in the present invention, and an equal amount of butyl xanthate was used to replace the sodium diisobutyl dithiophosphinate in the present invention. Other conditions were the same as those in Example 1.

[0053] The final copper concentrate has a copper grade of 25.25%, an arsenic content of 0.56%, and a copper recovery rate of 83.21%.

[0054] Comparative Example 2

[0055] The ore is sorted by the conventional sorting method, the stirring and drug removal effect is cancelled, and the third concentrated concentrate is subjected to the fourth concentration (without adding drugs in the fourth concentration), that is, flotation replaces the strong magnetic separation, and other conditions are consistent with Example 1.

[0056] The final copper concentrate has a copper grade of 26.08%, an arsenic content of 0.62%, and a copper recovery rate of 88.32%.

[0057] Comparative Example 3

[0058] The other conditions are consistent with those in Example 1, except that the stirring and de-doping effect is eliminated, that is, the concentrate of the third concentration is directly subjected to the fourth concentration by strong magnetic separation.

[0059] The final copper concentrate has a copper grade of 26.25%, an arsenic content of 0.42%, and a copper recovery rate of 88.06%.

[0060] Example 2

[0061] The copper ore used in this embodiment has a Cu grade of 0.8% and an As content of 0.85%. The copper minerals in the ore are mainly in the form of chalcopyrite, containing a small amount of bornite and covellite; the arsenic is mainly arsenopyrite. The gangue minerals mainly include calcite, quartz, feldspar, chlorite, etc.

[0062] A method for separating copper sulfide ore containing arsenopyrite comprises the following steps:

[0063] S1: Grind the raw ore to a particle size of -0.074 mm, accounting for 90%. Then, add 1000 g / t of NaOH (measured according to the raw ore, the same below), 1400 g / t of composite inhibitor (the mass ratio of polyaspartic acid and pyrogallic acid is 1:3), 40 g / t of sodium diisobutyl dithiophosphinate and 40 g / t of pine oil to the slurry in sequence. The dosing interval is 4 minutes. After the reagents act for 4 minutes, aeration flotation is performed to obtain rougher concentrate and rougher tailings.

[0064] S2: adding 700 g / t of a composite inhibitor (the mass ratio of polyaspartic acid to pyrogallic acid is 1:3) to the rougher concentrate described in step S1, and after the agent acts for 4 minutes, performing the first concentration to obtain the first concentrate and the first concentrated tailings;

[0065] S3: adding 350 g / t of composite inhibitor (the mass ratio of polyaspartic acid and pyrogallic acid is 1:3) to the first concentrate described in step S2, and after the agent acts for 4 minutes, performing a second concentration to obtain a second concentrate and a second concentrated tailings, wherein the second concentrated tailings are returned to the first concentration operation;

[0066] S4: adding 175 g / t of composite inhibitor (the mass ratio of polyaspartic acid and pyrogallic acid is 1:3) and 10 g / t of sodium diisobutyl dithiophosphinate to the second concentrate in step S3 in sequence, with an interval of 4 min for adding the inhibitors. After the reagents act for 4 min, a third concentration is performed to obtain a third copper concentrate and a third concentrated tailings, wherein the third concentrated tailings are returned to the second concentration operation;

[0067] S5: adding 500 g / t of sodium sulfide and 400 g / t of ethylenediaminetetraacetic acid to the third concentrated concentrate in step S4, and removing the drug at a stirring speed of 600 rpm and a stirring time of 8 min;

[0068] S6: The dedoped concentrate in step S5 is subjected to a fourth strong magnetic concentration at a magnetic induction intensity of 0.8 T, a stroke of 15 mm, and a frequency of 20 times / minute to obtain high-quality copper concentrate and magnetically separated tailings, wherein the magnetically separated tailings are returned to the third concentration operation;

[0069] S7: adding 20 g / t of sodium diisobutyl dithiophosphinate to the roughing tailings described in step S1, and after the agent acts for 4 minutes, performing the first scavenging to obtain the first scavenging concentrate and the first scavenging tailings, wherein the first scavenging concentrate is combined with the first concentrating tailings described in step S2 and then returned to the roughing action;

[0070] S8: Add 200 g / t of composite inhibitor (the mass ratio of polyaspartic acid and pyrogallic acid is 1:3) and 10 g / t of sodium diisobutyl dithiophosphinate to the first sweep tailings ore described in step S7 in sequence, with a dosing interval of 4 minutes. After the reagents act for 4 minutes, aerate and float to obtain a second sweep concentrate and a second sweep tailings, wherein the second sweep concentrate is returned to the first sweep operation.

[0071] The final copper concentrate has a copper grade of 29.85%, an arsenic content of 0.32%, and a copper recovery rate of 94.43%.

[0072] Comparative Example 4

[0073] The ore was sorted by a conventional sorting process, lime (1400 g / t) and sodium sulfite (1000 g / t) were used to replace the composite inhibitor and pH adjuster (NaOH) in the present invention, and an equal amount of ethionamide was used to replace the sodium diisobutyl dithiophosphinate in the present invention; the stirring and drug removal effect was cancelled, and the third concentrated concentrate was subjected to a fourth concentration (no drug was added in the fourth concentration), that is, flotation replaced strong magnetic separation, and other conditions were consistent with Example 2.

[0074] The final copper concentrate has a copper grade of 27.32%, an arsenic content of 0.72%, and a copper recovery rate of 91.32%.

[0075] Comparative Example 5

[0076] The other conditions were the same as those in Example 2, except that a single amount of polyaspartic acid was used to replace the composite inhibitor, that is, polyaspartic acid was not added, in order to analyze the effect of polyaspartic acid in the composite inhibitor.

[0077] The final copper concentrate has a copper grade of 28.02%, an arsenic content of 0.55%, and a copper recovery rate of 92.05%.

[0078] Comparative Example 6

[0079] The other conditions were the same as those in Example 2, except that a single pyrogallic acid was used in an equal amount to replace the composite inhibitor, that is, no pyrogallic acid was added, in order to analyze the effect of pyrogallic acid in the composite inhibitor.

[0080] The final copper concentrate has a copper grade of 27.46%, an arsenic content of 0.62%, and a copper recovery rate of 91.65%.

[0081] Example 3

[0082] The copper ore used in this embodiment has a Cu grade of 0.48% and an As content of 2.08%. The copper minerals in the ore are mainly in the form of chalcopyrite, containing a small amount of bornite and covellite; the arsenic is mainly arsenopyrite. The gangue minerals mainly include quartz, feldspar, chlorite, etc.

[0083] A method for separating copper sulfide ore containing arsenopyrite comprises the following steps:

[0084] S1: Grind the raw ore to a particle size of -0.074 mm, accounting for 95%. Then, add 1200 g / t of NaOH (measured according to the raw ore, the same below), 1600 g / t of composite inhibitor (the mass ratio of polyaspartic acid and pyrogallic acid is 1:4), 20 g / t of sodium diisobutyl dithiophosphinate and 20 g / t of pine oil to the slurry in sequence. The dosing interval is 5 minutes. After the reagents act for 5 minutes, aerate and float to obtain rougher concentrate and rougher tailings.

[0085] S2: adding 800 g / t of a composite inhibitor (the mass ratio of polyaspartic acid to pyrogallic acid is 1:3) to the rougher concentrate described in step S1, and after the agent acts for 5 minutes, performing the first concentration to obtain the first concentrate and the first concentrated tailings;

[0086] S3: adding 400 g / t of a composite inhibitor (the mass ratio of polyaspartic acid to pyrogallic acid is 1:4) to the first concentrate described in step S2, and after the agent acts for 5 minutes, performing a second concentration to obtain a second concentrate and a second concentrated tailings, wherein the second concentrated tailings are returned to the first concentration operation;

[0087] S4: adding 200 g / t of composite inhibitor (the mass ratio of polyaspartic acid and pyrogallic acid is 1:4) and 5 g / t of sodium diisobutyl dithiophosphinate to the second concentrate in step S3 in sequence, with an interval of 5 min for adding the inhibitors. After the reagents act for 5 min, a third concentration is performed to obtain a third copper concentrate and a third concentrated tailings, wherein the third concentrated tailings are returned to the second concentration operation;

[0088] S5: adding 600 g / t of sodium sulfide and 400 g / t of ethylenediaminetetraacetic acid to the third concentrated ore in step S4, and removing the drug at a stirring speed of 800 rpm and a stirring time of 10 min;

[0089] S6: The dedoped concentrate in step S5 is subjected to a fourth strong magnetic concentration at a magnetic induction intensity of 1.0 T, a stroke of 20 mm, and a stroke of 30 times / minute to obtain high-quality copper concentrate and magnetically separated tailings, wherein the magnetically separated tailings are returned to the third concentration operation;

[0090] S7: adding 10 g / t of sodium diisobutyl dithiophosphinate to the roughing tailings described in step S1, and after the agent acts for 5 minutes, performing the first scavenging to obtain the first scavenging concentrate and the first scavenging tailings, wherein the first scavenging concentrate is combined with the first concentrating tailings described in step S2 and then returned to the roughing action;

[0091] S8: Add 250 g / t of composite inhibitor (the mass ratio of polyaspartic acid and pyrogallic acid is 1:4) and 5 g / t of sodium diisobutyl dithiophosphinate to the first sweep tailings ore described in step S7 in sequence, with a dosing interval of 5 minutes. After the reagents act for 5 minutes, aerate and float to obtain a second sweep concentrate and a second sweep tailings, wherein the second sweep concentrate is returned to the first sweep operation.

[0092] The final copper concentrate has a copper grade of 26.63%, an arsenic content of 0.38%, and a copper recovery rate of 90.03%.

[0093] Comparative Example 7

[0094] The ore was sorted by a conventional sorting process, lime (1800 g / t) and permanganate (1200 g / t) were used to replace the composite inhibitor and pH adjuster (NaOH) in the present invention, and an equal amount of ethionamide was used to replace the sodium diisobutyl dithiophosphinate in the present invention; the stirring and drug removal effect was cancelled, and the third concentrated concentrate was subjected to a fourth concentration (no drug was added in the fourth concentration), that is, flotation replaced strong magnetic separation, and other conditions were consistent with Example 3.

[0095] The final copper concentrate has a copper grade of 24.10%, an arsenic content of 0.92%, and a copper recovery rate of 87.02%.

[0096] Comparative Example 8

[0097] The other conditions were the same as those in Example 3, except that an equal amount of butyl xanthate was used instead of sodium diisobutyl dithiophosphinate.

[0098] The final copper concentrate has a copper grade of 26.13%, an arsenic content of 0.42%, and a copper recovery rate of 87.23%.

[0099] Comparative Example 9

[0100] The other conditions are consistent with those in Example 3, except that an equal amount of sodium sulfide is used to replace EDTA in the stirring and drug removal operation, that is, EDTA is not added, in order to analyze the effect of EDTA.

[0101] The final copper concentrate has a copper grade of 25.16%, an arsenic content of 0.58%, and a copper recovery rate of 89.72%.

[0102] Comparative Example 10

[0103] The other conditions are consistent with those in Example 3, except that an equal amount of ethylenediaminetetraacetic acid is used to replace sodium sulfide in the stirring and drug removal operation, that is, sodium sulfide is not added, in order to analyze the effect of sodium sulfide.

[0104] The final copper concentrate has a copper grade of 25.16%, an arsenic content of 0.58%, and a copper recovery rate of 89.72%.

[0105] According to the t-test, the difference in copper recovery rate between the present invention and comparative example 1 is significant at the p<0.01 level, proving that the technical effect is statistically significant; the obtained copper concentrate meets the first-class requirements in YS / T 318-2007 "Copper Concentrate" (Cu≥25%, As≤0.4%), and can be directly used in the pyrometallurgical process.

[0106] In summary, it can be seen that the "flotation-strong magnetic separation" combined process proposed in the present invention can achieve efficient separation of copper sulfide ores containing arsenopyrite. The composite inhibitor of polyaspartic acid and pyrogallic acid exerts a strong positive synergistic effect, can selectively inhibit arsenopyrite, and has less impact on copper sulfide minerals. The sodium diisobutyl dithiophosphinate collector can enhance the recovery of copper sulfide minerals, and the stirring and drug removal operation promotes the effect of strong magnetic separation and arsenic removal. Compared with the conventional flotation separation method of arsenic-containing copper sulfide ores, the arsenic content in the copper concentrate obtained by the present invention is significantly reduced, and the copper recovery rate is increased by 3 to 8 percentage points. The results of Examples 1 to 3 confirm that the present invention has good adaptability to the separation of copper sulfide ores containing arsenopyrite, and the copper grade of the obtained copper concentrate is greater than 26%, and the arsenic content is less than 0.3%. In particular, strong magnetic separation promotes the deep removal of arsenopyrite in the copper concentrate.

[0107] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for separating arsenopyrite-containing copper sulfide ore, characterized in that: The following steps are involved: S1: Grind the raw ore, add pH adjuster, composite inhibitor, high-efficiency collector and frother into the slurry in sequence, and perform roughing after the action of the agents to obtain roughing concentrate and roughing tailings; S2: adding composite inhibitors to the roughing concentrate described in step S1 in sequence, and after the action of the agents, performing the first concentration to obtain the first concentrated concentrate and the first concentrated tailings; adding composite inhibitors to the first concentrated concentrate, and after the action of the agents, performing the second concentration to obtain the second concentrated concentrate and the second concentrated tailings, wherein the second concentrated tailings are returned to the first concentration operation; Adding composite inhibitors and high-efficiency collectors to the second concentration concentrate, and performing the third concentration after the action of the agents, to obtain the third concentration concentrate and the third concentration tailings, wherein the third concentration tailings are returned to the second concentration operation; S3: adding sodium sulfide and ethylenediaminetetraacetic acid to the third concentrated concentrate in step S2 to perform a stirring and drug removal operation; S4: performing a fourth strong magnetic concentration on the dedoped concentrate in step S3 to obtain high-quality copper concentrate and magnetically separated tailings, wherein the magnetically separated tailings are returned to the third concentration operation; S5: adding a high-efficiency collector to the roughing tailings described in step S1, and after the action of the agent, performing a first scavenging to obtain a first scavenging concentrate and a first scavenging tailings, wherein the first scavenging concentrate is combined with the first concentrated tailings described in step S2 and returned to the roughing action; adding a composite inhibitor and a high-efficiency collector to the first scavenging tailings, and after the action of the agent, performing a second scavenging to obtain a second scavenging concentrate and a second scavenging tailings, wherein the second scavenging concentrate is returned to the first scavenging operation.

2. The method for separating arsenopyrite-containing copper sulfide ore according to claim 1, characterized in that: In step S2, the amount of composite inhibitor added to the rougher concentrate is 600-800 g / t; The amount of composite inhibitor added to the first concentrate is 300-400 g / t; The amount of composite inhibitor added to the second concentrate is 150-200g / t; The amount of combined collector added to the second concentrate is 5-10g / t.

3. The separation method of arsenopyrite-containing copper sulfide ore according to claim 1, characterized in that: In the step S5, the amount of high-efficiency collector added to the first sweep is 10-20 g / t; The amount of composite inhibitor added to the second sweep is 150-200g / t; The amount of high-efficiency collector added to the second sweep is 5-10g / t.

4. The separation method of arsenopyrite-containing copper sulfide ore according to claim 1, characterized in that: The particle size of -0.074 mm in the ore pulp in step S1 accounts for 85-95 wt %; the amount of the composite inhibitor added to the ore pulp is 1200-1600 g / t; The pH adjusting agent in step S1 is NaOH, and the amount of NaOH added is 900-1200 g / t, measured according to the original ore; The foaming agent in step S1 is pine oil, and the addition amount of pine oil is 10-20 g / t.

5. The separation method of arsenopyrite-containing copper sulfide ore according to claim 1, characterized in that: The composite inhibitor in steps S1, S2 and S5 is a mixture of polyaspartic acid and pyrogallic acid, and the mass ratio of polyaspartic acid to pyrogallic acid is 1:2-4.

6. The separation method of arsenopyrite-containing copper sulfide ore according to claim 1, characterized in that: In the steps S1, S2 and S5, the high-efficiency collector is sodium diisobutyl dithiophosphinate; the interval for adding the agents in sequence is 3 to 5 minutes, and the agent action time is 3 to 5 minutes.

7. The separation method of arsenopyrite-containing copper sulfide ore according to claim 1, characterized in that: The stirring in step S3 includes a stirring speed of 400 to 800 rpm and a stirring time of 5 to 10 min; the added amounts of sodium sulfide and ethylenediaminetetraacetic acid are 300 to 500 g / t and 200 to 400 g / t, respectively.

8. The separation method of arsenopyrite-containing copper sulfide ore according to claim 1, characterized in that: The strong magnetic separation conditions in step S4 include: magnetic induction intensity of 0.5-1.0 T, stroke of 10-20 mm, and stroke frequency of 10-30 times / minute.

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