臺灣博碩士論文加值系統

重金屬污染物不像有機污染物能被生物分解或以適當化學方法轉化成無害之小分子，其只能轉化為較不具毒性之形式，因此，若具有毒性形式之重金屬存在於環境當中，會被生物體不斷地吸收累積，而無法自體內分解或排除，於是重金屬污染之控制成為環境工程之重大課題。
本研究結合酸瀝取與離子交換樹脂，對污泥中之重金屬進行去除與回收，重金屬污泥中所含之重金屬主要為二價的銅、鋅、鎘與鎳和三價的鉻與鐵。實驗結果顯示，在離子交換實驗中，鉻離子與其他五種離子明顯不同，鉻離子與氫離子的平衡反應為放熱反應，其它離子與氫離子則為吸熱反應；以酸瀝取劑去除污泥中之重金屬實驗，鉻金屬離子比其他離子難以自污泥中被去除。另外，三種不同裝置的酸萃取-離子交換循環回流實驗中顯示，以替換管柱方式進行實驗可有效地去除污泥中的重金屬，使用60克樹脂進行實驗300分鐘後，污泥中殘餘重金屬量只剩原始的0.35 %。與不使用離子交換樹脂的實驗結果比較，使用替換管柱方式之循環回流實驗不但可使污泥中重金屬的萃取效果提高19 %，還可使用較少的酸萃取劑即可達到相同的重金屬萃取結果。

Heavy metal contaminants, unlike organic pollutants that can be converted into non-hazardous small molecules by chemical treatments and/or bio-decomposition, they can only be transformed to a less-toxic form. If heavy metal existing as a toxic form in the environment, it might enter human or other animal bodies and accumulate constantly in the organisms. That is why the control of the heavy metal contamination becomes more and more important in environmental engineering field.
This study combines acid treatment with ion exchange process to remove and recover heavy metals from sludge contenting divalent metals of copper, zinc, cadmium, and nickel and trivalent metals of chromium and iron. The experimental results for chromium ion are quite different from other metal ions; the ion exchange process between chromium and hydrogen is found to be exothermic while those between other metal ions and hydrogen are endothermic. Chromium is the most difficultly extractable ion from sludge by acid treatment. Different experimental setups of re-circulation systems for heavy metal removal were also examined. Among them, the refreshed-column re-circulation system achieved the best heavy metal removal efficiency. Only 0.35 % of the heavy metal ions remained in the residue after 300 min using 60 g resin. In comparison with the acid leaching only, using the refreshed-column re-circulation system can not only increase 19 % heavy metal extraction efficiency but also achieve the same extraction efficiency with less amounts of acid extractant.

ACKNOWLEDGMENTS i
ABSTRACT (English) ii
ABSTRACT (Chinese) iii
TABLE OF CONTENTS iv
LIST OF TABLES vii
LIST OF FIGURES ix
GLOSSARY OF NOTATION xii
CHAPTER 1 INTRODUCTION 1
1.1 Background 1
1.2 Objectives and Scope 4
CHAPTER 2 LITERATURE REVIEW 5
2.1 Ion-exchange 5
2.2 Adsorption Isotherm of Heavy Metal Exchanging 8
2.2.1 Langmuir Isotherm 8
2.2.2 Freundlich Isotherm 10
2.2.3 Separation Factor 11
2.2.4 Selectivity Coefficient Model 12
2.3 Thermodynamic Functions of Heavy Metal Exchanging 13
2.4 Treatment of Heavy Metal Contaminated Sludge 14
2.5 Full Factorial Design 15
2.5.1 23 Full Factorial Design 15
2.5.2 Analysis of Variance 19
CHAPTER 3 EXPERIMENT 23
3.1 Experimental Apparatus, Chemicals and Equipment 23
3.2 Procedures 23
3.2.1 Samples Preparation and Digestion 23
3.2.2 Resin Pretreatment 26
3.2.3 23 Full Factorial Design 26
3.2.4 High Temperature Heavy Metal Sludge Extraction 28
3.2.5 Combined System Experiment 31
3.2.6 Ion-exchange Equilibriums of Heavy Metal Ions 31
3.2.7 Re-circulation Experiments 33
(a) Single-column Re-circulation System 33
(b) Four-column Re-circulation System 38
(c) Refreshed-column Re-circulation System 38
3.2.8 Extra Test of Re-circulation Experiment 38
3.3 AA Calibration Curves 39
CHAPTER 4 RESULTS AND DISCUSSION 46
4.1 Heavy Mental Content in Sludge 46
4.2 DOE Result of Heavy Metal Removal from Sludge 46
4.3 Effects of L/S Ratio and Extractant Concentration 51
4.4 Effect of Reaction Time 59
4.4.1 Extraction and Ion-exchange Model 63
4.5 Equilibrium Isotherm of Heavy Metal Ions 75
4.5.1 Langmuir and Freundlich Isotherms 75
4.5.2 Separation Factor 81
4.5.3 Selectivity Coefficient Model 83
4.6 Re-circulation Experiment 91
4.6.1 Single-column Re-circulation 91
4.6.2 Four-column Re-circulation 98
4.6.3 Refreshed-column Re-circulation 98
CHAPTER 5 CONCLUSIONS 105
REFERENCES 107

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