CN114602658A - Zinc blende flotation combined inhibitor and application thereof - Google Patents

Abstract

The invention discloses a sphalerite flotation combined inhibitor and an application thereof, belonging to the technical field of copper-zinc sulfide mineral flotation separation. The combined inhibitor of the present invention comprises an organic inhibitor and an inorganic inhibitor, the organic inhibitor is lac red pigment (referred to as lac red), and the inorganic inhibitor is composed of ZnSO ₄ , Ca(OH) ₂ , CaCl ₂ and one or both of Na ₂ S, the total amount of the inorganic inhibitor is 1500-3600 g/t, and the total amount of the inorganic inhibitor is 500-1125 g/t. The combined inhibitor of the invention is suitable for the flotation separation of chalcopyrite and sphalerite, can selectively inhibit sphalerite, increase the floatability difference between sphalerite and chalcopyrite, and can be used in neutral It can effectively realize the flotation separation of sphalerite and chalcopyrite under the conditions of low alkalinity and low alkalinity, and has the advantages of non-toxic environmental protection, good stability, low dosage and strong applicability.

Description

A sphalerite flotation combined inhibitor and its application

technical field

The invention specifically relates to a sphalerite flotation combined inhibitor and application thereof, belonging to the technical field of copper-zinc sulfide mineral flotation separation.

Background technique

As important metal materials, copper and zinc play an important role in the modernization construction. With the continuous development of mineral resources, high-quality mineral resources are decreasing day by day. Comprehensive utilization of complex and refractory copper-zinc sulfide ore resources has become a way to alleviate the shortage of resources. one of the effective ways.

The copper minerals in the copper-zinc sulfide ore are mainly chalcopyrite, and the zinc minerals are mainly sphalerite. The reasons for the difficulty of flotation and separation of the two are mainly as follows: (1) The relationship between the inlaid minerals is complex and the monomer dissociates. (2) Activation of sphalerite by copper ions; (3) staggered effect of floatability between copper-zinc sulfide minerals; (4) pyrite, pyrrhotite, other associated minerals and slime Influence; (5) Influence of flotation process and flotation method. Among them, the complex intercalation characteristics of Cu-Zn minerals and the activation of sphalerite by Cu ²⁺ ions are the main reasons for the difficulty in separation.

In production practice, the process of suppressing zinc and floating copper is often used to realize the separation of copper and zinc. The effective suppression of sphalerite is the key to efficient recovery of copper minerals. Existing sphalerite inhibitors are mainly divided into inorganic inhibitors and organic inhibitors.

The inorganic inhibitors of sphalerite mainly include cyanide, zinc sulfate, sulfurous acid (sulfur dioxide) and its salts, sodium sulfide, etc. The order of their inhibition of sphalerite is as follows: cyanide>zinc sulfate>sulfurous acid (sulfur dioxide) and Its salt > sodium sulfide. Except for cyanide, the inhibition effect of several other agents on sphalerite is not good. Therefore, the commonly used sphalerite inhibitor formulations in most processing plants at home and abroad are inorganic combination agents based on zinc sulfate, such as the combination of zinc sulfate and lime, the combination of zinc sulfate and sodium sulfite, etc. In particular, Japan often uses sulfur dioxide in combination with zinc sulfate to inhibit sphalerite.

The organic inhibitors of sphalerite can be divided into macromolecular organic inhibitors and small molecular organic inhibitors according to their molecular weight and the number of groups. The macromolecular organic inhibitors are mainly dextrin and polysaccharide inhibitors (starch, dextrin, cellulose, chitosan, etc.). Small molecule organic inhibitors are mostly used in actual production for thioglycolic acid, ethylenediaminetetraacetic acid, tannin small molecule inhibitors, and azo drugs.

In production, it is found that a single inorganic inhibitor is not effective in treating some complex copper-zinc sulfide ores, while organic inhibitors are often combined with inorganic inhibitors and organic inhibitors because of their high cost and unsatisfactory effect alone. use. Therefore, it is of great significance to find a new combination inhibitor with good inhibitory effect, strong adaptability, small dosage, non-toxic and environmental protection for realizing the efficient separation of copper-zinc sulfide ores.

SUMMARY OF THE INVENTION

The present invention aims to provide a combination inhibitor for sphalerite flotation that is non-toxic, environmentally friendly, has strong adaptability and a small amount of consumption. The combined inhibitor is suitable for the flotation separation of chalcopyrite and sphalerite, which can selectively inhibit sphalerite, increase the floatability difference between chalcopyrite and chalcopyrite, and effectively realize sphalerite and yellow sphalerite. Flotation separation of copper ore.

The organic inhibitor is lac red pigment (referred to as lac red); the inorganic inhibitor is one or two of ZnSO ₄ , Ca(OH) ₂ , CaCl ₂ and Na ₂ S.

Another object of the present invention is to provide the application of the sphalerite flotation inhibitor: the inhibitor is applied to the flotation separation of sphalerite and chalcopyrite in copper-zinc sulfide ore, and the specific steps are:

Step 1: Grinding, grinding the copper-zinc sulfide ore to -0.074mm, accounting for 70~80%.

Step 2: Adjust the pulp, adjust the pulp concentration to 20%~30%, and adjust the pulp pH to 7~11.

Step 3: Chalcopyrite flotation, in the roughing stage, firstly add inorganic inhibitors and stir for 3 minutes, then add organic inhibitors and stir for 3 minutes, and carry out 1~2 times of roughing, 1~2 times of sweeping, and 2~4 times of beneficiation , 1 to 3 times of fine sweeping selection; among them, the finely swept concentrates are combined and returned to the fine I, and the rest of the medium mines are returned to the upper level in order to form a closed circuit; the roughing, sweeping, selection and fine sweeping are all conventional craft.

Further, in step 3, 1500-3600 g/t inorganic inhibitor and 500-1125 g/t organic inhibitor are added during the flotation process.

Further, in step 3, the required amount of collector and foaming agent are sequentially added to the thickening and sweeping selection, wherein the collector is nitrile yellow, and the foaming agent is MIBC, both of which are conventional ore dressing agents.

Further, the organic inhibitor described in the present invention can undergo a complex reaction with Zn ²⁺ , ^{Ca 2+} in the inorganic inhibitor and Cu ²⁺ in the solution to generate a hydrophilic substance, reducing the effect of Cu ²⁺ on flash. Activation of zinc ore.

Further, the generated hydrophilic substances still have a certain number of carbonyl groups and hydroxyl groups, and these groups can react with Zn ²⁺ on the surface of sphalerite and Cu ²⁺ substituted for Zn ²⁺ , and adsorb on the surface of sphalerite. , making the surface hydrophilic and inhibited.

The present invention has the following advantages:

(1) In the combined inhibitor of the invention, the organic inhibitor and metal ions are complexed and adsorbed on the surface of sphalerite, thereby competing with the collector molecules for adsorption, reducing the collection performance of the collector for sphalerite, and at the same time , the organic inhibitor contains multiple carbonyl, hydroxyl, carboxyl and other hydrophilic groups, which can further increase the surface hydrophilic properties of sphalerite and reduce its floatability. In addition, the organic inhibitor can also complex the inevitable ions in the pulp , reducing the activation of sphalerite by inevitable ions; inorganic inhibitors cooperate with organic inhibitors to selectively inhibit sphalerite in alkaline environment.

(2) The organic inhibitor shellac red in the combined inhibitor of the present invention can form a complex with Zn ²⁺ and Ca ²⁺ in the inorganic inhibitor to form a complex and adsorb on the surface of sphalerite to enhance the hydrophilic performance of the mineral surface , reducing the floatability of sphalerite.

(3) The combined inhibitor of the present invention has the characteristics of non-toxicity and environmental protection, good selective inhibition and strong adaptability, and can be widely used in the field of flotation and separation of copper-zinc sulfide minerals.

Detailed ways

The present invention will be further described in detail below with reference to the examples, but the embodiments of the present invention are not limited thereto.

The mineral processing test methods in the following examples are conventional flotation methods unless otherwise specified. The rotating speed of the flotation machine is 1200r/min, and all the agents, except MIBC foaming agent, are prepared with water as the medium.

Example 1

A sphalerite flotation combination inhibitor and an application method thereof. Taking copper-zinc sulfide ore as an object, the raw ore has a Cu grade of 1.59% and a Zn grade of 3.14%, the copper-bearing minerals are mainly chalcopyrite, and the zinc-bearing minerals are mainly flash Zinc ore; carry out the flotation closed-circuit process of "one coarse, two sweeps, three fine sweeps and two fine sweeps" for the raw ore; in which, the fine sweep concentrates are combined and returned to the concentrate I, and the remaining medium mines are returned to the previous level in sequence, including the following steps. :

Step 1: Grind the copper-zinc sulfide ore to -0.074mm accounting for 75%.

Step 2: Adjust the slurry concentration to 20%, and add lime to adjust the pH to 10.

Step 3: For the ore pulp described in step 2, 900g/t of ZnSO ₄ and Na ₂ S solution were added for rough selection, and the mass ratio of the two was 1:1, and then 300g/t of shellac red solution was added, followed by collecting Sweeping agent and foaming agent, flotation for 4 minutes after sizing; Sweep I and Sweeping II were added with collector and foaming agent in turn, after sizing, flotation for 3min and 2min respectively; the three selection times were 3min, 2min and 2min respectively; The dosing procedure of the first fine sweeping selection is the same as that of the crude I, and the two fine sweeping selection times are 3 min and 2 min respectively; the flotation indexes of the fine and tailings in this embodiment are shown in Table 1.

Example 2

A sphalerite flotation combination inhibitor and an application method thereof. Taking copper-zinc sulfide ore as an object, the raw ore has a Cu grade of 1.2% and a Zn grade of 4.13%, the copper-bearing minerals are mainly chalcopyrite, and the zinc-bearing minerals are mainly sphalerite Zinc mine. The flotation closed-circuit process of "one coarse, two sweeps, three fine sweeps, and three fine sweeps" is carried out on the raw ore. Among them, the finely swept concentrates are combined and returned to the fine I, and the remaining medium ores are returned to the previous level in sequence, which specifically includes the following steps:

Step 1: Grind the copper-zinc sulfide ore to -0.074mm, accounting for 80%.

Step 2: Adjust the slurry concentration to 30%, and add lime to adjust the pH to 8.

Step 3: For the ore pulp described in step 2, add 1800g/t Ca(OH) ₂ solution to crude I, then add 450g/t shellac red solution, then add collector and foaming agent, and float after mixing. Select 5min; Sweep I and Sweep II add collector and foaming agent in turn, flotation for 4min, 3min respectively after sizing; 4min, 3min, 2min respectively for the three selection times; the first fine sweeping and dosing procedure is the same as that of Coarse I , and the three fine-sweeping times were 3min, 3min, and 2min, respectively. The flotation indexes of the concentrate and tailings of this embodiment are shown in Table 1.

Example 3

A sphalerite flotation combination inhibitor and an application method thereof. Taking copper-zinc sulfide ore as an object, the raw ore has a Cu grade of 0.57% and a Zn grade of 2.39%, the copper-bearing minerals are mainly chalcopyrite, and the zinc-bearing minerals are mainly flash Zinc mine. The flotation closed-circuit process of "one coarse, two sweeps, two fine sweeps, and one fine sweep" is carried out on the raw ore; among them, the fine swept concentrates are combined and returned to the fine I, and the rest of the medium mines are returned to the previous level in sequence, which specifically includes the following steps:

Step 1: Grind the copper-zinc sulfide ore to -0.074mm, accounting for 80%.

Step 2: Adjust the slurry concentration to 20%, and add lime to adjust the pH to 7.

Step 3: For the ore pulp described in step ₂ , add 900g/t ZnSO4 solution to crude I, then add 450g/t shellac red solution, then add collector and foaming agent, and flotation for 4min after mixing; Sweep I and Sweep II were added with collector and foaming agent in turn, and flotation was performed for 3 minutes and 3 minutes respectively after sizing; the two selection times were 3 minutes and 2 minutes respectively; The time is 3 minutes.

The flotation indexes of the concentrate and tailings of this embodiment are shown in Table 1.

Example 4

Taking copper-zinc sulfide ore as the object, the raw ore has a Cu grade of 2.16% and a Zn grade of 2.97%. The copper-bearing minerals are mainly chalcopyrite, and the zinc-bearing minerals are mainly sphalerite. The flotation closed-circuit process of "two coarse, two sweeps, three fine and two fine sweeps" is carried out on the raw ore. Among them, the finely swept concentrates are combined and returned to the fine I, and the remaining medium ores are returned to the previous level in sequence.

A sphalerite flotation combined inhibitor and an application method thereof, specifically comprising the following steps:

Step 1: Grind the copper-zinc sulfide ore to -0.074mm, accounting for 75%.

Step 2: Adjust the slurry concentration to 20%, and add lime to adjust the pH to 9.

Step 3: For the ore pulp described in step 2, add 1050g/t CaCl ₂ solution to crude I, then add 450g/t shellac red solution, then add collector and foaming agent, and flotation for 5min after sizing, Add 500g/t CaCl ₂ solution to crude II, then add 225g/t shellac red solution, then add collector and foaming agent, and flotation for 4min after sizing; Foaming agent, flotation for 2min and 2min after sizing, respectively; the three times of selection are 4min, 3min and 2min respectively; the dosing procedure for the first cleaning and selection is the same as that of Coarse I, and the time for the second cleaning and selection is 3min and 2min respectively.

The flotation indexes of the concentrate and tailings of this embodiment are shown in Table 1.

Example 5

Taking copper-zinc sulfide ore as the object, the raw ore has a Cu grade of 2.32% and a Zn grade of 1.96%. The copper-bearing minerals are mainly chalcopyrite, and the zinc-bearing minerals are mainly sphalerite. The flotation closed-circuit process of "two coarse one sweeps four fine sweeps and two fine sweeps" is carried out on the raw ore; among them, the finely swept concentrates are combined and returned to the fine I, and the rest of the medium ores are returned to the previous level in sequence.

A sphalerite flotation combined inhibitor and an application method thereof, specifically comprising the following steps:

Step 1: Grind the copper-zinc sulfide ore to -0.074mm, accounting for 70%.

Step 2: Adjust the slurry concentration to 25%, and add lime to adjust the pH to 11.

Step 3: For the pulp described in Step 2, add 600 g/t Na ₂ S solution to crude I, then add 200 g/t shellac red solution, then add collector and foaming agent, and flotation for 5 min after mixing , 300g/t Na ₂ S solution was added to crude II, then 100g/t shellac red solution was added, then collector and foaming agent were added, and flotation was carried out for 3 minutes after sizing; Foaming agent, flotation for 2 minutes after pulping; the four selection times are 4 minutes, 3 minutes, 3 minutes and 2 minutes respectively. The dosing procedure of the first fine scanning and selection was the same as that of crude I, and the two fine scanning and selection times were 3 min and 2 min respectively.

The flotation indexes of the concentrate and tailings of this embodiment are shown in Table 1.

Comparative Example 1

The properties of raw ore, grinding fineness, pulp concentration, pulp pH, and flotation process described in Comparative Example 1 are the same as those in Example 1. The difference is that only organic inhibitors are added in Comparative Example 1. Ⅰ 450g/t each.

Comparative Example 2

Comparative example 2 is the same as the raw ore properties, grinding fineness, pulp concentration, pulp pH, and flotation process described in Example 1, the difference is that only inorganic inhibitors are added in Comparative Example 2, and the dosage is roughing, fine sweeping. Ⅰ 1350g/t each, wherein the mass ratio of ZnSO ₄ and Na ₂ S is 1:1.

Table 1 shows the flotation indexes of the concentrate and tailings of the above comparative examples.

Table 1 Copper-zinc separation flotation results of embodiment and comparative example

From the comparative examples 1~2, it can be seen that the separation effect of adding organic inhibitor or inorganic inhibitor alone is worse than that of adding combined inhibitor, and the dosage of single addition is larger than that of single agent in the combined inhibitor, which is not the most ideal copper and zinc. Isolate inhibitors.

It can be seen from Examples 1 to 5 that the combined inhibitor of the present invention can better inhibit sphalerite, and has little effect on chalcopyrite. The combined inhibitor has a small dosage and strong applicability, and can effectively achieve copper Zinc separation.

Claims (6)

1. A blende flotation combined depressant, wherein the combined depressant consists of an organic depressant and an inorganic depressant;

the organic inhibitor is lac redPigment, the inorganic inhibitor is ZnSO₄、Ca(OH)₂、CaCl₂And Na₂One or two of S;

the mass ratio of the organic inhibitor to the inorganic inhibitor is 1: 2-1: 4.

2. The application of the sphalerite flotation combined inhibitor in claim 1, wherein the combined inhibitor is applied to flotation separation of chalcopyrite and sphalerite in copper-zinc sulfide ore, and specifically comprises the following steps:

step 1: grinding the copper-zinc sulfide ore to a fineness of-0.074 mm which accounts for 70-80%;

step 2: adjusting the concentration of the ore pulp to 20-30% and the pH of the ore pulp to 7-11;

and step 3: and (3) carrying out flotation on the chalcopyrite, adding an inorganic inhibitor and stirring for 3min at a roughing stage, adding an organic inhibitor and stirring for 3min, and carrying out roughing for 1-2 times, scavenging for 1-2 times, fine concentration for 2-4 times and fine scavenging for 1-3 times, wherein the fine scavenging concentrates are combined and then returned to the fine I, and the rest middlings are returned to the previous stage in sequence to form a closed circuit.

3. The use of a blende flotation combination depressant according to claim 2, characterized in that: in the step 3, the total dosage of the inorganic inhibitor is 1500-3600 g/t, and the total dosage of the inorganic inhibitor is 500-1125 g/t.

4. The use of a blende flotation combination depressant according to claim 2, characterized in that: the roughing time is 3-5 min each time, the scavenging time is 2-4 min, the selecting time is 2-4 min, and the fine scavenging time is 2-4 min.

5. The use of a blende flotation combination depressant according to claim 2, characterized in that: and (4) sequentially adding the collecting agent and the foaming agent with required dosage in rough dressing and scavenging.

6. The use of a blende flotation combination depressant according to claim 2, characterized in that: when the roughing operation is one time, the dosage of the crude I combined inhibitor is 1200-2250 g/t, and the dosage of the fine sweeping I combined inhibitor is 1200-2250 g/t; the roughing operation is carried out twice, wherein the dosage of the crude I combined inhibitor is 800-1500 g/t, the dosage of the crude II combined inhibitor is 400-725 g/t, and the dosage of the fine sweeping I combined inhibitor is 800-1500 g/t.