Treatment of pharmaceutical antibiotic wastewater using photocatalytic processes with commercial tio2 powder

VIETNAM NATIONAL UNIVERSITY, HANOI VIETNAM JAPAN UNIVERSITY OLADELE HONOUR ADEDAYO TREATMENT OF PHARMACEUTICAL ANTIBIOTIC WASTEWATER USING PHOTOCATALYTIC PROCESSES WITH COMMERCIAL TiO2 POWDER MASTER’S THESIS VIETNAM NATIONAL UNIVERSITY, HANOI VIETNAM JAPAN UNIVERSITY OLADELE HONOUR ADEDAYO TREATMENT OF PHARMACEUTICAL ANTIBIOTIC WASTEWATER USING PHOTOCATALYTIC PROCESSES WITH COMMERCIAL TiO2 POWDER MAJOR: ENVIRONMENTAL ENGINEERING CODE: 8520320.01 RESEARCH SUPERVISORS: Dr TRAN THI VIET HA Associate Prof Dr NGUYEN MINH PHUONG Hanoi, 2020 ACKNOWLEDGMENT I would like to express my deepest gratitude to my principal supervisor, Dr Tran Thi Viet Ha for her immense support, good recommendations, essential criticisms, great feedbacks, and invaluable advice all through the period of this research She has shaped my learning experience and made me better So also to my second supervisor, Associate Prof Nguyen Minh Phuong, Deputy Head, Lab of Environmental Chemistry, Faculty of Chemistry, Hanoi University of Science, Vietnam, thank you for her timely suggestion, her help, and necessary guidance in relation to this research Furthermore, I would like to specially appreciate Dr Babatunde Koiki, Department of Chemical Sciences, University of Johannesburg, DFC, South Africa for his constant encouragement and immense absolute support throughout my study Thank you so much, I am deeply indebted In addition, I am grateful to VNU Vietnam Japan University, Ritsumeikan University, both MEE teaching and non-teaching staff including Prof Jun Nakajima, Prof Cao The Ha, Assoc Prof Ikuro Kasuga, Assoc Prof Sato Keisuke, Dr Nguyen Thi An Hang for the valuable teachings, opportunities, and devoted support throughout my Master’s degree program at VJU Finally, I would like to express my heartfelt gratitude to my family and friends for their prayers, massive loving support and relentless faith in me all through the period of my study You’re one in a million, this study would not have been accomplished without them Thank you for making this dream a reality Oladele Honour Adedayo Hanoi, August 2020 i TABLE OF CONTENTS ACKNOWLEDGMENT i LIST OF TABLES iv LIST OF FIGURES v LIST OF ABBREVIATIONS vi INTRODUCTION Research Objectives Structure of thesis CHAPTER LITERATURE REVIEW 1.1 Antibiotics pollution in the environment 1.2 Recent methods of water and wastewater treatment 1.2.1.Treatment by activated sludge 1.2.2 Membrane Filtration 1.2.3 Chlorination 1.2.4 Adsorption method 10 1.2.5 Photolysis 11 1.2.6 Electrochemical oxidation 11 1.3 Advanced oxidation processes 14 1.3.1 UV/O3 method 14 1.3.2 UV/O3 /H2O2 method 15 1.3.3 Fenton method 15 1.3.4 Heterogeneous Photocatalysis process 15 1.4 Mechanism of photocatalysis 17 CHAPTER MATERIALS AND METHODS 20 2.1 Materials 20 2.1.1 Preparation of glassware and apparatus 21 2.1.2 Preparation of sample solution 21 2.1.3 Equipments Used 22 2.2 Methodologies 23 2.2.1 Survey Methodology 23 2.2.2 Characterization of the TiO2 material 23 2.2.3 Experimental design and set-up 24 2.2.4 Experimental procedure 25 2.3 Analytical methods 27 CHAPTER RESULTS AND DISCUSSION 28 3.1 The analysis of the survey carried out during the study 28 3.2 The characterization result of the photocatalyst 31 3.2.1 Morphology analysis using Scanning Electron Microscope (SEM) 31 3.2.2 Fourier Transform Infrared Spectroscopy (FTIR) analysis 33 3.3 Photodegradation of Antibiotic pollutant 34 ii 3.3.1 Effect of initial concentration on the removal of TC with TiO 34 3.3.2 Effect of catalyst dose on the degradation efficiency of TC with TiO2 35 3.3.3 Effect of pH value on the degradation efficiency of TC with TiO 37 3.3.4 Effect of temperature on the degradation efficiency of TC with TiO 39 3.3.5 The removal of TC with the optimized conditions 40 CHAPTER CONCLUSION 41 REFERENCES 42 APPENDICE 49 iii LIST OF TABLES Table 1.1 The advantages and limitations of various methods utilized for the treatment of wastewater 13 Table 1.2 The removal efficiencies of various target pollutants using different kinds of photocatalyst 16 Table 2.1 Chemical Structure and the properties of Tetracycline (TC) 13 Table 3.1 Questions and responses of the survey participants, total number of participants =123 21 iv LIST OF FIGURES Figure 1.1 Schematic diagram of detailed mechanism of photocatalytic reaction 18 Figure 2.1 Images of some chemicals and apparatus used during the experiments, a) Tetracycline crystalline powder b) Titanium (IV) oxide, anatase powder c) the 500mL volumetric glass handmade dark beaker 21 Figure 2.2 The equipments used during this research 22 Figure 2.3 Schematic illustration of the set-up of the photocatalytic experiment 24 Figure 2.4 Overview of the experimental procedure 26 Figure 2.5 Showing the standard calibration curve of TC 27 Figure 3.1 Distribution based on age groups 28 Figure 3.2 distribution based on educational qualifications 28 Figure 3.3 The SEM images and EDX spectra of TiO2 particle 32 Figure 3.4 The mapping images of a) TiO2 material consisting of b) titanium and c) oxygen elemental particles 33 Figure 3.5 The Fourier transform infrared spectra of TiO2 material using the FT/IR4600typeA machine 34 Figure 3.6 The effect of initial concentration on TC removal efficiency, Volume of the sample solution= 200 mL; TiO2 dosage = 0.1g/L, TC concentration= 40 ppm, temperature= 25℃, Total reaction time = 180 min, absorbance wavelength for tetracycline = 357 nm 35 Figure 3.7 The effect of catalyst dose on Tc removal efficiency, Volume of the sample solution= 200 mL; TC concentration= 40 ppm, temperature= 25℃, Total reaction time = 180 min, absorbance wavelength for tetracycline = 357 nm 36 Figure 3.8 a) Effect of pH on the removal efficiency of Tc, Volume of the sample solution= 200 mL; TiO2 dosage = 0.1g/L, TC concentration= 40 ppm, temperature= 25℃, Total reaction time = 180 min, absorbance wavelength for tetracycline = 357 nm b) the pH0 vs 𝒑𝑯∆ using the salt addition method 38 Figure 3.9 Effect of temperature on the removal efficiency of Tc, Volume of the sample solution= 200 mL; TiO2 dosage = 0.1g/L, TC concentration= 40 ppm, temperature= 25℃, 35℃, 45℃ Total reaction time = 180 min, absorbance wavelength for tetracycline = 357 nm 39 Figure 3.10 the optimized condition on the removal efficiency of Tc, Volume of the sample solution= 200 mL; TC concentration= 40 ppm, TiO2 dosage = 0.1g/L, pH = 7, Temperature= 45℃, Total reaction time = 180 min, absorbance wavelength for tetracycline = 357 nm 40 v LIST OF ABBREVIATIONS AOPs Advanced Oxidation Processes APIs Active pharmaceutical ingredients AS Activated sludge BDD Boron-doped diamond electrode CD Conduction band EDX Energy dispersive x-ray spectroscopy FTIR Fourier-transform infrared spectroscopy MF Membrane filtration PPCPs Pharmacological and personal care products SEM Scanning Electron Microscope STPs Sewage treatment plants TC Tetracycline TiO2 Titanium dioxide TOC Total organic carbon UV Ultraviolet VB Valence band vi INTRODUCTION Antibiotics were developed to restrain and destroy certain microorganisms, nonetheless, based on the chemical structures, antibiotics are commonly categorized into macrolides, quinolone, sulfonamides, aminoglycosides, and tetracycline (TC) (Binh et al., 2018) Antibiotics have long been widely used for the prevention of human and animal diseases Although most antibiotics cannot be fully absorbed, approximately 90% (Halling-Sorensen et al., 1998) were discharged into the environment with the fecal matter of patients and livestock in an unaltered form and as metabolites when utilized as manure, results in certain levels of contaminants, thereby infiltrating the aquatic ecosystem even at low concentration As shown in the Figure below, antibiotics exist in the environment primarily from pharmaceutical intake by human and through animal breeding The pathway for both animal and human antibiotic deposits existence in the environment comprises of expired antibiotics discarded from hospitals; antibiotic remains in medical appliances and vials utilized in the hospital; prescribed antibiotic drugs discharged through the patient’s feces and urine Likewise, the route of antibiotic existence in the environment through animal/ livestock breeding may involve low doses of antibiotic residues which have accumulated over a relatively long term ingestion The route of the existence of pharmaceutical deposits in the water environment (Haller et al., 2002) Several studies in recent years have implied that the pervasiveness of pharmacological and personal care products (PPCPs) and their metabolites are typically found in the sewage treatment plants (STPs) effluent, also in water environment owing to the heavy load from pharmaceutical companies which are discharged into rivers, lakes and other superficial waters The occurrence of these pollutants in water could be largely attributed to the incapability of most STPs to achieve complete degradation with only the biological oxidation process, which is a contributory factor to the prevalence of Eco toxicological implications for the aquatic microorganisms (Richards & Cole, 2006) Presently, in several developed countries such as the United States and the European Union, the challenges from antibiotic pollution have become an important environmental issue and related researches are evolving rapidly Every human life activity generates wastes, more directly related to the country or citizen’s standard of living and the quantity of wastes produced over time Around 23% of the global population lives in developed nations and expend 78% of the available resources; however, 82% of waste materials are yielded (Halling-Sorensen et al., 1998) Furthermore, it should also be noted that the amount of accumulated waste tends to increase remarkably in direct contrast to the level of industrialization of a country Presently, approximately 5,000,000 identified substances have been reported, with roughly 70,000 usages worldwide, and a recent estimate of 1,000 new chemicals are reportedly incorporated in the list each year (Kumar & Vyas, 2013) The problems associated with appropriate water treatment and resources cannot be handled objectively but have to be managed by a wide range of procedures Issues associated with toxic effects of organic compounds that are very active in water even at trace levels must be eradicated through the disinfection of water utilized by the general populace especially in the rural communities In order to tackle this wider range of issues, advanced processes that vary due to complexity levels of these problems and their scales for application are required Formerly, waste products have been disposed of and eliminated by discharging them directly into the environment without treatment, not until the depleting self- purifying efficacy of the environment has been exhausted and the permissible standards were particle cannot adsorb anymore which would compel the molecules of the pollutant to block the photons, hence the removal efficiency would decrease However, at low concentration of 40 ppm, TC was completely degraded and chosen as the optimum pollutant initial concentration Dark Light Dark Light Figure 3.6 The effect of initial concentration on TC removal efficiency, Volume of the sample solution= 200 mL; TiO2 dosage = 0.1g/L, TC concentration= 40 ppm, temperature= 25℃, Total reaction time = 180 min, absorbance wavelength for TC = 357 nm 3.3.2 Effect of catalyst dose on the degradation efficiency of TC with TiO2 The dosage of photocatalyst highly affects the rate of heterogeneous photodegradation reaction, as significant increases are usually detected Overall, to prevent wasteful use of the catalyst, the optimum dosage must be estimated so as to achieve maximum absorption of effective photons (Prabha & Lathasree, 2014) For this experiment, varying photocatalyst ranging from 0.1g/L, 0.3g/L, and 0.5g/L were investigated to determine their effects on the removal of 40 ppm TC pollutants As seen in Fig.3.7, the percentages of TC removal were 98.9%, 92.9%, and 78.7%, thus there was no 35 significant increase in the degradation rate when the TiO2 dosage was increased, rather it indicated a negative effect Similarly, (Mozia et al., 2013) reported a decline in the removal efficiency of diclofenac TiO2 loading was increased to 0.3g/L, but no substantial influence on degradation was observed for catalyst dose ranging between 0.05 – 0.2g/L 100 0.1 g/L 0.3 g/L 0.5 g/L Removal Efficiency (%) 80 60 Dark 40 Light 20 0 20 40 60 80 100 120 140 160 180 200 Time (min) Figure 3.7 The effect of catalyst dose on TC removal efficiency, Volume of the sample solution= 200 mL; TC concentration= 40 ppm, temperature= 25℃, Total reaction time = 180 min, absorbance wavelength for TC = 357 nm Although, other findings have claimed that “catalyst loading tends to have both benefits and limitations to the process of photodegradation”, however, reducing the catalyst load had shown to decrease both the amount of photons absorbed as well as, increases the rate of degradation process The reduction in the amount of catalyst loading also enhances the transparency of the sample solution which further enables easy penetration of the light intensity, thus, improving the photochemical reaction (Bagheri et al., 2017) Hence, to avoid unnecessary excess catalyst and also ensure appropriate absorption of light photons for utter degradation, 0.1g/Loading was selected as the optimum catalyst 36 dose for subsequent experiments 3.3.3 Effect of pH value on the degradation efficiency of TC with TiO2 The most significant parameter in ensuring effective photodegradation is the pH value, as hydroxyl radical formation is greatly dependent on the influence of pH (Jiao et al., 2008), so also alters the surface of the photocatalyst, dissociates the pollutant and changes the structure of the pollutants in the aqueous solution (Etacheri et al., 2012) The point of zero charge (pHpzc) is commonly used to depict where the pH value of a photocatalyst at the surface charge density is equal to zero Initial pH is amongst the most crucial parameters in the photodegradation activities due to its influence on the photocatalyst’s surface charge and ionizing nature As shown in Figure 3.8a, the effect of pH on TC removal efficiency was determined by evaluating different initial pH values ranging from 3-9, whilst other parameters remained constant After 120 mins of irradiation, 62%, 97%, and 22% of TC were removed at pH 3.0, 7.0, and 9.0, respectively Evidently, TC in the neutral solution showed quicker degradation than in the acidic and alkaline solution Similar findings were reported by other study that MWCNT/TiO2 nano-composite were used to study the enhanced photocatalytic degradation of tetracycline and real pharmaceutical wastewater (Ahmadi et al., 2017) Nevertheless, the effects of pH values on the process of TC photodegradation are quite complex to interpret due to its numerous functions such as influencing the adsorption rate of TC on the surface of the TiO2 catalyst The pHpzc for anatase TiO2 was evaluated at 6.2 using the salt addition method (Figure 3.6b) which corresponds to the value reported by other researcher (Zeng, 2013) Thus, at pH solution > pHpzc, the charge on the surface of the catalyst is negative, and for pH solution < pHpzc, the charge on the surface of the catalyst is positive as shown in equation (17) and (18) (Zeng, 2013) Ti-OH + OH- ↔ TiO- + H2O (17) Ti-OH + H+ ↔ TiOH2+ (18) The neutral surface charge will be when pH solution = pHpzc Thus, in the acidic and neutral pH medium, degradation of TC was more favorable than in the alkaline medium Therefore, in this study, the neutral pH =7 is the optimal and most favorable medium 37 with a removal efficiency of 97% Tc Removal efficiency (%) 100 pH pH pH 80 (a) av 60 40 Dark Light Dark Light 20 0 20 40 60 80 100 120 140 160 180 200 Time (min) pH (b) - pH Initial bv pH Final Point of Zero charge = 6.2 -2 -4 pH 10 12 Initial Figure 3.8 a) Effect of pH on the removal efficiency of Tc, Volume of the sample solution= 200 mL; TiO2 dosage = 0.1 g/L, TC concentration = 40 ppm, temperature= 38 25℃, Total reaction time = 180 min, absorbance wavelength for TC = 357 nm, b) the pH0 vs 𝒑𝑯∆ 2using the salt addition method 3.3.4 Effect of temperature on the degradation efficiency of TC with TiO2 Temperature has been considered to be a valuable parameter while investigating the conditions that influence the photodegradation of pollutants (Behnajady et al., 2006) This study examined the effects of varying temperatures ranging from 25 oc, 35oc, and 45oc with 0.1g/L of TiO2 on the removal of 40 ppm TC pollutants, and 98.5%, 99.1%, 99.7% of TC were degraded respectively which could be said to show a slight increment as the temperature changes But, the optimal temperature was observed at 45 oc with a removal efficiency of 99.7% The result as seen in Figure 3.9 showed that as the temperature increased, a significant rise in the reaction rate was observed thereby enabling a faster removal efficiency, which has been the case in numerous findings ascertaining that temperature is directly proportional to the rate of the chemical reaction However, at a very high temperature, the reaction pathway is hindered, and adsorption capability becomes low thereby weakening the oxidation of the direct hole on the surface of the TiO2 photocatalyst which may cause desorption to occur (C Chen et al., 2011) 100 Removal Efficiency (%) Temp = 25OC Temp = 35OC Temp = 45OC 80 60 40 Dark Light Dark Light 20 20 40 60 80 100 120 140 160 180 Time (mins) Figure 3.9 Effect of temperature on the removal efficiency of Tc, Volume of the sample solution= 200 mL; TiO2 dosage = 0.1g/L, TC concentration= 40 ppm, 39 temperature= 25℃, 35℃, 45℃ Total reaction time = 180 min, absorbance wavelength for tetracycline = 357 nm 3.3.5 The removal of TC with the optimized conditions This study conducted quite several experiments to optimize the following experimental variables; at an initial concentration of 40 ppm, 0.1g/L of TiO2 photocatalyst, pH =7, and temperature at 25oC The result obtained as shown in fig.3.10 indicated that under optimum conditions, the removal efficiency was 99.7% after 180 mins in the presence of oxygen Thus, utter degradation was observed 100 Degradation efficiency Removal Efficiency(%) 80 60 40 Dark Light 20 Dark 0 20 Light 40 60 80 100 120 140 160 180 Time (mins) Figure 3.10 the optimized condition on the removal efficiency of Tc, Volume of the sample solution= 200 mL; TC concentration= 40 ppm, TiO2 dosage = 0.1g/L, pH = 7, Temperature= 45℃, Total reaction time = 180 min, absorbance wavelength for tetracycline = 357 nm 40 CHAPTER CONCLUSION This research provides an overview of the basic concepts and mechanisms of the photocatalytic process, methods, and how experimental variables affect the efficiency of this process Firstly, the survey analysis 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VIETNAM JAPAN UNIVERSITY OLADELE HONOUR ADEDAYO TREATMENT OF PHARMACEUTICAL ANTIBIOTIC WASTEWATER USING PHOTOCATALYTIC PROCESSES WITH COMMERCIAL TiO2 POWDER MAJOR: ENVIRONMENTAL ENGINEERING CODE:... attitude towards antibiotic use such as practices of using antibiotics with regards to their daily routine and health (three statements), 3) knowledge of antibiotics and treatment of pharmaceutical. .. spectra of TiO2 material using the FT/IR4600typeA machine 3.3 Photodegradation of Antibiotic pollutant 3.3.1 Effect of initial concentration on the removal of TC with TiO2 The chemical composition of