Combined inhibitor for flotation and arsenic removal of copper-arsenic bulk concentrate and application method of combined inhibitor

Abstract

The invention discloses a combined inhibitor for flotation and arsenic removal of copper-arsenic bulk concentrate and an application method of the combined inhibitor, and relates to the technical field of mineral separation. The combined inhibitor is composed of an inhibitor A and an inhibitor B. The inhibitor A is a mixture of magnesium ammonium chloride and aluminum sulfate, and the inhibitor B is a mixture of tartaric acid and carboxymethyl chitosan. According to the method, strong inhibition of the arsonite and the tetrahedrite in the copper-arsenic bulk concentrate is achieved through ultrasonic coupling mechanical stirring oxidation and the combined effect of the combined inhibitor. The combined inhibitor is green and free of pollution, the application method is simple and convenient, industrial production is easy, arsenic-containing minerals are selectively inhibited under the addition of non-oxidizing chemical reagents, non-arsenic-containing copper sulfide is efficiently separated through the ethionine ester and ethyl xanthate combined collecting agent, and the good copper and arsenic separation effect is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of ore dressing, and in particular to a combined inhibitor for flotation arsenic removal of copper-arsenic mixed concentrate and an application method thereof. Background Art

[0002] Copper ore is an important strategic metal mineral resource. Copper metal is widely used in many fields such as wires, cables, pipelines, construction, automobiles, aerospace, etc. The acquisition of copper raw materials mainly comes from the separation and enrichment of copper-containing ores, among which the contribution rate of copper sulfide ore exceeds 80%. With the large-scale development of copper ore resources, the overall resources tend to be depleted. At the same time, a large number of copper mines have high arsenic content of harmful impurities. Arsenic often coexists with copper sulfide minerals in the form of arsenic-containing minerals (such as arsenopyrite) or forms arsenic-containing copper minerals (such as arsenic copper ore, arsenic tetrahedrite, etc.) as the main element of the mineral. The presence of arsenic will affect the performance of the smelting products and will be accompanied by serious safety and environmental hazards in the process. The existing copper sulfide smelting process is usually suitable for copper concentrate materials with low arsenic content (0.3-0.5%). For copper concentrates with high arsenic content, it is often necessary to match them with low-arsenic copper concentrates for pyrometallurgical smelting, but the process is complicated and costly, and the subsequent treatment of wastewater and waste residue is difficult. Therefore, pre-removal of arsenic impurities in copper concentrate is of great significance for the clean production of copper metallurgy.

[0003] Flotation arsenic removal is one of the effective means to achieve copper-arsenic separation and improve product quality. The flotation separation of typical copper sulfide minerals (chalcopyrite, chalcocite, bornite, covellite, etc.) and arsenopyrite, arsenic copper sulfide, arsenic copper ore, etc. is relatively difficult. The reason is that these minerals have similar surface properties and good natural floatability, and the selectivity of mineral processing agents for minerals is poor. At the same time, ions in the slurry can easily deteriorate the effect of mineral separation. For example, copper ions have an activating effect on arsenopyrite, increasing the difficulty of mineral separation. In comparison, the flotation separation of non-arsenic copper sulfide minerals and arsenic copper minerals is more difficult, because the mineral surfaces are rich in Cu and S active particles, and the floatability is very close. Therefore, the research and development of flotation separation technology for non-arsenic copper sulfide minerals and arsenic copper minerals is of great practical significance for improving product quality and efficient and comprehensive utilization of mineral resources.

[0004] Flotation separation of copper and arsenic has always been a hot topic for mineral processing workers. However, the existing flotation separation process and technology of non-arsenic copper sulfide minerals and arsenic copper sulfide minerals need to be improved, especially for the flotation arsenic removal method of high-arsenic copper concentrate. Therefore, developing a copper concentrate arsenic removal method with good sorting effect and strong adaptability, optimizing the copper concentrate product plan, is conducive to improving the quality of copper concentrate and promoting the sales of copper concentrate. Summary of the invention

[0005] The purpose of the present invention is to provide a combined inhibitor for flotation arsenic removal of copper-arsenic mixed concentrate and its application method to solve the problems existing in the above-mentioned prior art. The present invention provides a flotation combined inhibitor and a beneficiation method for copper-arsenic mixed concentrate containing sulfur-arsenic copper ore and arsenic tetrahedrite, which suppresses arsenic-containing copper sulfide minerals through ultrasonic coupling mechanical stirring pretreatment and multi-component inhibitors, and then uses a combined collector to capture copper sulfide minerals, thereby solving the problem of poor separation of copper and arsenic sulfide minerals and improving the quality of copper concentrate.

[0006] To achieve the above object, the present invention provides the following solutions:

[0007] The present invention provides a combined inhibitor for flotation arsenic removal of copper-arsenic mixed concentrate, which is composed of an inhibitor A and an inhibitor B;

[0008] The inhibitor A is a mixture of ammonium magnesium chloride and aluminum sulfate; the inhibitor B is a mixture of tartaric acid and carboxymethyl chitosan.

[0009] As a further preferred embodiment of the present invention, the mass ratio of ammonium magnesium chloride to aluminum sulfate in the inhibitor A is 50-70:30-50; the mass ratio of tartaric acid to carboxymethyl chitosan in the inhibitor B is 60-80:20-40;

[0010] The mass ratio of the inhibitor A to the inhibitor B is (1.5-4):1.

[0011] The present invention also provides the use of the combined depressant in flotation arsenic removal of copper-arsenic mixed concentrate. The arsenic content in the copper-arsenic mixed concentrate is 2.5% to 4.0%.

[0012] The present invention further provides a method for flotation arsenic removal of copper-arsenic mixed concentrate using the above combined depressant, comprising the following steps:

[0013] Firstly, the copper-arsenic mixed concentrate pulp is pretreated by ultrasonic coupling mechanical stirring, and then the flotation arsenic removal process of roughing, scavenging and cleaning is carried out;

[0014] The pH adjuster, the inhibitor A, the inhibitor B, the combined collector and the frother are added in sequence in the roughing and the cleaning respectively;

[0015] The scanning selects and sequentially adds the inhibitor A, the inhibitor B and the combined collector;

[0016] The collector is a combined collector consisting of ethionamide and ethyl xanthate.

[0017] As a further preferred embodiment of the present invention, the mass ratio of ethionamide to ethyl xanthate is 60-80:20-40.

[0018] As a further preferred embodiment of the present invention, the ultrasonic power of the ultrasonic coupled mechanical stirring pretreatment is 600-1000W, the frequency is 10-20kHz, the time is 4-8min, and the stirring speed is 800-1500r / min.

[0019] As a further preferred embodiment of the present invention, the flotation arsenic removal process adopts a roughing process, three scavenging processes and a secondary cleaning process; the pH adjusting agent is sodium carbonate; the pH of the pulp is adjusted to 7.5-9 by using the pH adjusting agent. The frother is a frother 2 # Oil.

[0020] As a further preferred embodiment of the present invention, based on the copper-arsenic mixed concentrate ore, the addition amount of the sodium carbonate is 400-800 g / t, the addition amount of the inhibitor A is 600-800 g / t, the addition amount of the inhibitor B is 200-400 g / t, the addition amount of the combined collector is 40-80 g / t, and the addition amount of the frother 2 is 200-400 g / t. # The amount of oil added is 30-60g / t.

[0021] As a further preference of the present invention, the dosage of pH adjuster, inhibitor A, inhibitor B, combined collector and frother used in the first concentration is half of the corresponding reagents in the roughing selection, and the dosage of pH adjuster, inhibitor A, inhibitor B, combined collector and frother used in the second concentration is half of the reagents used in the first concentration, and the intermediate ore is returned in sequence.

[0022] Specifically, the tailings from the first selection are combined with the concentrate from the first scavenging and returned to the roughing operation, the tailings from the second selection are returned to the first selection operation, the concentrate from the second scavenging is returned to the first scavenging operation, and the concentrate from the third scavenging is returned to the second scavenging operation.

[0023] More preferably, after adding the sodium carbonate, inhibitor A, inhibitor B, ethionamide and ethyl xanthate combined collector and frother, stirring is performed for 3 to 6 minutes respectively.

[0024] As a further preferred embodiment of the present invention, the amount of the inhibitor A added in the third sweep is 60-80 g / t, the amount of the inhibitor B added is 20-40 g / t, and the amount of the combined collector added is 5-10 g / t.

[0025] As a further preferred embodiment of the present invention, the -0.038 mm particle size of the copper-arsenic mixed concentrate ore accounts for 80 to 90 wt%.

[0026] The ultrasonic coupled mechanical stirring pretreatment in the present invention can effectively oxidize arsenic copper ore and chalcopyrite, and promote the formation of a stable complex anion [AsO4] on the surface of the mineral. 3-, it has a strong affinity for magnesium and aluminum metal ions. Inhibitor A in the flotation combination depressor can selectively inhibit arsenic-containing copper sulfide minerals such as arsenic copper sulfide ore and arsenic copper sulfide ore, while having little effect on non-arsenic-containing copper sulfide minerals such as chalcopyrite and chalcocite. The dissolved metal ions of ammonium magnesium chloride and aluminum sulfate in inhibitor A will react with [AsO4] 3- Form hydrophilic compounds, thereby preventing the collector from adsorbing on the surface of arsenic copper ore and chalcopyrite. 2+ 、Al 3+ NH4 after dissolution of ammonium magnesium chloride + Through electrostatic action, it adsorbs on the negatively charged surface of copper sulfide and arsenic tetrahedrite, thereby increasing the hydrophilicity of the mineral surface and increasing the difference in the surface active particles of arsenic-containing copper sulfide and non-arsenic-containing copper sulfide minerals. The inhibitor B in the flotation combination inhibitor of the present invention will further interact with the surface of the arsenic-containing copper sulfide mineral after the action of inhibitor A, thereby strengthening the inhibition of the mineral. Since carboxymethyl chitosan contains -NH2, -COOH and -OH functional groups, and tartaric acid is rich in -COOH and -OH functional groups, they have a strong affinity for the adsorbed Mg 2+ 、Al 3+ The surface of the arsenic-containing copper sulfide mineral has excellent adsorption and chelation capabilities, and forms a water film with water molecules by hydrogen bonding, which has a strong inhibitory effect on the arsenic-containing copper sulfide mineral. Therefore, the combined inhibition of the present invention creates good conditions for the selective flotation separation of copper and arsenic.

[0027] The present invention discloses the following technical effects:

[0028] The present invention uses ultrasonic coupling mechanical stirring to oxidize the surface of arsenic sulfide copper ore and arsenic chalcopyrite, and then combines inhibitors through the technology of "multi-component ion passivation and modification-organic compound coupling modification" to achieve selective inhibition of arsenic sulfide copper minerals such as arsenic sulfide copper ore and arsenic chalcopyrite.

[0029] The ultrasonic coupled mechanical stirring pretreatment of the invention effectively oxidizes the surface of arsenite and tetrahedrite, and avoids the addition of oxidizing chemical reagents.

[0030] The combined inhibitor of the present invention promotes the formation of a strong hydrophilic film on the surface of arsenic-containing copper sulfide minerals such as arsenic copper sulfide and arsenic tetrahedrite through the synergistic effect of inorganic and organic compounds, thereby achieving strong inhibition of the minerals.

[0031] The combined flotation depressant of the invention is green and pollution-free to the environment, has a simple application method and is easy for industrial production. The combined collector of ethionamide and ethyl xanthate can efficiently separate non-arsenic copper sulfide and achieve a good copper and arsenic separation effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0033] Figure 1 This is an application flow chart of the flotation arsenic removal of copper-arsenic mixed concentrate of the present invention.

[0034] Figure 2 This is a flow chart of the experimental study on the flotation behavior of a single mineral in Example 6 of the present invention. DETAILED DESCRIPTION

[0035] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0036] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0037] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0038] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0039] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0040] Unless otherwise specified, "parts" in the present invention are parts by mass.

[0041] Example 1

[0042] In the copper-arsenic mixed concentrate subjected to flotation dearsenicization in this embodiment, the Cu content is 19.65%, the As content is 2.86%, the S content is 19.35%, and the Fe content is 9.54%. The phase analysis results show that the copper minerals mainly exist in the form of chalcopyrite, arsenic copper ore, and chalcocite, and a small amount of chalcocite.

[0043] In the combined inhibitor for flotation arsenic removal of copper-arsenic mixed concentrate of this embodiment, inhibitor A is a mixture of ammonium magnesium chloride (50 parts) and aluminum sulfate (50 parts); inhibitor B is a mixture of tartaric acid (60 parts) and carboxymethyl chitosan (40 parts);

[0044] The collector used in this example is a combination of ethionamide (60 parts) and ethyl xanthate (40 parts).

[0045] Flotation arsenic removal from copper-arsenic mixed concentrate:

[0046] (1) grinding the copper-arsenic mixed concentrate (i.e., the selected ore, the same below) to a powder content of about 70 wt% with a particle size of -0.038 mm;

[0047] (2) the copper-arsenic mixed concentrate slurry after grinding was subjected to ultrasonic coupling mechanical stirring pretreatment under the conditions of ultrasonic power of 600 W, frequency of 10 kHz, time of 4 min, and stirring speed of 800 r / min;

[0048] (3) To the pretreated slurry, based on the mass of the sorted ore, add 400 g / t of sodium carbonate (adjusting the pH value of the slurry to 7.5), 600 g / t of inhibitor A (300 g / t of ammonium magnesium chloride + 300 g / t of aluminum sulfate), 200 g / t of inhibitor B (120 g / t of tartaric acid + 80 g / t of carboxymethyl chitosan), 60 g / t of collector (36 g / t of ethiocarbamate + 24 g / t of ethyl xanthate) and 200 g / t of frother 200 g / t. # The oil was 30 g / t, and the stirring and slurry mixing time was 3 min, 3 min, 3 min, 4 min and 3 min respectively. Then, Figure 1The process is to flotate and remove arsenic from copper-arsenic mixed concentrate. After one roughing, three scavenging and two concentrating (the dosage of concentrating I is half of the corresponding reagent of roughing, and the dosage of concentrating II is half of the corresponding reagent of concentrating I; the reagent system of scavenging III is, inhibitor A 60g / t (ammonium magnesium chloride 30g / t + aluminum sulfate 30g / t), inhibitor A 20g / t (tartaric acid 12g / t + carboxymethyl chitosan 8g / t), collector 5g / t (ethiocarbamate 3g / t + ethyl xanthate 2g / t), and the middlings are returned in sequence), the flotation foam product is low-arsenic copper concentrate (mainly containing chalcopyrite), and the product at the bottom of the flotation machine tank is high-arsenic copper concentrate (mainly containing sulfur-arsenic copper ore and arsenic tetrahedrite). The test results are shown in Table 1.

[0049] Comparative Example 1

[0050] The other conditions are consistent with those in Example 1, except that tartaric acid and carboxymethyl chitosan are used to replace inhibitor A in equal amounts at a mass ratio of 1.5:1, that is, inhibitor A (ammonium magnesium chloride and aluminum sulfate) is not added, and the effect of a single inhibitor B is analyzed. The test results are shown in Table 1.

[0051] Comparative Example 2

[0052] The other conditions are consistent with those in Example 1, except that ammonium magnesium chloride and ammonium aluminum sulfate are used in equal amounts in a mass ratio of 1:1 to replace the adjuster B, that is, the inhibitor B (tartaric acid and carboxymethyl chitosan) is not added, and the effect of the single inhibitor A is analyzed. The test results are shown in Table 1.

[0053] Comparative Example 3

[0054] The other conditions are consistent with those in Example 1, except that the ultrasonic coupled mechanical stirring pretreatment of the copper-arsenic mixed concentrate slurry is not performed. The test results are shown in Table 1.

[0055] Example 2

[0056] The other conditions are consistent with those in Example 1, except that the inhibitor A contains 60 parts of ammonium magnesium chloride (the dosage is increased from 300 g / t to 360 g / t) and 40 parts of aluminum sulfate (the dosage is reduced from 300 g / t to 240 g / t). The effect of increasing the mass ratio of ammonium magnesium chloride to aluminum sulfate from 50:50 to 60:40 is analyzed. The test results are shown in Table 1.

[0057] Example 3

[0058] The other conditions are consistent with those in Example 1, except that the inhibitor A contains 70 parts of ammonium magnesium chloride (the dosage is increased from 300 g / t to 420 g / t) and 30 parts of aluminum sulfate (the dosage is reduced from 300 g / t to 180 g / t). The effect of increasing the mass ratio of ammonium magnesium chloride to aluminum sulfate from 50:50 to 70:30 is analyzed. The test results are shown in Table 1.

[0059] Table 1 Flotation test results / %

[0060]

[0061] Example 4

[0062] In the copper-arsenic mixed concentrate subjected to flotation dearsenicization in this embodiment, the Cu content is 21.65%, the As content is 3.04%, the S content is 21.35%, and the Fe content is 11.68%. The phase analysis results show that the copper minerals mainly exist in the form of chalcopyrite, arsenic copper ore, and chalcopyrite.

[0063] In the combined inhibitor for flotation arsenic removal of copper-arsenic mixed concentrate of this embodiment, the inhibitor A is a mixture of ammonium magnesium chloride (60 parts) and aluminum sulfate (40 parts); the inhibitor B is a mixture of tartaric acid (80 parts) and carboxymethyl chitosan (20 parts);

[0064] The collector used in this example is a combination of ethionamide (80 parts) and ethyl xanthate (20 parts).

[0065] Flotation arsenic removal from copper-arsenic mixed concentrate:

[0066] (1) grinding the copper-arsenic mixed concentrate (i.e., the selected ore, the same below) to a powder content of about 80 wt% with a particle size of -0.038 mm;

[0067] (2) the copper-arsenic mixed concentrate slurry after grinding was subjected to ultrasonic coupling mechanical stirring pretreatment under the conditions of ultrasonic power of 800 W, frequency of 15 kHz, time of 6 min, and stirring speed of 1200 r / min;

[0068] (3) To the pretreated slurry, based on the mass of the sorted ore, add 600 g / t of sodium carbonate (adjusting the pH value of the slurry to 8.5), 700 g / t of inhibitor A (420 g / t of ammonium magnesium chloride + 280 g / t of aluminum sulfate), 300 g / t of inhibitor B (210 g / t of tartaric acid + 90 g / t of carboxymethyl chitosan), 80 g / t of collector (56 g / t of ethiocarbamate + 24 g / t of ethyl xanthate) and 20 g / t of frother. # The oil was 50 g / t, and the stirring and slurry mixing time was 5 min, 4 min, 4 min, 4 min and 4 min respectively. Then, Figure 1The process is to flotation and remove arsenic from the copper-arsenic mixed concentrate. After one roughing, three scavenging and two concentrating (the dosage of the reagent for concentrating I is half of the corresponding reagent for roughing, and the dosage of the reagent for concentrating II is half of the corresponding reagent for concentrating I; the reagent system for scavenging III is: inhibitor A 70g / t (ammonium magnesium chloride 42g / t + aluminum sulfate 28g / t), inhibitor A 30g / t (tartaric acid 21g / t + carboxymethyl chitosan 9g / t), collector 8g / t (ethionamide 5.5g / t + ethyl xanthate 2.5g / t), and the middlings are returned in sequence), the flotation foam product is low-arsenic copper concentrate (mainly containing chalcopyrite), and the product at the bottom of the flotation machine tank is high-arsenic copper concentrate (mainly containing sulfur-arsenic copper ore and arsenic tetrahedrite). The test results are shown in Table 2.

[0069] Comparative Example 4

[0070] The other conditions are consistent with those of Example 4, except that tartaric acid and carboxymethyl chitosan are used to replace inhibitor A in equal amounts at a mass ratio of 7:3, that is, inhibitor A (ammonium magnesium chloride and aluminum sulfate) is not added, and the effect of a single inhibitor B is analyzed. The test results are shown in Table 2.

[0071] Comparative Example 5

[0072] The other conditions are consistent with those of Example 4, except that ammonium magnesium chloride and aluminum sulfate are used in equal amounts in a mass ratio of 3:2 to replace the adjuster B, that is, the inhibitor B (tartaric acid and carboxymethyl chitosan) is not added, and the effect of the single inhibitor A is analyzed. The test results are shown in Table 2.

[0073] Comparative Example 6

[0074] The other conditions were consistent with those in Example 4, except that an equal amount of magnesium ammonium chloride was used instead of aluminum sulfate, i.e., no aluminum sulfate was added, in order to analyze the effect of aluminum sulfate in inhibitor A. The test results are shown in Table 2.

[0075] Comparative Example 7

[0076] The other conditions are consistent with those of Example 4, except that the ammonium magnesium chloride is replaced by aluminum sulfate of equal mass, i.e., no ammonium magnesium chloride is added, and the effect of the ammonium magnesium chloride in the inhibitor A is analyzed. The test results are shown in Table 2.

[0077] Comparative Example 8

[0078] The other conditions were consistent with those in Example 4, except that an equal amount of tartaric acid was used to replace carboxymethyl chitosan, that is, no carboxymethyl chitosan was added, in order to analyze the effect of carboxymethyl chitosan in inhibitor B. The test results are shown in Table 2.

[0079] Comparative Example 9

[0080] The other conditions were the same as those in Example 4, except that an equal amount of carboxymethyl chitosan was used to replace tartaric acid, i.e., no tartaric acid was added, in order to analyze the effect of tartaric acid in inhibitor B. The test results are shown in Table 2.

[0081] Table 2 Flotation test results / %

[0082]

[0083] Example 5

[0084] In the copper-arsenic mixed concentrate subjected to flotation dearsenicization in this embodiment, the Cu content is 23.65%, the As content is 3.85%, the S content is 22.65%, and the Fe content is 15.68%. The phase analysis results show that the copper minerals in the mixed concentrate are mainly in the form of chalcopyrite and arsenic copper sulfide; the gangue minerals are mainly serpentine and talc.

[0085] In the combined inhibitor for flotation arsenic removal of copper-arsenic mixed concentrate of this embodiment, inhibitor A is a mixture of ammonium magnesium chloride (70 parts) and aluminum sulfate (30 parts); inhibitor B is a mixture of tartaric acid (70 parts) and carboxymethyl chitosan (30 parts);

[0086] The collector used in this example is a combination of ethionamide (70 parts) and ethyl xanthate (30 parts).

[0087] Flotation arsenic removal from copper-arsenic mixed concentrate:

[0088] (1) grinding the copper-arsenic mixed concentrate (i.e., the selected ore, the same below) to a powder content of about 85 wt % with a particle size of -0.038 mm;

[0089] (2) the copper-arsenic mixed concentrate slurry after grinding was subjected to ultrasonic coupling mechanical stirring pretreatment under the conditions of ultrasonic power of 800 W, frequency of 20 kHz, time of 8 min, and stirring speed of 1500 r / min;

[0090] (3) To the pretreated slurry, based on the mass of the sorted ore, add 800 g / t of sodium carbonate (adjusting the slurry pH to 9), 800 g / t of inhibitor A (480 g / t of ammonium magnesium chloride + 320 g / t of aluminum sulfate), 400 g / t of inhibitor B (280 g / t of tartaric acid + 120 g / t of carboxymethyl chitosan), 80 g / t of collector (56 g / t of ethiocarbamate + 24 g / t of ethyl xanthate) and 20 g / t of frother. # The oil was 60g / t, and the stirring and slurry mixing time was 6min, 6min, 6min, 6min and 6min respectively. Then, Figure 1The process is to flotate and remove arsenic from the copper-arsenic mixed concentrate. After one roughing, three scavenging and two concentrating (the dosage of the concentrating I is half of the corresponding reagent of the roughing, and the dosage of the concentrating II is half of the corresponding reagent of the concentrating I; the reagent system of scavenging III is, inhibitor A 80g / t (ammonium magnesium chloride 48g / t + aluminum sulfate 32g / t), inhibitor A 30g / t (tartaric acid 21g / t + carboxymethyl chitosan 9g / t), collector 8g / t (ethiocarbamate 5.5g / t + ethyl xanthate 2.5g / t), and the middlings are returned in sequence), the flotation foam product is low-arsenic copper concentrate (mainly containing chalcopyrite), and the product at the bottom of the flotation machine tank is high-arsenic copper concentrate (mainly containing sulfur-arsenic copper ore and arsenic tetrahedrite). The test results are shown in Table 3.

[0091] Comparative Example 10

[0092] The other conditions are consistent with those in Example 5, except that the ultrasonic coupled mechanical stirring pretreatment of the copper-arsenic mixed concentrate slurry was not performed. The test results are shown in Table 3.

[0093] Comparative Example 11

[0094] The other conditions are consistent with those in Example 5, except that the dosage of inhibitor B is 800 g / t (the mass ratio of tartaric acid to carboxymethyl chitosan is unchanged), that is, the mass ratio of inhibitor A to inhibitor B is 1:1. The sorting effect of reducing the mass ratio of inhibitor A to inhibitor B is analyzed, and the test results are shown in Table 3.

[0095] Comparative Example 12

[0096] The other conditions are consistent with those in Example 5, except that the dosage of inhibitor A is 2000 g / t (the mass ratio of ammonium magnesium chloride and aluminum sulfate remains unchanged), that is, the mass ratio of inhibitor A to inhibitor B is 5:1. It is intended to analyze the sorting effect of increasing the mass ratio of inhibitor A to inhibitor B. The test results are shown in Table 3.

[0097] Table 3 Flotation test results / %

[0098]

[0099]

[0100] In summary, it can be seen that the combined use of inhibitor A (ammonium magnesium chloride and aluminum sulfate) and inhibitor B (tartaric acid and carboxymethyl chitosan) has exerted a strong positive synergistic effect, and the combined use of ultrasonic coupled mechanical stirring pretreatment and combined inhibitors further improves the effect of copper-arsenic separation. The copper-arsenic mixed concentrate can selectively inhibit arsenic-containing copper sulfide minerals (sulfur arsenic copper ore, arsenic copper pyrochlore) after ultrasonic coupled mechanical stirring pretreatment, inhibitor A and inhibitor B in sequence. On this basis, ethylthiocarbamate and ethyl xanthate combined collectors achieve effective removal of arsenic from the copper-arsenic mixed concentrate. Comparing the results of the combined use of inhibitor A and inhibitor B (Example 1 and Example 4), the results of Comparative Example 1 and Comparative Example 4 show that when inhibitor B (tartaric acid and carboxymethyl chitosan, other conditions are the same) is used alone, the arsenic content of the low-arsenic copper concentrate increases from 0.26% and 0.28% to 1.26% and 1.76%, and the copper grade decreases by about 1%. The results of Comparative Examples 2 and 5 show that when inhibitor A (ammonium magnesium chloride and aluminum sulfate, other conditions are the same) is used alone, the arsenic content of the low-arsenic copper concentrate increases from 0.26% and 0.28% to 1.08% and 1.36%, and the copper grade decreases by about 1%. In addition, when only inhibitor A or a single component of inhibitor B is not used (Comparative Examples 6 to 9), the arsenic removal effect decreases significantly. The results of Example 2 and Example 3 show that within the recommended range of the mass ratio of the inhibitor components (i.e., the mass ratio of ammonium magnesium chloride and aluminum sulfate in inhibitor A is 50-70:30-50; the mass ratio of tartaric acid and carboxymethyl chitosan in inhibitor B is 60-80:20-40; the mass ratio of inhibitor A to inhibitor B is (1.5-4):1), by changing the mass ratios of ammonium magnesium chloride and aluminum sulfate, tartaric acid and carboxymethyl chitosan, respectively, the arsenic content of the low-arsenic copper concentrate does not change much (all less than 0.3%), and a good separation index can still be obtained. However, the results of Comparative Examples 11 and 12 show that by reducing the mass ratio of inhibitor A to inhibitor B to 1:1 or increasing the mass ratio of inhibitor A to inhibitor B to 5:1, the arsenic removal effect decreases. The results of Comparative Examples 3 and 10 show that the ultrasonic coupled mechanical stirring pretreatment plays a significant positive role in the flotation arsenic removal of copper-arsenic mixed concentrate. Without this pretreatment, the arsenic content of the low-arsenic copper concentrate increased from 0.26% (Example 1) and 0.27% (Example 5) to 0.95% and 1.95%, and the copper grade decreased by about 1%. The results of Examples 1 to 5 confirm that the present invention has good adaptability to the flotation arsenic removal of copper-arsenic mixed concentrate.

[0101] Example 6

[0102] Chalcopyrite / chalcocite and pyrocatechite / tetrahedrite single mineral flotation test: 2g chalcopyrite / chalcocite or pyrocatechite / tetrahedrite single mineral (-0.038mm particle size accounts for 85%) was added into a 45mL hanging trough flotation machine, and ultrasonic coupled mechanical stirring pretreatment was carried out under the conditions of ultrasonic power of 800W, frequency of 15kHz, time of 5min, stirring speed of 1400r / min, sodium carbonate was added to adjust the solution pH to 8.5, inhibitor A 70mg / L (ammonium magnesium chloride 40mg / L, aluminum sulfate 30mg / L), inhibitor B 30mg / L (tartaric acid 20mg / L, carboxymethyl chitosan 10mg / L), combined collector 23mg / L (ethiocarbamate 15mg / L, ethyl xanthate 8mg / L) and 2 # Oil (0.2 mg / L) was added, and the slurry was adjusted for 5 min, 4 min, 4 min, 4 min and 4 min respectively, and the foam was scraped for 4 min, and the foam product was collected. The recovery rate of each flotation product was calculated based on the weight of the foam product, and the results are shown in Table 4.

[0103] Table 4 Results of single mineral flotation tests on chalcopyrite / chalcocite and arsenite / tetrahedrite

[0104]

[0105] Table 4 shows that under the combined action of ultrasonic coupled mechanical stirring pretreatment, inhibitor A and inhibitor B, arsenic copper and chalcopyrite are strongly inhibited, while chalcopyrite and chalcocite still maintain good floatability. After the collector is added, the difference in flotation recovery between chalcopyrite and arsenic copper and chalcocite reaches 89.2% and 88%, respectively, and the difference in flotation recovery between chalcopyrite and arsenic copper and chalcocite reaches 89.7% and 85.5%, respectively, indicating that the use of ultrasonic coupled mechanical stirring pretreatment and the above combined inhibitor can selectively inhibit arsenic-containing copper sulfide minerals. The results of the single mineral flotation test of chalcopyrite / chalcocite and arsenic copper / chalcocite provide important technical support for the present invention.

[0106] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A combined inhibitor for flotation arsenic removal of copper-arsenic mixed concentrate, characterized in that: It is composed of inhibitor A and inhibitor B; The inhibitor A is a mixture of ammonium magnesium chloride and aluminum sulfate; the inhibitor B is a mixture of tartaric acid and carboxymethyl chitosan.

2. The combined inhibitor for flotation arsenic removal of copper-arsenic mixed concentrate according to claim 1, characterized in that: The mass ratio of ammonium magnesium chloride to aluminum sulfate in the inhibitor A is 50-70:30-50; the mass ratio of tartaric acid to carboxymethyl chitosan in the inhibitor B is 60-80:20-40; The mass ratio of the inhibitor A to the inhibitor B is (1.5-4):

1.

3. Use of the combined depressant as described in any one of claims 1 to 2 in flotation removal of arsenic from copper-arsenic mixed concentrate.

4. A method for flotation arsenic removal from copper-arsenic mixed concentrate using the combined depressant according to claim 1, characterized in that: The following steps are involved: Firstly, the copper-arsenic mixed concentrate pulp is pretreated by ultrasonic coupling mechanical stirring, and then the flotation arsenic removal process of roughing, scavenging and cleaning is carried out; The pH adjuster, the inhibitor A, the inhibitor B, the combined collector and the frother are added in sequence in the roughing and the cleaning respectively; The scanning selects and sequentially adds the inhibitor A, the inhibitor B and the combined collector; The combined collector is a combined collector consisting of ethionamide and ethyl xanthate.

5. The method according to claim 4, characterized in that The ultrasonic power of the ultrasonic coupled mechanical stirring pretreatment is 600-1000W, the frequency is 10-20kHz, and the time is 4-8min.

6. The method according to claim 4, characterized in that The flotation arsenic removal process adopts a method of one roughing selection, three scavenging selections and two cleaning selections; the pH adjuster is sodium carbonate, and the pH adjuster is used to adjust the pulp pH to 7.5-9.

7. The method according to claim 6, characterized in that When performing the roughing, based on the copper-arsenic mixed concentrate ore, the amount of sodium carbonate added is 400-800 g / t, the amount of inhibitor A added is 600-800 g / t, the amount of inhibitor B added is 200-400 g / t, the amount of the combined collector added is 40-80 g / t, and the amount of the foaming agent added is 30-60 g / t.

8. The method according to claim 7, characterized in that The amount of pH adjuster, inhibitor A, inhibitor B, combined collector and frother used in the first selection is half of the corresponding agents in the rough selection, and the amount of pH adjuster, inhibitor A, inhibitor B, combined collector and frother used in the second selection is half of the agents used in the first selection.

9. The method according to claim 7, characterized in that: In the third sweep, the amount of the inhibitor A added is 60-80 g / t, the amount of the inhibitor B added is 20-40 g / t, and the amount of the combined collector added is 5-10 g / t.

10. The method according to claim 4, characterized in that The -0.038 mm particle size of the copper-arsenic mixed concentrate ore accounts for 80 to 90 wt %.

Images