臺灣博碩士論文加值系統

磁性顆粒作為吸附劑可以克服水溶液中微小顆粒的回收問題，磁性顆粒(Fe3O4)先以水玻璃對其表面做SiO2 層包覆，以保護磁性顆粒使其避免在水溶液中因水解而遭受破壞，再利用硝酸鋁抑制磁性顆粒表面的矽溶出，由於胺基質子化可使表面帶正電荷，即可利用表面的正電荷對在水溶液中帶負電荷的磷酸鹽進行吸附，故將以SiO2 包覆完的Fe3O4 利用硝酸鋁抑制矽溶出，再利用一長鏈氯基當作媒介，使Diethylenetriamine(DETA，二乙烯三胺)可在磁性顆粒表面做胺基之修飾。再利用此胺基磁性吸附劑對水溶液中的磷酸鹽進行吸附實驗，實驗中分別對水溶液pH 值、磷酸鹽濃度及吸附劑添加量等參數進行探討，並進行等溫吸附實驗(40℃)、動力吸附及脫附實驗。經由pH 値影響實驗發現，最佳吸附條件的pH 値為3±0.1。將等溫吸附實驗數據代入分析後發覺其符合Langmuir 吸附模式，並估算其最大吸附量及自由能分別為48.19 mg g-1 與-17.81 kJ mol-1。由動力吸附實驗求得吸附的活化能為20.20 kJ mol-1。實驗後的胺基磁性吸附劑經外加磁場回收，以鹼性溶液脫附所吸附的磷酸鹽後，進行重複吸附實驗，發現其對磷酸鹽的吸附能力稍有衰減，以重複使用三次為佳。

A magnetic adsorbent, amine-functionalized silica magnetite (NH2-Al/SiO2/Fe3O4), has been synthesized to behave as an cationic adsorbent by adjusting the pH value of the aqueous solution to make amino groups protonated. NH2-Al/SiO2/Fe3O4 was used to adsorb phosphate ions in an aqueous solution in a batch system, and the maximum adsorption were found to occur at pH 3.0. The adsorption equilibrium data were all fitted the Langmuir isotherm equation reasonably well, and the maximum adsorption capacities of phosphate ions were more than 40 mg g–1 and increased with elevating temperature. The enthalpy (ΔH 0 ) and entropy (ΔS 0 ) values of NH2-Al/SiO2/Fe3O4 with the adsorption reaction of phosphate ions were 11.98 KJ mol-1 and 0.095 KJ (T mol)-1, respectively. A pseudo-second-order model also could best describe the adsorption kinetics, and the derived activation energy for phosphate ions was 20.20 kJ mol-1. The optimum condition to desorb phosphate ions from NH2-Al/SiO2/Fe3O4 is provided by a solution with 0.05 M NaOH.

摘要 I
Abstract II
目錄 III
圖目錄 V
表目錄 VII
第一章 緒論 1
1.1. 研究緣起 1
1.1.1 磁性顆粒簡介 1
1.1.2 磁性顆粒合成 1
1.1.3 磁性載體技術與應用 2
1.1.4 磷酸鹽的污染 3
1.2 研究目標 4
第二章 文獻回顧 6
2.1 Fe3O4簡介 6
2.1.1 氧化鐵 6
2.1.2 磁性載體Fe3O4 10
2.1.3 磁學性質 12
2.1.3.1 磁性材料分類 12
2.1.3.2 磁區與磁滯曲線 13
2.1.3.3 磁性與粒徑關聯 16
2.2 SiO2/Fe3O4 顆粒 18
2.2.1 膠體粒子生成機制 18
2.2.1.1 均質成核(homogeneous nucleation)與表面成長(surface growth) 理論 18
2.2.1.2 膠體穩定與凝聚 18
2.2.2 SiO2特性介紹 21
2.2.3 SiO2包覆Fe3O4 26
2.3 Al/SiO2/Fe3O4顆粒 28
2.4 粒子表面修飾 30
2.4.1粒子的表面修飾 30
2.4.2以3-chloropropyltrimethoxysilane(3-氯丙基三甲氧基矽烷)修飾Al/SiO2/Fe3O4顆粒 33
2.4.3合成3-chloropropyltrimethoxysilane(3-氯丙基三甲氧基矽烷)文獻整理 34
2.4.4胺官能基修飾具長鏈氯基之Al/SiO2/Fe3O4顆粒 34
2.4.5合成胺基文獻整理 35
2.5 磷酸鹽介紹 38
2.5.1 磷酸鹽簡介 38
2.5.2 含磷酸鹽廢水及吸附法應用於處理磷酸鹽 38
2.6 吸附理論 41
2.6.1 吸附類型 41
2.6.2 等溫吸附理論 41
2.6.3 熱力學研究 42
2.6.4 吸附動力學 43
2.6.5 影響吸附的因子 44
第三章 材料與方法 45
3.1實驗藥品與儀器 45
3.1.1 實驗藥品 45
3.1.2 儀器 46
3.2 特性分析 47
3.2.1 FT-IR分析 47
3.2.2 紫外光-可見光光譜儀(UV-VIS spectrometry)分析 47
3.2.3 XRD分析 48
3.2.4 BET比表面積分析 48
3.2.5 磁性分析(Vibrating Sample Magnetometer, VSM) 49
3.3合成方法 50
3.3.1 SiO2包覆Fe3O4 50
3.3.2 Al/SiO2/Fe3O4 50
3.3.3以長鏈氯基修飾Al/SiO2/Fe3O4 50
3.3.4胺基修飾具有長鏈氯基的Al/SiO2/Fe3O4 50
3.4吸附實驗 51
3.4.1 等溫吸附實驗 51
3.4.2 動力吸附實驗 52
3.4.3 脫附實驗 52
3.4.4 重複實驗 52
第四章 結果與討論 54
4.1合成吸附劑之討論 54
4.1.1 FT-IR分析 54
4.1.2 UV-VIS分析 57
4.1.3 XRD分析 59
4.1.4 BET分析 61
4.1.5 VSM分析 62
4.2 吸附實驗之討論 63
4.2.1 pH值影響 63
4.2.2 空白吸附實驗 66
4.2.3 等溫吸附實驗 67
4.2.4 動力吸附實驗 70
4.2.5 脫附實驗 74
4.2.6 重複實驗 77
第五章 結論 78
參考文獻 80

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