Combined collector for chalcopyrite in low-copper high-sulfur copper-sulfur ore and application thereof

Abstract

The application discloses a combined collector for chalcopyrite in low-copper high-sulfur copper-sulfur ore and application thereof, and belongs to the technical field of mineral separation. The combined collector comprises pyridine methanol and ethyl xanthate. Firstly, the ore is crushed and ground to achieve monomer dissociation among minerals, and a small amount of lime is added to adjust the pH to 8-9 during the grinding; pyridine methanol and ethyl xanthate are used as the selective combined collector for chalcopyrite, and after one roughing, two scavenging and two cleaning operations, copper concentrate and copper tailings are obtained; the copper tailings are subjected to desliming operation, polymeric ferric sulfate and sodium carbonate are used for activation, and in the process of one roughing, three scavenging and three cleaning, sulfur concentrate and tailings are obtained. The efficient selective copper combined collector pyridine methanol and ethyl xanthate can greatly reduce the dosage of pyrite inhibitor, and simultaneously reduce the use of subsequent pyrite activator, and has the advantages of wide application range and high product index.

Description

TECHNICAL FIELD

[0001] The present application relates to a combined collector for chalcopyrite in low-copper high-sulfur copper-sulfur ore and its application, and in particular to the technical field of mineral separation. BACKGROUND

[0002] Copper is an indispensable metal in human social production and life, and has wide application in modern agriculture, industry and national defense construction. Copper-sulfur ore is one of the important sources of copper metal production, and flotation is the main technology for the separation and recovery of such ore. However, the natural floatability of copper and sulfur is close, and the interaction between the components in the ore slurry is large, making it difficult to separate them.

[0003] At present, the processing method of copper-sulfur ore is to use lime as the depressant and xanthate as the collector to realize the flotation separation of copper and sulfur in high-alkali process. With the ore becoming increasingly lean, fine and hybrid, the environmental pollution caused by traditional process, the low copper recovery rate, the large loss of associated precious metals, and the difficulty and high cost of subsequent activation of pyrite are increasingly prominent. The invention patent with application number 202211202761.6 discloses a high-efficiency pyrite depressant in copper-sulfur separation, which realizes the efficient flotation separation of chalcopyrite and pyrite at low alkalinity, but is only applicable to the theoretical level, and the feasibility in actual application still needs to be considered. The invention patent with application number CN202111405719.X discloses a high-efficiency copper collector, which realizes the separation of copper-sulfur minerals, but requires high-alkali depression of lime, which has the problem of high subsequent activation cost. SUMMARY

[0004] To solve the above-mentioned defects in the copper-sulfur separation process, one of the purposes of the present application is to provide a combined collector for chalcopyrite in low-copper high-sulfur copper-sulfur ore, which can realize the separation of copper and sulfur under low-alkali conditions and take into account the recovery of pyrite at low cost.

[0005] The technical solution of the present application is: a combined collector for chalcopyrite in low-copper high-sulfur copper-sulfur ore, which comprises pyridine methanol and ethyl xanthate, and the mass ratio of pyridine methanol to ethyl xanthate is 4-5:1.

[0006] The second purpose of the present application is to provide the application of the combined collector for chalcopyrite in low-copper high-sulfur copper-sulfur ore, and the specific steps are as follows:

[0007] (1) First, add lime to the copper-sulfur ore to adjust the pH to 8-9, and then grind to obtain a copper-sulfur monomer dissociation slurry. The mass proportion of lime added is 500-700 g / t, and the grinding fineness of copper-sulfur ore is 74-75% of -0.074 μm, so as to achieve copper-sulfur monomer dissociation;

[0008] (2) adding the combined collector and the frother No.2 oil into the copper-sulfur monomer dissociation slurry obtained in step (1) in sequence, and obtaining copper concentrate and copper tailings after a roughing-three scavenging-two cleaning process, wherein the middlings product returns to the previous stage in sequence to form a closed circuit, and the adding amount of the combined collector is 60-80 g / t;

[0009] (3) adding the combined activator, the collector II and the frother into the copper tailings obtained in step (2) in sequence after desliming and thickening operation, and obtaining sulfur concentrate and tailings after a roughing-three scavenging-three cleaning process, wherein the middlings product returns to the previous stage in sequence to form a closed circuit, the combined activator is a combination of polymeric ferric sulfate and sodium carbonate, the collector II includes ethyl xanthate, isopropyl xanthate and isobutyl xanthate, the polymeric ferric sulfate is used in an amount of 1000-1500 g / t, the sodium carbonate is used in an amount of 800-1000 g / t, and the total adding amount of the collector II is 180-200 g / t, wherein the mass ratio of ethyl xanthate, isopropyl xanthate and isobutyl xanthate is 2:3:5.

[0010] The desliming and thickening operation in step (3) is specifically as follows: the copper tailings are subjected to a first-stage thickening operation to obtain first-stage thickener overflow and first-stage thickener underflow, the first-stage thickener overflow is subjected to classification by a hydrocyclone to remove slimes of-10 μm particle size, and the first-stage thickener underflow and the cyclone underflow are subjected to a second-stage thickening operation to obtain second-stage thickener overflow and second-stage thickener underflow, the second-stage thickener overflow returns to the first-stage thickening operation, and the second-stage thickener underflow is subjected to pyrite activation flotation operation.

[0011] Preferably, the roughing operation in step (2) lasts for 5-6 minutes, the scavenging operation lasts for 4-5 minutes, and the cleaning operation lasts for 4-5 minutes.

[0012] Preferably, the roughing operation in step (3) lasts for 5-6 minutes, the scavenging operation lasts for 4-5 minutes, and the cleaning operation lasts for 4-5 minutes.

[0013] The principle of the application is that pyridine methanol contains two electron donors of O atom and N atom, and can form a stable five-membered chelate ring with Cu metal on the surface of chalcopyrite in space (as shown below). The test results show that pyridine methanol has extremely weak collecting ability for pyrite under the weak alkaline condition of lime, but has good collecting ability for chalcopyrite. Therefore, a small amount of lime is used to produce a certain inhibiting effect on pyrite under low alkaline conditions, while retaining high floatability of chalcopyrite; pyridine methanol is used to ensure the grade of copper concentrate, and a small amount of ethyl xanthate is used to ensure the overall recovery rate of copper; in subsequent sulfur flotation operation, due to the small degree of inhibition of pyrite, a small amount of activator and relatively low xanthate such as ethyl xanthate, isopropyl xanthate and isobutyl xanthate are used as the collector to achieve efficient recovery of pyrite.

[0014]

[0015] Schematic diagram of pyridine methanol chelation with copper

[0016] Advantages of the present application:

[0017] (1) The pyridine methanol in the combined collector of chalcopyrite of the present application has strong selectivity, and in combination with ethyl xanthate, the separation of chalcopyrite from pyrite and gangue in copper sulfide ore can be significantly improved under low alkalinity conditions, and the grade and recovery rate of copper concentrate can be improved.

[0018] (2) Compared with high-alkali inhibition using a large amount of lime, the copper-sulfur separation method used in the present application under low alkalinity can improve the copper recovery rate by about two percentage points while ensuring the quality of copper concentrate.

[0019] (3) Compared with high-alkali inhibition using a large amount of lime, the copper-sulfur separation method used in the present application under low alkalinity can reduce the amount of activator used by nearly half in the activation and flotation of pyrite, greatly saving the cost of reagents.

[0020] (3) The method of the present application has good separation effect on copper-sulfur minerals, and the overall recovery of copper-sulfur resources is more sufficient, taking into account the dual advantages of economy and environmental protection. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 Process flowchart of the present application. DETAILED DESCRIPTION

[0022] The present application will be further described in detail below in conjunction with specific examples, but the scope of protection of the present application is not limited to the content described.

[0023] The minerals used in the following examples were taken from a certain copper mine in Yunnan Province, with a copper grade of 0.5-0.6% and a total sulfur grade of 8-10%; among them, the main copper-containing mineral was chalcopyrite, accounting for 80-85%; the rest was secondary copper mineral, accounting for 10-15%; and the main pyrite was pyrite.

[0024] Example 1: This example corresponds to a low-grade copper-sulfur ore, with a total copper grade of 0.52% and a total sulfur grade of 8.73%

[0025] The combined collector of chalcopyrite of the present application was used for copper-sulfur separation, which included pyridine methanol and ethyl xanthate, and the mass ratio of pyridine methanol to ethyl xanthate was 5:1, and the flotation flowchart is as shown in Figure 1 , and the specific steps are as follows:

[0026] (1) First, 500g / t of lime was added to the mill to adjust the pH of the copper-sulfur ore to 8, and then grinding was carried out, and the grinding degree was-0.074μm 74%, to obtain a copper-sulfur monomer dissociation slurry;

[0027] (2) the copper-sulfur monomer dissociation slurry obtained in step (1) is sequentially added with 30 g / t of the combined collector, 10 g / t of the frother No. 2 oil for roughing operation, to obtain roughing concentrate and roughing tailings, 15 g / t of the combined collector, 10 g / t of the frother No. 2 oil is added to the roughing tailings for scavenging I operation, to obtain scavenging I concentrate and scavenging I tailings, 10 g / t of the combined collector, 5 g / t of the frother No. 2 oil is continuously added to the scavenging I tailings for scavenging II operation, to obtain scavenging II concentrate and scavenging II tailings, 5 g / t of the collector, 5 g / t of the frother No. 2 oil is added to the scavenging II tailings for scavenging III operation, to obtain copper tailings and scavenging III concentrate, wherein the scavenging III concentrate returns to the scavenging II operation, the scavenging II concentrate returns to the scavenging I operation, to form a closed loop; the roughing concentrate is subjected to cleaning I operation without adding reagents, to obtain cleaning I concentrate and cleaning I tailings, the cleaning I tailings is mixed with the scavenging I concentrate and returns to the roughing operation, to form a closed loop; the cleaning I concentrate is subjected to one-time blank cleaning II operation, to obtain copper concentrate and cleaning II tailings, the cleaning II tailings returns to the cleaning I operation;

[0028] The copper concentrate and copper tailings are obtained under the process of one roughing, three scavenging, two cleaning; the roughing operation time is 5 minutes, the scavenging operation is 5 minutes, and the cleaning operation is 4 minutes;

[0029] (3) the copper tailings is subjected to desliming and concentration operation, and the desliming and concentration operation is specifically as follows: the copper tailings is subjected to one-stage thickening operation, to obtain one-stage thickener overflow and one-stage thickener underflow, the one-stage thickener overflow is subjected to classification in a hydrocyclone to remove -10 μm size slimes, and the one-stage thickener underflow and the cyclone sand are subjected to two-stage thickening operation, to obtain two-stage thickener overflow and two-stage thickener underflow, the two-stage thickener overflow returns to the one-stage thickening operation, and the two-stage thickener underflow is subjected to pyrite activation flotation operation;

[0030] (4) before the pyrite activation flotation, 1800 g / t of the combined activator is sequentially added, wherein the polymeric ferric sulfate is 1000 g / t, the sodium carbonate is 800 g / t, the collector II is 80 g / t, and the frother No. 2 oil is 20 g / t, and the middling product returns in sequence, to obtain sulfur concentrate and tailings under the process of one roughing, three scavenging, three cleaning; wherein the roughing operation time is 5 minutes, the scavenging operation time is 5 minutes, and the cleaning operation is 4 minutes, wherein the scavenging I operation collector II is 45 g / t, and the frother is 10 g / t; the scavenging II operation collector II is 35 g / t, and the frother is 5 g / t; the scavenging III operation collector II is 20 g / t, and the frother is 5 g / t, and the cleaning does not add reagents.

[0031] The flotation product indexes of Example 1 are shown in Table 1.

[0032] Table 1: Flotation product indexes of Example 1

[0033]

[0034] As can be seen from Table 1, when the relatively low-grade raw ore is treated by the method of the present application, under low-alkali conditions, a copper concentrate with a copper grade of 19.92% and a copper recovery of 91.55% is obtained; after desliming, a sulfur concentrate with a sulfur grade of 47.68% and a sulfur recovery of 79.84% is obtained, achieving remarkable separation effect and concentrate index.

[0035] Example 2: This example 2 corresponds to a raw ore with high copper and sulfur grades, with a total copper grade of 0.59% and a total sulfur grade of 9.92%. The chalcopyrite combined collector of the present application is used for copper-sulfur separation, which includes pyridine methanol and ethyl xanthate, and the mass ratio of pyridine methanol to ethyl xanthate is 4:1, and the flotation flow chart is as shown in Figure 1 , and the specific steps are as follows:

[0036] (1) First, 700 g / t of lime is added to the mill to adjust the pH of the copper-sulfur ore to 9, and then grinding is performed to a fineness of -0.074 μm of 75%, obtaining a copper-sulfur monomer dissociation slurry;

[0037] (2) The copper-sulfur monomer dissociation slurry obtained in step (1) is sequentially added with 35 g / t of the combined collector, 10 g / t of the frother No. 2 oil for roughing operation, to obtain a roughing concentrate and a roughing tailing, 20 g / t of the combined collector, 10 g / t of the frother No. 2 oil is added to the roughing tailing for scanning operation I, to obtain scanning I concentrate and scanning I tailing, 15 g / t of the combined collector, 5 g / t of the frother No. 2 oil is continuously added to the scanning I tailing for scanning operation II, to obtain scanning II concentrate and scanning II tailing, 10 g / t of the combined collector, 5 g / t of the frother No. 2 oil is added to the scanning II tailing for scanning operation III, to obtain a copper tailing and scanning III concentrate, wherein the scanning III concentrate returns to the scanning II operation, the scanning II concentrate returns to the scanning I operation, forming a closed loop; the roughing concentrate is subjected to cleaning I operation without adding reagents, to obtain cleaning I concentrate and cleaning I tailing, the cleaning I tailing is mixed with the scanning I concentrate and returned to the roughing operation, forming a closed loop; the cleaning I concentrate is subjected to one-time blank cleaning II operation, to obtain a copper concentrate and cleaning II tailing, and the cleaning II tailing returns to the cleaning I operation;

[0038] Under the one-roughing-three-scanning-two-cleaning process, a copper concentrate and a copper tailing are obtained; the roughing operation time is 5 minutes, the scanning operation time is 5 minutes, and the cleaning operation time is 4 minutes;

[0039] (5) the desliming and thickening operation of the copper tailings, the desliming and thickening operation being specifically as follows: the copper tailings are subjected to a first-stage thickening operation to obtain first-stage thickener overflow and first-stage thickener underflow, the first-stage thickener overflow is subjected to classification by a hydrocyclone to remove -10 μm size fraction of slime, and the first-stage thickener underflow and the cyclone underflow are subjected to a second-stage thickening operation to obtain second-stage thickener overflow and second-stage thickener underflow, the second-stage thickener overflow is returned to the first-stage thickening operation, and the second-stage thickener underflow is subjected to the pyrite activation flotation operation;

[0040] The combined activator is added in a total amount of 2500 g / t before the pyrite activation flotation, wherein the polymeric ferric sulfate is used in an amount of 1500 g / t, the sodium carbonate is used in an amount of 1000 g / t, the collector II is used in an amount of 90 g / t, the mass ratio of ethyl xanthate, isopropyl xanthate and isobutyl xanthate is 2:3:5, the frother No. 2 oil is used in an amount of 20 g / t, and the middling product is returned in sequence, and a sulfur concentrate and a tailing are obtained under a process of one roughing, three scavenging and three cleaning, wherein the roughing operation lasts for 5 minutes, the scavenging operation lasts for 5 minutes, and the cleaning operation lasts for 4 minutes, wherein the collector II is used in an amount of 50 g / t and the frother is used in an amount of 10 g / t in the scavenging I operation, the collector II is used in an amount of 40 g / t and the frother is used in an amount of 5 g / t in the scavenging II operation, the collector II is used in an amount of 20 g / t and the frother is used in an amount of 5 g / t in the scavenging III operation, and no reagent is added in the cleaning operation.

[0041] The flotation product indexes of Example 2 are shown in Table 2.

[0042] Table 2: Flotation product indexes of Example 2

[0043]

[0044] Compared with Example 1, when the relatively high-grade raw ore is treated by the method of the present application, the required amounts of lime, combined collector I, collector II and activator need to be appropriately increased; Example 2 produces a copper concentrate with a copper grade of 20.01% and a copper recovery of 91.55%, and a sulfur concentrate with a sulfur grade of 48.52% and a sulfur recovery of 78.80%. The flotation indexes of Example 2 are similar to those of Example 1, indicating that the method has strong adaptability to the treatment of this type of copper-sulfur ore and can achieve good copper-sulfur separation.

[0045] Example 3: This Example 3 is a comparative example of Example 1, and the process variables are described in the specific implementation manner, and the conditions not described are the same as those of Example 1.

[0046] The specific operation steps are as follows:

[0047] (1) In this Example 3, 2000 g / t of lime is added during grinding to adjust the pH to 11.

[0048] (2) The collector III used in the copper flotation of this example 3 is prepared by mixing pentyl xanthate and ethyl xanthate at a ratio of 1:1, and the dosage and adding method are the same as those in example 1.

[0049] (3) The dosage of the ferric sulfide activator polymeric ferric sulfate used in the copper flotation of this example 3 is 3000 g / t, and the dosage of sodium carbonate is 1500 g / t.

[0050] The flotation indexes of this example 3 are shown in Table 3 below.

[0051] Table 3 Flotation product indexes of comparative example 1

[0052]

[0053] As shown in Table 3, this example 3 obtains a copper concentrate with a copper grade of 20.12% and a copper recovery of 89.77%, and a sulfur concentrate with a sulfur grade of 46.35% and a sulfur recovery of 76.77%. Although the copper concentrate obtained by this method has a slightly higher grade, the copper recovery is reduced by about 1.8 percentage points compared with example 1. In addition, the copper recovery of the sulfur concentrate index is increased by about 1.9 percentage points, and the grade and recovery of the sulfur concentrate are slightly lower.

[0054] Example 4: This example is a comparative example of example 2. The ore type treated in this example is the same as that in example 2, and the process variables are described in the specific implementation manner. The conditions not described are the same as those in example 2.

[0055] The specific operation steps are as follows:

[0056] (1) In this example 4, 3000 g / t of lime is added during grinding to adjust the pH to about 12.

[0057] (2) The collector III used in the copper flotation of this example 4 is prepared by mixing pentyl xanthate and ethyl xanthate at a ratio of 1:1, and the dosage and adding method are the same as those in example 2.

[0058] (3) The dosage of the ferric sulfide activator polymeric ferric sulfate used in the copper flotation of this example 4 is 4000 g / t, and the dosage of sodium carbonate is 1000 g / t.

[0059] The flotation indexes of this example 4 are shown in Table 4 below.

[0060] Table 4 Flotation product indexes of this example 4

[0061]

[0062] As can be seen from Table 4, the copper concentrate with a copper grade of 20.05% and a copper recovery of 89.03% and the sulfur concentrate with a sulfur grade of 48.21% and a sulfur recovery of 78.68% are obtained in Example 4. Compared with Example 2, the copper grade of the copper concentrate, the sulfur grade of the sulfur concentrate and the sulfur recovery of the sulfur concentrate are similar, but the copper recovery is lost by 2.5 percentage points in the sulfur concentrate.

[0063] The results of Example 3 and Example 4 show that the separation of copper-sulfur minerals can be achieved under high alkaline conditions using a large amount of lime. However, since the copper minerals are also inhibited to a certain extent, the copper minerals are not effectively enriched in the copper selection stage and are lost in the subsequent sulfur concentrate. At the same time, due to the large amount of pyrite depressant used in the copper selection stage, a large amount of activator is required to activate the pyrite in the subsequent sulfur selection stage, and the activation effect is affected to a certain extent, resulting in a decrease in the recovery rate of the sulfur concentrate. Therefore, the overall recovery effect of the method for treating this type of ore in Example 3 and Example 4 is poor, and the production cost is higher.

[0064] Example 5: This example is a comparative example of Example 1. The ore type treated in Example 5 is the same as that in Example 1, and the process variables are described in the specific implementation manner. The conditions not described are the same as those in Example 1.

[0065] The specific operation steps are as follows:

[0066] (1) The collector for the copper selection operation is pyridine methanol alone, and the dosage is 60 g / t. The addition method is the same as that in Example 1.

[0067] The flotation indexes of this example are shown in Table 5 below:

[0068] Table 5 Flotation product indexes of Example 5

[0069]

[0070] As can be seen from Table 5, the copper concentrate with a copper grade of 22.68% and a copper recovery of 63.68% and the sulfur concentrate with a sulfur grade of 47.21% and a sulfur recovery of 79.60% are obtained in this example. The results of this example show that although the selectivity of using pyridine methanol alone as a collector is strong, the collection capacity is not enough, and a small amount of low-grade xanthate (such as ethyl xanthate) needs to be used.

[0071] The above only describes the preferred embodiments of the present application. It should be noted that for ordinary skilled persons in the technical field, some improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. The application of a combined collector for chalcopyrite in low-copper, high-sulfur copper sulfide ores, characterized in that, This combined collector comprises pyridine methanol and ethyl xanthate, with a mass ratio of pyridine methanol to ethyl xanthate of 4-5:

1. This combined collector can achieve copper-sulfur separation under low-alkali conditions. Pyridine methanol contains both O and N atoms as electron donors and can form a stable five-membered chelate ring with Cu metal on the surface of chalcopyrite. Furthermore, under the weakly alkaline conditions of lime, pyridine methanol exhibits extremely weak collecting ability for pyrite but good collecting ability for chalcopyrite. The specific steps for applying this combined collector to chalcopyrite in low-copper, high-sulfur copper-sulfur ores are as follows: (1) First, lime is added to the copper-sulfur ore to adjust the pH to 8-9, and then the ore is ground to obtain copper-sulfur monomer-dissociated slurry; (2) In the copper-sulfur monomer dissociation slurry obtained in step (1), a combination collector and frother No. 2 oil are added in sequence. After a roughing, scavenging and cleaning process, copper concentrate and copper tailings are obtained. The middlings products are returned to the previous stage in sequence to form a closed loop. (3) After the copper tailings obtained in step (2) are deslimed and thickened, they enter the pyrite activation flotation operation. Combined activator, collector II and frother are added in sequence to carry out the process of roughing, scavenging and cleaning to obtain pyrite concentrate and tailings. The middlings are returned to the previous stage in sequence to form a closed loop. The desliming and thickening operation is as follows: the copper tailings are thickened in one stage to obtain the overflow of the thickener and the underflow of the thickener. The overflow of the thickener enters the hydrocyclone for classification to remove the sludge of -10μm size. The underflow of the thickener and the hydrocyclone sediment enter the second stage thickening operation to obtain the overflow of the thickener and the underflow of the thickener. The overflow of the thickener returns to the first stage thickening operation and the underflow of the thickener enters the pyrite activation flotation operation.

2. The application of the combined collector for chalcopyrite in low-copper, high-sulfur copper sulfide ore according to claim 1, characterized in that: The combined activator in step (3) is a combination of polyferric sulfate and sodium carbonate. Collector II includes ethyl xanthate, isopropyl xanthate and isobutyl xanthate, wherein the amount of polyferric sulfate is 1000-1500 g / t and the amount of sodium carbonate is 800-1000 g / t.

3. The application of the combined collector for chalcopyrite in low-copper, high-sulfur copper sulfide ore according to claim 1, characterized in that: The amount of combined collector added in step (2) is 60-80 g / t.

4. The application of the combined collector for chalcopyrite in low-copper, high-sulfur copper sulfide ore according to claim 1, characterized in that: In step (1), the mass ratio of lime added is 500~700g / t.

5. The application of the combined collector for chalcopyrite in low-copper, high-sulfur copper sulfide ore according to claim 1, characterized in that: In step (1), the fineness of the copper-sulfur ore grinding is 0.074 mm, accounting for 74-75%, which achieves the dissociation of copper-sulfur monomers.

6. The application of the combined collector for chalcopyrite in low-copper, high-sulfur copper sulfide ore according to claim 2, characterized in that: The total addition amount of collector II is 180-200 g / t, in which the mass ratio of ethyl xanthate, isopropyl xanthate and isobutyl xanthate is 2:3:5.

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