CN115321544A - Ultrasonic oscillation-electric adsorption cleaning method and purification process of high-purity quartz sand - Google Patents
Ultrasonic oscillation-electric adsorption cleaning method and purification process of high-purity quartz sand Download PDFInfo
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Abstract
The invention discloses an ultrasonic oscillation-electric adsorption cleaning method and a purification process of high-purity quartz sand. The method uses ultrapure water as a treatment fluid of the high-purity quartz sand, utilizes ultrasonic oscillation to assist in separating metal ions and charged particles on the surface of the quartz sand, and meanwhile adsorbs the metal ions, the charged particles and the like in the solution to the electrodes on two sides through an electro-adsorption technology, so that the purpose of efficiently removing impurities attached to the surface of the high-purity quartz sand is achieved, and the problem that the purity of the quartz sand is difficult to improve due to impurity residues in the existing quartz sand purification process is solved. The high-purity quartz sand purification process provided by the invention utilizes ultrasonic oscillation cleaning and an electro-adsorption technology, can effectively remove metal cations and charged particles remained on the surface of the quartz sand after the flotation and acid leaching processes, and can realize the preparation of 4N8 and 5N high-purity quartz sand by matching with the subsequent high-temperature dehydroxylation and high-temperature chlorination processes.
Description
Technical Field
The invention relates to the technical field of quartz sand treatment, in particular to an ultrasonic oscillation-electric adsorption cleaning method and a purification process for high-purity quartz sand.
Background
High purity silica sand generally refers to high purity SiO in a total amount of impurities of < 50ppm 2 The crystal is a quartz product obtained by taking natural quartz minerals with high purity as raw materials and carrying out a series of physical and chemical purification treatments such as crushing, water quenching, color separation, flotation, acid leaching, alkali leaching, high-temperature dehydroxylation, chlorination and the like, is an important upstream raw material in the industries such as solar photovoltaic, optical fiber communication, semiconductor, microchip, electric light source and the like, and is used in high and new technologyThe technology occupies an important strategic position in the surgical industry.
At present, only a few countries such as the United states, norway, germany and the like master the preparation technology of the high-purity quartz, the research and development of the domestic high-purity quartz is relatively lagged, 4N8 (SiO) 2 > 99.998%) or more, depending on the import.
Therefore, the purification process of the high-purity quartz sand is further optimized, the impurity content in the high-purity quartz sand is reduced, and the method is one of important problems which need to be solved urgently in development of new energy, new materials and other strategic emerging industries.
The existing purification process flow of high-purity quartz sand comprises one or two of acid leaching and alkali leaching processes, namely, acid/alkali solution (such as hydrochloric acid, nitric acid, hydrofluoric acid, sodium hydroxide and the like) is utilized to react with impurity minerals in the quartz sand, and a large amount of OH is introduced in the acid leaching/alkali leaching process - 、NO 3 - Plasma anions, also react to produce a large amount of Al 3+ 、Fe 3+ And finally, repeatedly washing with ultrapure water to remove the residual impurity ions on the surfaces of the reaction liquid and the quartz sand.
The unit cell structure of quartz is a Si — O tetrahedron, the surface of which can be considered to be negatively charged in the general sense: the metal cations, positively charged particles in solution, can coordinate with O in Si-O tetrahedra to form chemical bonds, thereby adsorbing on the surface of the quartz crystal. Finally, residual metal cations and charged particles can be attached to the surface of the quartz sand, so that the purity and the quality of the high-purity quartz sand are reduced, and the metal ions have great influence on the quality and the application of the quartz sand.
The multi-time rinsing mode of ultrapure water only gradually reduces the ion concentration in the aqueous solution, but cannot completely remove impurity ions and charged particles. Meanwhile, the surface of the quartz crystal can adsorb metal ions in a chemical bond forming mode, and some impurities can be remained in the grooves and cracks of the quartz particles. Finally, the residual impurity ions and charged particles adhere to the surface of the silica sand, thereby reducing the purity and quality of the high-purity silica sand.
At present, aiming at the problem of residual impurities such as metal ions after flotation and acid/alkali leaching in the purification process of high-purity quartz sand:
application number of invention patent application with CN 201910383342.9' SiO 2 The purification method of the high-purity quartz sand with the purity of more than or equal to 99.99 percent is provided, the impurities in gaps of quartz particles can be cleaned by utilizing ultrasonic washing, and the method has the advantages of high washing speed and good washing effect. This patent technique rinses quartz sand through ultrasonic oscillation, washes repeatedly than traditional ultrapure water and possesses better clean effect. However, after metal cations and particles with positive charges adsorbed on the surface of quartz are separated under the action of ultrasonic waves, and after the ultrasonic oscillation is turned off, charged ions/particles are adsorbed on the surface of quartz sand particles again under the action of negative charges on the surface of quartz sand, so that the technical scheme mainly aims at cations and anions dissociated in the treatment fluid and cannot achieve a good effect on impurity ions/particles adsorbed on the surface of quartz sand.
The invention patent application No. CN202210197454.7 provides a method and a device for purifying high-purity quartz sand, the method comprises soaking high-purity quartz sand in silica sol, and using nanometer SiO 2 The microparticles adsorb various micro impurities, molecules, ions in the solution. The nano SiO is enabled to be applied to the alternating current power supply at two sides of the water tank 2 The particles move back and forth to remove impurities in the high-purity quartz sand and finally separate the nano SiO 2 And mixing with high-purity quartz to obtain the high-purity quartz product. The patented technology has more defects in practical application, on one hand, the particle diameter of high-purity quartz sand is usually dozens to hundreds of microns, and SiO in silica sol 2 The particles are nano-sized, and the mixed solution can be obviously layered due to the great difference of the particle sizes; on the other hand, silica sol is metastable phase, nano SiO 2 The particles always have the tendency of spontaneous aggregation, the stability of the sol system highly depends on the conditions of Zeta potential, brownian motion and solvent obstruction, and the electrodes applied on two sides of the water tank and the contact with quartz sand can quickly destroy the stable system of the silica sol, so that the nano SiO 2 The particles are gathered and deposited on the bottom of the water tank and the surface of the quartz sand, which causes the technical proposal that the nano SiO is repeatedly moved in the gaps of the high-purity quartz particles 2 The particle removal of the residual impurities on the surface of the quartz sand is difficult to realize, the separation of the particle and the quartz sand is difficult, and new impurities are introduced into the high-purity quartz sand more easily through silica sol.
Disclosure of Invention
Aiming at the technical problems and the defects existing in the field, the invention provides an ultrasonic oscillation-electric adsorption cleaning method for high-purity quartz sand, which uses ultrapure water as a treatment fluid for the high-purity quartz sand, and utilizes ultrasonic oscillation to assist in separating metal ions and charged particles on the surface of the quartz sand, and simultaneously adsorbs the metal ions, the charged particles and the like in the solution to electrodes on two sides through an electric adsorption technology, thereby realizing the purpose of efficiently removing impurities attached to the surface of the high-purity quartz sand, and solving the problem that the purity of the quartz sand is difficult to improve due to impurity residues in the existing quartz sand purification process.
An ultrasonic oscillation-electric adsorption cleaning method of high-purity quartz sand adopts an ultrasonic oscillation-electric adsorption cleaning device, the ultrasonic oscillation-electric adsorption cleaning device comprises a reaction container and an ultrasonic generator, the interior of the reaction container is divided into a quartz sand area in the middle and polar plate areas on two sides through a filter screen, the ultrasonic generator can generate ultrasonic oscillation in the quartz sand area, and a negative plate and a positive plate which are externally connected with a direct-current power supply are respectively arranged in the polar plate areas on the two sides;
the ultrasonic oscillation-electric adsorption cleaning method comprises the following steps:
electronic-grade ultrapure water and quartz sand to be cleaned are put into a quartz sand area of the reaction container to be cleaned, ultrasonic oscillation is started, impurity ions and charged particles adsorbed on the surface of the quartz sand are separated in an auxiliary mode, and meanwhile direct current is conducted to the cathode plates and the anode plates on the two sides, so that charged impurities are enriched on the cathode plates and the anode plates on the two sides.
The filter screen can prevent quartz sand from entering the polar plate areas on two sides from the quartz sand area.
According to the invention, the quartz sand and impurities adsorbed on the surface of the quartz sand are separated by using ultrasonic oscillation assistance, and free impurity ions and charged particles adsorbed on the surface of the quartz sand in the solution are adsorbed on the electrodes on two sides by using an electric adsorption technology, so that the purity and quality of the high-purity quartz can be effectively improved on the basis of not introducing any new impurities.
In a preferred embodiment, in the ultrasonic oscillation-electric adsorption cleaning method, the frequency of the ultrasonic oscillation is 15 to 100kHz.
In a preferred example, in the ultrasonic oscillation-electric adsorption cleaning method, the direct current voltage of the cathode plate and the anode plate is 50-500V in the ultrasonic oscillation-electric adsorption cleaning process.
In a preferred example, the ultrasonic oscillation-electric adsorption cleaning method comprises the steps of carrying out ultrasonic oscillation-electric adsorption cleaning for multiple times, wherein the duration of each time is 10-120 min, carrying out dehydration treatment on quartz sand after each time, simultaneously transferring a negative plate and an anode plate into another container filled with ultrapure water, carrying out reverse electrification for desorption, and repeatedly using the cleaned negative plate and anode plate for ultrasonic oscillation-electric adsorption cleaning.
The invention also provides the application of the ultrasonic oscillation-electric adsorption cleaning method or the ultrasonic oscillation-electric adsorption cleaning device in the purification of high-purity quartz sand.
As a general inventive concept, the present invention also provides a purification process of high purity quartz sand, comprising the steps of:
s1, water quenching;
s2, crushing and grinding;
s3, magnetic separation;
s4, flotation;
s5, acid leaching;
s6, adopting the ultrasonic oscillation-electric adsorption cleaning method;
s7, removing hydroxyl;
s8, chlorination at high temperature.
In a preferred embodiment, the purification process further comprises a color separation process before the water quenching in step S1, to remove colored mineral impurities in the quartz ore with a particle size of less than 5 cm.
In a preferred embodiment, the step S1 of the purification process of high-purity quartz sand specifically includes: heating quartz ore, quickly adding into tap water for water quenching, cooling to below 100 deg.C, taking out, filtering, dewatering, and oven drying. Wherein, the heating temperature of the quartz ore is preferably 600-1200 ℃, the heating time is preferably 1-6 h, the drying temperature is preferably 80-140 ℃, and the drying time is preferably 0.5-4 h.
In a preferred embodiment, the step S2 of the purification process of high-purity quartz sand specifically includes: and (3) crushing the quartz raw material obtained in the step (S1) into a coarse material, and then carrying out dry ball milling to obtain a fine material. The particle size of the coarse material is preferably less than 3mm. The particle size of the fines is preferably less than 300 μm;
in a preferred embodiment, in the purification process of the high-purity quartz sand, the magnetic field strength adopted in the magnetic separation in the step S3 is 0.8-2.0T.
In a preferred embodiment, in the purification process of high-purity quartz sand, step S4 employs multi-stage flotation, the alkaline solution in the pH regulator used in the flotation is KOH and/or NaOH, and the acidic solution is at least one of sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, and oxalic acid.
In a preferred embodiment, in the purification process of high-purity quartz sand, in the step S5, the acid used for acid leaching is at least one of sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid and oxalic acid. The acid leaching temperature is preferably 60-100 ℃, and the acid leaching time is preferably 2-8 h.
In a preferred embodiment, the purification process of the high-purity quartz sand comprises the step S7 of removing hydroxyl at the high temperature of 900-1600 ℃ and the temperature of 2.0 multiplied by 10 -6 ～1.0×10 -5 Pa high vacuum condition. The heat preservation time is preferably 1-5 h;
in a preferred embodiment, in the purification process of the high-purity quartz sand, the temperature of the high-temperature chlorination in the step S8 is 1400-1650 ℃, the time is 0.5-8.0 h, and the introduced chlorination gas is Cl 2 And/or HCl.
The high-purity quartz sand purification process provided by the invention utilizes ultrasonic oscillation cleaning and an electro-adsorption technology, can effectively remove metal cations and charged particles remained on the surface of the quartz sand after the flotation and acid leaching processes, and can realize the preparation of 4N8 and 5N high-purity quartz sand by matching with the subsequent high-temperature dehydroxylation and high-temperature chlorination processes.
Compared with the prior artCompared with the prior art, the method uses ultrapure water as the treatment fluid and uses ultrasonic oscillation to separate impurities, so that no new impurities are introduced, the problem of separation of high-purity quartz and other media is solved, the impurities attached to the surface of the high-purity quartz sand can be effectively removed, and finally SiO can be obtained 2 The purity reaches 5N (SiO) 2 More than 99.999%) of high-purity quartz sand product.
Drawings
FIG. 1 is a schematic structural diagram of an ultrasonic oscillation-electric adsorption cleaning device according to the present invention;
in the figure: 1-cathode plate, 2-anode plate, 5-reaction container, 6, 7-filter screen, 8-ultrasonic generator, 9-electronic grade ultrapure water and 10-quartz sand.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
As shown in fig. 1, the ultrasonic oscillation-electric adsorption cleaning device of the present invention includes a reaction container 5 and an ultrasonic generator 8, the interior of the reaction container 5 is divided into a quartz sand area located in the middle and polar plate areas on two sides by filter screens 6 and 7, the ultrasonic generator 8 can generate ultrasonic oscillation in the quartz sand area, and the polar plate areas on two sides are respectively provided with a cathode plate 1 and an anode plate 2 externally connected with a dc power supply.
In a particular embodiment, the ultrasonic generator 8 may be an ultrasonic probe.
Example 1
The operation of the present invention is illustrated by the purification of gangue quartz ore from Madagasca.
1) And (4) color selection, namely preliminarily crushing the quartz ore in a mine and a factory, and preliminarily removing colored mineral impurities in the quartz ore by successively manually selecting and mechanically color selecting the quartz ore with the particle size of less than 5 cm.
2) Water quenching, namely putting the quartz ore obtained in the step 1) into a high-temperature box type furnace, heating to 900 ℃, keeping the temperature for 1h, taking out, quickly putting the quartz ore into a tank filled with tap water for water quenching, taking out the quartz ore after cooling to below 100 ℃, filtering, dehydrating, then putting into a blast drying oven, and drying for 4h at the temperature of 105 +/-2 ℃.
3) Crushing and grinding, namely crushing the quartz raw material which is dried after water quenching in the step 2) by using a jaw crusher to obtain a coarse material with the particle size of less than 1.5 mm; and (3) carrying out dry grinding by using a planetary ball mill and zirconia ball stone, and screening quartz sand with the particle size of less than 300 mu m for further purification.
4) And (4) magnetic separation, namely performing magnetic separation on the quartz sand obtained in the step 3) for three times by using a magnetic separator, wherein the magnetic field intensity is 1.4T.
5) And (5) performing flotation, namely further removing silicate mineral impurities from the quartz sand obtained in the step 4) by utilizing multi-stage flotation. A first stage: adding dodecylamine as a trapping agent into water, and taking second oil as a foaming agent; adding quartz sand accounting for 20 percent of the total mass of water, dodecylamine and second oil, adding NaOH solution and hydrofluoric acid solution as pH regulators, regulating the pH of the solution to 2.0-3.0, removing aluminosilicate impurities such as feldspar and the like through a flotation machine, washing to be neutral, drying, and repeating for three times; and a second stage: naOH and hydrochloric acid are used as pH regulators to regulate the pH of the solution to 2.0-3.0, tetradecyltrimethylammonium chloride is added as a trapping agent, phenethyl ester is used as a foaming agent, aluminosilicate minerals such as kaolinite, mica and the like are removed through a flotation machine, and the steps of washing the aluminosilicate minerals to be neutral, drying the aluminosilicate minerals and repeating the steps for three times.
6) Acid leaching, namely performing acid leaching treatment on the quartz sand obtained in the step 5), and using HCl with the concentration of 20% and H with the concentration of 20% 2 SO 4 And HF with a concentration of 10%, pouring quartz into a container (made of tetrafluoroethylene) containing the acid solution, and performing acid leaching at 85 deg.C for 5 h.
7) Ultrasonic oscillation-electric adsorption, namely putting the quartz sand obtained in the step 6) into an ultrasonic oscillation-electric adsorption cleaning device shown in the structure of the figure 1, firstly cleaning the quartz sand for multiple times by using tap water until the pH value of the detection solution is neutral, and then performing dehydration treatment. And then cleaning the quartz sand by using electronic grade ultrapure water, starting ultrasonic oscillation (25 kHz) during the cleaning process, assisting in separating impurity ions and charged particles adsorbed on the surface of the quartz sand, and electrifying the electrodes on two sides (250V direct current voltage) to enrich the charged impurities on the electrode plates on the two sides. After the electric adsorption process is carried out for 30min, the electrode plate is moved to another container filled with the ultrapure water solution, reverse electrification is carried out to carry out desorption, the electrode plate is cleaned, and meanwhile, dehydration treatment is carried out on the quartz sand. The above process using washing-dewatering was repeated three times.
8) Dehydroxylating, transferring the quartz sand obtained in step 7) to a high temperature high vacuum furnace at 1600 deg.C and 7.0 × 10 -6 Keeping the temperature for 4 hours under the condition of Pa vacuum degree for high-temperature dehydroxylation treatment.
9) High-temperature chlorination, namely putting the quartz sand obtained in the step 8) into high-temperature chlorination equipment, and introducing Cl at 1550 DEG C 2 Gas, chlorination treatment was performed for 3 hours.
Example 2
Example 2 is intended to illustrate the purification process of high purity quartz in the present invention, and the raw materials and purification processes and equipment used are substantially the same as those in example 1, and example 2 is different from example 1 in that: in the purification step (7) of example 2, the washing process did not employ electro-adsorption technology for assisted impurity removal.
The specific step 7) of example 2 is: putting the quartz sand obtained in the step 6) into an ultrasonic oscillation-electric adsorption cleaning device shown in a structure of figure 1, firstly cleaning the quartz sand for multiple times by using tap water until the pH value of the detection solution is neutral, and then carrying out dehydration treatment. And then cleaning the quartz sand by using electronic grade ultrapure water, and starting ultrasonic oscillation (25 kHz) during the cleaning process to assist in separating impurity ions and charged particles adsorbed on the surface of the quartz sand. And after 30min, dehydrating the quartz sand. The above cleaning-dehydration process using ultrapure water was repeated three times.
The impurity contents of the quartz sand in examples 1 and 2 were measured using an inductively coupled plasma atomic emission mass spectrometer (ICP-MS), and the results of the measurements are shown in table 1 for SiO of examples 1 and 2 2 The contents are respectively 99.9992% and 99.9981%.
Table 1 impurity content (ppm) of high purity silica sand products in example 1 and example 2
| Al | Ca | K | Mg | P | Fe | Na | Cr | Ti | |
| Example 1 | 4.053 | 1.033 | 0.899 | 0.766 | 0.564 | 0.229 | 0.254 | 0.177 | 0.152 |
| |
8.343 | 4.302 | 1.247 | 1.357 | 0.847 | 0.774 | 0.798 | 0.263 | 0.324 |
| Mn | Ni | Zr | Cu | B | Ge | Li | Ga | ||
| Example 1 | 0.123 | 0.063 | 0.041 | 0.034 | 0.053 | 0.005 | 0.003 | 0.001 | |
| Example 2 | 0.349 | 0.071 | 0.287 | 0.052 | 0.067 | 0.004 | 0.017 | 0.003 |
Example 3
The process of the invention is illustrated by the purification of vein quartz ore from andela, india.
1) And (4) color selection, namely preliminarily crushing the quartz ore in a mine and a factory, and preliminarily removing colored mineral impurities in the quartz ore by successively manually selecting and mechanically color selecting the quartz ore with the particle size of less than 5 cm.
2) Water quenching, namely putting the quartz ore obtained in the step 1) into a high-temperature box type furnace, heating to 900 ℃, keeping the temperature for 1h, taking out the quartz ore, quickly putting the quartz ore into a tank filled with tap water for water quenching, taking out the quartz ore, filtering, dehydrating after the quartz ore is cooled to be below 100 ℃, then putting the quartz ore into a blast drying oven, and drying for 4h at the temperature of 105 +/-2 ℃.
3) Crushing and grinding, namely crushing the quartz raw material which is subjected to water quenching and drying in the step 2) by using a jaw crusher to obtain a coarse material with the particle size of less than 1.5 mm; and (3) carrying out dry grinding by using a planetary ball mill and zirconia ball stone, and screening quartz sand with the particle size of less than 300 mu m for further purification.
4) And (4) magnetic separation, namely performing magnetic separation on the quartz sand obtained in the step 3) for three times by using a magnetic separator, wherein the magnetic field intensity is 1.4T.
5) And (5) performing flotation, namely further removing silicate mineral impurities from the quartz sand obtained in the step 4) by utilizing multi-stage flotation. A first stage: adding dodecylamine as a trapping agent into water, and taking second oil as a foaming agent; adding quartz sand accounting for 20 percent of the total mass of water, dodecylamine and second oil, adding NaOH solution and hydrofluoric acid solution as pH regulators, regulating the pH of the solution to 2.0-3.0, removing aluminosilicate impurities such as feldspar and the like through a flotation machine, washing to be neutral, drying, and repeating for three times; and a second stage: naOH and hydrochloric acid are used as pH regulators to regulate the pH of the solution to 2.0-3.0, tetradecyltrimethylammonium chloride is added as a trapping agent, phenethyl ester is used as a foaming agent, aluminosilicate minerals such as kaolinite, mica and the like are removed through a flotation machine, and the steps of washing the aluminosilicate minerals to be neutral, drying the aluminosilicate minerals and repeating the steps for three times.
6) Acid leaching, namely performing acid leaching treatment on the quartz sand obtained in the step 5), and using HCl with the concentration of 20% and H with the concentration of 20% 2 SO 4 And 10% HF, and the quartz was poured into a container (tetrafluoroethylene material) containing the acid solution, and acid-dipped at 85 ℃ for 5 hours.
7) Ultrasonic oscillation-electric adsorption, namely putting the quartz sand obtained in the step 6) into an ultrasonic oscillation-electric adsorption cleaning device shown in the structure of figure 1, firstly cleaning the quartz sand for multiple times by using tap water until the pH value of the detection solution is neutral, and then performing dehydration treatment. And then cleaning the quartz sand by using electronic grade ultrapure water, starting ultrasonic oscillation (20 kHz) during the period, assisting in separating impurity ions and charged particles adsorbed on the surface of the quartz sand, and electrifying the electrodes on two sides (380V direct current voltage) to enrich the charged impurities on the electrode plates on the two sides. After the electric adsorption process is carried out for 30min, the electrode plate is moved to another container filled with the ultrapure water solution, reverse electrification is carried out to carry out desorption, the electrode plate is cleaned, and meanwhile, dehydration treatment is carried out on the quartz sand. The above process using washing-dehydration was repeated three times.
8) Dehydroxylating, transferring the quartz sand obtained in step 7 into a high temperature high vacuum furnace at 1550 deg.C and 7.0 × 10 -6 Keeping the temperature for 4h under the condition of Pa vacuum degree for high-temperature dehydroxylation treatment.
9) High-temperature chlorination, namely putting the quartz sand obtained in the step 8 into high-temperature chlorination equipment, and introducing Cl at 1600 DEG C 2 Gas, chlorination treatment was performed for 3 hours.
Example 4
Example 4 is intended to illustrate the purification process of high purity quartz in the present invention, and the raw materials and purification processes and equipment used are substantially the same as those used in example 3, and example 4 differs from example 3 in that: in the purification step 7) of example 4, the washing process did not employ electro-adsorption technology for assisted impurity removal.
The specific step 7) of example 4 is: putting the quartz sand obtained in the step 6) into an ultrasonic oscillation-electric adsorption cleaning device shown in a structure of figure 1, firstly cleaning the quartz sand for multiple times by using tap water until the pH value of the detection solution is neutral, and then dehydrating the quartz sand. And then cleaning the quartz sand by using electronic grade ultrapure water, and starting ultrasonic oscillation (25 kHz) during the cleaning process to assist in separating impurity ions and charged particles adsorbed on the surface of the quartz sand. And dehydrating the quartz sand after 30 min. The above cleaning-dehydration process using ultrapure water was repeated three times. The impurity contents of the quartz sand in examples 3 and 4 were measured using an inductively coupled plasma atomic emission mass spectrometer (ICP-MS), and the results of the measurements are shown in table 2 for SiO of examples 3 and 4 2 The contents were 99.9976% and 99.9953%, respectively.
Table 2 impurity content (ppm) of the high purity silica sand products of example 3 and example 4
| Al | Ca | Fe | Mn | Na | Mg | K | Ti | Cr | |
| Example 1 | 12.920 | 3.089 | 2.088 | 1.850 | 1.232 | 0.358 | 0.783 | 0.354 | 0.434 |
| Example 2 | 21.108 | 11.874 | 2.610 | 2.965 | 1.656 | 1.033 | 2.276 | 0.466 | 0.850 |
| Ni | P | Zr | Cu | Li | B | Ge | Ga | ||
| Example 1 | 0.338 | 0.189 | 0.093 | 0.081 | 0.113 | 0.007 | 0.009 | 0.002 | |
| Example 2 | 0.960 | 0.213 | 0.653 | 0.124 | 0.142 | 0.006 | 0.053 | 0.006 |
According to the ultrasonic oscillation-electric adsorption cleaning method and the purification process, high temperature, high pressure and jet flow in the cavitation process can be utilized in ultrasonic oscillation, metal ions and charged particles adsorbed on the surface of quartz sand and mineral impurities in gaps on the surface of the quartz sand are separated from the quartz sand without dead angles, and meanwhile, the electric adsorption which is started can adsorb the stripped charged impurities such as metal cations and the like onto the electrode plates on two sides, so that the purification of the quartz sand is realized.
In the prior art, silica sol is used as a treatment liquid in the step of cleaning quartz sand, so that impurities adsorbed on the surface of the quartz sand are stripped. The technical scheme takes ultrapure water as treatment liquid, and impurities adsorbed on the surface of the quartz sand are separated by ultrasonic oscillation. Compared with the prior art, the technical scheme has the following advantages:
a) The purity of the quartz sand is better kept, and the ultrapure water does not contain other minerals, so that the purity of the quartz sand is better improved.
b) The process is simpler and more convenient, and the subsequent separation of the high-purity quartz sand and the nano SiO is not required to be considered 2 The process of (1).
c) The process is stable, and no nanometer SiO caused by instability of the system after the electrification of the silica sol exists 2 Deposition problems.
d) The impurity removal effect is more outstanding, the ultrasonic wave can generate cavitation phenomenon when being transmitted in the liquid, and tens of thousands of bubbles can be 1 multiplied by 10 -4 s, the micro jet flow with strong impact force and local high temperature and high pressure (about 5000 ℃, 5000 kPa) can be generated and broken rapidly within the time of the cavitation bubbles, the micro jet flow with strong impact force can be generated at the speed of 110m/s at the moment of collapse of the cavitation bubbles, the cleaning effect on impurities attached to the surfaces or gaps of quartz sand particles is strong, and the cleaning effect is superior to that of the cleaning effect by utilizing nano SiO with negative charges 2 The particles are adsorbed on the surface of the quartz sand by ions.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (9)
1. The ultrasonic oscillation-electric adsorption cleaning method for the high-purity quartz sand is characterized in that an ultrasonic oscillation-electric adsorption cleaning device is adopted, the ultrasonic oscillation-electric adsorption cleaning device comprises a reaction container (5) and an ultrasonic generator (8), the interior of the reaction container (5) is divided into a quartz sand area in the middle and polar plate areas on two sides through filter screens (6 and 7), the ultrasonic generator (8) can generate ultrasonic oscillation in the quartz sand area, and a negative plate (1) and a positive plate (2) which are externally connected with a direct current power supply are respectively arranged in the polar plate areas on the two sides;
the ultrasonic oscillation-electric adsorption cleaning method comprises the following steps:
electronic-grade ultrapure water (9) and quartz sand (10) to be cleaned are put into a quartz sand area of the reaction container (5) to be cleaned, ultrasonic oscillation is started, impurity ions and charged particles adsorbed on the surface of the quartz sand (10) are separated in an auxiliary mode, and meanwhile direct current is conducted to the cathode plate (1) and the anode plate (2) on the two sides, so that the charged impurities are enriched to the cathode plate (1) and the anode plate (2) on the two sides.
2. The ultrasonic oscillation-electro-adsorption cleaning method according to claim 1, wherein the frequency of the ultrasonic oscillation is 15 to 100kHz.
3. The ultrasonic oscillation-electro-adsorption cleaning method according to claim 1, wherein the dc voltage of the cathode plate (1) and the anode plate (2) is 50-500V during the ultrasonic oscillation-electro-adsorption cleaning process.
4. An ultrasonic oscillation-electric adsorption cleaning method according to claim 1 or 3, characterized in that the ultrasonic oscillation-electric adsorption cleaning process is performed for multiple times, the duration of each time is 10-120 min, after each time, the quartz sand (10) is dehydrated, meanwhile, the cathode plate (1) and the anode plate (2) are transferred to another container filled with ultrapure water, the reverse electrification is performed to perform desorption, and the cleaned cathode plate (1) and the cleaned anode plate (2) are repeatedly used for ultrasonic oscillation-electric adsorption cleaning.
5. The utility model provides an ultrasonic wave vibrates-electrosorption belt cleaning device, its characterized in that includes reaction vessel (5) and supersonic generator (8), and reaction vessel (5) is inside to divide through filter screen (6, 7) and to be located the quartz sand district in the middle of and the polar plate district of both sides, and supersonic generator (8) can produce the ultrasonic wave and vibrate in the quartz sand district, be equipped with external DC power supply's negative plate (1) and anode plate (2) in the polar plate district of both sides respectively.
6. The use of the ultrasonic oscillation-electro-adsorption cleaning method according to any one of claims 1 to 4 or the ultrasonic oscillation-electro-adsorption cleaning device according to claim 5 in the purification of high-purity quartz sand.
7. A purification process of high-purity quartz sand is characterized by comprising the following steps:
s1, water quenching;
s2, crushing and grinding;
s3, magnetic separation;
s4, flotation;
s5, acid leaching;
s6, adopting the ultrasonic oscillation-electric adsorption cleaning method of any one of claims 1 to 5;
s7, removing hydroxyl;
s8, chlorination at high temperature.
8. The process of purifying high purity quartz sand according to claim 7, further comprising a color separation process of removing colored mineral impurities in the quartz ore having a particle size of less than 5cm before the water quenching of step S1.
9. The process for purifying high purity silica sand according to claim 7, wherein,
the step S1 specifically includes: heating quartz ore, quickly putting into tap water for water quenching, cooling the quartz ore to below 100 ℃, taking out, filtering, dehydrating and drying; wherein the heating temperature of the quartz ore is 600-1200 ℃, the heating time is 1-6 h, the drying temperature is 80-140 ℃, and the drying time is 0.5-4 h;
the step S2 specifically includes: crushing the quartz raw material obtained in the step S1 into coarse materials, and then carrying out dry ball milling to obtain fine materials; the particle size of the coarse material is less than 3mm; the particle size of the fine material is less than 300 mu m;
s3, the magnetic field intensity adopted by the magnetic separation is 0.8-2.0T;
s4, adopting multi-stage flotation, wherein an alkali solution in a pH regulator adopted by the flotation is KOH and/or NaOH, and an acid solution is at least one of sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid and oxalic acid;
s5, acid adopted for acid leaching is at least one of sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid and oxalic acid, the acid leaching temperature is 60-100 ℃, and the acid leaching time is 2-8 hours;
step S7 dehydroxylation at 900-1600 deg.C and 2.0 × 10 -6 ～1.0×10 -5 The reaction is carried out under the condition of Pa high vacuum, and the heat preservation time is 1-5 h;
the temperature of the high-temperature chlorination in the step S8 is 1400-1650 ℃, the time is 0.5-8.0 h, and the introduced chlorination gas is Cl 2 And/or HCl.
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