Quartz sand reverse flotation combined agent and application thereof

Abstract

The application discloses a quartz sand reverse flotation combined medicament and application thereof, and belongs to the technical field of quartz sand processing. The quartz sand reverse flotation combined medicament comprises the following components in proportion by weight: 1-1.5 parts of dodecanamide, 2-3 parts of hydroxamic acid and 1-1.5 parts of a non-ionic surfactant. The hydroxamic acid can be chelated with metal ion on the surface of associated minerals, is attached to the surface of the mineral grains and makes the mineral grains hydrophobic. In addition, electrostatic adsorption occurs between the dodecanamide and the hydroxamic acid, so that the dodecanamide is adsorbed and combined with the unpaired mineral grain chelation sites of the hydroxamic acid, the efficiency of capturing the associated minerals is improved, and the purpose of efficiently reverse-flotation of the quartz sand is achieved. The application further discloses a method for performing quartz sand reverse flotation by using the quartz sand reverse flotation combined medicament. The quartz sand reverse flotation combined medicament and the quartz sand reverse flotation method have the advantages of high operation safety factor, environmental friendliness and good flotation effect.

Description

Technical Field

[0001] This invention relates to the field of quartz sand processing technology, specifically to a quartz sand reverse flotation reagent combination and its application. Background Technology

[0002] High-purity quartz sand typically refers to quartz powder with a SiO2 content of 99.9% or higher, usually produced from high-grade natural quartz minerals through purification technology. The unique crystal structure and lattice variation of high-purity quartz sand give it characteristics such as high temperature resistance, low coefficient of thermal expansion, high insulation, and corrosion resistance. Currently, low- and mid-range (3N and 4N) high-purity quartz sand has been domestically produced, while high-end (>4N8) high-purity quartz sand is mainly imported. High-purity quartz sand with a purity of 4N8 or higher is mainly used in high-tech fields such as photovoltaics, communications, semiconductors, and chip manufacturing. Therefore, the processing and purification technology of high-purity quartz sand is a key research focus.

[0003] The main impurity minerals in quartz ore include mica, feldspar, apatite, and ilmenite. These minerals often occur together with quartz. Achieving efficient separation of quartz from other associated impurity minerals is an essential prerequisite for the preparation of high-purity quartz sand. Flotation is one of the most important processes in the purification of high-purity quartz sand and is also the main process for removing other associated impurity minerals from coarse quartz sand. The design of flotation reagent combinations is crucial for reducing quartz loss and improving flotation efficiency.

[0004] In the prior art, Chinese patent document CN102600982A discloses a fluorine-free, low-acid anionic and cation-ionic reverse flotation process for quartz sand. This invention employs a two-stage reverse flotation process. In the first stage of flotation, sulfuric acid is added first, followed by a propylene diamine cationic collector, and then a frother is added, followed by stirring and skimming. In the second stage of flotation, sodium carbonate is added first, followed by an anionic collector composed of sodium petroleum sulfonate and octyl hydroxamic acid, followed by a frother, stirring and skimming. The flotation process in this invention can efficiently remove metallic impurities such as Fe and Al.

[0005] Chinese patent document CN114392836A discloses a processing technology for high-purity quartz sand. In the flotation process of this invention, sulfuric acid is first used to adjust the pH of the pulp to 3-4, and amine collectors are used to float mica. Then, hydrochloric acid is used to adjust the pH of the pulp to 4-5, and sulfonated petroleum is used as a collector to float iron-containing minerals. Finally, hydrofluoric acid is used to adjust the pH to 2-3, and amines are used as collectors to float feldspar. High-purity quartz sand is thus prepared.

[0006] Chinese patent document CN115367763A discloses a process for preparing high-purity quartz sand. This invention employs a multi-stage flotation process. The first stage involves adding dodecylamine as a capture agent and No. 2 oil as a frother to water; adding 25% (by weight) of quartz sand (water + dodecylamine + No. 2 oil), along with NaOH solution and hydrofluoric acid solution as pH adjusters to adjust the pH to 2.0-3.0; removing aluminosilicate impurities such as feldspar using a flotation machine; drying after washing to neutrality; and repeating this process three times. The second stage involves adjusting the pH to 2.0-3.0 using NaOH and hydrochloric acid as pH adjusters; adding tetradecyltrimethylammonium chloride as a capture agent and phenethyl ester as a frother; removing aluminosilicate minerals such as kaolinite and mica using a flotation machine; drying after washing to neutrality; and repeating this process three times.

[0007] However, in the aforementioned existing technologies, the flotation process is complex, involving various flotation reagents and feeding steps, and the purity and recovery rate of the quartz sand after flotation need to be further improved. Summary of the Invention

[0008] To address the aforementioned technical problems and shortcomings in the field, this invention provides a quartz sand reverse flotation reagent, comprising dodecylamide, isohydroxamic acid, and a nonionic surfactant. These components work synergistically to achieve high flotation selectivity, significantly improving the purity and recovery rate of the quartz sand product. Furthermore, the reagent is simple and convenient to use, with a high operational safety factor and is environmentally friendly.

[0009] The specific technical solution adopted is as follows:

[0010] A reverse flotation reagent for quartz sand comprises the following components by weight: 1-1.5 parts dodecylamide, 2-3 parts isohydroxamic acid, and 1-1.5 parts nonionic surfactant.

[0011] The quartz sand reverse flotation reagent of this invention consists of a specific ratio of dodecylamide, isohydroxamic acid, and a nonionic surfactant. The composition is simple, and the flotation effect is excellent. On the one hand, isohydroxamic acid can chelate with metal ions of impurities on the surface of associated minerals, adhering to the surface of the mineral particles and making them hydrophobic. On the other hand, the amide group in dodecylamide is an electron-donating group, and the hydroxamic acid group is an electron-withdrawing group. The electrostatic adsorption of these two molecules leads to the interpenetrating adsorption of dodecylamide, which combines with the unpaired chelation sites of isohydroxamic acid on the mineral particles, improving the capture efficiency of associated minerals and achieving the purpose of highly efficient reverse flotation of quartz sand. The nonionic surfactant has high surface activity in water, low surface tension, and low critical micelle concentration. It can generate foam during the flotation process, and its appropriate concentration can increase the floatation rate of impurity minerals. If the dodecylamide content is too high, it will increase the viscosity of the foam and reduce the fluidity of the flotation foam, thus leading to a decrease in flotation performance. If the isohydroxamic acid content is too high, it will cause excessive quartz sand to be entrained in the flotation foam, increasing the quartz sand loss rate.

[0012] Preferably, the nonionic surfactant is a fatty alcohol polyoxyethylene ether, which has good foaming effect and is relatively economical, making it suitable for industrial production.

[0013] Preferably, the isohydroxamic acid is at least one of octylhydroxamic acid, salicylic acid, or benzohydroxamic acid.

[0014] The present invention also provides a method for reverse flotation of quartz sand using the aforementioned quartz sand reverse flotation reagent combination, comprising the following steps:

[0015] (1) Prepare an aqueous solution by mixing the quartz sand reverse flotation reagent with water at a mass ratio of 1:2-5 for later use;

[0016] (2) Add water to the quartz sand to make the first slurry, and add pH adjuster and aqueous solution of quartz sand reverse flotation reagent obtained in step (1) to the first slurry in sequence. Stir and aerate to obtain rough quartz sand. Add water to the rough quartz sand to make the second slurry, and add pH adjuster and aqueous solution of quartz sand reverse flotation reagent obtained in step (1) to the second slurry in sequence. Stir and aerate to obtain quartz concentrate sand.

[0017] Preferably, the pH adjuster is at least one of hydrochloric acid, sulfuric acid, oxalic acid, or acetic acid.

[0018] Preferably, the particle size of the raw material quartz sand is 50-200 mesh.

[0019] Preferably, in the process of preparing rough quartz sand, the mass concentration of the first slurry is 45-55%; after adding a pH adjuster, the pH value of the first slurry is adjusted to 2-5; the amount of quartz sand reverse flotation reagent added is 40-120 g / t based on the solid mass in the first slurry.

[0020] Preferably, in the process of preparing quartz concentrate, the mass concentration of the second slurry is 60-70%; after adding a pH adjuster, the pH value of the second slurry is adjusted to 3-6; the amount of quartz sand reverse flotation reagent added is 20-100 g / t based on the mass of ore in the second slurry.

[0021] Preferably, the stirring speed during the process is 500-2000 rpm, and the time is 3-8 minutes.

[0022] Preferably, the impurity element content in the quartz concentrate obtained by the reverse flotation method of the present invention is ≤20ppm, the purity of the quartz concentrate is ≥99.998%, and the quartz sand recovery rate is not less than 98.5%. The impurity elements include Al, B, Ba, Ca, Cr, Cu, Fe, Ge, K, Li, Mg, Mn, Na, Ni, P, Ti, or Zr.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] (1) The quartz sand reverse flotation reagent combination of the present invention has a simple composition, the raw materials are easy to obtain, and the flotation effect is excellent. It can specifically remove impurities and associated minerals in quartz sand, such as ilmenite, zoisite, rutile, apatite, feldspar, etc. Among them, isohydroxamic acid can chelate with impurity metal ions on the surface of associated minerals, attach to the surface of mineral particles and make them hydrophobic; in addition, the amide group in dodecylamide is an electron-donating group, and the hydroxamic acid group is an electron-withdrawing group. The electrostatic adsorption of the two molecules leads to the interpenetrating adsorption of dodecylamide, which combines with the unpaired chelation sites of isohydroxamic acid in mineral particles, thereby improving the capture efficiency of associated minerals and achieving the purpose of efficient reverse flotation of quartz sand.

[0025] (2) The quartz sand reverse flotation combination reagent and the quartz sand reverse flotation method provided by the present invention have the advantages of high operation safety factor and environmental friendliness. The quartz sand reverse flotation method of the present invention can greatly improve the purity and recovery rate of the quartz sand after flotation. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] The present invention will be further described below with reference to specific embodiments.

[0028] Example 1

[0029] In this embodiment, the quartz sand reverse flotation reagent consists of 1 part dodecylamide, 2 parts benzohydroxyxamic acid and 1 part fatty alcohol polyoxyethylene ether, by weight.

[0030] Specifically, using 60-170 mesh quartz sand from India, which has undergone preliminary crushing and screening, as raw material, the method of reverse flotation of quartz sand using this quartz sand reverse flotation reagent combination is explained:

[0031] (1) Take 5g dodecylamide, 10g benzoyl hydroxamic acid and 5g fatty alcohol polyoxyethylene ether in a glass beaker, add 100mL deionized water, stir until completely dissolved to prepare an aqueous solution for later use.

[0032] (2) The raw quartz sand sample was subjected to roughing and cleaning reverse flotation using a quartz sand reverse flotation reagent aqueous solution. The process conditions were as follows: 100 kg of coarse quartz sand (raw quartz sand) was added to the flotation cell, and deionized water was added to adjust the slurry concentration to 50%. After thorough mixing, sulfuric acid was added to adjust the pH of the slurry to 3. Then, the quartz sand reverse flotation reagent aqueous solution obtained in step (1) was added (the amount of quartz sand reverse flotation reagent added was 8 kg based on the solid mass of the slurry). 0g / t), stir for 5min, aerate and float, the product obtained in the flotation cell is rough quartz sand; then add deionized water to the rough quartz sand to adjust the slurry mass concentration to 60%, add sulfuric acid to adjust the pH of the slurry to 4, then add the aqueous solution of quartz sand reverse flotation reagent obtained in step (1) (the amount of quartz sand reverse flotation reagent added is 60g / t based on the solid mass in the slurry), stir for 5min, aerate and float, the product obtained in the flotation cell is quartz concentrate sand.

[0033] Comparative Example 1

[0034] The reverse flotation reagent in Comparative Example 1 differs from the quartz sand reverse flotation reagent in Example 1, the only difference being that it does not contain dodecylamide. The aqueous solution of the reverse flotation reagent was prepared using 10g of benzohydroxyxamic acid, 5g of fatty alcohol polyoxyethylene ether, and 100mL of deionized water.

[0035] Using the reverse flotation reagent aqueous solution from Comparative Example 1, the raw quartz sand sample (same as in Example 1) was subjected to a roughing and cleaning reverse flotation process following the same steps as in Example 1 to obtain quartz concentrate sand.

[0036] The impurity content of the quartz concentrate sand in Example 1 and Comparative Example 1 was characterized using inductively coupled plasma optical emission spectrometry (ICP-OES). The characterization test results are shown in Table 1. The purity of the quartz concentrate sand obtained in Example 1 was 99.9984%, and the quartz sand recovery rate was 98.8%. The purity of the quartz concentrate sand obtained in Comparative Example 1 was 99.9972%, and the quartz sand recovery rate was 96.9%.

[0037] Table 1. Impurity content (ppm) of the quartz concentrate sand prepared in Example 1 and Comparative Example 1.

[0038] Example 1 5.37 0.13 0.03 1.88 0.02 0.1 0.97 0.49 0.87 Comparative Example 1 12.3 0.15 0.04 3.15 0.01 0.05 2.56 0.51 0.82 project Li Mg Mn Na Ni P Ti Zr Example 1 0.26 0.05 0.03 3.13 0.02 0.6 2.3 0.21 Comparative Example 1 0.24 0.04 0.03 3.45 0.01 0.98 3.51 0.24

[0039] Example 2

[0040] In this embodiment, the quartz sand reverse flotation reagent consists of 1 part dodecylamide, 2 parts benzohydroxyxamic acid and 1 part fatty alcohol polyoxyethylene ether, by weight.

[0041] Specifically, using 50-200 mesh quartz sand from India, which has undergone preliminary crushing and screening, as raw material, the method of reverse flotation of quartz sand using this quartz sand reverse flotation reagent combination is explained:

[0042] (1) Take 5g dodecylamide, 10g benzoyl hydroxamic acid and 5g fatty alcohol polyoxyethylene ether in a glass beaker, add 80mL of deionized water, stir until completely dissolved to prepare an aqueous solution for later use;

[0043] (2) The raw quartz sand sample was subjected to roughing and cleaning reverse flotation using a quartz sand reverse flotation reagent aqueous solution. The process conditions were as follows: 100 kg of coarse quartz sand (raw quartz sand) was added to the flotation cell, and deionized water was added to adjust the slurry concentration to 55%. After thorough mixing, sulfuric acid was added to adjust the pH of the slurry to 4. Then, the quartz sand reverse flotation reagent aqueous solution obtained in step (1) was added (the amount of quartz sand reverse flotation reagent added was 1 kg based on the solid mass of the slurry). 00g / t), stir for 5min, aerate and float, the product obtained in the flotation cell is rough quartz sand; then add the rough quartz sand back into deionized water to adjust the slurry mass concentration to 70%, add sulfuric acid to adjust the pH of the slurry to 5, then add the aqueous solution of quartz sand reverse flotation reagent obtained in step (1) (the amount of quartz sand reverse flotation reagent added is 80g / t based on the solid mass in the slurry), stir for 5min, aerate and float, the product obtained in the flotation cell is quartz concentrate sand.

[0044] Comparative Example 2

[0045] The reverse flotation reagent in Comparative Example 2 differs from the quartz sand reverse flotation reagent in Example 2, the only difference being that it does not contain benzohydroxyxamic acid. The aqueous solution of the reverse flotation reagent was prepared using 5g of dodecylamide, 5g of fatty alcohol polyoxyethylene ether, and 80mL of deionized water.

[0046] Using the reverse flotation reagent aqueous solution from Comparative Example 2, the raw quartz sand ore sample (same as in Example 2) was subjected to roughing and cleaning reverse flotation according to the same steps as in Example 2 to obtain quartz concentrate sand.

[0047] The impurity content of the quartz concentrate sand in Example 2 and Comparative Example 2 was characterized using inductively coupled plasma optical emission spectrometry (ICP-OES). The characterization test results are shown in Table 2. The purity of the quartz concentrate sand obtained in Example 2 was 99.9982%, and the quartz sand recovery rate was 98.5%. The purity of the quartz concentrate sand obtained in Comparative Example 2 was 99.9965%, and the quartz sand recovery rate was 97.3%.

[0048] Table 2. Impurity content (ppm) of the quartz concentrate sand prepared in Example 2 and Comparative Example 2.

[0049] Example 2 5.51 0.12 0.05 2.35 0.01 0.1 1.1 0.53 0.87 Comparative Example 2 11.24 0.1 0.05 5.36 0.02 0.12 4.95 0.52 2.24 project Li Mg Mn Na Ni P Ti Zr Example 2 0.26 0.06 0.04 3.22 0.03 0.56 2.71 0.18 Comparative Example 2 0.24 0.05 0.01 5.25 0.02 0.75 4.21 0.15

[0050] Example 3

[0051] In this embodiment, the quartz sand reverse flotation reagent consists of 1.5 parts dodecylamide, 3 parts octyl hydroxamic acid and 1 part fatty alcohol polyoxyethylene ether, by weight.

[0052] Specifically, using 50-200 mesh quartz sand from India, which has undergone preliminary crushing and screening, as raw material, the method of reverse flotation of quartz sand using this quartz sand reverse flotation reagent combination is explained:

[0053] (1) Take 6g dodecylamide, 12g octyl hydroxamic acid and 4g fatty alcohol polyoxyethylene ether in a glass beaker, add 100mL deionized water, stir until completely dissolved to prepare an aqueous solution for later use.

[0054] (2) The raw quartz sand sample was subjected to roughing and cleaning reverse flotation using a quartz sand reverse flotation reagent aqueous solution. The process conditions were as follows: 100 kg of coarse quartz sand (raw quartz sand) was added to the flotation cell, and deionized water was added to adjust the slurry concentration to 50%. After thorough mixing, sulfuric acid was added to adjust the pH of the slurry to 4. Then, the quartz sand reverse flotation reagent aqueous solution obtained in step (1) was added (the amount of quartz sand reverse flotation reagent added was 10 kg based on the solid mass of the slurry). 0g / t), stir for 5min, aerate and float, the product obtained in the flotation cell is rough quartz sand; then add deionized water to the rough quartz sand to adjust the slurry mass concentration to 65%, add sulfuric acid to adjust the pH of the slurry to 5, then add the aqueous solution of quartz sand reverse flotation reagent obtained in step (1) (the amount of quartz sand reverse flotation reagent added is 100g / t based on the solid mass in the slurry), stir for 5min, aerate and float, the product obtained in the flotation cell is quartz concentrate sand.

[0055] Comparative Example 3

[0056] The anti-flotation reagent in Comparative Example 3, by weight, consisted of 1.5 parts dodecylamide, 3 parts octyl hydroxamic acid, and 3 parts fatty alcohol polyoxyethylene ether. The aqueous solution of the anti-flotation reagent was prepared using 6 g of dodecylamide, 12 g of octyl hydroxamic acid, 12 g of fatty alcohol polyoxyethylene ether, and 100 mL of deionized water.

[0057] Using the reverse flotation reagent aqueous solution from Comparative Example 3, the raw quartz sand ore sample (same as in Example 3) was subjected to a roughing and cleaning reverse flotation process following the same steps as in Example 3 to obtain quartz concentrate sand.

[0058] The impurity content of the quartz concentrate sand in Example 3 and Comparative Example 3 was characterized using inductively coupled plasma optical emission spectrometry (ICP-OES). The characterization test results are shown in Table 3. The purity of the quartz concentrate sand obtained in Example 3 was 99.9982%, and the quartz sand recovery rate was 98.7%. The purity of the quartz concentrate sand obtained in Comparative Example 3 was 99.9981%, and the quartz sand recovery rate was 95.3%.

[0059] Table 3. Impurity content (ppm) of the quartz concentrate sand prepared in Example 3 and Comparative Example 3.

[0060] Example 3 5.56 0.14 0.03 2.33 0.03 0.11 1.36 0.55 0.97 Comparative Example 3 5.48 0.12 0.03 2.69 0.07 0.1 1.51 0.56 0.98 project Li Mg Mn Na Ni P Ti Zr Example 3 0.26 0.06 0.04 3.17 0.01 0.45 3.15 0.22 Comparative Example 3 0.25 0.06 0.05 3.13 0.04 0.64 2.92 0.31

[0061] The embodiments described above provide a detailed explanation of the technical solutions of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, additions, or similar substitutions made within the scope of the principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A silica sand reverse flotation reagent combination, characterized in that, Based on parts by weight, it comprises the following components: 1-1.5 parts dodecylamide, 2-3 parts isohydroxamic acid, and 1-1.5 parts nonionic surfactant; wherein the nonionic surfactant is fatty alcohol polyoxyethylene ether.

2. The quartz sand reverse flotation reagent according to claim 1, characterized in that, The isohydroxamic acid is at least one of octylhydroxamic acid, salicylic acid, or benzohydroxamic acid.

3. A method for reverse flotation of quartz sand, characterized in that, The quartz sand reverse flotation reagent combination described in claim 1 or 2 is used.

4. The method for reverse flotation of quartz sand according to claim 3, characterized in that, Includes the following steps: (1) Prepare an aqueous solution by mixing the quartz sand reverse flotation reagent with water at a mass ratio of 1:2-5 for later use; (2) Add water to the quartz sand to make the first slurry, and add pH adjuster and aqueous solution of quartz sand reverse flotation reagent obtained in step (1) to the first slurry in sequence. Stir, and perform aeration flotation to obtain rough quartz sand. Add water to the rough quartz sand to make the second slurry, and add pH adjuster and aqueous solution of quartz sand reverse flotation reagent obtained in step (1) to the second slurry in sequence. Stir, and perform aeration flotation to obtain quartz concentrate sand.

5. The method for reverse flotation of quartz sand according to claim 4, characterized in that, The pH adjuster is at least one of hydrochloric acid, sulfuric acid, oxalic acid, or acetic acid.

6. The method for reverse flotation of quartz sand according to claim 4, characterized in that, The particle size of the raw material, quartz sand, is 50-200 mesh.

7. The method for reverse flotation of quartz sand according to claim 4, characterized in that, In the process of preparing rough quartz sand, the mass concentration of the first slurry is 45-55%; after adding a pH adjuster, the pH value of the first slurry is adjusted to 2-5; the amount of quartz sand reverse flotation reagent added is 40-120 g / t based on the solid mass in the first slurry.

8. The method for reverse flotation of quartz sand according to claim 4, characterized in that, In the process of preparing quartz concentrate, the mass concentration of the second slurry is 60-70%; after adding a pH adjuster, the pH value of the second slurry is adjusted to 3-6; the amount of quartz sand reverse flotation reagent added is 20-100 g / t based on the ore mass in the second slurry.

9. The method for reverse flotation of quartz sand according to claim 4, characterized in that, The content of impurity elements in the quartz concentrate is ≤20 ppm, and the impurity elements include Al, B, Ba, Ca, Cr, Cu, Fe, Ge, K, Li, Mg, Mn, Na, Ni, P, Ti and Zr.