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研究生: 康伯瑄
Bo-Syuan Kang
論文名稱: 以聚甲基丙烯酸甲酯固定普魯士藍進行水中銫移除
Cesium removal with Prussian blue fixed by poly (methly methacrylate)
指導教授: 李篤中
Duu-Jong, Lee
口試委員: Christopher Whiteley
Christopher Whiteley
鄭智嘉
Chih-Chia, Cheng
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: 86
中文關鍵詞: 懸浮聚合聚甲基丙烯酸甲酯普魯士藍銫吸附
外文關鍵詞: suspension polymerization, poly (methyl methacrylate) (PMMA), Prussian blue (PB), Cesium (Cs) adsorption
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本研究使用聚甲基丙烯酸甲酯作為擔體乘載普魯士藍,合成一具有高吸附能力之吸附劑,以此模擬水中放射性銫之吸附行為,由於普魯士藍在吸附過程中會釋放微量鐵離子的問題,因此必須進行材料最適化之探討。在本研究中分為兩部分,其一為聚甲基丙烯酸甲酯乘載普魯士藍顆粒的反應參數最適化: 顆粒合成採用懸浮聚合法,以控制變因實驗方法找出各配方及反應條件對顆粒形成的尺寸與幾何形貌的影響性,藉以了解聚合過程中控制顆粒尺寸的控制變因,再根據銫離子移除率、鐵離子洩漏濃度配合田口式品質工程法進行反應參數最適化,並以此決定最適配方及反應條件。其二為吸附行為的研究: 以非放射性銫-133配置原水進行吸附實驗。首先以杯瓶實驗測試普魯士藍-壓克力顆粒之動態及靜態動力學性質,再將顆粒以隨機填充方法於填充床中裝填進行連續吸附實驗,檢視其穿透曲線並以數學模型模擬自來水廠之快濾池配置,用以評估在快濾池進行放射性銫吸附之可行性,最後提供具有放射性銫淨化能力顆粒之製備方法及應用於填充床之操作參數,在突發核災時可做為應對之手段。


  The main objective in this research, poly (methyl methacrylate) (PMMA) is used as a support medium to load Prussian blue (PB), forming a high performance adsorbent. This adsorbent is used to simulate radioactive cesium (Cs) adsorption behavior in both deionized water and sea water. Since PB decomposes during the adsorption process and releases iron (Fe) ions into water, the optimization of bead performance is described. The first of objectives in this study is the optimization, methodology, and synthesis process for PB-PMMA beads, the effects of variables to PB-PMMA bead performance can be estimated, and then the most suitable reaction conditions and methodology for PB-PMMA bead synthesis determined. The second part of this study is the adsorption behavior of cesium towards the PB-PMMA beads. Non-radioactive 133Cs is used to prepare a standard solution for use in an adsorption experiment. First, a batch experiment is employed for understanding the kinetic properties for Cs removal and Fe leakage. Second, in order to establish the breakthrough curve and comparison with the simulation of rapid filtration in a water plant, a fixed bead adsorption experiment is employed using PB-PMMA beads packed randomly into a column. Third, in order to isolate and remove radioactive Cs from polluted water, the feasibility of using PB-PMMA bead in a rapid filtration method can be evaluated.

Acknowledgement I 中文摘要 II Abstract III Table of contents IV List of figures VI List of tables VIII Chapter1. Introduction 1 Chapter2. Literature review 3 2-1 Fukushima accident 3 2-2 Treatment of nuclear pollution 5 2-3 Material design 5 2-3-1 Prussian blue (PB) 6 2-3-1-1 Introduction of PB 7 2-3-1-2 Cs removing mechanism 7 2-3-2 Poly (methyl methacrylate) (PMMA) 8 2-3-3 Polymerization methods 9 2-3-3-1 Free radical polymerization 9 2-3-3-2 Bulk polymerization 11 2-3-3-3 Suspension polymerization 11 2-4 PB-PMMA beads 12 2-5 Adsorption kinetics 13 Chapter3. Materials and methods 15 3-1 Experimental material 15 3-1-1 Chemicals 15 3-1-2 Preparation of PB-PMMA beads 17 3-1-3 Preparation of raw solution for adsorption experiments 18 3-1-3-1 Cesium DIW [50 ppb] 18 3-1-3-2 Cesium contained in artificial seawater 18 3-2 Experimental methods 19 3-2-1 PB-PMMA bead morphology characterization 19 3-2-2 Quantization of PB Loading content 19 3-2-3 Batch adsorption experiments 21 3-2-3-1 Cs dynamic adsorption kinetics in DIW 21 3-2-3-2 Adsorption isotherm 24 3-2-4 Suspension polymerization reaction yield 26 3-2-5 Evaluation of PB-PMMA bead stability 27 3-2-5-1 Swelling ratio in artificial sea water 27 3-2-5-2 Heat treatment effect to Cs removal of PB-PMMA bead 27 3-2-6 Fixed bead adsorption 28 3-2-6-1 PB-PMMA bead packed column breakthrough test 28 3-2-6-2 PB-PMMA bead packed column rapid filtration test 28 3-2-7 Simulation of rapid filtration 31 3-2-7-1 Mathematic model 31 3-2-7-2 Model fitting 33 Chapter4. Result and discussion 34 4-1 Determination of parameters for PB-PMMA bead synthesis 34 4-2 Bead product morphology characterization 38 4-2-1 Sieving analysis for PB-PMMA bead 38 4-2-2 Surface topography of PB-PMMA bead 40 4-2-2-1 Surface morphology of PB-PMMA bead 40 4-2-2-2 PB-PMMA bead cross section structure and element profile survey 41 4-3 Quantization of PB Loading content 44 4-4 Evaluation of the stability of the PB-PMMA bead 46 4-4-1 Swelling ratio in artificial sea water 46 4-4-2 Heat treatment effect to Cs removal of PB-PMMA bead 47 4-5 Batch adsorption experiment 48 4-5-1 Cs removal and kinetics in batch system 48 4-5-1-1 Cs dynamic adsorption kinetics of PB-PMMA bead at 25 ℃ 49 4-5-1-2 Temperature effect on PB-PMMA bead Cs adsorption kinetics 51 4-5-1-3 PB-PMMA bead Cs adsorption isotherm 54 4-5-2 Fe leakage in batch system 58 4-5-3 Cs removal kinetics in artificial sea water 59 4-6 Fixed bead adsorption 60 4-6-1 Breakthrough test 60 4-6-2 Effect of different parameters on Cs removal 63 4-7 Mathematic model fitting of rapid filtration model 64 Chapter5. Conclusions 65 Appendix A. The PB-PMMA bead optimization 68 References 69

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