CN116924415A - Preparation method of ultra-high purity quartz sand - Google Patents
Preparation method of ultra-high purity quartz sand Download PDFInfo
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- CN116924415A CN116924415A CN202310758550.9A CN202310758550A CN116924415A CN 116924415 A CN116924415 A CN 116924415A CN 202310758550 A CN202310758550 A CN 202310758550A CN 116924415 A CN116924415 A CN 116924415A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 239000006004 Quartz sand Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 50
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 239000002738 chelating agent Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 239000003463 adsorbent Substances 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 9
- 239000012498 ultrapure water Substances 0.000 claims abstract description 9
- 230000009172 bursting Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 26
- 239000004576 sand Substances 0.000 claims description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- -1 halosilane Chemical compound 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004880 explosion Methods 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 8
- 210000003000 inclusion body Anatomy 0.000 abstract 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 21
- 238000004821 distillation Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229960001484 edetic acid Drugs 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 210000003462 vein Anatomy 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- 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
Abstract
The invention discloses a preparation method of ultra-high purity quartz sand, which is characterized in that an organic silicon source is used as a raw material, metal ion adsorbent and metal ion chelating agent are utilized to remove metal impurities of the organic silicon source, then the purified organic silicon source is reacted with ultrapure water, the obtained product is dried to obtain silica particles with open pores, the silica pores are closed by high-temperature roasting, and then inclusion in the silica is removed by a microwave bursting method, so that the ultra-high purity quartz sand is obtained. The preparation method provided by the invention overcomes the problems that metal ion impurities are difficult to remove in the ore purification process in the prior art, the finished product contains metal impurities which affect the product quality, and the quartz sand has more inclusion bodies and porous structure, so that the purity of the quartz sand is lower, and the purity of the prepared quartz sand is higher than 99.999%, so that the preparation method has a good application prospect.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a method for preparing ultra-high purity quartz sand by using an organosilicon source as a raw material through chemical synthesis.
Background
The ultra-high purity silica sand, which generally means silica sand having a silica content of 99.995% or more, is a main raw material for a silica crucible, a silica ingot, a silica tube, and the like. At present, the main source of quartz sand in the market is obtained by purifying natural ore, and because of the complex ore components and structure, the common quartz ore is difficult to purify to more than 99.99 percent, the ultra-high purity quartz sand is basically obtained by purifying clean natural crystal produced by only a few mineral veins, and the mineral veins are very limited in resources, so that the production of the ultra-high purity quartz sand is limited. Along with the development of the semiconductor industry, the purity requirement on quartz products is higher and higher, and the natural ore purification method is difficult to purify the silicon dioxide in the ore to more than 99.999 percent, so that the requirement of the existing semiconductor industry on high-purity quartz sand can not be met.
Therefore, it is desirable to provide a method for preparing ultra-high purity quartz sand to solve the problem of low purity of quartz sand prepared by natural ore purification.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a preparation method of ultra-high purity quartz sand, which solves the problem that the purity of quartz sand prepared by natural ore purification is low.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of the ultra-high purity quartz sand comprises the steps of taking an organosilicon source as a raw material, removing metal impurities of the organosilicon source by utilizing a metal ion adsorbent and a metal ion chelating agent, then reacting the purified organosilicon source with ultrapure water, drying the obtained product to obtain silica particles with open pores, then roasting at a high temperature to enable the pores of the silica to be closed, and then removing inclusion in the silica by utilizing a microwave bursting method to obtain the ultra-high purity quartz sand.
Further, the method comprises the following steps:
s1, adding a metal ion adsorbent into an organosilicon source, stirring for 0.5-10 h at 20-80 ℃ at 200-1000 rpm, and then filtering with an organic filter membrane of 0.1-1 um;
s2, adding a polyvalent metal ion chelating agent into the organosilicon source filtered in the step S1, stirring for 0.5-10 hours at the temperature of 20-80 ℃ at 200-1000 r/min, then distilling and purifying at the temperature of 100-300 ℃ to remove polyvalent metal ion impurities in the organosilicon source, and filtering with an organic filter membrane of 0.1-1 um;
s3, adding a monovalent metal ion chelating agent into the organosilicon source from which the multivalent metal ions are removed in the step S2, stirring for 0.5-10 hours at 20-80 ℃ at 200-1000 rpm, distilling and purifying at 100-300 ℃ to remove monovalent metal ion impurities in the organosilicon source, and then filtering with an organic filter membrane of 0.1-1 um to obtain a high-purity organosilicon source with the total metal impurity content less than 1ppm;
s4, adding ultrapure water into the purified organic silicon source obtained in the step S3, and reacting for 0.5-24 hours at 15-100 ℃ to obtain high-purity orthosilicic acid solution;
s5, drying the high-purity orthosilicic acid solution obtained in the step S4 to obtain silica particles with open pores;
s6, placing the silica particles obtained in the step S5 into a vacuum heating furnace, heating to 700 ℃ from room temperature for 2 hours under the vacuum degree of-0.02 to-0.1 mPa, heating to 1250 ℃ for 4 hours, and heating to 1600 ℃ for 4 hours to obtain the silica particles with closed pores; the impurity metal content in the obtained silicon dioxide particles is less than 10ppm, and the purity is more than 99.999%; in this step, the vacuum degree is introduced in order to avoid introducing impurities in the air; the heating temperature and heating time are controlled to the values because the heating temperature is insufficient for SiO 2 The crystal form is not transformed, the pores can not be closed, and the heating temperature is too high to ensure SiO 2 Will melt and the structure will be destroyed; the heating time is too short, siO 2 The reaction cannot be completed, the air holes may be partially not closed, and the energy consumption is wasted due to overlong heating time.
S7, grinding the silicon dioxide particles obtained in the step S6 into powder with the particle size of 50-200 mu m, placing the powder in a high-power microwave heating furnace, and performing microwave explosion for 0.5-8 hours at the constant temperature of 600-800 ℃ under the microwave power of 1000-4000W to remove fine inclusion in the silicon dioxide, thereby obtaining the ultra-high purity quartz sand with the inclusion content less than 100 ppm. In this step, the inclusion includes a gas inclusion, a gas-liquid inclusion, and a liquid inclusion. The temperature is controlled between 600 and 800 ℃ to keep the substances in the inclusion in an active state, and substances with insufficient activity or energy consumption can be wasted when the temperature exceeds a set range; the above ranges of microwave power and microwave time are set because too low microwave power can cause insufficient internal expansion degree of the silicon dioxide and can not remove inclusion, and too high microwave power can cause too high temperature to cause the damage of the silicon dioxide structure; and the microwave time is too short, so that the internal expansion is insufficient, inclusion cannot be removed, and the energy consumption is wasted due to too long time.
Further, the organic silicon source in the step S1 is silicate, halogenated silane, silanol or silyl ether.
Further, in the step S1, the metal ion adsorbent is activated carbon or modified silica gel.
Further, the polyvalent metal ion chelating agent in the step S2 is EDTA, HEDP, EGTA, DTPA, NTA, HEDTA, citric acid, citrate, organic polyphosphonic acid or inorganic polyphosphate.
Further, the monovalent metal ion chelating agent in step S3 is a crown ether or a cryptate.
Further, the mass ratio of the organic silicon source to the metal ion adsorbent in the step S1 is 1:0.1 to 0.5.
Further, the mass ratio of the organosilicon source to the polyvalent metal ion chelating agent in the step S2 is 1:0.1 to 1.
Further, in the step S3, the mass ratio of the organosilicon source to the monovalent metal ion chelating agent is 1:0.1 to 1.
Further, the molar ratio of the organosilicon source to the ultrapure water in the step S4 is 1: 40-120, the reaction temperature is 15-100 ℃, and the reaction time is 0.5-8h.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the preparation method of the ultra-high purity quartz sand, the organic silicon source is used as the raw material, and the metal ion adsorbent and the metal ion chelating agent are used for purifying the raw material, so that the technical problem that metal ion impurities are difficult to remove in the ore purification process in the prior art, and the quality of the finished product is influenced by the metal impurities contained in the finished product after the finished product is prepared is solved; and the problems of more inclusion and porous structure of synthetic silicon dioxide in the general synthetic quartz sand are solved by using the high-temperature roasting and microwave bursting methods, and the ultra-high purity quartz sand with less inclusion and closed pores is obtained. And the purity of the quartz sand prepared by the method is more than 99.999 percent, and the problem that the purity of the quartz sand prepared by the natural ore purification method is lower is solved.
2. Compared with the method for purifying ore by acid, the method has the advantages of no violent reaction, easy operation, no generation of acid waste liquid containing chlorine, nitrate, fluorine and the like in the reaction process, and little environmental pollution.
3. The equipment used by the invention is common equipment in laboratories, and the equipment cost is lower than that of large-scale equipment required by the prior art.
4. According to the invention, the purity of quartz sand is further improved by simultaneously reducing the content of metal ions and the content of micro inclusion, so that the problem that the quartz sand with more inclusion cannot be applied to the inner layer of the quartz crucible is solved.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to specific examples.
Numerical ranges in this disclosure are understood to also specifically disclose each intermediate value between the upper and lower limits of the ranges. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control. As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The experimental methods used in the present invention are conventional methods unless otherwise specified.
The materials, reagents and the like used in the present invention can be synthesized by a method of purchase or known method unless otherwise specified.
In the quantitative test of the invention, three repeated experiments are set, and the results are averaged.
Example 1
The preparation method of the ultra-high purity quartz sand comprises the following steps:
(1) 1000g of industrial grade ethyl silicate and 100g of activated carbon particles are taken and put into a round bottom flask, the flask is put into an oil bath pot and heated to 60 ℃ for constant temperature, a crescent stirring paddle is used for stirring, the stirring speed is 500 revolutions per minute, the reaction is carried out for 2 hours, after the reaction is finished, the ethyl silicate is filtered by a suction filtration device with a sand core, and an organic filter membrane with 0.45um is filtered;
(2) Transferring the ethyl silicate obtained in the step (1) into a round-bottom flask, adding 300g of EDTA (ethylene diamine tetraacetic acid) into the round-bottom flask, heating the flask to the constant temperature of 60 ℃, stirring the mixture by a crescent stirring paddle at the stirring speed of 500 revolutions per minute, reacting for 4 hours, after the reaction is finished, introducing the round-bottom flask into a distillation device, heating the oil bath to the temperature of 200 ℃ to start distillation, collecting distillate, evaporating the distillate to dryness, and filtering the distilled ethyl silicate by a suction filtration device with a sand core, and filtering the distilled ethyl silicate by an organic filter membrane with the thickness of 0.45 um;
(3) Transferring the ethyl silicate obtained in the step (2) into a round-bottom flask, adding 100g of 12-crown-4 crown ether, 100g of 18-crown-6 crown ether and 100g of 15-crown-5 crown ether into the round-bottom flask, heating the flask to a constant temperature of 60 ℃, stirring the flask by using a crescent stirring paddle at a stirring speed of 500 r/min, reacting for 4h, after the reaction is finished, introducing the round-bottom flask into a distillation device, heating the oil bath to 120 ℃ to start distillation, taking the distillate, namely 15-crown-5 crown ether, distilling until no liquid is distilled, changing the container, heating to 200 ℃ to continue distillation, taking the distillate, namely ethyl silicate, distilling until no liquid is distilled, and filtering the distilled ethyl silicate by a sand-cored suction filtration device, and filtering with an organic filter membrane of 0.45 un; the metal ion content in the ethyl silicate obtained at this time was <1ppm;
(4) Adding 8640g of ultrapure water (resistivity is more than 15MΩ) into the ethyl silicate obtained in the step (3), heating to 60 ℃ in a water bath, magnetically stirring for 800 revolutions per minute, and reacting for 24 hours at constant temperature to obtain a high-purity orthosilicic acid solution;
(5) Placing the orthosilicic acid solution in the step (4) in a baking oven at 120 ℃ for baking to obtain silica particles with open pores;
(6) Placing the silica particles in the step (5) into a vacuum furnace, vacuumizing to-0.05 mPa, heating to 700 ℃ at a speed of 5 ℃/min, keeping the temperature for 2 hours, then continuously heating to 1250 ℃ at a speed of 5 ℃/min, keeping the temperature for 4 hours, continuously heating to 1600 ℃ at a speed of 5 ℃/min, and keeping the temperature for 4 hours to obtain the silica particles with closed pores and metal ion content less than 10 ppm;
(7) Grinding the silicon dioxide particles in the step (6) into silicon dioxide powder with the particle size of 100um by using a three-roller grinder, placing the silicon dioxide powder into a high-power microwave heating furnace, heating the microwave heating furnace to 800 ℃, adjusting the microwave power to 3000W, and reacting at constant temperature for 4 hours to obtain ultra-high purity quartz sand with inclusion content of <100ppm, metal ion content of <10ppm and silicon dioxide purity of > 99.999%;
the metal ion impurity content in the resulting silica sand is tested by ICP-MS according to the GB/T3284-2015 standard requirements as shown in table 1:
TABLE 1 Metal ion impurity content (Unit: ug/g) in the silica sand obtained in EXAMPLE 1
| Al | Ti | Fe | Mn | Li | Ni | Cu | Co | Na | K | Mg | Ca | Zr | Cr | Ba |
| 0.18 | 0.03 | 0.36 | 0.01 | 0.01 | 0.03 | <0.01 | 0.02 | 1.99 | 2.10 | 0.01 | 0.06 | <0.01 | 0.01 | 0.01 |
As is clear from Table 1, the silica sand prepared by the present invention has a metal ion content of <10ppm and a silica purity of >99.999%.
Example 2
The preparation method of the ultra-high purity quartz sand comprises the following steps:
(1) 1000g of industrial ethyl silicate and 200g of modified silica gel microbeads are put into a round bottom flask, the flask is put into an oil bath pot and heated to the constant temperature of 60 ℃, a crescent stirring paddle is used for stirring, the stirring speed is 500 revolutions per minute, the reaction is carried out for 4 hours, after the reaction is finished, the ethyl silicate is subjected to suction filtration through a suction filtration device with a sand core, and an organic filter membrane with the thickness of 0.45um is arranged;
(2) Transferring the ethyl silicate obtained in the step (1) into a round-bottom flask, adding 300g of HEDP (hydroxyethylidene-1, 1-diphosphonic acid) into the round-bottom flask, heating the flask to a constant temperature of 60 ℃, stirring the mixture by a crescent stirring paddle at a stirring speed of 500 revolutions per minute, reacting for 4 hours, after the reaction is finished, introducing the round-bottom flask into a distillation device, heating the oil bath to 220 ℃ to start distillation, taking distillate, namely ethyl silicate, distilling until no liquid is distilled, and filtering the distilled ethyl silicate by a suction filtration device with a sand core, and filtering the mixture with an organic filter membrane of 0.45 um;
(3) Transferring the ethyl silicate obtained in the step (2) into a round-bottom flask, adding 200g of cave ether k222 into the round-bottom flask, heating the flask to the constant temperature of 60 ℃, stirring the mixture by using a crescent stirring paddle at the stirring speed of 500 r/min, reacting for 4h, after the reaction is finished, introducing the round-bottom flask into a distillation device, heating the oil bath to 220 ℃ for distillation, taking out distillate, namely ethyl silicate, distilling until no liquid is distilled, and filtering the distilled ethyl silicate by using a suction filtration device with a sand core, and filtering the distilled ethyl silicate by using an organic filter membrane of 0.45 un; the metal ion content in the ethyl silicate obtained at this time was <1ppm;
(4) Adding 6912g of ultrapure water (resistivity is more than 15MΩ) into the ethyl silicate obtained in the step (3), heating to 60 ℃ in a water bath, magnetically stirring for 800 revolutions per minute, and reacting for 24 hours at constant temperature to obtain high-purity orthosilicic acid solution;
(5) Placing the orthosilicic acid solution in the step (4) in a baking oven at 120 ℃ for baking to obtain silica particles with open pores;
(6) Placing the silica particles in the step (5) into a vacuum furnace, vacuumizing to-0.05 mPa, heating to 700 ℃ at a speed of 5 ℃/min, keeping the temperature for 2 hours, then continuously heating to 1250 ℃ at a speed of 5 ℃/min, keeping the temperature for 4 hours, continuously heating to 1600 ℃ at a speed of 5 ℃/min, and keeping the temperature for 4 hours to obtain the silica particles with closed pores and metal ion content less than 10 ppm;
(7) Grinding the silicon dioxide particles in the step (6) into silicon dioxide powder with the particle size of 100um by using a three-roller grinder, placing the silicon dioxide powder into a high-power microwave heating furnace, heating the microwave heating furnace to 800 ℃, adjusting the microwave power to 3000W, and reacting at constant temperature for 4 hours to obtain ultra-high purity quartz sand with inclusion content of <100ppm, metal ion content of <10ppm and silicon dioxide purity of > 99.999%;
the metal ion impurity content in the resulting silica sand is tested by ICP-MS according to the GB/T3284-2015 standard requirements as shown in table 2:
TABLE 2 Metal ion impurity content (Unit: ug/g) in the silica sand obtained in EXAMPLE 2
As is clear from Table 2, the silica sand prepared by the present invention has a metal ion content of <10ppm and a silica purity of >99.999%.
In conclusion, the method utilizes the organic silicon source as the raw material, adopts the metal ion adsorbent and the metal ion chelating agent to purify the raw material, and solves the technical problem that metal ion impurities are difficult to remove in the ore purification process in the prior art, and the metal impurities contained in the finished product after the finished product is manufactured have influence on the quality of the product; and the problems of more inclusion and porous structure of synthetic silicon dioxide in the general synthetic quartz sand are solved by using the high-temperature roasting and microwave bursting methods, and the ultra-high purity quartz sand with less inclusion and closed pores is obtained. And the purity of the quartz sand prepared by the method is more than 99.999 percent, and the problem that the purity of the quartz sand prepared by the natural ore purification method is lower is solved.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the technical solution, and those skilled in the art should understand that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the present invention, and all such modifications and equivalents are included in the scope of the claims.
Claims (10)
1. A preparation method of ultra-high purity quartz sand is characterized in that an organic silicon source is used as a raw material, metal ion adsorbent and metal ion chelating agent are utilized to remove metal impurities of the organic silicon source, then the purified organic silicon source is reacted with ultrapure water, the obtained product is dried to obtain silica particles with open pores, the silica pores are closed by high-temperature roasting, and then inclusion in the silica is removed by a microwave bursting method, so that the ultra-high purity quartz sand is obtained.
2. The method for preparing ultra-high purity silica sand according to claim 1, comprising the steps of:
s1, adding a metal ion adsorbent into an organosilicon source, stirring for 0.5-10 h at 20-80 ℃ at 200-1000 rpm, and then filtering with an organic filter membrane of 0.1-1 um;
s2, adding a polyvalent metal ion chelating agent into the organosilicon source filtered in the step S1, stirring for 0.5-10 hours at the temperature of 20-80 ℃ at 200-1000 r/min, then distilling and purifying at the temperature of 100-300 ℃ to remove polyvalent metal ion impurities in the organosilicon source, and filtering with an organic filter membrane of 0.1-1 um;
s3, adding a monovalent metal ion chelating agent into the organosilicon source from which the multivalent metal ions are removed in the step S2, stirring for 0.5-10 hours at 20-80 ℃ at 200-1000 rpm, distilling and purifying at 100-300 ℃ to remove monovalent metal ion impurities in the organosilicon source, and then filtering with an organic filter membrane of 0.1-1 um to obtain a high-purity organosilicon source with the total metal impurity content less than 1ppm;
s4, adding ultrapure water into the purified organic silicon source obtained in the step S3, and reacting for 0.5-24 hours at 15-100 ℃ to obtain high-purity orthosilicic acid solution;
s5, drying the high-purity orthosilicic acid solution obtained in the step S4 to obtain silica particles with open pores;
s6, placing the silica particles obtained in the step S5 into a vacuum heating furnace, heating to 700 ℃ from room temperature for 2 hours under the vacuum degree of-0.02 to-0.1 mPa, heating to 1250 ℃ for 4 hours, and heating to 1600 ℃ for 4 hours to obtain the silica particles with closed pores; the impurity metal content in the obtained silicon dioxide particles is less than 10ppm, and the purity is more than 99.999%;
s7, grinding the silicon dioxide particles obtained in the step S6 into powder with the particle size of 50-200 mu m, placing the powder in a high-power microwave heating furnace, and performing microwave explosion for 0.5-8 hours at the constant temperature of 600-800 ℃ under the microwave power of 1000-4000W to remove fine inclusion in the silicon dioxide, thereby obtaining the ultra-high purity quartz sand with the inclusion content less than 100 ppm.
3. The method for preparing ultra-high purity silica sand according to claim 2, wherein the organosilicon source in step S1 is silicate, halosilane, silanol, or silyl ether.
4. The method for preparing ultra-high purity silica sand according to claim 2, wherein the metal ion adsorbent in step S1 is activated carbon or modified silica gel.
5. The method for preparing ultra-high purity silica sand according to claim 2, wherein the polyvalent metal ion chelating agent in step S2 is EDTA, HEDP, EGTA, DTPA, NTA, HEDTA, citric acid, citrate, organic polyphosphonic acid or inorganic polyphosphate.
6. The method for preparing ultra-high purity silica sand according to claim 2, wherein the monovalent metal ion chelating agent in step S3 is crown ether or cryptate.
7. The method for preparing ultra-high purity silica sand according to claim 2, wherein the mass ratio of the organosilicon source to the metal ion adsorbent in step S1 is 1:0.1 to 0.5.
8. The method for preparing ultra-high purity silica sand according to claim 2, wherein the mass ratio of the organosilicon source to the polyvalent metal ion chelating agent in step S2 is 1:0.1 to 1.
9. The method for preparing ultra-high purity silica sand according to claim 2, wherein the mass ratio of the organosilicon source to the monovalent metal ion chelating agent in step S3 is 1:0.1 to 1.
10. The method for preparing ultra-high purity silica sand according to claim 2, wherein the molar ratio of the organosilicon source to the ultra-pure water in step S4 is 1: 40-120, the reaction temperature is 15-100 ℃, and the reaction time is 0.5-8h.
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