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研究生: 李珣琦
Li, Hsun-Chi
論文名稱: 太陽能產業切削矽泥分選碳化矽及矽之研究
The Separation of Silicon Carbide and Silicon from Silicon Slurry in Solar Energy Industry
指導教授: 陳偉聖
Chen, Wei-Sheng
學位類別: 博士
Doctor
系所名稱: 工學院 - 資源工程學系
Department of Resources Engineering
論文出版年: 2018
畢業學年度: 106
語文別: 中文
論文頁數: 58
中文關鍵詞: 切削矽泥浮選法碳化矽再利用
外文關鍵詞: Waste Silicon Slurry, Silicon Carbide, Flotation Method
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  • 由於太陽能產業日漸蓬勃的發展,矽晶圓的產能也日漸提高,同時也會形成更多切削矽泥。切削矽泥的產生是來自於矽晶圓的切割過程所產生的廢棄物,組成主要是矽、碳化矽、金屬粒子與醇類水溶液。
    目前環保署的統計,每年約有2萬公噸的切削矽泥產生,而切削矽泥的處理方式是以焚化及掩埋為主。由於切削矽泥的組成主要是由碳化矽及矽,因此如果可以將切削矽泥中的碳化矽及矽有效的回收並且再利用,即可建立起切削矽泥的資源循環。
    切削矽泥分選方式,主要可分為物理法、化學法及浮選。物理分選主要是以重力、離心、電泳法為主,化學分選主要是以酸溶浸漬為主,浮選法分選主要是以顆粒表面的親、疏水性做為分選方法。本研究利用浮選法分選切削矽泥中的碳化矽及矽,在浮選的過程中探討礦漿濃度、氧化還原電位等浮選條件,提高切削矽泥。由本研究的結果可以得知,當礦漿條件為1:5,粗選礦漿電位為-400mV,氫氟酸濃度為0.8M,氣體條件為氮氣,精選礦漿電位為300mV,氫氟酸濃度為0.6M,氣體條件為氮氣且增加活性劑氟化鈉為最佳化條件浮選,切削矽泥經浮選所獲得之沉礦碳化矽純度為98.2%及浮礦矽純度為71.5%。

    The growth of the solar energy industry has resulted in increasing wafer production. Wafers are primarily cut using silicon ingot crystal, wire saw, silicon carbide (SiC), and slurry. After cutting and processing, approximately 50% of the wafers become waste silicon slurry, which is composed of silicon, SiC, metal particles, and alcohol aqueous solution.
    According to statistics from Taiwan’s Environmental Protection Administration, approximately 20,000 tons of waste silicon slurry is produced each year, the majority of which is incinerated or buried. The mainly components of waste silicon slurry are SiC and Si; therefore, if these components could be effectively recycled and reuse, a resource cycle from waste silicon slurry could be established.
    Methods for separating waste silicon slurry include physical, chemical, and flotation methods. Physical separation mainly comprises using gravity, centrifuge, and electrophoresis; chemical separation requires soaking the waste silicon slurry in acid solution; and flotation separation utilizes the particle surface hydrophilicity and hydrophobicity. In this study, the flotation method was employed to separate SiC and Si from waste silicon slurry. During the flotation process, the flotation criteria were examined to increase the recycle rate of SiC and Si, including pulp density and oxidation reduction potential. The results revealed the optimal conditions for using the flotation method to separate waste silicon slurry, which resulted in a SiC grade of 98.2% and a Si grade of 71.5%.

    中文摘要 I EXTENDED ABSTRACT II 誌謝 VII 目 錄 IX 表目錄 XI 圖目錄 XII 第一章 緒論 1 1-1、前言 1 1-2、研究動機與目的 6 第二章 文獻回顧及理論基礎 7 2-1、切削矽泥資源化技術 7 2-1-1、物理分選 7 2-1-2、化學分選 10 2-1-3、浮選 11 2-2、浮選之理論基礎 12 2-2-1、接觸角 13 2-2-2、親水性、疏水性 13 2-2-3、礦漿氧化還原電位 14 第三章 實驗方法及步驟 16 3-1 研究流程架構 16 3-2、特性分析 17 3-2-1、粒徑分析 18 3-2-2、電子顯微鏡分析 18 3-2-3、成分半定量分析 18 3-2-4、成分定量分析 19 3-2-5、晶相分析 19 3-2-6、界達電位分析 19 3-3、浮選操作 20 3-3-1、浮選設備 20 3-3-2、浮選條件 20 3-3-3、浮選純度、回收率及分選效率之分析 21 3-4、實驗藥品 23 第四章 結果與討論 24 4-1、切削矽泥特性分析 24 4-1-1、粒徑分析結果 24 4-1-2、電子顯微鏡分析結果 25 4-1-3、成分分析結果 25 4-1-4、晶相分析結果 27 4-1-5、表面帶電性分析結果 27 4-2、浮選試驗 28 4-2-1、礦物自浮性探討 28 4-2-2、礦物顆粒表面改質之探討 29 4-2-3、礦漿濃度之探討 31 4-2-4、浮選藥劑之探討 32 4-2-5、浮選條件小結 34 4-3、分選效率之探討 35 4-3-1、表面改質之探討 35 4-3-2、礦漿電位之探討 36 4-3-3、氣體條件探討 40 4-4、最佳化切削矽泥資源化成效之探討 44 第五章 結論與建議 49 5-1、結論 49 5-2、建議 50 參考文獻 51

    1.Sarti, D. and Einhaus, R.,” Silicon Feedstock for the Multi-Crystalline Photovoltaic Industry”, Solar Energy Material and Solar Cells, 72, p.27~p.40, 2002.
    2. Green, M. A., “Photovoltaics: technology overview.”, Energy Policy, 28, p.989~998, 2000.
    3. T. Surek,,”Crystal growth and materials research in photovoltaics: progress and challenges”,Journal of Crystal Growth 275,p.292~ 304,2005。
    4.Branker, K., Pathak, M.J.M., Pearce, J. M.,” A review of solar photovoltaic levelized cost of electricity.” Renew. Sustain. Energy Rev, 15 (9), p.4470-4482, 2011.
    5.Chen W., Hong J., Yuan X., Liu J., “Environmental impact assessment of monocrystalline silicon solar photovoltaic cell production: a case study in China.” Journal of Cleaner Production in press, Retrieved from September 30, 2015, http://www.sciencedirect.com/science/article/pii/S0959652615011130
    6.IEA, International Energy agency (2014). National survey report of PV power application in China 2013, Retrieved from September 27, 2015, http://iea-pvps.org/index.php?id=93&eID=dam_frontend_push&docID=2195.
    7.財團法人光電科技工業協進會,”全球太陽光電市場與台灣”, 財團法人光電科技工業協進會,2011。
    8. 陳伯耕:矽晶圓製造業資源化應用技術手冊,經濟部工業局與財團法人台灣綠色生產力基金會,台北(2007)。
    9.Y. S. Tsuo, J. M. Gee, P. Menna., D. S. Strebkov, A. Pinov and V. Zadde, , “Environmentally Benign Silicon Solar Cell Manufacturing “, Presented at the 2nd world Conference and Exhibition on Photovoltaic Solar Energy Conversion, p.6-10, 1998.
    10.W. Y. Peng and Y. S. Liao, “Study of electrical discharge machining technology for slicing silicon ingots, Journal of Material Processing Technology”, 140, p.278-279, 2003.
    11. 行政院環境保護署事業廢棄物申報及管理系統: http://waste.epa.gov.tw/prog/IndexFrame.asp?Func=2
    12. T. Y. Wang, Y. C. Lin, C. Y. Tai, C. C. Fei, M. Y. Tseng and C. W. Lan, “Recovery of silicon from kerf loss slurry waste for photovoltaic applications’”, Progress in photovoltaics: research and applications, 17, p.155-163, 2009.
    13. Yen-Chih Lin and Clifford Y. Tai, “Recovery of silicon powder from kerfs loss slurry using phase-transfer separation method.”, Separation and purification technology, 74, p.170-177, 2010.
    14藍崇文;林彥志;王珽玉;戴怡德,”切割矽泥回收方法”,專利編號:I337983,2011。
    15. Yen-Chin Lin, Teng-Yu Wang, Chung-Wen Lan and Clifford Y. Tai, “Recovery of silicon powder from kerf loss slurry by centrifugation.”, Powder Technology, 200, p.216-223, 2010.
    16.戴怡德,”碳化矽之回收方法”,專利編號:201144221,2011。
    17. Suning Liu, kai Huang and Hongmin Zhu, Recovery of powder from silicon wiresawing slurries by tuning the particle potential combined with centrifugation, Separation and purification technology, 118, p.448-454, 2013.
    18. 李宗樺” 矽泥廢料定量技術與其沉降行為研究”國立台北科技大學,2014。
    19. 李韋皞, 許致瑋, 鄭大偉, 林欽山,利用濕式渦錐進行矽晶圓切割矽泥資源化之研究。中國鑛冶工程學會,57卷4期,p.84-96,2012。
    20. Chih-Wei Hsu, Wei-Hao Lee, Ta-Wui Cheng and Chin-Shan Lin, “A Study on Recovery of Silicon Carbide from Silicon Sawing Waste byHydrocyclone.”, The 12th International Symposium on East Asian Resources Recycling Technology, p.134-138, 2013.
    21.楊志中,”矽晶圓切割研磨廢棄物的回收處理方法及其設備”,專利編號:I504573,2015。
    22. Sergii A. Sergiienko, Boris V. Pogorelov and Vladimir B. Daniliuk, Silicon and Silicon carbide powders recycling technology from wire-saw cutting waste in slicing process of silicon ingots. Separation and purification technology, 133, p.16-21, 2014,.
    23. Shigehiro Nishijima, Yoshinobu Izumi, Shin-Ichi Takeda, Hiroki Suemoto, Atsushi Nakahira and Shin-Ichi Horie, Recycling of abrasives from wasted slurry by superconducting magnetic separation, IEEE Transactions on applied superconductivity, 13(2), p.1596-1599, 2003.
    24. Yung-Fu Wu and Yuan-Ming Chen, “Separation of silicon and silicon carbide using an electrical field.”, Separation and purification technology, 68, p.70-74, 2009.
    25. Tzu-Hsuan Tsai, “Modified sedimentation system for improving of silicon and silicon carbide in recycling of sawing waste.”, Separation and purification technology, 78, p.16-20 , 2011.
    26.Tzu-Hsuan Tsai and Jui-hsiung Huang, “Metal removal from silicon sawing waste using the electrokinetic method.”, 40, p1-5, 2009.
    27. Tzu-Hsuan Tsai, “Silicon sawing waste treatment by electrophoresis and gravitational setting.”, Journal of Hazardous Materials, 189, p.526-530, 2011.
    28. 黃伯涵,”以電泳法及重力法進行矽及碳化矽分離之研究”,國立台灣大學,2007。
    29. 施郁霈,”自矽泥廢料中回收切割液之研究”,國立台北科技大學,2010。
    30.Xiu-qin Wei, Chuan-qiang Yin, Yue-peng Wan and Lang Zhou, Effect of wet oxidation on recovery of silicon from wire saw slurry by liquid-liquid extraction, Separation and purification technology, 149,p. 457-461, 2015.
    31. 程東科, 蕭立殷:矽晶圓切割廢料之處理方法,證書號數:I421930,2013。
    32.藍崇文;林彥志;王珽玉;戴怡德,”回收矽泥之方法”,專利編號:I347305,2008。
    33. 楊家福,” 切割矽泥回收矽的應用研究”,國立台灣大學,2017。
    34. 林祐翔,”含切削油廢矽泥資源回收之研究”大葉大學,2012。
    35. Muhlbauer, A., Diers, V., Walther, A. and Grabmaier, J. G., “Removal of C/SiC from liquid silicon by directional solidification”, Journal of Crystal Growth, v.108, p.41~52, 1991.
    36.張祖恩,”半導體廢料回收及稀有金屬純化精煉技術研發3年計畫”,國立成功大學,2013。
    37. TOMITA, TAKASHI,”矽及碳化矽之製造方法及製造裝置”,專利編號:201202139,2012。
    38.賀蘭鴻、郭美玲、馬克富、朱華全及張黃文,”乳化藥劑在煤泥選應用”,中國科技論文,2010。
    39.歐樂民、黃思捷及朱陽戈,”硫化礦浮選體系中金屬離子對石英浮選行為的影響”中南大學學報,第43卷,第2期,2012
    40.張秀梅與郭德,”浮選劑對煤表面電位的影響”,煤炭工程,第2期,2004。
    41.張建鋒、楊長生、王曉昌及金同軌,” 濾料表面電位測定”,西安建築科技大學學報,第33卷,第3期,2001
    42. Hrushikesh Sahoo, Swagat S. Rath, Danda S. Rao, Barada K. Mishra and Bisweswar Das,” Role of silica and alumina content in the flotation of iron ores.”, international Journal of Mineral processing, 148, p.83-91, 2016.
    43.H. K. Lin, J. L. Oleson, J. T. Hollow and D. E. Walsh,” Characterization and flotation of gold in carbon fine at the Fort Knox mine Alaska.”, Minerals and Metallurgical Processing, vol. 19 No.1, p.21-24, 2002.
    44.J. Iskra, Flotation properties of silicon carbide I. Flotation of silicon carbide with anionic and cationic collector, Ceramics International. 23, p.337-342, 1997.
    45.J. Iskra, Flotation properties of silicon carbide II. On the Influence of Multivalent Cations on the Flotation of Silicon Carbide with Sodium Oleate, Ceramics International. 23, p.343-348, 1997.
    46.萬用波,”熱化學浮選法處理含油污泥的試驗研究”,油氣田環保保護,第24卷,第4期,2014
    47. Junji Shibata, Norihiro Murayama and Kengo Nagae, Flotation Separation of SiC from Wastes in the Silicon Wafer Slicing Process, KAGAKU KOGAKU RONBUNSHU, 32(1), p.93-98, 2006. doi:10.1252/kakoronbunshu.32.93.
    48.張育誠、吳國光及焦鴻文,”疏水性材料”,能源報導,2011
    49. Oo K.Z., Shibayamy A., Miyazaki T., Kuzuno E., Fujita T., Tsuji Y., Yen W. T., “Study of mutual separation of silicon and quartz using liquid-liquid extraction.”, International Journal of Society of Materials Engineering Resources, 10, p.71-74, 2002.
    50. W. Barthlott and C.Neinhuis, Planta,202, p.1-8,1997.
    51. 陳紘珉,”隱匿於蓮花中的超疏水現象”,奈米通訊,22卷,第4期,2015
    52. E. F Hare, E. G. Shafrin and W. A. Zisman, J.phys. Chem., 58, p.236-239, 1954.
    53.羅先平,”難選鉛鋅硫化礦電位調控浮選機裡與應用”,冶金工業出版社,2010。
    54.譚文慶, 姚國成, 願幗華, 邱冠周, 王錠佐,”硫化礦物的浮選電化學與浮選行為”,中國有色金屬學報,第21卷,第10期,2011。
    55. Tzu-Hsuan Tsai, Yu-Pei Shih and Yung-Fu Wu, “Recycling silicon wire-saw slurries: Separation of silicon and silicon carbide in a ramp settling tank under an applied electrical field.”, Journal of the Air & Waste Management Association, 63(5), p.521-527, 2013.
    57. 林彥志,”矽泥中矽粉之回收”,國立台灣大學,2010。
    58.F. M. Ernsberger, “Structural effects in the chemical reactivity of silica and silicates.”, Journal of physics and chemistry of solids, Vol. 13, p.347-351, 1960.
    59. H. K. Lin, D. E. Walsh, S. H. Sonderland, C. Bissue and A. Debrah, “ Floatability of metallic iron fines from comminution circuits and their effect on flotation of a sulfide ore, Minerals and Metallurgical Processing.”, vol. 25 No.4, p.206-210, 2008.
    60.Zhiguang Guo, Feng Zhou, Jingcheng Hao and Weimin Liu, “Stable biomimetic super-hydrophobic engineering materials.”, Journal of the American Chemical Society, 127, p.15670-15671, 2005.
    61.E.Larsen, R. A. Kleiv, “Flotation of quartz from quartz-feldspar mixtures by the HF method, Minerals Engineering.”, 98, p. 49-51, 2016.
    62.李文鐘,選礦學,世界書局,1979。
    63. Bhagyalaxmi Kar, Hrushikesh Sahoo, Swagat S. Rath and B. Das, “Investigations on different starches as depressants for iron ore flotation”, Minerals Engineering, 49, p.1-6, 2013.
    64. Przemyslaw B. Kowalczuk, Emilia Zaleska and Oliver Danczak, “Flotation of carbonaceous copper shale-quartz mixture with poly(ethylene glycol) alkyl ethers”, Trans. Nonferrous Met. Soc. China, 25, p.314~318, 2015.
    65.聶光華、孫體昌、劉志紅及羅國菊,”氟離子對碳化鹽礦物浮選影響極其機理”,中國有色金屬學報,第24卷,第12期,2014
    66.林健三與林健榮,”固體廢棄物處理”,高立圖書有限公司,2017。

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