Fine separation method of alaite type high-purity quartz raw material and high-purity quartz

Abstract

The invention provides a fine separation method of alaite type high-purity quartz raw materials and high-purity quartz, and the fine separation method comprises the following steps: crushing, grinding and grading the alaite type high-purity quartz raw materials to obtain raw material sand; the raw material sand is subjected to two-stage high-gradient magnetic separation, and high-purity quartz raw sand and iron-containing magnetic substances can be obtained; the high-purity quartz rough sand is subjected to mica preferential flotation, and quartz rough concentrate and mica concentrate can be obtained; the quartz rough concentrate is subjected to feldspar preferential flotation, and first quartz concentrate and feldspar concentrate can be obtained; the first quartz concentrate is subjected to directional Ca flotation, and second quartz concentrate and quartz middlings can be obtained; the second quartz concentrate is sequentially subjected to first-time oscillation acid leaching, calcination water quenching and second-time oscillation acid leaching, and high-purity quartz can be obtained. The high-purity quartz is prepared according to the method. The method has the beneficial effect that the problem that a large amount of solid waste generated in the purification process of the alaite type high-purity quartz raw material cannot be treated is effectively solved.

Description

Technical Field

[0001] The present invention relates to the technical field of non-metallic ore beneficiation. Specifically, it relates to a fine separation method for albite-type high-purity quartz raw materials and high-purity quartz. Background Art

[0002] High-purity quartz has a dual meaning of resources and materials. As a material, it refers to quartz sand and its products with a SiO 2 purity of more than 99.99%; as a resource, it refers to high-purity quartz sand raw material ore minerals that can be used for processing, purification, and separation. Different high-purity quartz sands have a wide range of uses. However, high-purity quartz sand with a purity of 4N8 (SiO 2 purity of 99.998%) or above required by emerging industries such as semiconductor chips and solar photovoltaics is an indispensable and irreplaceable key basic material, and its raw material ore minerals are scarce resources formed under extremely harsh geological conditions and with extremely limited distribution. The West relies on the unique albite-type high-purity quartz sand supply in Spruce Pine, North Carolina, USA.

[0003] More and more industries have relatively high requirements for the purity of quartz sand. Taking the product IOTA-CG high-end product index of the US company Unimin as an example, not only does the SiO 2 purity need to meet the requirement of 99.9981%, but the content of its single-element elements also needs to meet the standard, such as Li < 0.5 ppm, Na < 1 ppm, K < 0.7 ppm, Ca < 0.6 ppm, etc. Exceeding the standard of the Ca element will cause the melting point and softening point of the product to decrease, and reduce the service life of the product in a high-temperature environment. At present, domestic albite-type high-purity quartz raw materials can already be made into high-purity quartz sand with a SiO 2 purity greater than 99.998%, but there is still a certain gap between its Ca element and the IOTA-CG index. Therefore, it is very important and meaningful to try to find a way to remove the Ca element directionally during the fine separation process.

[0004] During the fine separation process of quartz sand, it mainly aims at separating gangue minerals from quartz. The main method is flotation treatment. Flotation is a technology for selectively separating hydrophobic and hydrophilic substances. By adding regulators, surfactants, and collectors, the difference in surface hydrophobicity between gangue minerals and quartz particles is enhanced. Gangue minerals are hydrophobic and will float with the bubbles, while the surface of quartz particles is hydrophilic and accumulates at the bottom of the flotation cell. The floating gangue minerals are scraped away from the pulp by a scraper to achieve the separation effect. The existing quartz flotation technology is often a cationic reverse flotation system, which has limited collecting ability for feldspar and limited collecting ability for other free metal impurity elements in the pulp system. The surface activator used in reverse flotation is usually hydrofluoric acid and sodium fluoride containing fluoride ions, which react with Ca ions in the pulp system and on the particle surface to form CaF precipitation, adhering to the surface and gaps of mineral particles. The existing reverse flotation technology has weak targeted adsorption ability for CaF and cannot separate quartz particles adsorbed with a large amount of CaF from relatively pure quartz particles, thus affecting the purity of the final quartz concentrate product. Therefore, it is of great significance to provide a fine separation method for alaskite-type high-purity quartz raw materials and high-purity quartz. Summary of the Invention

[0005] Aiming at the deficiencies existing in the prior art, the purpose of the present invention is to solve one or more of the problems existing in the above prior art. For example, one of the purposes of the present invention is to provide a fine separation method for alaskite-type high-purity quartz raw materials that can effectively collect feldspar, remove Ca elements directionally, and improve the SiO 2 purity. Another purpose of the present invention is to provide high-purity quartz with a high purity of ≥99.9980% and a low Ca element content.

[0006] To achieve the above purpose, on the one hand, the present invention provides a fine separation method for alaskite-type high-purity quartz raw materials, which may include: crushing, grinding, and classifying the alaskite-type high-purity quartz raw materials to obtain raw material sand of -80 to +200 mesh; performing two-stage high-gradient magnetic separation operations on the raw material sand to obtain high-purity quartz rough sand and iron magnetic substances; performing preferential flotation operations on the high-purity quartz rough sand to obtain quartz rough concentrate and mica concentrate; performing preferential flotation operations on the quartz rough concentrate to obtain first quartz concentrate and feldspar concentrate; performing directional Ca flotation operations on the first quartz concentrate to obtain second quartz concentrate and quartz middlings; and performing the first oscillating acid leaching operation, calcination and water quenching operation, and the second oscillating acid leaching operation on the second quartz concentrate in sequence to obtain high-purity quartz.

[0007] According to one or more exemplary embodiments of one aspect of the present invention, the two-stage high-gradient magnetic separation operations may include: two-stage magnetic separation, wherein the magnetic field strength of the first stage is 1.2 to 1.5 T, and the magnetic field strength of the second stage is 1.7 to 2.0 T. The magnetic substances obtained in the two stages are mixed as the iron magnetic substances.

[0008] According to one or more exemplary embodiments of one aspect of the present invention, the preferential flotation operation of mica may include: a preferential rough flotation operation of mica and a preferential scavenging flotation operation of mica carried out in sequence. Among them, in the preferential rough flotation operation of mica: the high-purity quartz raw sand is slurried as sand, the pH is adjusted to 3-4, a silicate inhibitor UP-1 and an amine cationic collector NY-1 are added to obtain a first quartz rough concentrate and a first mica concentrate; in the preferential scavenging flotation operation of mica: the first quartz rough concentrate is slurried, the pH is adjusted to 3-4, and an amine cationic collector NY-1 is added to obtain a second quartz rough concentrate and a second mica concentrate.

[0009] According to one or more exemplary embodiments of one aspect of the present invention, the preferential flotation operation of feldspar may include: a preferential rough flotation operation of feldspar, a first preferential scavenging flotation operation of feldspar, and a second preferential scavenging flotation operation of feldspar carried out in sequence. Among them, in the preferential rough flotation operation of feldspar: the quartz rough concentrate obtained from the preferential flotation operation of mica is slurried, the pH is adjusted to 2-3, an activator HF, an amine cationic collector NY-1, and an anionic collector NY-2 are added to obtain a third quartz rough concentrate and a first feldspar concentrate; in the first preferential scavenging flotation operation of feldspar: the third quartz rough concentrate is slurried, the pH is adjusted to 2-3, an activator HF, an amine cationic collector NY-1, and an anionic collector NY-2 are added to obtain a fourth quartz rough concentrate and a second feldspar concentrate; in the second preferential scavenging flotation operation of feldspar: the fourth quartz rough concentrate is slurried, the pH is adjusted to 2-3, and an amine cationic collector NY-1 is added to obtain a first quartz concentrate and a third feldspar concentrate.

[0010] According to one or more exemplary embodiments of one aspect of the present invention, in the preferential flotation operation of mica or the preferential flotation operation of feldspar, the pH can be adjusted by an acidic pH adjuster, and the acidic pH adjuster includes at least one of sulfuric acid, hydrochloric acid, and nitric acid, with a mass fraction of 5-10%.

[0011] According to one or more exemplary embodiments of one aspect of the present invention, the directional Ca flotation operation may include: a directional Ca flotation impurity removal roughing operation and a directional Ca flotation cleaning operation carried out in sequence. Among them, in the directional Ca flotation impurity removal roughing operation: the first quartz concentrate obtained from the preferential flotation operation of feldspar is washed until the pH is neutral, and then slurried, the pH is adjusted to 10-11, a silicate inhibitor UP-2 and a fatty acid anionic collector NY-3 are added to obtain a fifth quartz rough concentrate and a first quartz middling; in the directional Ca flotation cleaning operation: the fifth quartz rough concentrate is slurried, the pH is adjusted to 10-11, and a fatty acid anionic collector NY-3 is added to obtain a second quartz concentrate and a second quartz middling.

[0012] According to one or more exemplary embodiments of one aspect of the present invention, in the directional Ca flotation operation, the pH can be adjusted using an alkaline pH adjuster, and the alkaline pH adjuster includes at least one of NaOH and Na 2 CO 3 solution, with a mass fraction of 10-20%.

[0013] According to one or more exemplary embodiments of one aspect of the present invention, the first shock acid leaching operation / the second shock acid leaching operation may include: using a reverse oscillator with a rotation speed controlled at 30-60 r / min, a temperature controlled at 60-100 °C, an acid leaching time controlled at 16-24 h, and the leaching agent includes at least two of hydrochloric acid, hydrofluoric acid, and nitric acid, with a mass fraction controlled at 10-20%.

[0014] According to one or more exemplary embodiments of one aspect of the present invention, the calcination and water quenching operation may include: the calcination temperature is controlled at 800-1200 °C, the calcination time is controlled at 30-60 min; water quenching is carried out using pure water.

[0015] Another aspect of the present invention provides a high-purity quartz, which may include a product prepared by the fine separation method of the albite-type high-purity quartz raw material described above; the SiO 2 purity of the high-purity quartz is ≥99.998%, and the Ca element content is ≤0.8 ppm.

[0016] Compared with the prior art, the beneficial effects of the present invention include at least one of the following:

[0017] (1) Achieve the fine separation of feldspar, mica and quartz from albite-type high-purity quartz raw materials, effectively solve the problem that a large amount of solid waste generated during the purification of albite-type high-purity quartz raw materials cannot be treated, avoid or reduce environmental pollution, avoid or reduce resource waste, and also increase the enterprise's benefits.

[0018] (2) Compared with the traditional flotation operation process, the present invention adopts a combination of three-product preferential flotation operation and directional flotation operation, which not only ensures a high purity of the obtained quartz concentrate, but also ensures the fine separation of feldspar mica and quartz concentrate.

[0019] (3) The present invention overcomes the problems that the existing conventional cationic reverse flotation system has limited separation effect on quartz and gangue minerals and weak targeted adsorption ability for CaF, realizes the deep separation of quartz and gangue minerals, reduces the Ca grade in the product, and improves the economic value of the concentrate product. Description of the Drawings

[0020] Through the following description in conjunction with the drawings, the above and other objects and features of the present invention will become clearer, where:

[0021] Figure 1 Shows a process flow schematic diagram of a fine separation method for granite-type high-purity quartz raw materials;

[0022] Figure 2A Shows the morphology of the concentrate under a microscope after flotation of quartz concentrate under the traditional process;

[0023] Figure 2B Shows the morphology of the concentrate under a microscope after flotation of quartz concentrate under the process flow of the present invention. Detailed implementation manners

[0024] In the following, a fine separation method for granite-type high-purity quartz raw materials and high-purity quartz of the present invention will be described in detail with reference to the accompanying drawings and exemplary embodiments.

[0025] In the description of the present application, it should be understood that the terms "first", "second", "third", "fourth", "fifth", etc. are only for convenient description and easy distinction, and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of the indicated technical features. Thus, the features defined with "first", "second", "third", "fourth", "fifth", etc. may explicitly or implicitly include one or more of such features. In the description of the present invention, unless otherwise specified, the meaning of "a plurality" and "several" is two or more. The particle size expressions existing in the present application, such as +80, -200 mesh, etc., mean that the particles are on the sieve of 80 mesh and under the sieve of 200 mesh, that is, the particles that cannot pass through the mesh of 80 mesh and the particles that can pass through the mesh of 200 mesh; negative numbers indicate that the particles can pass through the mesh of the specified mesh number, and the particle size is smaller than the mesh size; positive numbers indicate that the particles cannot pass through the mesh of the specified mesh number, and the particle size is larger than the mesh size.

[0026] In the present invention, due to the limited collecting effect of traditional cationic collectors on gangue minerals and other metal ions during the current high-purity quartz purification process, and the problem that CaF precipitation will be generated in the flotation system during the purification process and adsorbed on the surface and micropores of some quartz particles, resulting in a relatively high CaF grade in the subsequent quartz concentrate product, which affects the quality of quartz products. A fine separation method of "preferential flotation of mica and feldspar + directional flotation of CaF" is proposed, which combines an anionic collector (NY-2) and an anionic collector (NY-3), greatly improving the collecting ability of free metal ions in the solution system during the flotation process and quartz particles adsorbed with CaF, thereby effectively improving the SiO 2 purity of the obtained quartz, enabling the product to have a broader market space and increasing the enterprise benefits.

[0027] Exemplary embodiment 1

[0028] This exemplary embodiment provides a fine separation method for albite-type high-purity quartz raw materials.

[0029] Figure 1 The process flow diagram of the fine separation method for albite-type high-purity quartz raw materials is shown; Figure 2A The morphology of the concentrate under the microscope after flotation of quartz concentrate under the traditional process is shown; Figure 2B The morphology of the concentrate under the microscope after flotation of quartz concentrate under the process of the present invention is shown. The following will be combined with Figures 1 to 2B to describe the fine separation method for albite-type high-purity quartz raw materials of this exemplary embodiment.

[0030] As Figure 1 shown in, the fine separation method of the present invention mainly includes: coarsely crushing, finely crushing, and grinding the albite raw materials, performing screening and classification, the raw materials with a particle size of +80 mesh need to be returned to grinding, the raw materials with a particle size of -200 mesh can be directly used as industrial building materials, and the raw materials with a particle size of -80 to +200 mesh enter the next stage for one-stage magnetic separation and two-stage magnetic separation. After magnetic separation, mica preferential flotation rougher operation, mica preferential flotation scavenging operation, feldspar preferential flotation rougher operation, feldspar preferential flotation scavenging one operation, feldspar preferential flotation scavenging two operation, cleaning, directional Ca flotation for impurity removal rougher operation, directional Ca flotation cleaning operation, primary acid leaching, calcination and water quenching, and secondary acid leaching are carried out, and finally high-purity quartz sand products are obtained. In this process, mica concentrate can be obtained in the mica preferential flotation stage, feldspar concentrate can be obtained in the feldspar preferential flotation stage, and quartz middlings can be obtained in the directional Ca flotation stage.

[0031] The present invention uses "cationic collector + anionic collector + anionic collector" to finely separate quartz and gangue minerals, and the design steps include: 1. Crushing, grinding and classification operation; 2. High-gradient magnetic separation operation; 3. Mica preferential flotation operation; 4. Feldspar preferential flotation operation; 5. Directional Ca impurity removal operation; 6. High-temperature oscillating acid leaching operation; 7. Calcination and water quenching operation; 8. Secondary high-temperature oscillating acid leaching operation.

[0032] Further, the process is as follows: First, the albite-type high-purity quartz raw materials are respectively subjected to coarse crushing and fine crushing operations and then enter the ball mill for grinding operations. Then, screening and classification operations are carried out by an 80-200 mesh double-deck vibrating screen. The product with a particle size of +80 mesh is returned to the ball mill for grinding operations, the product with a particle size of -200 mesh is stockpiled, and the qualified particle size product with a particle size of -80 to +200 mesh enters the two-stage high-gradient magnetic separator for magnetic separation operations. The magnetic separation concentrate enters the subsequent flotation operations.

[0033] The flotation process adopts an overall flotation process flow that couples the "mica and feldspar preferential flotation + directional Ca impurity removal flotation" process. The mica preferential flotation adopts a one-rough-one-scavenge process, the feldspar preferential flotation adopts a one-rough-two-scavenge process, and the directional Ca impurity removal flotation process adopts a one-rough-one-scavenge process.

[0034] For the qualified particle size of -80 to +200 mesh materials, a mica preferential flotation process is carried out using an acidic regulator, a cationic collector NY-1, and an inhibitor UP-1. For the obtained quartz concentrate, a feldspar preferential flotation process is carried out using an acidic regulator, a feldspar surface activator HF (hydrofluoric acid), a cationic collector NY-1, and an anionic collector NY-2. For the obtained quartz concentrate, an alkaline regulator, an anionic collector NY-3, and an inhibitor UP-2 are added, and a quartz concentrate is obtained through a one-roughing and one-scavenging directional Ca flotation removal process. Then, through high-temperature oscillating acid leaching operation, calcination and water quenching operation, and secondary high-temperature oscillating acid leaching operation, SiO 2 high-purity quartz sand products with a SiO purity ≥ 99.998% and a Ca element content ≤ 0.8 ppm can be obtained.

[0035] Specifically, the fine separation method of the leucogranite-type high-purity quartz raw material in this exemplary embodiment may include the following steps:

[0036] S1. The leucogranite-type high-purity quartz raw material is crushed, ground, and classified to obtain raw material sand with a particle size of -80 to +200 mesh.

[0037] Specifically, the leucogranite-type high-purity quartz raw material first undergoes a crushing and grinding operation. The leucogranite-type high-purity quartz raw material is used as the raw ore and is coarsely crushed and finely crushed to 1 - 2 mm, and then through grinding and classification, three groups of materials with a particle size of +80 mesh, -80 to +200 mesh, and -200 mesh are obtained. Then, through screening and classification operations, qualified particle size high-purity quartz raw material sand with a particle size of -80 to +200 mesh can be obtained.

[0038] S2. The raw material sand is subjected to two-stage high-gradient magnetic separation operations to obtain high-purity quartz rough sand and iron-containing magnetic substances.

[0039] Specifically, the high-purity quartz raw material sand with a particle size of -80 to +200 mesh is subjected to two-stage high-gradient magnetic separation for iron removal to obtain high-purity quartz rough sand with a qualified particle size of -80 to +200 mesh and iron-containing magnetic substances. The two-stage high-gradient magnetic separation operations may include: two-stage magnetic separation. Among them, the magnetic field intensity of the first stage can be 1.2 - 1.5 T, and the magnetic field intensity of the second stage is 1.7 - 2.0 T. The magnetic substances obtained in the two stages are mixed to obtain the iron-containing magnetic substances obtained in S2.

[0040] S3. The high-purity quartz rough sand is subjected to a mica preferential flotation operation to obtain quartz rough concentrate and mica concentrate.

[0041] Specifically, the mica preferential flotation operation may include: a mica preferential flotation rougher operation and a mica preferential flotation scavenger operation carried out in sequence.

[0042] S301. Mica preferential flotation rougher operation.

[0043] The high-purity quartz sand is slurried, the pH is adjusted to 3-4, a silicate inhibitor UP-1 and an amine cationic collector NY-1 are added to obtain a first quartz rough concentrate and a first mica concentrate.

[0044] S302. Mica preferential flotation scavenging operation.

[0045] The first quartz rough concentrate is slurried, the pH is adjusted to 3-4, and an amine cationic collector NY-1 is added to obtain a second quartz rough concentrate and a second mica concentrate.

[0046] The sum / mix of the first mica concentrate and the second mica concentrate obtained in the process of steps S301-S302 is the mica concentrate obtained in S3.

[0047] S4. Perform a feldspar preferential flotation operation on the quartz rough concentrate to obtain a first quartz concentrate and a feldspar concentrate.

[0048] Specifically, the feldspar preferential flotation operation may include: a feldspar preferential flotation rougher operation, a first feldspar preferential flotation scavenging operation, and a second feldspar preferential flotation scavenging operation performed in sequence.

[0049] S401. Feldspar preferential flotation rougher operation.

[0050] The quartz rough concentrate obtained from the mica preferential flotation operation (the second quartz rough concentrate obtained in step S302) is slurried, the pH is adjusted to 2-3, an activator HF, an amine cationic collector NY-1, and an anionic collector NY-2 are added to obtain a third quartz rough concentrate and a first feldspar concentrate.

[0051] S402. First feldspar preferential flotation scavenging operation.

[0052] The third quartz rough concentrate is slurried, the pH is adjusted to 2-3, an activator HF, an amine cationic collector NY-1, and an anionic collector NY-2 are added to obtain a fourth quartz rough concentrate and a second feldspar concentrate.

[0053] S403. Second feldspar preferential flotation scavenging operation.

[0054] The fourth quartz rough concentrate is slurried, the pH is adjusted to 2-3, and an amine cationic collector NY-1 is added to obtain a first quartz concentrate and a third feldspar concentrate.

[0055] The sum / mix of the first feldspar concentrate, the second feldspar concentrate, and the third feldspar concentrate obtained in the process of steps S401-S403 is the feldspar concentrate obtained in S4.

[0056] S5. Perform a directional Ca flotation operation on the first quartz concentrate to obtain a second quartz concentrate and a quartz middling.

[0057] Specifically, the directional Ca flotation operation may include: a directional Ca flotation impurity removal rougher operation and a directional Ca flotation cleaner operation carried out in sequence.

[0058] S501. Directional Ca flotation impurity removal rougher operation.

[0059] The first quartz concentrate obtained from the feldspar preferential flotation operation is washed to a neutral pH, then subjected to pulp adjustment, with the pH adjusted to 10 - 11, and a silicate inhibitor UP-2 and a fatty acid anionic collector NY-3 are added to obtain a fifth quartz rough concentrate and a first quartz middling.

[0060] S502. Directional Ca flotation cleaner operation.

[0061] The fifth quartz rough concentrate is subjected to pulp adjustment, with the pH adjusted to 10 - 11, and a fatty acid anionic collector NY-3 is added to obtain a second quartz concentrate and a second quartz middling.

[0062] The sum / mix of the first quartz middling and the second quartz middling obtained during the processes of steps S501 - S502 is the quartz middling obtained in S5.

[0063] S6. The second quartz concentrate is successively subjected to a first oscillating acid leaching operation, a calcination and water quenching operation, and a second oscillating acid leaching operation to obtain high-purity quartz.

[0064] In this exemplary embodiment, the silicate inhibitor UP-1 may include sodium silicate; the silicate inhibitor UP-2 may include sodium fluorosilicate; the amine cationic collector NY-1 may include one of dodecylamine, octadecylamine, and propylenediamine; the anionic collector NY-2 is a fatty acid collector and a sulfonate collector, including one of oleic acid, sodium oleate, sodium petroleum sulfonate, and sodium dodecylbenzenesulfonate; the fatty acid anionic collector NY-3 includes one of sodium oleate and long carbon chain carboxyl modified oxidized paraffin soap. In the present invention, the mass fractions of the solutions of UP-1, UP-2, NY-1, NY-2, and NY-3 can all be 1 - 10%.

[0065] In this exemplary embodiment, in step S1, the crushing equipment used can be divided into a coarse crushing and a fine crushing operation. The equipment for the coarse crushing operation can be a jaw crusher, and the equipment for the fine crushing operation can be a pair-roll crusher. The particle sizes for screening and classification are 80 and 200 mesh.

[0066] In this exemplary embodiment, in step S3, during the preferential flotation operation of mica, the flotation equipment used can be an XFD type flotation machine with a volume of 1.5 - 3 L and a rotational speed of 1800 - 2000 r / min. The pH is adjusted using an acidic pH adjuster, which can include at least one of sulfuric acid, hydrochloric acid, and nitric acid, and the mass fraction can be 5 - 10%. The flotation scraping time can be controlled within 5 - 10 min, and the air inflow can be controlled within 0.2 - 0.4 m 3 / h.

[0067] In this exemplary embodiment, step S301 can specifically include: slurrying the qualified particle size raw sand obtained in S2 at a solid-liquid ratio of 20% - 40% concentration, then adding an acidic pH adjuster to adjust the pH of the pulp to between 3 and 4, adding UP-1 and NY-1 respectively, and conducting the rough flotation operation of mica preferential flotation to obtain the first quartz rough concentrate and the first mica concentrate products.

[0068] In step S301, the dosage of the inhibitor UP-1 can be 150 - 300 g / t; the dosage of the collector NY-1 can be 100 - 200 g / t; the time interval between each reagent is controlled within 2 - 5 min. The flotation scraping time can be controlled within 5 - 10 min, and the air inflow can be controlled within 0.2 - 0.4 m 3 / h.

[0069] In this exemplary embodiment, step S302 can specifically include: adding the first quartz rough concentrate obtained in S301 to pure water for re-slurrying, then adding an acidic pH adjuster to continue adjusting the pH of the pulp to between 3 and 4, adding NY-1, and conducting the scavenging flotation operation of mica preferential flotation to obtain the second quartz rough concentrate and the second mica concentrate products.

[0070] In step S302, the dosage of the collector NY-1 can be controlled within 50 - 100 g / t, and the time interval between each reagent is controlled within 2 - 5 min. The flotation scraping time can be controlled within 5 - 10 min, and the air inflow can be controlled within 0.2 - 0.4 m 3 / h.

[0071] During the process of steps S301 - S302, the first mica concentrate product and the second mica concentrate product are mixed to obtain the mica concentrate product.

[0072] In this exemplary embodiment, in step S4, during the preferential flotation operation of feldspar, the flotation equipment used can be an XFD type flotation machine with a volume of 1.5 - 3 L, and the rotational speed is controlled within 1800 - 2000 r / min. The pH is adjusted using an acidic pH adjuster, which can include at least one of sulfuric acid, hydrochloric acid, and nitric acid, and the mass fraction can be 5 - 10%. The flotation scraping time is controlled within 5 - 10 min, and the air inflow is controlled within 0.2 - 0.4 m 3 / h.

[0073] In this exemplary embodiment, step S401 may specifically include: adding the second quartz rough concentrate product obtained in S3 to pure water for re-slurrying, adding an acidic pH adjuster to adjust the pH of the pulp to between 2 and 3, adding HF, NY-1, and NY-2 respectively, and performing a rough flotation operation for preferential flotation of feldspar to obtain a third quartz rough concentrate and a first feldspar concentrate product.

[0074] In step S401, the feldspar activator may be hydrofluoric acid with a mass fraction of 10-20%, and the dosage is controlled at 800-2000 g / t; the dosage of collector NY-1 is controlled at 150-300 g / t; the dosage of collector NY-2 is controlled at 50-150 g / t; the interval time between each reagent is controlled at 2-5 min. The flotation scraping time is controlled at 5-10 min, and the aeration volume is controlled at 0.2-0.4 m 3 / h.

[0075] In this exemplary embodiment, step S402 may specifically include: adding the third quartz rough concentrate obtained in S401 to pure water for continuous re-slurrying, adding an acidic pH adjuster to adjust the pH of the pulp to between 2 and 3, adding HF, NY-1, and NY-2 respectively, and performing a first scavenging operation for preferential flotation of feldspar to obtain a fourth quartz rough concentrate and a second feldspar concentrate product.

[0076] In step S402, the dosage of the activator used is controlled at 500-1500 g / t; the dosage of collector NY-1 is controlled at 150-300 g / t; the dosage of collector NY-2 is controlled at 50-150 g / t; the interval time between each reagent is controlled at 2-5 min. The flotation scraping time is controlled at 5-10 min, and the aeration volume is controlled at 0.2-0.4 m 3 / h.

[0077] In this exemplary embodiment, step S403 may specifically include: adding the fourth quartz rough concentrate obtained in S402 to pure water for re-slurrying, adding an acidic pH adjuster to adjust the pH of the pulp to between 2 and 3, adding NY-1, and performing a second scavenging operation for preferential flotation of feldspar to obtain a first quartz concentrate and a third feldspar concentrate product.

[0078] In step S403, the dosage of collector NY-1 used is controlled at 75-150 g / t; the interval time between reagents is controlled at 2-5 min. The flotation scraping time is controlled at 5-10 min, and the aeration volume is controlled at 0.2-0.4 m 3 / h.

[0079] During steps S401-S403, the first feldspar concentrate product, the second feldspar concentrate product, and the third feldspar concentrate product are mixed to obtain a feldspar concentrate product.

[0080] In this exemplary embodiment, in step S5, during the directional Ca flotation operation, the flotation equipment used can be an XFD type flotation machine with a volume of 0.75 - 1.5 L and a rotational speed controlled at 1800 - 2000 r / min. The pH is adjusted using an alkaline pH adjuster, and the alkaline pH adjuster includes at least one of NaOH and Na 2 CO 3 solution, with a mass fraction of 10 - 20%. The flotation froth scraping time is controlled at 5 - 10 min, and the air inflow rate is controlled at 0.2 - 0.4 m 3 / h.

[0081] In this exemplary embodiment, step S501 may specifically include: washing the first quartz concentrate product obtained in S4 with pure water and alcohol until the pH is neutral, then adding pure water to re-slurry to a concentration of 20 - 30%, adding an alkaline pH adjuster to adjust the pulp pH to between 10 and 11, and then adding UP-2 and NY-3 respectively to conduct a directional Ca flotation roughing operation to obtain a fifth quartz rough concentrate and a first quartz middling.

[0082] In step S501, the dosage of the inhibitor UP-2 is controlled at 600 - 1200 g / t; the dosage of the collector NY-3 is controlled at 400 - 800 g / t; the time interval between each reagent is controlled at 2 - 5 min. The flotation froth scraping time is controlled at 5 - 10 min, and the air inflow rate is controlled at 0.1 - 0.3 m 3 / h.

[0083] In this exemplary embodiment, step S502 may specifically include: adding pure water to the fifth quartz rough concentrate obtained in S501 to re-slurry, adding an alkaline pH adjuster to maintain the pulp pH at between 10 and 11, adding NY-3 to conduct a directional Ca flotation cleaning operation to obtain a second quartz concentrate and a second quartz middling.

[0084] In step S502, the dosage of the collector NY-3 is controlled at 200 - 600 g / t; the time interval of the reagent is controlled at 2 - 5 min. The flotation froth scraping time is controlled at 5 - 10 min, and the air inflow rate is controlled at 0.1 - 0.3 m 3 / h.

[0085] During the process of steps S501 - S502, the first quartz middling and the second quartz middling are mixed to obtain a quartz middling product.

[0086] In this exemplary embodiment, step S6 may specifically include: subjecting the second quartz concentrate obtained in S5 to high-temperature reverse oscillation acid leaching to obtain a third quartz concentrate; subjecting the obtained third quartz concentrate to high-temperature calcination and water quenching operations to obtain a fourth quartz concentrate; and subjecting the obtained fourth quartz concentrate to high-temperature reverse oscillation acid leaching again to obtain a fifth quartz concentrate. The finally obtained fifth quartz concentrate is the final high-purity quartz product.

[0087] Further, in step S6, the first oscillation acid leaching operation may include: using a reverse oscillation machine with a rotation speed controlled at 30 - 60 r / min, a temperature controlled at 60 - 100 °C, an acid leaching time controlled at 16 - 24 h, and the leaching agent including at least two of hydrochloric acid, hydrofluoric acid, and nitric acid, with a mass fraction controlled at 10 - 20%.

[0088] The calcination and water quenching operations may include: controlling the calcination temperature at 800 - 1200 °C and the calcination time at 30 - 60 min. Preferably, pure water is used for water quenching.

[0089] The second oscillation acid leaching operation may include: using a reverse oscillation machine with a rotation speed controlled at 30 - 60 r / min, a temperature controlled at 60 - 100 °C, an acid leaching time controlled at 16 - 24 h, and the leaching agent including at least two of hydrochloric acid, hydrofluoric acid, and nitric acid, with a mass fraction controlled at 10 - 20%.

[0090] From Figures 2A to 2B it can be seen that Figure 2A the number of impurity particles in Figure 2B is significantly more than that in Figure 2A , that is, the number of impurity particles in the quartz concentrate obtained by the traditional method process is significantly more than that in the quartz concentrate (fifth quartz concentrate / high-purity quartz) finally obtained by the process flow of the method of the present invention. And Figure 2A shows that red and yellow coloring impurities and gangue mineral mica can be clearly observed under a microscope, and it is clearly visible in the circled area in Figure 2B ; while the particles in

[0091] Exemplary Embodiment 2

[0092] This exemplary embodiment provides a high-purity quartz.

[0093] The high-purity quartz may include the product prepared by the fine separation method of the leucogranite-type high-purity quartz raw material described in the above exemplary embodiment 1.

[0094] The SiO of the high-purity quartz in this exemplary embodiment 2Purity ≥ 99.998% and Ca element content ≤ 0.8 ppm.

[0095] To better understand the above exemplary embodiments of the present invention, the following further illustrates them with specific examples.

[0096] Example 1

[0097] (1) Crushing, grinding, classification and magnetic separation process.

[0098] The high-purity quartz raw ore used comes from the albite ZK-1 in a certain area. 2 kg of the sample is coarsely crushed by a jaw crusher and finely crushed by a pair-roll crusher to less than 2 mm, then enters a ball mill for grinding operation and is classified by an 80- and 200-mesh double-layer vibrating screen to obtain 1 kg of qualified granular quartz raw ore rough sand with a particle size of -80 to +200 mesh.

[0099] (2) The preferential flotation of mica adopts a one-roughing and one-cleaning process.

[0100] The quartz raw ore rough sand is mixed with pure water to adjust the pulp concentration to 30%, and then the preferential flotation operation of mica is carried out using an XFD type 3L single-cell flotation machine. First, an acidic regulator is added to adjust the pulp pH to 3.5. In this experiment, the preferred regulator is hydrochloric acid with a mass fraction of 10%. Then, an inhibitor UP-1 is added, and the dosage of UP-1 is preferably 150 g / t. Then, a cationic collector NY-1 is added. In this case, the preferred cationic collector is dodecylamine, with a dosage of 100 g / t. The interval between the agents is 2 min, the flotation scraping time is 5 min, and the stirring rate is preferably 2000 r / min. After adding pure water to re-adjust the pulp (the solid-liquid ratio can be not considered here, and re-adjust the pulp to the standard liquid level of the flotation cell), an acidic regulator and a cationic collector (dodecylamine) are added respectively for the cleaning operation. The foam product is mica concentrate, and the product in the cell is quartz rough concentrate.

[0101] (3) The preferential flotation of feldspar adopts a one-roughing and two-cleaning process.

[0102] The quartz rough concentrate is added with pure water to re-adjust the pulp. First, an acidic pH regulator is added to adjust the pulp to 2 - 3, then an activator (HF), a cationic collector NY-1, and an anionic collector NY-2 are added. Among them, the acidic regulator is preferably a hydrochloric acid solution with a mass fraction of 10%; the cationic collector NY-1 is preferably a dodecylamine solution with a mass fraction of 10%, with a dosage of 150 g / t; the activator is preferably a hydrofluoric acid solution with a mass fraction of 20%, and the dosage of HF is 1500 g / t (during roughing) and 1000 g / t (during the first cleaning). The dosage of the anionic collector is 50 g / t. The interval between the agents is 2 min, the flotation scraping time is 5 min, and the stirring rate is preferably 2000 r / min, and the one-roughing and two-cleaning process operation of preferential feldspar flotation is carried out.

[0103] The dosages of the cationic collector NY-1 and the anionic collector NY-2 remain unchanged, and other flotation process parameters also remain unchanged (rougher flotation, first scavenger flotation). Only the cationic collector NY-1 is added in the second scavenger flotation, and its dosage is halved to 75 g / t while other process parameters remain unchanged.

[0104] Finally, feldspar concentrate, quartz rough concentrate, and the first quartz concentrate are obtained; the yield of the quartz rough concentrate is approximately 14%.

[0105] (4) The directional Ca removal flotation process adopts a one-roughing and one-scavenging process.

[0106] The flotation quartz rough concentrate obtained in the previous step is repeatedly washed with ultrapure water and alcohol until the pH is neutral, and then the XFD type 0.75L is used for the directional Ca flotation impurity removal process. The pulp concentration is adjusted to 20%, and the alkaline regulator preferably 10% by mass of Na 2 CO 3 solution is added, the pulp pH is 10, the dosage of the inhibitor UP-2 is 600 g / t, and the dosage of the anionic collector NY-3 is 400 g / t (rougher flotation). Other flotation process parameters are the same as those in the preferential flotation. The interval between each reagent during the flotation process is 2 min, the flotation froth scraping time is 5 min, and the stirring rate is 2000 r / min. Only the anionic collector NY-3 is added in the directional Ca flotation impurity removal scavenging process, and its dosage is halved to 200 g / t. Finally, the flotation quartz concentrate is obtained. The rougher tailings and the scavenger tailings are mixed into the quartz flotation middlings. The yield of the flotation quartz concentrate is 75.6%.

[0107] (5) High-temperature oscillating acid leaching operation, calcination and water quenching operation, secondary high-temperature oscillating acid leaching operation.

[0108] The flotation quartz concentrate obtained in the last step of step (4) above is repeatedly washed with pure water and alcohol until the pH is neutral. Weigh 50 g of the flotation quartz concentrate and add it to a high-temperature flipping oscillator for high-temperature flipping oscillating acid leaching operation. The leaching agent used this time is preferably HF:HCl = 1:3, the total mass fraction of the mixed acid is 20%, the leaching temperature is controlled at 80 °C, the flipping speed is 30 r / min, and the acid leaching time is 24 h. After the acid leaching, the quartz concentrate is repeatedly washed with pure water until the pH is neutral to obtain the first acid-leached quartz fine sand.

[0109] Put the quartz fine sand into a quartz boat for high-temperature calcination and water quenching operation. The temperature set in the high-temperature furnace is 1100 °C, the calcination time is 1 h. After the calcination, put the quartz fine sand into pure water for water quenching, and then put it into an oven for drying to obtain the quartz fine sand after the calcination and water quenching operation.

[0110] The calcined and water-quenched quartz concentrate is subjected to a high-temperature flipping and shaking secondary acid leaching operation again. The process parameter conditions are the same as those of the first acid leaching operation. After the acid leaching is completed, it is repeatedly washed with ultrapure water until the pH is neutral and then dried. Subsequently, it can be sent to ICP-OES for testing the impurity element content.

[0111] After this step (5), high-purity quartz can finally be obtained, with its SiO 2 purity ≥ 99.998% and the Ca element content ≤ 0.8 ppm.

[0112] Furthermore, the quartz concentrate (the fifth quartz concentrate / high-purity quartz) obtained under the process flow of the present invention is compared with the quartz concentrate under the traditional flotation and acid leaching process flow. The results are shown in Table 1 below.

[0113] Table 1 Analysis results of ZK-1 high-purity quartz concentrate

[0114]

[0115] It can be seen from Table 1 that the fine separation method of the albite-type high-purity quartz raw material of the present invention can more effectively improve various impurity elements in the concentrate, especially the Ca element. The purity of its concentrate has a relatively obvious improvement compared with the purity of the traditional process.

[0116] In summary, the advantages proposed by the present invention include at least one of the following:

[0117] (1) The fine separation method of the albite-type high-purity quartz raw material of the present invention can effectively collect feldspar, directionally remove the Ca element, and increase the SiO 2 purity.

[0118] (2) Through the fine separation method of the albite-type high-purity quartz raw material of the present invention, high-purity quartz can be obtained. Specifically, the SiO 2 purity ≥ 99.9980%; the Ca element content is low, with the content ≤ 0.8 ppm.

[0119] (3) The present invention combines the three-product preferential flotation operation with the directional flotation operation, and combines cationic and anionic collectors, which not only ensures the high purity of the quartz concentrate obtained by this method, but also ensures the fine separation of feldspar mica and quartz concentrate, effectively solving the problem of a large amount of solid waste generated during the purification process of albite-type high-purity quartz raw materials, which leads to environmental pollution and resource waste. It not only improves the environmental problem, but also increases the enterprise benefits.

[0120] (4) The present invention solves the problem that during the purification process, CaF precipitation is generated in the flotation system and adsorbs on the surfaces and micropores of some quartz particles, resulting in a relatively high CaF grade in the subsequent quartz concentrate product, thus affecting the quality of quartz products. It greatly improves the collecting ability for free metal ions in the solution system during the flotation process and quartz particles adsorbed with CaF, effectively improving the SiO 2 purity of the obtained quartz, enabling the product to have a broader market space and increasing the enterprise's benefits.

[0121] Although the present invention has been described above in conjunction with exemplary embodiments, those skilled in the art should clearly understand that various modifications and changes can be made to the exemplary embodiments of the present invention without departing from the spirit and scope defined by the claims.

Claims

1. A fine separation method for white granite type high-purity quartz raw material, characterized in that: The method comprises: The white granite type high-purity quartz raw material is crushed, ground and classified to obtain -80 to +200 mesh raw sand; The raw sand is subjected to two-stage high-gradient magnetic separation to obtain high-purity quartz rough sand and ferromagnetic materials; The high-purity quartz rough sand is subjected to mica preferential flotation operation to obtain quartz rough concentrate and mica concentrate; The quartz rough concentrate is subjected to feldspar preferential flotation operation to obtain the first quartz concentrate and the feldspar concentrate; The first quartz concentrate is subjected to directional Ca flotation operation to obtain the second quartz concentrate and quartz middlings; The second quartz concentrate is subjected to a first shock acid leaching operation, a calcination water quenching operation and a second shock acid leaching operation in sequence to obtain high-purity quartz.

2. The fine separation method of white granite type high-purity quartz raw material according to claim 1 is characterized in that: The two-stage high-gradient magnetic separation operation includes: two-stage magnetic separation, wherein the magnetic field strength of the first stage is 1.2-1.5T, and the magnetic field strength of the second stage is 1.7-2.0T, and the magnetic materials obtained in the two stages are mixed to form the ferromagnetic material.

3. The fine separation method of white granite type high-purity quartz raw material according to claim 1 is characterized in that: The mica priority flotation operation includes: mica priority flotation roughing operation and mica priority flotation sweeping operation performed in sequence, wherein: Mica priority flotation roughing operation: high-purity quartz rough sand is slurried with sand, the pH is adjusted to 3-4, silicate inhibitor UP-1 and amine cationic collector NY-1 are added to obtain the first quartz rough concentrate and the first mica concentrate; Mica preferential flotation sweeping operation: the first quartz rough concentrate is slurried, the pH is adjusted to 3-4, and an amine cationic collector NY-1 is added to obtain a second quartz rough concentrate and a second mica concentrate.

4. The fine separation method of white granite type high-purity quartz raw material according to claim 1 is characterized in that: The feldspar priority flotation operation includes: a feldspar priority flotation roughing operation, a feldspar priority flotation scavenging operation 1 and a feldspar priority flotation scavenging operation 2 which are carried out in sequence, wherein: Feldspar priority flotation roughing operation: the quartz rough concentrate obtained from the mica priority flotation operation is slurried, the pH is adjusted to 2-3, and activator HF, amine cationic collector NY-1 and anionic collector NY-2 are added to obtain the third quartz rough concentrate and the first feldspar concentrate; Feldspar preferential flotation scavenging operation 1: the third quartz rough concentrate is slurried, the pH is adjusted to 2-3, and the activator HF, the amine cationic collector NY-1 and the anionic collector NY-2 are added to obtain the fourth quartz rough concentrate and the second feldspar concentrate; The second operation of feldspar preferential flotation scavenging is to slurry the fourth quartz rough concentrate, adjust the pH to 2-3, add amine cationic collector NY-1, and obtain the first quartz concentrate and the third feldspar concentrate.

5. The fine separation method of granite type high-purity quartz raw material according to claim 3 or 4, characterized in that: In the mica preferential flotation operation or the feldspar preferential flotation operation, an acidic pH adjuster is used to adjust the pH, and the acidic pH adjuster includes at least one of sulfuric acid, hydrochloric acid and nitric acid, with a mass fraction of 5-10%.

6. The fine separation method of white granite type high-purity quartz raw material according to claim 1 is characterized in that: The directional Ca flotation operation includes: directional Ca flotation roughing operation and directional Ca flotation cleaning operation carried out in sequence, wherein: Directed Ca flotation and impurity removal roughing operation: The first quartz concentrate obtained from the feldspar priority flotation operation is washed to a neutral pH, and then slurry is adjusted to a pH of 10-11, and silicate inhibitor UP-2 and fatty acid anion collector NY-3 are added to obtain the fifth quartz rough concentrate and the first quartz middlings; Directed Ca flotation and concentration operation: the fifth quartz coarse concentrate is slurried, the pH is adjusted to 10-11, and a fatty acid anion collector NY-3 is added to obtain the second quartz concentrate and the second quartz middlings.

7. The fine separation method of white granite type high-purity quartz raw material according to claim 6, characterized in that: In the directional Ca flotation operation, an alkaline pH adjuster is used to adjust the pH, and the alkaline pH adjuster includes at least one of NaOH and Na2CO3 solution, with a mass fraction of 10-20%.

8. The fine separation method of white granite type high-purity quartz raw material according to claim 1, characterized in that: The first shock acid leaching operation / the second shock acid leaching operation includes: using a reverse shock machine, controlling the speed at 30-60r / min, controlling the temperature at 60-100°C, controlling the acid leaching time at 16-24h, and the leaching agent including at least two of hydrochloric acid, hydrofluoric acid and nitric acid, and the mass fraction is controlled at 10-20%.

9. The fine separation method of white granite type high-purity quartz raw material according to claim 1, characterized in that: The calcination and water quenching operation includes: controlling the calcination temperature at 800-1200° C. and the calcination time at 30-60 min; and using pure water for water quenching.

10. A high purity quartz, characterized in that: The high-purity quartz is prepared by the fine separation method of the granite-type high-purity quartz raw material according to any one of claims 1 to 9; the SiO2 purity of the high-purity quartz is ≥99.998%, and the Ca element content is ≤0.8ppm.

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