跳到主要內容

簡易檢索 / 詳目顯示

研究生: 林漢宗
Han-Zong Lin
論文名稱: 鋼鐵業副產物衍生磷酸陶瓷固化劑之研究
Study on Developing CBPC Stabilizer using Steel Making Wastes
指導教授: 王鯤生
Kuen-Sheng Wang
口試委員:
學位類別: 碩士
Master
系所名稱: 工學院 - 環境工程研究所
Graduate Institute of Environmental Engineering
畢業學年度: 93
語文別: 中文
論文頁數: 236
中文關鍵詞: 焚化飛灰鋼鐵業副產物磷酸陶瓷固化劑
外文關鍵詞: steel industry waste, Chemically Bonded Phosphate, MSWI fly ash
相關次數: 點閱:9下載:0
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報
  • 本研究針對電弧爐集塵灰、高爐礦泥、鑄鐵集塵灰與熱軋礦泥等鋼鐵鑄造業副產物具有微細顆粒與含有大量氧化鐵之特性,以及晶圓廠廢磷酸的穩定化特性,經由化學計量式與試拌程序混合產製磷酸陶瓷固化劑,並探討磷酸濃度與硼酸劑量對固化體之性質影響實驗,獲得固液比等磷酸陶瓷固化劑配方;同時,以各類固化劑配方固化不同劑量的飛灰,探討飛灰固化量對磷酸陶瓷固化體的新拌與硬固性質,溶出特性,以及微結構的影響,藉此獲得各類磷酸陶瓷固化體的最佳飛灰固化量。最後,以水泥固化為比較基準對各類固化劑進行經濟效益評估。
    實驗結果顯示電弧爐集塵灰、高爐礦泥、鑄鐵集塵灰與熱軋礦泥的化學組成會與磷酸產生明顯反應的氧化金屬總含量,以電弧爐集塵灰與熱軋礦泥為較高(達54%),高爐礦泥次之(38%),鑄鐵集塵灰最低(35%)。前述此四類磷酸陶瓷固化劑的配方:每克鋼鐵業副產物需要磷酸量分別為0.84克、0.68克、0.68克與0.98克,固液比分別為0.52、0.60、0.80與0.30;最佳的硼酸緩凝劑使用量為2wt.%。磷酸濃度過高可能因激烈發泡反應而對固化體的新拌與硬固性質產生不利影響,建議適當磷酸濃度應低於75%以下,而不宜過高。此四種磷酸陶瓷飛灰固化體之TCLP結果均符合法規值,對於Pb與Cu的穩定效果最佳,但部分固化體的抗壓強度低於法規值;電弧
    爐集塵灰、高爐礦泥、鑄鐵集塵灰等磷酸陶瓷固化體之最大飛灰固化量分別為20%、25%、30%,而熱軋礦泥磷酸陶瓷固化體則不適合應用於固化飛灰。電弧爐集塵灰與鑄鐵集塵灰兩種磷酸陶瓷固化劑比傳統水泥固化劑
    深具經濟性,因此具有資源化與市場競爭潛力。


    Chemically bonded phosphate ceramics (CBPCs) are produced by acid-base reactions between an inorganic oxide and either phosphoric acid solution or an acid-phosphate solution. By taking the advantage of forming chemical phosphate bond and the ability to capsulate wastes, the CBPCs can be used to solidify and/or stabilize toxic wastes. Typical reactants of this acid-base process (i.e., MgO, Fe2O3, and phosphoric acid) can be provided with by industrial wastes: iron-oxide-containing wastes can be obtained from steel making plants, and waste phosphoric acid from IC foundry plants. Some of the iron oxide may also be obtained from the MSWI fly ash. These industrial wastes provide an excellent opportunity to evaluate the feasibility of developing phosphate ceramics from wastes (referred to as WDPCs), and to assess their further applicability to solidify and/or stabilize MSWI fly ash. Accordingly, this study investigated the feasibility of developing phosphate ceramics from wastes such as electric arc furnace dust (EAF dust), blast furnace wet dust (BF dust), cast iron dust (CI dust), and hot-roll wet dust (HR dust); as well as waste phosphoric acid. In this study, the waste-derived
    phosphate ceramics (WDPCs) were further evaluated by their capacity to solidify and/or stabilize MSWI fly ash.
    The results indicate that the reactive inorganic oxides, mainly iron (III) oxide, in EAF dust, BF wet dust, CI dust, and HR wet dust were found to be 54, 38, 35, and 54% (w/w), respectively. Each gram of the dusts, stoichiometrically, required 0.84, 0.68, 0,68, and 0.98 gram of phosphoric acid (pure) respectively to produce proper WDPCs, or 1.53, 1.24, 1.24, and 1.77 gram for phosphoric acid of averaged 55% concentration. The WDPCs were fabricated by adding water to the previous formula at a solid-to-liquid ratio as determined by a workable viscosity of the WDPC pastes. The
    determination resulted in an appropriate solid- to-liquid ratio of 0.52, 0.60, 0.80, and 0.30, respectively for the tested EAF dust, BF dust, CI dust, and HR dust respectively. Phosphoric acid concentration less than 75% was recommended to avoid vigorous acid-base reaction and the excessive forming, which adversely affected the quality of the WDPC pastes. For all WDPC samples, the leaching concentrations of the target metals resulting from the TCLP test were found to be in compliance with the US EPA''s regulatory thresholds. The effect of solidification/stabilization for Pb and Cu was especially significant. However, some WDPCs failed to develop sufficient regulatory compressive strength for solidified monolith. One the other hand, of the four WDPCs tested, the
    maximum ratio for MSWI fly ash to be solidified was found to be 20, 25, and 30% (w/w) for phosphate ceramics derived from the corresponding EAF dust, BF dust, and CI dust; whereas that derived from HR wet dust failed in
    solidifying/stabiling MSWI fly ash.
    Solidification/stabilization of MSWI fly ash with WDPCs is economically competitive with other disposal methods such as traditional cement
    solidification process and can have the added attractiveness of being beneficial to the waste disposal.

    目錄 第一章 前 言·································································1 1-1 研究緣起與目的···························································1 1-2 研究內容·································································2 第二章 文獻回顧······························································3 2-1 都市垃圾焚化飛灰的來源與性質·············································3 2-1-1 飛灰產源及產量·······························3 2-1-2 飛灰物化特性···························································5 2-1-3 飛灰之化學元素分布特性·················································8 2-2 傳統固化與穩定化之文獻回顧··············································12 2-2-1 固化/穩定化原理······························12 2-2-2 磷酸穩定化相關文獻回顧················································15 2-3 磷酸陶瓷的發展背景與應用················································18 2-3-1 磷酸陶瓷的發展背景····················································18 2-3-2 磷酸陶瓷的特色························································18 2-3-3 磷酸陶瓷的應用範圍····················································20 2-4 磷酸陶瓷固化的原理與影響因子············································26 2-4-1 二價氧化金屬原料·····························26 2-4-2 三價氧化金屬原料·····························28 2-4-3 溶解度··································30 2-4-4 顆粒比表面積對於反應之影響············································34 2-4-5 影響因子······························································35 第三章 實驗材料與方法·······················································37 3-1 實驗流程································································37 3-2 實驗配置································································40 3-2-1 磷酸陶瓷固化劑配方實驗················································40 3-2-2 硼酸用量實驗··························································40 3-2-3 磷酸濃度實驗··························································41 3-2-4 飛灰固化量配比試驗····················································41 3-3 實驗材料與方法··························································42 3-3-1 實驗材料·································42 3-3-2 實驗與分析設備························································53 3-4 實驗操作································································55 3-4-1 前處理··································55 3-4-2 試體的製備與養護······················································55 3-5 實驗分析································································58 第四章結果與討論································67 4-1 飛灰與各類廢棄物衍生磷酸陶瓷原料的基本性質······························67 4-1-1 物理性質······························································67 4-1-2 化學特性······························································76 4-1-3 重金屬總量與溶出特性··················································79 4-1-4 物種型態與微觀結構····················································81 4-1-5 總結··································································88 4-2 前置試驗································································89 4-2-1 磷酸陶瓷固化劑之配方··················································89 4-2-2 磷酸陶瓷固化劑之固液比················································91 4-2-3 硼酸劑量對新拌漿體性質之影響··········································96 4-3 磷酸濃度試驗···························································100 4-3-1 磷酸濃度對新拌漿體之性質影響·········································100 4-3-2 磷酸濃度對固化體之物化性質影響·······································104 4-3-3 磷酸濃度對固化體之微結構影響·········································110 4-3-4 總結·································································118 4-4 磷酸陶瓷固化飛灰實驗···················································120 4-4-1 飛灰固化量對新拌漿體之性質影響·······································120 4-4-2 飛灰固化量對磷酸陶瓷固化體之物理性質影響·····························134 4-4-3 飛灰固化量對固化體之重金屬溶出特性與耐水性影響·······················150 4-4-4 飛灰固化量對磷酸陶瓷固化體之微觀結構影響·····························195 4-4-5 總結·································································215 4-5 磷酸陶瓷固化劑經濟性分析···············································220 第五章結論與建議···························································225 5-1 結論····································225 5-2 建議···································································229 參考文獻···································································230

    參考文獻
    Alba, S., Kambayashi, F., and Okada, M., “Ash Melting Treatment by Rotating
    Type Surface Melting Furnace,” Waste Management, 16(5/6), 431(1996).
    Alba, N., Gasso, S., Lacorte, T., and Baldasano, J.M., “Characterization of
    municipal solid waste incineration residues from facilities with different air pollution control system,” Journal of Air & Waste Management Association,
    47, 1170-1179(1997).
    Buchholz B.A., and Landsberger S., “Leaching Dynamics Studies of Municipal
    Solid Wsate Incinerator Ash,” Air & Waste Management Association, 45,
    579(1995).
    Chen, X., J.V. Wright, J.L. Conca and L.M. Peurrung, ”Effects of pH on Heavy
    Metal Sorption on Mineral Aapatite,” Environment Science Technology, 31,
    624-631(1997).
    Chen Chris C.Y., Kirk Donald, “Behaviour of Metals Under the Conditions of
    Roasting MSW Incinerator Fly Ash With Chlorinating,” Journal of Hazadous
    Materials, 64, 75(1999).
    Crannell, B.S., T.T. Eighmy, J.E. Krzanowski, J.D. Eusden Jr, E. Shaw and C.A.
    Francis, ”Heavy Metal Stabilization in Municipal Solid Waste Combustion
    Bottom Ash Using Soluble Phosphte,” Waste Management, 20,
    135-148(2000).
    Derie R., “A New Way to Stabilize Fly Ash from Municipal Incinerators,” Waste
    Management, 16(8), 711(1996).
    Eighmy T.T., J.D. Eusden and J.E. Krzanoeski, “Comprehensive Approach toward
    Understanding Element Speciation and Leaching Behavior in Municipal Solid
    Waste Incineration Electrostatic Precipitator Ash,“ Environmental Science &
    Technology, 29(3), 629(1995).
    Eighmy, T.T., B.S. Crannell, L.G. Butler, F.K. Cartledge, E.F. Emery, J.E.
    Krzanowski, J.D. Eusden, E.L. Shaw and Francis, C.A., ”Heavy Metal
    Stabilization in Municapal Solid Waste Combustion Dry Scrubber Residue
    Using Soluble Phosphate,” Environment Science Technology, 31,
    3330-3338(1997).
    E. Soud?e, J. P?ra*, “Mechanism of setting reaction in magnesia-phosphate cements”Cement and Concrete Research, 30, 315-321(1999).
    Gilliam, T., Spence, R., Bostick, W., and Schoemaker, J., “Solidification/stabilization of Tc in cement-based grouts,” in Proc. 2nd Annual Gulf Coast Haz. Substance Research Center Symp., Beumont, TX. (1990).
    Gong Y., and Kirk D.W., “Behaviour of Municipal Solid Waste Incinerator Fly
    Ash. I:Gene ral Leaching Study,” Journal of Hazardous Materials, 36,
    249(1994).
    Hamernik, J.D., and Frantz, G..C., ”Physical and Chemical Properties of Municipal Solid Waste Fly Ash,” ACI Materials Journal, 88(3), 204(1991).
    Helena Manninen, Annilli Perkiu, Juha Palonen, Kari Peltola and Juhani
    Ruuskanen, ”Trace Metal Emissions From Co-combustion of Refuse Derived
    and Packaging Derived Fuels in a Circulationg Fluidzed Bed Boiler,”
    Chemosphere, 32(12), 2457-2469(1996).
    Hettiarachchi, G.M., G.M. Pierzynski and M.D. Ranson, “In Situ Stabilization of Soil Lead Using Phosphorus and Manganese Oxide,” Environment Science
    Technology, 34, 4614-4619(2000).
    IAWG (The International Ash Working Group), ”Municipal Solid Waste
    Incinerator Residues,” Elsevie, (1997).
    Iori J., Balg J., and Wieckert C., “Detoxification of Municipal Waste Incineration Residues by Vitrification,” ABB Review, 6/7, 9(1995).
    Jakob A., Stucki S., and Kuhn P., “Evaporation of Heavy Metals during the Heat
    Treatment of Municipal Solid Waste Incinerator Fly Ash,” Enviromental
    Science & Technology, 29(9), 2429(1995).
    Kanazawa, T., ed., ” Inorganic Phosphate Materials,” Elsevier, New York:
    121(1989).
    Kingery, W., “Fundamental Studies of Phosphate Bonding in Refractories, II.
    Cold–setting Properties,” J. Am. Ceram. Soc., 33, 242–247(1950).
    Kida Akiko, Noma Yukio and Imada Teruji, “Chemical Speciation and Leaching
    Properties of Elements in Municipal Incinerator Ashes,” 16, Nos 5/6,527(1996).
    Klein D.H., Andren A.W., Lawasani M.H., West R.E., Environ. Sci. Technol.,
    9,862-9,869(1976).
    Lee P.H., Delay I., Nasserzadeh V., and et al., “Characterization, Decontamunation and Health Effects of Fly Ash from Waste Incinerators,” Enviromental Progress, 17(4), 261(1998).
    Ma, Q.Y., T.J. Logan and S.J. Traina, ”In Situ Lead Immobilization by Apatite,”Environment Science Technology, 27, 1803-1810(1993).
    Ma, Q.Y., T.J. Logan and S.J. Traina, ”Effects of NO3-,Cl-,F-,SO42-,and CO3
    2- on Pb2+ Immobilization by Hydroxyapatite,” Environment Science Technology,
    28, 408-418(1994).
    Ma, Q.Y., T.J. Logan and S.J. Traina, ”Lead Immobilization from Aqueous
    Solutions and Contaminated Soils Using Phosphate Rocks,” Environment Science Technology, 29, 1118-1126(1995).
    Mangialardi T., Paolini A.E., Polerrini A., and Sirini P., “Optimization of the solidification/stabilization prosess of MSW fly ash in cementitious matrices,”Journal of Hazardous Materials, B70, 53-70(1999).
    McCarthy, G., White, W., Smith, D., Lasaga, A., Ewing, R., Nicol, A., and Roy, R.,“Mineral Models for Crystalline Hosts for Radionuclides in Radioactive
    Waste Disposal,” in The Waste Package, Vol. 1, ed. R. Roy. Pergamon Press,
    New York: 184-232(1982).
    Nzihou, A., and P. Sharrock, ”Calcium Phosphate Stabilization of Fly Ash with
    Chloride Extraction,” Waste Management, 22, 235-239(2002).
    Ontiveros J.T., Hurley T.L., and Kosson D.S., “Physical Properties and Chemical Species Distributions Within Municipal Waste Combuster Ashes,“ Environmental Progress, 8(3), 200(1989).
    Oxtoby, D., Nachtrieb, N., and Freeman, W., “Chemistry, Science of Change,”
    SaundersCollege Pub., Philadelphia: 372-375 (1990).
    Philipp P. Bosshard, Reinhard Bachofen and Helmut Brandl “Metal Leaching of
    Fly Ash From Municipal Waste Incineration by Aspergillus niger,”Enviromaent Science & Technology, 30(10), 3066(1996).
    Pourbaix, M., “Atlas of Electrochemical Equilibria in Aqueous Solutions,”
    Pergamon Press, New York (1967).
    Pourbaix, M., “Atlas of Electrochemical Equilibria in Aqueous Solutions,” New
    York, Pergamon Press(1976).
    Puigdomenech, I., and Bruno, J., “Plutonium Solubilities,” Tech. Report 91-04.Swedish Nuclear Fuel and Waste Management Co., Stockholm(1991).
    Richer U., Birnbaum L., “Detailed Investigations of Filter Ashes From Municipal Solid Waste Incineration,” Waste Management & Research, 16(2), 190
    (1998).
    Singh, D., Wagh, A., Cunnane, J., and Mayberry, J., “Chemically Bonded
    Phosphate Ceramics for Low-Level Mixed-Waste Stabilization,” J. Environ.Sci. Health, A32(2): 527-541 (1997).
    Sliva, P., and Scheetz, B., “An ICPP Aluminum Phosphate Ceramic Waste Form:
    Synthesis and Room-Temperature Aqueous Stability,” in Nuclear Waste
    Management, Advances in Ceramics Vol. 8, Amer. Ceram. Soc.: Westerville,OH, 263-272 (1984).
    S. Y. Jeong and A. S. Wagh “Chemically Bonded Phosphate Ceramics:Cementing
    The Gap Between Ceramics and Cements,” 9700 S. Cass Avenue, Argonne,IL 60439,(2002).
    Theodoratos, P., N. Papassiopi and A. Xenidis, “Evaluation of Monobasic Calcium Phosphate for The Immobilization of Heavy Metals in Contaminated Soils
    from Lavrion,” Journal of Hazardous Materials, B94, 135-146(2002).
    V.M. Malhotra, ”Fly Ash in Contrete,” ACI SP85-3,(1986).
    Wadge A., Hutton M., and Peterson P.J., ”The Concentrations and Particle Size
    Relationships of Selected Trace Elements in Fly ashes from U.K. Coal-Fired
    Power Plants and Refuse Incinerator,” The Science of the Total Encironment,
    54, 13(1996).
    Wagh, A., Singh, D., Sutaria, M., Kurokawa, S., and Mayberry, J.,“Low-Temperature-Setting Phosphate Ceramics for Stabilizing DOE Problem Low-Level Mixed Waste: II. Performance Studies of Final Waste Forms,” in Proc. Waste Management, 94 Conf., Tucson,AZ (1994).
    Wagh, A., Singh, D., Jeong, S., and Strain, R., ”Ceramicrete Stabilization of
    Low-Level Mixed Wastes - A Complete Story,” in Proc. 18th DOE Low-Level Radioactive Waste Management Conf., Salt Lake City, USDOE, May 20-22 (1997).
    Wagh, A., Jeong, S., and Singh, D. “Mercury stabilization in chemically bonded
    phosphate ceramics,” Ceramic Transactions, 87, 63-73. (1998).
    Wagh, A., Strain, R., Jeong, S., Reed, D., Krouse T., and Singh, D., (a).“Stabilization of Rocky Flats Pu-Contaminated Ash within Chemically Bonded Phosphate Ceramics,” J. Nucl. Mater., 265: 295-307 (1999).
    Wagh, A., Singh, D., and Jeong, S., “Chemically bonded phosphate ceramics for
    stabilization and solidification of mixed waste, Hazardous and Radioactive
    Waste Treatment Technologies Handbook,” Boca Raton, FL, CRC Press,6.3-1-6.3-18. (2001).
    Wagh, A., and Jeong, S., ” Chemically bonded phosphate ceramics: Part III:
    Reduction mechanism and its application to iron phosphate ceramics,” submitted
    to Amer. Ceram. Soc. (2001).
    Wagh, A.S., Singh, D. and Jeong, S.Y., ”Chemically Bonded Phosphate Ceramics for Stabilization and Solidification of Mixed Waste” 9700 S. Cass Avenue, Argonne, IL 60439.(2002).
    Wang, Y.M., T.C. Chen, K.J. Yen and M.F. Shue, “Stabilization of An Elevated
    Heavy Metal Contaminated Site,” Journal of Hazardous Materials, B88,63-74(2001).
    Wescot, J., Nelson, R., Wagh, A., and Singh, D., Jan., “Low-Level and Mixed
    Radioactive Waste In-Drum Solidification,” Practice Periodical of Hazardous and Radioactive Waste Management: 4-7 (1998).
    Wiles, Carlton C., “Municipal Solid Waste Combustion Ash :State-of-the-knowledge,” Journal of Hazardous Materiar, 47, 325(1996).
    Wunsch P., Greilinger C., Bienick D., and Kettrup A., ”Investingation of the
    Binding of Heavy Metals in Thermally Treated Residues From Waste Incineration,” Chemosphere, 32(11), 2211(1996).
    Xavier Querol, Andres Alastuey, Jose Luis, Fernandes-Turiel and Angel Lopez-Soler, “Synthesis of Zeolite by Alkaline Activation of Ferro-Aluminous Fly Ash,” Fuel, 74(8), 1226 (1995).
    Xavier Querol, Jose Luis, Fernandes-Turiel and Angel Lopez-Soler, “Trace
    Element in Coal and Their Behavior During Combustion in a Large Power Station,” Fuel, 74(3), 331-343(1995).
    Xu, Y., and F.W. Schwartz, ”Sorption of Zn2+ and Cd2+ on Hydroxyapatite
    Surfaces,” Environment Science Technology, 28, 1472-1480(1994).
    Young, J. F., “A review of pore structure of cement paste and concrete and its
    influence on permeability,” Permeability concrete, ACI SP 108-1: 1-18(1988).
    「中華民國環境保護統計月報」,第195期(2005)。
    王鯤生, 「一般廢棄物焚化灰渣之有害物質特性研究」,行政院環境保護署委
    託報告,EPA-85-E3H1-09-02,台北(1996)。
    林正芳,「重金屬污泥之水泥固化及其再利用之可行性研究」,碩士論文,國立
    台灣大學環境工程學研究所,台北(1984)。
    陳俊英、許順珠、張宏岳,「事業廢棄物中間處理後資源化之研究(固化中間處
    理)」,行政院環境保護署,台北(1991)。
    楊金鐘、吳裕民,「垃圾焚化灰渣穩定化產物再利用之可行性探討」,一般廢棄
    物焚化灰渣資源化技術與實務研討會論文集,第43 頁,台北(1996)。
    楊盛行、林正芳、王繼國,廢棄物處理與再利用,國立空中大學,台北(2003)。
    廖錦聰,「從日本的經驗談台灣焚化灰渣資源化方向」,一般廢棄物焚化灰渣資
    源化技術與實務研討會論文集,第29 頁,台北(1996)。

    QR CODE
    :::