CN111874913B - Method for purifying quartz by chloridizing roasting - Google Patents

Method for purifying quartz by chloridizing roasting Download PDF

Info

Publication number
CN111874913B
CN111874913B CN202010721087.7A CN202010721087A CN111874913B CN 111874913 B CN111874913 B CN 111874913B CN 202010721087 A CN202010721087 A CN 202010721087A CN 111874913 B CN111874913 B CN 111874913B
Authority
CN
China
Prior art keywords
quartz
vein
concentrate
solution
leaching
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010721087.7A
Other languages
Chinese (zh)
Other versions
CN111874913A (en
Inventor
李育彪
柯春云
肖蕲航
王志杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan University of Technology WUT
Original Assignee
Wuhan University of Technology WUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan University of Technology WUT filed Critical Wuhan University of Technology WUT
Priority to CN202010721087.7A priority Critical patent/CN111874913B/en
Publication of CN111874913A publication Critical patent/CN111874913A/en
Application granted granted Critical
Publication of CN111874913B publication Critical patent/CN111874913B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a method for purifying quartz by chloridizing roasting, which comprises the following steps: (1) Grinding and magnetically separating the vein quartz raw ore to remove impurities to obtain a nonmagnetic product; (2) Pickling the nonmagnetic product by using a dilute hydrochloric acid solution to obtain vein quartz concentrate; (3) Adding acid into the vein quartz concentrate to adjust the pH value to 2-3, and adding an anion collecting agent and a cation collecting agent into the vein quartz concentrate to perform flotation treatment; (4) Mixing the floated vein quartz concentrate with a chlorinating agent, roasting for 5-9 h at 850-950 ℃, and performing water quenching treatment after roasting is finished; (5) Mixing the chloridized roasted vein quartz concentrate with a leaching solution, and carrying out hot-pressing leaching treatment, wherein the hot-pressing leaching temperature is 240-260 ℃, the time is 2-6 hours, and the leaching solution is a mixed solution of a sulfuric acid solution and an ammonium chloride solution. The method can obtain the quartz sand with higher purity, does not use hydrofluoric acid in the preparation process, and is environment-friendly.

Description

Method for purifying quartz by chloridizing roasting
Technical Field
The invention belongs to the technical field of processing and purifying of nonmetallic minerals, and particularly relates to a method for purifying quartz by chlorination roasting.
Background
Quartz (quartz) of the formula SiO2It is an important non-metallic mineral material, and common quartz sand is commonly used for ceramics, glass products and the like. And high purity quartz (high purity quartz), siO2The content is more than or equal to 99.9 percent, and the quartz glass has excellent thermal property, optical property, electrical property and the like, is a raw material for manufacturing monocrystalline silicon, polycrystalline silicon, quartz glass, optical fibers, solar cells and integrated circuit substrates, is widely applied to the fields of optical fiber communication, aerospace, war industry, electronic technology and the like, and the high-purity quartz material becomes more and more important along with the rapid development of electronic information technology. High-purity quartz sand to SiO2The content is required to be high, and the content of impurity elements (such as Fe, al, K, na and the like) is required to be reduced to a very low level.
The high-purity quartz is mainly prepared from natural quartz, but the quartz resources in China are scarce, and the preparation of the high-purity quartz sand by using low-purity quartz to replace increasingly exhausted quartz resources is gradually a new way. The vein quartz is formed under the action of hydrothermal solution, the structure is compact and blocky, the main component is quartz, the vein quartz reserves in China are rich, and the application prospect of preparing high-purity quartz sand by using the vein quartz as a raw material is wide. The gangue usually contains gangue minerals such as mica, feldspar, calcite and kaolinite, and the impurity elements mainly comprise Mg, al, fe, ca, na, K and other elements. Mai Shi mineral and impurity elements contained in Mai Shi YingNot removed, then SiO2The content can not meet the use requirement, the added value of the product is low, and therefore, the gangue quartz needs to be purified to reduce gangue minerals and impurity elements.
At present, quartz sand is mainly soaked by mixed acid of hydrofluoric acid, hydrochloric acid, hydrofluoric acid, sulfuric acid and the like to purify quartz, but the used mixed acid basically contains hydrofluoric acid, and fluorine element contained in the hydrofluoric acid can cause serious pollution to the environment, so that the method is not in accordance with the environmental protection concept advocated by the current society. Therefore, the method can effectively remove the gangue minerals in the gangue quartz, reduce the content of impurity elements and improve SiO2The content meets the requirement of the industry on high-purity quartz sand, and the preparation method of the high-purity quartz sand, which is environment-friendly and pollution-free, has important economic benefit and practical significance.
Disclosure of Invention
The invention aims to overcome the technical defects and provide a method for purifying quartz by chloridizing roasting, which can effectively reduce the content of impurity elements in the vein quartz to obtain quartz sand with higher purity, does not use hydrofluoric acid in the preparation process, is environment-friendly, and solves the technical problem that the environment is polluted by using hydrofluoric acid in the prior art.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the invention provides a method for purifying quartz by chloridizing roasting, which comprises the following steps:
s1, grinding vein quartz raw ore, and performing magnetic separation and impurity removal to obtain a nonmagnetic product;
s2, pickling the nonmagnetic product by using a dilute hydrochloric acid solution to obtain vein quartz concentrate;
s3, adding acid into the vein quartz concentrate to adjust the pH value to 2-3, adding an anion collecting agent and a cation collecting agent into the vein quartz concentrate to perform flotation treatment, and removing impurities to obtain the vein quartz concentrate after flotation;
s4, mixing the floated vein quartz concentrate with a chlorinating agent, roasting for 5-9 hours at 850-950 ℃, and performing water quenching treatment on the floated vein quartz concentrate after roasting is finished to obtain chloridized roasted vein quartz concentrate;
and S5, mixing the chloridized roasted vein quartz concentrate with a leaching solution, and carrying out hot-pressing leaching treatment, wherein the hot-pressing leaching temperature is 240-260 ℃, the hot-pressing leaching time is 2-6 h, the leaching solution is a mixed solution of a sulfuric acid solution and an ammonium chloride solution, and after the hot-pressing leaching is finished, washing a hot-pressing leaching product to be neutral, filtering and drying to obtain the high-purity quartz sand.
Compared with the prior art, the invention has the beneficial effects that:
1. the method for purifying quartz by chloridizing roasting provided by the invention can remove iron films on the surfaces of magnetic separation impurity minerals and quartz sand by carrying out magnetic separation and acid washing on vein quartz raw ores, preliminarily reduce the impurity content in the vein quartz raw ores, then carry out floatation treatment by using an anion collecting agent and a cation collecting agent under an acidic condition, the anion collecting agent and the cation collecting agent form a synergistic action to increase the adsorption on the surfaces of feldspar and mica and promote the floatation, thereby achieving the separation of the vein quartz minerals and the quartz, removing the feldspar and mica impurity minerals with higher impurity content, then carrying out chloridizing roasting, adding a chloridizing agent, and carrying out different expansion forces due to different thermal expansion coefficients in the roasting process of 850-950 ℃, meanwhile, through water quenching treatment, cracks are generated on the surfaces of the quartz particles, crystal boundaries, gas-liquid inclusion bodies and mineral inclusion bodies under the actions of cold shrinkage force, internal heating expansion force and the like, so that minerals in impurity mineral inclusion bodies are exposed, the contact surface area of subsequent leaching is increased due to the existence of a large number of cracks, the exposed impurity metal elements react with chlorides, the boiling point of the converted chlorides is low, the chlorides are easy to remove in the subsequent leaching treatment, and finally, hot-pressing leaching is performed at 240-260 ℃ through sulfuric acid solution and ammonium chloride solution, si-O bonds can be well destroyed, and silicate minerals such as mica, feldspar and the like in quartz sand are dissolved and removed;
2. the method for purifying quartz by chloridizing roasting provided by the invention uses low SiO2Preparing SiO from vein quartz2The content is more than or equal to 99.9wt% of high-purity quartz sand, and the content of impurity elements in the high-purity quartz sand is low, so that the requirement of the industry on the high-purity quartz sand can be met, a fluorine-containing solvent is not used in the preparation process, the method is environment-friendly and pollution-free, the utilization rate of quartz resources is high, the economic benefit is good, and the method is suitable for industrial popularization and use.
Drawings
FIG. 1 is a flow chart of the process for purifying quartz by chloridizing roasting according to the present invention;
FIG. 2 is an XRD pattern spectrogram of raw gangue quartz ore;
FIG. 3 is a diagram of an inclusion of a raw gangue quartz ore, in which FIG. 3 (a) is a band profile of the inclusion under a view of 50 μm, FIG. 3 (b) is a band profile of the inclusion under a view of 50 μm, FIG. 3 (c) is a band profile of the inclusion under a view of 100 μm, and FIG. 3 (d) is a band profile of the inclusion under a view of 50 μm;
FIG. 4 is a micrograph of a raw vein quartz, FIG. 4 (a) is a surface image of vein quartz particles, FIG. 4 (b) is a distribution image of vein quartz with different particle sizes, FIG. 4 (c) is a diagram of a crystal pith in vein quartz, and FIG. 4 (d) is a diagram of a quartz fine vein formed at a later stage passing through quartz, wherein Q represents quartz and Q represents quartz1Represents muscovite, Q2Representing biotite, H red-brown iron ore and C chalcedony.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
FIG. 1 is a process flow diagram of the chloridizing roasting to purify quartz according to the present invention. As shown in FIG. 1, an embodiment of the present invention provides a method for purifying quartz by chloridizing roasting, the method comprising the steps of:
(1) Grinding and magnetically separating the vein quartz raw ore to remove impurities to obtain a nonmagnetic product;
(2) Pickling the non-magnetic product with dilute hydrochloric acid solution to obtain vein quartz concentrate;
(3) Adding acid into the vein quartz concentrate to adjust the pH value to 2-3, adding an anion collecting agent and a cation collecting agent into the vein quartz concentrate to perform flotation treatment, and removing impurities to obtain the vein quartz concentrate after flotation;
(4) Mixing the floated vein quartz concentrate with a chlorinating agent, roasting at 850-950 ℃ for 5-9 h, and after roasting is finished, performing water quenching treatment on the floated vein quartz concentrate to obtain chloridized roasted vein quartz concentrate;
(5) Mixing the chloridized roasted vein quartz concentrate with the leaching solution, carrying out hot-pressing leaching treatment, wherein the hot-pressing leaching temperature is 240-260 ℃, the hot-pressing leaching time is 2-6 h, the leaching solution is a mixed solution of a sulfuric acid solution and an ammonium chloride solution, and after the hot-pressing leaching is finished, washing a hot-pressing leaching product to be neutral, filtering and drying to obtain the high-purity quartz sand.
In the embodiment of the invention, in the step (1), after the vein quartz raw ore is ground, vein quartz sand with the grain size of 50-140 meshes is prepared.
In the embodiment of the invention, in the step (1), the magnetic field intensity for magnetic separation and impurity removal is 1.0-1.4T, and the pulp flow rate is 0.5-2cm.s-1。
In the example of the present invention, in the step (2), the liquid-solid ratio of the nonmagnetic product to the dilute hydrochloric acid solution was 500g.L-1I.e. 1L of dilute hydrochloric acid solution per 500g of non-magnetic product. In order to better remove the metal film on the surface of the vein quartz sand, in some preferred embodiments of the invention, the mass fraction of the dilute hydrochloric acid is 10%.
In the embodiment of the invention, in the step (2), in order to make the non-magnetic product and the dilute hydrochloric acid solution fully contact to remove the metal film on the surface of the vein quartz sand, the acid washing is carried out under the stirring condition, the stirring rotating speed is 1600-2000 rpm, and the acid washing time is 15-25 min.
In the embodiment of the invention, in the step (2), after the acid washing is finished, the acid washing product is washed by ultrapure water, and after filtration and vacuum drying, vein quartz concentrate is obtained. The temperature and time of vacuum drying can be determined by those skilled in the art according to practical conditions, as long as sufficient drying of the vein quartz concentrate can be ensured, and the present invention is not limited to this.
In the embodiment of the invention, in the step (3), the pH is adjusted to 2 to 3 by using a sulfuric acid solution with a mass fraction of 10%.
In order to achieve a better flotation effect, the anion collector can better perform chemical adsorption and physical adsorption with feldspar and mica, the cation collector can perform association and hydrogen bond adsorption with the feldspar and mica, and the anion collector can have better synergistic effect.
In order to better remove the feldspar and mica minerals with high impurity content, in some preferred embodiments of the invention, in the step (3), the adding amount of the anionic collector is 150-300g.t-1The adding amount of the cation collecting agent is 400-700g.t-1Namely, 150-300 g of anion collecting agent is added into each ton of ore pulp, and 400-700 g of cation collecting agent is added into each ton of ore pulp.
In the embodiment of the invention, in the step (3), after the flotation treatment, the vein quartz concentrate is washed to be neutral by using ultrapure water, and after filtration and vacuum drying, the vein quartz concentrate after flotation is obtained. The temperature and time of vacuum drying can be determined by those skilled in the art according to practical situations, as long as sufficient drying of the vein quartz concentrate can be ensured, and the invention is not further limited to this.
In order to lower the phase transition point of the quartz, change the unit cell parameters of the quartz, form more cracks and facilitate subsequent impurity leaching, in some preferred embodiments of the invention, in step (4), the chlorinating agents are NaCl, KCl and NH4At least one of Cl and the doping amount of the chlorinating agent is 0.02-2 per mill of the mass of the vein quartz concentrate after flotation. More preferably, when the chlorinating agent is NaCl, the doping amount is 0.02 per mill to 0.2 per mill of the mass of the vein quartz concentrate after flotation; when the chlorinating agent is KCl, the doping amount is 0.02-0.2 per mill of the mass of the vein quartz concentrate after flotation; when the chlorinating agent is NH4And Cl, wherein the doping amount of the Cl is 0.2-2 per mill of the mass of the vein quartz concentrate after flotation.
In the embodiment of the invention, in the step (4), after the water quenching treatment, the vein quartz concentrate is washed by ultrapure water, and after filtration and vacuum drying, the chloridized and roasted vein quartz concentrate is obtained. The temperature and time of vacuum drying can be determined by those skilled in the art according to practical conditions, as long as sufficient drying of the vein quartz concentrate can be ensured, and the present invention is not limited to this.
In order to fully dissolve silicate minerals such as mica and feldspar in quartz, in some preferred embodiments of the invention, in the step (5), the liquid-solid ratio of chloridized roasted vein quartz concentrate to leachate is 5mL-1Namely, 5mL of leaching solution is added into each gram of chloridized roasted vein quartz concentrate.
In order to achieve better leaching effect and fully dissolve and remove silicate minerals such as mica and feldspar in quartz, in some preferred embodiments of the invention, in step (5), the concentration of sulfuric acid solution in the leachate is 0.1-0.5 mol.L-1The concentration of ammonium chloride solution is 0.4-0.8 mol.L-1。
In the examples of the present invention, in step (5), siO in high purity silica sand2The content is more than or equal to 99.9wt percent.
In order to further illustrate the present invention, the following examples are given to further illustrate the present invention. The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified; materials, reagents and the like used in examples of the present invention are commercially available unless otherwise specified.
Example 1:
embodiment 1 of the present invention provides a method for purifying quartz by chloridizing roasting, comprising the steps of:
(1) Magnetic separation and impurity removal: grinding and sieving the vein quartz raw ore to prepare vein quartz sand with the particle size of 50-140 meshes, adding the vein quartz sand into a high-gradient magnetic separator, and controlling the flow rate of ore pulp to be 1cm.s-1Carrying out magnetic separation under the condition that the magnetic field intensity is 1.2T to obtain a non-magnetic product;
(2) Acid washing for impurity removal: adding the nonmagnetic product into a dilute HCl solution with the mass fraction of 10 percentAcid washing is carried out in the process, and the solid-to-solid ratio of acid washing liquid is 500g.L-1Acid washing is carried out under the condition of stirring, the stirring speed is 1600rpm, the acid washing is carried out for 25min, after the acid washing is finished, the acid washing product is washed by ultrapure water for 2-3 times, and then the vein quartz concentrate is obtained after filtration and vacuum drying;
(3) Flotation treatment: adding 10 percent of H by mass into vein quartz concentrate2SO4Adjusting pH of the solution to 3, and adding 200g.t into vein quartz concentrate-1Anionic collector sodium dodecyl sulfonate and 600g.t-1Carrying out flotation on cationic collector dodecylamine, stirring, aerating, finally scraping bubbles until no bubbles exist, removing silicate gangue minerals such as feldspar, mica and the like in quartz sand, cleaning, filtering and vacuum-drying gangue quartz concentrate after flotation treatment;
(4) Chloridizing roasting: adding NaCl with the mass fraction of 0.02 per mill into the floated vein quartz concentrate, uniformly mixing, roasting at 900 ℃ for 7 hours, immediately taking out quartz sand after roasting, pouring the quartz sand into ultrapure water for water quenching treatment, and then washing, filtering and vacuum drying the quartz sand by using the ultrapure water;
(5) Hot-pressing leaching: adding the chloridized roasted vein quartz concentrate into a hydrothermal reaction kettle filled with the leaching solution for hot-pressing leaching treatment, wherein the liquid-solid ratio of the chloridized roasted vein quartz concentrate to the leaching solution is 5mL.g-1The leaching solution has a concentration of 0.5mol.L-1And the concentration of the sulfuric acid solution is 0.6mol.L-1Mixed solution of ammonium chloride solution of (4); and (3) carrying out hot-pressing leaching at 250 ℃ for 6h, washing the hot-pressing leaching product to be neutral by using ultrapure water after the hot-pressing leaching is finished, filtering and drying in vacuum to obtain the high-purity quartz sand.
The obtained product is analyzed and tested by ICP-MS, and SiO in quartz sand2The contents and the contents of each impurity element are shown in Table 1.
Example 2:
embodiment 2 of the present invention provides a method for purifying quartz by chloridizing roasting, comprising the steps of:
(1) Magnetic separation and impurity removal: grinding and sieving vein quartz raw ore to prepare the quartz powder with the particle size of 50 to upAdding the vein quartz sand of 140 meshes into a high-gradient magnetic separator, wherein the flow rate of ore pulp is 1cm.s-1Carrying out magnetic separation under the condition that the magnetic field intensity is 1.0T to obtain a non-magnetic product;
(2) Acid washing for impurity removal: adding the nonmagnetic product into a dilute HCl solution with the mass fraction of 10% for acid washing, wherein the solid-to-solid ratio of the acid washing solution is 500g.L-1Acid washing is carried out under the stirring condition, the stirring speed is 2000rpm, the acid washing is carried out for 15min, after the acid washing is finished, the acid washing product is washed by ultrapure water for 2-3 times, and then the vein quartz concentrate is obtained after filtration and vacuum drying;
(3) Flotation treatment: adding 10 percent of H by mass into vein quartz concentrate2SO4The pH of the solution was adjusted to 2.5 and 300g.t was added to the gangue quartz concentrate-1Anionic collector sodium dodecyl sulfonate and 400g.t-1Carrying out flotation on a cationic collecting agent dodecylamine, stirring, inflating, finally scraping bubbles until no bubbles exist, removing silicate gangue minerals such as feldspar, mica and the like in quartz sand, cleaning, filtering and vacuum-drying gangue quartz concentrate after flotation treatment;
(4) Chloridizing and roasting: adding KCl with the mass fraction of 0.02 per thousand into the floated vein quartz concentrate, uniformly mixing, roasting at 900 ℃ for 5 hours, immediately taking out quartz sand after roasting, pouring the quartz sand into ultrapure water for water quenching, washing with the ultrapure water, filtering and vacuum drying;
(5) Hot-pressing leaching: adding the chloridized roasted vein quartz concentrate into a hydrothermal reaction kettle filled with the leaching solution for hot-pressing leaching treatment, wherein the liquid-solid ratio of the chloridized roasted vein quartz concentrate to the leaching solution is 5mL.g-1The leaching solution is 0.5mol.L-1And the concentration of the sulfuric acid solution is 0.6mol.L-1Mixed solution of ammonium chloride solution of (4); and (3) carrying out hot-pressing leaching at 250 ℃ for 6h, washing the hot-pressing leaching product to be neutral by using ultrapure water after the hot-pressing leaching is finished, filtering and drying in vacuum to obtain the high-purity quartz sand.
The obtained product is analyzed and tested by ICP-MS, and SiO in quartz sand2The contents and the contents of the respective impurity elements are shown in Table 1.
Example 3:
embodiment 3 of the present invention provides a method for purifying quartz by chloridizing roasting, comprising the steps of:
(1) Magnetic separation and impurity removal: grinding and sieving the vein quartz raw ore to prepare vein quartz sand with the particle size of 50-140 meshes, adding the vein quartz sand into a high-gradient magnetic separator, and controlling the flow rate of ore pulp to be 0.5cm.s-1Carrying out magnetic separation under the condition that the magnetic field intensity is 1.0T to obtain a non-magnetic product;
(2) Acid washing and impurity removal: adding the nonmagnetic product into a dilute HCl solution with the mass fraction of 10% for acid washing, wherein the solid-to-solid ratio of the acid washing solution is 500g.L-1Acid washing is carried out under the condition of stirring, the stirring speed is 2000rpm, the acid washing is carried out for 15min, after the acid washing is finished, the acid washing product is washed by ultrapure water for 2-3 times, and then the vein quartz concentrate is obtained after filtration and vacuum drying;
(3) Flotation treatment: adding 10% of H by mass into vein quartz concentrate2SO4The pH of the solution was adjusted to 2.5 and 300g.t was added to the gangue quartz concentrate-1Anionic collector sodium dodecyl sulfonate and 400g.t-1Carrying out flotation on a cationic collecting agent dodecylamine, stirring, inflating, finally scraping bubbles until no bubbles exist, removing silicate gangue minerals such as feldspar, mica and the like in quartz sand, cleaning, filtering and vacuum-drying gangue quartz concentrate after flotation treatment;
(4) Chloridizing and roasting: adding KCl with the mass fraction of 0.02 per mill into the floated vein quartz concentrate, uniformly mixing, roasting at 950 ℃ for 5 hours, immediately taking out quartz sand after roasting, pouring the quartz sand into ultrapure water for water quenching treatment, washing with the ultrapure water, filtering, and drying in vacuum;
(5) Hot-pressing leaching: adding the chloridized roasted vein quartz concentrate into a hydrothermal reaction kettle filled with the leaching solution to carry out hot-pressing leaching treatment, wherein the liquid-solid ratio of the chloridized roasted vein quartz concentrate to the leaching solution is 5mL-1The leaching solution has a concentration of 0.5mol.L-1The concentration of the sulfuric acid solution is 0.4mol.L-1Mixed solution of ammonium chloride solution of (4); hot-press leaching at 240 deg.C for 6 hr, and heatingAnd washing the pressure leaching product to be neutral by ultrapure water, filtering and drying in vacuum to obtain the high-purity quartz sand.
The obtained product is analyzed and tested by ICP-MS, and SiO in quartz sand2The contents and the contents of the respective impurity elements are shown in Table 1.
Example 4:
embodiment 4 of the present invention provides a method for purifying quartz by chloridizing roasting, comprising the steps of:
(1) Magnetic separation and impurity removal: grinding and screening raw vein quartz ore to prepare vein quartz sand with the grain diameter of 50-140 meshes, adding the vein quartz sand into a high-gradient magnetic separator, and controlling the flow rate of ore pulp to be 2cm.s-1Carrying out magnetic separation under the condition that the magnetic field intensity is 1.4T to obtain a non-magnetic product;
(2) Acid washing and impurity removal: adding the nonmagnetic product into a dilute HCl solution with the mass fraction of 10% for acid washing, wherein the solid-to-solid ratio of the acid washing solution is 500g.L-1Acid washing is carried out under the stirring condition, the stirring speed is 1800rpm, the acid washing is carried out for 20min, after the acid washing is finished, the acid washing product is washed by ultrapure water for 2-3 times, and then the vein quartz concentrate is obtained after filtration and vacuum drying;
(3) Flotation treatment: adding 10% of H by mass into vein quartz concentrate2SO4Adjusting pH of the solution to 2, and adding 150g.t to the vein quartz concentrate-1Anionic collector sodium dodecyl sulfate and 700g.t-1Carrying out flotation on a cationic collecting agent dodecylamine, stirring, inflating, finally scraping bubbles until no bubbles exist, removing silicate gangue minerals such as feldspar, mica and the like in quartz sand, cleaning, filtering and vacuum-drying gangue quartz concentrate after flotation treatment;
(4) Chloridizing and roasting: adding NH with the mass fraction of 2 per mill into the vein quartz concentrate after flotation4Cl, uniformly mixing, roasting at 850 ℃ for 9h, immediately taking out quartz sand after roasting, pouring the quartz sand into ultrapure water for water quenching treatment, then washing with the ultrapure water, filtering and vacuum drying;
(5) Hot-pressing leaching: adding chloridized roasted vein quartz concentrate into a hydrothermal reaction kettle filled with leaching solution for hot-pressing leachingAnd (4) performing treatment, wherein the liquid-solid ratio of chloridized roasted vein quartz concentrate to leachate is 5mL-1The leaching solution is 0.3mol-1And the concentration of the sulfuric acid solution of (2) is 0.6mol.L-1Mixed solution of ammonium chloride solution of (4); and (3) carrying out hot-pressing leaching at 260 ℃ for 4h, washing the hot-pressing leaching product to be neutral by using ultrapure water after the hot-pressing leaching is finished, filtering and drying in vacuum to obtain the high-purity quartz sand.
The obtained product is analyzed and tested by ICP-MS, and SiO in quartz sand2The contents and the contents of each impurity element are shown in Table 1.
Fig. 2 is an XRD chart of the raw gangue quartz ore, and it can be seen from fig. 2 that the main phase of the raw gangue quartz ore is quartz and also contains other small amounts of other impurities.
FIG. 3 is a diagram showing inclusions of vein quartz raw ore used in examples 1 to 4 of the present invention. FIG. 3 (a) is a distribution diagram showing a band shape of an enclosure under a view of 50 μm, FIG. 3 (b) is a distribution diagram showing a band shape of an enclosure under a view of 50 μm, FIG. 3 (c) is a distribution diagram showing a band shape of an enclosure under a view of 100 μm, and FIG. 3 (d) is a distribution diagram showing a band shape of an enclosure under a view of 50 μm. As can be seen from fig. 3, the gas-liquid inclusions in the mai quartz are distributed in a strip shape or a bead shape, and the number of inclusions is large, which results in increased difficulty in removal.
FIG. 4 is a micrograph of a vein quartz raw ore used in examples 1 to 4 of the present invention, wherein FIG. 4 (a) is a result of observation under a mirror, and the rest is a result of observation under an orthogonal light; FIG. 4 (a) is a surface view of a vein quartz particle, FIG. 4 (b) is a distribution view of vein quartz with different particle diameters, FIG. 4 (c) is a view of the middle crystal pith of vein quartz, FIG. 4 (d) is a view of the quartz fine vein formed at the later stage, wherein Q represents quartz, Q1Represents muscovite, Q2Representing biotite, H red limonite and C chalcedony, as can be seen from fig. 4, quartz is mainly divided into two groups of different sizes, a small amount of radial quartz, and quartz may be formed in two to three stages according to crystal holes, fine vein cutting of quartz, and the like.
TABLE 1 SiO of vein quartz raw ore and products of examples2Content and content of each impurity element
Figure BDA0002600037650000081
Figure BDA0002600037650000091
As can be seen from Table 1, the SiO content of the high purity silica sand obtained in examples 1 to 4 of the present invention2The content can reach at least more than 99.9wt%, and the content of impurity elements such as Al, fe, K, na and the like is far lower than that of vein quartz raw ore, so that the prepared high-purity quartz sand can meet the requirement of the industry on the high-purity quartz sand, and a fluorine-containing solvent is not used in the preparation process, so that the preparation method is environment-friendly and pollution-free.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.

Claims (8)

1. A method for purifying quartz by chloridizing roasting is characterized by comprising the following steps:
s1, grinding vein quartz raw ore, and performing magnetic separation and impurity removal to obtain a nonmagnetic product;
s2, pickling the nonmagnetic product by using a dilute hydrochloric acid solution to obtain vein quartz concentrate; the liquid-solid ratio of the nonmagnetic product to the dilute hydrochloric acid solution is 500g.L-1The mass fraction of the dilute hydrochloric acid is 10 percent;
s3, adding acid into the vein quartz concentrate to adjust the pH value to 2-3, adding an anion collecting agent and a cation collecting agent into the vein quartz concentrate to perform flotation treatment, and removing impurities to obtain the vein quartz concentrate after flotation; the anion collector is sodium dodecyl sulfate, the cation collector is dodecylamine, and the addition amount of the anion collector is 150-300 g.t-1The adding amount of the cationic collector is 400-700 g.t-1；
S4, mixing the floated vein quartz concentrate with a chlorinating agent, roasting for 5-9 h at 850-950 ℃, and after roasting, performing water quenching treatment on the floated vein quartz concentrate to obtain chloridized roasted vein quartz concentrate;
and S5, mixing the chloridized roasted vein quartz concentrate with a leaching solution, and carrying out hot-pressing leaching treatment, wherein the hot-pressing leaching temperature is 240-260 ℃, the hot-pressing leaching time is 2-6 h, the leaching solution is a mixed solution of a sulfuric acid solution and an ammonium chloride solution, and after the hot-pressing leaching is finished, washing a hot-pressing leaching product to be neutral, filtering and drying to obtain the high-purity quartz sand.
2. The method for purifying quartz through chloridizing roasting according to claim 1, wherein the magnetic field intensity for magnetic separation impurity removal is 1.0-1.4T, and the pulp flow rate is 0.5-2 cm.s-1。
3. The method for purifying quartz through chloridizing roasting according to claim 1, wherein the acid washing is carried out under stirring conditions, the stirring speed is 1600-2000 rpm, and the acid washing time is 15-25 min.
4. The method for purifying quartz through chloridizing roasting according to claim 1, wherein the pH is adjusted to 2 to 3 by using a 10% sulfuric acid solution.
5. The method for purifying quartz through chloridizing roasting according to claim 1, wherein the chlorinating agent is NaCl, KCl and NH4And Cl, and the doping amount of the chlorinating agent is 0.02-2 per mill of the mass of the vein quartz concentrate after flotation.
6. The method for purifying quartz through chloridizing roasting according to claim 1, wherein the liquid-solid ratio of chloridized roasted vein quartz concentrate to leachate is 5mL-1。
7. The method for purifying quartz through chloridizing roasting according to claim 1, wherein the concentration of sulfuric acid solution in the leachate is 0.1-0.5mol.L-1The concentration of the ammonium chloride solution is 0.4-0.8 mol-1。
8. The method for purifying quartz through chloridizing roasting according to claim 1, wherein SiO in the high-purity quartz sand2The content is more than or equal to 99.9wt percent.
CN202010721087.7A 2020-07-24 2020-07-24 Method for purifying quartz by chloridizing roasting Active CN111874913B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010721087.7A CN111874913B (en) 2020-07-24 2020-07-24 Method for purifying quartz by chloridizing roasting

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010721087.7A CN111874913B (en) 2020-07-24 2020-07-24 Method for purifying quartz by chloridizing roasting

Publications (2)

Publication Number Publication Date
CN111874913A CN111874913A (en) 2020-11-03
CN111874913B true CN111874913B (en) 2022-11-01

Family

ID=73200167

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010721087.7A Active CN111874913B (en) 2020-07-24 2020-07-24 Method for purifying quartz by chloridizing roasting

Country Status (1)

Country Link
CN (1) CN111874913B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113735128A (en) * 2021-08-16 2021-12-03 武汉理工大学 Preparation method of high-purity quartz sand
CN114436266A (en) * 2022-01-28 2022-05-06 合肥综合性国家科学中心能源研究院(安徽省能源实验室) Method for purifying quartz by microwave heating chlorination roasting

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102602942B (en) * 2012-03-25 2013-12-25 连云港金瑞照明电器有限公司 Method for preparing high-purity quartz sand
CN103332694B (en) * 2013-06-09 2015-02-18 宁夏富乐德石英材料有限公司 Preparation method of raw material sand for quartz crucible
CN106000621B (en) * 2016-06-01 2019-04-19 安徽晶晶石英科技有限公司 A kind of method of the compound purifying quartz sand of chlorination-acidleach
CN107899753B (en) * 2017-10-09 2019-12-27 中南大学 Anion combined collector for fluorine-free flotation separation of quartz and feldspar and preparation method and application thereof

Also Published As

Publication number Publication date
CN111874913A (en) 2020-11-03

Similar Documents

Publication Publication Date Title
CN111874914B (en) Method for preparing 4N high-purity quartz sand by taking pegmatite quartz as raw material
CN111874915A (en) Method for preparing high-purity quartz sand by taking vein quartz as raw material
CN111874913B (en) Method for purifying quartz by chloridizing roasting
CN110510620A (en) The method of purification of glass sand tailing
CN102600982B (en) Fluoride-free low-acid zwitterion quartz sand reverse flotation process
CN107185708A (en) A kind of method that high-purity quartz is prepared with mine tailing
CN102824961A (en) Beneficiation method for producing quartz and feldspar by using river and lake sands
CN103964444A (en) Method for producing high-purity quartz sand
CN114684826A (en) Preparation method of high-purity quartz sand
CN1891625A (en) Method for producing superfine high-purity silicon dioxide
CN113441283A (en) Method for direct flotation of quartz from quartz and feldspar mixed ore under neutral pH condition
Wei et al. Flotation behavior, collector adsorption mechanism of quartz and feldspar-quartz systems using PEA as a novel green collector
CN104190533B (en) Method for recovering quartz in iron tailing and quartz mine prepared by same
CN103183351B (en) The method of chloridizing roasting-leaching method purifying silicon dioxide ore
Li et al. Recovery and preparation of high-grade silica from iron ore tailings by S-HGMS coupling with acid leaching technology: Description of separation mechanism and leaching kinetics
CN115709999A (en) Method for extracting high-purity quartz sand from granite pegmatite
CN114392836B (en) Processing technology of high-purity quartz sand
KR20130104164A (en) Method for preparing high purity silica using reverse flotation
CN116177585A (en) Method for purifying calcium fluoride from fluorine-containing sludge
CN113751187A (en) Quartz fine sand and preparation method and application thereof
CN109290050A (en) A kind of low Fe-spodumene preparation method
CN116605883A (en) Method for preparing 4N 7-grade high-purity quartz sand from muscovite type granite quartz
CN114436266A (en) Method for purifying quartz by microwave heating chlorination roasting
CN112916199A (en) Quartz raw material purification method
CN112619883A (en) Method for preparing super-white glass material by purifying fine quartz sandstone

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant