臺灣博碩士論文加值系統

本實驗製備凍乾吸附劑(幾丁聚醣-草酸、幾丁聚醣-酒石酸)、烘乾吸附劑(幾丁聚醣-草酸、幾丁聚醣-酒石酸)，吸附實驗以不同的銅離子起始濃度、溫度、pH為實驗變數，以探討其對金屬離子吸附的影響。利用FTIR、TGA、XRD分析幾丁聚醣-草酸(酒石酸)凍乾吸附劑、幾丁聚醣-草酸(酒石酸)烘乾吸附劑的性質。幾丁聚醣-草酸(酒石酸)凍乾吸附劑、幾丁聚醣-草酸(酒石酸)烘乾吸附劑最大吸附量被觀察在pH 5。幾丁聚醣-草酸及幾丁聚醣-酒石酸凍乾吸附劑在Langmuir等溫模式中，其最大吸附量qL分別為227.27mg/g、175.44 mg/g。以動力學吸附模式探討，實驗數據顯示幾丁聚醣-草酸及幾丁聚醣-酒石酸凍乾吸附劑吸附行為較符合擬二階動力學吸附模式，說明化學吸附為速率決定步驟。在熱力學模式中幾丁聚醣-草酸及幾丁聚醣-酒石酸凍乾吸附劑求出其自由能為負值，表示吸附行為為自發性反應，而焓為正值，表示吸附過程為吸熱反應，熵值為正值，表示亂度增加。

Chitosan-oxalate (CO) and chitosan-tartrate (CT) adsorbents, prepared by freeze-dried and oven-dried, were used for treatment of Cu(II) ion from aqueous solution. The effects of the initial pH value of the solution, contact time, temperature and the initial Cu(II) ion concentration on the adsorption of Cu(II) ion were investigated. The characterization of CO and CT adsorbents were investigated by IR, XRD and TGA. The maximum adsorption amount was observed at pH 5 for both CO and CT adsorbents. The adsorption isotherms were better fitted by the Langmuir equation. The maximum theoretical Cu(II) ion adsorption capacities of CO and CT adsorbents prepared by freeze-dried were 227.27 mg/g and 175.44 mg/g respectively. The adsorption kinetics were well described by the pseudo-second order equation, indicating that chemical adsorption is the rate-limiting step for the CO and CT adsorbents. The negative values of gibbs free energy of adsorption indicated the spontaneous adsorption of Cu(II) ion on the CO and CT adsorbents, while the positive enthalpy change indicated an endothermic adsorption process.

目錄
明志科技大學碩士學位論文指導教授推薦書 i
明志科技大學碩士學位論文口試委員會審定書 ii
明志科技大學學位論文授權書 iii
誌謝 iv
中文摘要 v
Abstract vi
目錄 vii
表目錄 xi
圖目錄 xii
第一章 前言 1
1-1 研究動機 1
1-2 研究項目 2
1-2-1 吸附劑製程 2
1-2-2 吸附劑吸附行為探討 2
1-2-3 SEM分析 2
1-2-4 XRD分析 2
1-2-5 TGA分析 2
1-2-6 FTIR分析 3
第二章 文獻回顧 4
2-1 重金屬來源 4
2-2 重金屬汙染物的處理 4
2-3 銅的特性 5
2-3-1 銅的危害 6
2-4 幾丁質(chitin) 7
2-4-1 幾丁聚醣(chitosan) 8
2-4-2 幾丁質與幾丁聚醣的製備方法 9
2-4-3 幾丁質與幾丁聚醣的特性 11
2-4-4 幾丁質與幾丁聚醣的應用 12
2-4-5 幾丁聚醣吸附重金屬之特性 16
2-5 交聯劑的應用 18
2-6 吸附理論 20
2-7 等溫吸附模式 21
2-8 動力學吸附模式 24
2-9 熱力學吸附模式 27
第三章 實驗方法與設備 28
3-1 實驗藥品 28
3-2 實驗設備與分析儀器 29
3-3 凍乾吸附劑 31
3-3-1 草酸濃度製成凍乾吸附劑 31
3-3-2 酒石酸濃度製成凍乾吸附劑 32
3-4 烘乾吸附劑 33
3-4-1 草酸濃度製成烘乾吸附劑 33
3-4-2 酒石酸濃度製成烘乾吸附劑 34
3-5 吸附劑吸附銅離子溶液之方法 35
3-6 吸附劑吸附銅離子溶液之吸附實驗 36
3-6-1 等溫吸附實驗 36
3-6-2 動力學吸附探討 38
3-6-3 不同pH值吸附實驗 38
3-6-4 不同溫度吸附實驗 40
3-7 銅離子溶液分析 42
3-8 吸附劑表面形態觀察 42
3-9 吸附劑晶形結構分析 42
3-10 吸附劑熱重損失分析 42
3-11 吸附劑官能基分析 42
第四章 實驗結果與討論 43
4-1 電子顯微鏡SEM分析 43
4-1-1 SEM下之探討 43
4-2 吸附劑吸附平衡實驗 46
4-2-1 幾丁聚醣-草酸吸附劑 46
4-2-2 幾丁聚醣-酒石酸吸附劑 47
4-3 等溫吸附模式探討 48
4-3-1 幾丁聚醣-草酸等溫吸附 48
4-3-2 幾丁聚醣-酒石酸等溫吸附 50
4-4 動力學吸附探討 53
4-4-1 幾丁聚醣-草酸動力學吸附 53
4-4-2 幾丁聚醣-酒石酸動力學吸附 56
4-5 pH值對吸附的影響 60
4-5-1 不同pH值幾丁聚醣-草酸(酒石酸)凍乾與幾丁聚醣-草酸(酒石酸)烘乾吸附劑吸附實驗 60
4-6 熱力學吸附探討 61
4-6-1 幾丁聚醣-草酸熱力學吸附 61
4-6-2 幾丁聚醣-酒石酸熱力學吸附 62
4-7 X光散射儀（XRD）之探討 64
4-8 FTIR之探討 65
4-8 TGA之探討 66
第五章 結論 67
參考文獻 69

表目錄
表2-1 藍色胞質素在血液中的功能 6
表2-2 幾丁質與幾丁聚醣的化學性質 11
表2-3 幾丁質與幾丁聚醣的應用範圍 12
表2-4 幾丁質與幾丁聚醣在機能性食品之應用 13
表2-5 幾丁質與幾丁聚醣應用在生醫材料 14
表4-1 幾丁聚醣-草酸及幾丁聚醣-酒石酸之RL值對Langmuir等溫吸附模式吸附判定 51
表4-2 幾丁聚醣-草酸及幾丁聚醣-酒石酸之Langmuir等溫吸附模式數據 52
表4-3 幾丁聚醣-草酸及幾丁聚醣-酒石酸之Freundlich等溫吸附模式數據 52
表4-4 幾丁聚醣-草酸及幾丁聚醣-酒石酸之擬一階吸附動力模式數據 58
表4-5 幾丁聚醣-草酸及幾丁聚醣-酒石酸之擬二階吸附動力模式數據 59
表4-6 幾丁聚醣-草酸及幾丁聚醣-酒石酸之內部擴散吸附動力模式數據 59
表4-7 幾丁聚醣-草酸及幾丁聚醣-酒石酸之熱力學吸附模式數據(△H0 & △S0) 63
表4-8 幾丁聚醣-草酸及幾丁聚醣-酒石酸之熱力學吸附模式數據(△G0) 63

圖目錄
圖2-1 幾丁質的化學結構 7
圖2-2 幾丁聚醣的化學結構 8
圖2-3 幾丁質製備流程 9
圖2-4 幾丁聚醣製備流程 10
圖2-5 幾丁聚醣吸附金屬離子的反應類型[31]（a）離子交換（b）螯合 17
圖2-6 幾丁聚醣經不同交聯劑交聯後的結構式[37]（a）chitosan（b）chitosan-glutaraldehyde（c）chitosan-epichlorohydrin（d）chitosan-ethylene glycol diglycidyl ether 19
圖3-1 ICP-OES（感應耦合電漿放射光譜儀） 30
圖3-2 SEM（掃描式電子顯微鏡） 30
圖3-3 草酸凍乾吸附劑 31
圖3-4 酒石酸凍乾吸附劑 32
圖3-5 草酸烘乾吸附劑 33
圖3-6 酒石酸烘乾吸附劑 34
圖3-7 配製硫酸銅溶液 35
圖3-8 吸附劑吸附未知濃度銅離子溶液（mg/L） 35
圖3-9 不同初始濃度之吸附劑吸附銅離子 37
圖3-10 不同pH值之吸附劑吸附銅離子 39
圖3-11 不同溫度之吸附劑吸附銅離子 41
圖4-1 幾丁聚醣-草酸凍乾吸附劑 44
圖4-2 幾丁聚醣-草酸烘乾吸附劑 44
圖4-3 幾丁聚醣-酒石酸凍乾吸附劑 45
圖4-4 幾丁聚醣-酒石酸烘乾吸附劑 45
圖4-5 幾丁聚醣-草酸吸附劑之銅離子吸附量變化情形 46
圖4-6 幾丁聚醣-酒石酸吸附劑之銅離子吸附量變化情形 47
圖4-7 幾丁聚醣-草酸之Langmuir 等溫吸附模式 49
圖4-8 幾丁聚醣-草酸之Freundlich 等溫吸附模式 49
圖4-9 幾丁聚醣-酒石酸之Langmuir等溫吸附模式 50
圖4-10 幾丁聚醣-酒石酸之Freundlich等溫吸附模式 51
圖4-11 幾丁聚醣-草酸之擬一階吸附動力模式 54
圖4-12 幾丁聚醣-草酸之擬二階吸附動力模式 54
圖4-13 幾丁聚醣-草酸之內部擴散吸附動力模式 55
圖4-14 幾丁聚醣-酒石酸之擬一階吸附動力模式 57
圖4-15 幾丁聚醣-酒石酸之擬二階吸附動力模式 57
圖4-16 幾丁聚醣-酒石酸之內部擴散吸附動力模式 58
圖4-17 不同pH值下吸附劑吸附銅離子的吸附量 60
圖4-18 幾丁聚醣-草酸之熱力學吸附模式 61
圖4-19 幾丁聚醣-酒石酸之熱力學吸附模式 62
圖4-20 幾丁聚醣與不同交聯劑的XRD 64
圖4-21 幾丁聚醣與不同交聯劑的FTIR 65
圖4-22 幾丁聚醣與不同交聯劑的TGA 66

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