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

Abstract

The application 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 components of the combined inhibitor include sodium periodate and mercaptosuccinic acid, and the mass ratio of the sodium periodate to the mercaptosuccinic acid is 1:3-1:7. The combined inhibitor is composed of the sodium periodate and the mercaptosuccinic acid, is used in the process of separating copper and lead from a lead sulfide ore, and is used for accurately and effectively inhibiting galena, thereby reducing the influence of the combined inhibitor on chalcopyrite flotation, and finally making the lead sulfide ore have excellent flotation separation effect and obtaining high-grade copper and lead concentrates.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of mineral processing and non-ferrous metal flotation, and relates to a high-selectivity combined depressant for copper-lead separation and application thereof. BACKGROUND

[0002] Copper, lead and other non-ferrous metals are important resources for promoting industrial production and technological progress, and are widely used in the fields of national defense, semiconductors and electricity. The main sources of copper and lead ores are sulfide ores, but because copper and lead sulfide ores have similar floatability and are usually associated, and the mineral particle size is small, the flotation separation of copper-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 depressing lead and floating copper. The depressants are divided into inorganic and organic depressants, among which the organic depressants are more concerned due to their wide sources, low cost and environmental friendliness. However, many common organic depressants, such as carboxymethyl cellulose, starch, polyacrylamide, etc., have the disadvantages of poor solubility and difficulty in settling, which limits their application effect in industry. In contrast, the application of high-efficiency inorganic depressants in industry is increasingly developed. Common inorganic depressants include bichromate, potassium permanganate, sodium cyanide, etc., although these depressants have strong selectivity and wide application range, but they have high toxicity and will produce cyanide-containing wastewater after use, which is difficult to handle and causes serious threat to the environment and human health.

[0004] In the existing process of depressing lead and floating copper, the depressant also has the problem of relatively limited effectiveness, which leads to incomplete separation of copper and lead, and serious mutual inclusion of copper and lead in the concentrate, resulting in mixed concentrate. The traditional single depressant cannot effectively solve this problem and cannot meet the separation requirements of complex sulfide ores,

[0005] Therefore, it is necessary to provide a high-selectivity combined depressant for copper-lead separation, which is applied to the flotation process of lead sulfide ore, and based on the chemical synergistic effect of mixed medication, a more precise selective inhibition effect is realized. At the same time, the use of the depressant avoids the harm to the environment and human health. SUMMARY

[0006] In order to overcome the problems in the background art, the application uses sodium periodate and mercaptosuccinic acid to form a combined depressant, and applies it to the flotation process of lead sulfide ore, to precisely select the inhibition of galena, while almost not affecting the flotation of chalcopyrite, thereby realizing the efficient separation of galena and chalcopyrite, and the combined depressant does not contain toxic substances, avoiding the harm to the environment and human body caused by the use of the combined depressant.

[0007] In order to achieve the above purpose, the application realizes the technical scheme as follows:

[0008] The present application discloses a high-selectivity copper-lead separation combined inhibitor, which is prepared by mixing sodium periodate solution and sulfmercapto succinic acid solution, wherein the mass ratio of sodium periodate to sulfmercapto succinic acid is 1:3-1:7, the concentration of the sodium periodate solution is 0.5-2.5%, and the concentration of the sulfmercapto succinic acid solution is 1.0-5.0%.

[0009] Preferably, the sulfmercapto succinic acid has a molecular formula of C4H6O4S and a structural formula of

[0010]

[0011] The present application also discloses an application of the combined inhibitor in lead sulfide ore flotation process, which comprises the following steps:

[0012] (1) ball milling the raw ore until the grinding fineness of-0.074 mm is 85%-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 the step (1) to obtain copper-lead mixed concentrate and copper-lead mixed tailings;

[0014] (3) performing concentration and dehydration treatment on the copper-lead mixed concentrate obtained in the step (2), and then performing flotation separation to obtain copper concentrate and lead concentrate.

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

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

[0017] Preferably, in the step (2), the 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 into the slurry obtained in the step S1, stirring for 3-5 min, then adding 10-50 g / t of ethylthiuram sodium and 5-30 g / t of butyl xanthate respectively, stirring for 3-5 min, finally adding 5-20 g / t of pine oil, stirring for 1-2 min, and then performing copper-lead mixed rough separation for 3-6 min to obtain copper-lead mixed rough separation concentrate and copper-lead mixed rough separation tailings;

[0020] S3: the copper-lead mixed concentrate obtained in step S2 is subjected to three copper-lead mixed cleaning in turn, wherein, in the first copper-lead mixed cleaning, 1000-2000 g / t of lime is added, and stirring is performed for 3-5 min, then 500-1000 g / t of zinc sulfate and 250-500 g / t of sodium sulfite are added at the same time, and stirring is performed for 3-5 min, in the second copper-lead mixed cleaning, 500-1000 g / t of lime is added, and stirring is performed for 3-5 min, then 250-500 g / t of zinc sulfate and 125-250 g / t of sodium sulfite are added at the same time, and stirring is performed for 3-5 min, and the third copper-lead mixed cleaning is blank cleaning, and the time for each copper-lead mixed cleaning is 3-6 min;

[0021] The copper-lead mixed tailings obtained in step S2 are subjected to two copper-lead mixed scavenging in turn, to obtain copper-lead mixed tailings, wherein, in the first copper-lead mixed scavenging, 5-25 g / t of ethylthiuram and 2.5-15 g / t of butyl xanthate are added at the same time, and stirring is performed for 3-5 min, then 2.5-10 g / t of pine oil is added, and stirring is performed for 1-2 min, in the second copper-lead mixed scavenging, 2.5-12.5 g / t of ethylthiuram and 1.25-7.5 g / t of butyl xanthate are added at the same time, and stirring is performed for 3-5 min, then 1.25-5 g / t of pine oil is added, and stirring is performed for 1-2 min, and the time for each scavenging is 2-4 min;

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

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

[0024] Q1: water is added to the copper-lead mixed concentrate for slurry preparation, and acid or alkali is added to adjust the pH of the slurry to 6-10, to obtain a copper-lead mixed concentrate slurry;

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

[0026] Q3: the copper-lead separation rough concentrate obtained in step Q2 is subjected to three copper-lead separation cleanings in turn to obtain a copper concentrate, wherein, in the first copper-lead separation cleaning, 100-500 g / t of the combined depressant is added, and stirring is performed for 2-3 min, in the second copper-lead separation cleaning, 50-250 g / t of the combined depressant is added, and stirring is performed for 2-3 min, and the third copper-lead separation cleaning is a blank cleaning, and the time for each copper-lead separation cleaning is 3-6 min;

[0027] The copper-lead separation rough concentrate obtained in step Q2 is subjected to two copper-lead separation cleanings in turn to obtain a lead concentrate, wherein, in the first copper-lead separation cleaning, 5-12.5 g / t of Z-200 is added, and stirring is performed for 2-3 min, then 1-8 g / t of pine oil is added, and stirring is performed for 1-2 min, in the second copper-lead separation cleaning, 2.5-5 g / t of Z-200 is added, and stirring is performed for 2-3 min, then 0.5-4 g / t of pine oil is added, and stirring is performed for 1-2 min, and the time for each cleaning is 2-4 min;

[0028] The copper-lead mixed concentrate flotation separation is a 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] In the present application, "g / t" refers to the addition amount of the reagent relative to the raw ore, for example, 100 g / t of zinc sulfate refers to that 100 g of zinc sulfate is added for processing 1 ton of raw ore.

[0031] The present application has the following beneficial effects:

[0032] 1. The present application first uses sodium periodate and mercaptosuccinic acid in combination to form a combined depressant, which can effectively produce precise inhibition effect and inhibit galena, while almost not affecting the flotation of chalcopyrite, and finally the copper concentrate obtained has a copper grade of greater than 20%, a lead grade of less than 3%, and a copper recovery rate of greater than 89%.

[0033] 2. The combined depressant of the present application does not contain toxic substances, and during use, it will not have toxic effects on the environment and human body. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 The present application is a flotation process flow chart for lead sulfide ore. DETAILED DESCRIPTION

[0035] The present application will be further described in detail below in combination with specific examples.

[0036] In the examples and comparative examples of the present application, commercially available analytical pure chemicals are used for experiments, unless otherwise specified.

[0037] Example 1

[0038] In this example, the raw ore is a low-grade copper-lead-zinc sulfide ore from Dali, Yunnan, containing 0.42% copper, 0.58% lead, and 0.60% zinc. The main copper-containing mineral is chalcopyrite, and the main lead-containing mineral is galena. The combined depressant (SM-Pb) is prepared by mixing sodium periodate and mercaptosuccinic acid at a mass ratio of 1:5. The concentration of sodium periodate solution is 1.5%, and the concentration of mercaptosuccinic acid is 3.0%.

[0039] In this example, the following method is used to separate the raw ore by flotation:

[0040] (1) Wet ball milling of the raw ore is performed using a ball mill. During ball milling, 3000g / t of lime is added. The milling is continued until the grinding fineness reaches 85% of the total mass of the raw ore with a particle size of -0.074mm, obtaining a ground product.

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

[0042] (3) 1500g / t of zinc sulfate and 750g / t of sodium sulfite are added to the slurry as zinc depressants, stirring for 4 minutes. Then, 40g / t of ethylthiuram sodium and 25g / t of butyl xanthate are added as collectors, stirring for 4 minutes. Finally, 16g / t of pine oil is added, stirring for 1 minute. Then, 5 minutes of copper-lead bulk roughing is performed, obtaining copper-lead bulk roughing concentrate and copper-lead bulk roughing tailings.

[0043] (4) The copper-lead bulk roughing concentrate is subjected to three copper-lead bulk cleanings. In the first copper-lead bulk cleaning, 1500g / t of lime is added, stirring for 4 minutes. Then, 750g / t of zinc sulfate and 375g / t of sodium sulfite are added simultaneously, stirring for 4 minutes. In the second copper-lead bulk cleaning, 750g / t of lime is added, stirring for 4 minutes. Then, 375g / t of zinc sulfate and 187.5g / t of sodium sulfite are added simultaneously, stirring for 4 minutes. The third copper-lead bulk cleaning is a blank cleaning, each copper-lead bulk cleaning lasting 5 minutes, obtaining copper-lead bulk concentrate. At the same time, the copper-lead bulk roughing tailings are subjected to two copper-lead bulk scavengings. In the first copper-lead bulk scavenging, 20g / t of ethylthiuram sodium and 12.5g / t of butyl xanthate are added simultaneously, stirring for 4 minutes. Then, 8g / t of pine oil is added, stirring for 1 minute. In the second copper-lead bulk scavenging, 10g / t of ethylthiuram sodium and 6.25g / t of butyl xanthate are added simultaneously, stirring for 4 minutes. Then, 4g / t of pine oil is added, stirring for 1 minute. Each scavenging lasts for 3 minutes, obtaining copper-lead bulk tailings.

[0044] (5) Concentrate and dewater the copper-lead mixed concentrate, and then add sodium hydroxide or sulfuric acid to the copper-lead mixed concentrate to adjust the pulp to pH = 8.

[0045] (6) Add 200 g / t of activated carbon to the copper-lead mixed concentrate pulp, 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 copper-lead mixed concentrate roughing to obtain copper-lead separation roughing concentrate and copper-lead separation roughing tailings.

[0046] (7) Perform three copper-lead separation cleanings on the copper-lead separation roughing concentrate, wherein, in the first copper-lead separation cleaning, add 300 g / t of SM-Pb, stir for 2 min, and float for 3 min; in the second copper-lead separation cleaning, add 150 g / t of SM-Pb, stir for 2 min, and float for 3 min; in the third copper-lead separation cleaning, perform blank cleaning without adding reagents, and float for 3 min to obtain copper concentrate. At the same time, perform two cleanings on the copper-lead separation roughing tailings, wherein, in the first cleaning, add 8 g / t of Z-200, stir for 2 min, add 2.5 g / t of pine oil, stir for 1 min, and float for 3 min; in the second cleaning, add 4 g / t of Z-200, stir for 2 min, add 1.25 g / t of pine oil, stir for 1 min, and float for 3 min to obtain lead concentrate.

[0047] Example 2

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

[0049] In this example, the following method is used to float and separate the raw ore:

[0050] (1) Use a ball mill to wet ball mill the raw ore. When ball milling, add 2000 g / t of lime. Ball mill until the grinding fineness of the ground ore is 95% of the total mass of the raw ore with a particle size of -0.074 mm to obtain the ground ore product.

[0051] (2) Prepare the ground ore product into a pulp with a mass percentage of 30%.

[0052] (3) adding 2000 g / t zinc sulfate and 1000 g / t sodium sulfite as zinc depressants to the ore pulp, stirring for 5 min, then adding 50 g / t ethylthiuram sodium and 30 g / t butyl xanthate as collectors, stirring for 5 min, and finally adding 20 g / t pine oil, stirring for 2 min, and then performing 6 min copper-lead bulk roughing to obtain copper-lead bulk roughing concentrate and copper-lead bulk roughing tailings.

[0053] (4) performing three times of copper-lead bulk cleaning on the copper-lead bulk roughing concentrate, wherein 1000 g / t of lime is added in the first copper-lead bulk cleaning, stirring for 5 min, then 1000 g / t of zinc sulfate and 500 g / t of sodium sulfite are added at the same time, stirring for 5 min, 500 g / t of lime is added in the second copper-lead bulk cleaning, stirring for 5 min, then 500 g / t of zinc sulfate and 250 g / t of sodium sulfite are added at the same time, stirring for 5 min, and the third copper-lead bulk cleaning is blank cleaning, each copper-lead bulk cleaning for 6 min, to obtain copper-lead bulk concentrate. Meanwhile, two times of copper-lead bulk scavenging is performed on the copper-lead bulk roughing tailings, wherein 25 g / t of ethylthiuram sodium and 15 g / t of butyl xanthate are added at the same time in the first copper-lead bulk scavenging, stirring for 5 min, then 10 g / t of pine oil is added, stirring for 2 min, 12.5 g / t of ethylthiuram sodium and 7.5 g / t of butyl xanthate are added at the same time in the second copper-lead bulk scavenging, stirring for 5 min, then 5 g / t of pine oil is added, stirring for 2 min, each scavenging for 4 min, to obtain copper-lead bulk tailings.

[0054] (5) performing concentration and dehydration treatment on the copper-lead bulk concentrate, then adding sodium hydroxide or sulfuric acid to the copper-lead bulk concentrate to adjust the pulp to obtain copper-lead bulk concentrate pulp with pH = 6.

[0055] (6) adding 300 g / t of activated carbon to the copper-lead bulk concentrate pulp, stirring for 6 min, then adding 200 g / t of SM-Pb, stirring for 3 min, then adding 10 g / t of Z-200, stirring for 3 min, and finally adding 15 g / t of pine oil, stirring for 1 min. Then performing 6 min copper-lead bulk cleaning to obtain copper-lead separation roughing concentrate and copper-lead separation roughing tailings.

[0056] (7) The copper-lead separation rough concentrate is subjected to three times of copper-lead separation cleaning, wherein, in the first time of copper-lead separation cleaning, 100 g / t of SM-Pb is added, stirring for 2 min, and flotation for 3 min; in the second time of copper-lead separation cleaning, 50 g / t of SM-Pb is added, stirring for 2 min, and flotation for 3 min; in the third time of copper-lead separation cleaning, it is blank cleaning without adding reagents, and flotation for 3 min, to obtain copper concentrate. At the same time, the copper-lead separation rough tailings are subjected to two times of scavenging, wherein, in the first time of scavenging, 5 g / t of Z-200 is added, stirring for 3 min, 8 g / t of pine oil is added, stirring for 1 min, and flotation for 3 min; in the second time of scavenging, 2.5 g / t of Z-200 is added, stirring for 3 min, 4 g / t of pine oil is added, stirring for 1 min, and flotation for 3 min, to obtain lead concentrate.

[0057] Example 3

[0058] In this embodiment, a certain copper-lead sulfide mixed concentrate in Zhaotong, Yunnan is used for experiment. Since the ore material is already a copper-lead mixed concentrate, the flotation does not need to start from the raw ore, but can directly start 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 depressor (SM-Pb) is prepared by sodium periodate and mercaptosuccinic acid in a mass ratio of 1:7, wherein the sodium periodate solution concentration is 2.5%, and the mercaptosuccinic acid concentration is 5.0%.

[0059] In this embodiment, the following method is used to separate the raw ore by flotation:

[0060] (1) The copper-lead mixed concentrate is subjected to concentration and dehydration treatment, and then sodium hydroxide or sulfuric acid is added to the copper-lead mixed concentrate for slurry conditioning to obtain a copper-lead mixed concentrate slurry with pH = 10.

[0061] (2) 200 g / t of activated carbon is added to the copper-lead mixed concentrate slurry, stirring for 5 min, then 1000 g / t of SM-Pb is added, stirring for 5 min, then 25 g / t of Z-200 is added, stirring for 3 min, and finally 8 g / t of pine oil is added, stirring for 1 min. Then, 4 min of copper-lead mixed concentrate roughing is carried out to obtain copper-lead separation rough concentrate and copper-lead separation rough tailings.

[0062] (3) The copper-lead separation rough concentrate is subjected to three times of copper-lead separation cleaning, wherein, in the first time of copper-lead separation cleaning, 500 g / t of SM-Pb is added, stirring is carried out for 3 min, and flotation is carried out for 3 min; in the second time of copper-lead separation cleaning, 250 g / t of SM-Pb is added, stirring is carried out for 3 min, and flotation is carried out for 4 min; in the third time of copper-lead separation cleaning, blank cleaning is carried out without adding reagents, and flotation is carried out for 4 min, to obtain a copper concentrate. Meanwhile, the copper-lead separation rough tailings are subjected to two times of scavenging, wherein, in the first time of scavenging, 12.5 g / t of Z-200 is added, stirring is carried out for 3 min, 4 g / t of pine oil is added, stirring is carried out for 1 min, and flotation is carried out for 3 min; in the second time of scavenging, 5 g / t of Z-200 is added, stirring is carried out for 3 min, 2 g / t of pine oil is added, stirring is carried out for 1 min, and flotation is carried out for 3 min, to obtain a lead concentrate.

[0063] Example 4

[0064] In this example, the raw ore is a low-grade copper-lead-zinc sulfide ore in Jiangxi, the raw ore contains 0.46% of copper, 0.61% of lead, and 0.76% of zinc, the copper-containing mineral is mainly chalcopyrite, and the lead-containing mineral is mainly galena. The combined depressant (SM-Pb) is prepared by mixing sodium periodate and mercaptosuccinic acid at 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] In this example, the raw ore is subjected to flotation separation by using the following method:

[0066] (1) The raw ore is subjected to wet ball milling by using a ball mill, lime 4000 g / t is added during the ball milling, and the ball milling is carried out until the grinding fineness of the ground ore product is 90% of the total mass of the raw ore in terms of the ore particles with a particle size of-0.074 mm.

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

[0068] (3) 1500 g / t of zinc sulfate and 500 g / t of sodium sulfite are added to the slurry as zinc depressants, stirring is carried out for 3 min, then 10 g / t of ethylthiuram sodium and 5 g / t of butyl xanthate are added as collectors, stirring is carried out for 3 min, finally 5 g / t of pine oil is added, stirring is carried out for 1 min, and then 3 min of copper-lead mixed rough cleaning is carried out, to obtain a copper-lead mixed rough cleaning concentrate and a copper-lead mixed rough cleaning tailings.

[0069] (4) The copper-lead mixed roughing concentrate was subjected to three copper-lead mixed selections, wherein, during the first copper-lead mixed selection, 2000 g / t of lime was added and stirred for 5 minutes, and then 750 g / t of zinc sulfate and 250 g / t of sodium sulfite were added at the same time and stirred for 5 minutes; during the second copper-lead mixed selection, 1000 g / t of lime was added and stirred for 5 minutes, and then 375 g / t of zinc sulfate and 125 g / t of sodium sulfite were added at the same time and stirred for 5 minutes; the third copper-lead mixed selection was a blank selection, and each copper-lead mixed selection was 5 minutes 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 ethyl thiocyanate and 8 g / t butyl xanthate were added simultaneously, stirred for 3 minutes, and then 5 g / t pine oil was added and stirred for 1.5 minutes. During the second copper-lead mixed scavenging, 8 g / t ethyl thiocyanate and 4 g / t butyl xanthate were added simultaneously, stirred for 3 minutes, and then 2.5 g / t 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 and stirred for 3 min. 600 g / t of SM-Pb was then added and stirred for 4 min. 16 g / t of Z-200 was then added and stirred for 2.5 min. Finally, 5 g / t of pine oil was added and stirred for 1.5 min. The copper-lead mixed concentrate was then subjected to roughing for 6 min to obtain a copper-lead separation roughing concentrate and a copper-lead separation roughing tailing.

[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 minutes, and floated for 6 minutes; in the second copper-lead separation and selection, 150 g / t of SM-Pb was added, stirred for 2.5 minutes, and floated for 6 minutes; in the third copper-lead separation and selection, blank selection was performed, no reagent was added, and floated for 6 minutes 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 2.5 minutes, 2.5 g / t of pine oil was added, stirred for 1.5 minutes, and floated for 2 minutes; in the second scavenging selection, 4 g / t of Z-200 was added, stirred for 2.5 minutes, 1.25 g / t of pine oil was added, stirred for 1.5 minutes, and floated for 2 minutes 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 and recovery rates, are similar to those in Example 1.

[0074] Example 5

[0075] In this example, the raw ore is a low-grade copper-lead-zinc sulfide ore from Baoshan, Hunan Province, containing 0.51% copper, 0.63% lead, and 0.83% zinc. The main copper-containing mineral is chalcopyrite, and the main lead-containing mineral is galena. The combined depressant (SM-Pb) is prepared by mixing sodium periodate and mercaptosuccinic acid at a mass ratio of 1:5. The concentration of sodium periodate solution is 1.0%, and the concentration of mercaptosuccinic acid is 2.0%.

[0076] In this example, the following method is used to separate the raw ore by flotation:

[0077] (1) Wet ball milling of the raw ore is performed using a ball mill. During ball milling, 3000g / t of lime is added. The milling is continued until the grinding fineness reaches 85% of the total mass of the raw ore with a particle size of -0.074mm. The milled product is obtained.

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

[0079] (3) 1000g / t of zinc sulfate and 1000g / t of sodium sulfite are added to the slurry as zinc depressants, and stirred for 4 minutes. Then, 30g / t of ethylthiuram sodium and 20g / t of butyl xanthate are added as collectors, and stirred for 4 minutes. Finally, 5g / t of pine oil is added, and stirred for 1 minute. Then, 5 minutes of copper-lead bulk roughing is performed, and copper-lead bulk roughing concentrate and copper-lead bulk roughing tailings are obtained.

[0080] (4) The copper-lead bulk roughing concentrate is subjected to three times of copper-lead bulk cleaning. In the first copper-lead bulk cleaning, 1500g / t of lime is added, and stirred for 4 minutes. Then, 500g / t of zinc sulfate and 500g / t of sodium sulfite are added simultaneously, and stirred for 4 minutes. In the second copper-lead bulk cleaning, 750g / t of lime is added, and stirred for 4 minutes. Then, 250g / t of zinc sulfate and 250g / t of sodium sulfite are added simultaneously, and stirred for 4 minutes. The third copper-lead bulk cleaning is a blank cleaning, and each copper-lead bulk cleaning is performed for 4 minutes. Copper-lead bulk concentrate is obtained. At the same time, the copper-lead bulk roughing tailings are subjected to two times of copper-lead bulk scavenging. In the first copper-lead bulk scavenging, 5g / t of ethylthiuram sodium and 2.5g / t of butyl xanthate are added simultaneously, and stirred for 3 minutes. Then, 2.5g / t of pine oil is added, and stirred for 1 minute. In the second copper-lead bulk scavenging, 2.5g / t of ethylthiuram sodium and 1.25g / t of butyl xanthate are added simultaneously, and stirred for 3 minutes. Then, 1.25g / t of pine oil is added, and stirred for 1 minute. Each scavenging is performed for 3 minutes, and copper-lead bulk tailings are obtained.

[0081] (5) Concentrate and dewater the copper-lead bulk concentrate, then add sodium hydroxide or sulfuric acid to the copper-lead bulk concentrate to obtain a copper-lead bulk concentrate slurry with pH = 7.

[0082] (6) Add 100 g / t of activated carbon to the copper-lead bulk concentrate slurry, stir for 6 min, then add 800 g / t of SM-Pb, stir for 4 min, then add 20 g / t of Z-200, stir for 3 min, and finally add 2 g / t of pine oil, stir for 2 min. Then perform 3 min copper-lead bulk roughing to obtain a copper-lead separation roughing concentrate and a copper-lead separation roughing tailing.

[0083] (7) Perform three copper-lead separation cleanings on the copper-lead separation roughing concentrate, wherein, in the first copper-lead separation cleaning, add 400 g / t of SM-Pb, stir for 4 min, and float for 3 min; in the second copper-lead separation cleaning, add 200 g / t of SM-Pb, stir for 3 min, and float for 4 min; and in the third copper-lead separation cleaning, perform a blank cleaning without adding any reagent, and float for 4 min, to obtain a copper concentrate. Meanwhile, perform two cleanings on the copper-lead separation roughing tailing, wherein, in the first cleaning, add 10 g / t of Z-200, stir for 3 min, add 1 g / t of pine oil, stir for 2 min, and float for 3 min; and in the second cleaning, add 5 g / t of Z-200, stir for 3 min, add 0.4 g / t of pine oil, stir for 2 min, and float for 3 min, to obtain a lead concentrate.

[0084] In this embodiment, the copper grade, lead grade, and yield recovery rate of the copper concentrate and lead concentrate are similar to those of Example 1.

[0085] Comparative Example 1

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

[0087] Comparative Example 2

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

[0089] Comparative Example 3

[0090] In this comparative example, the copper concentrate and lead concentrate are obtained by flotation separation using the same method as in Example 3, except that mercaptobutandioic acid is used to replace the combined depressant.

[0091] Comparative Example 4

[0092] The comparative example uses the same method as example 3 to float and separate copper concentrate and lead concentrate, the difference is that the comparative example uses a combination of sodium periodate and sodium mercaptoacetate as a combination inhibitor instead of the combination inhibitor of the application.

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

[0094] Table 1

[0095]

[0096] As can be seen from Table 1, using the combination inhibitor of the application for floatation separation of lead sulfide ore can effectively and accurately inhibit galena, has less effect on chalcopyrite flotation, effectively separates copper and lead, and finally can obtain copper concentrate with high copper grade and low lead grade, and high recovery rate.

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

[0098] Table 2

[0099]

[0100] As can be seen from the comparison of comparative example 1 and example 1, using potassium dichromate as an inhibitor, the yield, grade and recovery rate of the final product are lower than those of the combination inhibitor, especially the copper concentrate yield decreases more obviously. When potassium dichromate is used as an inhibitor, it contains heavy metal elements, which has great harm to the environment and human health. In addition, when potassium dichromate is used as an inhibitor, it has a greater effect on chalcopyrite flotation, resulting in a more serious decrease in copper concentrate yield.

[0101] As can be seen from the comparison of comparative example 2-3 and example 3, using single sodium periodate or mercaptosuccinic acid as an inhibitor, copper and lead are severely intermingled, resulting in mixed concentrate, which shows that single sodium periodate or mercaptosuccinic acid has weak inhibitory effect on lead ore. The application greatly improves the effect of the combination inhibitor by using sodium periodate and mercaptosuccinic acid together.

[0102] As can be seen from comparative example 4, when sodium periodate and sodium mercaptoacetate are used as a combination inhibitor, copper and lead are severely intermingled, and there is almost no inhibitory effect, which shows that other mercapto-based organic inhibitors cannot replace mercaptosuccinic acid in the combination inhibitor of the application, further proving the uniqueness of the high-selectivity copper-lead separation combination inhibitor of the application.

[0103] In summary, by using sodium periodate and mercaptosuccinic acid in combination, a combined inhibitor is formed, which is applied to the process of flotation separation of copper and lead concentrate from lead sulfide ore, can significantly play the precise inhibition effect on lead ore, and reduce the influence on chalcopyrite floating, so as to keep the flotation separation of lead sulfide ore at a high yield and recovery rate, and the copper and lead concentrate with high grade.

[0104] Finally, the above examples are only used to illustrate the technical solutions of the present application, but not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced equivalently without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A highly selective copper-lead separation combined inhibitor, characterized by: The combined inhibitor is prepared 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 = 1:3-1:7, 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. The 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 depressant according to any one of claims 1-2 in a lead sulfide ore flotation process, 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 the grinding product; (2) performing copper-lead mixed flotation on the grinding product obtained in step (1) to obtain copper-lead mixed concentrate and copper-lead mixed tailings; (3) The copper-lead mixed concentrate obtained in step (2) is concentrated and dehydrated, and then subjected to flotation separation 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), 2000-4000 g / t of lime is added during ball milling.

6. The use according to claim 3, characterized in that: In step (2), the specific process of copper-lead mixed flotation includes 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 ore pulp 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 copper-lead mixed roughing for 3-6 min 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 and stirred for 3-5 minutes, 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 minutes; during the second copper-lead mixed selection, 500-1000 g / t of lime is added and stirred for 3-5 minutes, 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 minutes; the third copper-lead mixed selection is a blank selection, and the copper-lead mixed selection time for each time is 3-6 minutes; The copper-lead mixed roughing tailings obtained in step S2 are subjected to two copper-lead mixed scavenging operations in sequence to obtain copper-lead mixed tailings, wherein during the first copper-lead mixed scavenging operation, 5-25 g / t ethyl sulfoxide and 2.5-15 g / t butyl xanthate are simultaneously added, stirred for 3-5 minutes, and then 2.5-10 g / t pine oil is added and stirred for 1-2 minutes; during the second copper-lead mixed scavenging operation, 2.5-12.5 g / t ethyl sulfoxide and 1.25-7.5 g / t butyl xanthate are simultaneously added and stirred for 3-5 minutes, and then 1.25-5 g / t pine oil is added and stirred for 1-2 minutes, and each scavenging operation takes 2-4 minutes; The copper-lead mixed flotation is a flotation closed-circuit process.

7. The use according to claim 3, characterized in that: In 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 to prepare the slurry, and add acid or alkali to adjust the slurry pH to 6-10 to obtain the copper-lead mixed concentrate slurry; Q2: adding 100-300 g / t of activated carbon to the copper-lead mixed concentrate slurry obtained in step Q1, stirring for 3-6 minutes, then adding 200-1000 g / t of a combined inhibitor, stirring for 3-5 minutes, then adding 10-25 g / t of Z-200, stirring for 2-3 minutes, and finally adding 2-15 g / t of pine oil, stirring for 1-2 minutes, and then performing a 3-6 minute 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 minutes; during the second copper-lead separation and concentration, 50-250 g / t of a combined inhibitor is added and stirred for 2-3 minutes; the third copper-lead separation and concentration is a blank concentration, and the copper-lead separation and concentration time for each step is 3-6 minutes; The copper-lead roughing tailings obtained in step Q2 are subjected to two copper-lead separation scavenging operations in sequence to obtain a lead concentrate, wherein during the first copper-lead separation scavenging operation, 5-12.5 g / t of Z-200 is added and stirred for 2-3 minutes, and then 1-8 g / t of pine oil is added and stirred for 1-2 minutes; during the second copper-lead separation scavenging operation, 2.5-5 g / t of Z-200 is added and stirred for 2-3 minutes, and then 0.5-4 g / t of pine oil is added and stirred for 1-2 minutes. The scavenging time for each operation is 2-4 minutes; 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%.

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