Zinc mineral inhibition method and zinc sulfide mineral combination inhibitor

Abstract

The invention discloses a zinc mineral inhibition method and a zinc sulfide mineral combined inhibitor. The method comprises: adding amino acid to the mixed concentrate slurry in an amount of 200-400 g / t 矿浆 , stirring for the first time under heating conditions to obtain a first slurry; adding a dithiocarbamate containing a hydrophilic group to the first slurry in an amount of 200 to 400 g / t 矿浆 The present invention adopts amino acid and dithiocarbamate containing hydrophilic group as zinc sulfide mineral combined inhibitor, thereby strengthening zinc sulfide mineral inhibition, improving mixed concentrate separation efficiency and reducing reagent dosage.

Description

Technical Field

[0001] The invention relates to the technical field of ore dressing, in particular to a zinc mineral inhibition method and a zinc mineral inhibitor. Background Art

[0002] The commonly used flotation process for lead-zinc sulfide ores or copper-zinc ores is the priority flotation process, that is, according to the floatability of the minerals, the lead (copper) and zinc minerals are selected in turn to obtain high-quality lead (copper) and zinc concentrates. It is a commonly used flotation process for lead-zinc sulfide ores or copper-zinc ores. However, when the lead-zinc minerals or copper-zinc minerals are aggregates or densely coexisting, and the ore grade is relatively poor, it is not appropriate to use the priority flotation process. At this time, the mixed flotation process is often used to separate the useful mineral aggregates from the gangue to obtain copper-zinc or lead-zinc mixed concentrates, and the mixed concentrates are then separated into copper-zinc or lead-zinc.

[0003] However, copper sulfate needs to be added to activate zinc sulfide minerals during mixed flotation, which greatly increases the floatability of zinc sulfide minerals and makes them difficult to suppress, making the separation of copper-zinc and lead-zinc more difficult. At present, the inhibitors commonly used to suppress zinc sulfide minerals activated by copper ions include sodium sulfide, sodium bisulfite, sodium sulfite, zinc sulfate, and a mixed solution of sodium carbonate and zinc sulfate, among which the most commonly used is a combination of zinc sulfate and sodium sulfite. However, the inventors of the present application have found that the above-mentioned inhibitors have the disadvantages of high mutual content of (copper) lead-zinc concentrates after separation and large dosage of the inhibitors. Summary of the invention

[0004] According to one embodiment of the present invention, the purpose is to provide a zinc mineral inhibition method and a zinc sulfide mineral combination inhibitor, which uses amino acids and dithiocarbamates containing hydrophilic groups as zinc sulfide mineral combination inhibitors, thereby enhancing zinc sulfide mineral inhibition, improving the separation efficiency of mixed concentrates (low mutual content of lead / copper and zinc concentrates), and reducing the amount of reagents used.

[0005] The above purpose can be achieved by implementing the following technical solutions:

[0006] According to one aspect of the present invention, a zinc mineral inhibition method is provided, comprising: adding amino acid to a mixed concentrate slurry, performing a first stirring under heating conditions, and obtaining a first slurry, wherein the amount of the amino acid added is 200 to 400 g / t 矿浆 ; Adding dithiocarbamate containing a hydrophilic group to the first slurry, stirring for a second time to obtain a second slurry, wherein the amount of dithiocarbamate containing a hydrophilic group added is 200 to 400 g / t 矿浆 .

[0007] Optionally, in the step of performing the first stirring under heating conditions, the slurry temperature is controlled to be 40-60° C., and the first stirring time is 20-30 min.

[0008] Optionally, the amino acid is one or more of aspartic acid, methionine, lysine, and glycine. Optionally, the dithiocarbamate containing a hydrophilic group is dihydroxyethyl dithiocarbamate. Further optionally, the dihydroxyethyl dithiocarbamate is one or more of sodium dihydroxyethyl dithiocarbamate, ammonium dihydroxyethyl dithiocarbamate, and potassium dihydroxyethyl dithiocarbamate.

[0009] Optionally, before adding the amino acid, the method further comprises: thickening and removing the drug from the mixed concentrate slurry, and adjusting the slurry concentration to 40-50%.

[0010] Optionally, before adding the dithiocarbamate containing a hydrophilic group, the method further comprises: adjusting the concentration of the first slurry to 30-35%.

[0011] Optionally, the second stirring time is 3 to 5 minutes.

[0012] Optionally, the method further comprises: adding a collector to the second slurry, stirring for a third time, and obtaining a third slurry; and performing separation flotation on the third slurry to obtain a lead / copper concentrate and a zinc concentrate.

[0013] Optionally, the third stirring time is 2 to 3 minutes; and / or, the amount of collector added is 10 to 20 g / t of slurry.

[0014] Optionally, the separation flotation adopts one roughing, two fine and two sweeping operations; wherein, during the fine operation, the dithiocarbamate containing a hydrophilic group is added; the addition amount of the dithiocarbamate containing a hydrophilic group is 20-60 g / t 矿浆 .

[0015] Optionally, the mixed concentrate is a lead-zinc mixed concentrate or a copper-zinc mixed concentrate, and the grade of the lead / copper concentrate obtained by separation and flotation is higher than 55%.

[0016] According to another aspect of the present invention, a zinc sulfide mineral combination inhibitor is provided, comprising an amino acid and a dithiocarbamate containing a hydrophilic group, wherein the zinc sulfide mineral combination inhibitor is added to the slurry in a staged dosing and stirring manner, and the amino acid addition and stirring are performed under heating conditions; wherein the amount of the amino acid added is 200 to 400 g / t 矿浆 The amount of dithiocarbamate containing hydrophilic groups is 200-400 g / t 矿浆 .

[0017] Optionally, the amino acid is one or more of aspartic acid, methionine, lysine, and glycine. Optionally, the dithiocarbamate containing a hydrophilic group is dihydroxyethyl dithiocarbamate. Further optionally, the dihydroxyethyl dithiocarbamate is one or more of sodium dihydroxyethyl dithiocarbamate, ammonium dihydroxyethyl dithiocarbamate, and potassium dihydroxyethyl dithiocarbamate.

[0018] Optionally, the amino acid action conditions are: the slurry temperature is controlled at 40-60°C and the stirring time is 20-30 minutes; and / or, the dithiocarbamate action conditions containing a hydrophilic group are: the stirring time is 3-5 minutes, and the slurry temperature is the natural cooling temperature of the slurry after adding amino acids and stirring.

[0019] Beneficial effects: In the above embodiment of the present invention, amino acids and dithiocarbamates containing hydrophilic groups are used as zinc sulfide inhibitors, and a staged dosing method is adopted to effectively reduce the mutual inclusion of (copper) lead and zinc concentrates, improve the (copper) lead and zinc separation efficiency, and reduce the dosage of reagents. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 1 is a schematic flow diagram of a zinc mineral inhibition method according to an embodiment of the present invention. DETAILED DESCRIPTION

[0021] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0022] A zinc sulfide mineral combination inhibitor provided in one embodiment of the present invention comprises an amino acid and a dithiocarbamate containing a hydrophilic group. A zinc mineral inhibition method using the zinc sulfide mineral combination inhibitor comprises: adding an amino acid to a mixed concentrate slurry, performing a first stirring under heating conditions, and obtaining a first slurry; the amount of the amino acid added is 200 to 400 g / t 矿浆 ; Adding dithiocarbamate containing a hydrophilic group to the first slurry, stirring for a second time, to obtain a second slurry; the amount of dithiocarbamate containing a hydrophilic group added is 200 to 400 g / t 矿浆In this embodiment, amino acids and dithiocarbamates containing hydrophilic groups are used as combined inhibitors of zinc sulfide minerals, and are added to the ore pulp in a staged dosing and stirring manner. At the same time, the action conditions of the addition of amino acids are controlled under heating conditions, which effectively reduces the mutual inclusion of (copper) lead and zinc concentrate after subsequent separation and flotation, improves the separation efficiency of (copper) lead and zinc, and reduces the dosage of reagents.

[0023] Figure 1 The process of the zinc mineral inhibition method in one embodiment is schematically shown. Figure 1 As shown, a zinc mineral inhibition method comprises the following steps:

[0024] 1) After the copper-zinc or lead-zinc mixed concentrate slurry is thickened and de-doped, it is sent to the first mixing tank, water is added to adjust the slurry concentration to 40-50%, and 200-400g / t of amino acid is added. 矿浆 , for example 200g / t 矿浆 , 250g / t 矿浆 、300g / t 矿浆 、350g / t 矿浆 , 400g / t 矿浆 etc., and the slurry temperature is controlled to be 40-60°C, such as 40°C, 45°C, 50°C, 55°C, 60°C, etc., and the stirring time is controlled to be 20-30min, such as 20min, 22min, 24min, 26min, 28min, 30min, etc. The amount of amino acid should not be too much, as too much will affect the recovery rate of lead and copper.

[0025] The mixed concentrate in this embodiment is a lead-zinc mixed concentrate or a copper-zinc mixed concentrate, which is a mixed concentrate obtained by separating the useful mineral aggregate from the gangue when the mixed flotation process is used for the sulfide lead (copper) zinc ore. The mixed concentrate can improve the subsequent lead (copper) zinc separation efficiency by adopting the above method. The slurry concentration is adjusted before adding the amino acid to provide more favorable working conditions for the amino acid.

[0026] The amino acid can be one or more of aspartic acid, methionine, lysine, and glycine. The inventors of the present application have found that the above amino acids can form amino acid chelated zinc on the surface of zinc sulfide under heating conditions. The substance is a stable cyclic chelate that can be adsorbed on the surface of zinc sulfide minerals, which has a good flotation inhibition effect. Moreover, the action conditions of the amino acid in this embodiment are: the slurry temperature is controlled at 40 to 60°C, and the stirring time is 20 to 30 minutes. The inventors of the present application have also found that under these conditions, it is more conducive to the formation of amino acid chelated zinc, so that the amino acid is adsorbed on the surface of zinc sulfide minerals, thereby achieving a better flotation inhibition effect. Too high or too low a temperature will affect the flotation inhibition effect.

[0027] 2) The slurry enters the second mixing tank, water is added to adjust the slurry concentration to 30-35%, and 200-400 g / t of dithiocarbamate containing hydrophilic groups is added 矿浆 , for example 200g / t 矿浆 , 250g / t 矿浆 、300g / t 矿浆 、350g / t 矿浆 , 400g / t 矿浆 etc., the stirring time is 3 to 5 minutes, and the slurry temperature is the natural cooling temperature of the slurry flowing out of the first stirring barrel. By adjusting the slurry concentration, more favorable working conditions are provided for the combined inhibitor. By controlling the amount of zinc sulfide mineral combined inhibitor added, the two are interspersed and attached to the surface of zinc sulfide mineral, thereby improving the flotation inhibition effect; moreover, the amount of drug used is reduced, overcoming the defect of large amount of drug used in the prior art. The amount of dithiocarbamate containing hydrophilic groups should not be too much, as too much will affect the recovery rate of lead and copper.

[0028] The hydrophilic group of the dithiocarbamate containing a hydrophilic group may be a hydroxyl group, etc. For example, the dithiocarbamate containing a hydrophilic group may be dihydroxyethyl dithiocarbamate, etc. The salt may be a sodium salt, an ammonium salt, a potassium salt, etc. Specifically, for example, the cation part of the dithiocarbamate containing a hydrophilic group may be Na + , K + NH4 + , the anion structure is shown below:

[0029]

[0030] It should be noted that the synthesis method of dithiocarbamate containing hydrophilic groups is not limited in the embodiments of the present invention, and the synthesis method disclosed in the prior art can be used. Taking sodium dihydroxyethyl dithiocarbamate as an example, the action principle and effect of it and amino acids are further explained below: the operating conditions of the first stirring barrel can promote amino acids to form amino acid chelated zinc on the surface of zinc sulfide, which is a stable cyclic chelate that can be adsorbed on the surface of zinc sulfide minerals; the sodium dihydroxyethyl dithiocarbamate added to the second stirring barrel can also form dihydroxyethyl dithiocarbamate zinc with zinc, which can also be stably adsorbed on the surface of zinc sulfide minerals; amino acid chelated zinc and dihydroxyethyl dithiocarbamate zinc both have hydrophilic groups, and the two act synergistically and are interspersed and attached to the surface of zinc sulfide minerals, which can greatly increase the hydrophilicity of zinc sulfide minerals and have a good flotation inhibition effect.

[0031] 3) The ore pulp enters the third mixing tank and 10-20g / t of black powder is added 矿浆 , the stirring time is 2 to 3 minutes. Among them, the black medicine can be 25# black medicine, aniline black medicine, butyl ammonium black medicine, etc.

[0032] 4) Lead-zinc or copper-zinc separation flotation, the separation operation can adopt one-stage roughing, two-stage cleaning and two-stage scavenging operations. Lead / copper concentrate and zinc concentrate are obtained by separation flotation, and the grade of lead / copper concentrate obtained by the above method can reach 57%, and the zinc content is only about 5.5%. It can be seen that the lead / copper and zinc concentrates contain little each other, and the lead / copper and zinc separation efficiency is high. In addition, the cleaning operation can add inhibitors containing hydrophilic groups such as sodium dihydroxyethyl dithiocarbamate as appropriate, for example, the addition amount can be 20-60g / t 矿浆 Specifically, for example, the first concentration addition amount can be 40-60 g / t 矿浆， The amount of the second concentration can be 20-40g / t 矿浆 etc.; black medicine can be added as appropriate during the sweeping and selection operations.

[0033] In this embodiment, amino acids and dithiocarbamates containing hydrophilic groups, such as sodium dihydroxyethyl dithiocarbamate, are used as zinc sulfide combined inhibitors, and the dosage of the two is controlled in stages, thereby effectively reducing the mutual inclusion of (copper) lead and zinc concentrates, improving the separation efficiency of (copper) lead and zinc, and reducing the dosage of reagents; and the staged addition of the drugs can enable the amino acids to obtain better effects at higher temperatures.

[0034] In addition, by controlling the operating conditions of the first stirring barrel, the amino acid is promoted to form a stable cyclic chelate, namely, amino acid chelated zinc, on the surface of zinc sulfide; based on this, dithiocarbamate containing a hydrophilic group, such as sodium dihydroxyethyl dithiocarbamate, is added to the second stirring barrel to form dihydroxyethyl dithiocarbamate zinc with zinc, which can also be stably adsorbed on the surface of the zinc sulfide mineral; amino acid chelated zinc and dihydroxyethyl dithiocarbamate zinc both have hydrophilic groups, and the two act synergistically and are interspersed and attached to the surface of the zinc sulfide mineral, which greatly increases the hydrophilicity of the zinc sulfide mineral and plays a good flotation inhibition effect.

[0035] The implementation manner of the present invention and its effects are further described below in conjunction with specific embodiments.

[0036] Example 1

[0037] A certain lead-zinc mixed concentrate contains 12.11% lead and 36.86% zinc.

[0038] After the mixed concentrate is thickened and de-doped, it enters the first mixing tank, where water is added to adjust the pulp concentration to 45%, and 300g / t of glycine is added. 矿浆 , the slurry temperature is controlled at 50℃, and the stirring time is 25min; then the slurry enters the second stirring barrel, water is added to adjust the slurry concentration to 30%, and 300g / t sodium dihydroxyethyl dithiocarbamate is added 矿浆, stirring time is 3min; the slurry enters the third mixing barrel, and 15g / t No. 25 black medicine is added 矿浆 , stirring time is 3min. Then the slurry enters the lead-zinc separation process, the separation process is one roughing, two concentrating and two scavenging operations; the dosage of sodium dihydroxyethyl dithiocarbamate in the two concentrating operations is 50g / t 矿浆 and 25g / t 矿浆 ; The dosage of No. 25 black medicine in the two sweeping operations is 5g / t 矿浆 and 2g / t 矿浆 .

[0039] The final lead concentrate grade is 56.12%, the recovery rate is 97.33%, and the zinc content is 5.81%.

[0040] Example 2

[0041] The difference from Example 1 is that the amount of glycine is 200 g / t, the slurry temperature is controlled at 45° C., and the stirring time is 20 min. The lead concentrate grade is 56.01%, the recovery rate is 97.34%, and the zinc content is 6.01%.

[0042] Example 3

[0043] The difference from Example 1 is that the amount of glycine is 400 g / t, the slurry temperature is controlled at 55° C., and the stirring time is 30 min. The lead concentrate grade is 56.16%, the recovery rate is 97.32%, and the zinc content is 5.63%.

[0044] Example 4

[0045] The difference from Example 1 is that the dosage of sodium dihydroxyethyl dithiocarbamate is 200 g / t. The lead concentrate obtained finally has a grade of 55.65%, a recovery rate of 97.53%, and a zinc content of 6.43%.

[0046] Example 5

[0047] The difference from Example 1 is that the dosage of sodium dihydroxyethyl dithiocarbamate is 400 g / t. The lead concentrate obtained finally has a grade of 56.78%, a recovery rate of 96.88%, and a zinc content of 5.23%.

[0048] Comparative Example 1

[0049] The difference from Example 1 is that no amino acid is added and the amount of sodium dihydroxyethyl dithiocarbamate is 600g / t 矿浆 The final lead concentrate grade is 53.12%, the recovery rate is 97.76%, and the zinc content is 7.84%.

[0050] Comparative Example 2

[0051] The difference from Example 1 is that no sodium dihydroxyethyl dithiocarbamate is added, and the amount of amino acid is 600g / t 矿浆 The final lead concentrate grade is 52.23%, the recovery rate is 98.04%, and the zinc content is 8.25%.

[0052] It can be seen from Comparative Examples 1 and 2 with Example 1 that, when the total amount of the inhibitor is the same, the combined effect of amino acid and sodium dihydroxyethyl dithiocarbamate is better than that of a single inhibitor.

[0053] Some of the above embodiments of the present invention also have the following advantages and beneficial effects:

[0054] (1) Amino acids and sodium dihydroxyethyl dithiocarbamate were used as combined inhibitors of zinc sulfide minerals, and the inhibitors were added in stages to strengthen the inhibition of zinc sulfide minerals, effectively reduce the mutual inclusion of (copper) lead and zinc concentrate, and improve the separation efficiency of (copper) lead and zinc.

[0055] (2) The amino acid reaction is carried out under heating conditions, that is, the slurry temperature is controlled at 40-60°C and the stirring time is 20-30 minutes. Under these conditions, it is more conducive to the formation of amino acid chelated zinc, so that the amino acid is adsorbed on the surface of the zinc sulfide mineral; and the subsequent sodium dihydroxyethyl dithiocarbamate is interlaced and attached to the surface of the zinc sulfide mineral, achieving a better flotation inhibition effect.

[0056] (3) Compared with the prior art, the amount of amino acid used in this combined inhibitor is 200-400 g / t 矿浆 ; The amount of dithiocarbamate containing hydrophilic groups, such as dihydroxyethyl dithiocarbamate, is 200-400 g / t 矿浆 , reducing the dosage of medicine.

[0057] (4) It is particularly suitable for the separation of copper-zinc or lead-zinc mixed concentrates in the mixed flotation process when the lead-zinc or copper-zinc minerals are in aggregate or dense co-ecology and the ore grade is relatively poor.

[0058] The description of the present invention is given for the purpose of illustration and description, and is not intended to be exhaustive or to limit the invention to the disclosed form. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments are selected and described in order to better illustrate the principles and practical applications of the present invention and to enable those of ordinary skill in the art to understand the present invention and thereby design various embodiments with various modifications suitable for particular uses.

Claims

1. A zinc mineral suppression method, characterized in that: include: Add amino acids to the mixed concentrate pulp, and stir for the first time under heating conditions to obtain the first pulp; the amount of amino acids added is 200-400g / t 矿浆 ; Adding dithiocarbamate containing a hydrophilic group to the first slurry, stirring for a second time, to obtain a second slurry; the amount of dithiocarbamate containing a hydrophilic group added is 200-400 g / t 矿浆 .

2. The zinc mineral suppression method according to claim 1, characterized in that: In the step of performing the first stirring under heating conditions, the slurry temperature is controlled to be 40-60° C., and the first stirring time is 20-30 minutes.

3. The zinc mineral suppression method according to claim 1, characterized in that: The amino acid is one or more of aspartic acid, methionine, lysine, and glycine; And / or, the dithiocarbamate containing a hydrophilic group is dihydroxyethyl dithiocarbamate; the dihydroxyethyl dithiocarbamate is one or more of sodium dihydroxyethyl dithiocarbamate, ammonium dihydroxyethyl dithiocarbamate, and potassium dihydroxyethyl dithiocarbamate.

4. The zinc mineral suppression method according to claim 1, characterized in that: Before adding amino acids, the method also includes: thickening and removing drugs from the mixed concentrate slurry, and adjusting the slurry concentration to 40-50%.

5. The zinc mineral suppression method according to claim 1, characterized in that: Before adding the dithiocarbamate containing a hydrophilic group, the method further comprises: adjusting the concentration of the first slurry to 30-35%.

6. The zinc mineral suppression method according to claim 1, characterized in that: The second stirring time is 3 to 5 minutes.

7. The zinc mineral suppression method according to claim 1, characterized in that: Also includes: adding a collector to the second slurry and stirring for a third time to obtain a third slurry; The third ore pulp is subjected to separation flotation to obtain lead / copper concentrate and zinc concentrate.

8. The zinc mineral suppression method according to claim 7, characterized in that: The third stirring time is 2 to 3 minutes; And / or, the collector is added in an amount of 10 to 20 g / t of slurry.

9. The zinc mineral suppression method according to claim 7, characterized in that: The separation flotation adopts one coarse, two fine and two sweeping; wherein, during the fine operation, the dithiocarbamate containing hydrophilic groups is added; the addition amount of the dithiocarbamate containing hydrophilic groups is 20-60g / t 矿浆 .

10. The zinc mineral suppression method according to claim 7, characterized in that: The mixed concentrate is a lead-zinc mixed concentrate or a copper-zinc mixed concentrate, and the grade of the lead / copper concentrate obtained by separation and flotation is higher than 55%.

11. A zinc sulfide mineral combination inhibitor, characterized in that: The zinc sulfide mineral combined inhibitor comprises amino acids and dithiocarbamates containing hydrophilic groups, wherein the zinc sulfide mineral combined inhibitor is added to the ore pulp in a stepwise manner and stirred, and the amino acid addition and stirring are performed under heating conditions; wherein the amount of the amino acid added is 200 to 400 g / t 矿浆 The amount of dithiocarbamate containing hydrophilic groups is 200-400 g / t 矿浆 .

12. The zinc sulfide mineral combination inhibitor according to claim 11, characterized in that: The amino acid is one or more of aspartic acid, methionine, lysine, and glycine; And / or, the dithiocarbamate containing a hydrophilic group is dihydroxyethyl dithiocarbamate; the dihydroxyethyl dithiocarbamate is one or more of sodium dihydroxyethyl dithiocarbamate, ammonium dihydroxyethyl dithiocarbamate, and potassium dihydroxyethyl dithiocarbamate.

13. The zinc sulfide mineral combination inhibitor according to claim 11, characterized in that: The amino acid action conditions are: the slurry temperature is controlled at 40-60°C and the stirring time is 20-30 minutes; And / or, the action conditions of the dithiocarbamate containing a hydrophilic group are: the stirring time is 3 to 5 minutes, and the slurry temperature is the natural cooling temperature of the slurry after the amino acid is added and stirred.

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