Preparation method and application of collector for separating quartz and spodumene by flotation

Abstract

The application discloses a preparation method of a collector for flotation separation of quartz and petalite, and belongs to the technical field of mineral processing. The collector AAT1 is obtained by mixing amine raw materials and oil raw materials in a certain proportion, heating the mixed raw materials in a water bath for a preset time, cooling to room temperature, filtering, determining the volume, adjusting pH, and the like.

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. Often, these minerals are considered tailings, resulting in a waste of resources. Quartz, an essential raw material, is experiencing a continuous increase in consumption with the booming semiconductor and battery industries. Lithium resources are rapidly increasing with the development of electric vehicles and new energy vehicles, so the recovery of petalite can alleviate the current shortage of lithium resources. Therefore, the recovery and separation of petalite and feldspar is of great significance.

[0003] Quartz and petalite have similar physical and chemical properties, so physical separation methods cannot effectively separate them. Currently, flotation is the most effective method for separating quartz and feldspar. The most mature method is the hydrofluoric acid method, which first adjusts the solution pH to 2 with sulfuric acid, then adds hydrofluoric acid to activate the feldspar and ultimately achieve separation. However, due to environmental and health hazards and equipment corrosion, this process is no longer used. Other researchers have studied fluorine-free acid-based methods, which have produced qualified products, but these methods also cause environmental damage and equipment corrosion. Furthermore, research on the flotation of petalite is extremely limited. Therefore, fluorine-free and acid-free methods for separating quartz and petalite hold great research value.

[0004] Before flotation of quartz feldspar, mica removal is typically required, which results in an alkaline slurry. Separating quartz and petalite directly in an alkaline environment can shorten the flotation process, save reagents, and reduce costs. Experiments have shown that single amine collectors have poor sorting properties, are difficult to dissolve, and have poor stability. 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 amount of reagent used.

[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. The raw materials are mixed in 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 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 to 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 setting is to set 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. The mineral to be floated is crushed and slurried to obtain a slurry;

[0016] S12. The pulp obtained in step S11 is subjected to a roughing flotation, using the collector AAT1 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 slurry 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 stabilizes;

[0019] The pH adjuster is NaOH, which is used to adjust 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 no adjusting agent NaOH was 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 are both negative in neutral and alkaline environments. Under neutral conditions, the Zeta potential of quartz with the addition of AATI obviously shifted 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 obviously shifted to the negative direction. This may be due to the OH - The effect of pH shifts the potential toward the negative direction. Under these conditions, the zeta potential of quartz significantly shifts positively by 17.6 mV after the addition of AAT1, a greater shift than under neutral conditions, indicating that pH adjustment facilitates the adsorption of AAT1 on the quartz surface. For petalite, the general trend is similar to that of quartz. However, overall, the change in zeta potential before and after the addition of AAT1 under neutral conditions (pH = 7) is smaller than that of quartz, increasing by only 3.9 mV. At the optimal pH, the addition of AATI increases the zeta potential by 5.6 mV. This indicates that DAM adsorbs more strongly on the quartz surface than petalite.

[0023] At the optimal pH, the contact angles of AAT1 with natural quartz and petalite were 15.56° and 14.03°, respectively. Both are hydrophilic minerals. Adding the modifier increased the contact angles of both materials. Under these conditions, the contact angle of quartz with AAT1 increased from 19.68° to 137.22°, while the contact angle of petalite increased from 15.48° to 42.50°. These results indicate that AATI can render both surfaces hydrophobic, but at the same dosage, the quartz surface is more hydrophobic, indicating greater adsorption of AAT1 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 adsorption of the novel collector on quartz and petalite is better at 3437.49 cm -1 、2924.78cm -1 、2850.00cm -1 、1745.37cm -1 、1624.89cm -1 Vibration peaks are generated at 3437.49 cm. They are primary amine, carboxylic acid, N-containing ester or cyclic. However, after the petalite is treated with collector, only primary amine and carboxylic acid (3437.49 cm -1 and 2924.78cm -1The stretching vibration peak of the amine reagent is disappeared, and the stretching vibration peak of the oil reagent is disappeared. It can be known that the amine reagent reacts with the oil reagent in the high-temperature process, and the substance can be adsorbed on the quartz surface, but not adsorbed on the eucryptite surface. Therefore, the new collector can be well adsorbed on the quartz surface, and the quartz and the eucryptite can be better separated.

[0025] The beneficial effects of the present application are as follows:

[0026] The application discloses a preparation method and application of a collector for separating quartz and eucryptite by flotation. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 The preparation method is shown in the process flowchart. DETAILED DESCRIPTION

[0028] The embodiments of the present application will be described in detail below, and the embodiments are only used for explaining the present application, and are not used for limiting the scope of the present application.

[0029] Embodiment 1

[0030] The raw material is a pure mineral of quartz and eucryptite selected from a certain dressing plant in Africa, wherein the content of SiO2 in the quartz reaches 98.72%, and the content of Li2O in the eucryptite reaches 4.10%.

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

[0032] In the flotation process, the slurry is stirred for 2 min first, then a pH regulator NaON is added to adjust the pH to 10.5, and then stirred for 3 min, then the collector AAT1 is added and stirred for 3 min, and then the foam layer is scraped for 3.5 min after the foam layer is stable; the dosage of the collector AAT1 is 400 g / t;

[0033] The quartz concentrate and the eucryptite tailings are obtained.

[0034] Through the experiment, the recovery rate of the quartz is more than 98%, and the recovery rate of the eucryptite is about 8%, and the separation effect is good.

[0035] Comparative Example 1

[0036] The raw material and process of the comparative example 1 are completely same as those of the embodiment 1, and the difference is that the collector used is dodecylamine, and the dosage of the dodecylamine is 200 g / t.

[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 6-8.

[0040] The recovery rate of quartz obtained by this experiment is 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. The difference is that the collector used is 1,8-diaminooctane, the amount of which 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. The difference is that the collector used is dihexamethylenetriamine, the amount of which is 1000g / t, and the pH is adjusted to between 9-11.

[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 material was derived from gravity-selected tailings from an African concentrator. The main minerals and their contents are shown in Table 1. Petalite is the most abundant at 22.71%, followed by albite at 20.70%, and quartz at 15.23%. Chemical multi-element analysis revealed SiO₂ content of 66.03% and Li₂O content of 1.79%.

[0049]

[0050] Flotation test: The flotation process first uses a roughing and three-sweeping process to remove lepidolite, followed by a roughing and one-sweeping process to remove spodumene. The resulting tailings product is deslimed and de-acidified, a total of three desliming processes. This produces a new raw ore product, which is then added to the flotation tank and stirred. After stirring for 5 minutes, the pH is adjusted to 10.5, stirred for 3 minutes, and CaCl2 is added. Stirring for another 3 minutes, AAT1 is added, and a roughing process is performed. The pH is then adjusted to 10.5, stirred for 3 minutes, and CaCl2 is added. Stirring for another 3 minutes, and then stirring for another 3 minutes. This process of one roughing and one-sweeping process is repeated to obtain a new product. (The roughing agent dosage is: CaCl2: 150g / t, AAT1: 100g / t. The scavenging agent dosage is: CaCl2: 70g / t, AAT1: 50g / t.)

[0051] Through this test, it can be obtained that the Li2O content in the tailings is about 2.2%. The tailings recovery rate can reach 30%, and the recovery rate of quartz products can reach about 15%, of which the SiO2 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 MgCl2 in an amount of 200 g / t.

[0054] Through this test, the content of Li2O in the tailings can be obtained to be about 2.1%. The recovery rate of tailings can reach 29%, and the recovery rate of quartz products can reach about 15%, of which the content of SiO2 is about 87%.

[0055] Example 4

[0056] The raw materials in this example are the same as those in Example 2, except that the pH adjuster used is NaCO3.

[0057] Through this test, the content of Li2O in the tailings was found to be about 1.7%, the recovery rate of the tailings was about 25%, the recovery rate of the quartz product was about 20%, and the content of SiO2 was about 67%.

[0058] Comparative Example 5

[0059] This comparative example used the same raw materials and process as Example 2, except that the collector used was a mixture of dodecylamine and N-dodecyl-1,3-propylenediamine. The roughing collector dosages were 50 g / t dodecylamine and 50 g / t N-dodecyl-1,3-propylenediamine. The scavenging collector dosages were 25 g / t dodecylamine and 25 g / t N-dodecyl-1,3-propylenediamine.

[0060] Through this test, the content of Li2O in the tailings can be obtained to be about 1.8%. The recovery rate of tailings can reach 33%, and the recovery rate of quartz products can reach about 12%, of which the content of SiO2 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. The raw materials are mixed in a preset ratio to obtain a mixed raw material; S2. The mixed raw material obtained in step S1 was heated in a water bath, heated for a preset time, cooled to room temperature, filtered, fixed to volume and adjusted to a pH of 8 to 11 to obtain a flotation separation of quartz and petalite collector AAT1; 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 and 1,8-diaminooctane; 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.

2. 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.

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

4. Use of the collector according to any one of claims 1 to 3, characterized in that: The following steps are involved: S11. The mineral to be floated is crushed and slurried to obtain a slurry; S12. The pulp obtained in step S11 is subjected to a roughing flotation, wherein the collector AAT1 is used in the roughing flotation to obtain quartz concentrate and petalite tailings.

5. The use according to claim 4, 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.

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

7. The use according to claim 6, characterized in that The pH adjuster is NaOH, which adjusts the pH of the slurry to 8-11; the collector is AAT1, and the dosage is 100-500 g / t.

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