CN111036417B - Sand composite inhibitor and application thereof - Google Patents

Sand composite inhibitor and application thereof Download PDF

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CN111036417B
CN111036417B CN201911138892.0A CN201911138892A CN111036417B CN 111036417 B CN111036417 B CN 111036417B CN 201911138892 A CN201911138892 A CN 201911138892A CN 111036417 B CN111036417 B CN 111036417B
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inhibitor
arsenopyrite
copper
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arsenic
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CN111036417A (en
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魏志聪
彭蓉
白睿
刘洋
王衡嵩
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Kunming University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/001Flotation agents
    • B03D1/018Mixtures of inorganic and organic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00Specified effects produced by the flotation agents
    • B03D2201/06Depressants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02Ores
    • B03D2203/04Non-sulfide ores

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  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a poisonous sand combined inhibitor and application thereof, and belongs to the technical field of poisonous sand flotation. The combined inhibitor comprises an organic inhibitor and an inorganic inhibitor, wherein the organic inhibitor is 1, 2-dihydroxy-9, 10-anthraquinone, and the inorganic inhibitor is CaO and Ca (ClO)2、Na2SO3And KMnO4One or two of them. Compared with a single inhibitor, the combined inhibitor can reduce the adsorption amount of the collecting agent on the surface of the arsenopyrite to a greater extent. The combined inhibitor has high inhibition selectivity to arsenopyrite and basically has no inhibition effect on copper sulfide ore; the adaptability is strong, and the method can effectively inhibit the arsenopyrite in the copper sulfide concentrate containing the chalcopyrite and the bornite. The combined inhibitor disclosed by the invention is small in dosage, safe, non-toxic, environment-friendly, easy to prepare and add, convenient to use, capable of effectively realizing flotation separation of arsenopyrite and copper sulfide ore, and wide in application prospect.

Description

Sand composite inhibitor and application thereof
Technical Field
The invention relates to a poisonous sand combined inhibitor and application thereof, belonging to the technical field of poisonous sand flotation.
Background
The three minerals of the copper arsenite, the chalcopyrite and the arsenopyrite usually exist in a compact symbiotic form, the forming conditions of the minerals are basically similar, and the floatability of the surfaces of the minerals is equivalent, so that in the process of recovering the copper minerals by flotation, the arsenic minerals are greatly enriched into the copper concentrate, the arsenic content in the copper concentrate is too high, the sale is influenced, and meanwhile, smoke containing arsenic is generated in the smelting process, and the environment is damaged. Therefore, copper-arsenic separation is always the focus of research of the scientists, and at present, the methods for copper-arsenic flotation separation are mainly divided into the following methods: firstly, a strong inhibitor method of the arsenopyrite is adopted, secondly, a high-efficiency copper mineral collector method is adopted, thirdly, methods of increasing the temperature of ore pulp, stirring for a long time, increasing the selection times and the like are adopted, and the research and the application of the arsenopyrite inhibitor are the most; currently, arsenopyrite inhibitors can be classified into three classes, inorganic inhibitors, organic inhibitors and combination inhibitors.
Currently applied to copper arsenic flotation separationThe inorganic inhibitor mainly comprises an alkaline inhibitor and an oxidation inhibitor. The alkali inhibitor mainly comprises lime, sodium sulfide, sodium hydroxide and the like, the lime is a pH regulator, the lime can promote the dissolution or oxidation of the surface of the mineral and can also regulate the acidity and alkalinity of the ore pulp, and in the test process, if heavy metal ions except arsenic do not exist in the ore pulp solution, the most effective arsenopyrite inhibitor is lime-SO2-Zn2+/CN-Complexes, if Cu is present in the pulp2+And ions, the lime-sodium sulfide method is used for inhibiting the arsenopyrite. The lime has wide source and low cost, but the dosage of the medicament is too large in the using process, and simultaneously, the generated foam is easy to be sticky, so that the quality of concentrate is not high, and simultaneously, a conveying pipeline is scaled to influence the subsequent production. In the copper-arsenic flotation separation process, the oxidant is added to accelerate the oxidation of the surface of the arsenopyrite and reduce the floatability of the arsenopyrite. The oxidizing agents found so far are mainly calcium hypochlorite, sodium hypochlorite, potassium permanganate, potassium dichromate, manganese dioxide, hydrogen peroxide, potassium peroxodisulfate, and the like. In the copper-arsenic flotation separation process, the required medicament dosage of the oxidant is large, and the oxidant is easy to generate inhibition effect on other metal sulfide minerals and influence the recovery of the minerals.
Organic inhibitors include xanthates and lignins. Wherein the xanthate comprises glycerol xanthate sodium and propyl xanthate sodium, and the lignin comprises sodium humate, sodium lignin sulfonate, polyacrylamide, fulvic acid, etc. The organic inhibitor can be adsorbed on the surface of the arsenopyrite in a hydrophilic substance or in an adsorption form in the experimental process, and a hydrophilic film is formed on the surface of the arsenopyrite, so that the floatability of the arsenopyrite is reduced. The organic inhibitor has small dosage, is nontoxic and harmless and is environment-friendly, but the existing arsenopyrite organic inhibitor has few types, is not mature in system, has great difference in inhibiting effect on different types of metal sulfide ores containing arsenic, and has certain inhibiting effect on pyrite, chalcopyrite and blende.
The novel inhibitor is mainly a code medicament which is mainly adsorbed on the surface of the arsenopyrite by hydrophilic groups in a chemical molecular formula contained in the medicament, so that the adsorption quantity of a collecting agent on the surface of the arsenopyrite is reduced, and the floatability of the collecting agent is reduced. However, when the existing novel inhibitor is used alone, the dosage of the required medicament is larger, and meanwhile, the novel inhibitor can inhibit other metal sulfide minerals and is not beneficial to mineral recovery.
The combined inhibitor is mainly formed by simply combining and using common inhibitors, and the common combined inhibitors at present are mainly combined and used by lime and sodium sulfite, lime and KN inhibitors, lime and Y-As, sodium humate and calcium hypochlorite, sodium humate and sodium hexametaphosphate.
In summary, the problems of the prior art are as follows: the inorganic inhibitor has the defects of large dosage of a pesticide, poor selectivity, high requirement on equipment, easy environmental pollution and the like in the copper-arsenic flotation separation process. The organic inhibitor has few types, immature system and poor selectivity, and has a certain inhibiting effect on partial mineral. The chemical components of the currently known novel inhibitor are incomplete, the single use effect is poor, and the dosage of the medicament is large, so that the recovery of useful metal minerals is not facilitated. The combined inhibitor is usually prepared by combining known inhibitors, and certain requirements exist on the drug-implanting property of the inhibitor to be combined and the acidity and alkalinity of ore pulp.
The three minerals of the arsenopyrite, the chalcopyrite and the arsenopyrite often exist in a compact symbiotic form, the forming conditions are basically similar, the floatability of the surfaces of the minerals is equivalent, and the Cu2+The activated arsenopyrite has strong activation effect on arsenopyrite, so that floatability of arsenic minerals is enhanced, and a large amount of arsenopyrite is enriched in copper concentrate, so that arsenic content in the concentrate product is too high, and smoke containing arsenic is generated in the smelting process, so that the environment is damaged. The used arsenic mineral inhibitor needs to have the characteristics of small medicament dosage, good selectivity, environmental friendliness and the like. In the flotation process, the inhibition effect on only arsenic minerals is required to be achieved, and the inhibition effect on target metal minerals is basically avoided. A novel inhibitor which has strong adaptability and can be used alone or in combination is developed and researched on the basis of the known inhibitor.
Disclosure of Invention
The invention aims to provide a small-dosage, strong-adaptability, high-selectivity, non-toxic and harmless arsenopyrite combined inhibitor, which comprises an organic inhibitor and an inorganic inhibitor; the mass ratio of the organic inhibitor to the inorganic inhibitor is 1-3: 1-11; the inhibitor can greatly reduce the arsenic content in the arsenic-containing copper concentrate.
The organic inhibitor is 1, 2-dihydroxy-9, 10-anthraquinone;
the inorganic inhibitor CaO, Ca (ClO)2、Na2SO3And KMnO4One or two of them.
Another object of the present invention is to provide the use of the arsenopyrite combination inhibitor: the inhibitor is used for flotation separation of copper sulfide ores and arsenopyrite in copper-arsenic bulk concentrates.
Further, the specific process of applying the inhibitor to the flotation separation of the copper sulfide ore and the arsenopyrite in the copper-arsenic bulk concentrate comprises the following steps: adjusting the copper-arsenic bulk concentrate to the required pulp concentration, adding an inorganic inhibitor and an organic inhibitor at the same time in a roughing stage, stirring for 3min, roughing the copper-arsenic bulk concentrate for 1 time, carrying out scavenging for 3-6 min and 2-3 times, carrying out scavenging for 2-5 min and 1-2 times of fine concentration each time, and obtaining the copper concentrate, wherein the fine concentration time is 2-5 min each time.
Preferably, the mass percentage concentration of the ore pulp is 20-30%.
Preferably, the inhibitor is prepared into an aqueous solution with a mass percentage concentration of 5% before use, the total amount of the added organic inhibitor is 100-300 g/t, and the total amount of the added inorganic inhibitor is 100-1100 g/t.
The principle of the invention is as follows: when inorganic inhibitor CaO, Ca (ClO)2When the organic inhibition can be combined with free Ca in the solution2+Forming hydrophilic complex to adsorb on the surface of arsenopyrite to enhance the hydrophilicity of arsenopyrite and realize the inhibition of arsenopyrite, 1, 2-dihydroxy-9, 10-anthraquinone and Ca2+The following reactions may occur:
Figure BDA0002280327250000031
when inorganic inhibitor Na2SO3Or KMnO4In time, KMnO4、Na2SO3And the organic inhibitor respectively oxidizes the surface of the arsenopyrite to prevent the action of the arsenopyrite surface and the collecting agent, when the two agents are used in combination, the degree of oxidization of the arsenopyrite surface is enhanced, the hydrophilicity of the arsenopyrite surface is stronger, and the organic inhibitor 1, 2-dihydroxy-9, 10-anthraquinone and the arsenopyrite surface can react as follows:
Figure BDA0002280327250000041
the invention has the beneficial effects that:
(1) compared with a single inhibitor, the combined inhibitor can reduce the adsorption amount of the collecting agent on the surface of the arsenopyrite to a greater extent; the organic inhibitor in the combined inhibitor can be mixed with Ca2+The formed complex is adsorbed on the surface of the arsenopyrite, so that the hydrophilicity of the arsenopyrite surface is enhanced, the floatability of the arsenopyrite surface is reduced, and the inhibiting effect on the arsenopyrite is enhanced.
(2) The combined inhibitor has high inhibition selectivity on arsenopyrite and basically has no inhibition effect on copper sulfide ore.
The combined inhibitor has strong adaptability and can effectively inhibit the arsenopyrite in the copper sulfide concentrate containing chalcopyrite and bornite.
(3) The combined inhibitor has small dosage, is safe and nontoxic, and is environment-friendly; the combined inhibitor has good stability, is easy to prepare and add, is convenient to use, can effectively realize the flotation separation of the arsenopyrite and the copper sulfide ore, and has wide application prospect.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited to the examples.
Example 1
A arsenopyrite combination inhibitor comprising an organic inhibitor and an inorganic inhibitor; the organic inhibitor is 1, 2-dihydroxy-9, 10-anthraquinone,the inorganic inhibitor Na2SO3The mass ratio of the organic inhibitor to the inorganic inhibitor is 1: 5; the inhibitor is prepared into an aqueous solution with the mass percentage concentration of 5% for adding before use.
The combined inhibitor is used for flotation separation of copper sulfide ores and arsenopyrite in copper-arsenic bulk concentrates:
in the copper arsenic bulk concentrate treated in this example: the Cu grade is 15.77 wt%, the As grade is 3.02 wt%, the copper-containing minerals are mainly chalcopyrite, and the arsenic-containing minerals are mainly arsenopyrite.
Flotation conditions are as follows: the mass concentration of the ore pulp is 30 percent, and Na in the combined inhibitor is added at the same time2SO3Stirring with 1, 2-dihydroxy-9, 10-anthraquinone for 3min (the addition of 1, 2-dihydroxy-9, 10-anthraquinone is 100g/t, Na)2SO3The addition amount of (2) is 500g/t), and copper concentrate products are obtained after 1 time of roughing (roughing time is 4min), 2 times of scavenging (scavenging time is 4min and 3min respectively) and 1 time of fine concentration (fine concentration time is 2min), and the grade and the recovery rate of the copper concentrate products are shown in table 1.
Example 2
A arsenopyrite combination inhibitor comprising an organic inhibitor and an inorganic inhibitor; the organic inhibitor is 1, 2-dihydroxy-9, 10-anthraquinone, and the inorganic inhibitor is Ca (ClO)2The mass ratio of the organic inhibitor to the inorganic inhibitor is 1: 2; the inhibitor is prepared into an aqueous solution with the mass percentage concentration of 5% for adding before use.
The combined inhibitor is used for flotation separation of copper sulfide ores and arsenopyrite in copper-arsenic bulk concentrates:
in the copper arsenic bulk concentrate treated in this example: the Cu grade is 16.48 wt%, the As grade is 5.44 wt%, the copper-containing minerals mainly comprise bornite and chalcocite, and the arsenic-containing minerals mainly comprise arsenopyrite.
Flotation conditions are as follows: the mass concentration of the ore pulp is 25 percent, and Ca (ClO) in the combined inhibitor is added2And 1, 2-dihydroxy-9, 10-anthraquinone was stirred for 3min (amount of 1, 2-dihydroxy-9, 10-anthraquinone 80g/t, Ca (ClO))2The dosage of the active ingredients is 160g/t), and the active ingredients are roughly sorted for 1 time (roughly sorting time is 5min), swept for 2 times (sweeping time is 4min and 3min), and finely sorted for 2 times (finely sorted)The separation time is 4min and 3min respectively) to obtain copper concentrate products, and the grade and the recovery rate are shown in table 1.
Example 3
A arsenopyrite combination inhibitor comprising an organic inhibitor and an inorganic inhibitor; the organic inhibitor is 1, 2-dihydroxy-9, 10-anthraquinone, and the inorganic inhibitor KMnO4The mass ratio of the organic inhibitor to the inorganic inhibitor is 2: 5; the inhibitor is prepared into an aqueous solution with the mass percentage concentration of 5% for adding before use.
The combined inhibitor is used for flotation separation of copper sulfide ores and arsenopyrite in copper-arsenic bulk concentrates:
in the copper arsenic bulk concentrate treated in this example: the Cu grade is 14.90 wt%, the As grade is 4.58 wt%, the copper-containing minerals mainly comprise chalcopyrite and bornite, and the arsenic-containing minerals mainly comprise arsenopyrite.
Flotation conditions are as follows: the mass concentration of the ore pulp is 30 percent, and KMnO in the combined inhibitor is added at the same time4Stirring with 1, 2-dihydroxy-9, 10-anthraquinone for 3min (the amount of 1, 2-dihydroxy-9, 10-anthraquinone is 200g/t, KMnO)4The dosage of the copper concentrate is 500g/t), and the copper concentrate product is obtained after 1 time of roughing (the roughing time is 4min), 2 times of scavenging (the scavenging time is 4min and 3min respectively) and 1 time of fine concentration (the fine concentration time is 2min), and the grade and the recovery rate of the copper concentrate product are shown in table 1.
Example 4
A arsenopyrite combination inhibitor comprising an organic inhibitor and an inorganic inhibitor; the organic inhibitor is 1, 2-dihydroxy-9, 10-anthraquinone, and the inorganic inhibitor is CaO and Na2SO3The mass ratio of the organic inhibitor to the inorganic inhibitor is 1: 5; the inhibitor is prepared into an aqueous solution with the mass percentage concentration of 5% for adding before use.
The combined inhibitor is used for flotation separation of copper sulfide ores and arsenopyrite in copper-arsenic bulk concentrates:
in the copper arsenic bulk concentrate treated in this example: the Cu grade is 21.76 wt%, the As grade is 6.27 wt%, the copper-containing minerals mainly comprise chalcopyrite, chalcocite and bornite, and the arsenic-containing minerals mainly comprise arsenopyrite.
Flotation conditions are as follows: the mass concentration of the ore pulp is 20 percent, and CaO and Na in the combined inhibitor are added simultaneously2SO3And 1, 2-dihydroxy-9, 10-anthraquinone, stirring for 3min (the dosage of 1, 2-dihydroxy-9, 10-anthraquinone is 50g/t, CaO and Na2SO3The dosage of the copper concentrate is 100g/t and 150g/t respectively, 1 time of roughing (the roughing time is 3min respectively), 2 times of scavenging (the scavenging time is 3min and 2min respectively) and 2 times of concentrating (the concentrating time is 3min and 2min respectively) are carried out to obtain the copper concentrate product, and the grade and the recovery rate are shown in table 1.
Example 5
A arsenopyrite combination inhibitor comprising an organic inhibitor and an inorganic inhibitor; the organic inhibitor is 1, 2-dihydroxy-9, 10-anthraquinone, and the inorganic inhibitor is Ca (ClO)2And KMnO4The mass ratio of the organic inhibitor to the inorganic inhibitor is 1: 4; the inhibitor is prepared into an aqueous solution with the mass percentage concentration of 5% for adding before use.
The combined inhibitor is used for flotation separation of copper sulfide ores and arsenopyrite in copper-arsenic bulk concentrates:
in the copper arsenic bulk concentrate treated in this example: the Cu grade is 18.45 wt%, the As grade is 2.32 wt%, the copper-containing minerals are mainly chalcopyrite, and the arsenic-containing minerals are mainly arsenopyrite.
Flotation conditions are as follows: the mass concentration of the ore pulp is 25 percent, and Ca (ClO) in the combined inhibitor is added2、KMnO4And 1, 2-dihydroxy-9, 10-anthraquinone was stirred for 3min (amount of 1, 2-dihydroxy-9, 10-anthraquinone 80g/t, Ca (ClO))2And KMnO4The dosage of the copper concentrate is 100g/t and 220g/t respectively, the yield of the copper concentrate is obtained after 12 times of roughing (the roughing time is 5min), 2 times of scavenging (the scavenging time is 3min and 2min respectively) and 1 time of fine concentration (the concentration time is 3min respectively), and the grade and the recovery rate are shown in table 1.
Comparative example 1
The treatment conditions of this example were the same as those of example 1 except that only the inorganic inhibitor Na was added2SO3Without addition of organic inhibitors, wherein Na2SO3The amount of (B) is 700 g/t.
Comparative example 2
The treatment conditions of this example were the same as those of example 1 except that 1, 2-dihydroxy-9, 10-anthraquinone, which is an organic inhibitor, was added alone and no inorganic inhibitor was added, and the amount of 1, 2-dihydroxy-9, 10-anthraquinone used was 400 g/t.
Table 1 example test results
Figure BDA0002280327250000081
TABLE 2 test results of comparative examples
Figure BDA0002280327250000082
As can be seen from table 1, when the arsenic mineral combination inhibitor of the present invention is added in the flotation separation process of the copper-arsenic bulk concentrate, the arsenic content in the obtained copper concentrate product in each example is greatly reduced, the arsenic grade is less than or equal to the maximum value specified in the nonferrous metal industry standard (YS/T318-2007), and the recovery rate of copper is over 93%, so that the flotation separation of copper sulfide ore and arsenic mineral is effectively realized.
The comparative data in table 2 show that the copper and arsenic can be separated by using the organic inhibitor or the inorganic inhibitor alone, but the dosage of the medicament used alone is large, and the grade and recovery rate of the copper concentrate product are not high when the copper concentrate product is used in combination; therefore, the combined use of the inorganic inhibitor and the organic inhibitor can effectively solve the problems, and the copper-arsenic separation is carried out more thoroughly.
The organic inhibitor can slowly oxidize the surface of the arsenopyrite, so that the hydrophilicity of the surface of the arsenopyrite is enhanced, and the floatability of the arsenopyrite is reduced. The organic inhibitor of the invention can react with Ca2+The reaction forms a complex, so that the complex is adsorbed on the surface of the arsenic mineral, the hydrophilicity of the arsenic mineral is enhanced, and the floatability of the arsenic mineral is reduced; the two are matched for use, so that the dosage of the medicament can be reduced to a greater extent, and the adsorption quantity of the arsenic mineral surface and the collecting agent is greatly reduced. Meanwhile, the organic inhibitor can oxidize and reduce the surface of the arsenopyriteThe adsorption quantity of the collecting agent on the surface of the arsenopyrite is reduced, so that the hydrophilicity of the arsenopyrite is enhanced, and the copper-arsenic separation is realized. The combined inhibitor has high inhibition selectivity to the arsenopyrite, strong adaptability and no inhibition effect on copper sulfide ores basically, can effectively realize the separation between copper sulfide ores and the arsenopyrite, has small dosage, is safe and nontoxic, is environment-friendly, has good stability, easy preparation and addition and convenient use, can effectively realize the flotation separation of the arsenopyrite and the copper sulfide ores, and has wide application prospect.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.

Claims (4)

1. A arsenopyrite combination inhibitor, characterized in that: the combined inhibitor comprises an organic inhibitor and an inorganic inhibitor; the mass ratio of the organic inhibitor to the inorganic inhibitor is 1-3: 1-11;
the organic inhibitor is 1, 2-dihydroxy-9, 10-anthraquinone;
the inorganic inhibitor is CaO, Ca (ClO)2、Na2SO3And KMnO4One or two of them;
the inhibitor is used for flotation separation of copper sulfide ores and arsenopyrite in copper-arsenic bulk concentrates.
2. The arsenopyrite combination inhibitor according to claim 1, wherein: the specific process of the inhibitor for flotation separation of the copper sulfide ore and the arsenopyrite in the copper-arsenic bulk concentrate comprises the following steps: adjusting the copper-arsenic bulk concentrate to the required pulp concentration, adding an inorganic inhibitor and an organic inhibitor at the same time in a roughing stage, stirring for 3min, roughing the copper-arsenic bulk concentrate for 1 time for 3-6 min, scavenging for 2-3 times for 2-5 min each time, and concentrating for 1-2 times to obtain copper concentrate, wherein the concentrating time is 2-5 min each time.
3. The use of the arsenopyrite combination inhibitor according to claim 2, wherein: the mass percentage concentration of the ore pulp is 20-30%.
4. The use of the arsenopyrite combination inhibitor according to claim 2, wherein: the inhibitor is prepared into an aqueous solution with the mass concentration of 5% before use, the total adding amount of the organic inhibitor is 100-300 g/t, and the total adding amount of the inorganic inhibitor is 100-1100 g/t.
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