Masters thesis of applied science pb (ii) removal from aqueous solution by biochar produced from giant reed

Pb (II) Removal from Aqueous Solution by Biochar Produced from Giant Reed A thesis submitted in fulfilment of the requirements for the degree of Master of Applied Science Eric York Bachelor of Science (Chemistry) Kwame Nkrumah University of Science and Technology Ghana School of Science College of Science, Technology, Engineering and Maths RMIT University November 2020 Declaration Declaration for candidates submitting a thesis I certify that except where due acknowledgement has been made, the work is that of the author alone; the work has not been submitted previously, in whole or in part, to qualify for any other academic award; the content of the thesis is the result of work which has been carried out since the official commencement date of the approved research program; any editorial work, paid or unpaid, carried out by a third party is acknowledged; and ethics procedures and guidelines have been followed I acknowledge the support I have received for my research through the provision of an Australian Government Research Training Program Scholarship Eric York Date: 18 November 2020 i Dedication I would like to dedicate this thesis to my late dad, who inspired my interest in science and motivated me to undertake this research ii Acknowledgements If it had not been the Lord on my side, let Israel say (Psalm 124:1) My greatest thanks and appreciation go to the almighty God for the love, protection and numerous blessings He has bestowed on me Father, my mouth will continually sing your praises This work would not have been possible without my supervisors A/Prof Samantha Richardson and Dr James Tardio, whose guidance and support were unwavering throughout the duration of my studies I would also like to thank all my colleagues and collaborators, who have contributed in some way towards me completing my master’s thesis I also thank the Commonwealth of Australia for an Australian Postgraduate Award I acknowledge RMIT University for the Research Stipend Scholarship Award for this Research Lastly, I would like to thank my partner, Florence Appiah, whose unconditional support and patience enabled me to complete this degree iii Table of Contents Declaration i Dedication ii Acknowledgements iii List of Figures vi List of Tables vii Abstract Chapter 1: Introduction Background 1.1 Trace Metals 1.2 Sources of Trace Metals in Aqueous Solution 1.3 Lead 1.4 Biochar Production 10 1.5 Feedstock for Biochar Production 11 1.6 Biochar Production by Slow Pyrolysis 15 1.7 Giant Reed (Arundo donax) 17 1.8 Arundo donax: Weed Potential 21 1.9 Use of Arundo donax in Constructed Wetlands 23 1.10 Generation of Biochar from Giant Reed 26 1.11 Use of Biochar for Removal of Trace Metals from Aqueous Phase 28 1.12 Mechanisms of Adsorption by Biochars 29 1.13 Adsorption Isotherm Models 30 1.15 Adsorption Kinetics 34 1.16 Properties of Biochar 34 1.17 Factors Affecting Adsorption of Contaminants on Biochar 35 1.18 Management of Spent Biochar 37 1.19 Potential Biochar Improvement Techniques 37 1.20 Environmental Impact of Biochar use for Trace Metal Decontamination 38 1.21 Sustainable Use of Biochar 39 1.22 Potential Application of Biochar 39 1.23 Conclusion 40 Chapter 2: Experimental 40 Materials and Methods 41 iv 2.1 Chemicals 41 2.2 Sample Preparation 41 2.3 Production of Biochar by Slow Pyrolysis 42 2.4 Biochar Properties 42 2.6 Measurement of Adsorption of Pb 2+ with Microwave-Plasma Atomic Adsorption Spectrometer (MP-AES) 51 2.7 Calculation of Adsorption Efficiency of Trace Metal 52 2.8 Data Modelling using the Langmuir, Freundlich and Temkin Equations 53 2.9 Statistical Analysis 54 Chapter 3: Characterisation of Biochars and Preliminary Adsorption Studies 55 3.1 Introduction 56 3.2 Experimental 57 3.3 Results and Discussion 58 3.4 Conclusions 70 Chapter 4: Adsorption of Pb(II) on Biochars – Studies on the Influence of some key Adsorption Test Parameters 71 4.1 Introduction 71 4.2 Experimental 72 4.3 Results and Discussion 72 4.3.5 Rates of Reaction: 82 Pseudo First Order Model 82 4.4 Conclusions 84 Chapter 5: Conclusions and Recommendations 86 5.1 Conclusions 86 5.2 Recommendations 87 5.3 Summary of Study 88 References 89 Appendix I: 102 v List of Figures Figure 1.1 Trace metal distribution Figure 1.2 Source of trace metals in the aqueous phase Figure 1.3 (a) Biomass feedstock for production of biochar; (b) biochar produced from the feed stocks 12 Figure 1.4 Slow pyrolysis set- up for biochar production 16 Figure 1.5 Illustrations of giant reed 27 Figure 2.1 (A) Raw biomass of giant reed; (B) Dry biomass of giant reed 41 Figure 2.2 Production of biochar by slow pyrolysis 42 Figure 2.3 Perkin Elmer 2400 Carbon, Hydrogen, Nitrogen, Sulphur and Oxygen Analyser 43 Figure 2.7 Perkin Elmer ATR Fourier Transformed Infra-Red Spectroscopy 46 Figure 2.9 500MHz Agilent DD2 nuclear magnetic resonance spectrometer 47 Figure 2.10 HANNA pH meter 48 Figure 2.11 Centrifuge tube on orbital shaker, Chiltern model 50 Figure 2.12 Agilent 4200 microwave plasma - atomic emission spectrophotometer 52 Figure 3.1 Weight loss of GR 500, GR 300 and GR biomass using TGA800, Perkin Elmer 59 Figure 3.2 Scanning electron micrograph of giant reed biochar produced at (A) 300 ℃ and (B) 500 ℃ 60 Figure 3.3 (A) BET Isotherm Linear Plot for GR 300 ℃; (B) BET Isotherm Linear Plot for GR 500 ℃ 61 Figure 3.4 Fourier transform infrared spectroscopy of giant reed biochar produced at 300 ℃ and 500 ℃ 63 Figure 3.5 Carbon-13 NMR of biochar produced at 300 ℃ 64 Figure 3.6 Carbon-13 NMR of biochar produced at 500 ℃ 65 Figure 3.7 XRD patterns of GR 500 and GR 300 Major diffraction lines for specific phases are marked 66 Figure 3.8 SEM-EDS analysis of GR 300 ℃ 67 Figure 3.9 EDS spectra for selected regions of GR 300 68 Figure 3.10 Pb2+ adsorption versus time for GR 300 and GR 500 69 Figure 4.1 Adsorption capacity versus initial Pb(II) concentration 73 Figure 4.2 Adsorption capacity versus solution pH 75 Figure 4.4 Adsorption capacity versus biochar particle size 76 Figure 4.5 Ce/qe versus Ce for GR 300 77 Figure 4.6 Ce/qe versus Ce for GR 500 78 Figure 4.7 Log Qe versus Log Ce for GR 300 79 Figure 4.8 Log Qe versus Log Ce for GR 500 80 Figure 4.9 Schematic diagrams for cooperative adsorption 81 vi List of Tables Table 1.1 The application of biochar produced from different feedstock and techniques in aqueous solution 13 Table 1.2 Advantages and disadvantages of A donax with respect to its use as a plant in constructed wetlands for wastewater treatment 24 Table 1.3 Environmental impact of the use of biochar and activated carbon 38 Table 1.4 Economic impact of biochar and activated carbon for trace metals adsorption 38 Table 2.1 Experimental design for adsorption and characterization of biochar produced in this study 48 Table 3.1 Elemental analysis of giant reed biochar 58 Table 3.2 Total surface area of biochar as attained by BET analysis 62 Table 3.3 pH of biochars from giant reed in deionised water 67 Table 4.1 Comparative results for Pb(II) removal using biochars prepared from different types of biomass 84 vii Abstract The presence of lead, a trace element in the environment, has been a serious concern especially with rapid urbanization, which has increased its concentration in the environment by several hundred fold The toxicity of this trace metal to aquatic life and humans has necessitated the development of effective and economical methods for the treatment of water Biochar has garnered attention as a means to sequester carbon and manage waste in the environment, particularly in soil and water Invasive biomass such as the giant reed is rich in lignin and the conversion of this biomass into char for environmental restoration is a prime area for further research The main aim of this investigation was to develop a low-cost solution to remove trace metals from the aqueous phase using biochar This study investigated (i) the effect of giant reed-based biochar produced at varying temperatures in the treatment of aqueous solutions polluted with lead; 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Vitae22(2): 148-149 100 101 Appendix I: Figure Calibration Curve for Pb (II) Figure The first – order kinetic plots for Pb (II) adsorption at various initial concentrations of 10, 20, 30, 40 and 50 mg.L-1by GR 300 ℃ 102 Figure The first-order plots for Pb (II) adsorption at various initial concentrations of 10, 20, 30, 40 and 50 mg.L-1by GR 500 ℃ Figure The second – order kinetic plots for Pb (II) adsorption at various initial concentrations of 10, 20, 30, 40 and 50 mg.L-1by GR 300 ℃ 103 Figure The second – order kinetic plots for Pb (II) adsorption at various initial concentrations of 10, 20, 30, 40 and 50 mg.L-1by GR 500 ℃ Table Pseudo first and second order kinetics parameters for adsorption of Pb (II) by GR 300℃ Conc (mg.L-1) pseudo first order model pseudo second order model qe actual qe K2 R2 qe 0.0005 0.199 0.997 0.2363 19.1 1.6038 0.0031 0.248 0.828 0.1082 0.99 58.3 30 1.647 0.0036 0.278 1.013 0.068 93.2 40 9.28 0.009 0.370 0.768 0.0565 0.98 148.3 50 3.35 0.0081 0.250 1.013 0.0467 0.99 166.5 qe K1 10 1.0808 20 R2 104 Table Pseudo first and second order kinetics parameters for adsorption of Pb (II) by GR 500℃ Conc (mg.L-1) pseudo first order model pseudo second order model qe actual qe K1 R2 qe K2 R2 qe 10 1.0068 * 10-5 0.25 0.1251 19.3 20 1.047 0.0003 0.25 0.4528 58.4 30 1.0869 0.0006 0.25 0.99 0.80 94.5 40 0.814 0.0054 0.25 1.1 148.5 50 2.018 0.0047 0.25 3.96 166.8 Figure Intra-particular diffusion parameters and diffusion coefficient plot for GR 300 ℃ 105 Figure Intra-particle diffusion parameters and diffusion coefficient plot for GR 500 ℃ Table Intra-particle diffusion parameters and diffusion coefficient for the adsorption of Pb (II) by GR 300 ℃ Diffusion Conc (mg.L-1) Intra Particle Diffusion Parameters Part Coefficient Part K1 I R2 K2 I2 R2 Di 10 0.226 0.2532 0.350 0.126 0.332 0.450 2.343* 10-09 20 0.4617 6.26 0.267 0.3617 6.36 0.467 1.666* 10-09 30 0.781 8.89 0.344 0.381 8.99 0.544 1.364* 10-09 40 0.82 10.4 0.295 0.72 10.41 0.395 1.190* 10-09 50 1.08 13.4 0.303 1.18 13.41 0.403 1.056* 10-09 106 Table Intra-particle diffusion parameters and diffusion coefficient for the adsorption of Pb (II) by GR 500 ℃ Diffusion Conc (mg.L-1) Intra Particle Diffusion Parameters Part Coefficient Part K1 I2 R2 K2 I2 R2 Di 10 0.125 1.1914 0.19 0.125 1.1914 0.19 2.34 *10-09 20 0.452 5.99 0.28 0.452 5.99 0.28 1.923* 10-09 30 0.794 9.01 0.34 0.794 9.01 0.34 1.67* 10-09 40 1.071 11.5 0.37 1.071 11.5 0.37 1.36* 10-09 50 3.96 44.97 0.34 3.96 44.97 0.34 1.19* 10-09 Figure Boyd Kinetic Plot for GR 300℃ 107 Figure Kinetic Plot for GR 500 ℃ 108 ... 88.79% of Pb (II) ions were removed by biochar in acidic solutions, whilst only 80.58% of Cu (II), 68.08% of Cd (II), 63.08% of Zn (II), 54.69% of Pb (II) and 36.70% of Co (II) ions were adsorbed by. .. time of 10 h Mohmoud (2012) investigated the use of activated carbon produced from giant reed for removal of Fe (II) from aqueous solution using batch experiments The adsorption performance of. .. production of biochar; (b) biochar produced from the feed stocks Adopted from EBC (2012) 12 Table 1.1 The application of biochar produced from different feedstock and techniques in aqueous solution