Flotation method for arsenic-containing copper sulfide ore

Abstract

The invention relates to the technical field of mineral separation, in particular to a flotation method for arsenic-containing copper sulfide ore, which comprises the following steps: firstly, roughly grinding raw ore, and carrying out sulfur suppression-copper and arsenic mixed separation under low alkalinity by adopting a process of one-time rough separation, two-time scavenging and two-time fine separation to obtain copper and arsenic bulk concentrate and tailings; and then, the copper and arsenic bulk concentrate is subjected to concentration regrinding-reagent removal, copper and arsenic separation is strengthened through the flow of one-time roughing, two-time scavenging and two-time concentration through size mixing, coupling regulation and control of a combined inhibitor and collecting of a collecting agent, and therefore efficient separation of the arsenic-containing copper sulfide ore is achieved. According to the method, the combined inhibitor is adopted for effectively regulating and controlling the surfaces of the arsenic-containing minerals, and the combined inhibitor achieves selective inhibition of the arsenic-containing sulfide minerals such as hematite, arsenhedrite and arsenopyrite through the technology of oxidation modification, metal ion modification and organic compound coupling modification.

Description

Technical Field

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

[0002] Copper is an important nonferrous metal and is widely used in the fields of electricity, light industry, machinery manufacturing, construction industry, national defense industry, etc. The acquisition of copper raw materials mainly comes from the separation and enrichment of copper sulfide ores. The copper-containing minerals in copper sulfide ores mainly include chalcopyrite, chalcocite, bornite, covellite, etc., and are associated with pyrite. Arsenic-containing minerals mainly include arsenopyrite, rhombic arsenite, arsenic copper ore and arsenic tetrahedrite. They are often closely associated with copper minerals, and their physical and chemical properties are similar to those of copper minerals. Conventional mineral processing reagent systems and mineral processing methods will cause arsenic-containing minerals, pyrite and copper minerals to be enriched simultaneously, resulting in excessive arsenic in copper concentrates. Because arsenic in high-arsenic copper concentrates will be converted into arsenic trioxide, hydrogen arsenide, arsenite and organic arsenic compounds during the smelting process, it is easy to corrode equipment and pollute the environment.

[0003] Flotation is the most commonly used technology for sorting arsenic-containing copper sulfide ores. How to achieve effective suppression of pyrite and selective separation of copper and arsenic sulfide minerals is the key to the processing of such ores. At present, the lime high-alkali process is an effective method to suppress pyrite, that is, by adding a large amount of lime, pyrite is strongly suppressed under the condition that the pH value of the slurry is usually greater than 11. Although this method is mature and can achieve ideal separation effects, the lime high-alkali process has the defects of large lime dosage, easy scaling of equipment and pipelines, unfavorable for precious metal recovery, and easy to cause alkaline mineral processing wastewater to pollute the environment. On the other hand, the flotation separation of copper sulfide minerals (chalcopyrite, chalcocite, bornite, covellite, etc.) and arsenopyrite, arsenic copper ore, chalcopyrite, 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. In addition, arsenic copper ore and chalcopyrite are copper-containing minerals that are not easy to suppress and will enter the concentrate, which will eventually cause the arsenic content of copper concentrate to exceed the standard. If the suppression of minerals is strengthened, it will cause the loss of copper resources. 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 and 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 (slurry 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, and the separation and enrichment of copper sulfide ore and arsenic-containing sulfide minerals are achieved. 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 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 isopropyl ethyl thiocarbamate and kerosene as collectors, low-arsenic copper concentrate and high-arsenic copper concentrate are obtained through grinding, copper roughing, copper concentrating, arsenic roughing, arsenic concentrating and arsenic scavenging. This method enriches most of the copper minerals in the low-arsenic copper concentrate, and a small part of the copper minerals in the high-arsenic copper concentrate. Since this method does not take into account the inhibitory effect of arsenic tetrahedrite, the arsenic content of the low-arsenic copper concentrate is easy to exceed the standard. Chinese patent document CN201410352506.9 discloses a "method for selecting copper concentrate from copper ores with high sulfur and arsenic content". This method first inhibits pyrite, preferentially floats copper minerals in steps, and then uses a re-grinding de-drug-oxidation method to mix lime and calcium hypochlorite, and preferentially oxidizes arsenic-free copper sulfide minerals with potassium permanganate, thereby selectively removing sulfur-arsenic copper ore from the copper concentrate. This method has the disadvantages of large amount of oxidant (calcium hypochlorite, potassium permanganate) and easy oxidation inhibition of arsenic-containing copper sulfide ore. Based on the above situation, the separation process and technology of arsenic-containing copper sulfide ore 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 accomplished through the technical route of "low alkalinity sulfur inhibition-copper-arsenic mixed selection-concentrate concentration and re-grinding and drug removal-combination 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 inhibition-copper arsenic mixed selection under low alkalinity to obtain copper-arsenic mixed concentrate and tailings; then, concentrating and re-grinding the copper-arsenic mixed concentrate 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 by collectors, so as to realize efficient separation of arsenic-containing copper sulfide ore.

[0008] Further, 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, 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 inhibitor, composite collector and frother to the scavenging I tailings obtained in step S2, and carrying out sulfur suppression-copper and 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-copper and arsenic mixed selection (scavenging I) operation;

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

[0013] S5: concentrating the copper-arsenic mixed concentrate obtained in step S4, adding activated carbon into a ball mill, and re-grinding and de-drugging;

[0014] S6: adding sodium hydroxide, inhibitor A, inhibitor B, collector and frother in sequence to the material ore obtained in step S5 to perform rough separation of copper and arsenic to obtain rougher concentrate and rougher tailings;

[0015] S7: adding inhibitor A, inhibitor B, collector and frother in sequence to the copper-arsenic separation rougher concentrate obtained in step S6 to perform copper-arsenic separation and concentration I to obtain 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 to the copper-arsenic separation and concentration I concentrate obtained in step S7 in sequence 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 carry out 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 (based on the original 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 ethionamide and butyl xanthate, and the foaming agent is pine oil.

[0022] Furthermore, in steps S1 to S3, the amounts of dextrin (calculated as raw 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 (calculated as raw 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; the amount of pine oil (calculated as raw 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 according to 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] Further, in steps S6, S7 and S8, the amounts of calcium hypochlorite and magnesium chloride 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 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 described in step S6 is 600-800 g / t.

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

[0028] Beneficial effects of the present invention:

[0029] In the prior art, the flotation process usually adopts a single roughing and fine selection process, while the present invention adopts the technical route of "low alkalinity sulfur inhibition-copper-arsenic mixed selection-concentration of concentrate and re-grinding and removing the reagent-copper-arsenic separation". Compared with the traditional lime high-alkali process, the inhibition effect of pyrite under low alkalinity conditions is still significant, and the amount of lime used is greatly reduced. Copper-arsenic mixed selection allows the mixed enrichment of copper-arsenic minerals in the roughing stage to avoid the loss of arsenic-containing minerals, creating conditions for subsequent separation. Concentration of concentrate and re-grinding and removing the reagent improves the grade of the concentrate, creating good conditions for subsequent copper-arsenic separation.

[0030] The present invention uses lime and dextrin as a combined inhibitor of pyrite to achieve selective inhibition of pyrite at low alkalinity (pH 8.5-9.5). Dextrin is rich in hydroxyl functional groups and can be effectively adsorbed on the surface of pyrite. Its combined use with lime can significantly enhance the hydrophilicity of the pyrite surface. Compared with the traditional process of high-alkali inhibition of pyrite with lime, the amount of lime used is significantly reduced, overcoming the problems of scaling of ore dressing 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, arsenic tetrahedrite, 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 sulfide, 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 collector from being adsorbed 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. The inhibitor B of the present invention will further interact with the surface of the arsenic-containing sulfide mineral 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 on 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 the As site on the mineral surface. Inhibitor B has a strong inhibitory effect on arsenic-containing sulfide minerals through organic compound coupling modification. 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 invention is green and pollution-free to the environment, has a simple application method and is easy for industrial production. The ethiocarbamate collector can efficiently separate non-arsenic copper sulfide, thereby achieving a good copper and arsenic separation effect.

[0034] Through laboratory experiments and industrial-scale tests, it was verified that the method of the present invention effectively suppressed pyrite under low alkalinity conditions, and the concentrate grade and recovery rate of the copper-arsenic separation process reached an ideal level. The copper grade of the low-arsenic copper concentrate obtained by the present invention is greater than 27%, and the arsenic content is less than 0.5%; the arsenic content in the high-arsenic copper concentrate is greater than 11%, and the total recovery rate of copper is greater than 93%, achieving effective recovery of copper and arsenic resources. Subsequently, the low-arsenic copper concentrate and the high-arsenic copper concentrate can be processed separately, reducing production costs and promoting the sales of copper concentrate.

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

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

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

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

[0039] Example 1

[0040] The copper ore contains 0.8% Cu, 0.18% As and 9.23% S. The copper minerals in the ore are mainly in the form of chalcopyrite, arsenic is mainly in the form of arsenic copper sulfide and arsenopyrite, and sulfur is mainly in the form of pyrite. The gangue minerals are mainly calcite, quartz, feldspar, etc.

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

[0042] S1: Add 400g / t of lime into the ball mill, and after the arsenic-containing copper sulfide ore is coarsely ground, the fineness of the material discharged from the ball mill is -0.074mm, accounting for 60%, and the pH value of the slurry is 8.5. Add 40g / t of dextrin, 6g / t of ethionamide, 8g / t of butyl xanthate and 10g / t of pine oil to the coarsely ground material in sequence, with an interval of 3min for adding drugs, stir for 3min, and then aerate and float to obtain sulfur-copper-arsenic mixed roughing concentrate and roughing 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 ethionamide, 4 g / t of butyl xanthate and 5 g / t of pine oil are added in sequence, with an interval of 3 min for adding the drugs, and after stirring for 3 min, aeration flotation is performed to obtain sulfur-copper-arsenic mixed selection scavenging I concentrate and scavenging I tailings, wherein the scavenging I concentrate is 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 interval of 3 min for adding the drugs, and after stirring for 3 min, aeration flotation is performed to obtain 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;

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

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

[0047] S6: adding 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 to the material ore obtained in step S5 in sequence, with an interval of 3 min for adding the drugs, stirring for 3 min, and then aerating and flotating to obtain a copper-arsenic separation roughing concentrate and roughing 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 interval of 3 min for adding the drugs, and after stirring for 3 min, aeration flotation was performed to obtain copper-arsenic separation selected I concentrate and selected I tailings;

[0049] S8: To the copper-arsenic separation and concentration I concentrate obtained in step S7, add inhibitor A 275 g / t (calcium hypochlorite 200 g / t, magnesium chloride 75 g / t), inhibitor B 75 g / t (sodium alginate 50 g / t, polyaspartic acid 25 g / t), ethionamide 1.5 g / t, pine oil 2.5 g / t in sequence, with an interval of 3 minutes for dosing, stir for 3 minutes and then perform aeration flotation to obtain concentration II concentrate (i.e., low-arsenic copper concentrate) and concentration II tailings, wherein the copper-arsenic separation and concentration II tailings are returned to the copper-arsenic separation and concentration I operation.

[0050] S9: adding 4 g / t of ethionamide to the copper-arsenic separation roughing tailings obtained in step S6, stirring for 3 minutes and then aerating and flotating to obtain copper-arsenic separation scavenging I concentrate and scavenging I tailings, wherein the scavenging I concentrate and the concentrating I tailings are combined and returned to the copper-arsenic separation roughing operation;

[0051] S10: Add 2 g / t of ethionamide to the scavenging I tailings obtained in step S9, stir for 3 minutes and then perform aeration flotation 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. The test results are shown in Table 1.

[0052] Comparative Example 1

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

[0054] Comparative Example 2

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

[0056] Comparative Example 3

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

[0058] Comparative Example 4

[0059] The other conditions were the same as those in Example 1, except that sodium alginate and polyaspartic acid were used to replace inhibitor A in equal amounts at a mass ratio of 2:1, i.e., inhibitor A (calcium hypochlorite and magnesium chloride) was not added, and the effect of a single inhibitor B was analyzed. 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 embodiment has a Cu grade of 1.2%, an As content of 0.35%, and an S content of 12.63%. The copper mineral in the ore mainly exists in the form of chalcopyrite, the arsenic mainly exists in the form of arsenic tetrahedrite and arsenic copper sulfide, and the sulfur mainly exists in the form of pyrite. The gangue minerals mainly include calcite, quartz, feldspar, chlorite, etc.

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

[0066] S1: 600g / t of lime is added to the ball mill. After the arsenic-containing copper sulfide ore is coarsely ground, the fineness of the material discharged from the ball mill is -0.074mm, accounting for 65%, and the pH value of the slurry is 9. 60g / t of dextrin, 10g / t of ethiocarbamate, 16g / t of butyl xanthate and 16g / t of pine oil are added to the coarsely ground material in sequence, with an interval of 4min for dosing, and after stirring for 4min, aeration flotation is performed to obtain sulfur-copper-arsenic mixed roughing concentrate and roughing 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 ethionamide, 8 g / t of butyl xanthate and 8 g / t of pine oil are added in sequence, with a dosing interval of 4 min, and aerated flotation is performed after stirring for 4 min to obtain sulfur-copper-arsenic mixed selection scavenging I concentrate and scavenging I tailings, wherein the scavenging I concentrate is 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 ethionamide, 4 g / t of butyl xanthate and 4 g / t of pine oil are added in sequence, with a dosing interval of 4 min, and aerated flotation is performed after stirring for 4 min to obtain 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 rough concentrate obtained in step S1 is subjected to two concentrations to obtain a copper-arsenic mixed concentrate. The tailings of concentration I are returned to the roughing operation, and the tailings of concentration II are returned to the concentration I operation;

[0070] S5: The copper-arsenic mixed concentrate obtained in step S4 is concentrated, and the concentration of the concentrated pulp is 60%. 500 g / t of activated carbon is added to the ball mill for re-grinding and drug removal. The fineness of the material discharged from the ball mill after re-grinding 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 ethionamide, and 16 g / t of pine oil are sequentially added to the material ore obtained in step S5, with an interval of 4 min for adding the medicines, and after stirring for 4 min, aeration flotation is performed to obtain a rough concentrate and tailings for copper-arsenic separation;

[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 interval of 4 min for adding the medicines, and after stirring for 4 min, aeration flotation was performed to obtain copper-arsenic separation selected I concentrate and selected I tailings;

[0073] S8: To the copper-arsenic separation and concentration 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 ethionamide, and 4 g / t of pine oil are added in sequence, with an interval of 4 min for dosing, and after stirring for 4 min, aeration flotation is performed to obtain a concentrated II concentrate (i.e., a low-arsenic copper concentrate) and a concentrated II tailings, wherein the copper-arsenic separation and concentration II tailings are returned to the copper-arsenic separation and concentration I operation.

[0074] S9: adding 6 g / t of ethionamide to the copper-arsenic separation roughing tailings obtained in step S6, stirring for 4 minutes and then aerating and flotating to obtain copper-arsenic separation scavenging I concentrate and scavenging tailings, wherein the scavenging I concentrate and the concentrating I tailings are combined and returned to the copper-arsenic separation roughing operation;

[0075] S10: Add 3 g / t of ethionamide to the scavenging I tailings obtained in step S9, stir for 4 minutes and then perform aeration flotation 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. The test results are shown in Table 2.

[0076] Comparative Example 5

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

[0078] Comparative Example 6

[0079] The other conditions are consistent with those in Example 2, except that magnesium chloride is replaced by calcium hypochlorite of equal mass, i.e., magnesium chloride is not added, and the effect of magnesium chloride in inhibitor A is analyzed. The test results are shown in Table 2.

[0080] Comparative Example 7

[0081] The other conditions are consistent with those in Example 2, except that magnesium chloride of equal mass is used to replace calcium hypochlorite, that is, calcium hypochlorite is not added, and the effect of calcium hypochlorite in inhibitor A is analyzed. The test results are shown in Table 2.

[0082] Comparative Example 8

[0083] The other conditions were consistent with those in Example 2, except that sodium alginate was used to replace polyaspartic acid, that is, polyaspartic acid was not 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] The other conditions were consistent with those in Example 2, except that sodium alginate was replaced by polyaspartic acid of equal mass, i.e., sodium alginate was not added, and the effect of sodium alginate in inhibitor B was analyzed. 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 embodiment has a Cu grade of 0.7%, an As content of 0.55%, and an S content of 14.68%. The copper mineral in the ore mainly exists in the form of chalcopyrite, the arsenic mainly exists in the form of arsenopyrite and arsenic copper sulfide, and the sulfur mainly exists in the form of pyrite. The gangue minerals mainly include calcite, quartz, feldspar, chlorite, etc.

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

[0092] S1: Add 800g / t of lime into the ball mill, and after the arsenic-containing copper sulfide ore is coarsely ground, the fineness of the material discharged from the ball mill is -0.074mm, accounting for 60%, and the pH value of the slurry is 9.5. Add 80g / t of dextrin, 12g / t of ethiocarbamate, 20g / t of butyl xanthate and 20g / t of pine oil to the coarsely ground material in sequence, with an interval of 5min for adding the drugs, stir for 5min, and then aerate and float to obtain sulfur-copper-arsenic mixed roughing 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 are added in sequence, with an interval of 5 min for adding the drugs, and after stirring for 5 min, aeration flotation is performed to obtain sulfur-copper-arsenic mixed selection scavenging I concentrate and scavenging I tailings, wherein the scavenging I concentrate is 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 interval of 5 min for adding the drugs, and after stirring for 5 min, aeration flotation is performed to obtain 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;

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

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

[0097] S6: adding 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 to the material ore obtained in step S5 in sequence, with an interval of 5 min for adding the drugs, stirring for 5 min, and then aerating and flotating to obtain a copper-arsenic separation roughing concentrate and roughing 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 interval of 5 min for adding the medicines, and after stirring for 5 min, aeration flotation was performed to obtain copper-arsenic separation selected I concentrate and selected I tailings;

[0099] S8: To the copper-arsenic separation and concentration 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 ethionamide, and 5 g / t of pine oil are added in sequence, with an interval of 5 min for dosing. After stirring for 5 min, aeration flotation is performed to obtain a concentrated II concentrate (i.e., a low-arsenic copper concentrate) and a concentrated II tailings, wherein the copper-arsenic separation and concentration II tailings are returned to the copper-arsenic separation and concentration I operation.

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

[0101] S10: Add 4 g / t of ethionamide to the scavenging I tailings obtained in step S9, stir for 5 minutes and then perform aeration flotation 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. The test results are shown in Table 3.

[0102] Comparative Example 10

[0103] The other conditions are consistent with those in Example 3, except that butyl xanthate is used in an equal amount to replace ethiocarbamate in the flotation separation of copper and arsenic, and the effect of ethiocarbamate is analyzed. 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, and 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) exerts a strong positive synergistic effect, and the combined inhibitor can selectively inhibit arsenic-containing sulfide minerals (sulfur arsenic copper ore, arsenic copper and arsenopyrite). On this basis, ethiocarbamate strengthens the separation effect of copper and arsenic.

[0108] The results of Example 1, Comparative Examples 3 and Comparative Examples 4 show that when inhibitor A or inhibitor B is used alone, the arsenic content of the low-arsenic copper concentrate increases from 0.42% to 0.83% (inhibitor A) and 0.95% (inhibitor B), the copper grade decreases by about 6% (inhibitor A) and 4% (inhibitor B), and the recovery rate decreases by nearly 12% (inhibitor A) and 10% (inhibitor B). The results of Example 2 and Comparative Examples 5 to 9 further show that under the combination of a single component in inhibitor A or inhibitor B, the separation effect of copper and arsenic decreases significantly, wherein the arsenic content of the low-arsenic copper concentrate is greater than 0.5%, and the grade of the copper concentrate decreases by 2 to 4 percentage points. The results of Example 3 and Comparative Example 10 further show that ethiocarbamate is more effective than butyl xanthate in strengthening the flotation separation of copper and arsenic, and the copper grade and copper recovery rate of the low-arsenic copper concentrate are increased 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 in the high-arsenic copper concentrate is greater than 11%, and the total recovery rate of copper is greater than 93%, thereby achieving effective recovery of copper and arsenic resources.

[0109] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A flotation method for arsenic-containing copper sulfide ore, characterized in that: include: The raw ore is coarsely ground, and the process of "one roughing, two scavenging and two concentrating" is adopted to carry out sulfur-inhibiting-copper-arsenic mixed selection under low alkalinity to obtain copper-arsenic mixed concentrate and tailings; then, the copper-arsenic mixed concentrate is concentrated and re-grinded-de-drug, and the copper-arsenic separation is enhanced by slurry adjustment, coupled regulation of combined inhibitors and collection by collectors, and the process of "one roughing, two scavenging and two concentrating" is adopted, thereby realizing the efficient separation of arsenic-containing copper sulfide ore.

2. The flotation method of arsenic-containing copper sulfide ore according to claim 1, characterized in that: The specific steps include: 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, performing sulfur inhibition-copper-arsenic mixed selection, and obtaining roughing concentrate and roughing tailings; S2: adding lime, pyrite inhibitor, composite collector and frother to the roughing tailings obtained in step S1, and performing sulfur-inhibition-copper-arsenic mixed selection to obtain scavenging I concentrate and scavenging I tailings, wherein the scavenging I concentrate is returned to the sulfur-inhibition-copper-arsenic mixed selection operation; S3: adding lime, pyrite inhibitor, composite collector and frother to the scavenging I tailings obtained in step S2, and performing sulfur-inhibiting-copper-arsenic mixed selection to obtain scavenging II concentrate and scavenging II tailings, wherein the scavenging II concentrate is returned to the sulfur-inhibiting-copper-arsenic mixed selection operation; S4: The rough concentrate obtained in step S1 is subjected to two concentrations to obtain a copper-arsenic mixed concentrate; wherein the tailings of concentration I are returned to the roughing operation, and the tailings of concentration II are returned to the concentration I operation; S5: concentrating the copper-arsenic mixed concentrate obtained in step S4, adding activated carbon into a ball mill, and re-grinding and de-drugging; S6: adding sodium hydroxide, inhibitor A, inhibitor B, collector and frother in sequence to the material ore obtained in step S5 to perform rough separation of copper and arsenic to obtain rougher concentrate and rougher tailings; S7: adding inhibitor A, inhibitor B, collector and frother in sequence to the copper-arsenic separation rougher concentrate obtained in step S6 to perform copper-arsenic separation and concentration I to obtain concentrated I concentrate and concentrated tailings; S8: adding inhibitor A, inhibitor B, collector and frother to the copper-arsenic separation scavenging I tailings obtained in step S6 in sequence to carry out copper-arsenic separation scavenging II to obtain scavenging II concentrate and scavenging II tailings, wherein the copper-arsenic separation scavenging II concentrate is returned to the copper-arsenic separation scavenging I operation; 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 concentration II concentrate and concentration II tailings, wherein the copper-arsenic separation and concentration II tailings are returned to the copper-arsenic separation and concentration I operation; 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; S11: Add a collector to the scavenging I tailings obtained in step S9 to carry out copper-arsenic separation scavenging II to obtain scavenging II concentrate and scavenging II tailings, wherein the scavenging II concentrate is returned to the copper-arsenic separation scavenging I operation.

3. The flotation method of arsenic-containing copper sulfide ore according to claim 2, characterized in that: In step S1, the amount of lime added to the ball mill is 400-800 g / t, calculated based on the raw ore material; 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.

4. The flotation method of arsenic-containing copper sulfide ore according to claim 2, characterized in that: In steps S1-3, the pyrite inhibitor is dextrin, the composite collector is ethiocarbamate and butyl xanthate, and the foaming agent is pine oil.

5. The flotation method of arsenic-containing copper sulfide ore according to claim 2, characterized in that: In steps S1 to S3, the dosage of dextrin is 40 to 80 g / t, 20 to 40 g / t and 10 to 20 g / t respectively; the dosage of ethionamide and butyl xanthate is (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; the dosage of pine oil is 10 to 20 g / t, 5 to 10 g / t and 2.5 to 10 g / t, calculated based on the original ore material.

6. The flotation method of arsenic-containing copper sulfide ore according to claim 2, characterized in that: 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 material.

7. The flotation method of arsenic-containing copper sulfide ore according to claim 2, characterized in that: In step S5, the concentration of the concentrated pulp is 50-70%; the amount of activated carbon added is 400-500g / t; and the fineness of the material discharged from the ball mill is re-grinded to -0.038mm, accounting for 80-90%, based on the amount of copper-arsenic mixed coarse concentrate.

8. The flotation method of arsenic-containing copper sulfide ore according to claim 2, characterized in that: In steps S6-8, 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.

9. The flotation method of arsenic-containing copper sulfide ore according to claim 2, characterized in that: In steps S6, S7 and S8, the amounts of calcium hypochlorite and magnesium chloride 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 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 in step S6 is 600-800 g / t.

10. The flotation method of arsenic-containing copper sulfide ore according to claim 2, characterized in that: In steps S9 and S10, the collector is ethionamide, and the addition amount is 4-8 g / t and 2-4 g / t respectively.

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