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UNIVERSITI PUTRA MALAYSIA

FABRICATION AND CHARACTERIZATION OF ION-IMPRINTED

POLYMER FOR REMOVAL OF MERCURY

SITI KHADIJAH BT AB. RAHMAN

FS 2017 75

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FABRICATION AND CHARACTERIZATION OF ION-IMPRINTED POLYMER FOR REMOVAL OF MERCURY

By

SITI KHADIJAH BT AB. RAHMAN

Thesis Submitted to the School of Graduate Studies, Universiti Putra Malaysia, in Fulfilment of the Requirements for the Degree of Doctor of

Philosophy

May 2017

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COPYRIGHT

All material contained within the thesis, including without limitation text, logos, icons, photographs and all other artwork, is copyright material of Universiti Putra Malaysia unless otherwise stated. Use may be made of any material contained within the thesis for non-commercial purposes from the copyright holder. Commercial use of material may only be made with the express, prior, written permission of Universiti Putra Malaysia.

Copyright © Universiti Putra Malaysia

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DEDICATION

To my lovely husband, Fardiyuz bin Abdul Mutalib, who has encouraged me all the way, and whose encouragement has made sure that I give it all it takes to finish my Ph.D. study in Universiti Putra Malaysia; To my children Ahmad Asyraf and Ahmad Ameen, the symbol of love and giving. Both of you have been my best cheerleaders; To my loving parents, family members and friends for their endless support; To all the people in my life who touch my heart; ... I dedicate this research.

Thank you. My love for you all can never be quantified. God bless you.

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Abstract of thesis presented to the Senate of Universiti Putra Malaysia in fulfilment of the requirements for the degree of Doctor of Philosophy

FABRICATION AND CHARACTERIZATION OF ION IMPRINTED-POLYMER FOR REMOVAL OF MERCURY

By

SITI KHADIJAH BT AB. RAHMAN

May 2017

Chair : Professor Nor Azah Yusof, PhD Faculty : Science Mercury (Hg) is a natural trace component found in the petroleum reservoir. The presence of Hg is detrimental to petroleum production facilities as it forms corrosion induced through Hg amalgamates. Moreover, it has an effect on human beings if it is discharged into the waterways and atmosphere leading to severe, acute and chronic poisoning. Ion imprinted polymer (IIP) being one of the latest adsorbents which is alternative technique that is more selective and effective than the conventional removal method of Hg. IIP is synthetic polymers having a predetermined selectivity for a template ion, which makes them ideal materials to be used in removal processes. In this study, the IIP was developed for the removal of Hg(II) ions from aqueous solutions and actual samples. The IIP particles and monoliths was prepared by thermal polymerization technique with Hg(II) as a template ions, [2-(methacryloyloxy)ethyl] trimethylammonium cysteine (MAETC) as a ligand, methacrylic acid (MAA) as a functional monomer, 2-hydroxyethyl methacrylate ethylene glycol (HEMA) as a co-monomer, dimethacrylamide (EGDMA) as a cross-linker, benzoyl peroxide (BPO) as an initiator and methanol or acetonitrile as a porogen. The IIP-20A monolith was selected as the best monolithic IIP due to its high adsorption capacity and good physical properties. The prepared IIP-particle and all of the monolithic IIPs were characterized using Fourier transform infrared (FTIR), thermal gravimetric analysis (TGA), field emission scanning electron microscope (FESEM) and Brunauer Emmet-Teller (BET) for determining the polymerization and imprinting process occurred. In the down-flow technique of IIP-20A monolith, pH, dosage, initial concentration, reusability, selectivity and kinetic study were investigated.

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Removal of Hg(II) of pH dependent was found maximum at pH 4.7. The removal percentage of Hg(II) increased with increasing of adsorbent dose and the total uptake of Hg(II) increased with increasing initial concentration of Hg(II) ions. The kinetic study of Hg(II) adsorption by IIP-20A monolith was fit well with Adam’s Bohart model. The adsorbents have very good selectivity towards Hg(II) ions even in the presence of other metals (Pb(II), Cd(II), As(II) and Cr(III)) and can be reusable up to fifteen cycles. The comparison of removal test of Hg(II) ions for up-flow column technique (pilot plant-scale) showed that the IIP-20A monolith having good adsorption capacities compared with IIP-particle (packed in a coffee filter). Other than that, the IIP-20A monolith has been successfully applied for the recovery of trace Hg(II) in actual samples (river water, wastewater and condensate).

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Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai memenuhi keperluan untuk ijazah Doktor Falsafah

FABRIKASI DAN PENCIRIAN POLIMER CETAKAN ION UNTUK PENYINGKIRAN MERKURI

Oleh

SITI KHADIJAH BT AB. RAHMAN

Mei 2017

Pengerusi : Profesor Nor Azah Yusof, PhD Fakulti : Sains Mercury (Hg) adalah kesan komponen semulajadi yang terdapat dalam takungan petroleum. Kehadiran Hg mendatangkan keburukan dalam fasiliti penghasilan petroleum, kerana ia akan merangsang pembentukan hakisan melalui pencantuman Hg. Selain itu, ia mempunyai kesan ke atas manusia jika ia dilepaskan ke dalam laluan air dan atmosfera kerana membawa kepada keracunan yang amat teruk dan kronik. Polimer cetakan ion (IIP) ialah salah satu daripada penjerap terkini yang merupakan teknik alternatif yang lebih selektif dan berkesan jika di bandingkan dengan kaedah penyingkiran Hg yang konvensional. IIP adalah polimer sintetik yang mempunyai selektiviti terhadap ion tertentu. Justeru, ia menjadikan IIP sebagai bahan yang ideal untuk digunakan dalam proses penyingkiran. Dalam kajian ini, IIP telah dikembangkan bagi penyingkiran Hg(II) ion dari larutan akueus dan sampel sebenar. IIP dalam bentuk serbuk dan monolit telah disintesis menggunakan teknik pempolimeran haba dengan menggunakan Hg(II) ion sebagai acuan, [2- (metakriloiloksi) etil] trimetilammonium cysteine (MAETC) sebagai ligan, asid metakrilik (MAA) sebagai monomer berfungsi, 2-hidrosietil metakrilat etilena glikol (HEMA) sebagai monomer-bersama, etilena glikol dimetakrilat (EGDMA) sebagai penggabung, benzoil peroksida (BPO) sebagai pemula dan metanol atau asetonitril sebagai porogen. IIP-20A monolit telah dipilih sebagai polimer monolitik yang terbaik kerana kapasiti penjerapannya yang tinggi dan sifat-sifat fizikalnya yang baik. IIP dalam bentuk serbuk dan monolit yang telah dihasilkan telah dicirikan menggunakan Fourier inframerah (FTIR), analisis terma gravimetrik (TGA),

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medan pengimbas mikroskopi elektron (FESEM) dan Brunauer Emmet-Teller (BET) bagi menentukan proses pempolimeran dan pencetakan ion itu telah berlaku. Dalam kajian menggunakan teknik aliran ke bawah bagi IIP-20A monolit, kajian bagi kesan pH, dos penjerap, kepekatan awal, kemampuan kitar semula, ujian selektiviti dan kinetik telah dikaji. Penyingkiran maksimum Hg(II) bagi kesan pH telah dicapai pada pH 4.7. Manakala, peratusan penyingkiran Hg(II) meningkat dengan peningkatan dos bahan penjerap dan penjerapan bagi ion Hg(II) meningkat dengan peningkatan kepekatan awal bagi ion Hg(II). Ujian kinetik bagi penjerapan Hg(II) oleh IIP-20A monolit adalah sesuai dengan model Adam’s Bohart. Penjerap ini mempunyai selektiviti yang sangat baik kepada Hg (II) ion walaupun dengan kehadiran ion logam lain seperti Pb (II), Cd(II), As(II) dan Cr (III) dan penjerap ini juga boleh dikitar semula sehingga lima belas kali kitaran. Perbandingan ujian penyingkiran Hg(II) bagi teknik kolum aliran ke atas menunjukkan bahawa IIP-20A monolit mempunyai kapasiti jerapan yang sangat baik berbanding dengan IIP-serbuk yang dibungkus dalam penapis kopi. Selain itu, IIP-20A monolit telah berjaya diaplikasikan bagi menyingkirkan Hg(II) dalam sampel yang sebenar (air sungai, air kumbahan dan kondensat).

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ACKNOWLEDGEMENTS

All praise to Allah S.W.T. who has showered me with kindness and affection during the course of my study. His endless grace and love have provided me the strength to finish this study. I would like to express my sincere gratitude to my main supervisor, Prof. Dr. Nor Azah Yusof for her continuous support, supervision, patience, motivation, invaluable guidance, and immense knowledge throughout the phase of my Ph.D. study. Her guidance has greatly helped me during the time of research and writing of this thesis. I could not have imagined having a better advisor and mentor for my Ph.D. study. Besides my main supervisor, I would like to thank my co-supervisors, Assoc. Prof. Dr. Abdul Halim Abdullah and Prof. Dr. Azni Idris for their encouragement, constructive comments, constant advice and useful suggestions. I also would like to express my gratitude to all my lab mates for their help and support to finish my Ph.D. study. My special thanks to the staff of Jabatan Kimia, Jabatan Sains Alam Sekitar, Jabatan Pengurusan Tanah, Institut Biosains and Institut Teknologi Maju Universiti Putra Malaysia for their invaluable assistance, help, information, and co-operation. Last but not least, a special note of appreciation is extended to Ministry of Higher Education (MOHE) for their fully financial support in the form of My Brain15 (My Phd).

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This thesis was submitted to the Senate of Universiti Putra Malaysia and has been accepted as fulfilment of the requirement for the degree of Doctor of Philosophy. The members of the Supervisory Committee were as follows: Nor Azah bt Yusof, PhD Professor Faculty of Science Universiti Putra Malaysia (Chairman) Abdul Halim bin Abdullah, PhD Associate Professor Faculty of Science Universiti Putra Malaysia (Member) Azni bin Idris, PhD Professor Faculty of Engineering Universiti Putra Malaysia (Member)

________________________ ROBIAH BINTI YUNUS, PhD Professor and Dean School of Graduate Studies Universiti Putra Malaysia

Date:

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Declaration by graduate student

I hereby confirm that: � this thesis is my original work; � quotations, illustrations and citations have been duly referenced; � this thesis has not been submitted previously or concurrently for any other

degree at any other institutions; � intellectual property from the thesis and copyright of thesis are fully-owned

by Universiti Putra Malaysia, as according to the Universiti Putra Malaysia (Research) Rules 2012;

� written permission must be obtained from supervisor and the office of Deputy Vice-Chancellor (Research and Innovation) before thesis is published (in the form of written, printed or in electronic form) including books, journals, modules, proceedings, popular writings, seminar papers, manuscripts, posters, reports, lecture notes, learning modules or any other materials as stated in the Universiti Putra Malaysia (Research) Rules 2012;

� there is no plagiarism or data falsification/fabrication in the thesis, and scholarly integrity is upheld as according to the Universiti Putra Malaysia (Graduate Studies) Rules 2003 (Revision 2012-2013) and the Universiti Putra Malaysia (Research) Rules 2012. The thesis has undergone plagiarism detection software.

Signature: Date: Name and Matric No.: Siti Khadijah Bt Ab. Rahman (GS38668)

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Declaration by Members of Supervisory Committee

This is to confirm that: � the research conducted and the writing of this thesis was under our

supervision; � supervision responsibilities as stated in the Universiti Putra Malaysia

(Graduate Studies) Rules 2003 (Revision 2012-2013) are adhered to.

Signature:

Name of Chairman of Supervisory Committee: Prof. Dr. Nor Azah Bt Yusof Signature:

Name of Member of Supervisory Committee: Assoc. Prof. Dr. Abdul Halim Bin Abdullah Signature: Name of Member of Supervisory Committee: Prof. Dr. Azni Bin Idris

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TABLE OF CONTENTS

Page ABSTRACT i ABSTRAK iii ACKNOWLEDGEMENTS v APPROVAL vi DECLARATION viii LIST OF TABLES xiii LIST OF FIGURES xv LIST OF SCHEMES xvii LIST OF ABBREVIATIONS xviii CHAPTER 1 INTRODUCTION

1.1 Background of Research 1 1.2 Problem Statement 3 1.3 Objectives of this Research 4 2 LITERATURE REVIEW

2.1 Mercury 5 2.1.1 Mercury Pollution in South East Asia 5 2.1.2 Effect of Mercury 6 2.1.3 Actions to Avoid Consequences of Mercury 7 2.2 Adsorbent Technology for the Removal of Mercury 8 2.2.1 Activated Carbon 9 2.2.2 Natural Adsorbent 11 2.2.3 Nano adsorbent 12 2.2.4 Polymer Adsorbent 13 2.3 Ion Imprinted Polymer 15 2.4 Factor Affecting the Ion Imprinting Process 17 2.4.1 Ligand 17 2.4.2 Functional Monomer 17 2.4.3 Cross-linking Agents 18 2.4.4 Porogen 19 2.4.5 Initiator 20 2.4.6 Methods of Preparation for Ion Imprinted

Polymer 20

2.5 Physical Forms of Imprinting Polymer 21 2.5.1 Particle 21 2.5.2 Monolithic 23 2.6 Optimization of Physical Form of Ion Imprinted Polymer 26 2.6.1 Extrusion 26 2.6.2 Tableting 27 2.6.3 Packaging 27 2.7

Application of Ion Imprinted Polymers for Removal of Mercury in Actual Samples

28

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3 MATERIALS AND METHODS 3.1 Materials 31 3.2 Preparation of Solution 32 3.3 Preparation of Ion Imprinted Polymer 33 3.3.1 Synthesis of [2-(Methacryloyloxy)ethyl]

Trimethylammonium Cysteine 33

3.3.2 Scale up for the Preparation of Ion Imprinted Polymer Particle

33

3.3.3 Optimization of Physical Form of Ion Imprinted Polymer-Particle

34

3.3.4 Preparation of Ion Imprinted Polymer Monolith 37 3.3.5 The Extraction Process of Hg(II) 41 3.4 Characterization of Ion Imprinted Polymer 41 3.4.1 Fourier Transform Infrared Spectroscopy 41 3.4.2 Thermal Stability Study 41 3.4.3 Morphological Characterization 42 3.4.4 Surface Area and Porosity 42 3.5 Adsorption Study 43 3.5.1 Determination of Concentration of Hg(II) Ions 44 3.5.2

Adsorption of Hg(II) using Down-flow Technique with IIP-20A Monolith

45

3.5.3 Adsorption of Hg(II) using Up-flow Column Technique with IIP-Particle (Packed in Coffee Filter) and IIP-20A Monolith

46

3.5.4 Application of IIP-20A Monolith for Removal of Hg(II) in Actual Samples

49

4 RESULTS AND DISCUSSION

4.1 Proposed Mechanism for the Ion Imprinting of Hg(II) 52 4.1.1 Complexation Process between Ligand and

Metal Ion 52

4.1.2 Reaction Mechanism of Ion Imprinted Polymer 54 4.2 Preparation of Ion Imprinted Polymer 54 4.2.1 Synthesis of [2-(Methacryloyloxy)ethyl]

Trimethylammonium Cysteine 54

4.2.2 Scale up for the Preparation of Ion Imprinted Polymer Particle

56

4.2.3 Optimization of Physical Form of Ion Imprinted Polymer-Particle

56

4.2.4 Preparation of Ion Imprinted Polymer Monolith 59 4.2.5 The Extraction Process of Hg(II) 62 4.3 Characterization of Ion Imprinted Polymer 62 4.3.1 Fourier Transform Infrared Spectroscopy 63 4.3.2 Thermal Stability Study 66 4.3.3 Morphological Characterization 74 4.3.4 Surface Area and Porosity 78 4.4 Adsorption of Hg(II) using Down-flow Technique with IIP-

20A Monolith 82

4.4.1 Effect of pH 82 4.4.2 Effect of Dosage 83

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4.4.3 Effect of Initial Concentration 84 4.4.4 Selectivity Study 85 4.4.5 Reusability 86 4.4.6 Kinetic Study 87 4.5 Adsorption of Hg(II) using Up-flow Column Technique with

IIP-Particle (Packed in Coffee Filter) and IIP-20A Monolith 91

4.5.1 Effect of pH for IIP-Particle (Packed in Coffee Filter)

91

4.5.2 Effect of Flow Rate for IIP-Particle (Packed in Coffee Filter) and IIP-20A Monolith

92

4.5.3 Effect of Dosage for IIP-Particle (Packed in Coffee Filter) and IIP-20A Monolith

93

4.6 Application of IIP-20A Monolith for Removal of Hg(II) in Actual Samples

94

5 CONCLUSION AND RECOMMENDATIONS

5.1 Conclusion 96 5.2 Recommendations 97 REFERENCES 99 APPENDICES 110 BIODATA OF STUDENT 120 LIST OF PUBLICATIONS 121

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LIST OF TABLES

Table Page

1.1 Estimated world levels of mercury in natural gas and liquids 2 2.1 Removal of mercury by activated carbon 10 2.2 Removal of mercury by natural adsorbents 12 2.3 Mercury removal by nano adsorbents 14 2.4 Removal of mercury by polymer adsorbents 15 2.5 Porogens used in the preparation of ion imprinted polymer 20 2.6 Review of method preparation of ion imprinted polymer for

the removal of mercury 22

2.7 Review of ion imprinted polymer in particles form 24 2.8 Review of molecularly imprinted polymer in monolith form 25 2.9 Review of ion imprinted polymer for the removal of mercury 29 3.1 List of materials used in this research 31 3.2 List of scaling up for synthesizing of MAETC 33 3.3 List of scaling up for the preparation of IIP-particle 35 3.4 List of preparation for various types of monolithic IIPs 39 3.5 List of scaling up for the preparation of IIP-20A monolith 40 3.6 Summary of experimental condition for the removal of Hg(II)

by IIP-20A monolith 47

3.7 Experimental condition of the up-flow column method of IIP-particle (packed in coffee filter) and IIP-20A monolith packed column

50

4.1 List of scale-up for MAETC synthesis 56 4.2 List of scale-up for IIP-particle preparation 56 4.3 List of various types of IIP monoliths 60 4.4 List of scale-up for IIP-20A monolith preparation 62 4.5 Summary of frequency of vibrations for Monomer-MAA,

MAETC, IIP-particle and various types of IIP monoliths 68

4.6 Summary of thermal decomposition for Monomer-MAA, MAETC, IIP-particle and various types of IIP monoliths

7

4.7 Data of surface area, pore volume, average pore diameter, and isotherm type for the various types of IIPs

82

4.8 Thomas and Adam’s Bohart model parameter of Hg(II) adsorption on IIP-20A monolith

90

4.9 Removal percentage of Hg(II) by IIP-20A monolith for down-flow technique

95

4.10 Removal percentage of Hg(II) by IIP-20A monolith for up-flow column technique

95

A1.1 Evaluation of porogen factor for removal of Hg(II) 110 A2.1 Effect of pH on adsorption capacity of Hg(II) by IIP-20A

monolith 110

A2.2.1 Effect of dosage for IIP-20A monolith on removal percentage of Hg(II)

111

A2.2.2 Effect of dosage for IIP-20A monolith on adsorption capacity of Hg(II)

111

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A2.3 Effect of initial concentration on adsorption capacity of Hg(II) by IIP-20A monolith

112

A2.4 Reusability study for IIP-20A 112 A2.5 Selectivity study of IIP-20A monolith 113 A2.6.1 Kinetic study of Hg(II) adsorption by IIP-20A monolith 113 A2.6.2 Kinetic study and determination of reaction rate of IIP-20A

monolith using Thomas and Adam’s Bohart model 114

A3.1 Effect of pH on adsorption capacity of Hg(II) by IIP-particle (packed in coffee filter)

115

A3.2.1 Effect of flow rate on adsorption capacity of Hg(II) by IIP-particle (packed in coffee filter)

115

A3.2.2 Effect of flow rate on adsorption capacity of Hg(II) by IIP-20A monolith

116

A3.3.1 Removal percentage of Hg(II) by IIP-particle (packed in coffee filter)

116

A3.3.2 Removal percentage of Hg(II) by IIP-20A monolith 117 A4.1 Up-flow column technique (pilot plant-scale) of application of

IIP-20A for removal of Hg(II) from actual samples 117

A4.2 Down-flow technique (lab-scale) of application of IIP-20A for the removal of Hg(II) from actual samples

118

A5.1.1 Tableting of IIP-particle using bentonite as a binder 118 A5.1.2 Tableting of IIP-particle using PVP as a binder 119 A5.2 Packaging of IIP-particle in tea bags and coffee filter 119

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LIST OF FIGURES

Figure Page

2.1 The Principle of Ion Imprinting Procedure 16 2.2 Types of Functional Monomers Used in Non Covalent

Imprinting 18

3.1 Example of Compression Method of IIP Tablet 36 3.2 IIP-Particle Packed in (a) Tea Bag and (b) Coffee Filter

Paper 37

3.3 Formation of Monolithic IIPs using Molding Technique 38 3.4 Schematic Diagram for MRU (a) Solutions Before

Treatment (b) Solutions After Treatment (c) Glass Column and (d) Adsorbent (IIPs)

48

3.5 Picture for MRU (a) Solutions Before Treatment (b) Solutions After Treatment (c) Glass Column (d) IIPs and (e) Peristaltic Pump

48

3.6 Summary of Experimental Design 51 4.1 Optimization of Volume of Porogen 61 4.2 The Extraction of Hg(II) using Thiourea Solution 63 4.3 FTIR Spectra for Monomer-MAA, MAETC, IIP-Particle and

IIP-WP monolith 64

4.4 FTIR Spectra for IIP Monoliths with Porogen 67 4.5 TGA Thermograms for MAETC, Monomer-MAA, IIP-Particle

and IIP-WP Monolith 69

4.6 DTG Thermograms for MAETC, Monomer-MAA, IIP-Particle and IIP-WP Monolith

70

4.7 TGA Thermograms for IIP-WP, IIP-20M and IIP-20A Monolith

71

4.8 TGA Thermograms for IIP-5M, IIP-10M, IIP-30M, IIP-5A, IIP-10A and IIP-30A Monolith

71

4.9 DTG Thermograms for IIP-WP, IIP-20M and IIP-20A Monolith

72

4.10 DTG Thermograms for IIP-5M, IIP-10M, IIP-30M, IIP-5A, IIP-10A and IIP-30A Monolith

73

4.11 The Morphology of (a) IIP-Particle and (b) IIP-WP Monolith under the Magnification 50,000

75

4.12 The Morphology of (c) IIP-5M (d) IIP-10M (e) IIP-20M and (f) IIP-30M Monoliths under the Magnification 50,000

76

4.13 The Morphology of (g) IIP-5A (h) IIP-10A (i) IIP-20A and (j) IIP-30A Monoliths under the Magnification 50,000

77

4.14 BET and BJH Graph for (a) IIP-Particle and (b) IIP-WP Monolith

79

4.15 BET and BJH Graph for (c) IIP-5M, (d) IIP-10M, (e) IIP-20M and (f) IIP-30M Monolith

80

4.16 BET and BJH Graph for (g) IIP-5A, (h) IIP-10A, (i) IIP-20A and (j) IIP-30A Monolith

81

4.17 Effect of pH on Adsorption of Hg(II) by IIP-20A Monolith 83

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4.18 Removal Percentage and Adsorption Capacity of Hg(II) Ions for Different Dosage of IIP-20A Monolith

84

4.19 Effect of Concentration on Adsorption of Hg(II) by IIP-20A Monolith

85

4.20 Selectivity Study of Hg(II) Ions by IIP-20A Monolith in the Presence of Foreign Ions

86

4.21 Removal of Hg(II) Percentage for Reusability of IIP-20A Monolith

87

4.22 Breakthrough Curves for Hg(II) Adsorption by IIP-20A Monolith

88

4.23 Thomas Model for Adsorption of Hg(II) on IIP-20A Monolith

89

4.24 Adam’s Bohart Model for Adsorption of Hg(II) on IIP-20A Monolith

90

4.25 Effect of pH on Adsorption of Hg(II) by IIP-Particle (Packed in Coffee Filter)

92

4.26 Effect of Flow Rate on the Adsorption of Hg(II) By (a) IIP-Particle (Packed in Coffee Filter) and (b) IIP-20A Monolith

93

4.27 Removal of Hg(II) Percentage for Different Dosage of (a) IIP-Particle (Packed in Coffee Filter) and (b) IIP-20A Monolith

94

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LIST OF SCHEMES

Scheme Page

4.1 Proposed Reaction Mechanism for Synthesizing of MAETC as a Ligand

53

4.2 Proposed Reaction between MAETC (Ligand) and Hg(NO3)2 (Metal Ion)

53

4.3 Proposed Reaction Mechanism for Preparation of Ion Imprinted Polymer

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LIST OF ABBREVIATIONS

AC Activated carbon AFS Atomic fluorescence spectrometry BET Brunauer Emmett Teller BJH Barret-Joyner-Halenda CNTs Carbon nano-tubes CP Control polymer CVAAS Cold vapor atomic absorption spectrometry DTG Differential thermogravimetric analysis FAAS-CVAAS Flame atomic absorption spectrometric-Cold vapor

atomic absorption spectrometry FESEM Field emission scanning electron microscope FTIR Fourier transform infrared HPLC High performance liquid chromatography ICP-AES Inductively coupled plasma- atomic emission

spectroscopy ICP-MS Inductively coupled plasma- mass spectroscopy ICP-OES Inductively coupled plasma- optical emission

spectroscopy IIP Ion imprinted polymer IIP-10A Ion imprinted polymer monolith - 10 mL of acetonitrile IIP-10M Ion imprinted polymer monolith -10 mL of methanol IIP-20A Ion imprinted polymer monolith - 20 mL of acetonitrile IIP-20M Ion imprinted polymer monolith -20 mL of methanol IIP-30A Ion imprinted polymer monolith - 30 mL of acetonitrile IIP-30M Ion imprinted polymer monolith -30 mL of methanol IIP-5A Ion imprinted polymer monolith - 5 mL of acetonitrile IIP-5M Ion imprinted polymer monolith -5 mL of methanol IIP-monolith Ion imprinted polymer monolith IIP-particle Ion imprinted polymer particle IIP-WP Ion imprinted polymer monolith – without porogen LNG Liquefied natural gas MAC N-Methacrylol- (L)-cysteine MAETC [2-(Methacryloyloxy)ethyl] trimethylammonium cysteine MBT 2-mercaptobenzothiazole MIIP Metal ion imprinted polymer MIONPs Magnetic iron oxide nanoparticles MIPs Molecularly imprinted polymers MOTAC Methacryloyl(oxyethyl)trimethyl ammonium chloride MRS Mercury removal systems MRU Mercury removal unit MSS-AC Mango seeds shells-activated carbon MWCNTs Multi-walled carbon nanotubes NIPs Non imprinted polymers NMOs Nanosized metal oxides PEG Polyethylene glycol PEI Poly(ethyleneimine)

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PHEMA Poly(2-hydroxyethylmethacrylate) ppb Part per billion ppm Part per million ppt Part per trillion PVP Polyvinylpyrrolidone SE Southeast SPE Solid phase extraction TAR 4-(2-thiazolylazo) resorcinol TGA Thermal gravimetric analysis UATR Universal attenuated total reflectance VGAAAS- GTA-AAS

Vapour generation accessory-atomic absorption spectrometer-76 -graphite tube atomizer-atomic Absorption spectrometer- 96

WHO World health organization

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CHAPTER 1

INTRODUCTION

1.1 Background of Research

Mercury (Hg) is considered as a global pollutant due to its toxicity, persistence, long range of transport potential and bioaccumulation (Yun et al., 2013). Emission and distribution of Hg to the environment can occur from natural, anthropogenic and re-emitted sources (Zheng et al., 2012, Wang et al., 2012). Petrochemical industries (Gaulier et al., 2015), urban discharges, agricultural materials, mining and coal combustion, industrial discharges (Rodríguez et al., 2012), metal refining and manufacturing and chloralkali production (Wang et al., 2012) are the principal anthropogenic sources of Hg pollution in the environment.

Petroleum is one of the most important energy sources for the modern society, along with the raw material form any industrial products such as chemical fertilizer, plastics and more (Yun et al., 2013). Hg is a natural contaminant commonly found as traces in all fossil fuels including natural gas, gas condensates, crude oil, coal, tar sands and other bitumens that are processed in the petrochemical industries (Gaulier et al., 2015, de Jesus et al., 2013). A total of approximately 2000 tons per year of Hg are estimated to be released from petrochemical industries (fossil fuel combustion) and metal production combined. For instance, natural gas and liquid production frequently generate hydrocarbon streams containing trace levels of Hg, especially in Southeast (SE) Asia where Hg concentration can reach up to 1200 µg/L (wt) which is the highest value in the world (Sainal et al., 2007). Table 1.1 shows the hydrocarbons from different geological locations containing Hg in microgram levels. The values shown are estimations and may change from time to time, depending on geological factors and production practices (Sainal et al., 2007).

The effects of Hg in feeds on processing systems include equipment degradation, toxic waste generation, and poisoning of catalysts, which all tend to reduce the quality of the final products and increase the risk to the health and safety of the workers (Wilhelm and Bloom, 2000). Besides that, in the production of offshore oil and gas, water becomes contaminated with elemental, organic and inorganic Hg. The amount of components that are exposed to the environment increases with the volume of wastewater, condensate and produced water due to high petroleum demand and maturity of oil and gas wells. The wastewater, condensate and produced water shall be treated before being discharged to the environment or re-injected into the

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original reservoir, depending on its quality and environmental constraints (Chaturabul et al., 2015).

Table 1.1: Estimated world levels of mercury in natural gas and liquids

Location Mercury Concentration Gas (µg/m3) Liquid (µg/L)

Europe 100-150 - South America 50-120 50-100 Gulf of Mexico (USA) 0.02-0.4 - Overthrust Belt (USA) 5-15 1-5 Africa 80-100 500-1000 North Africa 50-80 20-50 Indonesia 200-300 10-500 Gulf of Thailand 100-400 400-1200 Malaysia 1-200 10-100

The toxic contaminants from these activities can enter into the environmental cycle and food chains easily, through emission during processing stages or unregulated disposal of wastes or accidents (Sainal et al., 2007). When Hg(II) solution is deposited in the sea, lakes or streams, the anaerobic bacteria convert it into methyl-mercury (CH3Hg+) (Wilcox et al., 2012). The toxicity of CH3Hg+ is associated with its bioaccumulation in the fish, which then enters the food chain, thereby influencing human health (Wilcox et al., 2012, Rodríguez et al., 2012). Symptoms of Hg poisoning can be numerous and may occur either rapidly or over long periods of time. High exposures of elemental Hg can cause kidney malfunction, respiratory failure, and death (Ganjali et al., 2011). According to the World Health Organization (WHO) guideline values, the limitation of Hg inside water is 1μg/L for the total Hg and 1μg/kg Hg in the air. In addition, WHO estimated a tolerable concentration of 0.2 μg/kg for long-term inhalation exposure to elemental Hg vapour and a tolerable intake of a total Hg of 2 μg/kg body weights per day (WHO, 2007).

From the above considerations, it has been proven that the removal of Hg(II) from actual samples is very important to protect the people and the environment. Various available commercial methods are available in petrochemical industries for mercury removal systems (MRS) in hydrocarbon streams such as impregnated activated carbon, adsorption on activated carbon by amalgamation with a metal (such as silver impregnated alumina, silver zeolites, metal sulphides, gold and metal oxides) (UK Essays, 2015), ion-exchange resin material, membrane filtration, electrochemical treatment technologies (Fu and Wang, 2011, Purkayastha et al., 2014), sulphur-containing molecular sieve, and ionic salt containing activated carbon (Sainal et al., 2007). However, these available commercial methods have several advantages and disadvantages. For instance, chemisorption on sulphur impregnated activated carbon is cheap and mostly used in the oil and gas industry. However, it has some disadvantages such as disposal problems

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when the adsorbent is contaminated with Hg and it is not efficient when treating hydrocarbon gas with the moisture content of more than 50% because the moisture can be adsorbed into the pore spaces of the activated carbon. Other than that, adsorption by amalgamation with a metal such as silver and gold has a high removal capacity of Hg but this adsorbent is very expensive (UK Essays, 2015).

For these reasons, the basic requirements for a successful MRS are the economics of the process and the removal medium needs to be capable of reducing Hg concentrations to extremely low and acceptable levels. Besides that, the selection of the MRS has been done as per the following criteria and considerations such as proven and reliable technology, process effectiveness for the removal of Hg, stable and robust (physically and chemically), has the ability to integrate with existing facilities (minimal modification to the existing facilities), and the removal agent should be inexpensive and easy to get (Sainal et al., 2007).

1.2 Problem Statement

Mercury removal systems (MRS) for both gas and processed liquid hydrocarbon streams are commercially available. The available MRS deals excellently with gas hydrocarbon because natural gases are normally present as elemental Hg at a bulk concentration. However, the conventional MRS for hydrocarbon liquid or hydrocarbon waste (such as produced water, wastewater and condensate) has not selective to target ion and may still render high Hg(II) content in the hydrocarbon waste above the environmental discharge limit (not greater than 0.005 mg/L).

Nowadays, the ion imprinted polymer (IIP) which is a suitable method for the removal of Hg(II) in actual sample due to high sample load capacity, high selectivity to target ion, easy preparation and reusable in repeated cycles. Generally, many IIP for the removal of Hg(II) from previous researchers were prepared IIP in particles formed. Unfortunately, when IIP in particles formed packed in the column it will increase the pressure of column, slow water transport and increase of risk of bubble formation. Therefore, IIP-particle packed column is not suitable to commercialize and apply to the industrial column.

In view of this, the suitable physical of the IIP was proposed as an alternative approach that to overcome the disadvantages and weaknesses of the conventional IIP-particle packed column. The present work proposes the determination of the performance of IIP for the removal of Hg(II) ions in aqueous solution and actual samples. Here, we scaled up the preparation of IIP in particles and monoliths form by bulk radical polymerization using [2-(Methacryloyloxy)ethyl] trimethylammonium cysteine (MAETC) as the metal

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complexing monomer. The physical form of the IIP-particle was optimized using extruded, tableting and packaging techniques for improving the pressure of column, and decreasing the risk of bubble formation in the column. The performances of IIP towards Hg(II) ions from aqueous solution were determined using the batch and column technique. Mercury removal unit (MRU) which was designed as well as a mimic with the actual of the petrochemical industry set up was used in the column technique. Besides that, the application of the developed IIP in the recovery of Hg(II) ions from actual samples was also studied. The commercialization of IIP as sorbents in MRU is very promising, considering the reducing of Hg(II) ions concentrations to extremely low and acceptable levels that can be achieved.

1.3 Objectives of this Research

The general objective of this research is to prepare an ion imprinted polymer (IIP) for the efficient and selective removal of Hg.The following specific objectives are designed to achieve the general objective:

i. To scale-up and optimize the preparation of ion imprinted polymer (IIP).

ii. To obtain the suitable physical form of IIP iii. To carry out spectroscopic, morphological and thermal stability for the

prepared IIP. iv. To determine the performance of IIP in the down-flow technique based

on the pH, dosage, initial concentration, kinetic, reusability and selectivity study.

v. To determine the performance of IIP using the up-flow column technique based on pH, dosage and flow rate.

vi. To evaluate the performance of the IIP on the analysis of actual samples (wastewater, condensate (from oil and gas industry) and river water).

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