高纯石英砂资源及加工技术分析
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摘要
高纯石英砂是微电子、光纤通信、航空航天等高新技术产业的基础原材料,战略地位非常重要。目前,制备高纯石英砂主要通过化学合成、天然水晶加工及石英矿物深度提纯。其中,通过化学合成和天然水晶加工的制备方法受原料、成本、产量等方面的制约,难以大规模工业应用;因此,通过石英矿物制备高纯石英砂的加工技术将是未来的主要研究方向。然而,我国对以石英矿物为原料制备高纯石英砂的相关研究起步晚、研究少,技术被欧美发达国家长期垄断,市场大量依靠进口。从原料分析出发,对比了用于制备高纯石英砂的石英原矿的矿物特性,得出花岗伟晶岩和脉石英是制备高纯石英砂的最理想原料。系统分析了石英原矿中的伴生脉石矿物类型以及Al、Fe、Ca、K等常见杂质元素的存在形式和附存状态,并着重分析了晶格杂质和包裹体杂质的晶体构型,指出了晶格杂质难以脱除是制约高纯石英砂品质的主要原因。从矿物加工专业角度,并依据不同的加工目的将现行的高纯石英砂加工技术分成4个大类,对各类生产工艺状况进行了详细的分析概括,指出了现行工艺技术的不足以及与国际先进技术水平间的差距。在此基础上提出,目前高纯石英砂生产和研究中存在的问题及未来的研究方向,为今后相关研究提供理论指导。
High-purity quartz sand is the basic raw material for high-tech industries such as microelectronics,optical fi?ber communication,and aerospace,having an important strategic position in the development of the national economy. At present,the preparation of high-purity quartz sand can be through chemical synthesis,natural crystal processing and deep pu?rification of quartz minerals. Among them,the preparation method by chemical synthesis and natural crystal processing is re?stricted by raw materials,cost,yield,and so on,which are difficult to be industrially applied in large scale.Therefore,pre?paring high-purity quartz sand through quartz mineralswill be the main research direction in the future. However,the related researches in China were started late and insufficient. The technologies were monopolized by developed countries for a long time. So,the high-purity quartz sand market ofour country is heavily dependent on imports. Based on the analysis of raw mate?rials,this paper compares the mineral properties of different quartz ores used to prepare high-purity quartz sand are compre?hensively compared. It is concluded that granitic pegmatite and vein quartz are the most ideal raw materials for the preparation of pure quartz sand. The types of accompanying gangues and the existing and attached states of common impurity elements such as Al,Fe,Ca and K in quartz minerals are systematically analyzed,especially the lattice impurities and inclusion impuri?ties. It is pointed out that the lattice impurities difficult to be removedis the main factor restricting the quality of high purity quartz sand.From the perspective of mineral processing,the current high-purity quartz sand processing technologiesare divid?ed into four categories according to the different processing purposes.Moreover,the production process status are summarized andanalysised in detail,which highlights the shortcomings of current craftsmanship and the gap with international advanced technology.On this basis,the problems existing in the production and the future research directions of high-purity quartz san?dare proposed,which provide some theoretical guidance for the related research in the future.
High-purity quartz sand is the basic raw material for high-tech industries such as microelectronics,optical fi?ber communication,and aerospace,having an important strategic position in the development of the national economy. At present,the preparation of high-purity quartz sand can be through chemical synthesis,natural crystal processing and deep pu?rification of quartz minerals. Among them,the preparation method by chemical synthesis and natural crystal processing is re?stricted by raw materials,cost,yield,and so on,which are difficult to be industrially applied in large scale.Therefore,pre?paring high-purity quartz sand through quartz mineralswill be the main research direction in the future. However,the related researches in China were started late and insufficient. The technologies were monopolized by developed countries for a long time. So,the high-purity quartz sand market ofour country is heavily dependent on imports. Based on the analysis of raw mate?rials,this paper compares the mineral properties of different quartz ores used to prepare high-purity quartz sand are compre?hensively compared. It is concluded that granitic pegmatite and vein quartz are the most ideal raw materials for the preparation of pure quartz sand. The types of accompanying gangues and the existing and attached states of common impurity elements such as Al,Fe,Ca and K in quartz minerals are systematically analyzed,especially the lattice impurities and inclusion impuri?ties. It is pointed out that the lattice impurities difficult to be removedis the main factor restricting the quality of high purity quartz sand.From the perspective of mineral processing,the current high-purity quartz sand processing technologiesare divid?ed into four categories according to the different processing purposes.Moreover,the production process status are summarized andanalysised in detail,which highlights the shortcomings of current craftsmanship and the gap with international advanced technology.On this basis,the problems existing in the production and the future research directions of high-purity quartz san?dare proposed,which provide some theoretical guidance for the related research in the future.
引文
[1]丁亚卓.低品位石英矿提纯制备高纯度石英的研究[D].沈阳:东北大学,2010.Ding Yazhuo.Investigation on the Preparation of High Purity Quartz from Low Grade Silica[D].Shenyang:Northeastern University,2010.
[2]Müller A,Wanvik J E,Ihlen P M.Petrological and chemical characterisation of high-purity quartz deposits with examples from Norway[J].Springer Geology,2012:71.
[3]Konstantinos I V,George C,Nikolas P B.Market of high purity quartz innovative applications[J].Procedia Economics and Finance,2015,24:734.
[4]中国粉体技术网.从进出口数据看中国石英与国外同行的差距[OL].2018-02-26.http://www.cnpowdertech.com/2018/hqzxt_0226/24649.html.China Powder Technology Network.Looking at the gap between Chinese quartz and foreign counterparts from import andexport data[OL].2018-02-26.http://www.cnpowdertech.com/2018/hqzxt_0226/24649.html.
[5]聂兰舰,王玉芬,向在奎,等.高纯合成石英粉的研究现状与发展趋势[J].电子元件与材料,2014,33(10):12.Nie Lanjian,Wang Yufen,Xiang Zaikui,et al.Research and development of high-purity synthetic silica powder[J].Electronic Components and Materials,2014,33(10):12.
[6]王泽杭.用硅石生产高纯石英粉的研究及工业应用[J].国外金属矿选矿,1998(6):23.Wang Zehang.Research and industrial application of high purity quartz produced from silica[J].Metallic Ore Dressing Abroad,1998(6):23.
[7]刘国库,张文军,马正先,等.硅石选矿提纯工艺研究现状[J].有色矿冶,2007,23(6):26.Liu Guoku,Zhang Wenjun,Ma Zhengxian,et al.Present situation of researching on purifying silica by mineral processing[J].Non-ferrous Mining and Metallurgy,2007,23(6):26.
[8]徐洪林.石英砂的工业利用及深加工技术[J].矿产保护与利用,1992(1):21.Xu Honglin.Industrial utilization and deep processing technology of quartz sand[J].Conservation and Utilization of Mineral Resources,1992(1):21.
[9]张晔,陈培荣.美国Spruce Pine与新疆阿尔泰地区高纯石英伟晶岩的对比研究[J].高校地质学报,2010,16(4):426.Zhang Ye,Chen Peirong.Characteristics of granitic pegmatite with High-purity quartz in Spruce Pine region,USA and Altay region of Xinjiang,China[J].Geological Journal of China Universities,2010,16(4):426.
[10]Platias S,Vatalis K I,Charalabidis G.Innovative processing techniques for the production of a critical raw material the high purity quartz[J].Procedia Economics and Finance,2013(5):597-604.
[11]钟乐乐.超高纯石英纯化制备及机理研究[D].武汉:武汉理工大学,2015.Zhong Lele.Study on Purifing Preparation and Mechanism of Ultra-pure Quartz[D].Wuhan:Wuhan University of Technology,2015.
[12]Müller A,Wiedenbeck M,Van-Den-Kerkhof A M,et al.Trace elements in quartz-a combined electron microprobe,secondary ion mass spectrometry,laser-ablation ICP-MS,and cathodoluminescence study[J].European Journal of Mineralogy,2003,15(4):747.
[13]Dennen W H.Stoichiometric substitution in natural quartz[J].Geochimica et Cosmochimica Acta,1966,30(12):1235.
[14]Roedder E.Fluid Inclusions-Reviews in Mineralogy[M].Washington:Mineralogical Society of America,1984:644.
[15]Simpson D R.Aluminum phosphate variants in feldspars[J].American Mineralogist,1977,62:351.
[16]McLaren A C,Cook R F,Hyde S T,et al.The mechanism of the formation and growth of water bubbles and associated dislocation loops in synthetic quartz[J].Physics and Chemistry of Minerals,1983,9(2):79.
[17]Harben P.The Industrial Mineral Handybook-a Guide to Markets,Specifications and Prices[M].Surrey K T:Industrial Minerals Information,2002:412.
[18]牛福生,徐晓军,高建国,等.石英砂选矿提纯工艺研究[J].云南冶金,2001,30(1):18.Niu Fusheng,Xu Xiaojun,Gao Jianguo,et al.Study on purifying quartzite by mineral processing[J].Yunnan Metallurgy,2001,30(1):18.
[19]金达表,张兄明,邹蔚蔚.高纯石英的加工工艺研究[J].中国非金属矿工业导刊,2004(4):44.Jin Dabiao,Zhang Xiongming,Zou Weiwei.Research on processing technology of high purity quartz[J].China Non-Metallic Mining Industry Guide,2004(4):44.
[20]田金星.高纯石英砂的提纯工艺研究[J].中国矿业,1999,8(3):55.Tian Jinxing.Researches of extraction technology of high-grade quartz sand[J].China Mining Magazine,1999,8(3):55.
[21]田辉明.利用脉石英制备高纯超细硅微粉的方法:中国,201110247392.8[P].2011-08-26.Tian Huimin.Method for preparing high-purity ultrafine silicon micropowder by using vein quartz:China,201110247392.8[P].2011-08-26.
[22]牛福生,倪文.高纯石英砂选矿提纯试验研究[J].中国矿业,2004,13(6):57.Niu Fusheng,Ni Wen.Study on high-purity quartzite by mineral processing[J].China Mining Magazine,2004,13(6):57.
[23]苏州中材非金属矿工业设计研究院有限公司.采用脉石英制备超细高纯石英材料的方法:中国,200410014058.8[P].2004-02-12.Suzhou Sinoma Non-Metallic Mining Industry Design and Research Institute Co.,Ltd.Method for preparing ultrafine high purity quartz material by using vein quartz:China,200410014058.8[P].2004-02-12.
[24]连云港金瑞照明电器有限公司.一种制备高纯石英砂的方法:中国,201210080340.0[P].2012-03-25.Lianyungang Jinrui Lighting Appliance Co.,Ltd.Method for preparing high-purity quartz sand:China,201210080340.0[P].2012-03-25.
[25]连云港市弘扬石英制品有限公司.一种以低品位石英矿为原料生产高品质石英砂的方法:中国,201310384893.X[P].2013-08-30.Lianyungang Hongyang Quartz Products Co.,Ltd.A method for producing high quality quartz sand with low grade quartz ore as raw material:China,201210080340.0[P].2012-03-25.
[26]蔡雅纯.一种高纯石英砂的生产方法:中国,201210416253.8[P].2012-10-26.Cai Yachun.Production method of high-purity quartz sand:China,201210416253.8[P].2012-10-26.
[27]新沂市中大石英科技有限公司.一种高纯石英砂制备方法:中国,201310343561.7[P].2013-08-09.Xinyi Zhongda Quartz Technology Co.,Ltd.A preparation method of high-purity quartz sand:China,201310343561.7[P].2013-08-09.
[28]安徽工业大学.一种制备高纯石英粉的方法:中国,200810023283.6[P].2008-04-07.Anhui University of Technology.Method for preparing high-purity quartz powder:China,200810023283.6[P].2008-04-07.
[29]汪灵,李彩侠,王艳,等.我国高纯石英加工技术现状与发展建议[J].矿物岩石,2011,31(4):110.Wang Ling,Li Caixia,Wang Yan,et al.China technologies present of high-purity quartz processing and the development propositions[J].Journal of Mineralogy and Petrology,2011,31(4):110.
[2]Müller A,Wanvik J E,Ihlen P M.Petrological and chemical characterisation of high-purity quartz deposits with examples from Norway[J].Springer Geology,2012:71.
[3]Konstantinos I V,George C,Nikolas P B.Market of high purity quartz innovative applications[J].Procedia Economics and Finance,2015,24:734.
[4]中国粉体技术网.从进出口数据看中国石英与国外同行的差距[OL].2018-02-26.http://www.cnpowdertech.com/2018/hqzxt_0226/24649.html.China Powder Technology Network.Looking at the gap between Chinese quartz and foreign counterparts from import andexport data[OL].2018-02-26.http://www.cnpowdertech.com/2018/hqzxt_0226/24649.html.
[5]聂兰舰,王玉芬,向在奎,等.高纯合成石英粉的研究现状与发展趋势[J].电子元件与材料,2014,33(10):12.Nie Lanjian,Wang Yufen,Xiang Zaikui,et al.Research and development of high-purity synthetic silica powder[J].Electronic Components and Materials,2014,33(10):12.
[6]王泽杭.用硅石生产高纯石英粉的研究及工业应用[J].国外金属矿选矿,1998(6):23.Wang Zehang.Research and industrial application of high purity quartz produced from silica[J].Metallic Ore Dressing Abroad,1998(6):23.
[7]刘国库,张文军,马正先,等.硅石选矿提纯工艺研究现状[J].有色矿冶,2007,23(6):26.Liu Guoku,Zhang Wenjun,Ma Zhengxian,et al.Present situation of researching on purifying silica by mineral processing[J].Non-ferrous Mining and Metallurgy,2007,23(6):26.
[8]徐洪林.石英砂的工业利用及深加工技术[J].矿产保护与利用,1992(1):21.Xu Honglin.Industrial utilization and deep processing technology of quartz sand[J].Conservation and Utilization of Mineral Resources,1992(1):21.
[9]张晔,陈培荣.美国Spruce Pine与新疆阿尔泰地区高纯石英伟晶岩的对比研究[J].高校地质学报,2010,16(4):426.Zhang Ye,Chen Peirong.Characteristics of granitic pegmatite with High-purity quartz in Spruce Pine region,USA and Altay region of Xinjiang,China[J].Geological Journal of China Universities,2010,16(4):426.
[10]Platias S,Vatalis K I,Charalabidis G.Innovative processing techniques for the production of a critical raw material the high purity quartz[J].Procedia Economics and Finance,2013(5):597-604.
[11]钟乐乐.超高纯石英纯化制备及机理研究[D].武汉:武汉理工大学,2015.Zhong Lele.Study on Purifing Preparation and Mechanism of Ultra-pure Quartz[D].Wuhan:Wuhan University of Technology,2015.
[12]Müller A,Wiedenbeck M,Van-Den-Kerkhof A M,et al.Trace elements in quartz-a combined electron microprobe,secondary ion mass spectrometry,laser-ablation ICP-MS,and cathodoluminescence study[J].European Journal of Mineralogy,2003,15(4):747.
[13]Dennen W H.Stoichiometric substitution in natural quartz[J].Geochimica et Cosmochimica Acta,1966,30(12):1235.
[14]Roedder E.Fluid Inclusions-Reviews in Mineralogy[M].Washington:Mineralogical Society of America,1984:644.
[15]Simpson D R.Aluminum phosphate variants in feldspars[J].American Mineralogist,1977,62:351.
[16]McLaren A C,Cook R F,Hyde S T,et al.The mechanism of the formation and growth of water bubbles and associated dislocation loops in synthetic quartz[J].Physics and Chemistry of Minerals,1983,9(2):79.
[17]Harben P.The Industrial Mineral Handybook-a Guide to Markets,Specifications and Prices[M].Surrey K T:Industrial Minerals Information,2002:412.
[18]牛福生,徐晓军,高建国,等.石英砂选矿提纯工艺研究[J].云南冶金,2001,30(1):18.Niu Fusheng,Xu Xiaojun,Gao Jianguo,et al.Study on purifying quartzite by mineral processing[J].Yunnan Metallurgy,2001,30(1):18.
[19]金达表,张兄明,邹蔚蔚.高纯石英的加工工艺研究[J].中国非金属矿工业导刊,2004(4):44.Jin Dabiao,Zhang Xiongming,Zou Weiwei.Research on processing technology of high purity quartz[J].China Non-Metallic Mining Industry Guide,2004(4):44.
[20]田金星.高纯石英砂的提纯工艺研究[J].中国矿业,1999,8(3):55.Tian Jinxing.Researches of extraction technology of high-grade quartz sand[J].China Mining Magazine,1999,8(3):55.
[21]田辉明.利用脉石英制备高纯超细硅微粉的方法:中国,201110247392.8[P].2011-08-26.Tian Huimin.Method for preparing high-purity ultrafine silicon micropowder by using vein quartz:China,201110247392.8[P].2011-08-26.
[22]牛福生,倪文.高纯石英砂选矿提纯试验研究[J].中国矿业,2004,13(6):57.Niu Fusheng,Ni Wen.Study on high-purity quartzite by mineral processing[J].China Mining Magazine,2004,13(6):57.
[23]苏州中材非金属矿工业设计研究院有限公司.采用脉石英制备超细高纯石英材料的方法:中国,200410014058.8[P].2004-02-12.Suzhou Sinoma Non-Metallic Mining Industry Design and Research Institute Co.,Ltd.Method for preparing ultrafine high purity quartz material by using vein quartz:China,200410014058.8[P].2004-02-12.
[24]连云港金瑞照明电器有限公司.一种制备高纯石英砂的方法:中国,201210080340.0[P].2012-03-25.Lianyungang Jinrui Lighting Appliance Co.,Ltd.Method for preparing high-purity quartz sand:China,201210080340.0[P].2012-03-25.
[25]连云港市弘扬石英制品有限公司.一种以低品位石英矿为原料生产高品质石英砂的方法:中国,201310384893.X[P].2013-08-30.Lianyungang Hongyang Quartz Products Co.,Ltd.A method for producing high quality quartz sand with low grade quartz ore as raw material:China,201210080340.0[P].2012-03-25.
[26]蔡雅纯.一种高纯石英砂的生产方法:中国,201210416253.8[P].2012-10-26.Cai Yachun.Production method of high-purity quartz sand:China,201210416253.8[P].2012-10-26.
[27]新沂市中大石英科技有限公司.一种高纯石英砂制备方法:中国,201310343561.7[P].2013-08-09.Xinyi Zhongda Quartz Technology Co.,Ltd.A preparation method of high-purity quartz sand:China,201310343561.7[P].2013-08-09.
[28]安徽工业大学.一种制备高纯石英粉的方法:中国,200810023283.6[P].2008-04-07.Anhui University of Technology.Method for preparing high-purity quartz powder:China,200810023283.6[P].2008-04-07.
[29]汪灵,李彩侠,王艳,等.我国高纯石英加工技术现状与发展建议[J].矿物岩石,2011,31(4):110.Wang Ling,Li Caixia,Wang Yan,et al.China technologies present of high-purity quartz processing and the development propositions[J].Journal of Mineralogy and Petrology,2011,31(4):110.
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