WO2025030863A1 - 一种高纯方石英的制备方法 - Google Patents

一种高纯方石英的制备方法 Download PDF

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WO2025030863A1
WO2025030863A1 PCT/CN2024/083450 CN2024083450W WO2025030863A1 WO 2025030863 A1 WO2025030863 A1 WO 2025030863A1 CN 2024083450 W CN2024083450 W CN 2024083450W WO 2025030863 A1 WO2025030863 A1 WO 2025030863A1
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purity
cristobalite
coupling agent
preparing high
purity cristobalite
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蒋学鑫
陈博
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Anhui Estone Material Technology Co Ltd
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Anhui Estone Material Technology Co Ltd
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    • 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
    • C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • 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

Definitions

  • the invention relates to the technical field of quartz sand, in particular to a method for preparing high-purity cristobalite.
  • Quartz is a silicon oxide with a framework structure. It has many isomorphous variants and seven crystal forms under normal pressure: ⁇ -quartz, ⁇ -quartz, ⁇ -tridymite, ⁇ 1-tridymite, ⁇ -tridymite, ⁇ -cristobalite and ⁇ -cristobalite.
  • the normal pressure transition temperatures between them are shown in Figure 4.
  • ⁇ -type refers to the crystal form that is stable at high temperatures
  • ⁇ -type refers to the crystal form that is stable at low temperatures. It is widely distributed in nature.
  • quartz usually refers to ⁇ -quartz.
  • High-purity quartz sand usually refers to quartz with a silicon dioxide content greater than 99.9%.
  • high-purity quartz products can be divided into four grades, namely high-end ⁇ (SiO2) ⁇ 99.998% (4N8), mid-to-high-end ⁇ ( SiO2 ) ⁇ 99.995% (4N5), mid-end ⁇ ( SiO2 ) ⁇ 99.99% (4N), and low-end ⁇ ( SiO2 ) ⁇ 99.9% (3N) (see "The concept of high-purity quartz and its raw material grade classification", Mineral Protection and Utilization, October 2022, Issue 5).
  • unprocessed natural quartz is difficult to meet the quality requirements of high-purity quartz.
  • high-purity quartz sand is a quartz sand product with extremely high SiO2 purity obtained by using natural quartz ore as raw material and undergoing a relatively complex purification process.
  • high-purity quartz sand also has strict requirements on product particle size (usually 40-200 mesh) and mineral phase. Therefore, the commonly mentioned amorphous silicon dioxide such as silicon micropowder and white carbon black are not high-purity quartz sand even if they are of high purity.
  • the impurity elements in natural quartz sand mainly include Al, K, Na, Li, Ca, Cu, B, Fe, Mn, Co, Ti, P, etc.
  • monovalent and divalent ions exist in the form of interstitial atoms at the charge imbalance defects in the quartz lattice.
  • trivalent, tetravalent, and pentavalent ions mainly exist in the lattice.
  • technicians have proposed a variety of processes.
  • Zhang Haiqi et al.'s "Research Progress on Impurity Characteristics and Deep Chemical Purification Technology in High-Purity Quartz” (Mineral Conservation and Utilization, August 2022, Issue 4) records the existing quartz sand purification technology.
  • the main methods for purifying natural quartz sand mainly include physical and chemical methods.
  • Physical purification mainly includes color sorting, scrubbing, gravity separation, magnetic separation and flotation processes, but gas-liquid inclusions and isomorphic impurities inside the lattice are the main sources of impurities, and these impurities are the key factors restricting the preparation of high-purity quartz products.
  • Physical purification cannot remove these impurities, so deep chemical purification is required.
  • Chemical deep purification mainly includes acid (alkali, salt) treatment and heat treatment.
  • Acid (alkali, salt) treatment mainly removes impurities that exist on the surface of quartz sand particles in the form of gas-liquid inclusions or embedded in the particles.
  • Heat treatment mainly uses high temperature to cause inclusions to burst and reduce gas-liquid impurities (which cannot be completely removed).
  • quartz stone Before quartz stone is processed into high-purity quartz sand, it needs to undergo pickling, flotation, magnetic separation, gravity separation, high-temperature water quenching, chlorination roasting and other steps.
  • the process is long, the pickling impurity removal efficiency is low, and it is complicated.
  • Exogenous impurities such as iron, sodium, aluminum and other metal elements are easily introduced during the impurity removal process.
  • hydrofluoric acid, hydrochloric acid and nitric acid used in pickling are of high concentration and large amount, which will produce a large amount of fluorine-containing and chlorine-containing wastewater during pickling, increasing the treatment cost.
  • the present invention provides a method for preparing high-purity cristobalite, wherein amorphous silicon dioxide is dried, calcined and broken up to obtain high-purity cristobalite.
  • the amorphous silicon dioxide includes but is not limited to being obtained by oxidation of metallic silicon;
  • the metal silicon oxidation includes any one of burning metal silicon, reacting metal silicon with high-purity water at high temperature, or converting metal silicon into silicon-containing organic matter, such as silane, and then calcining and converting it into amorphous nano silicon oxide.
  • the particle size of the amorphous silica is 5 nanometers to 1 micrometer.
  • the drying conditions are: 100°C-150°C for 1-2h.
  • the calcination conditions are: 1100° C.-1700° C. for 2-10 h.
  • the high-purity cristobalite has a particle size of 120-450 microns.
  • the total content of Al, B, Ca, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Ti and Zn elements in the high-purity cristobalite is less than 20 ppm.
  • the method further comprises a step of treating with a coupling agent.
  • the coupling agent is selected from any one of a silane coupling agent and a titanate coupling agent.
  • the silane coupling agent is a silane coupling agent containing only carbon, silicon, hydrogen and oxygen elements.
  • the carbon chain length of the silane coupling agent containing only carbon, silicon, hydrogen and oxygen elements does not exceed 5.
  • the present invention has the following beneficial effects:
  • Amorphous silica has a large specific surface area and is rich in hydroxyl groups. It is easy to cause holes in the quartz during the conversion process. In order to eliminate such holes, the present invention uses a coupling agent for surface treatment and then calcination. The data shows that the hydroxyl groups are greatly reduced.
  • the inventors selected a silane coupling agent with a shorter chain length, resulting in fewer holes in the cristobalite, and a certain degree of reduction in the calcination temperature and time.
  • the possible reason is that the silane coupling agent decomposes at high temperature to form silicon oxide. Since the silicon oxide formed by decomposition has a smaller particle size, it preferentially forms crystal nuclei, which promotes the overall crystal transformation;
  • the high-purity cristobalite obtained by the invention has fewer hydroxyl groups except for elements such as Al, B, Ca, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Ti, and Zn.
  • the present invention adopts silane coupling agent treatment to reduce the pores in cristobalite as well as the calcination temperature and time, thereby saving energy consumption.
  • FIG1 is an XRD diagram of high-purity cristobalite of Example 7.
  • FIG2 is an infrared spectrum of amorphous silicon dioxide A
  • FIG3 is an infrared spectrum of high-purity cristobalite of Example 7.
  • FIG. 4 is a diagram showing the normal pressure transition temperatures between various crystalline forms of silicon oxide.
  • the amorphous silicon dioxide of the present invention has a particle size of 5 nanometers to 1 micrometer and a specific surface area of 90 to 200 m 2 /g.
  • the source can be purchased from the market, such as Aladdin, or can be prepared by the following method.
  • Photovoltaic grade polysilicon is burned in oxygen and the conditions are controlled by conventional means to obtain high purity amorphous silicon dioxide of different particle sizes.
  • amorphous silicon dioxide (particle size 5 nm, specific surface area 200 m 2 /g) is marked as amorphous silicon dioxide A;
  • Amorphous silica (particle size 10 nm, specific surface area 150 m 2 /g) is labeled as amorphous silica B;
  • Amorphous silica (particle size 1 micrometer, specific surface area 90 m 2 /g) is marked as amorphous silica C.
  • Amorphous silicon dioxide A was dried at 100°C for 2 hours, calcined at 1170°C for 10 hours, cooled naturally, and dispersed by air flow to obtain high-purity cristobalite with a particle size of 120 microns.
  • Amorphous silicon dioxide A was dried at 150°C for 1 hour, calcined at 1700°C for 2 hours, cooled naturally, and dispersed by air flow to obtain high-purity cristobalite with a particle size of 200 microns.
  • Amorphous silicon dioxide B was dried at 100°C for 2 hours, calcined at 1170°C for 10 hours, cooled naturally, and dispersed by air flow to obtain high-purity cristobalite with a particle size of 380 microns.
  • Amorphous silicon dioxide C was dried at 100°C for 2 hours, calcined at 1170°C for 10 hours, cooled naturally, and dispersed by air flow to obtain high-purity cristobalite with a particle size of 630 microns.
  • Amorphous silica A3Kg, dried at 100°C for 2 hours, 30g coupling agent ( CH3O ) 3Si ( CH2 ) 7CH3 was mixed with 100g ethanol to obtain a modified liquid, the modified liquid was mixed evenly with the dried amorphous silica, dried (100°C, 2h), calcined at 1170°C for 8h, cooled naturally, and dispersed with air flow to obtain high-purity quartz with a particle size of 163 microns.
  • the ITOA-6 high-purity quartz produced by Unimin Corporation of the United States was dried at 100°C for 2 hours, calcined at 1170°C for 10 hours, cooled naturally, and dispersed with air flow to obtain high-purity cristobalite with a particle size of 230 microns.
  • the particle size, porosity and crystallinity of the prepared samples were measured.
  • the porosity was measured by nitrogen adsorption-desorption method, the particle size was measured by particle size analyzer, and the crystallinity was measured by XRD.
  • the results are shown in Table 2.
  • Table 3 shows the hydroxyl content (in ppm) in the materials of Examples 5-7 before and after the coupling agent treatment.
  • the hydroxyl content was calculated based on infrared spectroscopy, and the results are shown in Table 3.
  • Example 6 uses a long-chain silane coupling agent, and the porosity is relatively high.
  • the use of a short-chain silane coupling agent can achieve a higher crystallinity in a shorter time, which is more energy-efficient.
  • Figure 2 is the infrared spectrum of the raw material high-purity silicon dioxide.
  • the vibration peaks at 3410 cm -1 and 1642 cm -1 indicate that there are hydroxyl groups on its surface.
  • Figure 3 is the infrared spectrum of cristobalite. The absence of vibration peaks at 3410 cm -1 and 1642 cm -1 indicates that no hydroxyl groups can be detected on its surface.

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

本发明涉及石英砂技术领域，尤其涉及一种高纯方石英的制备方法,将无定型二氧化硅经过干燥、煅烧、打散得到高纯方石英。与现有技术相比，本发明的有益效果是：1、无定形二氧化硅比表面积较大，表面富含羟基，在转化为方石英过程中容易造成方石英中含有孔洞，为了消除这种孔洞，本发明采用了偶联剂进行表面处理，然后再煅烧，数据显示，羟基大大减少；2、在相同质量偶联剂下，发明人选用链长较短的硅烷偶联剂，方石英中的孔洞更少，且在煅烧温度、时间有一定幅度的降低，可能的原因是硅烷偶联剂高温分解形成氧化硅，由于分解形成的氧化硅粒径较小，优先形成晶核，促进了整体的晶型转化。

Description

一种高纯方石英的制备方法 技术领域
本发明涉及石英砂技术领域，尤其涉及一种高纯方石英的制备方法。
背景技术
石英(SiO2)是一种架状结构的硅的氧化物，有多种同质变体，常压下有七种晶型：α-石英、β-石英、α-鳞石英、β1-鳞石英、β-鳞石英、α-方石英和β-方石英，它们之间的常压转变温度如图4所示。其中β-型表示高温下稳定存在的晶型，α-型表示低温下稳定存在的晶型。在自然界中分布非常广泛，未特殊说明时，所谓的石英常指α-石英。
高纯石英砂通常是指二氧化硅含量大于99.9％的石英，按SiO2纯度可将高纯石英产品划分为4个等级，即高端ω(SiO2)≥99.998％(4N8)，中高端ω(SiO2)≥99.995％(4N5)，中端ω(SiO2)≥99.99％(4N)，低端ω(SiO2)≥99.9％(3N)(参见“高纯石英的概念及其原料品级划分”，矿产保护与利用，2022年10月，第5期)。但未经加工的天然石英难以达到高纯石英的质量要求。也就是说，高纯石英砂(high purity quartz)是以天然石英矿为原料，经过比较复杂的提纯工艺加工获得的SiO2纯度极高的石英砂产品。同时，由于受到后续制品制备过程的限制，高纯石英砂还对产品粒度(通常为40-200目)和矿物相等都有严格的要求。因此通常提到的硅微粉、白炭黑等非晶二氧化硅即便纯度很高，也不是高纯石英砂。
天然石英砂中的杂质元素主要包括Al、K、Na、Li、Ca、Cu、B、Fe、Mn、Co、Ti、P等，这些杂质元素中，一价、二价离子以填隙原子的形式存在于石英晶格中电荷不平衡缺陷处，作为补偿电荷，三价、四价、五价离子(类质同象杂质)主要存在于晶格内。为了去除石英砂中的杂质，技术人员提出了多种工艺，张海啟等人的“高纯石英中杂质特征及深度化学提纯技术研究进展”一文(矿产保护与利用，2022年8月，第4期)。记载了现有石英砂提纯技术，目前天然石英砂提纯的主要方法主要包括物理、化学两种方法。物理法提纯主要有色选、擦洗、重选、磁选和浮选等工艺，但气液包裹体和晶格内部类质同象杂质是主要的杂质来源，而这些杂质是制约高纯石英产品制备的关键性因素。物理法提纯无法去除这些杂质，需要进行化学法深度提纯。化学深度提纯主要包括酸(碱、盐)处理法和热处理法，酸(碱、盐)处理主要去除以气液包裹体形式存在石英砂颗粒表面或镶嵌于颗粒中的杂质，热处理法主要是利用高温使包裹体爆裂降低气液杂质(无法完全除净)。
相对于物理提纯方法而言，化学提纯操作复杂、成本较高，但在制备高纯石英时，化学处理是最有效的，也是必不可少的。
但现有技术存在以下问题：
1)石英石在加工成高纯石英砂之前需进行酸洗、浮选、磁选、重选、高温水淬、氯化焙烧等步骤，工艺过程长，酸洗除杂效率低，且复杂，除杂过程中容易引入外源性杂质，如铁、钠、铝等金属元素。
2)酸洗使用的氢氟酸、盐酸、硝酸，浓度高且用量大，酸洗时产生大量含氟、含氯废水，增加处理成本。
蒋学鑫等“天然石英中气-液杂质的热动力解吸”(硅酸盐学报2004年10月)一文， 进一步对石英中杂质对石英制品的影响进行了深入的研究，发现石英砂由于含有气液包裹体及表面含有较多的羟基(一般在80ppm以上)，在制造石英制品时容易产生气泡，影响制品品质。
发明内容
为了解决上述背景技术中提到的问题，本发明提供一种高纯方石英的制备方法，将无定型二氧化硅经过干燥、煅烧、打散得到高纯方石英。
优选的，所述无定形二氧化硅包括但不限于通过金属硅氧化获得；
所述金属硅氧化包括金属硅燃烧，或金属硅与高纯水高温反应，或金属硅转化为含硅有机物，如硅烷，然后煅烧转化为无定型纳米氧化硅中任意一种。
优选的，所述无定形二氧化硅的粒径为5纳米-1微米。
优选的，所述干燥条件为：100℃-150℃处理1-2h。
优选的，所述煅烧条件为：1100℃-1700℃处理2-10h。
优选的，所述高纯方石英粒径为120-450微米。
优选的，所述高纯方石英中Al、B、Ca、Cr、Cu、Fe、K、Li、Mg、Mn、Na、Ni、P、Ti、Zn元素总含量小于20ppm。
优选的，干燥后，还包括使用偶联剂处理的步骤。
优选的，所述偶联剂选自硅烷偶联剂、钛酸酯偶联剂中的任意一种。
优选的，为了减少杂质的引入，所述硅烷偶联剂为只含有碳、硅、氢、氧元素的硅烷偶联剂。
优选的，所述只含有碳、硅、氢、氧元素的硅烷偶联剂中碳链长度不超过5。
与现有技术相比，本发明的有益效果是：
1、无定形二氧化硅比表面积较大，表面富含羟基，在转化为方石英过程中容易造成方石英中含有孔洞，为了消除这种孔洞，本发明采用了偶联剂进行表面处理，然后再煅烧，数据显示，羟基大大减少；
2、在相同质量偶联剂下，发明人选用链长较短的硅烷偶联剂，方石英中的孔洞更少，且在煅烧温度、时间有一定幅度的降低，可能的原因是硅烷偶联剂高温分解形成氧化硅，由于分解形成的氧化硅粒径较小，优先形成晶核，促进了整体的晶型转化；
3、发明得到的高纯方石英与现有高纯石英相比，除了Al、B、Ca、Cr、Cu、Fe、K、Li、Mg、Mn、Na、Ni、P、Ti、Zn等元素外，羟基较少。
4、本发明采用硅烷偶联剂处理，减少了方石英中的孔隙以及煅烧温度、时间，能够节约能耗。
附图说明
图1为实施例7高纯方石英的XRD图；
图2为无定形二氧化硅A的红外谱图；
图3为实施例7高纯方石英的红外谱图；
图4为氧化硅各种晶型间常压转变温度图。
具体实施方式
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。
本发明的无定型二氧化硅粒径为5纳米-1微米，比表面积为90-200m2/g。来源可以通过市场购买，例如阿拉丁，也可以通过如下方法自制。
将光伏级多晶硅在氧气中燃烧，常规手段控制条件，得到不同粒径的高纯度无定型二氧化硅。
本发明中，无定型二氧化硅(粒径5纳米，比表面积200m2/g)标记为无定形二氧化硅A；
无定型二氧化硅(粒径10纳米，比表面积150m2/g)标记为无定形二氧化硅B；
无定型二氧化硅(粒径1微米，比表面积90m2/g)标记为无定形二氧化硅C。
实施例1
无定型二氧化硅A，在100℃干燥2小时、1170℃高温煅烧10h，自然冷却、气流打散，得到粒径为120微米高纯方石英。
实施例2
无定型二氧化硅A，在150℃干燥1小时、1700℃高温煅烧2h，自然冷却、气流打散，得到粒径为200微米高纯方石英。
实施例3
无定型二氧化硅B，在100℃干燥2小时、1170℃高温煅烧10h，自然冷却、气流打散，得到粒径为380微米高纯方石英。
实施例4(体现微米级原料制备高纯方石英的结果)
无定型二氧化硅C在100℃干燥2小时、1170℃高温煅烧10h，自然冷却、气流打散，得到粒径为630微米高纯方石英。
实施例5
无定型二氧化硅A3Kg，在100℃干燥2小时，将30g偶联剂(CH3O)3Si(CH2)10CH3与100g乙醇混合得到改性液，将改性液与干燥后的无定型二氧化硅混合均匀、干燥(100℃、2h)，在1170℃高温煅烧10h，自然冷却、气流打散，得到粒径为180微米高纯方石英。
实施例6
无定型二氧化硅A3Kg，在100℃干燥2小时，将30g偶联剂(CH3O)3Si(CH2)7CH3与100g乙醇混合得到改性液，将改性液与干燥后的无定型二氧化硅混合均匀、干燥(100℃、2h)，在1170℃高温煅烧10h，自然冷却、气流打散，得到粒径为157微米高纯方石英。
实施例7
无定型二氧化硅A3Kg，在100℃干燥2小时,将30g偶联剂(CH3O)3Si(CH2)5CH3与100g乙醇混合得到改性液，将改性液与干燥后的无定型二氧化硅混合均匀、干燥(100℃、2h)，在1170℃高温煅烧6h，自然冷却、气流打散，得到粒径为135微米高纯方石英。
对比例1
无定型二氧化硅A3Kg，在100℃干燥2小时，将30g偶联剂(CH3O)3Si(CH2)7CH3与100g乙醇混合得到改性液，将改性液与干燥后的无定型二氧化硅混合均匀、干燥(100℃、2h)，在1170℃高温煅烧8h，自然冷却、气流打散，得到粒径为163微米高纯方石英。
对比例2
将美国尤尼明公司型号ITOA-6高纯石英，在100℃干燥2小时、1170℃高温煅烧10h，自然冷却、气流打散，得到粒径为230微米高纯方石英。
结果与检测
对制得的样品采用ICP-OSE(检出限为1ppb)测试杂质离子，结果如表1所示：
表1原料和实施例样品杂质离子测试结果(单位ppm)
对制得的样品测量其粒径、孔隙率和结晶度。通过氮气吸附-脱附法测孔隙，通过粒度分析仪测量粒径，通过XRD测量结晶度，结果如表2所示。
表2
表3实施例5-7经过偶联剂处理前后物料中羟基含量(单位ppm)，羟基含量根据红外光谱计算，结果如表3所示。
表3

数据分析：从表1看，与原料相比产物的杂质含量有一定上升，可能的原因是制备过程中不可避免的污染。
表2中采用偶联剂处理后的物料，高温煅烧后，孔隙率显著降低。实施例6与实施例7相比，采用长链硅烷偶联剂，孔隙率相对较高，且采用短链硅烷偶联剂可以在较短时间内达到较高的结晶度，更为节能。
表3中物料经过偶联剂处理后，羟基含量显著降低，经过煅烧得到的方石英中，羟基含量进一步降低。
图2为原料高纯二氧化硅的红外图谱，在3410cm-1处和1642cm-1处有振动峰说明其表面带有羟基。
图3为方石英的红外图谱，在3410cm-1处和1642cm-1处没有振动峰说明其表面无法测出含有羟基。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (12)

  1. 一种高纯方石英的制备方法，其特征在于，将无定型二氧化硅经过干燥、煅烧、打散得到高纯方石英。
  2. 根据权利要求1所述的一种高纯方石英的制备方法，其特征在于，所述无定形二氧化硅包括但不限于通过金属硅氧化获得。
  3. 根据权利要求2所述的一种高纯方石英的制备方法，其特征在于，所述金属硅氧化为金属硅燃烧，或金属硅与高纯水高温反应，或金属硅转化为含硅有机物，如硅烷，然后煅烧转化为无定型纳米氧化硅中任意一种。
  4. 根据权利要求1所述的一种高纯方石英的制备方法，其特征在于，所述无定形二氧化硅的粒径为5纳米-1微米。
  5. 根据权利要求1所述的一种高纯方石英的制备方法，其特征在于，所述干燥条件为：100℃-150℃处理1-2h。
  6. 根据权利要求1所述的一种高纯方石英的制备方法，其特征在于，所述煅烧条件为：1100℃-1700℃处理2-10h。
  7. 根据权利要求1所述的一种高纯方石英的制备方法，其特征在于，所述高纯方石英粒径为120-450微米。
  8. 根据权利要求1所述的一种高纯方石英的制备方法，其特征在于，所述高纯方石英中Al、B、Ca、Cr、Cu、Fe、K、Li、Mg、Mn、Na、Ni、P、Ti、Zn元素总含量小于20ppm。
  9. 根据权利要求1所述的一种高纯方石英的制备方法，其特征在于，干燥后，还包括使用偶联剂处理的步骤。
  10. 根据权利要求8所述的一种高纯方石英的制备方法，其特征在于，所述偶联剂选自硅烷偶联剂、钛酸酯偶联剂中的任意一种。
  11. 根据权利要求10所述的一种高纯方石英的制备方法，其特征在于，所述硅烷偶联剂为只含有碳、硅、氢、氧元素的硅烷偶联剂。
  12. 根据权利要求11所述的一种高纯方石英的制备方法，其特征在于，所述只含有碳、硅、氢、氧元素的硅烷偶联剂中碳链长度不超过5。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN121266713A (zh) * 2025-12-10 2026-01-06 中南大学 一种基于卵石原料的光伏玻璃用石英砂干法制备工艺

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116873943B (zh) * 2023-08-07 2024-02-23 安徽壹石通材料科技股份有限公司 一种高纯方石英的制备方法
CN119241077B (zh) * 2024-09-20 2025-10-17 安徽壹石通材料科技股份有限公司 一种微晶石英陶瓷及其制备方法与应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4853198A (en) * 1987-03-23 1989-08-01 Nitto Chemical Industry Co., Ltd Process for producing unsintered cristobalite silica
US5154905A (en) * 1990-04-10 1992-10-13 Nitto Chemical Industry Co., Ltd. Method for producing unsintered cristobalite particles
CN1714053A (zh) * 2002-11-29 2005-12-28 信越石英株式会社 合成石英玻璃的制造方法及合成石英玻璃体
CN108821295A (zh) * 2018-07-24 2018-11-16 衢州市鼎盛化工科技有限公司 无定型二氧化硅制备超纯石英砂的方法
CN116873943A (zh) * 2023-08-07 2023-10-13 安徽壹石通材料科技股份有限公司 一种高纯方石英的制备方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2839725B2 (ja) * 1990-12-28 1998-12-16 新日鐵化学株式会社 高純度結晶質シリカの製造方法
JP2586973B2 (ja) * 1992-01-24 1997-03-05 日東化学工業株式会社 クリストバライトの製造方法
JP3661026B2 (ja) * 1994-04-13 2005-06-15 東ソー株式会社 クリストバライト粒子の製造方法
KR100720016B1 (ko) * 1999-12-28 2007-05-18 가부시키가이샤 와타나베 쇼코 실리카 입자, 합성 석영 가루 및 합성 석영 유리의 합성방법
JP4898014B2 (ja) * 2000-06-28 2012-03-14 ジャパンスーパークォーツ株式会社 合成石英粉の製造方法および石英ガラスルツボの製造方法
JP4371565B2 (ja) * 2000-11-08 2009-11-25 株式会社トクヤマ 石英ガラス前駆体及びその製造方法
JP2004131311A (ja) * 2002-10-09 2004-04-30 Honda Motor Co Ltd シリコン酸化物の製造方法
US9051203B2 (en) * 2012-09-13 2015-06-09 Shin-Etsu Quartz Products Co., Ltd. Black synthetic quartz glass with transparent layer and method for producing the same
CN106430912A (zh) * 2016-08-31 2017-02-22 中国建筑材料科学研究总院 低羟基石英玻璃的制备方法及石英玻璃
CN108675308B (zh) * 2018-06-21 2021-10-01 浙江仟源海力生制药有限公司 一种方英石的制备方法及含该方英石的蒙脱石标准对照品的制备方法
CN113307275B (zh) * 2021-03-05 2022-08-05 武汉大学 一种高纯结晶二氧化硅颗粒的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4853198A (en) * 1987-03-23 1989-08-01 Nitto Chemical Industry Co., Ltd Process for producing unsintered cristobalite silica
US5154905A (en) * 1990-04-10 1992-10-13 Nitto Chemical Industry Co., Ltd. Method for producing unsintered cristobalite particles
CN1714053A (zh) * 2002-11-29 2005-12-28 信越石英株式会社 合成石英玻璃的制造方法及合成石英玻璃体
CN108821295A (zh) * 2018-07-24 2018-11-16 衢州市鼎盛化工科技有限公司 无定型二氧化硅制备超纯石英砂的方法
CN116873943A (zh) * 2023-08-07 2023-10-13 安徽壹石通材料科技股份有限公司 一种高纯方石英的制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Characteristics of Impurities in High-Purity Quartz and Progress in Deep Chemical Purification Technology", CONSERVATION AND UTILIZATION OF MINERAL RESOURCES, August 2022 (2022-08-01)
JIANG XUEXIN ET AL.: "Thermal Kinetic Desorption of Gas-Liquid Impurities in Natural Quartz", JOURNAL OF THE CHINESE CERAMIC SOCIETY, October 2004 (2004-10-01)
See also references of EP4530255A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN121266713A (zh) * 2025-12-10 2026-01-06 中南大学 一种基于卵石原料的光伏玻璃用石英砂干法制备工艺

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