A flotation method for low-grade copper-cobalt ore

Abstract

The present invention belongs to the field of flotation, and particularly relates to a flotation method for low-grade copper-cobalt ore. The method comprises the following steps: grinding the raw copper-cobalt ore and then slurrying the raw ore to obtain raw ore slurry; then performing a sulfide ore roughing process to obtain a roughing concentrate a and a roughing tailing a; then performing a beneficiation treatment on the roughing concentrate a to obtain a copper-cobalt sulfide ore concentrate and a beneficiated middlings a; performing a scavenging treatment on the roughing tailing a to obtain a scavenging concentrate a and a copper-cobalt oxide ore scavenging tailing a; returning the beneficiated middlings a and the scavenging concentrate a to a first roughing process; performing a roughing treatment on the copper-cobalt oxide ore scavenging tailing a to obtain a roughing concentrate b and a roughing tailing b; performing beneficiation treatment on the roughing concentrate b to obtain a copper-cobalt oxide ore concentrate 1 and a beneficiated middlings b; performing a scavenging treatment on the roughing tailing b to obtain a scavenging concentrate b and a scavenging tailing b; and mixing the scavenging concentrate b and the beneficiated middlings b to perform a re-beneficiation treatment to obtain a copper-cobalt oxide ore concentrate 2. The present invention can improve the flotation recovery rate and selectivity of low-grade copper-cobalt ore by combining the process and the reagent.

Description

Technical Field

[0001] The present invention relates to the technical field of ore dressing, and in particular to the field of flotation of copper-cobalt ores. Background Art

[0002] Copper-cobalt oxide ore is a major source of copper and cobalt metals. However, the complex composition of the oxide minerals and their high oxidation rate present a significant challenge in the mineral processing industry. To achieve efficient flotation, large amounts of sulfiding agents must be added during the flotation process. Currently, sulfide-xanthate flotation is commonly used to recover copper-cobalt oxide ore both domestically and internationally. Due to the uneven surface properties of the minerals and the uneven and incomplete sulfidation process, resulting in distinct areas of complete sulfidation, incomplete sulfidation, and no sulfidation, effective recovery of copper-cobalt minerals is difficult. Furthermore, cobalt minerals exhibit poorer floatability than copper minerals, further complicating the flotation of copper-cobalt oxide ore. Conventional sulfide-xanthate flotation can effectively recover copper and cobalt from fully sulfided areas. However, conventional xanthate flotation methods struggle to effectively recover copper and cobalt from incompletely or completely unsulfided areas, contributing to the current low recovery rates of copper-cobalt oxide ore.

[0003] Chinese patent document CN 116586196A discloses a flotation method for cobalt oxide copper ore, wherein a roughing process employs conventional flotation methods and reagents to flot completely sulfided cobalt ore in the copper-cobalt oxide ore, effectively separating and recovering a copper-cobalt concentrate 1 and a first roughing tailing. For incompletely sulfided or completely unsulfided cobalt, a sulfiding agent and an activator, xylenol orange, are added, and a combined collector of hexadecyltrimethylammonium bromide and N-β-aminopropionamide is added to perform a second roughing process. The second roughing copper-cobalt concentrate is then cleaned and the second roughing tailing is scavenged, respectively. This achieves effective activation, separation, and recovery of incompletely sulfided cobalt and completely unsulfided cobalt, thereby improving the cobalt recovery rate. However, the cobalt grade in the tailings is still 0.13, and therefore, the process is not applicable to low-grade cobalt ores. Summary of the Invention

[0004] In view of the problems faced by the existing flotation of low-grade copper-cobalt ores, the present invention aims to provide a flotation method for low-grade copper-cobalt ores, aiming to improve the flotation recovery rate of copper and cobalt.

[0005] The copper and cobalt grades in low-grade copper-cobalt ores are low, and copper and cobalt are embedded in the complex physical forms of oxide ore and sulfide ore, resulting in poor flotation efficiency and effect. To address this problem, the present invention, after in-depth research, provides the following improvement scheme:

[0006] A flotation method for low-grade copper-cobalt ore comprises the following steps:

[0007] Step (1): Sulfide ore flotation

[0008] The copper-cobalt ore is ground and slurried to obtain an ore slurry; a sulfide ore roughing process is then performed to obtain a roughing concentrate a and a roughing tailing a; the roughing process includes a first roughing process and a second roughing process, wherein the collector a used in the first roughing process is a collector of formula 1, and the collector b used in the second roughing process is a combined collector containing the collector of formula 1 and the collector of formula 2;

[0009]

[0010] The R1 to R3 are independently C1 to C8 alkyl, C3 to C8 cycloalkyl or aromatic group, and the M is H, Na, K or NH4;

[0011] The rougher concentrate a is then subjected to a beneficiation treatment to obtain a copper-cobalt sulfide concentrate and a beneficiated middling a; the rougher tailings a are subjected to a scavenging treatment to obtain a scavenged concentrate a and a copper-cobalt oxide scavenged tailing a; the beneficiated middling a and the scavenged concentrate a are returned to the first roughing process;

[0012] Step (2): Flotation of oxide ore

[0013] The copper-cobalt oxide ore scavenging tailings a are subjected to roughing to obtain roughing concentrate b and roughing tailings b; the roughing concentrate b is subjected to concentrating treatment to obtain copper-cobalt oxide ore concentrate 1 and concentrating middlings b; the roughing tailings b are subjected to scavenging treatment to obtain scavenging concentrate b and scavenging tailings b; the scavenging concentrate b and the concentrating middlings b are mixed and re-concentrated to obtain copper-cobalt oxide ore concentrate 2;

[0014] Wherein, the flotation reagents used in the roughing, scavenging and reselection stages of step (2) include a sulfiding agent and a collector of formula 3;

[0015]

[0016] The R4 is a C2-C8 alkyl group, a C3-C8 cycloalkyl group or an aromatic group, and the M is H, Na, K or NH4.

[0017] To address the flotation difficulties of low-grade copper-cobalt ores, the present invention innovatively pre-carries out the flotation of the sulfide ore described in step 1 and the subsequent flotation of the oxide ore in step 2. Furthermore, the flotation system of the synergistic collector in step 1 and the sulfiding agent in step 2 (Formula 3) is combined with joint control of the reselection. This can solve the problem of difficulty in efficient recovery caused by the complex distribution and grade of low-grade copper-cobalt mineral phases, and can significantly improve the flotation recovery rate and efficiency of copper and cobalt.

[0018] In the present invention, the cobalt grade of the raw ore of the low-grade copper-cobalt ore is 0.07% to 0.20%, the copper grade is not higher than 3.5%, and the copper-cobalt oxidation rate exceeds 80%.

[0019] In the present invention, the raw ore can be crushed and pulped based on conventional means.

[0020] For example, if the crushing fineness of the raw ore is 2-4mm, the grinding fineness is less than 0.074mm, and the product accounts for 65%-80% of the total mass. The raw ore pulp concentration is 30%-35%.

[0021] In the present invention, Formula 1 is innovatively used to pre-process a first roughing operation to obtain a first roughing concentrate and a first roughing tailing. The pulp from the first roughing tailing is then subjected to a second roughing operation to obtain a second roughing concentrate and a second roughing tailing. The first roughing concentrate and the second roughing tailing are then combined to form a roughing concentrate a; the second roughing tailing is referred to as roughing tailing a. In the present invention, the combined control of the roughing collector is key to synergistically improving its compatibility with low-grade copper-cobalt ores and improving flotation efficiency and effectiveness.

[0022] In the present invention, in step (1), in the collector of formula 1, R1 is a C2-C6 alkyl group;

[0023] Preferably, in the first roughing stage, the amount of the collector of formula 1 added is 40-100 g / ton of ore, and further can be 50-80 g / ton of ore;

[0024] Preferably, a foaming agent is further added in the first roughing stage, and the added amount is 5-60 g / ton of ore, further 10-50 g / ton of ore.

[0025] In the present invention, the foaming agent used can be a component with foaming properties well known in the industry, for example, 2# oil.

[0026] In the present invention, in step (1), an adjusting agent is further added in the second roughing stage; the adjusting agent comprises at least one of sodium carbonate and sodium bicarbonate;

[0027] Preferably, in the combined collector of the second roughing stage, the weight ratio of the collector of formula 1 to the collector of formula 2 is 30-60:20-30;

[0028] Preferably, in the second roughing stage, the amount of the adjusting agent added is 200-400 g / ton of ore, and further can be 250-350 g / ton of ore; the amount of the combined collector added is 50-100 g / t;

[0029] In the present invention, in step (1), the beneficiation process includes four stages of beneficiation. The steps are, for example: the roughing concentrate a is subjected to a first beneficiation treatment to obtain a first beneficiation concentrate and a first beneficiation tailing (a first beneficiation middling, i.e., beneficiation middling a); the first beneficiation concentrate is subjected to a second beneficiation treatment to obtain a second beneficiation concentrate and a second beneficiation tailing; the second beneficiation concentrate is subjected to a third stage of beneficiation treatment to obtain a third concentrate and a second beneficiation tailing; the third concentrate is subjected to a fourth stage of beneficiation treatment to obtain a fourth concentrate and a fourth beneficiation tailing; the fourth concentrate is the copper-cobalt sulfide ore concentrate; the first beneficiation tailing is returned to the roughing stage, and the second to fourth beneficiation concentrates are returned to the previous stage of beneficiation in sequence.

[0030] In the present invention, an inhibitor is added in the first to third concentration stages; the inhibitor includes at least one of water glass and carboxymethyl cellulose; the amount of the inhibitor in the first concentration stage is 100-250 g / ton of ore, and further 150-200 g / ton of ore; the amount of the inhibitor in the second concentration stage is 40-60% of the amount of the inhibitor in the first concentration stage; and the amount of the inhibitor in the third concentration stage is 40-60% of the amount of the inhibitor in the second concentration stage.

[0031] In the present invention, in step (1), the roughing tailings a are subjected to the scavenging treatment using a collector of formula 1, wherein the addition amount of the collector of formula 1 in the scavenging stage is 30-60 g / ton of ore;

[0032] Preferably, the scavenged concentrate is returned to the roughing process of step (1); the scavenged tailings are copper-cobalt oxide ore scavenged tailings a, which are processed in step (2).

[0033] In the present invention, in step (2), the roughing process includes a first roughing process and a second roughing process performed sequentially. The steps are, for example: subjecting the scavenging tailings a to a first roughing process to obtain a first concentrate and a first tailing; subjecting the first tailings to a second roughing process to obtain a second concentrate and a second tailing; combining the first concentrate and the second concentrate to obtain a roughing concentrate b for use in a subsequent concentration process. The second tailings is the roughing tailings b used in the subsequent scavenging process.

[0034] In step 2 of the present invention, a vulcanizing activator is further added during the first roughing stage; the vulcanizing activator comprises at least one of ammonium bicarbonate and ammonium carbonate. During the first roughing stage, the amount of the vulcanizing agent added is 200-1000 g / ton of ore; the amount of the vulcanizing activator added is 50-500 g / ton of ore; the amount of the collector of formula 3 added is 40-100 g / ton of ore; and a foaming agent is further added during the first roughing stage, the amount of which is 5-30 g / ton of ore.

[0035] Preferably, in the first roughing stage, the amount of sulfiding agent added is 400-500 g / ton of ore; the amount of sulfiding activator added is 100-200 g / ton of ore; the amount of collector of formula 3 added is 50-60 g / ton of ore; and a foaming agent is also added in the first roughing stage, and its addition amount is 10-25 g / ton of ore.

[0036] In step 2 of the present invention, in the second roughing stage, the amount of the sulfiding agent added is 100-1000 g / ton of ore; and the amount of the collector of Formula 3 added is 50-200 g / ton of ore. Preferably, in the second roughing stage, the amount of the sulfiding agent added is 200-250 g / ton of ore; and the amount of the collector of Formula 3 added is 100-150 g / ton of ore.

[0037] In the present invention, in step (2), the concentrating stage includes two sequential concentrating processes. The steps are, for example, as follows: the rougher concentrate b is subjected to the first concentrating process to obtain a first concentrating concentrate and a second concentrating middlings; the first concentrating concentrate is subjected to the second concentrating process to obtain a second concentrating concentrate and a second concentrating middlings, wherein the second concentrating concentrate is the copper-cobalt oxide ore concentrate 1. The first concentrating middlings (concentrated middlings b) participate in the re-concentration process, and the second concentrating concentrate returns to the previous concentrating process.

[0038] Preferably, in the first concentrating stage, a sulfiding agent and a collector are added as shown in Formula 3; the amount of the sulfiding agent added is 100-300 g / ton of ore, preferably 150-200 g / ton of ore, and the amount of the collector added is 20-50 g / ton of ore, preferably 30-40 g / ton of ore.

[0039] In the present invention, in step (2), the scavenging process includes two scavenging processes, and the steps are, for example: subjecting the rougher tailings b to a first scavenging process to obtain a first scavenged concentrate and a first scavenged tailings; subjecting the first scavenged tailings to a second scavenging process to obtain a second scavenged concentrate and a second scavenged tailings; and mixing the first scavenged concentrate and the second scavenged concentrate as the scavenged concentrate b to participate in the reselection process. The second scavenged tailings is the final tailings.

[0040] The amount of the sulfiding agent added in the scavenging stage is 50-400 g / ton of ore, and the amount of the collector added in Formula 3 is 50-100 g / ton of ore. Furthermore, the amount of the sulfiding agent added in the scavenging stage is 100-200 g / ton of ore, and the amount of the collector added in Formula 3 is 50-80 g / ton of ore.

[0041] In the present invention, in step (2), the reselection process includes a roughing process of the scavenged concentrate b and the selected middlings b in step (2) to obtain a roughing concentrate c and a roughing tailing c;

[0042] The rougher concentrate c is subjected to beneficiation treatment to obtain copper-cobalt oxide concentrate 2 and beneficiated middlings c;

[0043] The rougher tailings c are subjected to scavenging treatment to obtain scavenged concentrate d and scavenged tailings d;

[0044] The scavenged concentrate d and the cleaned middlings c are returned to the roughing process;

[0045] The scavenging tailings d are returned to the roughing process of the copper-cobalt oxide ore scavenging tailings a in step (2).

[0046] In the present invention, during the reselection process of step (2), in the roughing and scavenging stages, the amount of sulfiding agent added is 100-200 g / ton of ore, and the amount of collector of formula 3 added is 40-80 g / ton of ore.

[0047] Beneficial effects

[0048] The present invention innovatively pre-carries out the flotation of the sulfide ore described in step 1 and the flotation process of the oxide ore in step 2, and further cooperates with the flotation system of the synergistic collector in step 1 and the sulfiding agent in step 2 (Formula 3) combined with the joint control of reselection. This can solve the problem of difficulty in efficient recovery caused by the complex intercalation and grade of low-grade copper and cobalt mineral phases, and can significantly improve the flotation recovery rate and efficiency of copper and cobalt.

[0049] The present invention has advanced mineral processing indicators, good repeatability and is easy to implement in industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 This is a process flow chart of the efficient flotation method for low-grade copper-cobalt oxide ore of Example 1. DETAILED DESCRIPTION

[0051] In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, a detailed description will be given below with reference to the accompanying drawings and specific embodiments.

[0052] Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art; unless otherwise specified, the reagents used in the examples are commercially available.

[0053] The object of the present invention is to provide a novel process for the flotation of an efficient copper-cobalt oxide ore, comprising the following steps:

[0054] (1) Grinding and slurrying: Grinding the raw copper-cobalt oxide ore and then slurrying to obtain raw ore slurry;

[0055] (2) Copper-cobalt sulfide ore roughing 1: After adding Formula 1 and a frother in sequence to the raw ore pulp in step (1), the easily floatable copper-cobalt sulfide ore is subjected to aeration flotation to obtain a first roughing copper-cobalt sulfide ore concentrate and a first roughing copper-cobalt sulfide ore tailings.

[0056] (3) Second roughing of copper-cobalt sulfide ore: Sodium carbonate or sodium bicarbonate, a combined collector of Formula 1 and Formula 2, and No. 2 oil are sequentially added to the first roughing copper-cobalt sulfide ore tailings slurry in step (2), and the difficult-to-float copper-cobalt ore is subjected to aeration flotation to obtain a second roughing copper-cobalt sulfide ore concentrate and a second roughing copper-cobalt sulfide ore tailings; the first roughing copper sulfide concentrate and the second roughing copper-cobalt sulfide ore concentrate are combined, and the copper-cobalt sulfide ore concentration operation is performed four times to obtain a copper-cobalt sulfide ore concentrate.

[0057] (4) Scavenging of copper-cobalt sulfide ore: Formula 1 is added to the second roughing copper-cobalt sulfide ore tailings slurry in step (3) to carry out scavenging of copper-cobalt sulfide ore. The scavenged copper-cobalt sulfide ore concentrate and the selected copper-cobalt sulfide ore middlings are combined and returned to the roughing first, and the scavenged tailings enter the roughing operation of copper-cobalt oxide ore.

[0058] (5) Roughing of copper-cobalt oxide ore: adding a sulfiding agent, a collector of formula 3 and a frother to the scavenging tailings slurry in step (4) in sequence, aerating and flotating the easily floatable copper-cobalt minerals to obtain a first roughing copper-cobalt oxide ore concentrate and a first roughing copper-cobalt oxide ore tailings.

[0059] Furthermore, the roughing operation is performed twice, and the roughing copper-cobalt oxide ore concentrate is subjected to two copper-cobalt oxide ore concentration operations to obtain copper-cobalt oxide ore concentrate 1 and the second roughing copper-cobalt oxide ore tailings.

[0060] (6) Scavenging of copper-cobalt oxide ore: adding a sulfiding agent and a collector of formula 3 to the second roughing copper oxide tailings slurry in step (5) in sequence to carry out scavenging operation.

[0061] The scavenging operation is repeated twice. The scavenging concentrate obtained is combined with the middlings from the first concentration operation of copper-cobalt oxide ore. After re-selection, copper oxide concentrate 2 and re-selection tailings are obtained. The re-selection tailings enter the first roughing operation. The second scavenging tailings are the final flotation tailings.

[0062] In the step (1), the cobalt grade of the oxidized copper-cobalt ore is 0.07% to 0.20%, the copper grade is not higher than 3.5%, and the copper-cobalt oxidation rate exceeds 80%.

[0063] In the step (1), the crushing fineness of the raw ore is 2-4 mm, and the product with a grinding fineness of less than 0.074 mm accounts for 65%-80% of the total mass.

[0064] The concentration of the raw ore pulp in step (1) is 30%-35%.

[0065] In the present invention, the scraping time of each stage of roughing and sweeping operation is 2 to 3 minutes, and the scraping time of the cleaning operation is 1 to 3 minutes.

[0066] This process utilizes a sulfide ore selection process followed by oxide ore selection. Copper-cobalt sulfide ore undergoes two-stage roughing, while flotation of copper-cobalt oxide ore also employs two-stage roughing to ensure total copper and cobalt recovery. A highly efficient combined collector is employed in the flotation of the copper-cobalt oxide ore, guaranteeing copper and cobalt oxide recovery. The combined activator of sodium sulfide and ammonium bicarbonate effectively activates the copper-cobalt oxide ore and increases its floatability, thereby improving its flotation rate and copper and cobalt recovery. Furthermore, the copper oxide selected middlings and scavenger concentrate are combined and reselected to produce a low-grade copper-cobalt oxide concentrate, effectively ensuring cobalt recovery.

[0067] In the following cases, as typical examples, the collector of Formula 1 can be a collector of Formula 1-A (a compound of Formula 1 in which R1 is a butyl group and M is H) or a collector of Formula 1-B (a compound of Formula 1 in which R1 is a pentyl group and M is H).

[0068] The collector of formula 2 can be formula 2-A (R2 and R3 are both ethyl compounds of formula 2)

[0069] The collector of formula 3 may be formula 3-A (a compound of formula 3 in which R4 is phenyl) or formula 3-B (a compound of formula 3 in which R4 is o-hydroxyphenyl).

[0070] In the following cases, the dosage of reagents refers to the weight used per ton of ore.

[0071] Example 1

[0072] The test sample is a copper-cobalt oxide ore with a cobalt grade of 0.07%, a copper grade of 1.40%, and an ore oxidation rate of 92%. The flotation process is as follows:

[0073] (1) Grinding and slurrying: The raw ore of the test sample cobalt oxide copper ore was ground to a fineness of less than 0.074 mm, and the product accounted for 75% of the total weight. Then water was added to adjust the slurry to a concentration of 30% to obtain raw ore slurry.

[0074] (2) 80 g of Formula 1-A and 48 g of 2# oil were added to each ton of raw ore pulp in sequence, and the mixture was stirred. The easily floatable copper-cobalt minerals were subjected to aeration flotation to obtain the first roughing copper sulfide concentrate and the first roughing copper sulfide tailings.

[0075] (3) 300 g / t of sodium carbonate, 60 g / t of formula 1-A, and 30 g / t of formula 2-A are sequentially added to the first roughing copper sulfide tailings slurry, and the difficult-to-float copper-cobalt ore is aerated and floated to obtain a second roughing copper sulfide concentrate and a second roughing copper sulfide tailings. After the first roughing and second roughing copper-cobalt sulfide concentrates are combined, a copper sulfide concentrate is obtained after four concentration operations, wherein 150 g / t of carboxymethyl cellulose is added in the first concentration stage, 75 g / t of carboxymethyl cellulose is added in the second concentration stage, and 37.5 g / t of carboxymethyl cellulose is added in the third concentration stage. The middling ore of the first concentration stage is processed in step (4);

[0076] (4) Add 1-A 40g / t to the second roughing copper sulfide tailings slurry for scavenging operation. The scavenging concentrate and the copper sulfide selected middlings are combined and returned to the roughing first. The scavenging copper sulfide tailings enter the copper oxide roughing.

[0077] (5) The copper sulfide tailings (copper sulfide tailings) were subjected to two-stage copper oxide roughing. The dosage of the roughing first sulfiding agent and the sulfiding activator were: sodium sulfide 400g / t, ammonium bicarbonate 100g / t, formula 3-A 50g / t, 2 # The amount of oil used is 24 g / t, the dosage of roughing disulfiding agent and collector is 200 g / t of sodium sulfide and 120 g / t of formula 3-A respectively. The difficult-to-float copper oxide ore is aerated and floated to obtain a second roughing copper oxide concentrate and a second roughing copper oxide tailings. The roughing copper oxide concentrate is subjected to two-stage copper oxide concentration operations to obtain copper oxide concentrate 1, wherein 150 g / t of sodium sulfide and 30 g / t of formula 3A are added in the first concentration stage.

[0078] (6) The copper oxide roughing tailings are subjected to two scavenging operations: copper oxide scavenging 1: sodium sulfide 200g / t and formula 3-A 60g / t are added to the second roughing copper oxide tailings slurry in sequence; copper oxide scavenging 2: sodium sulfide 200g / t and formula 3-A 60g / t are added to each ton of the first scavenging copper oxide tailings slurry in sequence to obtain scavenged concentrate and final tailings.

[0079] (7) The copper oxide selected middlings and scavenged concentrates are combined for reselection. The reselection operation is a one-roughing, one-scavenging, two-fine process. The amount of sodium sulfide used in the roughing and scavenging reselection is 200 g / t and 100 g / t, respectively. The amount of formula 3-A used is 80 g / t and 40 g / t, respectively. After reselection, a low-grade copper oxide concentrate 2 is obtained.

[0080] Example 2

[0081] The test sample is a copper-cobalt oxide ore with a cobalt grade of 0.11%, a copper grade of 2.35%, and an ore oxidation rate of 90%. The flotation process is as follows:

[0082] (1) Grinding and slurrying: The raw ore of the test sample cobalt oxide copper ore was ground to a fineness of less than 0.074 mm, and the product accounted for 75% of the total weight. Then water was added to adjust the slurry to a concentration of 30% to obtain raw ore slurry.

[0083] (2) Adding 50 g / t of Formula 1-A and 10 g / t of 2# oil to each ton of raw ore pulp in sequence, stirring, and aerating and flotating the easily floatable copper-cobalt minerals to obtain the first roughing copper sulfide concentrate and the first roughing copper sulfide tailings.

[0084] (3) Sodium carbonate (300 g / t), formula 1-A (33 g / t), and formula 2-A (25 g / t) were sequentially added to the first roughing copper sulfide tailings slurry, and the difficult-to-float copper-cobalt ore was aerated and floated to obtain a second roughing copper sulfide concentrate and a second roughing copper sulfide tailings. The first roughing and second roughing copper sulfide cobalt concentrates were combined and subjected to four concentration operations to obtain a copper sulfide concentrate, wherein 200 g / t of carboxymethyl cellulose was added in the first concentration stage, 100 g / t of carboxymethyl cellulose was added in the second concentration stage, and 50 g / t of carboxymethyl cellulose was added in the third concentration stage.

[0085] (4) Adding 1-A 33g / t to the second roughing copper sulfide tailings slurry to carry out scavenging operation, the scavenged concentrate returns to the previous operation, and the scavenged copper sulfide tailings enter the copper oxide roughing.

[0086] (5) The copper sulfide scavenging tailings were subjected to two-stage copper oxide roughing. The amounts of the first sulfiding agent and the sulfiding activator in the roughing were: 500 g / t sodium sulfide, 200 g / t ammonium bicarbonate, 60 g / t of Formula 3-A, and 14 g / t of 2# oil, respectively. The amounts of the second sulfiding agent and the collector in the roughing were: 250 g / t sodium sulfide and 100 g / t of Formula 3-A, respectively. The difficult-to-float copper oxide ore was subjected to aeration flotation to obtain a second roughing copper oxide concentrate and a second roughing copper oxide tailing. The roughing copper oxide concentrate was subjected to two copper oxide concentration operations to obtain copper oxide concentrate 1, wherein 200 g / t sodium sulfide and 40 g / t of Formula 3A were added in the first concentration stage.

[0087] (6) The copper oxide rougher tailings are subjected to two scavenging operations: copper oxide scavenging 1: sodium sulfide 100g / t and formula 3-A 60g / t are added to the second rougher copper oxide tailings slurry in sequence; copper oxide scavenging 2: sodium sulfide 100g / t and formula 3-A 60g / t are added to each ton of the first scavenged copper oxide tailings slurry in sequence to obtain scavenged concentrate and final tailings.

[0088] (7) The copper oxide selected middlings and scavenged concentrates are combined for reselection. The reselection operation is a one-roughing, one-scavenging, two-fine process. The dosage of sodium sulfide for roughing and scavenging in the reselection is 150 g / t and 100 g / t, respectively. The dosage of formula 3-A is 60 g / t and 40 g / t, respectively. After reselection, a low-grade copper oxide concentrate 2 is obtained.

[0089] Comparative Example 1

[0090] Compared with Example 1, the only difference is that in step 3, the combined collector is replaced by a single Formula 1-A, that is, an equal weight of Formula 1-A is used to replace the Formula 2-A, and the amount of collector used is the same as the combined collector in Example 1.

[0091] Comparative Example 2

[0092] Compared with Example 2, the only difference is that in steps 5 to 6, Formula 3-A is replaced by an equal weight of Formula 1-A.

[0093] Comparative Example 3

[0094] Compared with Example 2, the only difference is that the reselection operation in step 7 is not performed, and the selected middlings and scavenged concentrates of the copper-cobalt oxide ore are returned to the first roughing operation of the copper-cobalt oxide ore.

[0095] The following table lists the test results for Example 1, Example 2, and Comparative Examples 1, 2, and 3. The test results show that Example 1 has a total copper recovery rate of 89.59% and a total cobalt recovery rate of 50.53%. Example 2 has a total copper recovery rate of 88.77% and a total cobalt recovery rate of 55.34%. Because Formula 2-A was not added to Comparative Example 1, the total copper recovery rate and total cobalt recovery rate were 84.00% and 41.17%, respectively, representing decreases of 5.59% and 9.36%, respectively, compared to Example 1. Because Formula 1-A was substituted for Formula 3-A in Comparative Example 2, the total copper recovery rate and total cobalt recovery rate were 80.45% and 41.04%, respectively, representing decreases of 8.32% and 14.20%, respectively, compared to Example 2. Because no reselection was performed in Comparative Example 3, the total copper recovery rate and total cobalt recovery rate were only 76.24% and 38.06%, respectively.

[0096] Examples 1 and 2 described above are preferred embodiments of the present invention. The results demonstrate that the flotation process of the present invention can effectively improve the copper and cobalt recovery rate of low-grade copper-cobalt oxide ores. It should be noted that those skilled in the art may make various improvements and modifications without departing from the principles of the present invention, and such improvements and modifications are also within the scope of protection of the present invention.

[0097] Example 1

[0098]

[0099] Example 2:

[0100]

[0101] Comparative Example 1

[0102]

[0103] Comparative Example 2:

[0104]

[0105] Comparative Example 3:

[0106]

[0107] In summary, the process described in the present invention can meet the flotation requirements of low-grade copper-cobalt ores, achieving excellent flotation recovery and selectivity. Furthermore, it has the advantages of low cost and high environmental protection.

Claims

1. A flotation method for low-grade copper-cobalt ore, characterized in that: The following steps are involved: Step (1): Sulfide ore flotation Grinding the raw copper-cobalt ore and then slurrying it to obtain raw ore slurry; Subsequently, a sulfide ore roughing process is performed to obtain a roughing concentrate a and a roughing tailing a; the roughing process includes two roughing processes, a first roughing process and a second roughing process, wherein the collector a used in the first roughing process is a collector of formula 1, and the collector b used in the second roughing process is a combined collector containing the collector of formula 1 and the collector of formula 2; Formula 1 Formula 2 The R1-R3 are independently C1-C8 alkyl, C3-C8 cycloalkyl or aromatic groups, and the M is H, Na, K or NH4; The rougher concentrate a is then subjected to a beneficiation treatment to obtain a copper-cobalt sulfide concentrate and a beneficiated middling a; the rougher tailings a are subjected to a scavenging treatment to obtain a scavenged concentrate a and a copper-cobalt oxide scavenged tailing a; the beneficiated middling a and the scavenged concentrate a are returned to the first roughing process; Step (2): Flotation of oxide ore The copper-cobalt oxide ore scavenging tailings a are subjected to roughing to obtain roughing concentrate b and roughing tailings b; the roughing concentrate b is subjected to concentrating treatment to obtain copper-cobalt oxide ore concentrate 1 and concentrating middlings b; the roughing tailings b are subjected to scavenging treatment to obtain scavenging concentrate b and scavenging tailings b; the scavenging concentrate b and the concentrating middlings b are mixed and re-concentrated to obtain copper-cobalt oxide ore concentrate 2; Wherein, the flotation reagents used in the roughing, scavenging and reselection stages of step (2) include a sulfiding agent and a collector of formula 3; Formula 3 The R4 is a C2~C8 alkyl group, a C3~C8 cycloalkyl group or an aromatic group, and the M is H, Na, K or NH4.

2. The flotation method for low-grade copper-cobalt ore according to claim 1, wherein: The cobalt grade in the original ore is 0.07%~0.20%, the copper grade is no higher than 3.5%, and the copper-cobalt oxidation rate exceeds 80%.

3. The flotation method for low-grade copper-cobalt ore according to claim 1, wherein: The crushing fineness of the raw ore is 2-4mm, and the products with grinding fineness less than 0.074mm account for 65%-80% of the total mass.

4. The flotation method for low-grade copper-cobalt ore according to claim 1, wherein: The concentration of raw ore pulp is 30%-35%.

5. The flotation method for low-grade copper-cobalt ore according to claim 1, wherein: In step (1), in the collector of formula 1, R1 is a C2~C6 alkyl group.

6. The flotation method for low-grade copper-cobalt ore according to claim 1, wherein: In step (1), in the first roughing stage, the amount of the collector of formula 1 added is 40-100 g / ton of ore.

7. The flotation method for low-grade copper-cobalt ore according to claim 1, wherein: In step (1), a foaming agent is also added in the first roughing stage, and the amount added is 5-60g / ton of ore.

8. The flotation method for low-grade copper-cobalt ore according to claim 1, wherein: In step (1), an adjusting agent is further added in the second roughing stage; the adjusting agent includes at least one of sodium carbonate and sodium bicarbonate.

9. The flotation method for low-grade copper-cobalt ore according to claim 1, wherein: In step (1), in the combined collector of the second roughing stage, the weight ratio of the collector of formula 1 to the collector of formula 2 is 30-60:20-30.

10. The flotation method for low-grade copper-cobalt ore according to claim 1, wherein: In step (1), in the second roughing stage, the amount of the adjusting agent added is 200-400 g / t of ore; the amount of the combined collector added is 50-100 g / t.

11. The flotation method for low-grade copper-cobalt ore according to claim 1, wherein: In step (1), the beneficiation process includes four stages of beneficiation; among them, the middlings selected in the first stage are returned to the roughing process as the selected middlings a, and the selected tailings selected in the second to fourth stages are returned to the previous stage of beneficiation.

12. The flotation method for low-grade copper-cobalt ore according to claim 11, characterized in that: In step (1), an inhibitor is added in the first to third selection stages; the inhibitor comprises at least one of water glass and carboxymethyl cellulose.

13. The flotation method for low-grade copper-cobalt ore according to claim 12, wherein: In step (1), the dosage of the inhibitor in the first concentrating stage is 100-250 g / ton of ore.

14. The flotation method for low-grade copper-cobalt ore according to claim 13, wherein: In step (1), the dosage of the inhibitor in the first concentrating stage is 150-200 g / ton of ore.

15. The flotation method for low-grade copper-cobalt ore according to claim 13, wherein: In step (1), the amount of the inhibitor used in the second concentration stage is 40-60% of the amount of the inhibitor used in the first concentration stage; the amount of the inhibitor used in the third concentration stage is 40-60% of the amount of the inhibitor used in the second concentration stage.

16. The flotation method for low-grade copper-cobalt ore according to claim 1, characterized in that: In step (1), the scavenging treatment is carried out using a collector of formula 1, wherein the amount of the collector of formula 1 added in the scavenging stage is 30-60 g / ton of ore.

17. The flotation method for low-grade copper-cobalt ore according to claim 16, wherein: The scavenged concentrate is returned to the roughing process of step (1); the scavenged tailings are copper-cobalt oxide ore scavenged tailings a, which are processed in step (2).

18. The flotation method for low-grade copper-cobalt ore according to claim 1, characterized in that: In step (2), the roughing process includes a first roughing process and a second roughing process performed sequentially; the concentrates of the first roughing process and the second roughing process are combined as the roughing concentrate b for subsequent cleaning treatment; and the tailings of the second roughing process are used as the roughing tailings b for subsequent scavenging treatment; Wherein, a vulcanization activator is also added in the first roughing stage; the vulcanization activator includes at least one of ammonium bicarbonate and ammonium carbonate.

19. The flotation method for low-grade copper-cobalt ore according to claim 18, characterized in that: In step (2), in the first roughing stage, the amount of sulfiding agent added is 200-1000 g / ton of ore; the amount of sulfiding activator added is 50-500 g / ton of ore; and the amount of collector of formula 3 added is 40-100 g / ton of ore.

20. The flotation method for low-grade copper-cobalt ore according to claim 18, wherein: In step (2), a foaming agent is also added in the first roughing stage, and the amount added is 5-30g / ton of ore; In the second roughing stage, the amount of sulfiding agent added is 100-1000g / ton of ore; the amount of collector added is 50-200g / ton of ore.

21. The flotation method for low-grade copper-cobalt ore according to claim 18, wherein: In step (2), the concentration stage includes two sequential concentration processes, wherein the middlings from the first concentration stage are treated as the concentrated middlings b for reselection; the tailings from the second concentration stage are returned to the first concentration process, and the concentrate from the second concentration stage is the copper-cobalt oxide concentrate 1.

22. The flotation method for low-grade copper-cobalt ore according to claim 21, wherein: In step (2), in the first concentrating stage, a sulfiding agent and a collector of formula 3 are added; the amount of the sulfiding agent added is 100-300 g / ton of ore, and the amount of the collector of formula 3 added is 20-50 g / ton of ore.

23. The flotation method for low-grade copper-cobalt ore according to claim 21, wherein: In step (2), the scavenging process includes two scavenging processes, and the scavenged concentrate b participates in the reselection process; Among them, the addition amount of sulfiding agent in the scavenging stage is 50~400g / ton of ore, and the addition amount of the collector of formula 3 is 50~100g / ton of ore.

24. The flotation method for low-grade copper-cobalt ore according to claim 23, wherein: In step (2), the reselection process includes a roughing process of the scavenged concentrate b and the selected middlings b in step (2) to obtain a roughing concentrate c and a roughing tailing c; The rougher concentrate c is subjected to beneficiation treatment to obtain copper-cobalt oxide concentrate 2 and beneficiated middlings c; The rougher tailings c are subjected to scavenging treatment to obtain scavenged concentrate d and scavenged tailings d; The scavenged concentrate d and the cleaned middlings c are returned to the roughing process; The scavenging tailings d are returned to the roughing process of the copper-cobalt oxide ore scavenging tailings a in step (2).

25. The flotation method for low-grade copper-cobalt ore according to claim 23, wherein: During the reselection process of step (2), in the roughing and scavenging stages, the amount of sulfiding agent added is 100-200 g / ton of ore, and the amount of collector of formula 3 added is 40-80 g / ton of ore.

Images