A flotation method for arsenic-containing copper sulfide ore

Abstract

The present invention relates to the field of mineral processing technology, and more specifically to a flotation method for arsenic-containing copper sulfide ore, comprising: first, coarsely grinding the raw ore, and adopting a process of "one roughing, two scavenging, and two concentrating" to suppress sulfur-copper-arsenic mixed selection at low alkalinity to obtain a copper-arsenic mixed concentrate and tailings; then, concentrating and re-grinding the copper-arsenic mixed concentrate to remove the drug, and adopting a "one roughing, two scavenging, and two concentrating" process to enhance copper-arsenic separation through slurry adjustment, coupled regulation of a combined inhibitor, and collection with a collector, thereby achieving efficient sorting of arsenic-containing copper sulfide ore. The present invention uses a combined inhibitor to effectively regulate the surface of the arsenic-containing mineral. The combined inhibitor achieves selective inhibition of arsenic-containing sulfide minerals such as arsenic-containing copper sulfide ore, tetrahedrite, and arsenopyrite through the technology of "oxidative modification-metal ion modification-organic compound coupling modification."

Description

Technical Field

[0001] The present invention relates to the technical field of mineral processing, and in particular to a flotation method for arsenic-containing copper sulfide ore. Background Art

[0002] Copper is an important nonferrous metal widely used in the electrical, light industry, machinery manufacturing, construction, and defense industries. Copper raw materials are primarily obtained through the separation and enrichment of copper sulfide ores. The main copper-bearing minerals in copper sulfide ores include chalcopyrite, chalcocite, bornite, and covellite, along with associated pyrite. Arsenic-containing minerals include arsenopyrite, rhombohedrite, arsenicite, and tetrahedrite. These minerals often coexist closely with copper minerals, sharing physical and chemical properties similar to those of copper minerals. Conventional mineral processing reagent systems and methods can lead to the simultaneous enrichment of arsenic-bearing minerals, pyrite, and copper minerals, resulting in excessive arsenic content in copper concentrates. During the smelting process, arsenic in high-arsenic copper concentrates is converted into arsenic trioxide, arsine, arsenites, and organic arsenic compounds, which can corrode equipment and pollute the environment.

[0003] Flotation is the most commonly used technology for separating arsenic-containing copper sulfide ores. Effectively suppressing pyrite and selectively separating copper and arsenic sulfide minerals are key to processing these ores. Currently, the lime-alkaline process is an effective method for suppressing pyrite. This process involves adding large amounts of lime to strongly suppress pyrite at a slurry pH typically above 11. While this method is well-established and can achieve ideal separation results, it suffers from drawbacks such as high lime usage, prone to scaling of equipment and pipelines, hindering precious metal recovery, and potentially polluting the environment with alkaline beneficiation wastewater. Furthermore, flotation separation of copper sulfide minerals (such as chalcopyrite, chalcocite, bornite, and covellite) from arsenopyrite, arsenite, and chalcopyrite is more difficult. This is because these minerals have similar surface properties and good natural floatability, resulting in poor selectivity for these minerals in mineral processing agents. Furthermore, arsenite and chalcopyrite are copper-containing minerals that are difficult to suppress and will enter the concentrate, ultimately resulting in excessive arsenic levels in the copper concentrate. Intensified mineral suppression can lead to copper resource loss. Therefore, the research and development of flotation separation technology for arsenic-containing copper sulfide ores has important practical significance for improving product quality and efficient comprehensive utilization of mineral resources.

[0004] The processing of arsenic-containing copper sulfide ore resources is a hot topic in the field of mineral processing. Chinese patent document CN201810916019.9 discloses "a method for removing arsenic from copper ore". Through stage grinding-stage sorting, under high lime alkalinity (pulp pH = 10-12), a combination of ammonium chloride, aluminum sulfate, sodium thiosulfate or a combination of sodium thiosulfate, tannin extract, and calcium hypochlorite is used to inhibit arsenic-containing sulfide minerals, thereby achieving separation and enrichment of copper sulfide ore and arsenic-containing sulfide minerals. This method has a strong inhibitory effect on arsenopyrite, but the inhibitory effect on arsenic-containing copper sulfide ores (arsenic copper sulfide, arsenic tetrahedrite) is still unclear. In addition, since this method adopts a process of suppressing arsenic and preferentially flotating copper sulfide ores, it is easy to cause the loss of arsenic-containing copper sulfide ores in tailings. Chinese patent document CN201010229759.9 discloses "collectors and treatment methods for mineral processing of arsenic-containing copper ores". Using a mixture of isopropyl ethylthiocarbamate and kerosene as a collector, a process involving grinding, copper roughing, copper concentrating, arsenic roughing, arsenic concentrating, and arsenic scavenging yields low-arsenic copper concentrate and high-arsenic copper concentrate, respectively. This method concentrates the majority of copper minerals in the low-arsenic copper concentrate and a smaller portion in the high-arsenic copper concentrate. Because this method does not account for the inhibitory effect of tetrahedrite, the arsenic content in the low-arsenic copper concentrate easily exceeds the permitted limit. Chinese patent document CN201410352506.9 discloses a "method for extracting copper concentrate from copper ores with high sulfur and arsenic content." This method first suppresses pyrite, preferentially flots copper minerals in stages, and then utilizes a regrinding deoxidation process, using lime and calcium hypochlorite to prepare a slurry, followed by potassium permanganate to preferentially oxidize arsenic-free copper sulfide minerals, thereby selectively removing the arsenic-containing copper sulfide minerals from the copper concentrate. This method has the disadvantages of requiring a large amount of oxidant (calcium hypochlorite, potassium permanganate) and being susceptible to oxidation inhibition of arsenic-containing copper sulfide ores. Based on the above status quo, the separation process and technology of arsenic-containing copper sulfide ores need to be improved. Summary of the Invention

[0005] The object of the present invention is to provide a flotation method for arsenic-containing copper sulfide ore, which is achieved through the technical route of "low alkalinity sulfur inhibition - copper-arsenic mixed selection - concentrate concentration and re-grinding and drug removal - combined inhibitor coupling regulation - copper-arsenic 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 flotation method for arsenic-containing copper sulfide ore comprises: first, coarsely grinding the raw ore, adopting the process of "one roughing, two scavenging and two concentrating" to carry out sulfur-inhibiting-copper-arsenic mixed selection at low alkalinity to obtain copper-arsenic mixed concentrate and tailings; then, concentrating the copper-arsenic mixed concentrate, regrinding and removing the drug, and adopting the process of "one roughing, two scavenging and two concentrating" to strengthen the copper-arsenic separation through slurry adjustment, coupled regulation of combined inhibitors and collection with collectors, thereby realizing efficient separation of arsenic-containing copper sulfide ore.

[0008] Furthermore, the method specifically includes the following steps:

[0009] S1: adding lime to the ball mill to coarsely grind the arsenic-containing copper sulfide ore, sequentially adding pyrite inhibitor, composite collector and frother to the coarsely ground material, and performing sulfur inhibition-copper-arsenic mixed selection (roughing) to obtain roughing concentrate and roughing tailings;

[0010] S2: adding lime, pyrite inhibitor, composite collector and frother to the roughing tailings obtained in step S1 in sequence, and performing sulfur suppression-copper-arsenic mixed selection (scavenging I) to obtain scavenging I concentrate and scavenging I tailings, wherein the scavenging I concentrate is returned to the sulfur suppression-copper-arsenic mixed selection (roughing) operation;

[0011] S3: adding lime, pyrite depressant, composite collector and frother to the scavenging I tailings obtained in step S2 in sequence, and performing sulfur suppression and copper-arsenic mixed selection (scavenging II) to obtain scavenging II concentrate and scavenging II tailings, wherein the scavenging II concentrate is returned to the sulfur suppression and copper-arsenic mixed selection (scavenging I) operation;

[0012] S4: The coarse concentrate obtained in step S1 is subjected to two rounds of beneficiation to obtain a copper-arsenic mixed concentrate. The tailings from beneficiation I are returned to the roughing operation, and the tailings from beneficiation II are returned to the beneficiation I operation;

[0013] S5: Concentrating the copper-arsenic mixed concentrate obtained in step S4, adding activated carbon in a ball mill, and re-grinding and removing the drug;

[0014] S6: Sodium hydroxide, inhibitor A, inhibitor B, a collector, and a foaming agent are sequentially added to the material ore obtained in step S5 to perform rough separation of copper and arsenic to obtain a roughing concentrate and a roughing tailing;

[0015] S7: adding inhibitor A, inhibitor B, a collector, and a frother in sequence to the copper-arsenic separation rougher concentrate obtained in step S6 to perform copper-arsenic separation and concentration I, thereby obtaining a concentrated I concentrate and concentrated tailings;

[0016] S8: To the copper-arsenic separation scavenging I tailings obtained in step S6, inhibitor A, inhibitor B, collector and frother are added in sequence to carry out copper-arsenic separation scavenging II to obtain scavenging II concentrate and scavenging II tailings (i.e., high-arsenic copper concentrate), wherein the copper-arsenic separation scavenging II concentrate is returned to the copper-arsenic separation scavenging I operation.

[0017] S9: adding inhibitor A, inhibitor B, collector and frother in sequence to the copper-arsenic separation and concentration I concentrate obtained in step S7 to perform copper-arsenic separation and concentration II to obtain concentrated II concentrate (i.e., low-arsenic copper concentrate) and concentrated II tailings, wherein the copper-arsenic separation and concentration II tailings are returned to the copper-arsenic separation and concentration I operation;

[0018] S10: adding a collector to the copper-arsenic separation roughing tailings obtained in step S6, and performing copper-arsenic separation scavenging I to obtain copper-arsenic separation scavenging I concentrate and scavenging I tailings, wherein the scavenging I concentrate and the scavenging I tailings are combined and returned to the copper-arsenic separation roughing operation;

[0019] S11: Add a collector to the scavenging I tailings obtained in step S9 to perform copper-arsenic separation scavenging II to obtain scavenging II concentrate and scavenging II tailings (i.e., high-arsenic copper concentrate), wherein the scavenging II concentrate is returned to the copper-arsenic separation scavenging I operation.

[0020] Furthermore, in step S1, the amount of lime added to the ball mill is 400-800 g / t (calculated based on the raw ore); the coarse grinding is that the fineness of the material discharged from the ball mill is -0.074 mm, accounting for 60-65%, and the pH value of the slurry is 8.5-9.5.

[0021] Furthermore, in steps S1 to S3, the pyrite inhibitor is dextrin, the composite collector is ethiocarbamate and butyl xanthate, and the foaming agent is pine oil.

[0022] Furthermore, in steps S1 to S3, the amounts of dextrin used (calculated based on the original ore) are 40 to 80 g / t, 20 to 40 g / t, and 10 to 20 g / t, respectively; the amounts of ethionamide and butyl xanthate used (calculated based on the original ore) are (6 to 12 g / t, 8 to 20 g / t), (3 to 6 g / t, 4 to 10 g / t), and (1.5 to 3 g / t, 2 to 5 g / t), respectively; and the amount of pine oil used (calculated based on the original ore) is 10 to 20 g / t, 5 to 10 g / t, and 2.5 to 10 g / t.

[0023] Furthermore, the amounts of lime used in steps S2 and S3 (calculated based on the raw ore) are 200-400 g / t and 100-200 g / t, respectively.

[0024] Furthermore, in step S5, the concentration is such that the concentration of the concentrated pulp is 50-70%; the amount of activated carbon added (calculated based on the amount of copper-arsenic mixed coarse concentrate, the same below) is 400-500 g / t; and the regrinding is such that the fineness of the material discharged from the ball mill is -0.038 mm, accounting for 80-90%.

[0025] Furthermore, in steps S6 to S8, the inhibitor A is a mixture of calcium hypochlorite and magnesium chloride, the inhibitor B is a mixture of sodium alginate and polyaspartic acid; the collector is ethionamide, and the foaming agent is pine oil.

[0026] Furthermore, the amounts of calcium hypochlorite and magnesium chloride in steps S6, S7 and S8 are (800-1200 g / t, 300-600 g / t), (400-600 g / t, 150-300 g / t) and (200-400 g / t, 75-150 g / t), respectively; the amounts of sodium alginate and polyaspartic acid are (200-400 g / t, 100-300 g / t), (100-200 g / t, 50-150 g / t) and (50-100 g / t, 25-75 g / t); the amounts of ethionamide used are (6-12 g / t), (3-6 g / t) and (1.5-3 g / t) respectively; the amounts of pine oil used are 10-20 g / t, 5-10 g / t and 2.5-5 g / t; the amount of sodium hydroxide used in step S6 is 600-800 g / t.

[0027] Furthermore, in steps S9 and S10, the collector is ethionamide, and the addition amounts are 4-8 g / t and 2-4 g / t, respectively.

[0028] Beneficial effects of the present invention:

[0029] In existing technologies, flotation processes typically employ a single roughing and concentrating process. However, the present invention utilizes a "low-alkalinity sulfur suppression - copper-arsenic co-selection - concentrate concentration and re-grinding to remove the reagent - copper-arsenic separation" technical approach. Compared with traditional lime-high-alkalinity processes, the pyrite suppression effect remains significant under low-alkalinity conditions, while significantly reducing lime usage. Co-selection of copper and arsenic allows for the mixed enrichment of copper and arsenic minerals during the roughing stage, preventing the loss of arsenic-containing minerals and facilitating subsequent separation. Concentration of the concentrate and re-grinding to remove the reagent improves the concentrate grade, creating optimal conditions for subsequent copper-arsenic separation.

[0030] This invention uses lime and dextrin as a combined pyrite inhibitor, achieving selective pyrite inhibition at low alkalinity (pH 8.5-9.5). Dextrin is rich in hydroxyl functional groups, which effectively adsorb on the pyrite surface. Its combination with lime significantly enhances the hydrophilicity of the pyrite surface. Compared with traditional high-alkalinity pyrite inhibition processes using lime, the amount of lime used is significantly reduced, overcoming scaling issues in mineral processing equipment and pipelines.

[0031] The present invention adopts a combined inhibitor to effectively regulate the surface of arsenic-containing minerals. The combined inhibitor achieves selective inhibition of arsenic-containing sulfide minerals such as arsenic sulfide, chalcopyrite, and arsenopyrite through the technology of "oxidation modification-metal ion modification-organic compound coupling modification".

[0032] The calcium hypochlorite in the inhibitor A of the present invention can effectively oxidize arsenic sulfide minerals such as arsenic copper ore, arsenic tetrahedrite and arsenopyrite, and promote the formation of a stable complex anion [AsO4] on the surface of the mineral. 3-, improve the hydrophilicity of the mineral surface; the calcium and magnesium metal ions after the calcium hypochlorite and magnesium chloride in inhibitor A are dissolved will react with [AsO4] 3- Hydrophilic compounds are formed, thereby preventing the adsorption of collectors on the surface of arsenic-containing sulfide minerals. At the same time, calcium and magnesium metal ions are adsorbed on the surface of negatively charged arsenic-containing sulfide minerals through electrostatic action, achieving metal ion modification of the mineral surface and increasing the difference in surface active particles between arsenic-containing sulfide minerals and copper sulfide minerals. Inhibitor B of the present invention will further interact with the surface of arsenic-containing sulfide minerals after the action of inhibitor A, thereby strengthening the inhibition of the mineral. Sodium alginate and polyaspartic acid molecules contain -COOH and -OH functional groups, which have excellent adsorption capacity for the surface of arsenic-containing sulfide minerals that have adsorbed calcium and magnesium metal ions. At the same time, polyaspartic acid molecules contain -NH2, which has a strong chelating ability for As sites on the mineral surface. Inhibitor B has a strong inhibitory effect on arsenic-containing sulfide minerals through coupling modification with organic compounds. Therefore, the combined inhibition of the present invention creates good conditions for the selective flotation separation of copper and arsenic.

[0033] The combined inhibitor of the present invention is green and pollution-free to the environment, has a simple application method, and is easy to industrially produce. The ethionocarbamate collector can efficiently separate non-arsenic copper sulfide, achieving a good copper and arsenic separation effect.

[0034] Laboratory experiments and industrial-scale trials have demonstrated that the method of the present invention effectively suppresses pyrite production under low-alkalinity conditions, achieving ideal concentrate grade and recovery rates for copper-arsenic separation. The low-arsenic copper concentrate obtained by the present invention has a copper grade exceeding 27% and an arsenic content below 0.5%. The high-arsenic copper concentrate has an arsenic content exceeding 11%, and a total copper recovery rate exceeding 93%, achieving efficient recovery of copper and arsenic resources. Subsequently, the low-arsenic and high-arsenic copper concentrates can be processed separately, reducing production costs and promoting copper concentrate sales.

[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 following briefly introduces the drawings required for describing the embodiments. 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 creative work.

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

[0038] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. 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 making any creative efforts shall fall within the scope of protection of the present invention.

[0039] Example 1

[0040] A copper ore contains 0.8% Cu, 0.18% As, and 9.23% S. The copper minerals in the ore are primarily chalcopyrite, the arsenic primarily as thioarsenite and arsenopyrite, and the sulfur primarily as pyrite. The gangue minerals primarily include calcite, quartz, and feldspar.

[0041] A flotation method for arsenic-containing copper sulfide ore comprises the following steps:

[0042] S1: 400g / t of lime was added to a ball mill. After coarse grinding of arsenic-containing copper sulfide ore, the fineness of the material discharged from the ball mill was -0.074mm, accounting for 60%, and the pH value of the slurry was 8.5. 40g / t of dextrin, 6g / t of ethiocarbamate, 8g / t of butyl xanthate, and 10g / t of pine oil were added to the coarsely ground material in sequence, with a dosing interval of 3 minutes. After stirring for 3 minutes, aeration and flotation were performed to obtain a sulfur-inhibited, copper-arsenic mixed rougher concentrate and rougher tailings.

[0043] S2: To the roughing tailings obtained in step S1, 200 g / t of lime, 20 g / t of dextrin, 3 g / t of ethionyl carbamate, 4 g / t of butyl xanthate, and 5 g / t of pine oil were added in sequence, with a dosing interval of 3 minutes. After stirring for 3 minutes, aeration flotation was performed to obtain a sulfur-copper-arsenic mixed selection scavenging I concentrate and a scavenging I tailings, wherein the scavenging I concentrate was returned to the sulfur-copper-arsenic mixed selection (roughing) operation;

[0044] S3: To the scavenging I tailings obtained in step S2, 100 g / t of lime, 10 g / t of dextrin, 1.5 g / t of ethionamide, 2 g / t of butyl xanthate, and 2.5 g / t of pine oil are added in sequence, with an addition interval of 3 minutes. After stirring for 3 minutes, aeration flotation is performed to obtain a sulfur-inhibiting, copper-arsenic mixed scavenging II concentrate and scavenging II tailings, wherein the scavenging II concentrate is returned to the sulfur-inhibiting, copper-arsenic mixed scavenging I operation;

[0045] S4: The coarse concentrate obtained in step S1 is subjected to two rounds of beneficiation to obtain a copper-arsenic mixed concentrate. The tailings from beneficiation I are returned to the roughing operation, and the tailings from beneficiation II are returned to the beneficiation I operation;

[0046] S5: The copper-arsenic mixed concentrate obtained in step S4 is concentrated. The concentration of the concentrated pulp is 50%. 400 g / t of activated carbon is added to the ball mill for regrinding and drug removal. The fineness of the material discharged from the ball mill after regrinding is -0.038 mm, accounting for 80%;

[0047] S6: 600 g / t of sodium hydroxide, 1100 g / t of inhibitor A (800 g / t of calcium hypochlorite, 300 g / t of magnesium chloride), 300 g / t of inhibitor B (200 g / t of sodium alginate, 100 g / t of polyaspartic acid), 6 g / t of ethionamide, and 10 g / t of pine oil were added to the material ore obtained in step S5 in sequence, with an addition interval of 3 minutes. After stirring for 3 minutes, aeration flotation was performed to obtain a copper-arsenic separation rougher concentrate and rougher tailings;

[0048] S7: To the copper-arsenic separation rougher concentrate obtained in step S6, 550 g / t of inhibitor A (400 g / t of calcium hypochlorite, 150 g / t of magnesium chloride), 150 g / t of inhibitor B (100 g / t of sodium alginate, 50 g / t of polyaspartic acid), 3 g / t of ethionamide, and 5 g / t of pine oil were added in sequence, with an addition interval of 3 minutes. After stirring for 3 minutes, aeration flotation was performed to obtain a copper-arsenic separation and selected I concentrate and selected I tailings;

[0049] S8: To the copper-arsenic separation and beneficiation I concentrate obtained in step S7, 275 g / t of inhibitor A (200 g / t of calcium hypochlorite, 75 g / t of magnesium chloride), 75 g / t of inhibitor B (50 g / t of sodium alginate, 25 g / t of polyaspartic acid), 1.5 g / t of ethionine, and 2.5 g / t of pine oil were added in sequence, with an addition interval of 3 minutes. After stirring for 3 minutes, aeration flotation was performed to obtain a beneficiation II concentrate (i.e., a low-arsenic copper concentrate) and beneficiation II tailings, wherein the copper-arsenic separation and beneficiation II tailings were returned to the copper-arsenic separation and beneficiation I operation.

[0050] S9: Add 4 g / t of ethoxycarbonyl thiocarbamate to the copper-arsenic separation roughing tailings obtained in step S6, stir for 3 minutes, and then aerate and float to obtain a copper-arsenic separation scavenging I concentrate and scavenging I tailings, wherein the scavenging I concentrate and the scavenging I tailings are combined and returned to the copper-arsenic separation roughing operation;

[0051] S10: 2 g / t of ethionamide was added to the scavenging I tailings obtained in step S9, stirred for 3 minutes, and then subjected to aeration flotation to obtain scavenging II concentrate and scavenging II tailings (i.e., high-arsenic copper concentrate). The scavenging II concentrate was returned to the copper-arsenic separation scavenging I operation. The test results are shown in Table 1.

[0052] Comparative Example 1

[0053] Other conditions were consistent with those in Example 1, except that no dextrin was added to the sulfur-copper-arsenic mixed flotation, and the effect of single lime was analyzed. The test results are shown in Table 1.

[0054] Comparative Example 2

[0055] All other conditions were consistent with those of Example 1, except that the amount of lime was increased to replace dextrin in the sulfur-copper-arsenic mixed flotation, the amount of lime added to the mill was increased by 1200 g / t (pH ~ 11.5), and the amounts of lime used in scavenging I and scavenging II were 600 g / t and 300 g / t, respectively. The effect of single lime was analyzed, and the test results are shown in Table 1.

[0056] Comparative Example 3

[0057] Other conditions were consistent with those in Example 1, except that calcium hypochlorite and magnesium chloride were used in equal amounts in a mass ratio of 8:3 to replace inhibitor B, i.e., inhibitor B (sodium alginate and polyaspartic acid) was not added. The effect of single inhibitor A was analyzed. The test results are shown in Table 1.

[0058] Comparative Example 4

[0059] Other conditions were consistent with those in Example 1, except that sodium alginate and polyaspartic acid were used in equal amounts in a mass ratio of 2:1 to replace inhibitor A, i.e., inhibitor A (calcium hypochlorite and magnesium chloride) was not added. The effect of a single inhibitor B was analyzed, and the test results are shown in Table 1.

[0060] Table 1 Flotation test results / %

[0061]

[0062]

[0063] Example 2

[0064] The copper ore used in this example contains 1.2% Cu, 0.35% As, and 12.63% S. The copper minerals in the ore are primarily present as chalcopyrite, the arsenic is primarily present as chalcopyrite and chalcopyrite, and the sulfur is primarily present as pyrite. The gangue minerals primarily include calcite, quartz, feldspar, and chlorite.

[0065] A flotation method for arsenic-containing copper sulfide ore comprises the following steps:

[0066] S1: 600g / t of lime was added to a ball mill. After coarse grinding of arsenic-containing copper sulfide ore, the fineness of the material discharged from the ball mill was -0.074mm, accounting for 65%, and the pH value of the slurry was 9. 60g / t of dextrin, 10g / t of ethiocarbamate, 16g / t of butyl xanthate, and 16g / t of pine oil were added to the coarsely ground material in sequence, with a dosing interval of 4 minutes. After stirring for 4 minutes, aeration and flotation were performed to obtain a sulfur-inhibited, copper-arsenic mixed rougher concentrate and rougher tailings.

[0067] S2: To the roughing tailings obtained in step S1, 300 g / t of lime, 30 g / t of dextrin, 5 g / t of ethionyl carbamate, 8 g / t of butyl xanthate, and 8 g / t of pine oil were added in sequence, with a dosing interval of 4 minutes. After stirring for 4 minutes, aeration flotation was performed to obtain a sulfur-copper-arsenic mixed selection scavenging I concentrate and a scavenging I tailings, wherein the scavenging I concentrate was returned to the sulfur-copper-arsenic mixed selection (roughing) operation;

[0068] S3: To the scavenging I tailings obtained in step S2, 150 g / t of lime, 15 g / t of dextrin, 2.5 g / t of ethionyl carbamate, 4 g / t of butyl xanthate, and 4 g / t of pine oil are added in sequence, with a dosing interval of 4 minutes. After stirring for 4 minutes, aeration flotation is performed to obtain a sulfur-copper-arsenic mixed scavenging II concentrate and scavenging II tailings, wherein the scavenging II concentrate is returned to the sulfur-copper-arsenic mixed scavenging I operation;

[0069] S4: The coarse concentrate obtained in step S1 is subjected to two rounds of beneficiation to obtain a copper-arsenic mixed concentrate. The tailings from beneficiation I are returned to the roughing operation, and the tailings from beneficiation II are returned to the beneficiation I operation;

[0070] S5: The copper-arsenic mixed concentrate obtained in step S4 is concentrated. The concentration of the concentrated pulp is 60%. 500 g / t of activated carbon is added to the ball mill for regrinding and drug removal. The fineness of the material discharged from the ball mill after regrinding is -0.038 mm, accounting for 85%;

[0071] S6: 700 g / t of sodium hydroxide, 1500 g / t of inhibitor A (1000 g / t of calcium hypochlorite, 500 g / t of magnesium chloride), 500 g / t of inhibitor B (300 g / t of sodium alginate, 200 g / t of polyaspartic acid), 10 g / t of ethionylthiocarbamate, and 16 g / t of pine oil were added to the material ore obtained in step S5 in sequence, with an addition interval of 4 minutes. After stirring for 4 minutes, aeration flotation was performed to obtain a copper-arsenic separation rougher concentrate and tailings;

[0072] S7: To the copper-arsenic separation rougher concentrate obtained in step S6, 750 g / t of inhibitor A (500 g / t of calcium hypochlorite, 250 g / t of magnesium chloride), 250 g / t of inhibitor B (150 g / t of sodium alginate, 100 g / t of polyaspartic acid), 5 g / t of ethionamide, and 8 g / t of pine oil were added in sequence, with an addition interval of 4 minutes. After stirring for 4 minutes, aeration flotation was performed to obtain a copper-arsenic separation and selected I concentrate and selected I tailings;

[0073] S8: To the copper-arsenic separation and beneficiation I concentrate obtained in step S7, 375 g / t of inhibitor A (250 g / t of calcium hypochlorite, 125 g / t of magnesium chloride), 125 g / t of inhibitor B (75 g / t of sodium alginate, 50 g / t of polyaspartic acid), 2.5 g / t of ethionylthiocarbamate, and 4 g / t of pine oil were added in sequence, with an addition interval of 4 minutes. After stirring for 4 minutes, aeration flotation was performed to obtain a beneficiation II concentrate (i.e., a low-arsenic copper concentrate) and beneficiation II tailings, wherein the copper-arsenic separation and beneficiation II tailings were returned to the copper-arsenic separation and beneficiation I operation.

[0074] S9: Add 6 g / t of ethoxycarbonyl thiocarbamate to the copper-arsenic separation roughing tailings obtained in step S6, stir for 4 minutes, and then aerate and float to obtain a copper-arsenic separation scavenging I concentrate and scavenging tailings, wherein the scavenging I concentrate and the scavenging I tailings are combined and returned to the copper-arsenic separation roughing operation;

[0075] S10: 3 g / t of ethionamide was added to the scavenging I tailings obtained in step S9, stirred for 4 minutes, and then subjected to aeration flotation to obtain scavenging II concentrate and scavenging II tailings (i.e., high-arsenic copper concentrate). The scavenging II concentrate was returned to the copper-arsenic separation scavenging I operation. The test results are shown in Table 2.

[0076] Comparative Example 5

[0077] Other conditions were consistent with those in Example 2, except that no dextrin was added to the sulfur-copper-arsenic mixed flotation, and the effect of single lime was analyzed. The test results are shown in Table 2.

[0078] Comparative Example 6

[0079] Other conditions were consistent with those in Example 2, except that magnesium chloride was replaced with calcium hypochlorite of equal mass, i.e., no magnesium chloride was added. The effect of magnesium chloride in inhibitor A was analyzed, and the test results are shown in Table 2.

[0080] Comparative Example 7

[0081] Other conditions were consistent with those in Example 2, except that magnesium chloride of equal mass was used instead of calcium hypochlorite, i.e., no calcium hypochlorite was added. The effect of calcium hypochlorite in inhibitor A was analyzed, and the test results are shown in Table 2.

[0082] Comparative Example 8

[0083] Other conditions were consistent with those in Example 2, except that sodium alginate was used as a substitute for polyaspartic acid, i.e., no polyaspartic acid was added. The effect of polyaspartic acid in inhibitor B was analyzed, and the test results are shown in Table 2.

[0084] Comparative Example 9

[0085] Other conditions were consistent with those in Example 2, except that sodium alginate was replaced with polyaspartic acid of equal mass, i.e., no sodium alginate was added. The effect of sodium alginate in inhibitor B was analyzed, and the test results are shown in Table 2.

[0086] Table 2 Flotation test results / %

[0087]

[0088]

[0089] Example 3

[0090] The copper ore used in this example contains 0.7% Cu, 0.55% As, and 14.68% S. The copper minerals in the ore are primarily present as chalcopyrite, the arsenic is primarily present as arsenopyrite and thioarsenite, and the sulfur is primarily present as pyrite. The gangue minerals primarily include calcite, quartz, feldspar, and chlorite.

[0091] A flotation method for arsenic-containing copper sulfide ore comprises the following steps:

[0092] S1: 800g / t of lime was added to a ball mill. After coarse grinding of arsenic-containing copper sulfide ore, the fineness of the discharge material was -0.074mm, accounting for 60%, and the pH of the slurry was 9.5. 80g / t of dextrin, 12g / t of ethiocarbamate, 20g / t of butyl xanthate, and 20g / t of pine oil were added to the coarsely ground material in sequence, with a dosing interval of 5 minutes. After stirring for 5 minutes, aeration and flotation were performed to obtain a sulfur-inhibited, copper-arsenic mixed rougher concentrate and tailings.

[0093] S2: To the roughing tailings obtained in step S1, 400 g / t of lime, 40 g / t of dextrin, 6 g / t of ethionamide, 10 g / t of butyl xanthate, and 10 g / t of pine oil were added in sequence, with an addition interval of 5 minutes. After stirring for 5 minutes, aeration flotation was performed to obtain a sulfur-copper-arsenic mixed selection scavenging I concentrate and a scavenging I tailings, wherein the scavenging I concentrate was returned to the sulfur-copper-arsenic mixed selection (roughing) operation;

[0094] S3: To the scavenging I tailings obtained in step S2, 200 g / t of lime, 20 g / t of dextrin, 3 g / t of ethionamide, 5 g / t of butyl xanthate, and 5 g / t of pine oil are added in sequence, with an addition interval of 5 minutes. After stirring for 5 minutes, aeration flotation is performed to obtain a sulfur-inhibiting, copper-arsenic mixed scavenging II concentrate and scavenging II tailings, wherein the scavenging II concentrate is returned to the sulfur-inhibiting, copper-arsenic mixed scavenging I operation;

[0095] S4: The coarse concentrate obtained in step S1 is subjected to two rounds of beneficiation to obtain a copper-arsenic mixed concentrate. The tailings from beneficiation I are returned to the roughing operation, and the tailings from beneficiation II are returned to the beneficiation I operation;

[0096] S5: The copper-arsenic mixed concentrate obtained in step S4 is concentrated. The concentration of the concentrated pulp is 70%. 600 g / t of activated carbon is added to the ball mill for regrinding and drug removal. The fineness of the material discharged from the ball mill after regrinding is -0.038 mm, accounting for 90%;

[0097] S6: 800 g / t of sodium hydroxide, 1800 g / t of inhibitor A (1200 g / t of calcium hypochlorite, 600 g / t of magnesium chloride), 700 g / t of inhibitor B (400 g / t of sodium alginate, 300 g / t of polyaspartic acid), 12 g / t of ethionamide, and 20 g / t of pine oil were added to the material ore obtained in step S5 in sequence, with an addition interval of 5 minutes. After stirring for 5 minutes, aeration flotation was performed to obtain a copper-arsenic separation rougher concentrate and rougher tailings;

[0098] S7: To the copper-arsenic separation rougher concentrate obtained in step S6, 900 g / t of inhibitor A (600 g / t of calcium hypochlorite, 300 g / t of magnesium chloride), 350 g / t of inhibitor B (200 g / t of sodium alginate, 150 g / t of polyaspartic acid), 6 g / t of ethionamide, and 10 g / t of pine oil were added in sequence, with an addition interval of 5 minutes. After stirring for 5 minutes, aeration flotation was performed to obtain a copper-arsenic separation and selected I concentrate and selected I tailings;

[0099] S8: To the copper-arsenic separation and beneficiation I concentrate obtained in step S7, 450 g / t of inhibitor A (300 g / t of calcium hypochlorite, 150 g / t of magnesium chloride), 150 g / t of inhibitor B (100 g / t of sodium alginate, 75 g / t of polyaspartic acid), 3 g / t of ethionylthiocarbamate, and 5 g / t of pine oil were added in sequence, with an addition interval of 5 minutes. After stirring for 5 minutes, aeration flotation was performed to obtain a beneficiation II concentrate (i.e., a low-arsenic copper concentrate) and beneficiation II tailings, wherein the copper-arsenic separation and beneficiation II tailings were returned to the copper-arsenic separation and beneficiation I operation.

[0100] S9: adding 8 g / t of ethoxycarbonyl ethanoate to the copper-arsenic separation roughing tailings obtained in step S6, stirring for 5 minutes, and then aerating and flotating to obtain a copper-arsenic separation scavenging I concentrate and a scavenging I tailings, wherein the scavenging I concentrate and the scavenging I tailings are combined and returned to the copper-arsenic separation roughing operation;

[0101] S10: 4 g / t of ethionamide was added to the scavenging I tailings obtained in step S9, stirred for 5 minutes, and then subjected to aeration flotation to obtain scavenging II concentrate and scavenging II tailings (i.e., high-arsenic copper concentrate). The scavenging II concentrate was returned to the copper-arsenic separation scavenging I operation. The test results are shown in Table 3.

[0102] Comparative Example 10

[0103] Other conditions were consistent with those in Example 3, except that butyl xanthate was used in an equal amount to replace ethiocarbamate in the copper-arsenic flotation separation to analyze the effect of ethiocarbamate. The test results are shown in Table 3.

[0104] Table 3 Flotation test results / %

[0105]

[0106]

[0107] From the above, it can be seen that the combined use of lime and dextrin can effectively inhibit pyrite at low alkalinity, thereby improving the separation effect of copper and arsenic. The results of Example 1, Comparative Example 2 and Comparative Example 3 show that under low alkalinity of single lime (pH value is 8.5), the grade of copper concentrate decreases by about 3 percentage points; under high alkalinity of single lime (pH value is 11.5), the copper and arsenic separation indexes are compared with the copper and arsenic separation indexes when lime and dextrin are used together. The corresponding indexes change little, but the amount of lime is increased from 700g / t to 2100g / t. The combined use of inhibitor A (calcium hypochlorite and magnesium chloride) and inhibitor B (sodium alginate and polyaspartic acid) plays a strong positive synergistic effect. The combined inhibitor can selectively inhibit arsenic-containing sulfide minerals (sulfur arsenic copper, arsenic copper and arsenopyrite). On this basis, ethiocarbamate enhances the separation effect of copper and arsenic.

[0108] The results of Example 1, Comparative Examples 3, and Comparative Examples 4 show that the use of either Inhibitor A or Inhibitor B alone increased the arsenic content of the low-arsenic copper concentrate from 0.42% to 0.83% (Inhibitor A) and 0.95% (Inhibitor B), while the copper grade decreased by approximately 6% (Inhibitor A) and 4% (Inhibitor B), and the recovery rate decreased by nearly 12% (Inhibitor A) and 10% (Inhibitor B). The results of Example 2 and Comparative Examples 5-9 further demonstrate that the copper-arsenic separation efficiency is significantly reduced when a single component of Inhibitor A or Inhibitor B is used. The arsenic content of the low-arsenic copper concentrate is greater than 0.5%, and the copper concentrate grade decreases by 2-4 percentage points. The results of Example 3 and Comparative Example 10 further demonstrate that ethiocarbamate is more effective than butyl xanthate in enhancing the flotation separation of copper and arsenic, increasing the copper grade and copper recovery of the low-arsenic copper concentrate by nearly 1%. The results of Examples 1 to 3 confirm that the present invention has good adaptability to the flotation of arsenic-containing copper ores. The copper grade of the low-arsenic copper concentrate is greater than 27%, the arsenic content is less than 0.5%, the arsenic content of the high-arsenic copper concentrate is greater than 11%, and the total copper recovery rate is greater than 93%, achieving effective recovery of copper and arsenic resources.

[0109] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to the specific embodiments described. Obviously, many modifications and variations are possible based on the content of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A flotation method for arsenic-containing copper sulfide ore, characterized in that: include: The raw ore is coarsely ground, and sulfur-inhibited copper-arsenic mixed separation is carried out at low alkalinity using a "one-roughing, two-scavenging, and two-concentrating" process to produce a copper-arsenic mixed concentrate and tailings. The copper-arsenic mixed concentrate is then concentrated, reground, and de-doped. Through slurry adjustment, coupled regulation of combined depressants, and collection with collectors, the "one-roughing, two-scavenging, and two-concentrating" process is used to enhance copper-arsenic separation, thereby achieving efficient separation of arsenic-containing copper sulfide ores. The specific steps include: S1: Add lime to the ball mill to coarsely grind the arsenic-containing copper sulfide ore, and sequentially add pyrite inhibitor, composite collector and frother to the coarsely ground material to perform sulfur inhibition-copper-arsenic mixed separation to obtain rougher concentrate and rougher tailings; S2: adding lime, pyrite inhibitor, composite collector and frother to the rougher tailings obtained in step S1 in sequence, and performing sulfur suppression, copper and arsenic mixed selection to obtain scavenging I concentrate and scavenging I tailings, wherein the scavenging I concentrate is returned to the sulfur suppression, copper and arsenic mixed selection operation; S3: adding lime, pyrite inhibitor, composite collector and frother to the scavenging I tailings obtained in step S2 in sequence, and performing sulfur inhibition-copper and arsenic mixed separation to obtain scavenging II concentrate and scavenging II tailings, wherein the scavenging II concentrate is returned to the sulfur inhibition-copper and arsenic mixed separation operation; S4: The rougher concentrate obtained in step S1 is subjected to two rounds of beneficiation to obtain a copper-arsenic mixed concentrate; wherein the tailings of beneficiation I are returned to the rougher process, and the tailings of beneficiation II are returned to the beneficiation I process; S5: Concentrating the copper-arsenic mixed concentrate obtained in step S4, adding activated carbon in a ball mill, and re-grinding and removing the drug; S6: adding sodium hydroxide, inhibitor A, inhibitor B, a collector, and a frother in sequence to the material ore obtained in step S5 to perform copper-arsenic separation roughing to obtain copper-arsenic separation roughing concentrate and copper-arsenic separation roughing tailings; S7: adding inhibitor A, inhibitor B, a collector, and a frother to the copper-arsenic separation rougher concentrate obtained in step S6 in sequence to perform copper-arsenic separation and concentration I, thereby obtaining copper-arsenic separation and concentration I concentrate and copper-arsenic separation and concentration tailings; S8: adding inhibitor A, inhibitor B, collector and frother in sequence to the copper-arsenic separation and concentration I concentrate obtained in step S7 to perform copper-arsenic separation and concentration II to obtain copper-arsenic separation and concentration II concentrate and copper-arsenic separation and concentration II tailings, wherein the copper-arsenic separation and concentration II tailings are returned to the copper-arsenic separation and concentration I operation; S9: adding a collector to the copper-arsenic separation roughing tailings obtained in step S6, and performing copper-arsenic separation scavenging I to obtain copper-arsenic separation scavenging I concentrate and copper-arsenic separation scavenging I tailings, wherein the copper-arsenic separation scavenging I concentrate and the copper-arsenic separation scavenging I tailings are combined and returned to the copper-arsenic separation roughing operation; S10: Adding a collector to the scavenging I tailings obtained in step S9 to perform copper-arsenic separation scavenging II to obtain copper-arsenic separation scavenging II concentrate and copper-arsenic separation scavenging II tailings, wherein the copper-arsenic separation scavenging II concentrate is returned to the copper-arsenic separation scavenging I operation; In step S1, the amount of lime added to the ball mill is 400-800 g / t, calculated based on the raw ore; the coarse grinding means that the fineness of the material discharged from the ball mill is -0.074 mm, accounting for 60-65%, and the pH value of the slurry is 8.5-9.5; In steps S1 to S3, the amounts of dextrin used are 40 to 80 g / t, 20 to 40 g / t, and 10 to 20 g / t, respectively; the amounts of ethionocarbamate and butyl xanthate used are (6 to 12 g / t, 8 to 20 g / t), (3 to 6 g / t, 4 to 10 g / t), and (1.5 to 3 g / t, 2 to 5 g / t), respectively; and the amounts of pine oil used are 10 to 20 g / t, 5 to 10 g / t, and 2.5 to 10 g / t, respectively, calculated based on the raw ore. In step S5, the concentration of the concentrated pulp is 50-70%; the amount of activated carbon added is 400-500 g / t; the fineness of the material discharged from the ball mill is -0.038 mm, accounting for 80-90%, based on the amount of the copper-arsenic mixed concentrate; The amounts of calcium hypochlorite and magnesium chloride in steps S6, S7 and S8 are (800-1200 g / t, 300-600 g / t), (400-600 g / t, 150-300 g / t) and (200-400 g / t, 75-150 g / t), respectively; the amounts of sodium alginate and polyaspartic acid are (200-400 g / t, 100-300 g / t), (100-200 g / t, 50-150 g / t) and (50-100 g / t, 25-75 g / t), respectively; the amounts of ethionamide are (6-12 g / t), (3-6 g / t) and (1.5-3 g / t), respectively; the amounts of pine oil are 10-20 g / t, 5-10 g / t and 2.5-5 g / t; the amount of sodium hydroxide used in step S6 is 600-800 g / t.

2. The flotation method of arsenic-containing copper sulfide ore according to claim 1, wherein: In steps S1 to S3, the pyrite inhibitor is dextrin, the composite collector is ethiocarbamate and butyl xanthate, and the foaming agent is pine oil.

3. The flotation method of arsenic-containing copper sulfide ore according to claim 1, wherein: The amounts of lime used in steps S2 and S3 are 200-400 g / t and 100-200 g / t, respectively, calculated based on the raw ore.

4. The flotation method of arsenic-containing copper sulfide ore according to claim 1, wherein: In steps S6 to S8, inhibitor A is a mixture of calcium hypochlorite and magnesium chloride, inhibitor B is a mixture of sodium alginate and polyaspartic acid; the collector is ethionamide, and the foaming agent is pine oil.

5. The flotation method of arsenic-containing copper sulfide ore according to claim 1, wherein: In steps S9 and S10, the collector is ethionamide, and the addition amounts are 4-8 g / t and 2-4 g / t, respectively.

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