Flotation separation inhibitor for galena and chalcopyrite bulk concentrate and flotation separation method thereof

Abstract

The invention discloses a flotation separation inhibitor for galena and chalcopyrite bulk concentrate and a flotation separation method of the flotation separation inhibitor, and belongs to the technical field of mineral flotation. The invention provides an inhibitor which comprises the following components in percentage by mass: 10-40% of sodium hypochlorite, 10-40% of ferrous sulfate and 10-50% of manganese dichloride, and the use conditions of the inhibitor are as follows: the pH is 4-9, the total dosage is 0.5-3kg / t, and the reaction time is 5-8 minutes. After the inhibitor acts on the copper-lead bulk concentrate, copper concentrate and lead concentrate are obtained through the flotation process of one-time roughing and two-time concentration, and the separation efficiency reaches 80%-95%. The electroreduction regeneration conditions of the inhibitor are as follows: the voltage is 1.0-5.0 V, the reduction time is 20 minutes, the pH value is 4-9, and after reduction, the combined reagent can be repeatedly used for 5-7 times without additionally adding the combined inhibitor. The combined inhibitor is low in price and suitable for ore pulp from weak acidity to alkalinity, and regeneration of the inhibitor can be effectively achieved through the electric field reduction technology, so that the purpose of reducing the combined inhibitor is achieved.

Description

Technical Field

[0001] The invention relates to a flotation separation inhibitor of a mixed concentrate of galena and chalcopyrite and a flotation separation method thereof, belonging to the technical field of mineral flotation. Background Art

[0002] Galena is a typical sulfide ore and an important mineral for lead smelting. In my country's ore deposits, there are very few single galena ores. Galena often coexists with sulfide ores such as sphalerite, pyrite, and chalcopyrite. This type of ore is often called a complex sulfide ore.

[0003] For complex sulfide ores, pyrite can be inhibited by lime inhibitors, and sphalerite can be separated by zinc sulfate and sodium carbonate as inhibitors. However, the separation of galena and chalcopyrite is still difficult. The main reason why galena and chalcopyrite are difficult to separate is that the natural floatability of both minerals is very strong, and galena is very easily activated by copper ions in the solution, so there is no selective collector to achieve flotation separation. There are many inhibitors for galena, but most of them are macromolecular organic agents. These agents are adsorbed on the surface of galena through physical action. Generally, they have poor selectivity and large dosage, and are rarely used in actual mines. Galena inorganic inhibitors can generally oxidize the surface of galena and inhibit galena flotation, but inorganic inhibitors are mostly strong oxidants, which have the problems of large dosage, inconvenient transportation and purchase, and great harm to the environment. In addition, some agents must be used under heating conditions, which leads to increased production costs. Therefore, the application of traditional inorganic inhibitors, such as potassium permanganate, in the concentrator is also limited.

[0004] With the country's continuous demand for green mine construction, galena and chalcopyrite are in urgent need of green and efficient separation technology. Therefore, a combination of sodium hypochlorite, ferrous sulfate and manganese dichloride is used as a galena inhibitor. At the same time, an electric field is applied to the slurry to promote the regeneration of the inhibitor. The inhibitor can be recycled multiple times after one feeding, thus completing the oxidation inhibition of galena. Summary of the invention

[0005] In order to solve the problems existing in the current flotation separation process of galena and chalcopyrite, one of the purposes of the present invention is to provide a flotation separation inhibitor for a mixed concentrate of galena and chalcopyrite, wherein the inhibitor comprises, by mass percentage, 10% to 40% of sodium hypochlorite, 10% to 40% of ferrous sulfate, and 10% to 50% of manganese dichloride; wherein the total mass percentage of sodium hypochlorite, ferrous sulfate, and manganese dichloride is 100%.

[0006] Another object of the present invention is to provide a method for flotation separation of mixed concentrate of galena and chalcopyrite

[0007] The specific steps include:

[0008] (1) Grinding a mixed concentrate containing galena and chalcopyrite to obtain a slurry.

[0009] (2) adding an inhibitor to the ore pulp obtained in step (1) to carry out a reaction; the amount of the inhibitor added is 0.5 to 3 kg / t.

[0010] (3) filtering the ore pulp obtained in step (2) to obtain a filtrate and a mixed ore, adding water and a frother to the mixed ore for primary concentration to obtain a concentrate.

[0011] (4) The concentrate after the primary concentration is further concentrated to obtain copper concentrate and lead concentrate.

[0012] (5) The filtrate of (3) is electro-reduced by applying an external electric field to obtain a regenerated inhibitor.

[0013] Preferably, the pH of the slurry in step (1) is 3-6.

[0014] Preferably, in step (1), grinding to a fineness of -0.074 mm accounts for 75% to 85%.

[0015] Preferably, the reaction time in step (2) is 5 to 8 minutes.

[0016] Preferably, in step (3), water is added to make the concentration of the slurry 25% to 30%.

[0017] Preferably, the amount of the foaming agent added in step (3) is 50 g / t to 75 g / t, and the foaming agent is No. 2 oil.

[0018] Preferably, the cleaning time in step (3) is 14 to 18 minutes.

[0019] Preferably, no reagent is added in the secondary selection in step (4), and the secondary selection time is 7 to 9 minutes.

[0020] Preferably, the electric field in step (5) has an action potential of 1.0 to 5.0 V and lasts for 10 to 40 minutes.

[0021] Preferably, the regenerated combined inhibitor obtained in step (5) can be reused.

[0022] Beneficial Effects of the Invention

[0023] (1) Sodium hypochlorite, ferrous sulfate, and manganese dichloride are widely available and have little harm to the environment. Among the inhibitors composed of sodium hypochlorite, ferrous sulfate, and manganese dichloride, Fe 2+ and Mn 2+ It can activate hypochlorous acid to produce OH free radicals, and at the same time generate Fe 3+ and Mn 4+ions; OH radicals have strong oxidizing properties and can selectively oxidize galena, but have no inhibitory effect on the flotation of chalcopyrite, thereby promoting the separation of galena and chalcopyrite. In order to reduce the feed, the inhibitor is regenerated and the inhibitor solution is electro-reduced. The chloride ions in the positive electrode area are oxidized to chlorine gas, which is dissolved in water and regenerated to hypochlorous acid; Fe in the negative electrode area 3+ and Mn 4+ Reduced to Fe 2+ and Mn 2+ , thus completing the regeneration of the inhibitor.

[0024] (2) It can be used in the pH range of 4-9, avoiding corrosion of equipment by acidic slurry.

[0025] (3) The inhibitor raw material is regenerated through the action of the electric field, and the inhibitor solution is electro-reduced. The chloride ions in the positive electrode area are oxidized to chlorine gas, and the chlorine gas is dissolved in water and regenerated to hypochlorous acid; the Fe 3+ and Mn 4+ Reduced to Fe 2+ and Mn 2+ , thus completing the regeneration of the inhibitor. This can achieve the purpose of repeated use 5-7 times after one feeding, significantly reducing the dosage of the agent.

[0026] (4) The cost of electroreduction technology is low, the equipment is mature, and it is easy to implement in the concentrator. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The flotation process flow chart of the present invention. DETAILED DESCRIPTION

[0028] The technical solution of the present invention is further described below in conjunction with the accompanying drawings and through specific implementation methods. However, the following embodiments are only simple examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0029] Example 1

[0030] The inhibitor used in this embodiment includes, by mass percentage, 10% sodium hypochlorite, 40% ferrous sulfate, and 50% manganese dichloride.

[0031] The mixed concentrate of galena and chalcopyrite used in this embodiment comes from Yunnan, and the original ore contains 0.935% copper and 1.293% lead.

[0032] A method for flotation separation of mixed concentrate of galena and chalcopyrite, the specific steps are as follows:

[0033] (1) Grind the mixed concentrate of galena and chalcopyrite to a fineness of -0.074 mm, accounting for 75%, and prepare the slurry with sulfuric acid to a pH of 6.

[0034] (2) Add 1.5 kg / t of inhibitor to the slurry obtained in step (1) and react for 5 minutes.

[0035] (3) The ore pulp obtained in step (2) is filtered to obtain a filtrate and a mixed ore, water is added to the mixed ore to make the concentration of the mixed ore pulp 30%, and then 50 g / t of No. 2 oil is added to perform a first concentration, and the first concentration time is 14 minutes.

[0036] (4) After the first concentration, a second concentration is carried out, and the second concentration time is 7 minutes to obtain a foam product copper concentrate and a bottom product lead concentrate.

[0037] (5) The filtrate of (3) was electro-reduced for 30 min using an external electric field of 3.0 V to obtain a regenerated inhibitor.

[0038] The final products are copper concentrate with a copper grade of 20.17%, a lead grade of 1.52%, a copper recovery rate of 88.73%, and a lead recovery rate of 3.33%, and lead concentrate with a lead grade of 26.34%, a copper grade of 1.01%, a lead recovery rate of 89.34%, and a copper recovery rate of 3.40%.

[0039] Example 2

[0040] The content and composition of the inhibitor used in this embodiment are: 40% sodium hypochlorite, 10% ferrous sulfate, and 50% manganese dichloride.

[0041] The mixed concentrate of galena and chalcopyrite used in this embodiment comes from Guangxi, and the original ore contains 0.964% copper and 1.265% lead.

[0042] A method for flotation separation of mixed concentrate of galena and chalcopyrite, the specific steps are as follows:

[0043] (1) Grind the mixed concentrate of galena and chalcopyrite to a fineness of -0.074 mm, accounting for 85%, and prepare the slurry with sulfuric acid to a pH of 4.5.

[0044] (2) Add 1.5 g / t of inhibitor to the slurry obtained in step (1) and react for 5 minutes.

[0045] (3) The ore pulp obtained in step (2) is filtered to obtain a filtrate and a mixed ore, water is added to the mixed ore to make the concentration of the mixed ore pulp 25%, and then 50 g / t of No. 2 oil is added to perform a first concentration, and the first concentration time is 14 minutes.

[0046] (4) After the first concentration, a second concentration is carried out, and the second concentration time is 7 minutes to obtain a foam product copper concentrate and a bottom product lead concentrate.

[0047] (5) The filtrate of (3) is electro-reduced by applying an external electric field to obtain a regenerated inhibitor.

[0048] The final products are copper concentrate with a copper grade of 22.02%, a lead grade of 1.58%, a copper recovery rate of 89.09% and a lead recovery rate of 3.47%, and lead concentrate with a lead grade of 28.78%, a copper grade of 1.32%, a lead recovery rate of 90.03% and a copper recovery rate of 3.63%.

[0049] Example 3

[0050] The content and composition of the inhibitor used in this embodiment are: 40% sodium hypochlorite, 40% ferrous sulfate, and 20% manganese dichloride.

[0051] The mixed concentrate of galena and chalcopyrite used in this embodiment comes from Guizhou, and the original ore contains 0.935% copper and 1.291% lead.

[0052] A method for flotation separation of mixed concentrate of galena and chalcopyrite, the specific steps are as follows:

[0053] (1) Grind the mixed concentrate of galena and chalcopyrite to a fineness of -0.074 mm and a proportion of 80%, and prepare the slurry with sulfuric acid to a pH of 3.

[0054] (2) Add 1 g / t of inhibitor to the slurry obtained in step (1) and react for 6 minutes.

[0055] (3) The ore pulp obtained in step (2) is filtered to obtain a filtrate and a mixed ore, water is added to the mixed ore to make the concentration of the mixed ore pulp 25%, and then 50 g / t of No. 2 oil is added to perform a first concentration, and the first concentration time is 14 minutes.

[0056] (4) After the first concentration, a second concentration is carried out, and the second concentration time is 7 minutes to obtain a foam product copper concentrate and a bottom product lead concentrate.

[0057] (5) The filtrate of (3) is electro-reduced by applying an external electric field to obtain a regenerated inhibitor.

[0058] The final products are copper concentrate with a copper grade of 24.28%, a lead grade of 1.72%, a copper recovery rate of 95.71%, and a lead recovery rate of 6.43%, and lead concentrate with a lead grade of 30.92%, a copper grade of 1.13%, a lead recovery rate of 93.71%, and a copper recovery rate of 3.72%.

[0059] Example 4

[0060] The mixed concentrate of galena and chalcopyrite used in this embodiment comes from Guangxi, the original ore contains 1.023% copper and 1.452% lead, the specific steps are the same as those in Example 1, the inhibitor used is the regeneration inhibitor in Example 1, and the copper concentrate with a copper grade of 23.19%, a lead grade of 1.76%, a copper recovery rate of 94.91%, and a lead recovery rate of 6.62% and a lead concentrate with a lead grade of 30.88%, a copper grade of 1.21%, a lead recovery rate of 92.92%, and a copper recovery rate of 3.73%. It shows that the regeneration inhibitor can be recycled and the effect is very good. It is finally verified that the inhibitor of the present invention can be reused 7 times.

[0061] Comparative Example 1

[0062] As a comparison, the difference between this comparative example and Example 3 is that only sodium hypochlorite and manganese dichloride are used as depressants for flotation. The separation flotation steps and the dosage of reagents are the same as those in Example 3. The copper concentrate with a copper grade of 17.42%, a lead grade of 1.14%, a copper recovery rate of 77.58%, and a lead recovery rate of 4.83% and the lead concentrate with a lead grade of 27.09%, a copper grade of 1.61%, a lead recovery rate of 79.92%, and a copper recovery rate of 1.22% are finally obtained. The separation flotation effect of this comparative example is not as good as that of Example 3 because only Mn 2+ Activated sodium hypochlorite can only produce a small amount of OH free radicals and cannot fully oxidize galena.

[0063] Comparative Example 2

[0064] As a comparison, the difference between this comparative example and Example 3 is that only sodium hypochlorite and ferrous sulfate are used as depressants for flotation. The separation flotation steps and the dosage of reagents are the same as those in Example 3. The copper concentrate with a copper grade of 16.89%, a lead grade of 1.23%, a copper recovery rate of 78.06%, and a lead recovery rate of 4.64% and the lead concentrate with a lead grade of 26.52%, a copper grade of 1.40%, a lead recovery rate of 80.22%, and a copper recovery rate of 1.18% are finally obtained. The separation flotation effect of this comparative example is not as good as that of Example 3 because only Fe 2+ Activated sodium hypochlorite can only produce a small amount of OH free radicals and cannot fully oxidize galena.

[0065] Comparative Example 3

[0066] As a comparison, the difference between this comparative example and Example 3 is that only sodium hypochlorite is used as a depressant for flotation. The separation flotation steps and the dosage of the reagents are the same as those in Example 3. The copper concentrate with a copper grade of 16.34%, a lead grade of 1.03%, a copper recovery rate of 76.45%, and a lead recovery rate of 4.23% and the lead concentrate with a lead grade of 26.45%, a copper grade of 1.01%, a lead recovery rate of 78.34%, and a copper recovery rate of 1.12% are finally obtained. The separation flotation effect of this comparative example is not as good as that of Example 1. The separation flotation effect of this comparative example is not as good as that of Example 3 because Fe 2+ and Mn 2+ It can activate hypochlorous acid to produce OH free radicals, and at the same time generate Fe 3+ and Mn 4+ ions. ·OH free radicals have strong oxidizing properties. Sodium hypochlorite alone as an inhibitor cannot produce ·OH free radicals, so the oxidizing property is greatly weakened.

Claims

1. A flotation separation inhibitor for mixed concentrate of galena and chalcopyrite, characterized in that: The inhibitor comprises, calculated by mass percentage, 10% to 40% of sodium hypochlorite, 10% to 40% of ferrous sulfate, and 10% to 50% of manganese dichloride; wherein the total mass percentage of sodium hypochlorite, ferrous sulfate, and manganese dichloride is 100%.

2. A flotation separation method for a mixed concentrate of galena and chalcopyrite, characterized in that: The specific steps include: (1) grinding a mixed concentrate containing galena and chalcopyrite to obtain a slurry; (2) adding an inhibitor to the ore pulp obtained in step (1) to carry out a reaction; the amount of the inhibitor added is 0.5 to 3 kg / t; (3) filtering the ore pulp obtained in step (2) to obtain a filtrate and a mixed ore, and adding water and a frother to the mixed ore for primary concentration; (4) The concentrate after primary concentration is further subjected to secondary concentration to obtain copper concentrate and lead concentrate; (5) The filtrate of (3) is electro-reduced by applying an external electric field to obtain a regenerated inhibitor.

3. The flotation separation method of galena and chalcopyrite mixed concentrate according to claim 2, characterized in that: The pH of the slurry in step (1) is 3-6.

4. The method for flotation separation of galena and chalcopyrite mixed concentrate according to claim 2, characterized in that: In step (1), grinding to a fineness of -0.074 mm accounts for 75% to 85%.

5. The method for flotation separation of galena and chalcopyrite mixed concentrate according to claim 2, characterized in that: The reaction time in step (2) is 5 to 8 minutes.

6. The flotation separation method of galena and chalcopyrite mixed concentrate according to claim 2, characterized in that: In step (3), water is added to make the concentration of the slurry 25% to 30%.

7. The method for flotation separation of galena and chalcopyrite mixed concentrate according to claim 2, characterized in that: In step (3), the amount of the foaming agent added is 50 g / t to 75 g / t, and the foaming agent is No. 2 oil; and the first selection time is 14 to 18 minutes.

8. The method for flotation separation of galena and chalcopyrite mixed concentrate according to claim 2, characterized in that: In step (4), no reagent is added in the secondary selection, and the secondary selection time is 7 to 9 minutes.

9. The method for flotation separation of galena and chalcopyrite mixed concentrate according to claim 2, characterized in that: The electric field in step (5) has an action potential of 1.0 to 5.0 V and lasts for 10 to 40 minutes.

10. The method for flotation separation of galena and chalcopyrite mixed concentrate according to claim 2, characterized in that: The regenerated combined inhibitor obtained in step (5) can be reused.

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