High-selectivity copper-lead separation combined inhibitor and application thereof

Abstract

The invention discloses a high-selectivity copper-lead separation combined inhibitor and application thereof, and belongs to the technical field of mineral processing and non-ferrous metal flotation. The combined inhibitor comprises the following components: sodium periodate and mercaptosuccinic acid, wherein the mass ratio of the sodium periodate to the mercaptosuccinic acid is (1: 3)-(1: 7). According to the method, sodium periodate and mercaptosuccinic acid are combined to form the combined inhibitor, the combined inhibitor is used in the copper and lead flotation separation process of the lead sulfide ore, galena is accurately and effectively inhibited, meanwhile, the influence of the combined inhibitor on chalcopyrite flotation is reduced, the lead sulfide ore finally has the excellent flotation separation effect, and the flotation separation efficiency is improved. And high-grade copper and lead concentrates are obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral processing and nonferrous metal flotation, and relates to a highly selective copper-lead separation combined depressant and application thereof. Background Art

[0002] Nonferrous metals such as copper and lead are important resources for promoting industrial production and technological progress, and are widely used in defense, semiconductors, electrical and other fields. The main sources of copper and lead ores are sulfide ores, but since copper and lead sulfide ores have similar floatability and are usually coexistent, and the mineral particle size is small, the flotation separation of copper and lead sulfide ores has become a major challenge in mineral processing.

[0003] At present, the separation of copper-lead sulfide ores usually adopts the traditional flotation process of suppressing lead and floating copper. Depressants are divided into inorganic and organic depressants, among which organic depressants have received more attention due to their wide sources, low cost and environmental friendliness. However, many common organic depressants, such as carboxymethyl cellulose, starch, polyacrylamide, etc., have disadvantages such as poor solubility and difficulty in sedimentation, which limit their application effect in industry. In contrast, the application of high-efficiency inorganic depressants in industry is developing day by day. Common inorganic depressants include dichromate, potassium permanganate, sodium cyanide, etc. Although these depressants are highly selective and have a wide range of applications, they are highly toxic and will produce difficult-to-treat cyanide-containing wastewater after use, posing a serious threat to the environment and human health.

[0004] In the existing lead-suppression and copper-floating process, the inhibitor still has the problem of relatively limited effectiveness, resulting in incomplete copper-lead separation, serious copper-lead intercontinence in the concentrate, and ultimately producing mixed concentrate. Traditional single inhibitors are difficult to effectively solve this problem and cannot meet the separation requirements of complex sulfide ores.

[0005] Therefore, it is necessary to provide a highly selective copper-lead separation combined inhibitor, which can be applied to the flotation process of lead sulfide ores to achieve a more precise selective inhibition effect based on the chemical synergy of the mixed drugs, while avoiding the harm of the use of inhibitors to the environment and human health. Summary of the invention

[0006] In order to overcome the problems in the background technology, the present invention forms a combined inhibitor of sodium periodate and mercaptosuccinic acid, and uses it in the flotation process of lead sulfide ore, accurately selectively inhibits galena, while hardly affecting the flotation of chalcopyrite, thereby achieving efficient separation of galena and chalcopyrite, and there is no toxic substance in the combined inhibitor, avoiding harm to the environment and human body caused by the use of the combined inhibitor.

[0007] In order to achieve the above object, the present invention is implemented by the following technical solutions:

[0008] On the one hand, the present invention provides a highly selective copper-lead separation combined inhibitor, which is formed by mixing a sodium periodate solution and a mercaptosuccinic acid solution, wherein the mass ratio of sodium periodate to mercaptosuccinic acid is sodium periodate: mercaptosuccinic acid = 1:3 to 1:7, the concentration of the sodium periodate solution is 0.5 to 2.5%, and the concentration of the mercaptosuccinic acid solution is 1.0 to 5.0%.

[0009] Preferably, in the combined inhibitor, the molecular formula of mercaptosuccinic acid is C4H6O4S, and its structural formula is:

[0010]

[0011] Another aspect of the present invention provides the use of the above-mentioned combined depressant in the flotation process of lead sulfide ore, and the flotation process of lead sulfide ore comprises the following steps:

[0012] (1) ball milling the raw ore until the ore particles with a grinding fineness of -0.074 mm account for 85% to 95% of the total mass of the raw ore to obtain a grinding product;

[0013] (2) performing copper-lead mixed flotation on the grinding product obtained in step (1) to obtain a copper-lead mixed concentrate and a copper-lead mixed tailings;

[0014] (3) The copper-lead mixed concentrate obtained in step (2) is concentrated and dehydrated, and then flotation separated to obtain copper concentrate and lead concentrate.

[0015] Preferably, in step (1), the copper grade in the raw ore is 0.2-2.0%, and the lead grade is 0.5-5.5%.

[0016] Preferably, in step (1), 2000 to 4000 g / t of lime is added during ball milling.

[0017] Preferably, in step (2), the specific process of copper-lead mixed flotation comprises the following steps:

[0018] S1: preparing the grinding product into a slurry with a mass percentage concentration of 20-30%;

[0019] S2: adding 1000-2000 g / t of zinc sulfate and 500-1000 g / t of sodium sulfite to the slurry obtained in step S1, stirring for 3-5 min, then adding 10-50 g / t of ethyl dithiocarbamide and 5-30 g / t of butyl xanthate, stirring for 3-5 min, and finally adding 5-20 g / t of pine oil, stirring for 1-2 min, and then performing 3-6 min of copper-lead mixed roughing to obtain copper-lead mixed roughing concentrate and copper-lead mixed roughing tailings;

[0020] S3: The copper-lead mixed roughing concentrate obtained in step S2 is subjected to three copper-lead mixed selections in sequence to obtain a copper-lead mixed concentrate, wherein, during the first copper-lead mixed selection, 1000-2000 g / t of lime is added, stirred for 3-5 min, and then 500-1000 g / t of zinc sulfate and 250-500 g / t of sodium sulfite are added simultaneously, and stirred for 3-5 min; during the second copper-lead mixed selection, 500-1000 g / t of lime is added, stirred for 3-5 min, and then 250-500 g / t of zinc sulfate and 125-250 g / t of sodium sulfite are added simultaneously, and stirred for 3-5 min; the third copper-lead mixed selection is blank selection, and each copper-lead mixed selection time is 3-6 min;

[0021] The copper-lead mixed roughing tailings obtained in step S2 are subjected to two copper-lead mixed scavengings in sequence to obtain copper-lead mixed tailings, wherein during the first copper-lead mixed scavenging, 5-25 g / t ethyl thiocyanate and 2.5-15 g / t butyl xanthate are added simultaneously, stirred for 3-5 min, and then 2.5-10 g / t pine oil is added and stirred for 1-2 min; during the second copper-lead mixed scavenging, 2.5-12.5 g / t ethyl thiocyanate and 1.25-7.5 g / t butyl xanthate are added simultaneously, stirred for 3-5 min, and then 1.25-5 g / t pine oil is added and stirred for 1-2 min, and each scavenging time is 2-4 min;

[0022] The copper-lead mixed flotation is a flotation closed-circuit process.

[0023] Preferably, in step (3), the specific process of flotation separation of the copper-lead mixed concentrate comprises the following steps:

[0024] Q1: Add water to the copper-lead mixed concentrate for slurry adjustment, and add acid or alkali to adjust the slurry pH to 6-10 to obtain copper-lead mixed concentrate slurry;

[0025] Q2: Add 100-300 g / t of activated carbon to the copper-lead mixed concentrate slurry obtained in step Q1, stir for 3-6 min, then add 200-1000 g / t of combined inhibitor, stir for 3-5 min, then add 10-25 g / t of Z-200, stir for 2-3 min, finally add 2-15 g / t of pine oil, stir for 1-2 min, and then perform 3-6 min of separation and roughing of the copper-lead mixed concentrate to obtain a copper-lead separation roughing concentrate and a copper-lead separation roughing tailings;

[0026] Q3: The copper-lead separation roughing concentrate obtained in step Q2 is subjected to three copper-lead separation and concentration steps in sequence to obtain a copper concentrate, wherein during the first copper-lead separation and concentration, 100-500 g / t of a combined inhibitor is added and stirred for 2-3 min, during the second copper-lead separation and concentration, 50-250 g / t of a combined inhibitor is added and stirred for 2-3 min, and the third copper-lead separation and concentration is a blank concentration, and each copper-lead separation and concentration time is 3-6 min;

[0027] The copper-lead roughing tailings obtained in step Q2 are subjected to two copper-lead separation scavengings in sequence to obtain lead concentrate, wherein in the first copper-lead separation scavenging, 5-12.5 g / t of Z-200 is stirred for 2-3 min, and then 1-8 g / t of pine oil is added and stirred for 1-2 min, and in the second copper-lead separation scavenging, 2.5-5 g / t of Z-200 is stirred for 2-3 min, and then 0.5-4 g / t of pine oil is added and stirred for 1-2 min, and each scavenging time is 2-4 min;

[0028] The flotation separation of the copper-lead mixed concentrate is a flotation closed-circuit process.

[0029] Preferably, in the copper-lead mixed concentrate, the copper grade is 5.5-20%, and the lead grade is 9.5-30%.

[0030] The "g / t" mentioned in the present invention refers to the amount of reagent added relative to the original ore. For example, 100g / t of zinc sulfate means that 100g of zinc sulfate needs to be added to process 1 ton of original ore.

[0031] Beneficial effects of the present invention:

[0032] 1. The present invention is the first to use sodium periodate and mercaptosuccinic acid together to form a combined inhibitor, which can effectively produce a precise inhibition effect, inhibit galena, and hardly affect the floating of chalcopyrite. In the copper concentrate finally obtained, the copper grade is greater than 20%, the lead grade is less than 3%, and the copper recovery rate is greater than 89%.

[0033] 2. The combined inhibitor of the present invention does not contain highly toxic substances and will not cause toxic effects on the environment and human body during use. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 The present invention is a process flow chart of the flotation of lead sulfide ore. DETAILED DESCRIPTION

[0035] The present invention is further described in detail below in conjunction with specific embodiments.

[0036] In the examples and comparative examples of the present invention, chemical reagents not otherwise specified were all commercially available analytically pure reagents for the experiments.

[0037] Example 1

[0038] In this embodiment, the raw ore is a low-grade copper-lead-zinc sulfide ore in Dali, Yunnan, containing 0.42% copper, 0.58% lead, and 0.60% zinc. The copper-containing minerals are mainly chalcopyrite, and the lead-containing minerals are mainly galena. The combined inhibitor (SM-Pb) is prepared by sodium periodate and mercaptosuccinic acid in a mass ratio of 1:5, wherein the concentration of the sodium periodate solution is 1.5%, and the concentration of the mercaptosuccinic acid is 3.0%.

[0039] This embodiment adopts the following method to flotation separate the raw ore:

[0040] (1) The raw ore is wet-milled using a ball mill. During the ball milling, 3000 g / t of lime is added. The ore is milled until the ore particles with a grinding fineness of -0.074 mm account for 85% of the total mass of the raw ore, thereby obtaining a grinding product.

[0041] (2) The grinding product is prepared into a slurry with a mass percentage of 20%.

[0042] (3) 1500 g / t zinc sulfate and 750 g / t sodium sulfite were added to the slurry as zinc inhibitors and stirred for 4 min. Then, 40 g / t ethylthiocyanate and 25 g / t butyl xanthate were added as collectors and stirred for 4 min. Finally, 16 g / t pine oil was added and stirred for 1 min. Then, copper-lead mixed roughing was carried out for 5 min to obtain copper-lead mixed roughing concentrate and copper-lead mixed roughing tailings.

[0043] (4) The copper-lead mixed roughing concentrate was subjected to three copper-lead mixed selections, wherein, during the first copper-lead mixed selection, 1500 g / t of lime was added and stirred for 4 min, and then 750 g / t of zinc sulfate and 375 g / t of sodium sulfite were added simultaneously and stirred for 4 min; during the second copper-lead mixed selection, 750 g / t of lime was added and stirred for 4 min, and then 375 g / t of zinc sulfate and 187.5 g / t of sodium sulfite were added simultaneously and stirred for 4 min; the third copper-lead mixed selection was blank selection, and each copper-lead mixed selection was 5 min to obtain a copper-lead mixed concentrate. At the same time, the copper-lead mixed roughing tailings were subjected to two copper-lead mixed scavengings. During the first copper-lead mixed scavenging, 20 g / t ethyl thiocyanate and 12.5 g / t butyl xanthate were added simultaneously, stirred for 4 min, and then 8 g / t pine oil was added and stirred for 1 min. During the second copper-lead mixed scavenging, 10 g / t ethyl thiocyanate and 6.25 g / t butyl xanthate were added simultaneously, stirred for 4 min, and then 4 g / t pine oil was added and stirred for 1 min. The scavenging time for each time was 3 min to obtain copper-lead mixed tailings.

[0044] (5) The copper-lead mixed concentrate is concentrated and dehydrated, and then sodium hydroxide or sulfuric acid is added to the copper-lead mixed concentrate for slurry adjustment to obtain a copper-lead mixed concentrate slurry with a pH of 8.

[0045] (6) Add 200 g / t of activated carbon to the copper-lead mixed concentrate slurry, stir for 5 min, then add 600 g / t of SM-Pb, stir for 3 min, then add 16 g / t of Z-200, stir for 2 min, and finally add 5 g / t of pine oil, stir for 1 min. Then, perform 5 min of roughing of the copper-lead mixed concentrate to obtain a copper-lead separation roughing concentrate and a copper-lead separation roughing tailing.

[0046] (7) The copper-lead separation roughing concentrate was subjected to three copper-lead separation and selection, wherein, in the first copper-lead separation and selection, 300 g / t of SM-Pb was added, stirred for 2 min, and floated for 3 min; in the second copper-lead separation and selection, 150 g / t of SM-Pb was added, stirred for 2 min, and floated for 3 min; in the third copper-lead separation and selection, blank selection was performed, no reagent was added, and floated for 3 min to obtain copper concentrate. At the same time, the copper-lead separation roughing tailings were subjected to two scavenging selections, wherein, in the first scavenging selection, 8 g / t of Z-200 was added, stirred for 2 min, 2.5 g / t of pine oil was added, stirred for 1 min, and floated for 3 min; in the second scavenging selection, 4 g / t of Z-200 was added, stirred for 2 min, 1.25 g / t of pine oil was added, stirred for 1 min, and floated for 3 min to obtain lead concentrate.

[0047] Example 2

[0048] In this embodiment, the raw ore is a low-grade copper-lead-zinc sulfide ore in Xinjiang, the raw ore contains 0.36% copper, 0.44% lead, and 2.71% zinc, the copper-containing minerals are mainly chalcopyrite, and the lead-containing minerals are mainly galena. The combined inhibitor (SM-Pb) is prepared by sodium periodate and mercaptosuccinic acid in a mass ratio of 1:3, wherein the concentration of the sodium periodate solution is 0.5%, and the concentration of the mercaptosuccinic acid is 1.0%.

[0049] This embodiment adopts the following method to flotation separate the raw ore:

[0050] (1) The raw ore is wet-milled using a ball mill. During the ball milling, 2000 g / t of lime is added. The ore is milled until the ore particles with a grinding fineness of -0.074 mm account for 95% of the total mass of the raw ore, thereby obtaining a grinding product.

[0051] (2) The grinding product is prepared into a slurry with a mass percentage of 30%.

[0052] (3) Add 2000 g / t zinc sulfate and 1000 g / t sodium sulfite as zinc inhibitors to the slurry and stir for 5 min, then add 50 g / t ethylthiocyanate and 30 g / t butyl xanthate as collectors and stir for 5 min, finally add 20 g / t pine oil and stir for 2 min, then perform copper-lead mixed roughing for 6 min to obtain copper-lead mixed roughing concentrate and copper-lead mixed roughing tailings.

[0053] (4) The copper-lead mixed roughing concentrate is subjected to three copper-lead mixed selections, wherein, in the first copper-lead mixed selection, 1000 g / t of lime is added and stirred for 5 min, and then 1000 g / t of zinc sulfate and 500 g / t of sodium sulfite are added simultaneously and stirred for 5 min; in the second copper-lead mixed selection, 500 g / t of lime is added and stirred for 5 min, and then 500 g / t of zinc sulfate and 250 g / t of sodium sulfite are added simultaneously and stirred for 5 min; the third copper-lead mixed selection is blank selection, and each copper-lead mixed selection is 6 min to obtain a copper-lead mixed concentrate. At the same time, the copper-lead mixed roughing tailings were subjected to two copper-lead mixed scavengings. During the first copper-lead mixed scavenging, 25 g / t ethyl thiocyanate and 15 g / t butyl xanthate were added simultaneously, stirred for 5 min, and then 10 g / t pine oil was added and stirred for 2 min. During the second copper-lead mixed scavenging, 12.5 g / t ethyl thiocyanate and 7.5 g / t butyl xanthate were added simultaneously, stirred for 5 min, and then 5 g / t pine oil was added and stirred for 2 min. The scavenging time for each time was 4 min to obtain copper-lead mixed tailings.

[0054] (5) The copper-lead mixed concentrate is concentrated and dehydrated, and then sodium hydroxide or sulfuric acid is added to the copper-lead mixed concentrate for slurry adjustment to obtain a copper-lead mixed concentrate slurry with a pH of 6.

[0055] (6) Add 300 g / t of activated carbon to the copper-lead mixed concentrate slurry, stir for 6 min, then add 200 g / t of SM-Pb, stir for 3 min, then add 10 g / t of Z-200, stir for 3 min, and finally add 15 g / t of pine oil, stir for 1 min. Then, perform 6 min of roughing of the copper-lead mixed concentrate to obtain a copper-lead separation roughing concentrate and a copper-lead separation roughing tailing.

[0056] (7) The copper-lead separation roughing concentrate was subjected to three copper-lead separation and selection, wherein, in the first copper-lead separation and selection, 100 g / t of SM-Pb was added, stirred for 2 min, and floated for 3 min; in the second copper-lead separation and selection, 50 g / t of SM-Pb was added, stirred for 2 min, and floated for 3 min; in the third copper-lead separation and selection, blank selection was performed, no reagent was added, and floated for 3 min to obtain copper concentrate. At the same time, the copper-lead separation roughing tailings were subjected to two scavenging selections, wherein, in the first scavenging selection, 5 g / t of Z-200 was added, stirred for 3 min, 8 g / t of pine oil was added, stirred for 1 min, and floated for 3 min; in the second scavenging selection, 2.5 g / t of Z-200 was added, stirred for 3 min, 4 g / t of pine oil was added, stirred for 1 min, and floated for 3 min to obtain lead concentrate.

[0057] Example 3

[0058] In this embodiment, a copper-lead sulfide ore mixed concentrate in Zhaotong, Yunnan was used for the experiment. Since the ore material is already a copper-lead mixed concentrate, this embodiment does not need to start flotation from the original ore, and can directly start flotation from the copper-lead mixed concentrate. In the copper-lead mixed concentrate, the main metal minerals are galena and chalcopyrite, the Pb content is 20.66%, and the Cu content is 16.33%. The combined inhibitor (SM-Pb) is prepared by sodium periodate and mercaptosuccinic acid in a mass ratio of 1:7, wherein the concentration of the sodium periodate solution is 2.5%, and the concentration of the mercaptosuccinic acid is 5.0%.

[0059] This embodiment adopts the following method to flotation separate the raw ore:

[0060] (1) The copper-lead mixed concentrate is concentrated and dehydrated, and then sodium hydroxide or sulfuric acid is added to the copper-lead mixed concentrate for slurry adjustment to obtain a copper-lead mixed concentrate slurry with a pH of 10.

[0061] (2) Add 200 g / t of activated carbon to the copper-lead mixed concentrate slurry, stir for 5 min, then add 1000 g / t of SM-Pb, stir for 5 min, then add 25 g / t of Z-200, stir for 3 min, and finally add 8 g / t of pine oil, stir for 1 min. Then, perform 4 min of roughing of the copper-lead mixed concentrate to obtain a copper-lead separation roughing concentrate and a copper-lead separation roughing tailing.

[0062] (3) The copper-lead separation rougher concentrate was subjected to three copper-lead separation and selection, wherein, in the first copper-lead separation and selection, 500 g / t of SM-Pb was added, stirred for 3 minutes, and floated for 3 minutes; in the second copper-lead separation and selection, 250 g / t of SM-Pb was added, stirred for 3 minutes, and floated for 4 minutes; in the third copper-lead separation and selection, blank selection was performed, no reagent was added, and floated for 4 minutes to obtain copper concentrate. At the same time, the copper-lead separation rougher tailings were scavenged twice, wherein, in the first scavenging, 12.5 g / t of Z-200 was added, stirred for 3 minutes, 4 g / t of pine oil was added, stirred for 1 minute, and floated for 3 minutes; in the second scavenging, 5 g / t of Z-200 was added, stirred for 3 minutes, 2 g / t of pine oil was added, stirred for 1 minute, and floated for 3 minutes to obtain lead concentrate.

[0063] Example 4

[0064] In this embodiment, the raw ore is a low-grade copper-lead-zinc sulfide ore in Jiangxi, the raw ore contains 0.46% copper, 0.61% lead, and 0.76% zinc, the copper-containing minerals are mainly chalcopyrite, and the lead-containing minerals are mainly galena. The combined inhibitor (SM-Pb) is prepared by sodium periodate and mercaptosuccinic acid in a mass ratio of 1:4, wherein the concentration of the sodium periodate solution is 1.0%, and the concentration of the mercaptosuccinic acid is 2.0%.

[0065] This embodiment adopts the following method to flotation separate the raw ore:

[0066] (1) The raw ore is wet-milled using a ball mill. During the ball milling, 4000 g / t of lime is added. The ore is milled until the ore particles with a grinding fineness of -0.074 mm account for 90% of the total mass of the raw ore, thereby obtaining a grinding product.

[0067] (2) The grinding product is prepared into a slurry with a mass percentage of 25%.

[0068] (3) 1500 g / t zinc sulfate and 500 g / t sodium sulfite were added to the slurry as zinc inhibitors and stirred for 3 min. Then, 10 g / t ethylthiocyanate and 5 g / t butyl xanthate were added as collectors and stirred for 3 min. Finally, 5 g / t pine oil was added and stirred for 1 min. Then, copper-lead mixed roughing was carried out for 3 min to obtain copper-lead mixed roughing concentrate and copper-lead mixed roughing tailings.

[0069] (4) The copper-lead mixed roughing concentrate is subjected to three copper-lead mixed selections, wherein, in the first copper-lead mixed selection, 2000 g / t of lime is added and stirred for 5 min, and then 750 g / t of zinc sulfate and 250 g / t of sodium sulfite are added simultaneously and stirred for 5 min; in the second copper-lead mixed selection, 1000 g / t of lime is added and stirred for 5 min, and then 375 g / t of zinc sulfate and 125 g / t of sodium sulfite are added simultaneously and stirred for 5 min; the third copper-lead mixed selection is blank selection, and each copper-lead mixed selection is 5 min to obtain a copper-lead mixed concentrate. At the same time, the copper-lead mixed roughing tailings were subjected to two copper-lead mixed scavengings. During the first copper-lead mixed scavenging, 16 g / t of ethyl thiocyanate and 8 g / t of butyl xanthate were added simultaneously, stirred for 3 minutes, and then 5 g / t of pine oil was added and stirred for 1.5 minutes. During the second copper-lead mixed scavenging, 8 g / t of ethyl thiocyanate and 4 g / t of butyl xanthate were added simultaneously, stirred for 3 minutes, and then 2.5 g / t of pine oil was added and stirred for 1.5 minutes. The scavenging time for each time was 2 minutes to obtain copper-lead mixed tailings.

[0070] (5) The copper-lead mixed concentrate is concentrated and dehydrated, and then sodium hydroxide or sulfuric acid is added to the copper-lead mixed concentrate for slurry adjustment to obtain a copper-lead mixed concentrate slurry with a pH of 8.

[0071] (6) 100 g / t of activated carbon was added to the copper-lead mixed concentrate slurry, stirred for 3 min, then 600 g / t of SM-Pb was added, stirred for 4 min, then 16 g / t of Z-200 was added, stirred for 2.5 min, and finally 5 g / t of pine oil was added, stirred for 1.5 min. Then, the copper-lead mixed concentrate was roughly separated for 6 min to obtain a copper-lead separation rougher concentrate and a copper-lead separation rougher tailings.

[0072] (7) The copper-lead separation roughing concentrate was subjected to three copper-lead separation and selection, wherein, in the first copper-lead separation and selection, 300 g / t of SM-Pb was added, stirred for 2.5 min, and floated for 6 min; in the second copper-lead separation and selection, 150 g / t of SM-Pb was added, stirred for 2.5 min, and floated for 6 min; in the third copper-lead separation and selection, blank selection was performed, no reagent was added, and floated for 6 min to obtain copper concentrate. At the same time, the copper-lead separation roughing tailings were scavenged twice, wherein, in the first scavenging, 8 g / t of Z-200 was added, stirred for 2.5 min, 2.5 g / t of pine oil was added, stirred for 1.5 min, and floated for 2 min; in the second scavenging, 4 g / t of Z-200 was added, stirred for 2.5 min, 1.25 g / t of pine oil was added, stirred for 1.5 min, and floated for 2 min to obtain lead concentrate.

[0073] In this embodiment, the copper and lead grades in the copper concentrate and lead concentrate, as well as the yield recovery rate, are similar to those in Example 1.

[0074] Example 5

[0075] In this embodiment, the raw ore is a low-grade copper-lead-zinc sulfide ore in Baoshan, Hunan, containing 0.51% copper, 0.63% lead, and 0.83% zinc. The copper-containing minerals are mainly chalcopyrite, and the lead-containing minerals are mainly galena. The combined inhibitor (SM-Pb) is prepared by sodium periodate and mercaptosuccinic acid in a mass ratio of 1:5, with a sodium periodate solution concentration of 1.0% and a mercaptosuccinic acid concentration of 2.0%.

[0076] This embodiment adopts the following method to flotation separate the raw ore:

[0077] (1) The raw ore is wet-milled using a ball mill. During the ball milling, 3000 g / t of lime is added. The ore is milled until the ore particles with a grinding fineness of -0.074 mm account for 85% of the total mass of the raw ore, thereby obtaining a grinding product.

[0078] (2) The grinding product is prepared into a slurry with a mass percentage of 20%.

[0079] (3) 1000 g / t zinc sulfate and 1000 g / t sodium sulfite were added to the slurry as zinc inhibitors and stirred for 4 min. Then, 30 g / t ethylthiocyanate and 20 g / t butyl xanthate were added as collectors and stirred for 4 min. Finally, 5 g / t pine oil was added and stirred for 1 min. Then, copper-lead mixed roughing was carried out for 5 min to obtain copper-lead mixed roughing concentrate and copper-lead mixed roughing tailings.

[0080] (4) The copper-lead mixed roughing concentrate is subjected to three copper-lead mixed selections, wherein, in the first copper-lead mixed selection, 1500 g / t of lime is added and stirred for 4 min, and then 500 g / t of zinc sulfate and 500 g / t of sodium sulfite are added simultaneously and stirred for 4 min; in the second copper-lead mixed selection, 750 g / t of lime is added and stirred for 4 min, and then 250 g / t of zinc sulfate and 250 g / t of sodium sulfite are added simultaneously and stirred for 4 min; the third copper-lead mixed selection is blank selection, and each copper-lead mixed selection is 4 min to obtain a copper-lead mixed concentrate. At the same time, the copper-lead mixed roughing tailings were subjected to two copper-lead mixed scavengings. During the first copper-lead mixed scavenging, 5g / t ethyl thiocyanate and 2.5g / t butyl xanthate were added simultaneously, stirred for 3min, and then 2.5g / t pine oil was added and stirred for 1min. During the second copper-lead mixed scavenging, 2.5g / t ethyl thiocyanate and 1.25g / t butyl xanthate were added simultaneously, stirred for 3min, and then 1.25g / t pine oil was added and stirred for 1min. The scavenging time for each time was 3min to obtain copper-lead mixed tailings.

[0081] (5) The copper-lead mixed concentrate is concentrated and dehydrated, and then sodium hydroxide or sulfuric acid is added to the copper-lead mixed concentrate for slurry adjustment to obtain a copper-lead mixed concentrate slurry with a pH of 7.

[0082] (6) 100 g / t of activated carbon was added to the copper-lead mixed concentrate slurry, stirred for 6 min, then 800 g / t of SM-Pb was added, stirred for 4 min, then 20 g / t of Z-200 was added, stirred for 3 min, and finally 2 g / t of pine oil was added, stirred for 2 min. Then, the copper-lead mixed concentrate was roughly separated for 3 min to obtain a copper-lead separation rougher concentrate and a copper-lead separation rougher tailings.

[0083] (7) The copper-lead separation roughing concentrate was subjected to three copper-lead separation and selection, wherein, in the first copper-lead separation and selection, 400 g / t of SM-Pb was added, stirred for 4 minutes, and floated for 3 minutes; in the second copper-lead separation and selection, 200 g / t of SM-Pb was added, stirred for 3 minutes, and floated for 4 minutes; in the third copper-lead separation and selection, blank selection was performed, no reagent was added, and floated for 4 minutes to obtain copper concentrate. At the same time, the copper-lead separation roughing tailings were scavenged twice, wherein, in the first scavenging, 10 g / t of Z-200 was added, stirred for 3 minutes, 1 g / t of pine oil was added, stirred for 2 minutes, and floated for 3 minutes; in the second scavenging, 5 g / t of Z-200 was added, stirred for 3 minutes, 0.4 g / t of pine oil was added, stirred for 2 minutes, and floated for 3 minutes to obtain lead concentrate.

[0084] In this embodiment, the copper and lead grades in the copper concentrate and lead concentrate, as well as the yield recovery rate, are similar to those in Example 1.

[0085] Comparative Example 1

[0086] In this comparative example, the copper concentrate and the lead concentrate were obtained by flotation separation in the same manner as in Example 1, except that potassium dichromate was used to replace the combined depressant in this comparative example.

[0087] Comparative Example 2

[0088] In this comparative example, the copper concentrate and the lead concentrate were obtained by flotation separation in the same manner as in Example 3, except that sodium periodate was used to replace the combined depressant in this comparative example.

[0089] Comparative Example 3

[0090] In this comparative example, the copper concentrate and the lead concentrate were obtained by flotation separation in the same manner as in Example 3, except that mercaptosuccinic acid was used to replace the combined inhibitor in this comparative example.

[0091] Comparative Example 4

[0092] In this comparative example, the copper concentrate and the lead concentrate were obtained by flotation separation in the same manner as in Example 3, except that the combined inhibitor of sodium periodate and sodium thioglycolate was used in this comparative example to replace the combined inhibitor of the present invention.

[0093] The experimental results of Examples 1-3 are shown in Table 1.

[0094] Table 1

[0095]

[0096] It can be seen from Table 1 that the use of the combined inhibitor of the present invention for flotation separation of lead sulfide ore can effectively and accurately inhibit the release of lead ore, and has little effect on the flotation of chalcopyrite, so that copper and lead can be effectively separated, and finally a copper concentrate with a higher copper grade and a lower lead grade can be obtained, and the recovery rate is high.

[0097] The experimental results of Comparative Examples 1-4 are shown in Table 2.

[0098] Table 2

[0099]

[0100] By comparing Comparative Example 1 with Example 1, it can be seen that when potassium dichromate is used as an inhibitor, the final product yield, grade and recovery rate are lower than those of the combined inhibitor, especially the copper concentrate yield decreases significantly. When potassium dichromate is used as an inhibitor, it contains heavy metal elements, which causes it to be more harmful to the environment and human health. In addition, when potassium dichromate is used as an inhibitor, it has a greater impact on the floating of chalcopyrite, resulting in a more serious decrease in the copper concentrate yield.

[0101] By comparing Comparative Examples 2-3 with Example 3, it can be seen that when single sodium periodate or mercaptosuccinic acid is used as an inhibitor, copper-lead mutual inclusion is serious, and a mixed concentrate is finally produced, indicating that single sodium periodate or mercaptosuccinic acid has a weak inhibitory effect on galena. The present invention greatly improves the effect of the combined inhibitor by combining sodium periodate with mercaptosuccinic acid.

[0102] It can be seen from Comparative Example 4 that when sodium periodate and sodium thioglycolate are used as the combined inhibitor, the copper-lead mutual inclusion is serious and there is almost no inhibitory effect, which means that other thiol organic inhibitors cannot replace the mercaptosuccinic acid in the combined inhibitor of the present invention, which once again proves the uniqueness of the highly selective copper-lead separation combined inhibitor of the present invention.

[0103] In summary, the present invention combines sodium periodate and mercaptosuccinic acid to form a combined inhibitor, and applies it to the flotation separation of lead sulfide ore from copper and lead concentrates, which can significantly exert the precise inhibition effect of galena and reduce the influence on the flotation of chalcopyrite, so that the flotation separation of lead sulfide ore can be maintained at a high yield and recovery rate, while the copper and lead concentrates of higher grade can be obtained.

[0104] Finally, the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A highly selective copper-lead separation combined inhibitor, characterized in that: The combined inhibitor is prepared by mixing sodium periodate solution and mercaptosuccinic acid solution, wherein the mass ratio of sodium periodate to mercaptosuccinic acid is sodium periodate: mercaptosuccinic acid = 1:3-1:7, the concentration of the sodium periodate solution is 0.5-2.5%, and the concentration of the mercaptosuccinic acid solution is 1.0-5.0%.

2. A highly selective copper-lead separation combined inhibitor according to claim 1, characterized in that: In the combined inhibitor, the molecular formula of mercaptosuccinic acid is C4H6O4S, and its structural formula is:

3. Use of a highly selective copper-lead separation combined depressor according to any one of claims 1 to 2 in the flotation process of lead sulfide ore, characterized in that: The lead sulfide ore flotation process comprises the following steps: (1) ball milling the raw ore until the ore particles with a grinding fineness of -0.074 mm account for 85% to 95% of the total mass of the raw ore to obtain a grinding product; (2) performing copper-lead mixed flotation on the grinding product obtained in step (1) to obtain a copper-lead mixed concentrate and a copper-lead mixed tailings; (3) The copper-lead mixed concentrate obtained in step (2) is concentrated and dehydrated, and then flotation separated to obtain copper concentrate and lead concentrate.

4. The use according to claim 3, characterized in that: In the step (1), the copper grade in the raw ore is 0.2-2.0%, and the lead grade is 0.5-5.5%.

5. The use according to claim 3, characterized in that: In the step (1), 2000 to 4000 g / t of lime is added during ball milling.

6. The use according to claim 3, characterized in that: In the step (2), the specific process of copper-lead mixed flotation comprises the following steps: S1: preparing the grinding product into a slurry with a mass percentage concentration of 20-30%; S2: adding 1000-2000 g / t of zinc sulfate and 500-1000 g / t of sodium sulfite to the slurry obtained in step S1, stirring for 3-5 min, then adding 10-50 g / t of ethyl dithiocarbamide and 5-30 g / t of butyl xanthate, stirring for 3-5 min, and finally adding 5-20 g / t of pine oil, stirring for 1-2 min, and then performing 3-6 min of copper-lead mixed roughing to obtain copper-lead mixed roughing concentrate and copper-lead mixed roughing tailings; S3: The copper-lead mixed roughing concentrate obtained in step S2 is subjected to three copper-lead mixed selections in sequence to obtain a copper-lead mixed concentrate, wherein, during the first copper-lead mixed selection, 1000-2000 g / t of lime is added, stirred for 3-5 min, and then 500-1000 g / t of zinc sulfate and 250-500 g / t of sodium sulfite are added simultaneously, and stirred for 3-5 min; during the second copper-lead mixed selection, 500-1000 g / t of lime is added, stirred for 3-5 min, and then 250-500 g / t of zinc sulfate and 125-250 g / t of sodium sulfite are added simultaneously, and stirred for 3-5 min; the third copper-lead mixed selection is blank selection, and each copper-lead mixed selection time is 3-6 min; The copper-lead mixed roughing tailings obtained in step S2 are subjected to two copper-lead mixed scavengings in sequence to obtain copper-lead mixed tailings, wherein during the first copper-lead mixed scavenging, 5-25 g / t ethyl thiocyanate and 2.5-15 g / t butyl xanthate are added simultaneously, stirred for 3-5 min, and then 2.5-10 g / t pine oil is added and stirred for 1-2 min; during the second copper-lead mixed scavenging, 2.5-12.5 g / t ethyl thiocyanate and 1.25-7.5 g / t butyl xanthate are added simultaneously, stirred for 3-5 min, and then 1.25-5 g / t pine oil is added and stirred for 1-2 min, and each scavenging time is 2-4 min; The copper-lead mixed flotation is a flotation closed-circuit process.

7. The use according to claim 3, characterized in that: In the step (3), the specific process of flotation separation of copper-lead mixed concentrate is The following steps are involved: Q1: Add water to the copper-lead mixed concentrate for slurry adjustment, and add acid or alkali to adjust the slurry pH to 6-10 to obtain copper-lead mixed concentrate slurry; Q2: Add 100-300 g / t of activated carbon to the copper-lead mixed concentrate slurry obtained in step Q1, stir for 3-6 min, then add 200-1000 g / t of combined inhibitor, stir for 3-5 min, then add 10-25 g / t of Z-200, stir for 2-3 min, finally add 2-15 g / t of pine oil, stir for 1-2 min, and then perform 3-6 min of separation and roughing of the copper-lead mixed concentrate to obtain a copper-lead separation roughing concentrate and a copper-lead separation roughing tailings; Q3: The copper-lead separation roughing concentrate obtained in step Q2 is subjected to three copper-lead separation and concentration steps in sequence to obtain a copper concentrate, wherein during the first copper-lead separation and concentration, 100-500 g / t of a combined inhibitor is added and stirred for 2-3 min, during the second copper-lead separation and concentration, 50-250 g / t of a combined inhibitor is added and stirred for 2-3 min, and the third copper-lead separation and concentration is a blank concentration, and each copper-lead separation and concentration time is 3-6 min; The copper-lead roughing tailings obtained in step Q2 are subjected to two copper-lead separation scavengings in sequence to obtain lead concentrate, wherein in the first copper-lead separation scavenging, 5-12.5 g / t of Z-200 is stirred for 2-3 min, and then 1-8 g / t of pine oil is added and stirred for 1-2 min, and in the second copper-lead separation scavenging, 2.5-5 g / t of Z-200 is stirred for 2-3 min, and then 0.5-4 g / t of pine oil is added and stirred for 1-2 min, and each scavenging time is 2-4 min; The flotation separation of the copper-lead mixed concentrate is a flotation closed-circuit process.

8. The use according to claim 3, characterized in that: In the copper-lead mixed concentrate, the copper grade is 5.5-20%, and the lead grade is 9.5-30%.

Images