A combined depressor for arsenic removal from copper-arsenic mixed concentrate by flotation and its application method

Abstract

The application discloses a combined depressor for flotation and arsenic removal of copper-arsenic mixed concentrate and an application method thereof, and relates to the technical field of ore dressing.The combined depressor is composed of depressor A and depressor B, wherein the depressor A is a mixture of magnesium ammonium chloride and aluminum sulfate, and the depressor B is a mixture of tartaric acid and carboxymethyl chitosan.The combined depressor and ultrasonic coupling mechanical stirring oxidation are combined to realize strong depression of sulfur-arsenic-copper ore and arsenic-malachite in the copper-arsenic mixed concentrate.The combined depressor is green and pollution-free, the application method is simple and easy for industrial production, and the application method can selectively depress arsenic-containing minerals without adding oxidizing chemicals, and can efficiently separate non-arsenic-containing copper sulfide by using the combined collector of ethylthiuram and ethyl xanthate, so that good copper and arsenic separation effect is achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of mineral processing, in particular to a combined depressor for flotation and arsenic removal of copper-arsenic mixed concentrate and an application method thereof. BACKGROUND

[0002] Copper ore is an important strategic metal mineral resource, and metallic copper is widely used in many fields such as wires, cables, pipelines, buildings, automobiles, aerospace, etc. The acquisition of copper raw materials mainly comes from the separation and enrichment of copper-containing ores, of which the contribution rate of copper sulfide ore is more than 80%. With the large-scale development of copper resources, the overall resources tend to be lean, and at the same time, a large number of copper mines have high content of harmful impurities arsenic. 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 enargite, tennantite, etc.) as a body element of minerals. The presence of arsenic will affect the performance of smelting products and cause 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%), and high-arsenic copper concentrate often needs to be blended with low-arsenic copper concentrate for fire smelting. However, this process is complex and costly, and the treatment of subsequent wastewater and slag is difficult. Therefore, the pre-removal of arsenic impurities in copper concentrate is of great significance to the clean production of copper metallurgy.

[0003] Flotation and arsenic removal is one of the effective means to realize copper-arsenic separation and improve product quality. It is difficult to separate typical copper sulfide minerals (chalcopyrite, chalcocite, bornite, blue copper, etc.) from arsenopyrite, enargite, tennantite, etc. The reason is that these minerals have similar surface properties and good natural floatability, and the selectivity of mineral separation is poor. At the same time, ions in the ore pulp 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-containing copper sulfide minerals and arsenic-containing copper minerals is more difficult because the mineral surfaces are rich in Cu and S active sites, and the floatability is very close. Therefore, the development of flotation separation technology for non-arsenic-containing copper sulfide minerals and arsenic-containing copper minerals has important practical significance for improving product quality and efficient comprehensive utilization of mineral resources.

[0004] Copper and arsenic flotation separation has always been a hot issue for mineral processing workers. However, the existing process and technology for the flotation separation of non-arsenic-containing copper sulfide minerals and arsenic-containing copper sulfide minerals need to be improved, especially for the method of high-arsenic copper concentrate flotation and arsenic removal. Therefore, the development of a copper concentrate arsenic removal method with good separation effect and strong adaptability is beneficial to optimizing the copper concentrate product scheme, improving the quality of copper concentrate, and promoting the sale of copper concentrate. SUMMARY

[0005] The application aims to provide a combined inhibitor for flotation dearsenization of copper-arsenic mixed concentrate and a method for applying the same, so as to solve the problems existing in the prior art.

[0006] To achieve the above-mentioned object, the application provides the following solutions.

[0007] The application provides a combined inhibitor for flotation dearsenization of copper-arsenic mixed concentrate, which is composed of inhibitor A and inhibitor B.

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

[0009] As a further preferred embodiment of the application, the mass ratio of ammonium magnesium chloride to aluminum sulfate in the inhibitor A is 50-70:30-50; and 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 application also provides application of the combined inhibitor in flotation dearsenization of copper-arsenic mixed concentrate.

[0012] The application further provides a method for flotation dearsenization of copper-arsenic mixed concentrate by using the combined inhibitor, which comprises the following steps.

[0013] First, the copper-arsenic mixed concentrate slurry is subjected to ultrasonic coupling mechanical stirring pretreatment, and then subjected to the flotation dearsenization process of roughing, scavenging and cleaning.

[0014] The roughing and cleaning each add, in sequence, a pH adjusting agent, the inhibitor A, the inhibitor B, a combined collector and a frother.

[0015] The scavenging adds, in sequence, the inhibitor A, the inhibitor B and the combined collector.

[0016] The collector is a combined collector composed of ethyldithiurea and ethyl xanthate.

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

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

[0019] As a further preferred embodiment of the present application, the arsenic removal process by flotation adopts a mode of one roughing, three scavenging, and two cleaning; the pH regulator is sodium carbonate; the pH of the ore pulp is adjusted to 7.5-9 by using the pH regulator; the frother is frother 2 # Oil.

[0020] As a further preferred embodiment of the present application, the addition amount of the sodium carbonate is 400-800 g / t, the addition amount of the depressant A is 600-800 g / t, the addition amount of the depressant 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 # Oil is added in an amount of 30-60 g / t.

[0021] As a further preferred embodiment of the present application, the use amounts of the pH regulator, the depressant A, the depressant B, the combined collector, and the frother in the first cleaning are half of those in the roughing, the use amounts of the pH regulator, the depressant A, the depressant B, the combined collector, and the frother in the second cleaning are half of those in the first cleaning, and the middlings are sequentially returned.

[0022] Specifically, the tailings of the first cleaning and the concentrates of the first scavenging are combined and returned to the roughing operation, the tailings of the second cleaning are returned to the first cleaning operation, the concentrates of the second scavenging are returned to the first scavenging operation, and the concentrates of the third scavenging are returned to the second scavenging operation.

[0023] More preferably, after the sodium carbonate, the depressant A, the depressant B, the combined collector of ethyldithiocarbamate and ethyl xanthate, and the frother are added, stirring is performed for 3-6 min, respectively.

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

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

[0026] In the present application, the ultrasonic coupling mechanical stirring pretreatment can effectively oxidize sulfur arsenic copper ore and arsenic chalcocite, and promote the formation of a stable complex anion [AsO4] 3-, which has strong affinity to magnesium and aluminum metal ions. The depressant A in the flotation combination depressant can selectively inhibit arsenian copper minerals such as enargite and tennantite, and has less effect on non-arsenic-containing copper sulfide minerals such as chalcopyrite and chalcocite. The metal ions of magnesium ammonium chloride and aluminum sulfate in the depressant A after dissolution will form hydrophilic compounds with [AsO4] 3- , thereby preventing the adsorption of collectors on the surface of enargite and tennantite. At the same time, Mg 2+ , Al 3+ and NH4 + of the dissolved magnesium ammonium chloride are adsorbed on the surface of enargite and tennantite which is negatively charged through electrostatic interaction, thereby increasing the hydrophilicity of the mineral surface and increasing the difference between the surface active sites of arsenic-containing copper sulfide and non-arsenic-containing copper sulfide. The depressant B in the flotation combination depressant of the present application will further interact with the surface of the arsenic-containing copper sulfide mineral after the action of the depressant A, thereby strengthening the inhibition of the mineral. Since the carboxymethyl chitosan contains -NH2, -COOH and -OH functional groups, and tartaric acid is rich in -COOH and -OH functional groups, they have superior adsorption and chelation capacity on the surface of the arsenic-containing copper sulfide mineral which has adsorbed Mg 2+ , Al 3+ , and form a water film by hydrogen bonding with water molecules, thereby strongly inhibiting the arsenic-containing copper sulfide mineral. Therefore, the combination depressant of the present application creates good conditions for the selective flotation separation of copper and arsenic.

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

[0028] The present application realizes the selective inhibition of arsenic-containing copper sulfide minerals such as enargite and tennantite by ultrasonic coupling mechanical stirring to oxidize the surface of enargite and tennantite, and then by the technology of "multi-component ion passivation and modification-organic compound coupling modification".

[0029] The present application effectively oxidizes the surface of enargite and tennantite by ultrasonic coupling mechanical stirring pretreatment, thereby avoiding the addition of oxidizing chemical reagents.

[0030] The combination depressant of the present application forms a strong hydrophilic film on the surface of arsenic-containing copper sulfide minerals such as enargite and tennantite by the synergistic effect of inorganic and organic compounds, thereby achieving strong inhibition of the minerals.

[0031] The flotation combination depressant of the present application is green and pollution-free to the environment, and the application method is simple and easy for industrial production. The combination collector of ethyl xanthate and ethyl xanthate can efficiently separate non-arsenic-containing copper sulfide, thereby achieving good separation effect of copper and arsenic. BRIEF DESCRIPTION OF DRAWINGS

[0032] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed in the embodiments. Obviously, the drawings in the following description only represent some embodiments of the present application, and for those skilled in the art, other drawings can be obtained based on these drawings without any creative effort.

[0033] Figure 1 The application flow chart for the flotation arsenic removal of the copper-arsenic mixed concentrate of the present application.

[0034] Figure 2 The flow chart for the test study on the single mineral flotation behavior in the embodiment 6 of the present application. DETAILED DESCRIPTION

[0035] The various exemplary embodiments of the present application will now be described in detail, which should not be considered as limiting the present application, but should be understood as a more detailed description of some aspects, characteristics and embodiments of the present application.

[0036] It should be understood that the terms described in the present application are only for describing the specific embodiments, and are not used to limit the present application. In addition, for the numerical range in the present application, it should be understood that each intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. Each smaller range between any stated value or intermediate value in the stated range, and any other stated value or intermediate value in the stated range, is also included in the present application. The upper limit and the lower limit of these smaller ranges can be independently included or excluded from the range.

[0037] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application pertains. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, preferred methods and materials are described. All publications mentioned in the specification are incorporated by reference to disclose and describe the methods and / or materials in connection with which the publications are cited. The citation of any reference in the specification is not an admission that it is prior art with respect to the present application.

[0038] Many modifications and variations of the present application described in the specification are possible without departing from the scope or spirit of the present application, which will be apparent to those skilled in the art. Other implementations of the present application will be apparent to those skilled in the art from consideration of the specification and practice of the present application. The specification and examples of the present application are exemplary only.

[0039] As used herein, the terms "comprise", "comprising", "including", "include", "contain", "containing", "have", "having" or the like are open-ended terms that are intended to mean including, but not limited to.

[0040] Unless otherwise specified, the "parts" in the present application are all mass parts.

[0041] Example 1

[0042] The copper-arsenic mixed concentrate in this example was subjected to flotation arsenic removal, and the Cu content was 19.65%, the As content was 2.86%, the S content was 19.35%, and the Fe content was 9.54%. The phase analysis results showed that the copper minerals mainly existed in the form of chalcopyrite, enargite, and tennantite, and there was a small amount of chalcocite.

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

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

[0045] The copper-arsenic mixed concentrate was subjected to flotation arsenic removal:

[0046] (1) The copper-arsenic mixed concentrate (i.e. the sorted raw ore, the same below) was ground to a content of about 70wt% of-0.038mm ore powder;

[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 600W, frequency of 10kHz, time of 4min, and stirring speed of 800r / min;

[0048] (3) For the pretreated slurry, 400g / t of sodium carbonate (adjusting the pH value of the slurry to 7.5), 600g / t of depressor A (300g / t of ammonium magnesium chloride + 300g / t of aluminum sulfate), 200g / t of depressor B (120g / t of tartaric acid + 80g / t of carboxymethyl chitosan), 60g / t of collector (36g / t of ethyl thiuram sulfide + 24g / t of ethyl xanthate), and 30g / t of frother were added in turn according to the mass of the sorted raw ore, and the stirring and slurry time was 3min, 3min, 3min, 4min, and 3min respectively, then 300g / t of depressor A (150g / t of ammonium magnesium chloride + 150g / t of aluminum sulfate) and 100g / t of depressor B (60g / t of tartaric acid + 40g / t of carboxymethyl chitosan) were added, and the stirring and slurry time was 3min and 3min respectively. # Figure 1 ​The process is carried out for the flotation of copper-arsenic mixed concentrate to remove arsenic, after one roughing, three scavenging and two cleaning (the reagent dosage of cleaning I is half of the corresponding reagent of roughing, and the reagent dosage of cleaning II is half of the corresponding reagent of cleaning I; the reagent system of scavenging III is: depressant A 60 g / t (magnesium ammonium chloride 30 g / t + aluminum sulfate 30 g / t), depressant A 20 g / t (tartaric acid 12 g / t + carboxymethyl chitosan 8 g / t), collector 5 g / t (ethyl thiuram sulfide 3 g / t + ethyl xanthate 2 g / t), and the middlings are returned in sequence), the froth product of flotation is low-arsenic copper concentrate (mainly containing chalcopyrite), and the product at the bottom of the flotation cell is high-arsenic copper concentrate (mainly containing sulfide arsenic copper and arsenic tetrahedrite). The test results are shown in Table 1.

[0049] Comparative Example 1

[0050] The other conditions are consistent with those of Example 1, except that tartaric acid and carboxymethyl chitosan are used to replace depressant A in an equal amount at a mass ratio of 1.5:1, i.e., no depressant A (magnesium ammonium chloride and aluminum sulfate) is added, to analyze the effect of single depressant B. The test results are shown in Table 1.

[0051] Comparative Example 2

[0052] The other conditions are consistent with those of Example 1, except that magnesium ammonium chloride and aluminum sulfate are used to replace depressant B in an equal amount at a mass ratio of 1:1, i.e., no depressant B (tartaric acid and carboxymethyl chitosan) is added, to analyze the effect of single depressant A. The test results are shown in Table 1.

[0053] Comparative Example 3

[0054] The other conditions are consistent with those of Example 1, except that no ultrasonic coupling mechanical stirring pretreatment of copper-arsenic mixed concentrate slurry is performed. The test results are shown in Table 1.

[0055] Example 2

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

[0057] Example 3

[0058] The other conditions are consistent with Example 1, except that the magnesium ammonium chloride in the inhibitor A is 70 parts (the amount is increased from 300 g / t to 420 g / t) and the aluminum sulfate is 30 parts (the amount is decreased from 300 g / t to 180 g / t), the effect of the mass ratio of magnesium ammonium chloride to aluminum sulfate is analyzed from 50:50 to 70:30, and 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 for flotation arsenic removal in this example, 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, enargite, and tenorite.

[0063] In the combined inhibitor for flotation arsenic removal of the copper-arsenic mixed concentrate in this example, the inhibitor is a mixture of magnesium ammonium chloride (60 parts) and aluminum sulfate (40 parts); and 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 ethyl thiuram sulfide (80 parts) and ethyl xanthate (20 parts).

[0065] Flotation arsenic removal is carried out on the copper-arsenic mixed concentrate:

[0066] (1) The copper-arsenic mixed concentrate (i.e. the sorted raw ore, the same below) is ground to a content of about 80 wt% of -0.038 mm ore powder;

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

[0068] (3) For the pretreated slurry, according to the mass of the sorted raw ore, sodium carbonate 600 g / t (adjusting the pH value of the slurry to 8.5), inhibitor A 700 g / t (magnesium ammonium chloride 420 g / t + aluminum sulfate 280 g / t), inhibitor B 300 g / t (tartaric acid 210 g / t + carboxymethyl chitosan 90 g / t), collector 80 g / t (ethyl thiuram sulfide 56 g / t + ethyl xanthate 24 g / t), and frother 2 # oil 50 g / t are sequentially added, and the stirring and slurry time is 5 min, 4 min, 4 min, 4 min, and 4 min, respectively, then, according to the mass of the sorted raw ore, sodium carbonate 600 g / t (adjusting the pH value of the slurry to 8.5), inhibitor A 700 g / t (magnesium ammonium chloride 420 g / t + aluminum sulfate 280 g / t), inhibitor B 300 g / t (tartaric acid 210 g / t + carboxymethyl chitosan 90 g / t), collector 80 g / t (ethyl thiuram sulfide 56 g / t + ethyl xanthate 24 g / t), and frother 2 Figure 1The process is carried out for copper-arsenic mixed concentrate flotation to remove arsenic, after one roughing, three times of scavenging and two times of cleaning (the reagent dosage of cleaning I is half of the corresponding reagent of roughing, the reagent dosage of cleaning II is half of the corresponding reagent of cleaning I; the reagent system of scavenging III is: inhibitor A 70 g / t (magnesium ammonium chloride 42 g / t + aluminum sulfate 28 g / t), inhibitor A 30 g / t (tartaric acid 21 g / t + carboxymethyl chitosan 9 g / t), collector 8 g / t (ethyl thiuram sulfide 5.5 g / t + ethyl xanthate 2.5 g / t), and the middlings are returned in sequence), the froth product of flotation is low-arsenic copper concentrate (mainly containing chalcopyrite), and the product at the bottom of the flotation cell is high-arsenic copper concentrate (mainly containing sulfide arsenic copper ore and arsenic tetrahedrite), and 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 an equal amount at a mass ratio of 7:3, i.e., no inhibitor A (magnesium ammonium chloride and aluminum sulfate) is added, to analyze the effect of single inhibitor B, and 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 magnesium ammonium chloride and aluminum sulfate are used to replace inhibitor B in an equal amount at a mass ratio of 3:2, i.e., no inhibitor B (tartaric acid and carboxymethyl chitosan) is added, to analyze the effect of single inhibitor A, and the test results are shown in Table 2.

[0073] Comparative Example 6

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

[0077] Comparative Example 8

[0078] The other conditions are consistent with those of Example 4, except that the amount of carboxymethyl chitosan is replaced by an equal amount of tartaric acid, i.e., no carboxymethyl chitosan is added, to analyze the effect of carboxymethyl chitosan in inhibitor B, and the test results are shown in Table 2.

[0079] Comparative Example 9

[0080] The other conditions are consistent with those of Example 4, except that carboxymethyl chitosan is used to replace the same amount of tartaric acid, i.e. no tartaric acid is added, 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 this example, the Cu content of the copper-arsenic mixed concentrate for flotation and arsenic removal 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 mainly exist in the form of chalcopyrite and enargite; the gangue minerals mainly include serpentine and talc.

[0085] In the combined inhibitor for flotation and arsenic removal of the copper-arsenic mixed concentrate of this example, inhibitor A is a mixture of magnesium ammonium 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 ethyl thiuram sulfide (70 parts) and ethyl xanthate (30 parts).

[0087] The copper-arsenic mixed concentrate is subjected to flotation and arsenic removal:

[0088] (1) The copper-arsenic mixed concentrate (i.e. the sorted raw ore, the same below) is ground to a content of -0.038 mm ore powder of about 85 wt%;

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

[0090] (3) For the pretreated slurry, sodium carbonate 800 g / t (to adjust the pH value of the slurry to 9), inhibitor A 800 g / t (magnesium ammonium chloride 480 g / t + aluminum sulfate 320 g / t), inhibitor B 400 g / t (tartaric acid 280 g / t + carboxymethyl chitosan 120 g / t), collector 80 g / t (ethyl thiuram sulfide 56 g / t + ethyl xanthate 24 g / t), and frother 2 # oil 60 g / t are sequentially added in an amount of 800 g / t of the sorted raw ore, and the stirring and slurry mixing time is 6 min, 6 min, 6 min, 6 min, and 6 min, respectively, and then, the frother 2 Figure 1The process is carried out for copper-arsenic mixed concentrate flotation to remove arsenic, after one roughing, three scavenging and two cleaning (the reagent dosage of cleaning I is half of the corresponding reagent of roughing, and the reagent dosage of cleaning II is half of the corresponding reagent of cleaning I; the reagent system of scavenging III is: depressant A 80 g / t (magnesium ammonium chloride 48 g / t + aluminum sulfate 32 g / t), depressant A 30 g / t (tartaric acid 21 g / t + carboxymethyl chitosan 9 g / t), collector 8 g / t (ethyl thiuram sulfide 5.5 g / t + ethyl xanthate 2.5 g / t), and the middlings are returned in sequence), the froth product of flotation is low-arsenic copper concentrate (mainly containing chalcopyrite), and the product at the bottom of the flotation cell is high-arsenic copper concentrate (mainly containing sulfide arsenic copper and arsenic tetrahedrite). The test results are shown in Table 3.

[0091] Comparative Example 10

[0092] The other conditions are consistent with Example 5, except that no ultrasonic coupling mechanical stirring pretreatment is carried out on the copper-arsenic mixed concentrate slurry, and the test results are shown in Table 3.

[0093] Comparative Example 11

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

[0095] Comparative Example 12

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

[0097] Table 3: Flotation test results / %

[0098]

[0099]

[0100] As can be seen from the above, the combination of inhibitor A (magnesium ammonium chloride and aluminum sulfate) and inhibitor B (tartaric acid and carboxymethyl chitosan) has a strong positive synergistic effect, and the combination of ultrasonic coupling mechanical stirring pretreatment and the combination of inhibitors further improves the effect of copper-arsenic separation. The copper-arsenic mixed concentrate is sequentially subjected to ultrasonic coupling mechanical stirring pretreatment, the combined action of inhibitor A and inhibitor B, and then the arsenic-containing copper sulfide minerals (dacite, arsenic) are selectively inhibited. On this basis, the combination of ethion and ethyl xanthate collectors realizes the effective removal of arsenic in the copper-arsenic mixed concentrate. Compared with the results of the combination 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) is used alone (other conditions are the same), 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 Example 2 and Comparative Example 5 show that: when inhibitor A (magnesium ammonium chloride and aluminum sulfate) is used alone (other conditions are the same), 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 one single component of inhibitor A or inhibitor B is not used (Comparative Examples 6-9), the arsenic removal effect decreases significantly. The results of Example 2 and Example 3 show that: within the recommended mass ratio range of the inhibitor components (i.e. the mass ratio of magnesium ammonium 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), the mass ratio of magnesium ammonium chloride and aluminum sulfate, tartaric acid and carboxymethyl chitosan is changed, the arsenic content of the low-arsenic copper concentrate changes little (all less than 0.3%), and a good flotation index can still be obtained, but the results of Comparative Example 11 and Comparative Example 12 show that: when the mass ratio of inhibitor A to inhibitor B is reduced to 1:1 or increased to 5:1, the arsenic removal effect decreases. The results of Comparative Example 3 and Comparative Example 10 show that: the ultrasonic coupling mechanical stirring pretreatment plays an obvious positive role in the flotation arsenic removal of copper-arsenic mixed concentrate. Without this pretreatment, the arsenic content of the low-arsenic copper concentrate increases from 0.26% (Example 1) and 0.27% (Example 5) to 0.95% and 1.95%, and the copper grade decreases by about 1%. The results of Examples 1-5 confirm that the present application has good adaptability for the flotation arsenic removal of copper-arsenic mixed concentrate.

[0101] Example 6

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

[0103] Table 4 shows that under the combined action of ultrasonic coupling mechanical stirring pretreatment, inhibitor A and inhibitor B, tennantite and arsenian tetrahedrite are strongly inhibited, while chalcopyrite and digentle still maintain good floatability, after the addition of the collector, the difference between the flotation recovery rates of chalcopyrite and tennantite and arsenian tetrahedrite reaches 89.2% and 88% respectively, and the difference between the flotation recovery rates of digentle and tennantite and arsenian tetrahedrite reaches 89.7% and 85.5% respectively, which indicates that ultrasonic coupling mechanical stirring pretreatment and the use of the above-mentioned combined inhibitors can selectively inhibit arsenic-containing copper sulfide minerals. The single mineral flotation test research results of chalcopyrite / digentle and tennantite / arsenian tetrahedrite provide important technical support for the present application.

[0104]

[0105] Table 4 shows that under the combined action of ultrasonic coupling mechanical stirring pretreatment, inhibitor A and inhibitor B, tennantite and arsenian tetrahedrite are strongly inhibited, while chalcopyrite and digentle still maintain good floatability, after the addition of the collector, the difference between the flotation recovery rates of chalcopyrite and tennantite and arsenian tetrahedrite reaches 89.2% and 88% respectively, and the difference between the flotation recovery rates of digentle and tennantite and arsenian tetrahedrite reaches 89.7% and 85.5% respectively, which indicates that ultrasonic coupling mechanical stirring pretreatment and the use of the above-mentioned combined inhibitors can selectively inhibit arsenic-containing copper sulfide minerals. The single mineral flotation test research results of chalcopyrite / digentle and tennantite / arsenian tetrahedrite provide important technical support for the present application.

[0106] The above-described embodiments are only used to describe the preferred modes of the present application, and do not limit the scope of the present application, and various modifications and improvements to the technical solutions of the present application made by those skilled in the art without departing from the design spirit of the present application shall fall within the protection scope determined by the claims of the present application.

Claims

1. A combined depressant for flotation arsenic removal in 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 depressant 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 according to 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: First, 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 foaming agent are added in sequence in the roughing and cleaning respectively; The inhibitor A, the inhibitor B and the combined collector are sequentially added in the scanning; 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 of the pulp is adjusted to 7.5-9 by using the pH adjuster.

7. The method according to claim 6, characterized in that During the roughing, based on the copper-arsenic mixed concentrate, 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 foaming agent 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 foaming agent 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 accounts for 80-90 wt %.

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