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研究生： 吳柔靜
Rou-Jing Wu
論文名稱： 事業廢棄物合成鈣礬石去除含磷酸鹽廢水之研究
Removal of Phosphate Using Ettringite Synthesized from Industrial By-products
指導教授： 劉志成
Jhy-Chern Liu
口試委員: 王孟菊
Meng-Jiy Wang
郭俞麟
Yu-Lin Kuo
Suryadi Ismadji
Suryadi Ismadji
學位類別： 碩士
Master
系所名稱： 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年： 2016
畢業學年度： 104
語文別： 英文
論文頁數： 143
中文關鍵詞： 吸附 、鈣礬石 、羥基磷灰石 、工業副產物 、磷酸鹽 、沉澱 、廢水
外文關鍵詞： Adsorption, ettringite, hydroxyapatite, industrial by-products, phosphate, precipitation, wastewater
相關次數： 點閱：256  下載：6 
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  •  上一筆

    • 本研究評估工業廢棄物合成之鈣礬石去除水中磷酸鹽的效果，並探討不同平衡酸鹼值及磷酸鹽初始濃度對磷酸鹽去除的影響。實驗結果顯示，添加轉爐石、明礬與脫硫石膏在莫耳比([Ca]:[Al]:[SO4])為3:2:3，酸鹼值為11.74，反應溫度28°C下混合24小時，可成功合成鈣礬石，並進一步做為除磷材料。吸附反應於實驗進行24小時後達平衡，並可以擬二階動力學模型來描述。在平衡吸附反應實驗中可發現酸鹼值為影響實驗重要變因，磷酸鹽去除效果隨酸鹼值增加而增加。根據等溫吸附線趨勢，磷酸鹽去除可分為兩個過程。當磷酸鹽濃度在較低 (200-300 mg/L)的情況下，磷酸鹽去除符合Langmuir 和Freundlich等溫吸附模型；然而，磷酸鹽濃度在較高 (>300 mg/L)的情況下，吸附量和磷酸鹽濃度呈線性關係。此趨勢顯示，利用鈣礬石去除磷酸鹽的反應機制包含吸附和沉澱反應，在較低磷酸鹽濃度是沉澱-吸附機制；在較高磷酸鹽濃度則為沉澱機制。藉由晶相分析、表面分析及元素分析之實驗結果和PHREEQC模擬軟體預測產物之組成和分佈相互比較，結果顯示，反應主要沉澱物為羥基磷灰石。本研究充分利用含鈣之工業廢棄物合成高效除磷酸鹽材料，不僅可以減少對環境的影響，同時具有資源循環利用的效益。

    Removal of phosphate using ettringite synthesized from industrial by-products was evaluated in this study. Ettringite was synthesized by combining basic oxygen furnace (BOF) slag, alum and fuel-gas-desulfurization (FGD) gypsum at molar ratio ([Ca]:[Al]:[SO4]) of 3:2:3, pH 11.74, and 28°C for 24 h. Kinetic study showed that the adsorption reached equilibrium after 24 h and could be represented by pseudo second-order kinetic model. Equilibrium adsorption study revealed that pH was the most important factor, and phosphate removal increased with increasing pH. The mode of phosphate removal could be divided into two regions. At lower initial phosphate concentration (200 to 300 mg/L), experimental results fitted well with both Langmuir and Freundlich isotherm models. However, the adsorption density increased linearly with increasing phosphate concentration when at higher initial phosphate concentration (>300 mg/L), implying that phosphate removal by ettringtie was via both adsorption and precipitation. It means that the phosphate was removed mainly by surface precipitation in combination with adsorption at low initial phosphate concentration and by surface precipitation at high initial phosphate concentration. Judging from X-ray diffraction (XRD) and PHREEQC simulation, the main calcium phosphate precipitate is hydroxyapatite (HAP). This study demonstrated that it is feasible to synthesize highly effective phosphate removal material using industrial by-products.

    摘要 I Abstract II Acknowledgment III Contents IV List of Figures VI List of Tables VIII CHAPTER 1 INDRODUCTION 1-1 1.1 Background 1-1 1.2 Objectives 1-2 CHAPTER 2 LITERATURE REVIEW 2-1 2.1 Phosphate 2-1 2.1.1 Phosphate in wastewater 2-1 2.1.2 Technologies of phosphate removal and recovery 2-1 2.2 Ettringite 2-9 2.2.1. Introduction of ettringite 2-9 2.2.2. Synthesis of ettringite 2-9 2.2.3. Ettringite for contaminants removal 2-10 2.3 Kinetics of adsorption reaction 2-15 2.4 Adsorption isotherms 2-15 CHAPTER 3 METHODS AND MATERIALS 3-1 3.1 Materials and reagents 3-1 3.2 Instruments 3-2 3.3 Experimental method 3-3 3.3.1 Experimental framework and procedures 3-3 3.3.2 Characterization of industrial by-products 3-5 3.3.2.1 Total metal content - Aqua-regia digestion 3-5 3.3.2.2 Water content - weight method 3-5 3.3.3 Synthesis of ettringite 3-6 3.3.4 Phosphate removal and recovery 3-6 3.3.4.1 Kinetic study of phosphate removal 3-6 3.3.4.2 Equilibrium adsorption of phosphate 3-7 3.3.4.2.1. Effect of pH 3-7 3.3.4.2.2. Effect of phosphate initial concentration 3-8 3.3.4.3 Effect of dosing sequence 3-9 3.3.5 Sample analysis 3-9 3.3.5.1 X-ray diffraction (XRD) 3-9 3.3.5.2 Field-emission scanning electron microscope (FESEM) and energy dispersive X-ray spectrometer (EDX) 3-10 3.3.5.3 BET surface area 3-10 3.3.5.4 Thermogravimetric analysis 3-10 3.3.5.5 Inductively couple plasma-atomic emission spectrometry (ICP-AES) 3-10 3.3.5.6 Ion chromatography (IC) 3-11 3.3.6 Thermodynamic modeling software (PHREEQC) 3-11 CHAPTER 4 RESULTES AND DISCUSSION 4-1 4.1 Characterization of industrial by-products 4-1 4.1.1 Characterization of basic oxygen furnace (BOF) slag 4-1 4.1.2 Characterization of flue-gas-desulfurization (FGD) gypsum 4-7 4.2 Characterization of synthesized ettringite 4-11 4.2.1 X-ray diffraction aanalysis 4-11 4.2.2 Field-emission scanning electron microscope (FESEM) and energy dispersive X-ray spectrometer (EDX) analysis 4-14 4.2.4 Zeta potential 4-19 4.2.5 BET surface area 4-20 4.3 Phosphate removal 4-21 4.3.1 Kinetic study on phosphate removal 4-21 4.3.2 Effects of equilibrium pH 4-24 4.3.3 Adsorption isotherms study 4-26 4.4 Analysis of loaded ettringite 4-34 4.5 Effects of dosing sequence 4-47 CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS 5-1 5.1 Conclusions 5-1 5.2 Recommendations 5-2 REFERENCE R-1 APPENDIX A A-1 APPENDIX B B-1

    Albino, V., Cioffi, R., Marroccoli, M., Santoro, L., 1996. Potential application of ettringite generating systems for hazardous waste stabilization. Journal of Hazardous Materials 51, 241-252.

    Alvarez-Ayuso, E., Nugteren, H.W., 2005. Synthesis of ettringite: A way to deal with the acid wastewaters of aluminium anodising industry. Water Research 39, 65-72.

    Barca, C., Gerente, C., Meyer, D., Chazarenc, F., Andrer, Y., 2012. Phosphate removal from synthetic and real wastewater using steel slags produced in europe. Water Research 46, 2376-2384.

    Baur, I., Johnson, C.A., 2003. The solubility of selenate-AFt (3CaO•Al2O3•3CaSeO4•37.5H2O) and selenate-AFm (3CaO•Al2O3•CaSeO4•xH2O). Cement and Concrete Research 33, 1741-1748.

    Benyoucef, S., Amrani, M., 2011. Adsorption of phosphate ions onto low cost Aleppo pine adsorbent. Desalination 275, 231-236.

    Blanco, I., Molle, P., Miera, L.E.S.a.D., Ansola, G., 2016. Basic oxygen furnace steel slag aggregates for phosphorus treatment. Evaluation of its potential use as a substrate in constructed wetlands. Water Research 89, 355-365.

    Chen, H., Wang, D., Li, X., Yang, Q., Luo, K., Zeng, G., 2013. Biological phosphorus removal from real wastewater in a sequencing batch reactor operated as aerobic/extended-idle regime. Biochemical Engineering Journal 77, 147-153.

    Chen, S.S., Mehta, P.K., 1982. Zeta potential and surface area measurements on ettringite. Cement and Concrete Research 12, 257-259.

    Chrysochoou, M., Dermatas, D., 2006. Evaluation of ettringite and hydrocalumite formation for heavy metal immobilization: Literature review and experimental study. Journal of Hazardous Materials 136, 20-33.

    Cody, A.M., Lee, H., Cody, R.D., Spry, P.G., 2004. The effects of chemical environment on the nucleation, growth, and stability of ettringite [Ca3Al(OH)6]2(SO4)3•26H2O. Cement and Concrete Research 34, 869-881.

    Collier, N.C., Milestone, N.B., Gordon, L.E., Ko, S.C., 2014. The suitability of a supersulfated cement for nuclear waste immobilisation. Journal of Nuclear Materials 452, 457-464.

    Dalas, F., Pourchet, S., Rinaldi, D., Nonat, A., Sabio, S., Martinmosquet, 2015. Modification of the rate of formation and surface area of ettringite by polycarboxylate ether superplasticizers during early C3A–CaSO4 hydration. Cement and Concrete Research 69, 105-113.

    Dąbrowski, A., 2001. Adsorption-from theory to practice. Advances in Colloid and Interface Science 93, 135-224.

    Damidot, D., Glasser, F.P., 1992. Thermodynamic investigation of the CaO–Al2O3–CaSO4–H2O system at 50°C and 85°C. Cement and Concrete Research 22, 1171-1191.

    Do, D. D., 1998. Adsorption Analysis: Equilibria and Kinetics, London: Imperial College Press,.

    Dorozhkin, S.V., 2007. Calcium orthophosphates. Journal of Materials Science 42, 1061-1095.

    Ferrari, L., Kaufmann, J., Winnefeld, F., Plank, J., 2014. Impact of particle size on interaction forces between ettringite and dispersing comb-polymers in various electrolyte solutions. Journal of Colloid and Interface Science 419, 17-24.

    Gougar, M.L.D., Scheetz, B.E., Roy, D.M., 1996. Ettringite and C-S-H portland cement phases for waste ion immobilization: A review. Waste Management 16, 295-303.

    Guaya, D., Valderrama, C., Farran, A., Armijos, C., Cortina, J.L., 2015. Simultaneous phosphate and ammonium removal from aqueous solution by a hydrated aluminum oxide modified natural zeolite. Chemical Engineering Journal 271, 204-213.

    Gunawan, E.K., Warmadewanthi, Liu, J.C., 2010. Removal of phosphate and fluoride from optoelectronic wastewater by calcite. International Journal of Environmental Technology and Management 12 (2-4), 308-321.

    Han, C., Wang, Z., Yang, W., Wu, Q., Yang, H., Xueschool, X., 2016. Effects of pH on phosphorus removal capacities of basic oxygenfurnace slag. Ecological Engineering 89, 1-6.

    Hashem, F.S., Amin, M.S., 2014. Kinetic and thermal studies of removal of CrO42- ions by ettringite. Journal of Thermal Analysis and Calorimetry 116, 835-844.

    Hongo, T., Tsunashima, Y., Iizuka, A., Yamasaki, A., 2014. Synthesis of anion-exchange materials from concrete sludge and evaluation of their ability to remove harmful anions (borate, fluoride, and chromate). International Journal of Chemical Engineering and Applications 5 (4), 298-302.

    Iizuka, A., Takahashi, M., Nakamura, T., Yamasaki, A., 2014. Boron removal performance of a solid sorbent derived from waste concrete. Industrial & Engineering Chemistry Research 53, 4046-4051.

    Jha, V.K., Kameshima, Y., Nakajima, A., Okada, K., 2008. Utilization of steel-making slag for the uptake of ammonium and phosphate ions from aqueous solution. Journal of Hazardous Materials 156, 156-162.

    Köse, T.E., Kıvanc, B., 2011. Adsorption of phosphate from aqueous solutions using calcined waste eggshell. Chemical Engineering Journal 178, 34-39.

    Kaasik, A., Vohla, C., Motlep, R., Mander, U., Kirsimae, K., 2008. Hydrated calcareous oil-shale ash as potential filter media for phosphorus removal in constructed wetlands. Water Research 42, 1315-1323.

    Kanchana, P., Sekar, C., 2010. Influence of sodium fluoride on the synthesis of hydroxyapatite by gel method. Journal of Crystal Growth 312, 808-816.

    Kim, E.-H., Hwang, H.-K., Yim, S.-B., 2010. Phosphorus removal characteristics in hydroxyapatite crystallization using converter slag. Journal of Environmental Science and Health 41, 2531-2545.

    Komatsu, R., Norihiromizukoshi, Kojimakida, Katsuotsukamoto, 2009. In-situ observationofettringitecrystals. Journal of Crystal Growth 311, 1005-1008.

    Lu, N.C., Liu, J.C., 2010. Removal of phosphate and fluoride from wastewater by a hybrid precipitation–microfiltration process. Separation and Purification Technology 74, 329-335.

    Madzivire, G., Petrik, L.F., Gitari, W.M., Ojumu, T.V., Balfour, G., 2010. Application of coal fly ash to circumneutral mine waters for the removal of sulphates as gypsum and ettringite. Minerals Engineering 23, 252-257.

    Mantellato, S., Palacios, M., Flatt, R.J., 2016. Impact of sample preparation on the specific surface area of synthetic ettringite. Cement and Concrete Research 86, 20-28.

    Mccarthy, G.J., Hassett, D.J., J.A, 1992. Bender, synthesis, crystal structure and stability of ettringite, a material with potential applications in hazardous waste immobilization, advanced cementitious systems: Mechanisms and properties. Materials Research Society Symposium Proceedings Series 245, 129-145.

    Moschner, G.R., Lothenbach, B., Rose, J., Ulrich, A., Figi, R., Kretzschmar, R., 2008. Solubility of Fe–ettringite (Ca3[Fe(OH)6]2(SO4)3•26H2O). Geochimica et Cosmochimica Acta 72, 1-18.

    Moore, A.E., Taylor, H.F.W., 1970. Crystal structure of ettringite. Acta Crystallographica B26, 386-393.

    Myneni, S.C.B., Traina, S.J., Logan, T.J., Waychunas, G.A., 1997. Oxyanion behavior in alkaline environments: Sorption and desorption of arsenate in ettringite. Environmental Science and Technology 31, 1761-1768.

    Nguyen, T.A.H., Ngo, H.H., Guo, W.S., Zhang, J., Liang, S., Lee, D.J., Nguyen, P.D., Bui, X.T., 2014. Modification of agricultural waste/by-products for enhanced phosphate removal and recovery: Potential and obstacles. Bioresource Technology 169, 750-762.

    Nollet, L. M .L., 2007. Handbook of Water Analysis, 2nd edition, Boca Raton: CRC Press.

    Novillo, C., Guaya, D., Avendaño, A.a.-P., Armijos, C., Cortina, J.L., Cota, I., 2014. Evaluation of phosphate removal capacity of Mg/Al layered double hydroxides from aqueous solutions. Fuel 38, 72-79.

    Oladoja, N.A., Adelagun, R.O.A., Ololade, I.A., Anthony, E.T., Alfred, M.O., 2014. Synthesis of nano-sized hydrocalumite from a gastropod shell for aqua system phosphate removal. Separation and Purification Technology 124, 186-194.

    Oladoja, N.A., Ahmad, A.L., Adesina, O.A., Adelagun, R.O.A., 2012. Low-cost biogenic waste for phosphate capture from aqueous system. Chemical Engineering Journal 209, 170-179.

    Ouhadi, V.R., Yong, R.N., 2008. Ettringite formation and behaviour in clayey soils. Applied Clay Science 42, 258-265.

    Park, J.-Y., Byun, H.-J., Choi, W.-H., Kang, W.-H., 2008. Cement paste column for simultaneous removal of fluoride, phosphate, and nitrate in acidic wastewater. Chemosphere 70, 1429-1437.

    Parkhurst, D. L., Appelo, C. A. J., 1999. User's Guide to PHREEQC (Version 2)—Acomputer program, for speciation, batch reaction, one-dimensional transport, and inverse geochemical calculations. U. S. Geological Survey Water-Resource Investigations Report 99-4259, USGS: Denver, CO.

    Pengthamkeerati, P., Satapanajaru, T., Chularuengoaksorn, P., 2008. Chemical modification of coal fly ash for the removal of phosphate from aqueous solution. Fuel 87, 2469-2476.

    Perassi, I., Borgnino, L., 2014. Adsorption and surface precipitation of phosphate onto caco3–montmorillonite: Effect of ph, ionic strength and competition with humic acid. Geoderma 232-234, 600-608.

    Perkins, R.B., Palmer, C.D., 1999. Solubility of ettringite (Ca3[Fe(OH)6]2(SO4)3•26H2O) at 5–75°C. Geochimica et Cosmochimica Acta 63 (13/14), 1969-1980.

    Plank, J., Hirsch, C., 2007. Impact of zeta potential of early cement hydration phases on superplasticizer adsorption. Cement and Concrete Research 37, 537-542.

    Procctor, D.M., Fehling, K.A., Shay, E.C., Wittenborn, J.L., Green, J.J., Avent, C., Bigham, R.D., Connolly, M., Lee, B., Shepker, T.O., Zak, M.A., 2000. Physical and chemical characteristics of blast furnace, basic oxygen furnace, and electric arc furnace steel industry slags. Environmental Science and Technology 34, 1576-1582.

    Rathod, M., Mody, K., Basha, S., 2014. Efficient removal of phosphate from aqueous solutions by red seaweed, kappaphycus alverezii. Journal of Cleaner Production 84, 484-493.

    Riahi, K., Thayer, B.B., Mammou, A.B., Ammar, A.B., Jaafoura, M.H., 2009. Biosorption characteristics of phosphates from aqueous solution onto phoenix dactylifera l. Date palm fibers. Journal of Hazardous Materials 170, 511-519.

    Soukal, F.E., Ptacek, P., Opravil T., Havlic, J., Brandstetr J., Ovecka, Z., 2014. The synthesis and characterization of an expansive additive for M-type cements. Part III. The influence of gypsum and water-to-cement ratio on the formation of ettringite. Journal of Thermal Analysis and Calorimetry 115, 301-307.

    Saikia, N., Kato, S., Kojima, T., 2006. Behavior of B, Cr, Se, As, Pb, Cd, and Mo present in waste leachates generated from combustion residues during the formation of ettringite. Environmental Toxicology and Chemistry 25 (7), 1710-1719.

    Soetardji, J.P., Claudia, J.C., Ju, Y.-H., Hriljac, J.A., Chen, T.-Y., Soetaredjo, F.E., Santoso, S.P., Kurniawan, A., Ismadji, S., 2015. Ammonia removal from water using sodium hydroxide modified zeolite mordenite. RSC Advances 5, 83689-83699.

    Soetaredjo, F.E., Kurniawan, A., Ki, O.L., Ismadji, S., 2013. Incorporation of selectivity factor in modeling binary component adsorption isotherms for heavy metals-biomass system. Chemical Engineering Journal 219, 137-148.

    Terai, T., Mikuni, A., Komatsu, R., Ikeda, K., 2006. Synthesis of Cr (VI)-ettringite in portlandite suspension as a fuction of pH. Journal of the Ceramic Society of Japan 114 (4), 299-302.

    Tsunashima, Y., Iizuka, A., Akimoto, J., Hongo, T., Yamasaki, A., 2012. Preparation of sorbents containing ettringite phase from concrete sludge and their performance in removing borate and fluoride ions from waste water. Chemical Engineering Journal 200–202, 338-343.

    Wajima, T., Rakovan, J.F., 2013. Removal behavior of phosphate from aqueous solution by calcined paper sludge. Colloids and Surfaces A: Physicochemical and Engineering Aspects 432, 132-138.

    Wang, G., Qiu, L., Zhang, S., 2011. Hydrothermal modification of granular steel slag for phosphate removal. Bioinformatics and Biomedical Engineering, (iCBBE) 2011 5th International Conference on. IEEE, Wuhan, pp. 1-4.

    Wang, T., Dorner-Reisel, A., Ller, E.M., 2004. Thermogravimetric and thermokinetic investigation of the dehydroxylation of a hydroxyapatite powder. Journal of the European Ceramic Society 24, 693-698.

    Xu, K., Deng, T., Liu, J., Peng, W., 2010. Study on the phosphate removal from aqueous solution using modified fly ash. Fuel 89, 3668-3674.

    Yagi, S., Fukushi, K., 2012. Removal of phosphate from solution by adsorption and precipitation of calcium phosphate onto monohydrocalcite. Journal of Colloid and Interface Science 384, 128-136.

    Yan, Y., Sun, X., Ma, F., Li, J., Shen, J., Han, W., Liu, X., Wang, L., 2014. Removal of phosphate from wastewater using alkaline residue. Journal of Environmental Sciences 26, 970-980.

    Yang, S., Jin, P., Wang, X., Zhang, Q., Chen, X., 2016. Phosphate recovery through adsorption assisted precipitation using novel precipitation material developed from building waste: Behavior and mechanism. Chemical Engineering Journal 292, 246-254.

    Yang, S., Zhao, Y., Chen, R., Feng, C., Zhang, Z., Lei, Z., Yang, Y., 2013. A novel tablet porous material developed as adsorbent for phosphate removal and recycling. Journal of Colloid and Interface Science 396, 197-204.

    Yu, Y., Wu, R., Clark, M., 2010. Phosphate removal by hydrothermally modified fumed silica and pulverized oyster shell. Journal of Colloid and Interface Science 350, 538-543.

    Zhang, M., Reardon, E.J., 2003. Removal of b, cr, mo, and se from wastewater by incorporation into hydrocalumite and ettringite. Environmental Science and Technology 37, 2947-2952.

    Zhou, W., Huang, Z., Sun, C., Zhao, H., Zhang, Y., 2016. Enhanced phosphorus removal from wastewater by growing deep-sea bacterium combined with basic oxygen furnace slag. Bioresource Technology 214, 534-540.

    Zou, H., Wang, Y., 2016. Phosphorus removal and recovery from domestic wastewater in a novel process of enhanced biological phosphorus removal coupled with crystallization. Bioresource Technology 211, 87-92.

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