臺灣博碩士論文加值系統

本研究希望能夠發展出同時吸附鉻酸鹽與三價鉻之吸附劑，因此使用不同濃度的乙基黃原酸鉀、半胱胺酸、十二烷基硫酸鈉三種有機含硫陰離子插層鎂鋁層狀複合金屬氫氧化物，並利用共沉澱法製作成吸附劑，合成之吸附劑在溶液pH為4與5 被應用於吸附溶液中鉻酸鹽與三價鉻。製備完成之吸附劑利用XPS、XRD、SEM和FTIR鑑定其性質，並利用吸附平衡計算各類污染物之吸附容量以及探討可能的吸附機制。
研究結果顯示出，經過有機酸陰離子改質後之十二烷基硫酸鈉-LDHs、乙基黃原酸鹽-LDHs及半胱胺酸-LDHs皆可吸附本研究所選定的陽離子三價鉻及陰離子鉻酸鹽。經過有機酸陰離子改質後之LDHs可以與三價鉻產生錯合作用將其去除，在基本性質測定中發現改質後之LDHs 層間仍存在碳酸鹽，因此可以利用陰離子交換機制將鉻酸鹽去除，並由此確定已成功製作出鉻酸鹽與三價鉻之吸附劑。
經由改質所製成的吸附劑除了十二烷基硫酸鹽插層後所獲得的吸附效果較差外，另兩種陰離子有機物皆可對於設定的污染物產生高吸附容量。在不同溶液pH之條件下，十二烷基硫酸鹽在pH=5時吸附陽離子型重金屬污染物時有較佳吸附效果；乙基黃原酸鹽在pH4及pH5吸附陽離子及陰離子型重金屬污染物則差異不大；半胱胺酸則是pH=5時對陽離子及陰離子型重金屬污染物吸附有較佳效果。整體吸附劑之效率為：乙基黃原酸鹽-LDHs>半胱胺酸-LDHs>十二烷基硫酸鹽-LDHs。

The objective of this study is to develop an adsorbent that can simultaneously adsorb dichromate and chromium ion. Various concentrations of organic compounds, such as ethyl xanthate, L-cysteine and dodecyl sulfate, containing sulfur atom were used to intercalate Mg-Al layered double hydroxides (Mg-Al LDHs) through a co-precipitation method. The produced adsorbents were used to adsorb dichromate and chromium ion under pH 4 and 5. The adsorbents were characterized by XPS, SEM, FTIR and XRD. The adsorption capacity of target contaminants was calculated by adsorption equilibrium and the possible adsorption mechanism was discussed.
The results indicated the Mg-Al LDHs intercalated with ethyl xanthate, L-cysteine and dodecyl sulfate can effectively adsorb dichromate and chromium (III) ion. The adsorption mechanism for chromium ion was regarded as complexation reaction. Because carbonate was found in the interlayer, the adsorption mechanism for dichromate was assumed as anion exchange. The demonstrated the synthesized adsorbents can remove cationic and anionic heavy metal ions.
The adsorbents produced by the modification are in addition to the poor adsorption effect obtained after the dodecyl sulfonate intercalation, and the other two anionic organisms can produce high adsorption capacity for the contaminants. For the heavy metal solution at two pH values, the LDHs intercalated by dodecyl sulfonate adsorbs cationic heavy metal contaminants at pH= 5, and the LDHs intercalated by ethyl xanthate removed cationic and anionic heavy metals at pH4 and pH5. The LDHs intercalated by L-cysteine can generate a better effect for the cationic and anionic heavy metal ions at pH5. The overall efficiency of the adsorbent is decrease as the following order: ethyl xanthate-LDHs> cysteine-LDHs> dodecylsulfonate-LDHs.

摘要 I
Abstract III
目錄 V
圖目錄 IX
表目錄 XIII
第一章 前言 1
1-1 研究緣起 1
1-2 研究目的及內容 2
第二章 文獻回顧 4
2-1層狀複合金屬氫氧化物之特性 4
2-2 LDHs製備方法 7
2-2-1共沉澱法 7
2-2-2水熱合成法 8
2-2-3 煅燒復原法 9
2-2-4 離子交換法 9
2-2-5 即時合成法 10
2-3 合成LDHs影響因素 11
2-3-1 原料物質的比率 11
2-3-2晶化時間和溫度 11
2-3-3 pH值 11
2-4 LDHs之應用 12
2-5 常見產生鉻離子產業與處理方式 17
2-5-1 廢水中之鉻離子 17
2-5-2 鉻離子之處理方法 18
2-6等溫吸附曲線類型 23
第三章 實驗步驟與方法 27
3-1 研究架構 27
3-2 實驗藥品 29
3-3 實驗儀器 30
3-4 實驗項目及流程 34
3-4-1 水熱法製備Mg-Al LDHs 34
3-4-2 製備有機酸陰離子插層之LDHs 35
第四章 結果與討論 40
4-1 吸附劑基本性質 40
4-1-1 SEM之測定分析 40
4-1-2 FTIR之測定分析 43
4-1-3 XPS之測定分析 46
4-1-4 XRD之測定分析 49
4-2 Ex･Mg-Al LDHs對污染物之吸附 51
4-2-1 Ex･Mg-Al LDHs 之吸附等溫線 52
4-2-2 Ex･Mg-Al LDHs在pH=4之吸附量 60
4-2-3 Ex･Mg-Al LDHs在pH=5之吸附量 61
4-3 DS･Mg-Al LDHs對污染物之吸附 62
4-3-1 DS･Mg-Al LDHs 之吸附等溫線 62
4-3-2 DS･Mg-Al LDHs在pH=4之吸附量 68
4-3-3 DS･Mg-Al LDHs在pH=5之吸附量 68
4-4 L-cys･Mg-Al LDHs之吸附等溫線 69
4-4-1 L-cys･Mg-Al LDHs 之吸附等溫線 70
4-4-2 L-cys･Mg-Al LDHs 在pH=4之吸附量 77
4-4-3 L-cys･Mg-Al LDHs pH=5對污染物之吸附量 79
4-5 合成吸附劑之應用與評析 80
第五章 結論與建議 82
5-1 結論 82
5-2 未來建議 82
參考文獻 84




圖目錄

圖2-1 LDHs 結構示意圖[1] 4
圖2-2 典型液體吸附類型[40] 23
圖3-1 研究架構 28
圖3-2水熱合成法製備Mg-Al LDHs之流程 35
圖3-3共沉澱法合成LDHs流程圖 36
圖4-1鎂鋁水滑石及其插層過後之SEM圖 42
圖4-2 Mg-Al LDH及其插層過後之FTIR圖 46
圖4-3 XRD圖譜 51
圖4-4 pH=4時Ex･Mg-Al LDHs(60mmol)對鉻離子之吸附平衡曲線 54
圖4-5 pH=4時Ex･Mg-Al LDHs(60mmol)對鉻酸鹽之吸附平衡曲線 54
圖4-6 pH=4時Ex･Mg-Al LDHs(12.5mmol)對鉻離子之吸附平衡曲線 55
圖4-7 pH=4時Ex･Mg-Al LDHs(12.5mmol)對鉻酸鹽之吸附平衡曲線 55
圖4-8 pH=4時Ex･Mg-Al LDHs(6.25mmol)對鉻離子之吸附平衡曲線 56
圖4-9 pH=4時Ex･Mg-Al LDHs(6.25mmol)對鉻酸鹽之吸附平衡曲線 56
圖4-10pH=5時Ex･Mg-Al LDHs(60mmol)對鉻離子之吸附平衡曲線 57
圖4-11pH=5時Ex･Mg-Al LDHs(60mmol)對鉻酸鹽之吸附平衡曲線 57
圖4-12pH=5時Ex･Mg-Al LDHs(12.5mmol)對鉻離子之吸附平衡曲線 58
圖4-13pH=5時Ex･Mg-Al LDHs(12.5mmol)對鉻酸鹽之吸附平衡曲線 58
圖4-14pH=5時Ex･Mg-Al LDHs(6.25mmol)對鉻離子之吸附平衡曲線 59
圖4-15pH=5時Ex･Mg-Al LDHs(6.25mmol)對鉻酸鹽之吸附平衡曲線 59
圖4-16 pH=4時Ds･Mg-Al LDHs(60mmol)對鉻離子之吸附平衡曲線 64
圖4-17 pH=4時Ds･Mg-Al LDHs(60mmol)對鉻酸鹽之吸附平衡曲線 64
圖4-18 pH=4時Ds･Mg-Al LDHs(12.5mmol)對鉻離子之吸附平衡曲線 65
圖4-19 pH=4時Ds･Mg-Al LDHs(12.5mmol)對鉻酸鹽之吸附平衡曲線 65
圖4-20 pH=5時Ds･Mg-Al LDHs(60mmol)對鉻離子之吸附平衡曲線 66
圖4-21 pH=5時Ds･Mg-Al LDHs(60mmol)對鉻酸鹽之吸附平衡曲線 66
圖4-22 pH=5時Ds･Mg-Al LDHs(12.5mmol)對鉻離子之吸附平衡曲線 67
圖4-23 pH=5時Ds･Mg-Al LDHs(12.5mmol)對鉻離子之吸附平衡曲線 67
圖4-24 pH=4時L-cys･Mg-Al LDHs(60mmol)對鉻離子之吸附平衡曲線 71
圖4-25 pH=4時L-cys･Mg-Al LDHs(60mmol)對鉻酸鹽吸附平衡曲線 72
圖4-26 pH=4時L-cys･Mg-Al LDHs(6.25mmol)對鉻離子之吸附平衡曲線 72
圖4-27 pH=4時L-cys･Mg-Al LDHs(6.25mmol)對鉻酸鹽之吸附平衡曲線 73
圖4-28 pH=4時L-cys･Mg-Al LDHs(12.5mmol)對鉻離子之吸附平衡曲線 73
圖4-29 pH=4時L-cys･Mg-Al LDHs(12.5mmol)對鉻酸鹽之吸附平衡曲線 74
圖4-30 pH=5時L-cys･Mg-Al LDHs(60mmol)對鉻離子之吸附平衡曲線 74
圖4-31 pH=5時L-cys･Mg-Al LDHs(60mmol)對鉻酸鹽之吸附平衡曲線 75
圖4-32 pH=5時L-cys･Mg-Al LDHs(6.25mmol)對鉻離子之吸附平衡曲線 75
圖4-33 pH=5時L-cys･Mg-Al LDHs(6.25mmol)對鉻酸鹽之吸附平衡曲線 76
圖4-34 pH=5時L-cys･Mg-Al LDHs(12.5mmol)對鉻離子之吸附平衡曲線 76
圖4-35 pH=5時L-cys･Mg-Al LDHs(12.5mmol)對鉻酸鹽之吸附平衡曲線 77



表目錄

表3-1實驗藥品 30
表3-2儀器名稱、廠牌及型號 30
表4-1 各吸收波數下對應之有機官能基 43
表4-2各吸附劑XPS測定之元素組成百分比(％) 47
表4-3 Ex･Mg-Al LDHs在pH=4對污染物吸附量(mg/g) 60
表4-4 Ex･Mg-Al LDHs在pH=5對污染物吸附量(mg/g) 62
表4-5 DS･Mg-Al LDHs在pH=5對污染物吸附量(mg/g) 68
表4-6 DS･Mg-Al LDHs在pH=5對污染物吸附量(mg/g) 69
表4-7 L-cys･Mg-Al LDHs在pH=4對污染物之吸附量(mg/g) 78
表4-8 L-cys･Mg-Al LDHs在pH=5對污染物之吸附量(mg/g) 80

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