Plasma Modified Steel Processing By-Product for Removing Heavy Metals and Antibiotics from Water

282 Pages·2017·7.02 MB·English

by  Van Son Tran

Van Son Tran DOCTORAL THESIS 2017
PLASMA MODIFIED STEEL PROCESSING
BY-PRODUCT FOR REMOVING HEAVY
METALS AND ANTIBIOTICS FROM WATER
By
Van Son Tran
A dissertation
Submitted in fulfillment for the degree of
DOCTOR OF PHILOSOPHY
In
Environmental Engineering
University of Technology Sydney
New South Wales, Australia
June, 2017
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Van Son Tran DOCTORAL THESIS 2017
CERTIFICATE OF ORIGINAL AUTHORSHIP
I certify that the work in this thesis has not previously been submitted for a
degree nor has it been submitted as part of requirements for a degree except as part
of the collaborative doctoral degree and/or fully acknowledged within the text.
I also certify that the thesis has been written by me. Any help that I have
received in my research work and the preparation of the thesis itself has been
acknowledged. In addition, I certify that all information sources and literature used
are indicated in the thesis.
SIGNATURE OF STUDENT:

Van Son Tran
Date: 30 June 2017
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Van Son Tran DOCTORAL THESIS 2017
ACKNOWLEDGMENT
First of all, I owe my deepest gratitude to my principal supervisor, Prof. Huu
Hao Ngo for his continuous supports, guidance, time, patience and inspiration. I have
learnt a lot from his ideas, critical review of my study plans and papers, knowledge
and motivation which encouraged me to overcome many difficulties in the research
as well as other aspects of life to achieve this milestone. I also would like to thank
my supervisory committee, Dr. Wenshan Guo and Assoc. Prof. Cuong Ton-that for
their mentor supports, papers revising and useful comments on this dissertation.
I gratefully acknowledge the Australian government for awarding me the
Australia Awards Scholarship. The financial support from Centre for Technology in
Water and Wastewater, and the research collaboration between UTS and Shanghai
Advanced Research Institute/Tianjin Polytechnic University are also grateful.
The technical supports and guidance from Dr. Johir, the environmental
engineering laboratories, UTS are greatly appreciated. Also, I would like to thank Dr.
Andrzej from(cid:3)Water Reclamation and Management Scheme, Sydney Olympic Park
Authority for his supports and valuable advices. Many thanks go to Katie and other
staffs at Microstructure Analysis Unit, UTS and Dr. Alfonso, University of
Macquarie for guiding me to characterize the materials surface. I would like to
express my appreciation to Christian and Boshir for their technical assistances and
useful discussion. I am thankful to Jean, Ronald, Phuong, Hang, Van, Tram, Lam,
Chung, Lijuan for their supports and contributions.
Finally, I am hugely indebted to all my family, colleagues and friends for
their emotional supports, unconditional love and guidance.(cid:3)
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Van Son Tran DOCTORAL THESIS 2017
DEDICATION
This thesis is deeply dedicated to the following people:
To my respective parents, Xuan Hoa Tran & Thi Theu Nguyen
For their sacrifices, endless love, hard work and inspiration
To my wonderful wife, Thi Thuan Tran
For her constant love, supports and caring
To my lovely daughter and son, Ha Linh & Huy Phong
For bringing joy and hope

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Van Son Tran DOCTORAL THESIS 2017
TABLE OF CONTENTS
CERTIFICATE OF ORIGINAL AUTHORSHIP ..................................................... ii(cid:3)
ACKNOWLEDGMENT ......................................................................................... iii(cid:3)
DEDICATION ........................................................................................................ iv(cid:3)
TABLE OF CONTENTS .......................................................................................... v(cid:3)
NOMENCLATURES ............................................................................................ xiv(cid:3)
ABBREVIATIONS .............................................................................................. xvii(cid:3)
LIST OF TABLES ............................................................................................... xviii(cid:3)
LIST OF FIGURES ............................................................................................... xxi(cid:3)
LIST OF RESEARCH OUTCOMES .................................................................. xxvii(cid:3)
PhD DISSERTATION ABSTRACT .................................................................... xxix(cid:3)
CHAPTER 1 INTRODUCTION ............................................................................... 1(cid:3)
1.1. Problem statement ...................................................................................... 2(cid:3)
1.1.1. Heavy metals and antibiotics pollution in water and health risk .......... 2(cid:3)
1.1.2. Removal technologies of heavy metals and antibiotics from water...... 3(cid:3)
1.1.3. Adsorption of heavy metals and antibiotics by steel shavings ............. 4(cid:3)
1.2. Research hypotheses ................................................................................... 6(cid:3)
1.3. Objectives ................................................................................................... 6(cid:3)
1.4. Research significance ................................................................................. 7(cid:3)
1.5. Thesis outline .............................................................................................. 8(cid:3)
CHAPTER 2 LITERATURE REVIEW .................................................................. 11(cid:3)
2.1. Introduction .............................................................................................. 12(cid:3)
2.2. Heavy metal and antibiotics pollution in water ....................................... 12(cid:3)
2.2.1. Heavy metals pollution in water ....................................................... 12(cid:3)
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Van Son Tran DOCTORAL THESIS 2017
A. Definition, characteristics ................................................................. 12(cid:3)
B. Sources and occurrence of HMs in the environment ......................... 13(cid:3)
C. Adverse effects of the HMs pollution ............................................... 14(cid:3)
D. HMs relevant regulations ................................................................. 15(cid:3)
2.2.2. Antibiotics pollution in water ........................................................... 15(cid:3)
A. Definition, characteristics ................................................................. 15(cid:3)
B. Sources and occurrence of ABs in the environment .......................... 16(cid:3)
C. Adverse effects of the ABs pollution ................................................ 21(cid:3)
D. ABs relevant regulations .................................................................. 22(cid:3)
2.3. Technologies for the removal of heavy metals and antibiotics from water
................................................................................................................. 23(cid:3)
2.3.1. Heavy metals removal technologies ................................................. 23(cid:3)
A. Chemical precipitation ..................................................................... 24(cid:3)
B. Ion exchange .................................................................................... 24(cid:3)
C. Adsorption ....................................................................................... 25(cid:3)
D. Membrane filtration ......................................................................... 25(cid:3)
E. Coagulation-flocculation .................................................................. 26(cid:3)
F. Flotation ........................................................................................... 26(cid:3)
G. Electrochemical ............................................................................... 27(cid:3)
H. Electrodialysis .................................................................................. 27(cid:3)
K. Photocatalysis .................................................................................. 28(cid:3)
2.3.2. Antibiotics removal technologies ..................................................... 28(cid:3)
A. Conventional methods ...................................................................... 30(cid:3)
B. Oxidation and advanced oxidation processes .................................... 30(cid:3)
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Van Son Tran DOCTORAL THESIS 2017
C. Adsorption processes ........................................................................ 34(cid:3)
D. Membrane processes ........................................................................ 34(cid:3)
E. Combined processes .......................................................................... 36(cid:3)
2.3.3. Adsorption of HMs and ABs using typical low cost materials .......... 36(cid:3)
A. Natural minerals ............................................................................... 37(cid:3)
B. Agricultural waste and by-products ................................................... 42(cid:3)
C. Industrial waste and by-products ....................................................... 51(cid:3)
2.4. Adsorption of HMs and ABs using magnetic materials (iron-based
adsorbents) ............................................................................................................ 54(cid:3)
2.4.1. Introduction ...................................................................................... 54(cid:3)
2.4.2. Uptake mechanism of HMs and ABs from water by iron-based
adsorbents ........................................................................................................ 56(cid:3)
A. Removal pathway of HMs ................................................................ 56(cid:3)
B. ABs abatement mechanism ............................................................... 57(cid:3)
2.4.3. Application of iron adsorbents for removing heavy metals from
aqueous solution .............................................................................................. 57(cid:3)
2.4.4. Application of iron adsorbents for removing antibiotics from aqueous
solution ............................................................................................................ 58(cid:3)
2.4.5. Steel shavings as a novel adsorbent .................................................. 63(cid:3)
2.5. Gas plasma for modifying iron materials ................................................ 64(cid:3)
2.5.1. Introduction ...................................................................................... 64(cid:3)
2.5.2. Employed gas in plasma modification .............................................. 66(cid:3)
2.5.3. The usage of gas plasma for adsorbent modification ......................... 66(cid:3)
2.6. Conclusion and research gap ................................................................... 67(cid:3)
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Van Son Tran DOCTORAL THESIS 2017
2.6.1. Main findings from literature review ................................................ 67(cid:3)
2.6.2. Research gaps .................................................................................. 70(cid:3)
CHAPTER 3 MATERIALS AND METHODS ....................................................... 72(cid:3)
3.1. Materials................................................................................................... 73(cid:3)
3.1.1. Steel shavings .................................................................................. 73(cid:3)
3.1.2. Solutions of heavy metals ................................................................ 73(cid:3)
3.1.3. Solutions of antibiotics .................................................................... 74(cid:3)
3.2. Methods .................................................................................................... 74(cid:3)
3.2.1. Preparation of adsorbents ................................................................. 74(cid:3)
A. Raw steel shavings ........................................................................... 75(cid:3)
B. Plasma modified material ................................................................. 76(cid:3)
C. Comparison with a commercial iron material .................................... 77(cid:3)
3.2.2. Characterization methods ................................................................. 78(cid:3)
A. SEM-EDS ........................................................................................ 79(cid:3)
B. XRD ................................................................................................. 79(cid:3)
C. XPS .................................................................................................. 79(cid:3)
D. BET ................................................................................................. 80(cid:3)
E. Zeta potential and particle size distribution ....................................... 80(cid:3)
F. FTIR ................................................................................................ 81(cid:3)
3.2.3. Development of adsorbents from steel shavings ............................... 82(cid:3)
A. Particle size ...................................................................................... 82(cid:3)
B. Employed gas in plasma modification .............................................. 82(cid:3)
3.2.4. Batch adsorption experimental set-up for removing HMs ................. 82(cid:3)
A. Affecting factors on HMs adsorption from aqueous solutions ........... 82(cid:3)
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Van Son Tran DOCTORAL THESIS 2017
B. Isotherms and kinetics models of HMs adsorption ............................ 84(cid:3)
C. Competitive adsorption of HMs on raw and modified StS ................. 85(cid:3)
D. Desorption and regeneration ............................................................. 87(cid:3)
3.2.5. Batch adsorption experimental set-up for removing antibiotics ......... 87(cid:3)
A. Affecting factors on antibiotics adsorption from aqueous solutions ... 87(cid:3)
B. Isotherms and kinetics models of antibiotics adsorption .................... 89(cid:3)
C. Competitive adsorption of ABs on raw and modified StS .................. 90(cid:3)
D. Desorption and regeneration ............................................................. 91(cid:3)
3.2.6. Semi-pilot scale experimental set up for removing HMs and ABs from
synthesized wastewater .................................................................................... 92(cid:3)
A. Selecting the treatment designs for HMs and ABs removal ............... 92(cid:3)
B. A column design for HMs removal by nitrogen plasma modified steel
shavings ................................................................................................ 97(cid:3)
C. A column design for ABs removal by nitrogen plasma modified steel
shavings .............................................................................................. 100(cid:3)
3.2.7. Heavy metals analysis method ........................................................ 101(cid:3)
3.2.8. Analytical method of the antibiotic concentrations ......................... 102(cid:3)
3.2.9. Statistical analysis .......................................................................... 102(cid:3)
CHAPTER 4 DEVELOPMENT OF ADSORBENTS FROM STEEL SHAVINGS
FOR HEAVY METALS AND ANTIBIOTICS REMOVAL................................. 104(cid:3)
4.1. Introduction ............................................................................................ 105(cid:3)
4.2. Effects of particle size, employed gas to adsorptive removal of HMs ... 105(cid:3)
4.2.1. Particle size .................................................................................... 106(cid:3)
4.2.2. Employed gas in plasma modification ............................................ 106(cid:3)
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Van Son Tran DOCTORAL THESIS 2017
4.3. Effects of particle size, employed gas to adsorptive removal of ABs ... 107(cid:3)
4.3.1. Particle size ................................................................................... 107(cid:3)
4.3.2. Employed gas in plasma modification ............................................ 108(cid:3)
4.4. Characterization of adsorbents ............................................................. 109(cid:3)
4.4.1. Surface morphology ....................................................................... 110(cid:3)
4.4.2. Elementary composition ................................................................ 110(cid:3)
4.4.3. XRD spectrums ............................................................................. 113(cid:3)
4.4.4. BET ............................................................................................... 114(cid:3)
4.4.5. XPS ............................................................................................... 115(cid:3)
4.4.6. FTIR .............................................................................................. 118(cid:3)
4.4.7. Zeta potential ................................................................................. 118(cid:3)
4.4.8. Particle size distribution ................................................................. 119(cid:3)
4.5. Conclusion .............................................................................................. 121(cid:3)
CHAPTER 5 RAW AND PLASMA MODIFIED STEEL SHAVINGS FOR
REMOVING HEAVY METALS FROM AQUEOUS SOLUTION: A BATCH
STUDY ................................................................................................................ 124(cid:3)
5.1. Introduction ........................................................................................... 125(cid:3)
5.2. Affecting factors to removal efficiencies ............................................... 126(cid:3)
5.2.1. Solution pH ................................................................................... 126(cid:3)
5.2.2. Adsorbent dosage........................................................................... 129(cid:3)
5.2.3. Temperature/thermodynamic ......................................................... 130(cid:3)
5.3. Modeling of adsorption isotherm and kinetics ...................................... 132(cid:3)
5.3.1. Adsorption isotherm ...................................................................... 132(cid:3)
5.3.2. Adsorption kinetics ........................................................................ 135(cid:3)
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