Nghiên cứu sự phân hủy dư lượng dược phẩm cip trong nước thải được xử lý ro bằng các quá trình aop sử dụng các tác nhân oxy hóa khác nhau

TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ NỘI LUẬN VĂN THẠC SĨ Research on the degradation of CIP residues in RO treated wastewater by AOP processes using different oxidation agents Phan Thi Huong Quynh Ngành Kỹ thuật hóa học Giảng viên hướng dẫn: GVC.PGS.TS Nguyễn Minh Tân Viện: Kỹ thuật Hóa học Hà Nội, 2022 ACKNOWLEDGMENT It is the most challenging part of my thesis; I have many things that I desire to say, and I also have many people to whom I want to express my gratitude According to this, I am lost in words and not know where to start To begin with, when I began doing this study two years ago, I did not think that it had lasted so long After a long battle, this thesis is the report of my challenging process; although it can not illustrate all the time that I snuggled with experiments in the laboratory, my disappointment when failing in doing research, and my joy when seeing the results Firstly, I would like to thank Assoc Prof Nguyen Minh Tan from Hanoi University of Science and Technology guided me throughout the working process, provided all the equipment, and created conditions for me to develop and complete this thesis Secondly, I thank the School of Chemical Engineering for understanding and giving me more time to complete this project I would like to give my sincere thanks and deep gratitude to my parents because they have always supported me on my scientific path and have always cheered me on when I thought I would give up To Dr Nguyen Thi Thu Trang, Institute of Environmental Technology – Vietnam Academy of Science and Technology, who has always been patient with me, I not know what words I can use to show my happiness because I receive a lot of help from her Big thanks to MSc Pham Duc Chinh from INAPRO for all the scientific inputs and lab support; he had a vital role in my scientific path; I was greatly influenced by his scientific style and worked much harder words of encouragement Finally, to the students at INAPRO, I want to send a special thanks from my heart; if I not have your help, I cannot complete all the experiments in this research Phan Thi Huong Quynh Hanoi, 2021 i DECLARATION OF AUTHORSHIP I now declare that I have written the presented research thesis myself and have not used tools other than those specified The use of references in the project has been clearly stated in the references section The research team and I make the data and results presented in this project, and it is completely honest Furthermore, I certify that this research thesis or any part thereof has not been submitted for a degree or any other degree at any educational institution in Vietnam or abroad Hanoi, June 2022 Phan Thi Huong Quynh ii ABSTRACT The treatment of traces of pharmaceuticals residual, especially antibiotics residual, is a challenge for existing water treatment technologies A recently selected solution to overcome this obstacle is the application of advanced oxidation processes In this study, experiments were performed to evaluate the efficiency of CIP degradation by direct photolysis, UV/ TiO2, UV/ H2O2, and UV/ TiO2/ H2O2 The survey showed that a CIP concentration of 5mg/L is the most suitable for research The AOPs all handle CIP best when Re = 6546 and UV density at 225 W/m2 UV/ H2O2 system best cures CIP after 60 minutes; efficiency is about 99,16% at optimum working conditions Meanwhile, direct photolysis is less efficient when treating CIP; the best efficiency is only 11,64 % after one hour of decomposition The UV/ TiO2 system achieved an efficiency of 74,4% However, if TiO2 and H2O2 are combined at low concentrations, the process efficiency can be 93,21% CIP decomposes best in neutral media For the water matrix, the treatment of CIP in tap water is less effective than in RO and distilled water Keywords: Ciprofloxacin (CIP), advanced oxidation processes (AOPs), treatment, titanium dioxide, hydrogen peroxide iii TÓM TẮT Việc xử dư lượng dược phẩm nước thải, đặc biệt thuốc kháng sinh, thách thức công nghệ xử lý nước có Một giải pháp lựa chọn gần để khắc phục trở ngại áp dụng q trình oxy hóa tiên tiến Trong nghiên cứu này, thí nghiệm thực để đánh giá hiệu trình phân hủy CIP phương pháp quang phân trực tiếp, UV / TiO2, UV / H2O2 UV / TiO2 / H2O2 Cuộc khảo sát cho thấy nồng độ CIP 5,0 mg/ L thích hợp để nghiên cứu Các trình AOPs ứng dụng xử lý CIP tốt Re = 6546 mật độ UV 225 W/ m2 Hệ thống UV / H2O2 xử lý CIP tốt sau 60 phút; hiệu suất đạt khoảng 99,16% điều kiện làm việc tối ưu Trong đó, quang phân trực tiếp hiệu xử lý CIP; hiệu suất tốt sau phân hủy 11,64% Quá trình UV / TiO2 đạt hiệu suất 74,4% Tuy nhiên, kết hợp TiO2 H2O2 nồng độ thấp hiệu suất q trình đạt 93,21% Bên cạnh đó, CIP phân hủy tốt mơi trường pH trung tính Đối với nước, việc xử lý CIP nước máy hiệu RO nước cất Q trình UV / H2O2 tiêu thụ lượng nhất, trình UV/ TiO2/ H2O2 tiêu thụ lượng khơng đáng kể UV/ TiO2 q trình có giá trị EE/ O cao Keywords: Ciprofloxacin (CIP), advanced oxidation processes (AOPs), treatment, titanium dioxide, hydrogen peroxide iv Table of Contents ACKNOWLEDGMENT i DECLARATION OF AUTHORSHIP ii ABSTRACT iii TÓM TẮT iv TABLE OF FIGURES viii TABLE OF TABLES x ABBREVIATION AND SYMBOLS xi INTRODUCTION CHAPTER 1: OVERVIEW 1.1 Pharmaceuticals in the environment 1.2 Ciprofloxacin 1.3 Ciprofloxacin in Environment 1.3.1 Occurrence 1.3.2 Risks to the Environment and Humans 1.4 Potential treatment techniques 1.5 Advanced Oxidation Processes (AOPs): Overview 10 1.5.1 The superiority of Advanced oxidation processes 11 1.5.2 Classification of advanced oxidation processes (AOPs) 12 1.5.3 Characterization of typical advanced oxidation processes (AOPs) 13 1.6 Advanced Oxidation Processes (AOPs): Typical processes 16 1.6.1 UV direct photolysis 16 1.6.2 The H2O2/UV process 16 1.6.3 Heterogeneous photocatalysis 19 1.6.4 The UV/TiO2/H2O2 process 24 1.7 Current uses and challenging of AOPs 25 1.8 Research objective and research approach 26 1.8.1 Research objective 26 1.8.2 Research approach 27 CHAPTER 2: MATERIALS AND METHODS 28 2.1 Materials 28 v 2.1.1 Ciprofloxacin (CIP) 28 2.1.2 Titanium dioxide (TiO2) .29 2.1.3 Hydrogen peroxide (H2O2) 30 2.1.4 The reaction system 31 2.2 UV-Vis Spectroscopy 32 2.2.1 Measuring Sample Absorbance 35 2.2.2 CIP Concentration Standard Line .35 2.3 Calculation Formulas 35 2.3.1 CIP decomposition efficiency .35 2.3.2 Reynolds number 35 2.3.3 Energy consumption 36 2.3.4 Determination of kinetic constants of CIP degradation reaction 36 2.4 Data processing methods 37 CHAPTER 3: EXPERIMENTAL PROCEDURE 38 3.1 Experimental location 38 3.2 Experimental setup 38 3.2.1 Chemicals 38 3.2.2 Experimental instruments and equipment 39 3.3 CIP's calibration curve process 40 3.3.1 Sample preparation .40 3.3.2 Wavelength Selection 40 3.3.3 Procedure 41 3.4 Determine the effect of initial CIP concentration 41 3.4.1 Sample preparation .41 3.4.2 Procedure 41 3.5 Investigate factors affecting CIP degradation in water 41 3.5.1 Effect of UV photolysis on the degradation of CIP 41 3.5.2 Effect of UV intensity on the degradation of ciprofloxacin .42 3.5.3 Effect of TiO2 concentration on CIP degradation .42 3.5.4 Effect of H2O2 concentration on CIP degradation 43 3.5.5 Effect of TiO2 combined with H2O2 on CIP degradation 43 vi 3.5.6 Effect of pH on the degradation of CIP 44 3.6 Water matrix effects on CIP degradation 44 CHAPTER 4: RESULTS AND DISCUSSION 45 4.1 Influence of technological parameters on CIP treatment by AOPs 45 4.1.1 Effect of initial CIP concentration 45 4.1.2 Effect of UV intensity 46 4.1.3 Effect of UV process and TiO2 concentration on CIP degradation 47 4.1.4 Effect of H2O2 concentration on CIP degradation 51 4.1.5 Effect of hydrodynamic conditions on CIP treatment efficiency 54 4.1.6 Effect of TiO2 combined with H2O2 on CIP degradation 57 4.1.7 Effect of pH on the degradation of CIP 59 4.2 Water matrix effects on CIP degradation 61 4.3 Kinetics of advanced oxidation processes of CIP treatment and Energy consumption 64 4.3.1 Kinetics of advanced oxidation processes of CIP treatment 64 4.3.2 Energy consumption 67 CHAPTER 5: CONCLUSIONS AND OUTLOOK 70 5.1 Conclusions 70 5.2 Outlook 70 REFERENCES 72 APPENDIX A - CIP's calibration curve 80 APPENDIX B - List of published works 81 vii TABLE OF FIGURES Figure 1.1 Pharmaceuticals' main pathways for entering the environment [12] Figure 1.2 Wastewater treatment Figure 1.3 Chemical structure of ciprofloxacin Figure 1.4 The structural formula of ciprofloxacin Figure 1.5 Four levels of degradation of Advanced oxidation processes [52] 11 Figure 1.6 Classification of Advanced Oxidation Processes 13 Figure 1.7 Molecular structure of hydrogen peroxide 17 Figure 1.8 Hydrogen peroxide decomposition 17 Figure 1.9 Molecular structure of Titanium dioxide 20 Figure 1.10 Crystal structure of TiO2 20 Figure 1.11 Five Steps in Heterogeneous Photocatalysis Process 21 Figure 1.12 Photocatalytic mechanism 22 Figure 1.13 Band positions of selected semiconductor photocatalysts and redox potentials [68] 22 Figure 1.14 The UV/TiO2/H2O2 mechanism 24 Figure 1.15 The water purification system of Panasonic 26 Figure 2.1 Ciprofloxacin used in this research; a: Ciprofloxacin Kabi 200mg/100ml; b: Ciprofloxacin ≥ 98% 29 Figure 2.2.Titanium dioxide (Merck, Germany) 30 Figure 2.3 Hydrogen peroxide 30% (GHTech, China) 31 Figure 2.4 (a) Low-pressure mercury UV lamp inside a quartz tube; (b) Reactor 31 Figure 2.5 Experimental system; (a) diagram, (b) set-up system 32 Figure 2.6 A diagram showing the major components of a UV-Vis spectrophotometer [81] 33 Figure 2.7 Diagram of a cuvette-based UV-Vis spectroscopy system [81] 34 Figure 2.8 Perkin Eimer Lambda35 UV/Vis Spectrometer 35 Figure 3.1 Chemicals used in this study 38 Figure 3.2 Experimental equipment (a) Analytical balance OHAUS; (b) Filter 45 μm; (c) Centrifuge machine UNIVERSAL 320; (d) Umex UVA Messsystem; (e) pH meter; (f) Ultrasonic bath 39 Figure 3.3 Experiment setup 40 Figure 3.4 UV Spectrum of CIP; (a) standard solution; (b) CIP Kabi 41 Figure 3.5 Direct photolysis experimental procedure 42 Figure 4.1 Effect of initial CIP concentration, direct photolysis process, no pH adjustment, Re = 6546 45 Figure 4.2 The CIP degradation efficiency after 45 with [CIP]0 varied from to 20 mg/L; UV-only process 46 viii Figure 4.3 Effect of UV intensity on CIP treatment efficiency 47 Figure 4.4 The influence of TiO2 concentration on CIP degradation; (A) Re = 2000; (B) Re = 6546; (C) Re = 8560 49 Figure 4.5 Effect of H2O2 concentration on CIP degradation; (A) Re =2000; (B) Re =6546; (C) Re = 8650 53 Figure 4.6 Effect of hydrodynamic conditions on CIP treatment efficiency 55 Figure 4.7 Major steps in solid-liquid heterogeneous photocatalysis [84] 56 Figure 4.8 CIP degradation when treated with UV/ TiO2/ H2O2 58 Figure 4.9 The efficiency of CIP treatment by UV/ TiO2/ H2O2 process at different pH values 59 Figure 4.10 Ciprofloxacin ionized species [91] 60 Figure 4.11 The degradation rate constants of CIP at various pH values 61 Figure 4.12 CIP degradation by different AOPs and aqueous media (A) Decomposition of CIP in aqueous media by UV/ TiO2 process.; (B) Decomposition of CIP in aqueous media by UV/ TiO2/ H2O2 process; (C) Decomposition of CIP in aqueous media by UV/ H2O2 process; (D) The efficiency of AOPs when treating CIP in the water matrix 64 Figure 4.13 Compare different AOPs when treating CIP 65 Figure 4.14 The rate constants (kapp) and efficiency coefficients (R2) of CIPdegrading AOPs in the study 66 ix t90 when the CIP decomposes 90% With the design flow Q (L/min), the processing capacity of the AOP device will be calculated according to the formula: X= Q * t90 (L) (xvii) From X, it is possible to calculate the total energy dissipated by the device as (X * ԑ) W, where ԑ is the specific energy The number of standard equipment to use: N= X∗ε E (xviii) where E is the energy supplied to a device Cost of each unit from the manufacturer = C (USD) Total cost of N units = cost of AOP reactor = P = N x C Thus, from the constant kapp, it is possible to roughly calculate the device, energy, and cost of the advanced oxidation processes used to degrade CIP Table 4.6 below summarizes the kapp values and R2 efficiency coefficients of different advanced oxidation processes used in this study when treating CIP in the environment of purified water, filtered water after RO, and tap water Table 4.6 Kinetic parameters for the degradation of CIP Process Matrix water kapp (min-1) R2 UV/ TiO2 Distilled water 0,0301 0,979 UV/ H2O2 Distilled water 0,0842 0,998 UV/ TiO2/ H2O2 Distilled water 0,0572 0,9781 UV – only RO water 0,0022 0,977 UV/ TiO2 RO water 0,0190 0,987 UV/ H2O2 RO water 0,0815 0,998 UV/ TiO2/ H2O2 RO water 0,0482 0,981 UV/ TiO2 Tap water 0,0232 0,951 UV/ H2O2 Tap water 0,0624 0,991 UV/ TiO2/ H2O2 Tap water 0,0423 0,963 4.3.2 Energy consumption A sample calculation for the hybrid UV/ TiO2 process for CIP deterioration in RO water is presented below All other processes were estimated in the same way The results of these calculations are summarized in Table 4.7 67 The total electrical energy used in the treatability research for the UV/ TiO2 process was Pelec = 0,12 kW The volume of therapy was liters The treatment time required for 90% degradation of phenol using Eq (x) as: 𝑡𝑡90 = 2,3025851 𝑘𝑘𝑎𝑎𝑎𝑎𝑎𝑎 = 121,19 (min) The total energy dissipated by the device is : X*ε = Q* t90* ε = 43,37 1000 * 121,19* 0,12= 0,63 kW The initial concentration was 5,0 mg/L in this amount of time, and the final concentration was 1,28 mg/L Eq (ix) is used to determine the EE/O EE/O = 0,63∗121,19∗1000 5,0 ) 1,28 8∗60∗log ( = 268,79 (kWh/m3/order) Table 4.7 Summary of energy consumption of various AOPs for CIP degradation Water matrix k C0 C EE/ O (mg/L) (mg/L) (kWh/m3/order) (min-1) t90 (min) Single UV 0,0022 1046,63 5,0 4,42 221806,54 UV /TiO2 0,0190 121,19 5,0 1,28 268,79 0,0815 28,25 5,0 0,04 4,13 UV/ TiO2/ H2 O2 0,0482 47,77 5,0 0,34 21,19 UV /TiO2 0,0301 76,50 5,0 0,94 87,41 0,0842 27,35 5,0 0,036 3,78 0,0572 40,25 5,0 0,209 12,74 0,0232 99,25 5,0 1,46 199,78 0,0624 36,90 5,0 0,142 9,55 0,0423 54,43 5,0 0,496 32,02 Process UV/ H2O2 UV/ H2O2 UV/ TiO2/ H2 O2 RO water Distilled water UV /TiO2 UV/ H2O2 UV/ TiO2/ H2 O2 Tap water Almost the treatment of toxic organic compounds by UV/ H2O2 technology is more effective than AOPs using UV /TiO2 in matrix water; this process has also been used to treat wastewater in some small hospitals and high-end hotels If only in terms of reaction efficiency, energy consumption, equipment structure, and sludge generation, AOPs using UV/ H2O2 can be considered the most efficient among advanced oxidation processes Table 4.10 also shows the energy consumed 68 when using UV/ H2O2 to degrade CIP in the case of optimal kapp is 3,78 (kWh/m3/order) This result is about 20 times lower than that of AOPs using UV /TiO2 (when kapp is optimal) However, it is necessary to consider the fact that H2O2 is a compound that is easily degraded during storage and reaction, and at the same time, it has a high cost Moreover, the CIP treatment efficiency when combining TiO2 and H2O2 is close to using H2O2 alone In terms of energy, the combination of TiO2 and H2O2 mainly results in EE/ O below 50 kWh/m3/order Specifically, the highest value is 12,74 kWh/m3/order, and the lowest value is 32,02 kWh/m3/order These calculated energy values are not too high compared to using H2O2 alone as the oxidizing agent and much lower than the application of photocatalysis In addition, the amount of H2O2 needed for the combined process is only 1/5 of the UV/ H2O2 process Therefore, the combined process should be considered for further research and application Direct photolysis is not recommended for CIP treatment because of its inefficiency 69 CHAPTER 5: CONCLUSIONS AND OUTLOOK 5.1 Conclusions Through investigations of CIP removal by advanced oxidation processes using TiO2, H2O2, and UV on a pilot scale, the following conclusions can be drawn: The reaction of CIP decomposition in water with CIP concentration below 20 mg/L is first order The concentration of 5mg/L is the most suitable to investigate in this study Advanced oxidation processes treat CIP most efficiently when Re = 6546 and UV intensity is 225 W/m2 CIP decomposes best in a neutral environment (pH around 7,0) The efficiency of CIP treatment after 60 minutes by advanced oxidation processes was investigated as follows: UV-only < UV/ TiO2 < UV/ TiO2/ H2O2 < UV/ H2O2 At optimal conditions, UV/ H2O2 with 5,0 mM H2O2 degrades 99,16 % CIP UV/ TiO2 treated 74,4% CIP after one hour when TiO2 was at a concentration of 1,0 g/L Combining TiO2, H2O2 and UV gives an efficiency of 93,21 % with only 0,2 g/L TiO2 and 1,0 mM H2O2 Direct photolysis is the least efficient; after 60 minutes, only 11,64 % efficiency was achieved The degradation of CIP in the water matrix is as follows: Tap water < RO water < Distilled water The UV/ H2O2 process is still the most efficient The UV/ TiO2/ H2O2 process has outstanding CIP processing ability and is close to achieving the same efficiency as UV/ H2O2 Decomposition of CIP in tap water has low efficiency, especially with processes in the presence of TiO2 This result is predicted to be influenced by ions, organic compounds present in the water, and turbidity The UV/ H2O2 process consumes the least amount of energy, while the UV/ TiO2/ H2O2 process consumes negligible energy UV/ TiO2 is the highest EE/ O value process 5.2 Outlook In addition to the evaluation work, the following outstanding issues for further research remain after this dissertation Identification of the by-products of CIP degradation after treatment by different AOPs (UV-only, UV/ TiO2, UV/ TiO2/ H2O2, and UV/ H2O2) The by-products generated during CIP photocatalytic degradation can be identified by LC-MS method 70 Vibrio fischeri characterization Toxicity testing is carried out with a bioassay utilizing V fischeri following ISO 11348-3, "water quality determination of the inhibitory impact of water samples on the light emission of V fischeri (luminescent bacteria test)," using the freeze-dried bacteria technique Besides defining by-products It is crucial to assess the toxicity of CIP water, as decomposition products, if not fully mineralized, can represent a new threat to water Investigation of CIP decomposition under the VL/ TiO2/ H2O2 process Instead of using UV lamps, taking advantage of solar energy is a potential pathway TiO2 combined with H2O2 has been reported to be active in the visible light region Therefore, the process of using visible light needs to be investigated in terms of decomposition efficiency and energy consumption Wastewater system simulation to evaluate CIP degradation in the current treatment system Evaluate the CIP treatment capacity of AOPs, especially the UV TiO2/ H2O2 process for the simulated wastewater environment This is an important step before applying AOPs to real wastewater treatment Evaluating the ability to handle 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2003 79 APPENDIX A - CIP's calibration curve Calibration curve 2.500 2.000 A 1.500 1.000 0.500 0.000 10 15 20 25 CIP concentration (mg/L) 80 APPENDIX B - List of published works Phan Thi Huong Quynh, Nguyen Ngoc Anh, Nguyen Thi Thu Trang, “Research on factors affecting the treatment of Ciprofloxacin by photocatalysis.” Journal of Chemistry and Applications, 2(61), 2022 81