STUDY OF POLYAMINES-FUNCTIONALIZED PGMA BEADS AS ADSORBENTS FOR THE REMOVAL OF HEAVY METAL IONS FROM AQUEOUS SOLUTIONS LIU CHANGKUN NATIONAL UNIVERSITY OF SINGAPORE 2009 STUDY OF POLYAMINES-FUNCTIONALIZED PGMA BEADS AS ADSORBENTS FOR THE REMOVAL OF HEAVY METAL IONS FROM AQUEOUS SOLUTIONS LIU CHANGKUN (B Eng., Tianjin University) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF CHEMICAL AND BIOMOLECULAR ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2009 ACKNOWLEDGEMENT First and foremost, I would express my sincere gratitude to my supervisor, Prof Bai Renbi, for offering me a great chance of carrying out my research work in his laboratory His kind and continuous support has encouraged me to pursue my research curiosity, and his deep insight in the research area has greatly kept me on the right track of my research work Through his profound and conscientious discussions offered to me, I have mastered a great deal of knowledge and greatly broadened my views on research From his valuable and meticulous guidance, I have immensely developed my effective brainstorming, planning and scheduling skills His logic thinking, research enthusiasm and deep insight has inspired me and will be of great benefits to my life-long study My next gratitude goes to Prof Hong Liang, who has offered me kind guidance in my research work His willing to offer his academic help has greatly impressed me I would also like to show my thanks to my colleagues: Dr Zhang Xiong, Dr Li Nan, Dr Liu Chunxiu, Mr Han Wei, Mr Wee Kin Ho, Ms Han Hui, Ms Liu Cui, Ms Zhang Linzi and Mr Zhu Xiaoying, who have provided me with help and suggestions in my research work I would also appreciate the assistance from all the lab and professional officers in Department of Chemical and Biomolecular Engineering Finally, I would like to give my dearest thanks to my Father and Mother, my relatives and my late Grandfather, for their endless love, support and encouragement! I TABLE OF CONTENTS ACKNOWLEDGEMENT I TABLE OF CONTENTS II SUMMARY VI LIST OF TABLES XI LIST OF FIGURES XIII NOMENCLATURE XVII LIST OF SYMBOLS XX CHAPTER INTRODUCTION AND RESEARCH OBJECTIVES 1.1 Overview 1.2 Objectives and scopes of this study CHAPTER LITERATURE REVIEW 2.1 Review on heavy metals 2.1.1 Generals 2.1.2 Copper (Cu), lead (Pb), cobalt (Co), nickel (Ni), zinc (Zn) and cadmium (Cd) 2.2 Review on adsorption 2.2.1 Generals 2.2.2 Brief retrospection of adsorption 2.2.3 Importance of adsorption 2.2.4 Isotherm models of adsorption 2.2.4.1 Langmuir isotherm model 2.2.4.2 Freundlich isotherm model 2.2.4.3 Langmuir-Freundlich isotherm model 2.2.5 Kinetic models of adsorption 2.2.5.1 Pseudo-first-order model 2.2.5.2 Pseudo-second-order model 10 10 10 14 14 15 16 17 18 22 22 23 24 25 2.3 Review on Adsorbents 2.3.1 Characteristic of adsorbents 2.3.2 Types of adsorbents 2.3.2.1 Activated carbon 2.3.2.2 Zeolite (molecular sieves) 2.3.2.3 Silica Gel 2.3.2.4 Chitin and chitosan 26 26 27 27 28 28 28 II 2.3.2.5 Synthetic polymer adsorbents 29 2.3.3 Surface modification methods for the preparation of synthesized polymeric adsorbents for heavy metal ion removal 29 2.4 Amine-immobilized PGMA-based adsorbents for heavy metal ion removal 2.4.1 Suspension polymerization of PGMA polymers 2.4.2 PGMA-based polymers as adsorbent substrate 2.4.3 Ethyleneamines (polyamines) 2.4.3.1 Epoxy curing agents 2.4.3.2 Fuel additives 2.4.3.3 Chelating agents 2.4.4 Heavy metal ion removal with amine-immobilized PGMA-based adsorbents 2.4.5 Selectivity of heavy metal ion adsorption 2.4.5.1 Selective adsorbents 2.4.5.2 Approaches for heavy metal ion selectivity study 31 31 32 33 34 35 35 36 38 38 38 2.5 Characterization methods 2.5.1 X-ray photoelectron spectroscopy (XPS) 2.5.2 X-ray absorption fine structure (XAFS) 2.5.2.1 Generals 2.5.2.2 Fundamentals of x-ray absorption 2.5.2.3 Extended x-ray absorption fine structure (EXAFS) 2.5.2.4 X-ray absorption near edge structure (XANES) 2.5.2.5 XAFS data analysis 41 41 43 43 45 46 49 49 CHAPTER DIETHYLENETRIAMINE-GRAFTED POLY(GLYCIDYL METHACRYLATE) ADSORBENT FOR EFFECTIVE COPPER ION ADSORPTION 51 3.1 Introduction 53 3.2 Materials and methods 3.2.1 Materials 3.2.2 Preparation of DETA-grafted PGMA adsorbent 3.2.3 Batch adsorption experiments 3.2.4 Desorption experiments 3.2.5 Characterizations 57 57 57 58 60 61 3.3 Results and discussion 3.3.1 Grafting reaction of DETA with PGMA micro granules 3.3.2 Effect of pH on copper ions adsorption 3.3.3 Adsorption isotherm study 3.3.4 Effect of ionic strengths on adsorption kinetics and capacity 3.3.5 Desorption studies 63 63 64 70 72 75 3.4 Conclusions 81 III CHAPTER STUDY OF SELECTIVE REMOVAL OF COPPER AND LEAD IONS BY DIETHYLENETRIAMINE-FUNCTIONALIZED PGMA ADSORBENT: BEHAVIORS AND MECHANISMS 82 4.1 Introduction 84 4.2 Materials and methods 4.2.1 Materials 4.2.2 Preparation of P-DETA polymeric adsorbent 4.2.3 Batch adsorption study 4.2.4 Characterizations 87 87 87 88 91 4.3 Results 94 4.3.1 Properties of P-DETA adsorbent 94 4.3.2 Adsorption performance of P-DETA for copper and lead ions in single metal species system 96 4.3.3 Adsorption performance of P-DETA for copper and lead ions in binary metal species system 98 4.3.4 Mutual displacement of copper and lead ions 102 4.4 Discussion 4.4.1 Adsorption mechanisms of copper and lead ions on P-DETA 4.4.2 Selective adsorption mechanisms 4.4.3 Mechanism of metal ion displacement 104 104 108 110 4.5 Conclusions 112 CHAPTER PGMA-BASED ADSORBENTS FUNCTIONALIZED WITH DIFFERENT ALIPHATIC POLYAMINES: CHARACTERISTICS AND ADSORPTION PERFORMANCE FOR COPPER IONS 113 5.1 Introduction 115 5.2 Materials and methods 117 5.2.1 Materials 117 5.2.2 Factorial design for the preparation of polyamine-functionalized PGMA adsorbents (denoted as P-Amines) 117 5.2.3 Copper ion uptakes by P-Amine-x in the factorial design 118 5.2.4 Elemental and BET analysis 118 5.2.5 Potentiometric titration 119 5.2.6 XAFS (XANES and EXAFS) analysis 120 5.3 Results and discussion 5.3.1 Factorial Design 5.3.1.1 Effect of factorial design variables on amine contents of P-Amine-x 5.3.1.2 Effect of factorial design variables on copper ion adsorpion of P-Amine-x 5.3.1.3 Determination of the best reaction conditions for P-Amine-x 123 123 123 125 126 IV 5.3.2 BET and elemental analysis 5.3.3 Potentiometric titration study 5.3.4 Cu ion adsorption performance 5.3.5 XANES analysis 5.3.6 EXAFS analysis 5.3.7 Implication for Cu ion adsorption performance 5.4 Conclusions 127 128 137 139 141 145 152 CHAPTER EXTENDED STUDY OF DETA-FUNCTIONALIZED PGMA ADSORBENT FOR SELECTIVE ADSORPTION BEHAVIORS AND MECHANISMS FOR HEAVY METAL IONS OF Cu, Co, Ni, Zn AND Cd 153 6.1 Introduction 155 6.2 Materials and methods 6.2.1 Materials 6.2.2 Batch adsorption study 6.2.3 XANES and EXAFS analysis 158 158 158 159 6.3 Results and discussion 6.3.1 Adsorption isotherms of single metal ion species 6.3.2 Mutual displacement of the metal ions in binary system 6.3.3 XANES analysis 6.3.4 EXAFS analysis 6.3.5 Selectivity and stability constant 162 162 165 167 170 173 6.4 Conclusions 176 CHAPTER CONCLUSIONS AND RECOMMENDATIONS 177 7.1 Conclusions 178 7.2 Recommendations and future work 181 REFERENCE 184 LIST OF PUBLICATIONS 204 V SUMMARY Heavy metal ions are toxic, non-biodegradable and carcinogenic, and form a main class of pollutants in water and wastewater Adsorption has been one of the most efficient methods for the removal of heavy metal ions, especially at relatively low concentrations As the adsorption medium, amine-functionalized polymeric adsorbents have shown prospect over many other adsorbents and received increasing attention in recent years for the removal of heavy metal ions In this study, a focus has been placed on poly(glycidyl methacrylate) (PGMA) beads functionalized with various polyamines as the adsorbent The purpose of the study is to investigate the behaviors and mechanisms of the adsorbent in heavy metal ion adsorption and their relationship with the immobilized different polyamines The work included the preparation of PGMA beads and their functionalization with a series of aliphatic polyamines with increased numbers of amine groups and molecular chain lengths Then, adsorption experiments were conducted with the prepared adsorbent for a number of heavy metal ion species Various advanced analytical technologies were used to characterize the materials and elucidate the reactions or interactions and mechanisms involved in the various processes In the first part of the study, PGMA beads were prepared via the suspension polymerization method and were surface functionalized with diethylenetriamine (DETA) The prepared PGMA-DETA adsorbent was investigated for copper ion adsorption performance It was found that PGMA-DETA achieved excellent Cu ion adsorption performance at higher pH values in the pH range of 1-6, with high adsorption capacities and fast adsorption kinetics In addition, batch Cu ion desorption experiments showed that VI the desorption kinetics was very fast with a high desorption efficiency in dilute nitric acid solution Spectroscopic studies with FTIR and XPS were conducted to understand the adsorption and desorption mechanisms It was found that copper ion formed surface complex with the neutral amine groups during the adsorption onto PGMA-DETA, and surface complexation was one of the main adsorption mechanism It was also found that higher acid concentration may not result in higher desorption efficiency of the copper ionadsorbed PGMA-DETA, and HNO3 with the concentration of 0.1 M gave the highest copper ion desorption efficiency The desorption mechanism can be explained from the combined effects of both protonation-deprotonation equilibrium and Cu ion adsorptiondesorption equilibrium Then, a modified suspension polymerization method was used for the preparation of the PGMA beads with improved mechanical strength The PGMA beads were also subsequently surface functionalized with DETA The prepared adsorbent (denoted as PDETA) was examined for Cu and Pb ion adsorption through a series of single and binary metal species systems, with focus on the selective adsorption performance P-DETA was found to adsorb Cu or Pb ions significantly in the single species systems It was also found that P-DETA exhibited excellent selective adsorption performance towards Cu ions over Pb ions, and that the initially adsorbed Pb ions can be displaced by subsequently adsorbed Cu ions, when both Cu and Pb ions were present in the solution The greater electronegativity of Cu ions than Pb ions was proposed as the main factor to explain the selectivity of P-DETA for Cu ions over Pb ions The results show that the P-DETA adsorbent can potentially be used to effectively and selectively remove and separate heavy metal ions VII Another attempt has been made to investigate the effects of a series of aliphatic polyamines immobilized on PGMA beads for the adsorption of heavy metal ions PGMA beads were prepared as described in the previous work and were functionalized with ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and tetraethylenepentamine (TEPA), with increased molecular chain lengths and number of amine groups Then the different polyamine functionalized PGMA adsorbents were examined for Cu ion adsorption Elemental, BET, potentiometric titration and XAFS (XANES + EXAFS) analyses were conducted It was found that the immobilized polyamine densities decreased from EDA to TEPA, while the amine amounts increased with the use of ligands from EDA to TEPA When the immobilized polyamines were coordinated with Cu ions, the coordination number of Cu ion with nitrogen atoms in the polyamines followed the sequence of DETA < TETA < EDA < TEPA, and a tetrahedral coordination geometry with a nitrogen coordination number of 3-4 was indicated Hence, Cu ion adsorption performance on the different polyamines functionalized PGMA beads was dependant on the amine amounts, amine densities as well as the structures of Cu complex formed with the polyamine DETA functionalized PGMA adsorbent was found to have the highest Cu ion adsorption capacity than others due to its relatively high amine density and low coordination number A final attempt was made to examine the selectivity of P-DETA towards a number of different heavy metal species including Cu, Co, Ni, Zn and Cd ions It was found that PDETA showed a selective adsorption sequence of Cu > Co > Ni > Zn > Cd ions in the single species adsorption systems XANES analysis revealed a tetrahedral geometry for VIII Horák, D and P Shapoval Reactive Poly(Glycidyl Methacrylate) Microspheres Prepared by Dispersion Polymerization, J Polym Sci Pol Chem., 38, pp.3855-3863 2000 http://en.wikipedia.org/wiki/X-ray_photoelectron_spectroscopy http://www.dow.com/acrylic/products/gma.html http://www.dow.com/amines/pdfs/108-01347.pdf (Ethyleneamines, DOW) http://www.epa.gov/safewater/dwh/c-ioc/cadmium.html 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Selective Adsorption of Mercury Ions on Chitosan Beads Grafted with Polyacrylamide via Surface-Initiated Atom Transfer Radical Polymerization, Langmuir, 21, pp.11780-11787 2005 Conference Papers Liu, C and R.B Bai Surface Interactions of PGMA-DETA Polymeric Adsorbent in Copper Ion Removal, presented at 79th Colloid and Surface Science Symposium of American Chemical Society, Clarkson University, NY, USA, 12-15 June 2005 Liu, C and R.B Bai Humic Acid Removal with Aminated PGMA Beads, presented at 79th Colloid and Surface Science Symposium of American Chemical Society, Clarkson University, NY, USA, 12-15 June 2005 204 .. .STUDY OF POLYAMINES -FUNCTIONALIZED PGMA BEADS AS ADSORBENTS FOR THE REMOVAL OF HEAVY METAL IONS FROM AQUEOUS SOLUTIONS LIU CHANGKUN (B Eng., Tianjin University) A THESIS SUBMITTED FOR THE. .. of functional adsorbents for the removal and separation of heavy metal ions from water or wastewater The application of amine -functionalized PGMA- based adsorbents (denoted as aminePGMA) for heavy. .. separate heavy metal ions VII Another attempt has been made to investigate the effects of a series of aliphatic polyamines immobilized on PGMA beads for the adsorption of heavy metal ions PGMA beads