Preparation method and application of collecting agent for flotation separation of quartz and petalite

Abstract

The invention discloses a preparation method of a collecting agent for flotation separation of quartz and petalite. The preparation method comprises the following steps: mixing an amine raw material and an oil raw material according to a certain proportion; and heating the mixed raw materials in a water bath for a preset time, cooling to room temperature, filtering, fixing the volume, and adjusting the pH value to obtain the collecting agent AAT1. The invention further provides application of the collecting agent prepared through the preparation method of the collecting agent for flotation separation of quartz and petalite. The collecting agent AAT1 is used for carrying out flotation separation on the quartz and petalite, the recovery rate of the quartz reaches 98% or above, the recovery rate of the petalite is 8%, and the good separation effect is achieved.

Description

Technical Field

[0001] The invention belongs to the field of flotation reagents, and in particular relates to a preparation method and application of a collector for flotation separation of quartz and petalite. Background Art

[0002] In nature, quartz and feldspar often coexist or coexist with other minerals. Usually, quartz and feldspar are often regarded as tailings, resulting in a waste of resources. As an indispensable basic raw material, the consumption of quartz is continuing to rise with the booming development of the semiconductor and battery industries. With the development of electric vehicles and the rapid increase in demand for lithium from new energy sources, the recycling of petalite can alleviate the current shortage of lithium resources. Therefore, the recycling and separation of the two are of great significance.

[0003] Quartz and petalite have similar physical and chemical properties, so physical separation cannot separate them well. So far, flotation is the most effective method for separating quartz and feldspar. Among them, the most mature technology is the hydrofluoric acid method, which first adjusts the pH of the solution to 2 with sulfuric acid, and then adds hydrofluoric acid to activate the feldspar and finally achieve the purpose of separation. However, since this method is harmful to the environment and the body and also corrodes the equipment, this process is no longer used. Secondly, some scholars have studied the fluorine-free acid method to obtain qualified products, but this method will cause environmental damage and equipment corrosion. At the same time, there are very few studies on the flotation of petalite. Therefore, the fluorine-free and acid-free method for separating quartz and petalite has great research value.

[0004] Before flotation of quartz feldspar, mica removal is usually required, which makes the ore pulp alkaline. Separation of quartz petalite directly in an alkaline environment helps to shorten the flotation process, save reagents and reduce costs. Through experiments, it was found that a single amine collector has poor sorting properties, the reagent is difficult to dissolve, and the stability is poor. Summary of the invention

[0005] One of the purposes of the present invention is to provide a method for preparing a collector for flotation separation of quartz and petalite in an alkaline environment, which can efficiently separate quartz and petalite in an alkaline environment while improving the stability of the collector and reducing the dosage of the reagent.

[0006] A second object of the present invention is to provide an application of the collector.

[0007] The present invention provides a method for preparing a collector for flotation separation of quartz and petalite, comprising the following steps:

[0008] S1. Mixing the raw materials according to a preset ratio to obtain a mixed raw material;

[0009] S2. The mixed raw material obtained in step S1 is heated in a water bath for a preset heating time, cooled to room temperature, filtered, fixed to volume and adjusted to pH value to obtain a collector AAT1 for flotation separation of quartz and petalite.

[0010] Furthermore, in step S1, the raw materials include amine raw materials and oil raw materials; the amine raw materials include at least two of 1,10-diaminodecane, N-dodecyl-1,3-propylenediamine, 1,8-diaminooctane, and dodecylamine; the oil raw materials include one or more of kerosene, tung oil, and silicone oil; the molar ratio of the amine raw materials to the oil raw materials is (1-25):5; and the oil raw materials are between 0.5 and 2 times the total mass of the amine raw materials.

[0011] Furthermore, in step S2, the process conditions of water bath heating are: heating temperature is 60°C to 90°C, and heating time is more than 30 minutes.

[0012] Furthermore, the pH adjustment is specifically to adjust the pH of the final collector to 8-11.

[0013] Furthermore, the volume determination is to determine the volume of the filtered reagent to a solute concentration of 1-5 g / L while maintaining its pH at 8-11.

[0014] The present invention also provides an application of the collector for flotation separation of quartz and petalite, comprising the following steps:

[0015] S11. crushing and slurrying the mineral to be floated to obtain slurry;

[0016] S12. The pulp obtained in step S11 is subjected to a roughing flotation, and the collector AAT1 is used as the collector to obtain quartz concentrate and petalite tailings.

[0017] Furthermore, in step S11, the concentration of the ore pulp is 20% to 70%, and the floating particle size range is 38 to 75 μm;

[0018] Furthermore, in step S12, the roughing flotation is specifically as follows: stirring the pulp for 2 to 3 minutes, adding a pH adjuster and stirring for another 2 to 4 minutes, then adding a collector and stirring for another 2 to 4 minutes, and scraping the foam for 2 to 5 minutes after the foam layer is stable;

[0019] The pH adjuster is NaOH, which adjusts the pH of the slurry to 6-11; the collector is AAT1, and the dosage is 100-500 g / t.

[0020] Furthermore, for impure minerals, an activator is added during flotation.

[0021] Principle of the present invention:

[0022] By studying the Zeta potential of quartz and petalite before and after the action of collector AATI when the adjusting agent NaOH was not added, and the Zeta potential before and after the action of collector AATI when the pH was adjusted to 10.5 using NaOH, it can be seen that the Zeta potential of quartz and petalite is negative in neutral and alkaline environments. The Zeta potential of quartz with the addition of AATI under neutral conditions moved significantly to the positive direction, and the potential increased by 14.90mV. This is due to the adsorption of AAT1 on the quartz surface. After the pH was adjusted to the optimal value by NaOH, the Zeta potential of quartz moved significantly to the negative direction. This may be due to OH - The effect of ionization causes the potential to move to the negative direction. Under this condition, the Zeta potential of quartz with the addition of AAT1 obviously moves to the positive direction by 17.6 mV, which is more than that under neutral conditions, indicating that adjusting the pH helps the adsorption of AAT1 on the quartz surface. For petalite, the general trend is the same as that of quartz. But in general, the change in the Zeta potential before and after the addition of AAT1 under neutral conditions (pH = 7) is smaller than that of quartz, and it only rises by 3.9 mV. After adding AATI under the optimal pH condition, the Zeta potential rises by 5.6 mV. It can be seen that the adsorption of DAM on the quartz surface is stronger than that of petalite.

[0023] The contact angles of AAT1 with natural quartz and petalite under the optimum pH conditions are 15.56° and 14.03° respectively, both of which are hydrophilic minerals. After adding the adjuster, the contact angles of both increased. Under this condition, the contact angle of quartz with AAT1 increased from 19.68° to 137.22°, and the contact angle of petalite increased from 15.48° to 42.50°. The results show that AATI can make the surfaces of both hydrophobic, but at the same dosage, the quartz surface is more hydrophobic, which indicates that AAT1 is more adsorbed on the quartz surface. This is consistent with the Zeta potential results.

[0024] Therefore, the novel collector provided by the present invention has a better adsorption effect on the quartz surface. The adsorption of the novel collector on quartz and petalite can be further studied by infrared spectroscopy (FTIR). It can be found that after the collector is treated, the quartz has a 3437.49 cm -1 、2924.78cm -1 、2850.00cm -1 、1745.37cm -1 、1624.89cm -1 Vibration peaks are generated at 3437.49 cm-1, which are primary amines, carboxylic acids, N-containing esters or rings. However, after the petalite was treated with the collector, only primary amines and carboxylic acids (3437.49 cm-1) were formed. -1 and 2924.78cm -1). It can be seen that during the high temperature process, amine reagents reacted with oil substances, which can be adsorbed on the quartz surface, but not on the petalite surface. Therefore, the new collector has good adsorption on the quartz surface, which can better separate quartz and petalite.

[0025] Beneficial effects of the present invention:

[0026] The invention discloses a preparation method and application of a collector for flotation separation of quartz and petalite. In a flotation mineral experiment, the collector prepared by the method of the invention has a quartz recovery rate of more than 98%, and a petalite recovery rate of only 8%, and has a good separation effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The present invention is a process flow chart of the preparation method. DETAILED DESCRIPTION

[0028] The following is a clear and comprehensive description of the embodiments of the present invention. The embodiments are only used to explain the present invention and are not used to limit the scope of the present invention.

[0029] Example 1

[0030] The raw materials come from pure quartz petalite minerals selected by a mineral processing plant in Africa. 2 The content of Li in petalite reaches 98.72% 2 The O content reaches 4.10%.

[0031] The raw ore is crushed and slurried to obtain slurry, wherein the concentration of the slurry is 20%;

[0032] During the flotation process, the pulp was stirred for 2 minutes, pH adjuster NaON was added to adjust the pH to 10.5 and then stirred for 3 minutes, then collector AAT1 was added and stirred for 3 minutes, and the foam was scraped for 3.5 minutes after the foam layer was stable; the amount of collector AAT1 was 400g / t;

[0033] Quartz concentrate and petalite tailings are obtained.

[0034] Through this test, the recovery rate of quartz can be obtained to be more than 98%, while the recovery rate of petalite is about 8%, which has a good separation effect.

[0035] Comparative Example 1

[0036] The raw materials and process of this comparative example are exactly the same as those of Example 1, except that the collector used is dodecylamine, and the amount of dodecylamine used is 200g / t. The pH is adjusted to between 8-11

[0037] Through this test, the recovery rate of quartz can be obtained to be about 95%, and the recovery rate of petalite is about 20%.

[0038] Comparative Example 2

[0039] The raw materials and process of this comparative example are exactly the same as those of Example 1, except that the collector used is N-dodecyl-1,3-propylenediamine, and the amount used is 150g / t. The pH is adjusted to between 6 and 8

[0040] Through this test, the recovery rate of quartz can be obtained to be about 98%, while the recovery rate of petalite is below 5%. However, the reagent used in this comparative example is unstable and expensive, and has no economic value.

[0041] Comparative Example 3

[0042] The raw materials and process of this comparative example are exactly the same as those of Example 1, except that the collector used is 1,8-diaminooctane, the dosage is 1000 g / t, and the pH is adjusted to between 9 and 11.

[0043] Through this test, the recovery rate of quartz can be obtained to be above 90%, and the recovery rate of petalite is about 20%.

[0044] Comparative Example 4

[0045] The raw materials and process of this comparative example are exactly the same as those of Example 1, except that the collector used is dihexamethylenetriamine, the dosage is 1000 g / t, and the pH is adjusted to between 9 and 11.

[0046] Through this test, the recovery rate of quartz can be obtained to be above 90%, and the recovery rate of petalite can be obtained to be below 50%.

[0047] Example 2

[0048] The raw materials come from the re-selection tailings of a mineral processing plant in Africa. The main minerals and their contents in the raw ore are shown in Table 1. The most abundant content is petalite, which is 22.71%, followed by albite, which is 20.70%, and the content of quartz is 15.23%. Chemical multi-element analysis shows that SiO 2 The content of Li is 66.03 2 The O content is 1.79%.

[0049]

[0050] Flotation test: The flotation process first uses one roughing and three sweeping to remove lepidolite, and then uses one roughing and one sweeping to remove spodumene. The tailings product is deslimed and de-medicated. A total of three deslimings are performed to obtain a new raw ore product, which is added to the flotation tank for stirring. After stirring for 5 minutes, the pH is adjusted to 10.5, stirred for 3 minutes, and then CaCl is added. 2 , stir for 3 minutes, then add AAT1 for a rough selection, then adjust the pH to 10.5, stir for 3 minutes, and then add CaCl 2 , and then stir for 3 minutes and then stir for 3 minutes, a total of one roughing and one sweeping, and finally a new product is obtained. (The amount of roughing agent used is: CaCl 2 The dosage of scavenging agent is 150g / t, and the dosage of AAT1 is 100g / t. 2 The dosage is 70g / t, and the dosage of AAT1 is 50g / t. )

[0051] Through this test, the Li content in tailings can be obtained. 2 The O content is about 2.2%. The tailings recovery rate can reach 30%, and the recovery rate of quartz products can reach about 15%, of which SiO 2 The content is about 87%.

[0052] Example 3

[0053] The raw materials in this example are the same as those in Operation Example 2, except that the activator used is MgCl 2 The dosage is 200g / t.

[0054] Through this test, the Li content in tailings can be obtained. 2 The content of O is about 2.1%. The recovery rate of tailings can reach 29%, and the recovery rate of quartz products can reach about 15%, of which SiO 2 The content is about 87%.

[0055] Example 4

[0056] The raw materials in this example are the same as those in Operation Example 2, except that the pH adjuster used is NaCO 3 ,

[0057] Through this test, Li in tailings can be obtained 2 O content is about 1.7%. The recovery rate of tailings is about 25%, and the recovery rate of quartz products is about 20%, of which SiO 2 The content is about 67%.

[0058] Comparative Example 5

[0059] The raw materials and process of this comparative example are exactly the same as those of Example 2, except that the collector used is a mixture of dodecylamine and N-dodecyl-1,3-propylenediamine, wherein the amount of the roughing collector is: 50 g / t of dodecylamine and 50 g / t of N-dodecyl-1,3-propylenediamine. The amount of the scavenging collector is: 25 g / t of dodecylamine and 25 g / t of N-dodecyl-1,3-propylenediamine.

[0060] Through this test, Li in tailings can be obtained 2 O content is about 1.8%. The tailings recovery rate can reach 33%, and the recovery rate of quartz products can reach about 12%, of which SiO 2 The content is 85%.

Claims

1. A method for preparing a collector for flotation separation of quartz and petalite, characterized in that: The following steps are involved: S1. Mixing the raw materials according to a preset ratio to obtain a mixed raw material; S2. The mixed raw material obtained in step S1 is heated in a water bath for a preset heating time, cooled to room temperature, filtered, fixed to volume and adjusted to pH value to obtain a collector AAT1 for flotation separation of quartz and petalite.

2. The method for preparing a collector for flotation separation of quartz and petalite according to claim 1, characterized in that: In step S1, the raw materials include amine raw materials and oil raw materials; the amine raw materials include at least two of 1,10-diaminodecane, N-dodecyl-1,3-propylenediamine, 1,8-diaminooctane, and dodecylamine; the oil raw materials include one or more of kerosene, tung oil, and silicone oil.

3. The method for preparing a collector for flotation separation of quartz and petalite according to claim 2, characterized in that: The molar ratio of the amine raw material to the oil raw material is (1-25):5; the oil raw material is between 0.5 and 2 times the total mass of the amine raw material.

4. The method for preparing a collector for flotation separation of quartz and petalite according to claim 1, characterized in that: In step S2, the process conditions of water bath heating are: heating temperature is 60°C to 90°C, and heating time is more than 30 minutes.

5. The method for preparing a collector for flotation separation of quartz and petalite according to claim 1, characterized in that: The pH adjustment specifically refers to adjusting the pH of the final collector to 8-11.

6. The method for preparing a collector for flotation separation of quartz and petalite according to claim 1, characterized in that: The method of fixing the volume is to fix the volume of the filtered reagent to a solute concentration of 1-5 g / L while maintaining the pH value of the reagent at 8-11.

7. Use of the collector according to claims 1 to 6, characterized in that: The following steps are involved: S11. crushing and slurrying the mineral to be floated to obtain slurry; S12. The pulp obtained in step S11 is subjected to a roughing flotation, and the collector AAT1 is used as the collector to obtain quartz concentrate and petalite tailings.

8. The use according to claim 7, characterized in that: In step S11, the concentration of the ore pulp is 20% to 70%, and the floating particle size range is 38 to 75 μm.

9. The use according to claim 7, characterized in that: In step S12, the roughing flotation is specifically as follows: stirring the pulp for 2 to 3 minutes, adding a pH adjuster and stirring for another 2 to 4 minutes, then adding a collector and stirring for another 2 to 4 minutes, and scraping the foam for 2 to 5 minutes after the foam layer is stable.

10. The use according to claim 9, characterized in that: The pH adjuster is NaOH, which adjusts the pH of the slurry to 6-11; the collector is AAT1, and the dosage is 100-500 g / t.

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