A combined depressant for flotation separation of copper-zinc sulfide ores and its application

Abstract

The present invention discloses a combined inhibitor for flotation separation of copper-zinc sulfide ores and its application. The combined inhibitor comprises zinc sulfate and lycopersicon; the combined inhibitor is used as an inhibitor of sphalerite for flotation separation of chalcopyrite and sphalerite; the raw ore is crushed and ground, and then slurried to obtain a slurry to be floated; quicklime, the combined inhibitor zinc sulfate and lycopersicon, a collector, and a frother are sequentially added to the slurry to perform copper flotation operation to obtain copper concentrate and copper tailings; an activator, a collector, and a frother are sequentially added to the copper tailings to perform zinc flotation operation to obtain zinc concentrate and tailings. The combined inhibitor has a strong inhibitory effect on sphalerite and can effectively achieve flotation separation of chalcopyrite and sphalerite; the lycopersicon can enhance the inhibitory effect of zinc sulfate on sphalerite and can reduce the amount of zinc sulfate used, thereby improving the separation effect of copper-zinc sulfide ores while also reducing mineral processing costs.

Description

Technical Field

[0001] The present invention relates to a combined inhibitor for flotation separation of copper-zinc sulfide ores and its application, belonging to the field of mineral processing technology. Specifically, it relates to the application of zinc sulfate and lycopersicin as inhibitors of sphalerite activated by copper ions in the flotation separation process of copper-zinc sulfide ores. Background Art

[0002] Copper and zinc are important strategic nonferrous metals in my country, playing a crucial role in industrial and national economic development. They are widely used in the electrical, mechanical, metallurgical, and chemical industries. Copper-zinc sulfide ores, the primary source of copper and zinc, are widely distributed in my country. Most of the copper-zinc ores in my country are fine-grained, disseminated ores. Copper-zinc concentrates contain significant intercalation of copper and zinc minerals, making it difficult to effectively suppress sphalerite, which has been activated by copper ions. Therefore, the effective separation of copper-zinc ores is crucial for the efficient utilization of copper and zinc resources.

[0003] Flotation is the primary method for beneficiating copper-zinc sulfide ores in my country. However, the dense intergrowth of copper and zinc minerals makes it difficult to separate them, making separation difficult. Even when the grinding fineness reaches the required level for individual separation, the fineness of the ore particles due to over-grinding significantly reduces the floatation rate, making copper and other particles more easily dissolved and releasing unavoidable ions into the slurry. The copper ions in the slurry activate sphalerite, making the sphalerite surface similar in floatability to that of chalcopyrite, making copper and zinc separation difficult. In the copper-zinc flotation separation process, the selection of zinc mineral depressants plays a crucial role in improving beneficiation performance. Commonly used depressants for sphalerite include sodium cyanide, zinc sulfate, sodium sulfite, sodium thiosulfate, azo agents, and tannins. However, these agents have the disadvantages of high environmental pollution, high dosage, and high cost. Therefore, the development of green, non-toxic, and highly effective sphalerite depressants is a key research direction for achieving effective separation of lead and zinc ores and fully utilizing lead and zinc metal resources.

[0004] In recent years, organic depressants have gained widespread application in copper-zinc separation due to their widespread availability, low cost, and excellent selectivity. Furthermore, mineral processing professionals have discovered that combining inorganic and organic depressants can leverage their respective strengths to further enhance the inhibitory effect on sphalerite. The development of novel combined depressants is of great significance for improving copper-zinc separation reagent systems, reducing reagent costs, increasing copper and zinc resource utilization, and reducing environmental pollution. Summary of the Invention

[0005] In response to the shortcomings of the prior art, one of the objectives of the present invention is to provide a combined inhibitor for the flotation separation of copper-zinc sulfide ores. The combined inhibitor of the present invention comprises zinc sulfate and lycopersicin. The combined inhibitor has a good inhibitory effect on sphalerite activated by copper ions, is naturally degradable, and is environmentally friendly.

[0006] The combined depressant of the present invention is used as a sphalerite depressant for flotation separation of chalcopyrite and sphalerite, wherein the mass ratio of zinc sulfate to rosella red pigment is (2-4):1.

[0007] A second object of the present invention is to provide an application of the combined depressant in the flotation separation of copper-zinc sulfide ores, the specific steps of which are as follows:

[0008] (1) Crushing and grinding the raw ore and then slurrying to obtain the slurry to be flotated;

[0009] (2) Adding quicklime, combined inhibitors of zinc sulfate and lycopersicon erythritol, collectors, and frothers to the slurry in sequence to perform copper flotation operations to obtain copper concentrate and copper tailings;

[0010] (3) Add activator, collector and frother to the copper tailings in sequence to carry out zinc flotation operation to obtain zinc concentrate and tailings.

[0011] Step (1) grinding to a particle fineness of -0.074 mm accounting for 70% to 80%.

[0012] The amount of quicklime added in step (2) is 1500~2500g / t.

[0013] The copper flotation operation in step (2) includes one roughing, two scavenging and three concentrating operations, and the zinc flotation operation in step (3) includes one roughing, two scavenging and three concentrating operations.

[0014] In step (2), the collecting agents are butyl xanthate and Z-200, and the foaming agent is 2# oil, wherein the total amount of butyl xanthate is 40-60 g / t, the total amount of Z-200 is 50-80 g / t, and the total amount of 2# oil is 30-40 g / t; in step (3), the activator is copper sulfate, the collecting agent is butyl xanthate, and the foaming agent is 2# oil, wherein the total amount of copper sulfate is 200-250 g / t, the total amount of butyl xanthate is 55-80 g / t, and the total amount of 2# oil is 40-60 g / t.

[0015] The total amount of the combined inhibitor added in step (2) is 2000-3000 g / t.

[0016] The principle of the present invention is that the combined inhibitor of the present invention includes zinc sulfate and rosella lycopersicum, and the present invention mainly utilizes the synergistic inhibitory effect between the two agents. Since sphalerite in copper-zinc sulfide ore is activated by copper ions in the slurry and exhibits good floatability, when the combined inhibitor is added, rosella lycopersicum first chelates with the copper ions in the solution, consuming the dissolved copper ions in the slurry system, effectively preventing the copper ions from further activating sphalerite; and since the inorganic inhibitor is zinc sulfate, rosella lycopersicum can chelate with the Zn in the solution. 2+The hydrophilic substance generated by the reaction covers the surface of sphalerite, preventing it from reacting with the collector, thereby inhibiting the sphalerite activated by copper ions. The specific reaction process is shown in the following formula:

[0017]

[0018]

[0019] Compared with the conventional inorganic inhibitors in the prior art, the present invention has the following beneficial effects:

[0020] (1) The combined inhibitor for flotation separation of copper-zinc sulfide ores provided by the present invention and its application can achieve efficient separation of sphalerite and chalcopyrite, and has great theoretical and economic value for improving the beneficiation level of low-grade complex copper-zinc sulfide ores in my country and the utilization rate of copper-zinc metal resources.

[0021] (2) The combined inhibitor provided by the present invention is composed of zinc sulfate and lycopersicon. The combined inhibitor has the advantages of good water solubility, wide availability, and biodegradability, avoiding the problems of traditional cyanide inhibitors such as severe toxicity and severe environmental pollution. In addition, the addition of lycopersicon can reduce the amount of zinc sulfate used, solving the problem of sphalerite being activated by copper ions.

[0022] (3) The combined inhibitor used in the method of the present invention undergoes complexation with heavy metal ions in the mineral processing wastewater, which can effectively reduce the difficulty and treatment cost of wastewater return. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 A process flow chart of an embodiment of the present invention DETAILED DESCRIPTION

[0024] Example 1: This Example 1 investigated the flotation separation of a copper-zinc sulfide ore from Yunnan. The ore contained 0.90% Cu and 1.62% Zn. The copper in the ore existed primarily as chalcopyrite, while the zinc existed primarily as sphalerite. The gangue minerals primarily included quartz, pyrite, dolomite, and feldspar.

[0025] Comparative Example 1-1: Using conventional single inhibitor zinc sulfate as sphalerite inhibitor to separate copper and zinc, the flow chart is as follows: Figure 1 The specific steps are as follows:

[0026] (1) Crushing and grinding the raw ore and then slurrying to obtain the slurry to be flotated, of which the grinding fineness is -0.074mm accounting for 65%-75%;

[0027] (2) Add lime to the ore pulp to be floated at a dosage of 400 g / t; the dosage of inhibitor zinc sulfate is 1500 g / t; the dosages of collector butyl xanthate and Z-200 are 50 g / t and 20 g / t respectively; the dosage of frother 2 is 100 g / t ... # The oil dosage is 20 g / t, and copper roughing is carried out to obtain copper roughing concentrate and copper roughing tailings.

[0028] (3) Adding the inhibitor zinc sulfate to the copper roughing concentrate in step (2) in an amount of 600 g / t; adding the collector butyl xanthate and Z-200 in an amount of 20 g / t and 10 g / t respectively to copper concentration I, then adding the inhibitor zinc sulfate to the copper concentration I concentrate in an amount of 150 g / t to copper concentration II, and then subjecting the copper concentration II concentrate to a blank concentration III to obtain the final copper concentrate, wherein the middlings of copper concentration I, II, and III are returned to the copper roughing, copper concentration I, and copper concentration II respectively, forming a closed loop. Adding the collector butyl xanthate and Z-200 in an amount of 30 g / t and 10 g / t respectively to the copper roughing tailings, and adding the foaming agent 2 # The oil dosage is 20g / t, and copper scavenging I is carried out; then the collector butyl xanthate and Z-200 are added to the copper scavenging I tailings, the dosage is 30g / t and 10g / t respectively, and the foaming agent is 2 # The oil dosage is 10g / t for copper scavenging II, and the copper scavenging tailings are used as zinc roughing feed. The copper scavenging I and II concentrates are returned to the copper roughing and copper scavenging I respectively to form a closed circuit.

[0029] (4) Add 500g / t of lime, 100g / t of copper sulfate, 50g / t of butyl xanthate to the copper scavenging tailings in step (3). # The zinc roughing is carried out with 20g / t of oil to obtain zinc roughing concentrate and zinc roughing tailings. 200g / t of lime and 20g / t of butyl xanthate are added to the zinc roughing concentrate to carry out zinc concentration I; 10g / t of butyl xanthate is added to the zinc concentration I concentrate to carry out zinc concentration II, and finally the zinc concentration II concentrate is subjected to a blank concentration III to obtain the final zinc concentrate, wherein the middlings of zinc concentration I, II and III are respectively returned to the zinc roughing, zinc concentration I and zinc concentration II to form a closed circuit. 50g / t of copper sulfate, 30g / t of butyl xanthate, 2 # Oil 20g / t for zinc scavenging I; then add copper sulfate 20g / t, butyl xanthate 20g / t, 2 # The zinc scavenging II was carried out at 10 g / t oil, and the resulting tailings were the final total tailings, wherein the concentrates of zinc scavenging I and II were returned to the zinc roughing and zinc scavenging I respectively, forming a closed circuit. The test results of this example are shown in Table 1.

[0030] Comparative Example 1-2: This example uses the combined inhibitor to carry out flotation separation of copper-zinc sulfide ore, and the combined inhibitor includes zinc sulfate and rosella red pigment, and the mass ratio of the two is 2:1. Figure 1 The specific steps are as follows:

[0031] (1) Crushing and grinding the raw ore and then slurrying to obtain the slurry to be flotated, of which the grinding fineness is -0.074mm accounting for 65%-75%;

[0032] (2) Add lime to the ore pulp to be floated at a dosage of 400 g / t; the dosage of combined inhibitor zinc sulfate and lycopene is 1000 g / t and 500 g / t respectively; the dosage of collector butyl xanthate and Z-200 is 50 g / t and 20 g / t respectively; the dosage of frother 2 is 1000 g / t and 50 ... # The oil dosage is 20 g / t, and copper roughing is carried out to obtain copper roughing concentrate and copper roughing tailings.

[0033] (3) Add zinc sulfate and lycopene, a combined inhibitor, to the copper roughing concentrate in step (2), in amounts of 400 g / t and 200 g / t respectively; add butyl xanthate and Z-200, a collector, in amounts of 20 g / t and 10 g / t respectively, to copper concentration I, then add zinc sulfate and lycopene, a combined inhibitor, to the copper concentration I concentrate, in amounts of 100 g / t and 50 g / t respectively, to copper concentration II, and then perform blank concentration III on the copper concentration II concentrate to obtain the final copper concentrate, wherein the middlings of copper concentration I, II, and III are returned to the copper roughing, copper concentration I, and copper concentration II, respectively, to form a closed loop. Add butyl xanthate and Z-200, a collector, in amounts of 30 g / t and 10 g / t respectively, and a foaming agent 2 # The oil dosage is 20g / t, and copper scavenging I is carried out; then the collector butyl xanthate and Z-200 are added to the copper scavenging I tailings, the dosage is 30g / t and 10g / t respectively, and the foaming agent is 2 # The oil dosage is 10g / t for copper scavenging II, and the copper scavenging tailings are used as zinc roughing feed. The copper scavenging I and II concentrates are returned to the copper roughing and copper scavenging I respectively to form a closed circuit.

[0034] (4) Add 500g / t of lime, 100g / t of copper sulfate, 50g / t of butyl xanthate to the copper scavenging tailings in step (3). #The zinc roughing is carried out with 20g / t of oil to obtain zinc roughing concentrate and zinc roughing tailings. 200g / t of lime and 20g / t of butyl xanthate are added to the zinc roughing concentrate to carry out zinc concentration I; 10g / t of butyl xanthate is added to the zinc concentration I concentrate to carry out zinc concentration II, and finally the zinc concentration II concentrate is subjected to a blank concentration III to obtain the final zinc concentrate, wherein the middlings of zinc concentration I, II and III are respectively returned to the zinc roughing, zinc concentration I and zinc concentration II to form a closed circuit. 50g / t of copper sulfate, 30g / t of butyl xanthate, 2 # Oil 20g / t for zinc scavenging I; then add copper sulfate 20g / t, butyl xanthate 20g / t, 2 # The zinc scavenging II was carried out at a concentration of 10 g / t of oil, and the resulting tailings formed the final total tailings. The concentrates from zinc scavenging I and II were returned to the zinc roughing and zinc scavenging I, respectively, forming a closed loop. The test results of this example are shown in Table 1. The data in Table 1 demonstrate that the combined inhibitor of zinc sulfate and lycopersicin has high separation efficiency for copper-zinc sulfide ores, achieving excellent mineral processing performance.

[0035] Table 1 Test results of Example 1

[0036]

[0037] Example 2: This Example 2 conducted flotation separation experiments on a copper-zinc sulfide ore from Inner Mongolia. The ore contained 2.91% Cu and 1.72% Zn. The copper in the ore existed primarily as chalcopyrite, the zinc primarily as sphalerite, and the gangue minerals primarily included quartz, pyroxene, garnet, and feldspar.

[0038] Comparative Example 2-1

[0039] Conventional single inhibitor zinc sulfate is used as sphalerite inhibitor for copper and zinc separation. The flow chart is as follows: Figure 1 The specific steps are as follows:

[0040] (1) Crushing and grinding the raw ore and then slurrying to obtain the slurry to be flotated, of which the grinding fineness is -0.074mm accounting for 65%-75%;

[0041] (2) Add 2000g / t of inhibitor zinc sulfate to the ore pulp to be floated; the amounts of collector butyl xanthate and Z-200 are 60g / t and 20g / t respectively; the amount of frother 2 # The oil dosage is 20 g / t, and copper roughing is carried out to obtain copper roughing concentrate and copper roughing tailings.

[0042] (3) Add the inhibitor zinc sulfate to the copper roughing concentrate in step (2) in an amount of 750 g / t; the collector butyl xanthate and Z-200 in amounts of 20 g / t and 10 g / t respectively to perform copper concentration I, then add the inhibitor zinc sulfate to the copper concentration I concentrate in an amount of 375 g / t to perform copper concentration II, and then perform blank concentration III on the copper concentration II concentrate to obtain the final copper concentrate, wherein the middlings of copper concentration I, II, and III are returned to the copper roughing, copper concentration I, and copper concentration II respectively to form a closed loop. Add the collector butyl xanthate and Z-200 in amounts of 30 g / t and 10 g / t respectively to the copper roughing tailings, and the foaming agent 2 # The oil dosage is 20g / t, and copper scavenging I is carried out; then the collector butyl xanthate and Z-200 are added to the copper scavenging I tailings, the dosage is 30g / t and 15g / t respectively, and the foaming agent is 2 # The oil dosage is 10g / t for copper scavenging II, and the copper scavenging tailings are used as zinc roughing feed. The copper scavenging I and II concentrates are returned to the copper roughing and copper scavenging I respectively to form a closed circuit.

[0043] (4) Add 150g / t of copper sulfate and 60g / t of butyl xanthate to the copper scavenging tailings in step (3). # 10g / t of oil is used for zinc roughing to obtain zinc roughing concentrate and zinc roughing tailings. 200g / t of lime and 20g / t of butyl xanthate are added to the zinc roughing concentrate to carry out zinc concentration I; 100g / t of lime and 10g / t of butyl xanthate are added to the zinc concentration I concentrate to carry out zinc concentration II, and finally the zinc concentration II concentrate is subjected to a blank concentration III to obtain the final zinc concentrate, wherein the middlings of zinc concentration I, II and III are respectively returned to the zinc roughing, zinc concentration I and zinc concentration II to form a closed circuit. 100g / t of copper sulfate, 30g / t of butyl xanthate, 2 # Oil 20g / t for zinc scavenging I; then add copper sulfate 50g / t, butyl xanthate 20g / t, 2 # The zinc scavenging II was carried out at 10 g / t oil, and the resulting tailings were the final total tailings, wherein the concentrates of zinc scavenging I and II were returned to the zinc roughing and zinc scavenging I respectively, forming a closed circuit. The test results of this example are shown in Table 2.

[0044] Comparative Example 2-2

[0045] This embodiment uses the combined inhibitor to carry out flotation separation of copper-zinc sulfide ore, and the combined inhibitor includes zinc sulfate and rosella lycopene, and the mass ratio of the two is 2:1. Figure 1 The specific steps are as follows:

[0046] (1) Crushing and grinding the raw ore and then slurrying to obtain the slurry to be flotated, of which the grinding fineness is -0.074mm accounting for 65%-75%;

[0047] (2) Add zinc sulfate and lycopene as combined inhibitors to the ore pulp to be floated, with the dosages of 1500 g / t and 750 g / t respectively; butyl xanthate and Z-200 as collectors, with the dosages of 60 g / t and 20 g / t respectively; frother 2 # The oil dosage is 20 g / t, and copper roughing is carried out to obtain copper roughing concentrate and copper roughing tailings.

[0048] (3) Add zinc sulfate and lycopene as combined inhibitors to the copper roughing concentrate in step (2) in amounts of 500 g / t and 250 g / t, respectively; add butyl xanthate and Z-200 as collectors in amounts of 20 g / t and 10 g / t, respectively, to perform copper concentration I, then add zinc sulfate and lycopene as combined inhibitors to the copper concentration I concentrate in amounts of 250 g / t and 125 g / t, respectively, to perform copper concentration II, and then perform blank concentration III on the copper concentration II concentrate to obtain the final copper concentrate, wherein the middlings of copper concentration I, II, and III are returned to the copper roughing, copper concentration I, and copper concentration II, respectively, to form a closed loop. Add butyl xanthate and Z-200 as collectors in amounts of 30 g / t and 10 g / t, respectively, and frother 2 to the copper roughing tailings. # The oil dosage is 20g / t, and copper scavenging I is carried out; then the collector butyl xanthate and Z-200 are added to the copper scavenging I tailings, the dosage is 30g / t and 15g / t respectively, and the foaming agent is 2 # The oil dosage is 10g / t for copper scavenging II, and the copper scavenging tailings are used as zinc roughing feed. The copper scavenging I and II concentrates are returned to the copper roughing and copper scavenging I respectively to form a closed circuit.

[0049] (4) Add 150g / t of copper sulfate and 60g / t of butyl xanthate to the copper scavenging tailings in step (3). # 10g / t of oil is used for zinc roughing to obtain zinc roughing concentrate and zinc roughing tailings. 200g / t of lime and 20g / t of butyl xanthate are added to the zinc roughing concentrate to carry out zinc concentration I; 100g / t of lime and 10g / t of butyl xanthate are added to the zinc concentration I concentrate to carry out zinc concentration II, and finally the zinc concentration II concentrate is subjected to a blank concentration III to obtain the final zinc concentrate, wherein the middlings of zinc concentration I, II and III are respectively returned to the zinc roughing, zinc concentration I and zinc concentration II to form a closed circuit. 100g / t of copper sulfate, 30g / t of butyl xanthate, 2 # Oil 20g / t for zinc scavenging I; then add copper sulfate 50g / t, butyl xanthate 20g / t, 2 # The zinc scavenging II was carried out at 10 g / t oil, and the resulting tailings were the final total tailings, wherein the concentrates of zinc scavenging I and II were returned to the zinc roughing and zinc scavenging I respectively, forming a closed circuit. The test results of this example are shown in Table 2.

[0050] Table 2 Test results of Example 2

[0051]

[0052] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A combined depressant for flotation separation of copper-zinc sulfide ores, characterized in that: The combined inhibitor comprises zinc sulfate and rosella lycopene, and the combined inhibitor is used as a sphalerite inhibitor for the flotation separation of chalcopyrite and sphalerite, wherein the mass ratio of zinc sulfate to rosella lycopene is (2-4):

1.

2. An application of the combined depressant for flotation separation of copper-zinc sulfide ores according to claim 1, characterized in that: The specific steps are as follows: (1) Crushing and grinding the raw ore and then slurrying to obtain the slurry to be flotated; (2) Adding quicklime, combined inhibitors of zinc sulfate and lycopene, a collector, and a frother to the slurry in sequence to perform copper flotation operations to obtain copper concentrate and lead tailings; (3) Add activator, collector and frother to the copper tailings in sequence to carry out zinc flotation operation to obtain zinc concentrate and tailings.

3. The use of the combined depressant for flotation separation of copper-zinc sulfide ores according to claim 2, characterized in that: Step (1) grinding to a particle fineness of -0.074 mm accounting for 70% to 80%.

4. The use of the combined depressant for flotation separation of copper-zinc sulfide ores according to claim 2, characterized in that: The amount of quicklime added in step (2) is 1500~2500g / t.

5. The use of the combined depressant for flotation separation of copper-zinc sulfide ores according to claim 2, characterized in that: The copper flotation operation in step (2) includes one roughing, two scavenging and three concentrating operations, and the zinc flotation operation in step (3) includes one roughing, two scavenging and three concentrating operations.

6. The use of the combined depressant for flotation separation of copper-zinc sulfide ores according to claim 2, characterized in that: In step (2), the collecting agents are ethyl xanthate and Z-200, and the foaming agent is 2# oil, wherein the total amount of butyl xanthate is 40-60 g / t, the total amount of Z-200 is 50-80 g / t, and the total amount of 2# oil is 30-40 g / t; in step (3), the activator is copper sulfate, the collecting agent is butyl xanthate, and the foaming agent is 2# oil, wherein the total amount of copper sulfate is 200-250 g / t, the total amount of butyl xanthate is 55-80 g / t, and the total amount of 2# oil is 40-60 g / t.

7. The use of the combined depressant for flotation separation of copper-zinc sulfide ores according to claim 2, characterized in that: The total amount of the combined inhibitor added in step (2) is 2000-3000 g / t.

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