臺灣博碩士論文加值系統

為提升大麥萃取殘渣吸附去除水中重金屬離子的商品應用價值及效能，本研究以四種化學修飾法(包括磷酸鹽修飾法、檸檬酸修飾法、硫代硫酸鈉修飾法及甲醛修飾法)，配合硫脲架橋作用，修飾大麥萃取殘渣製成九種吸附劑，進行重金屬離子(Cu(Ⅱ)、Pb(Ⅱ)、及Zn(Ⅱ))批次吸附試驗，可同時處理食品加工廢棄物和移除廢水中重金屬離子，有益於提高廢棄物減量及再利用價值，更有助於永續環境利用。本研究探討影響吸附劑吸附重金屬離子之參數：如pH值、接觸時間、反應溫度、重金屬離子種類、混合重金屬離子之相互吸附競爭、及重金屬離子濃度等，並以等溫吸附平衡方程式、吸附動力學及吸附熱力學平衡模式來探討吸附效能。
比較各種經修飾化吸附劑對Cu(Ⅱ)、Pb(Ⅱ)、及Zn(Ⅱ)於最佳操作條件下吸附量為10.92、10.02、及9.21 mg/g；最差吸附量為3.08、4.07、及5.02 mg/g；最佳吸附pH為4.5～7.0。吸附反應穩定平衡時間約為60分鐘。以 Freundlich、Langmuir及Dubinin–Radushkevich equation三種等溫吸附平衡模式套用於等溫吸附平衡實驗數據，可計算各種吸附劑等溫吸附平衡常數及判斷屬於物理性或化學性吸附行為。以三種吸附動力模式( Pseudo first–order rate、Pseudo second–order rate 及 Intraparticle diffusion equation)評估發現Pseudo second–order rate equation 最適於描述修飾化吸附劑之吸附動力行為。由吸附熱力學特性參數（標準自由能（△Go）、焓值（△Ho）、及熵值（△So）變化）顯示吸附反應溫度從 15℃增至 70℃時，吸附Cu(Ⅱ)、Pb(Ⅱ)、及Zn(Ⅱ)反應主要為吸熱之自發性反應。在混合重金屬離子溶液中，受三種重金屬離子相互競爭吸附位置影響，吸附動力行為亦適合以Pseudo second–order rate equation描述，吸附熱力學特性亦主要為吸熱之自發性反應。

Four chemical modification methods were used to modify barley residual into adsorbent, including phosphorylation, sulfonation, sodium thiosulfate, citric acid, and formaldehyde modification. Those were used to increase the adsorption capacity of heavy metals compared with bare barley residual. The solid waste reduction and reuse at food processing plant could be promoted and the heavy metal ions could be removed from waste water in the same time. It is helpful and sustainable utilization of environmental resources. The adsorption capacity of heavy metal ions (Cu(Ⅱ), Pb(Ⅱ), and Zn(Ⅱ)) onto adsorbents was characterized by pH, contact time, contact temperature and heavy metal ions. The adsorption experimental data also evaluated with isothermal adsorption, adsorption dynamic and adsorption kinetic models.
The highest adsorption capacity of Cu(Ⅱ), Pb(Ⅱ)and Zn(Ⅱ) onto bare and modified adsorbents were 10.92, 10.02, and 9.21 mg/g, respectively. The lowest adsorption capacity for Cu(Ⅱ), Pb(Ⅱ) and Zn(Ⅱ) were 3.08, 4.07 and 5.02 mg/g, respectively. The optimum operation pH ranged between 4.5~7.0. 60 minutes was needed to reach equilibrium state of adsorption.
Three isothermal adsorption equations, Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) were used to evaluate the isothermal adsorption constants from experimental data and to judge the chemical or physical adsorption. The pseudo-second order rate equation fitted excellently the description of dynamic adsorption behavior of heavy metal ions (Cu(Ⅱ), Pb(Ⅱ) and Zn(Ⅱ)) onto adsorbents than the pseudo first-order rate, and intraparticle diffusion equation. The variations of thermodynamic parameters (free energy change (ΔG0), enthalpy change (ΔH0), entropy change (ΔS0)) indicated that the adsorption of Lead (II), Zinc (II) and Copper (II) was primarily endothermic process and the adsorption capacity increase with increasing temperature from 15 to 70 ℃.
Under the competition of other heavy metals onto the adsorptive sites in adsorbents, the adsorption behavior of heavy metal ion also fitted excellently the pseudo-second order rate equation and the calculated thermodynamic constants also indicated primarily the endothermic and spontaneous adsorption process.

圖目錄
中文摘要
Abstract
第一章 前言
1.1 研究緣由
1.2 研究目的
第二章 文獻回顧
2.1 重金屬污染控制的重要性
2.2 重金屬去除技術
2.2.1 傳統重金屬去除技術
2.2.2 有機物鍵結去除水中重金屬離子之可行性
2.2.3 生物性吸附劑介紹
2.2.4 影響吸附能力因子
2.3國內資源再生技術相關研究
2.4 化學修飾法原理
2.4.1硫脲架橋作用原理
2.4.2 檸檬酸修飾法原理
2.4.3 硫代硫酸鈉修飾處理法原理
2.4.4 甲醛修飾處理法原理
2.5 吸附理論
2.5.1 物理吸附
2.5.2 化學吸附
2.5.3 離子吸附
第三章 實驗材料與方法
3.1實驗流程
3.2 實驗設備
3.3 實驗材料及藥品
3.4 實驗材料
3.4.1 樣品前處理步驟
3.4.2 製備重金屬離子溶液
3.4.3 以化學修飾法製備吸附劑步驟
3.5 實驗分析方法
3.6 實驗步驟
3.7 等溫吸附模式計算
3.7.1 Freundlich 等溫吸附理論
3.7.2 Langmuir 等溫吸附理論
3.7.3 Dubinin-Radushkevich 方程式
3.8吸附動力學模式
3.8.1 Pseudo-first order rate equation
3.8.2 Pseudo-second order rate equation
3.8.3 Intraparticle diffusion equation
3.9吸附熱力學模式
第四章 結果與討論
4.1修飾化實驗最佳固液比
4.2修飾化吸附劑比表面積
4.3修飾化吸附劑在不同pH吸附效果
4.3.1修飾化吸附劑在不同pH對Cu(Ⅱ)吸附
4.3.2修飾化吸附劑在不同pH對Pb(Ⅱ)吸附
4.3.3修飾化吸附劑在不同pH對Zn(Ⅱ)吸附
4.3.4 比較修飾化吸附劑在不同pH吸附不同重金屬離子
4.4修飾化吸附劑之吸附平衡試驗
4.4.1 修飾化吸附劑對單一金屬溶液Cu(Ⅱ)之飽和吸附容量比較
4.4.2 修飾化吸附劑對單一金屬溶液Pb(Ⅱ)之飽和吸附容量比較
4.4.3 修飾化吸附劑對單一金屬溶液Zn(Ⅱ)之飽和吸附容量比較
4.4.4 混合型重金屬離子與修飾化吸附劑之競爭吸附平衡試驗
4.5 修飾化吸附劑對單一金屬及混合金屬溶液之等溫吸附平衡模式
4.5.1修飾化吸附劑對單一種重金屬溶液等溫吸附平衡模式
4.5.1.1 修飾化吸附劑對單一金屬溶液Cu(Ⅱ)之等溫吸附平衡曲線
4.5.1.2 修飾化吸附劑對單一金屬溶液Pb(Ⅱ)之等溫吸附平衡曲線
4.5.1.3 修飾化吸附劑對單一金屬溶液Zn(Ⅱ)之等溫吸附平衡曲線
4.5.2混合型重金屬離子競爭下修飾化吸附劑之等溫吸附平衡試驗
4.5.2.1 吸附競爭下修飾化吸附劑對Cu(Ⅱ)之等溫吸附平衡曲線
4.5.2.2 吸附競爭下修飾化吸附劑對Pb(Ⅱ)之等溫吸附平衡曲線
4.5.2.3 吸附競爭下修飾化吸附劑對Zn(Ⅱ)之等溫吸附平衡曲線
4.6 修飾化吸附劑對單一金屬及混合金屬溶液之吸附動力學
4.6.1修飾化吸附劑對單一金屬溶液之吸附動力學
4.6.2修飾化吸附劑對混合金屬溶液之吸附動力學
4.7 修飾化吸附劑對單一金屬及混合金屬溶液之吸附熱力學
4.7.1 修飾化吸附劑對單一金屬溶液之吸附熱力學
4.7.2 修飾化吸附劑對混合金屬溶液之吸附熱力學
第五章 結論與建議
5.1結論
5.2建議

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