i MINISTRY OF EDUCATION AND TRAINING MINISTRY OF NATIONAL DEFENCE ACADEMY OF MILITARY SCIENCE AND TECHNOLOGY Nguyen Thanh Binh STUDY ON ACTIVATED PERSULFATE BY ZERO VALENT IRON AND UV TO PRODUCE DUAL OXIDATION SYSTEM TO DEGRADE SOME AZO DYES IN WATER CHEMICAL DOCTORAL THESIS HA NOI - 2019 ii MINISTRY OF EDUCATION AND TRAINING MINISTRY OF NATIONAL DEFENCE ACADEMY OF MILITARY SCIENCE AND TECHNOLOGY Nguyen Thanh Binh STUDY ON ACTIVATED PERSULFATE BY ZERO VALENT IRON AND UV TO PRODUCE DUAL OXIDATION SYSTEM TO DEGRADE SOME AZO DYES IN WATER Major: Theoretical and Physical Chemistry Code: 44 01 19 CHEMICAL DOCTORAL THESIS ACADEMIC SUPERVISORS: Assoc Prof Dr TRAN Van Chung Prof Dr Sc DO Ngoc Khue HA NOI - 2019 i ACKNOWLEDGMENTS I assure that this is my own research The research results shown in the thesis are honest Scientific conclusions of the thesis have never been published in any other work The scientific data were fully cited th 15 December 2019 Author Nguyen Thanh Binh ii SPECIAL THANKS TO I would like to express my deep gratitude to Assoc Prof Dr Tran Van Chung and Prof Sc Dr Do Ngoc Khue for guiding deeply in helping me throughout the process of implementing and completing the thesis I would like to express my sincere thanks to the Heads and Staffs of the New Technology Institute/Academy of Military Science and Technology for supporting and creating favorable conditions for me in the process of implementing the thesis I would like to thank the Heads of the Academy of Military Science and Technology, the Training Department/Academy of Military Science and Technology for helping me throughout the study, research and completion of the thesis I would like to express my thanks to Heads of College of Chemical Defense Officer/Chemical Corps; Military Institute of Chemical-Environment/Chemical Corps; Institute of Chemistry - Materials/Academy of Military Science and Technology; Institute of Chemistry/Vietnam Academy of Science and Technology; Department of Chemistry/VNU University of Science/Vietnam National University, Hanoi; Department of Chemistry/Hanoi National University of Education helped, during the thesis implementation Sincere thanks to my family, relatives, colleagues and friends for caring, supporting, encouraging me to complete this project iii TABLE OF CONTENTS Page 1.1 1.2 ACKNOWLEDGMENTS i TABLE OF CONTENTS iii LIST OF SIGNS AND ABBREVIATION vi LIST OF TABLES x LIST OF GRAPHS xii INTRODUCTION Chapter OVERVIEW The basic concept of the oxidation processes based on free radicals 1.1.1 The concept and classification of advanced oxidation processes 1.1.2 The advanced oxidation processes based on free hydroxyl radicals 1.1.3 The advanced oxidation processes based on free sulfate radicals 11 Status of treatment technology for textile dye wastewater 22 1.2.1 Concept, classification of dyes 22 1.2.2 Azo dyes 22 1.2.3 Dye-contaminated wastewater 27 1.2.4 Current situation of domestic and foreign researches on 28 treatment technology of textile dye wastewater 1.3 Conclusion of chapter 31 Chapter RESEARCH SUBJECT AND METHODOLOGY 33 2.1 Research subject 33 2.2 Instruments and chemicals 33 2.2.1 Instruments 33 2.2.2 Chemicals 34 Methods of analysis 34 2.3.1 High performance liquid chromatography method 34 2.3.2 Inductively coupled plasma - mass spectrometry method 37 2.3.3 The volumetric titration method determining the 37 2.3 concentration of S2O8 2− iv 2.4 Experimental methods 39 2.4.1 Survey, evaluating the decomposition efficiency of AZOs in 39 systems: ZVI/AZOs, PS/AZOs, ZVI/PS/AZOs and ZVI/AZOs/UV, PS/AZOs/UV, ZVI/PS/AZOs/UV 2.4.2 Survey of factors affecting on the degradation efficiency of 40 AZOs in systems: ZVI/PS/AZOs and ZVI/PS/AZOs/UV • −• 2.4.3 Qualitative survey of free radicals OH and SO4 42 in ZVI/PS/AZOs and ZVI/PS/AZOs/UV systems • −• 2.4.4 Quantitative survey of free radicals OH and SO4 in 44 ZVI/PS/AZOs and ZVI/PS/AZOs/UV systems 2.4.5 The theoretical equations applied in reaction kinetic research 44 2.4.6 The basis of quantum computing methods 48 2.4.7 Treatment of dye wastewater of La Phu, Duong Noi and Van 51 Phuc villages 3.1 Chapter 3: RESULT AND DISCUSSION 52 Survey, evaluating the efficiency of the PS activation methods under 52 different conditions 3.1.1 The activated PS systems without UV 52 3.1.2 The activated PS systems with UV 56 3.1.3 Factors affect the AZOs decomposition in systems of 60 activated PS by ZVI under without and with UV conditions 3.2 Investigation of the kinetic characteristics of the AZOs 79 decomposition process in the activated persulfate system 3.2.1 The kinetic characteristics of the AZOs decomposition 80 in systems without UV 3.2.2 The kinetic characteristics of the AZOs decomposition in 82 system with UV 3.2.3 Results of calculating thermodynamic parameters according to Arrhenius and Eyring equations for systems: ZVI/PS/AZOs and 86 v ZVI/PS/AZOs/UV 3.3 • −• Research to determine free radicals OH and SO4 in the activated 97 persulfate systems by ZVI without UV and with UV • −• 3.3.1 Qualitative study of free radicals OH and SO4 in the 97 ZVI/PS/AZOs system • −• 3.3.2 Studying on quantification of free radicals OH, SO4 in the 99 activated persulfate systems by ZVI without and with UV 3.4 Calculating some quantumn structural parameters and proposing 110 MO, AY and BT decomposition mechanism in the activated persulfate system 3.4.1 Some structural parameters and ability of decomposing AZOs 110 3.4.2 The estimated mechanism of the AZOs decomposing in the 113 activated persulfate systems 3.5 Application of the activated persulfate system with UV to treat azo- 118 contaminated wastewater from some textile dyeing villages CONCLUSION 122 LIST OF PUBLISHED SCIENTIFIC WORKS 125 LIST OF REFERENCES Appendix 126 vi LIST OF SIGNS AND ABBREVIATIONS Signs Meaning λ Wavelength (nm) I Light intensity (Lux) # Activated Enthalpy (kJ/mol) ∆S # Activated Entropy (J/mol.K) Ψµ Molecular orbital function µ kB Boltzmann constant (1.381.10 ∆H K # -23 -1 J.K ) The reaction equilibrium constant forming an activated complex -1 -1 ε Adsorption constant (M cm ) R Gas constant (R=1.987 Cal/mol.K or R=8.314 J/mol.K) h Plank constant (h= 6.625.10 k Reaction rate constant Cµi Linear combination factor H(%) Efficiency Ea Activation energy (J/mole) Eµ Total energy of the molecule ∆G Free Gibbs energy (kJ/mol) ∆G # -34 Free activation Gibbs energy (kJ/mol) T Kelvin temperature (K) C Mole concentration (mole/L) i The orbital function i v E ο V A Tˆe ˆ H J.s) Light frequency (Hz) Redox standard potential (V) Volume (L) Pre-exponential constant The kinetic energy operator of electron The Hamilton operator vii ˆ U e −e ˆ U n −e r The potential energy operator of interaction between nucleus and electron The potential energy operator of interaction between electron and electron Reaction rate Abbreviation Phrases are abbreviated 2,4- D 2,4-Dichlorophenoxy acetic acid 2,4,5-T 2,4,5-Trichlorophenoxy acetic acid AC Activated Carbon AC-MW Activated Carbon – Micro wave ANPOs Advanced Non-Photochemical Oxidation Processes AO7 Orange acid AOPs Advanced Oxidation Processes APOPs Advanced Photochemical Oxidation Processes - APOPs AY Alizarine Yellow R AZOs The general form, which represents one of the azo: MO, AY and BT BOD Biochemical Oxygen Demand BT Mordant Black-T BTEX Benzene, Toluene, Methylbenzene, Xylene C.I Color Index COD Chemical Oxygen Demand DCE 1,2-dichloroethene DNT 2,4-dinitro toluene EDTA Ethylene diamine tetra acetic acid ETA Ethanol alcohol ETAD The Ecological and Toxicological Association of Dyes and Organic Pigments Manufacturers HPLC High Performance Liquid Chromatography ICP-MS Inductively Coupled Plasma- Mas Spectrometry ISCO In Situ Chemical Oxidation Appendix Results of the BT decomposition in the systems: 1.ZVI/BT, 2.PS/BT and 3.ZVI/PS/BT t [BT] Systems H%) C/C0 ln(C/C0) -2 (minute) (10 mM) 10.0000 0.00 1.0000 0.0000 9.9721 0.28 0.9972 -0.0028 10 9.9281 0.72 0.9928 -0.0072 15 9.8939 1.06 0.9894 -0.0107 20 9.8506 1.49 0.9851 -0.0151 25 9.8153 1.85 0.9815 -0.0186 30 9.7805 2.20 0.9781 -0.0222 10.0000 0.00 1.0000 0.0000 9.4821 5.18 0.9482 -0.0532 10 8.9781 10.22 0.8978 -0.1078 15 8.6389 13.61 0.8639 -0.1463 20 8.2991 17.01 0.8299 -0.1864 25 7.9893 20.11 0.7989 -0.2245 30 7.7864 22.14 0.7786 -0.2502 10.0000 0.00 1.0000 0.0000 8.5198 14.80 0.8520 -0.1602 (Conditions: CZVI= 10 7.2918 27.08 0.7292 -0.3158 0.5 g/L, CPS= mM, 15 6.1987 38.01 0.6199 -0.4782 CBT= 0.1 mM, pH= ο 4.5, t= 25 C) 20 5.4125 45.88 0.5413 -0.6139 25 4.5970 54.03 0.4597 -0.7772 30 4.1062 58.94 0.4106 -0.8901 1.ZVI/BT (Conditions: CZVI= 0.5g/L,CBT= 0.1 mM, ο pH= 4.5, t= 25 C) PS/BT (Conditions: CPS= mM, CBT= 0.1 mM, ο pH= 4.5, t= 25 C) ZVI/PS/BT Appendix Results of the MO decomposition in the systems ZVI/MO/UV, PS/MO/UV and ZVI/PS/MO/UV t [MO] Systems H%) C/C0 ln(C/C0) -2 (minute) (10 mM) 10.0000 0.00 1.0000 0.0000 = 9.7550 2.45 0.9755 -0.0248 0.1 0.5 g/L, CMO= mM, pH= 4.5, t= 25 10 9.4508 5.49 0.9451 -0.0565 15 9.1701 8.30 0.9170 -0.0866 ο 20 8.9499 10.50 0.8950 -0.1109 25 8.7810 12.19 0.8781 -0.1300 30 8.6041 13.96 0.8604 -0.1503 10.0000 0.00 1.0000 0.0000 7.8261 21.74 0.7826 -0.2451 10 6.4702 35.30 0.6470 -0.4354 15 5.3495 46.51 0.5350 -0.6256 20 4.5372 54.63 0.4537 -0.7903 25 3.9191 60.81 0.3919 -0.9367 30 3.3196 66.80 0.3320 -1.1028 ZVI/PS/MO/UV (Conditions: CZVI = 10.0000 0.00 1.0000 0.0000 5.2934 47.07 0.5293 -0.6361 0.5 g/L, CPS= mM, 10 3.0955 69.05 0.3095 -1.1727 CMO= 0.1 mM, pH= ο 4.5, t= 25 C I= 15 1.7177 82.82 0.1718 -1.7616 20 0.9319 90.68 0.0932 -2.3732 785Lux λ= 254 nm) 25 0.5915 94.08 0.0592 -2.8276 30 0.4108 95.89 0.0411 -3.1921 ZVI/MO/UV (Conditions: CZVI C I= 785 Lux λ= 254 nm) PS/MO/UV (Conditions: CPS= mM, CMO= 0.1 mM, ο pH= 4.5, t= 25 C I= 785 Lux λ= 254 nm) Appendix Results of the AY decomposition in the systems: ZVI/AY/UV, 2.PS/AY/UV and 3.ZVI/PS/AY/UV t [AY] Systems H%) C/C0 ln(C/C0) -2 (minute) (10 mM) 10.0000 0.00 1.0000 0.0000 9.6780 3.22 0.9678 -0.0327 (Conditions: CZVI = 0.5 10 9.4410 5.59 0.9441 -0.0575 g/L, CAY= 0.1 mM, 15 9.2850 7.15 0.9285 -0.0742 pH= 4.5, t= 25 C, I= 20 9.1704 8.30 0.9170 -0.0866 785 Lux, λ= 254 nm) 25 9.0704 9.30 0.9070 -0.0976 30 8.9026 10.97 0.8903 -0.1162 10.0000 0.00 1.0000 0.0000 7.8143 21.86 0.7814 -0.2466 (Conditions: CPS= 10 6.3697 36.30 0.6370 -0.4510 mM, CAY= 0.1 mM, 15 5.3262 46.74 0.5326 -0.6299 pH= 4.5, t= 25 C, I= 20 4.4980 55.02 0.4498 -0.7990 785 Lux, λ= 254 nm) 25 3.8055 61.95 0.3805 -0.9661 30 3.0546 69.45 0.3055 -1.1859 10.0000 0.00 1.0000 0.0000 5.7287 42.71 0.5729 -0.5571 10 3.7804 62.20 0.3780 -0.9728 15 2.8002 72.00 0.2800 -1.2729 20 1.9096 80.90 0.1910 -1.6557 25 1.2806 87.19 0.1281 -2.0553 30 0.9014 90.99 0.0901 -2.4064 ZVI/AY/UV ο PS/AY/UV ο ZVI/PS/AY/UV (Conditions: CZVI=0.5 g/L, CPS= mM, CAY= 0.1 mM, pH= 4.5, t= 25 ο C, I= 785Lux, λ= 254 nm) Appendix Results of the BT decomposition in the systems: 1.ZVI/BT/UV, 2.PS/BT/UV and 3.ZVI/PS/BT/UV t [BT] Systems H%) C/C0 ln(C/C) -2 (minute) (10 mM) 10.0000 0.00 1.0000 0.0000 9.7240 2.76 0.9724 -0.0280 (Conditions: CZVI = 0.5 10 9.5448 4.55 0.9545 -0.0466 g/L, CBT= 0.1 mM, pH= ο 4.5, t= 25 C, I= 785 Lux, λ= 254 nm) 15 9.3706 6.29 0.9371 -0.0650 20 9.2836 7.16 0.9284 -0.0743 25 9.2032 7.97 0.9203 -0.0830 30 9.1072 8.93 0.9107 -0.0935 10.0000 0.00 1.0000 0.0000 ZVI/BT/UV PS/BT/UV (Conditions: CPS= mM, 8.3993 16.01 0.8399 -0.1744 10 7.4015 25.99 0.7401 -0.3009 CBT= 0.1 mM, pH= 4.5, 15 6.7067 32.93 0.6707 -0.3995 t= 25 C, I= 785 Lux, λ= 20 6.1721 38.28 0.6172 -0.4825 254nm) 25 5.7084 42.92 0.5708 -0.5607 30 5.4093 45.91 0.5409 -0.6145 10.0000 0.00 1.0000 0.0000 = 0.5 7.3145 26.85 0.7315 -0.3127 g/L, CPS= mM, CBT= 0.1 mM, pH= 4.5, t= 25 10 5.5092 44.91 0.5509 -0.5962 15 4.1093 58.91 0.4109 -0.8893 ο 20 3.1068 68.93 0.3107 -1.1690 25 2.5084 74.92 0.2508 -1.3830 30 2.0147 79.85 0.2015 -1.6021 ο ZVI/PS/BT/UV (Conditions: CZVI C, I=785 Lux, λ= 254 nm) Appendix The results of the temperature influence on the MO decomposition in the ZVI/PS/MO systems: Conditions: CZVI=0.5g/L , CPS= 1mM , pH= 4.5, CMO= 0.1mM The ZVI/PS/MO ο system, t C changes ο t= 25 C ο t= 35 C ο t= 45 C ο t= 55 C t (minute) [MO] -2 (10 mM) H%) C/C0 ln(C/C0 10.0000 0.00 1.0000 0.0000 7.3678 26.32 0.7368 -0.3055 10 5.9465 40.54 0.5946 -0.5198 15 20 4.7929 4.0394 52.07 59.61 0.4793 0.4039 -0.7354 -0.9065 25 3.3372 66.63 0.3337 -1.0975 30 2.6350 73.65 0.2635 -1.3337 10.0000 0.00 1.0000 0.0000 6.5715 34.29 0.6572 -0.4198 10 4.1823 58.18 0.4182 -0.8717 15 20 2.7952 1.9561 72.05 80.44 0.2795 0.1956 -1.2747 -1.6316 25 1.4168 85.83 0.1417 -1.9542 30 1.0921 89.08 0.1092 -2.2145 10.0000 0.00 1.0000 0.0000 4.6739 53.26 0.4674 -0.7606 10 2.5746 74.25 0.2575 -1.3569 15 20 1.5141 0.7595 84.86 92.41 0.1514 0.0759 -1.8878 -2.5777 25 0.4057 95.94 0.0406 -3.2047 30 0.2053 97.95 0.0205 -3.8858 10.0000 0.00 1.0000 0.0000 3.8171 61.83 0.3817 -0.9631 10 1.5980 84.02 0.1598 -1.8338 15 20 0.6624 0.2585 93.38 97.41 0.0662 0.0259 -2.7145 -3.6554 25 0.1025 98.98 0.0102 -4.5806 30 0.0622 99.38 0.0062 -5.0805 Appendix 9.The results of the temperature influence on the AY decomposition in the ZVI/PS/AY system Conditions: CZVI=0.5 g/L , CPS= mM , pH= 4.5, CAY= 0.1 mM The ZVI/PS/AY t [AY] H%) C/C0 ln(C/C0 ο -2 (minute) system t C changes (10 mM) o t= 25 C o t= 35 C o t= 45 C o t= 55 C 10.0000 0.00 1.0000 0.0000 8.2461 17.54 0.8246 -0.1929 10 6.7203 32.80 0.6720 -0.3974 15 20 5.4005 4.3404 46.00 56.60 0.5401 0.4340 -0.6161 -0.8346 25 3.4023 65.98 0.3402 -1.0781 30 2.8576 71.42 0.2858 -1.2526 10.0000 0.00 1.0000 0.0000 6.9319 30.68 0.6932 -0.3665 10 4.8097 51.90 0.4810 -0.7320 15 20 3.3946 2.3723 66.05 76.28 0.3395 0.2372 -1.0804 -1.4387 25 1.9013 80.99 0.1901 -1.6601 30 1.6205 83.80 0.1620 -1.8199 10.0000 0.00 1.0000 0.0000 5.5815 44.19 0.5582 -0.5831 10 3.2440 67.56 0.3244 -1.1258 15 20 1.9821 1.2028 80.18 87.97 0.1982 0.1203 -1.6184 -2.1179 25 0.8534 91.47 0.0853 -2.4611 30 0.7154 92.85 0.0715 -2.6375 10.0000 0.00 1.0000 0.0000 4.1482 58.52 0.4148 -0.8799 10 2.0901 79.10 0.2090 -1.5654 15 20 1.1725 0.5901 88.27 94.10 0.1173 0.0590 -2.1434 -2.8300 25 0.3192 96.81 0.0319 -3.4444 30 0.2071 97.93 0.0207 -3.8771 Appendix 10 The results of the temperature influence on the BT decomposition in the ZVI/PS/BT system Conditions: CZVI=0.5 g/L, CPS= mM , pH= 4.5, CBT= 0.1 mM The ZVI/PS/BT t [BT] H%) C/C0 ln(C/C0 ο -2 (minute) system, t C changes (10 mM) o t= 25 C o t= 35 C o t= 45 C o t= 55 C 10.0000 0.00 1.0000 0.0000 8.5198 14.80 0.8520 -0.1602 10 7.2918 27.08 0.7292 -0.3158 15 20 6.1987 5.4125 38.01 45.88 0.6199 0.5413 -0.4782 -0.6139 25 4.5970 54.03 0.4597 -0.7772 30 4.1062 58.94 0.4106 -0.8901 10.0045 0.00 1.0000 0.0000 7.2901 27.04 0.7290 -0.3161 10 5.5212 44.70 0.5521 -0.5940 15 20 4.3087 3.4125 56.80 65.74 0.4309 0.3413 -0.8419 -1.0751 25 2.7970 71.89 0.2797 -1.2740 30 2.4262 75.59 0.2426 -1.4162 10.0251 0.00 1.0000 0.0000 6.3657 36.27 0.6366 -0.4517 10 4.4271 55.62 0.4427 -0.8148 15 20 3.2608 2.3844 67.26 76.00 0.3261 0.2384 -1.1206 -1.4336 25 1.8268 81.57 0.1827 -1.7000 30 1.5121 84.71 0.1512 -1.8891 10.0251 0.00 1.0000 0.0000 5.7002 42.91 0.5700 -0.5621 10 3.4502 65.37 0.3450 -1.0642 15 20 2.3014 1.7078 76.83 82.76 0.2301 0.1708 -1.4691 -1.7674 25 1.1390 88.43 0.1139 -2.1724 30 0.8509 91.31 0.0851 -2.4641 10 Appendix 11 The results of the temperature influence on the MO decomposition in the ZVI/PS/MO/UV system Conditions: CZVI=0.5 g/L, CPS= mM , pH= 4.5, CMO= 0.1 mM , I= 785 Lux, λ= 254 nm The ZVI/PS/MO/UV t [MO] H%) C/C0 ln(C/C0 ο -2 (minute) system, t C changes (10 mM) o t= 25 C o t= 35 C o t= 45 C o t= 55 C 10.0000 0.00 1.0000 0.0000 5.2934 47.07 0.5293 -0.6361 10 3.0955 69.05 0.3095 -1.1727 15 20 1.7177 0.9319 82.82 90.68 0.1718 0.0932 -1.7616 -2.3732 25 0.5915 94.08 0.0592 -2.8276 30 0.4108 95.89 0.0411 -3.1921 10.0000 0.00 1.0000 0.0000 4.1906 58.09 0.4191 -0.8697 10 2.1818 78.18 0.2182 -1.5224 15 20 1.1810 0.5561 88.19 94.44 0.1181 0.0556 -2.1363 -2.8894 25 0.3680 96.32 0.0368 -3.3023 30 0.1721 98.28 0.0172 -4.0623 10.0000 0.00 1.0000 0.0000 3.7749 62.25 0.3775 -0.9742 10 1.6715 83.28 0.1672 -1.7889 15 0.7162 92.84 0.0716 -2.6364 20 0.3019 96.98 0.0302 -3.5001 25 0.1152 98.85 0.0115 -4.4637 10.0000 0.00 1.0000 0.0000 2.8427 71.57 0.2843 -1.2578 10 1.1052 88.95 0.1105 -2.2026 15 0.3240 96.76 0.0324 -3.4296 20 0.1309 98.69 0.0131 -4.3357 25 0.0482 99.52 0.0048 -5.3340 11 Appendix 12 The results of the temperature influence on the AY decomposition in the ZVI/PS/AY/UV system Conditions: CZVI=0.5 g/L, CPS= mM , pH= 4.5, CAY= 0.1 mM , I= 785 Lux, λ= 254 nm The ZVI/PS/AY/UV t [AY] H%) C/C0 ln(C/C0) ο -2 (minute) system, t C changes (10 mM) o t= 25 C o t= 35 C o t= 45 C o t= 55 C 10.0000 0.00 1.0000 0.0000 5.7287 42.71 0.5729 -0.5571 10 3.7804 62.20 0.3780 -0.9728 15 20 2.8002 1.9096 72.00 80.90 0.2800 0.1910 -1.2729 -1.6557 25 1.2806 87.19 0.1281 -2.0553 30 0.9014 90.99 0.0901 -2.4064 10.0000 0.00 1.0000 0.0000 4.8319 51.68 0.4832 -0.7273 10 3.1090 68.91 0.3109 -1.1683 15 20 1.9016 1.1232 80.98 88.77 0.1902 0.1123 -1.6599 -2.1864 25 0.7301 92.70 0.0730 -2.6171 30 0.4513 95.49 0.0451 -3.0983 10.0000 0.00 1.0000 0.0000 4.4194 55.81 0.4419 -0.8166 10 2.4124 75.88 0.2412 -1.4220 15 20 1.2012 0.7003 87.99 93.00 0.1201 0.0700 -2.1193 -2.6588 25 0.4047 95.95 0.0405 -3.2072 30 0.2515 97.48 0.0252 -3.6827 10.0000 0.00 1.0000 0.0000 3.5835 64.17 0.3584 -1.0262 10 15 1.4993 0.6725 85.01 93.28 0.1499 0.0673 -1.8976 -2.6993 20 0.3101 96.90 0.0310 -3.4734 12 Appendix 13 The results of the temperature influence on the BT decomposition in the ZVI/PS/BT/UV system Conditions: CZVI= 0.5 g/L, CPS= mM , pH= 4.5, CBT= 0.1 mM, I= 785 Lux λ= 254 nm The ZVI/PS/BT/UV t [BT] H%) C/C0 ln(C/C0 ο -2 system, t C changes (minute) (10 mM) o t= 25 C o t= 35 C o t= 45 C o t= 55 C 10 15 20 25 30 10 15 20 25 30 10 15 20 25 30 10 15 20 25 30 10.0000 7.3145 5.5092 4.1093 3.1068 2.5084 2.0147 10.0000 6.5012 4.1248 2.8376 2.0110 1.4093 1.1232 10.0000 6.1383 3.5142 2.1369 1.2625 0.8186 0.5724 10.0000 5.2372 2.6230 1.2495 0.6902 0.3690 0.2253 13 0.00 26.85 44.91 58.91 68.93 74.92 79.85 0.00 34.92 58.63 71.48 79.73 85.74 88.59 0.00 38.54 64.73 78.47 87.20 91.63 94.09 0.00 47.53 73.62 87.33 92.91 96.12 97.55 1.0000 0.7315 0.5509 0.4109 0.3107 0.2508 0.2015 1.0000 0.6501 0.4125 0.2838 0.2011 0.1409 0.1123 1.0000 0.6138 0.3514 0.2137 0.1263 0.0819 0.0572 1.0000 0.5237 0.2623 0.1250 0.0690 0.0369 0.0225 0.0000 -0.3127 -0.5962 -0.8893 -1.1690 -1.3830 -1.6021 0.0000 -0.4306 -0.8856 -1.2596 -1.6040 -1.9595 -2.1864 0.0000 -0.4880 -1.0458 -1.5432 -2.0695 -2.5027 -2.8605 0.0000 -0.6468 -1.3383 -2.0798 -2.6733 -3.2995 -3.7929 Appendix 14 Results of the MO decomposition in the systems: 1.ZVI/PS/MO, 2.ZVI/PS/MO+ETA, ZVI/PS/MO+BTA, 4.MO Conditions: CZVI= 0.5 g/L, CPS= mM, ο CMO= 0.1mM, CETA=100mM, C BTA= 100 mM, pH= 4.5, t= 25 C Systems ZVI/PS/MO ZVI/PS/MO+ETA ZVI/PS/MO+BTA t (minute) [MO] -2 (10 mM) H%) C/C0 10.0000 0.00 1.0000 0.0000 7.3678 26.32 0.7368 -0.3055 10 5.9465 40.54 0.5946 -0.5198 15 4.7929 52.07 0.4793 -0.7354 20 4.0394 59.61 0.4039 -0.9065 25 3.3372 66.63 0.3337 -1.0975 30 2.6350 73.65 0.2635 -1.3337 10.0000 0.00 1.0000 0.0000 9.4164 5.84 0.9416 -0.0601 10 8.9772 10.23 0.8977 -0.1079 15 8.6835 13.17 0.8684 -0.1412 20 8.5013 14.99 0.8501 -0.1624 25 8.3208 16.79 0.8321 -0.1838 30 8.1023 18.98 0.8102 -0.2104 10.0000 0.00 1.0000 0.0000 8.6260 13.74 0.8626 -0.1478 10 7.7044 22.96 0.7704 -0.2608 15 7.1073 28.93 0.7107 -0.3415 20 6.4091 35.91 0.6409 -0.4449 25 6.1094 38.91 0.6109 -0.4928 30 5.5840 44.16 0.5584 -0.5827 14 ln(C/C0) Appendix 15 Results of the AY decomposition in the systems: 1.ZVI/PS/AY, 2.ZVI/PS/AY+ETA, ZVI/PS/AY+BTA, AY Conditions: CZVI= 0.5 g/L, CPS=1 mM, ο CAY= 0.1 mM, CETA= 100 mM, CBTA=100 mM, pH= 4.5, t= 25 C Systems ZVI/PS/AY ZVI/PS/AY+ETA ZVI/PS/AY+BTA t [AY] (minute) (10-2 mM) H%) C/C0 ln(C/C0) 10.0026 0.00 1.0000 0.0000 8.2461 17.56 0.8244 -0.1931 10 6.7203 32.81 0.6719 -0.3977 15 5.4005 46.01 0.5399 -0.6164 20 4.3404 56.61 0.4339 -0.8349 25 3.4023 65.99 0.3401 -1.0784 30 2.8576 71.43 0.2857 -1.2529 10.0159 0.00 1.0000 0.0000 9.3194 6.83 0.9317 -0.0707 10 8.8779 11.24 0.8876 -0.1193 15 8.5342 14.68 0.8532 -0.1588 20 8.3352 16.67 0.8333 -0.1824 25 8.1966 18.05 0.8195 -0.1991 30 8.0938 19.08 0.8092 -0.2117 10.0170 0.00 1.0000 0.0000 9.0286 9.74 0.9026 -0.1024 10 8.1076 18.95 0.8105 -0.2100 15 7.2499 27.52 0.7248 -0.3219 20 6.6538 33.48 0.6652 -0.4077 25 6.2123 37.89 0.6211 -0.4763 30 5.9100 40.92 0.5908 -0.5262 15 Appendix 16 Results of the BT decomposition in the systems: 1.ZVI/PS/BT, 2.ZVI/PS/BT+ETA, ZVI/PS/BT+BTA, BT Conditions: CZVI= 0.5 g/L, CPS= mM, ο CBT= 0.1 mM, CETA= 100 mM, CBTA=100 mM, pH= 4.5, t= 25 C Systems ZVI/PS/BT ZVI/PS/BT+ETA ZVI/PS/BT+BTA t (minute) [BT] -2 (10 mM) H(%) C/C0 ln(C/C0) 10.0000 0.00 1.0000 0.0000 7.9198 20.80 0.7920 -0.2332 10 6.7175 32.83 0.6718 -0.3979 15 5.6871 43.13 0.5687 -0.5644 20 5.1125 48.88 0.5113 -0.6709 25 4.6970 53.03 0.4697 -0.7557 30 4.3624 56.38 0.4362 -0.8296 10.0000 0.00 1.0000 0.0000 9.3113 6.89 0.9311 -0.0714 10 8.6097 13.90 0.8610 -0.1497 15 7.9772 20.23 0.7977 -0.2260 20 7.4353 25.65 0.7435 -0.2963 25 7.1029 28.97 0.7103 -0.3421 30 6.8691 31.31 0.6869 -0.3756 10.0000 0.00 1.0000 0.0000 8.9541 10.46 0.8954 -0.1105 10 8.2719 17.28 0.8272 -0.1897 15 7.6209 23.79 0.7621 -0.2717 20 7.0922 29.08 0.7092 -0.3436 25 6.6638 33.36 0.6664 -0.4059 30 6.3359 36.64 0.6336 -0.4564 16 Appendix 17 The kinetic equations of the AZOs decomposition in the systems: ZVI/PS/AZOs and ZVI/PS/AZOs/UV Conditions: CZVI= 0.5 g/L , CPS= mM , pH= 4.5, CAZOs= 0.1 mM, I= 785 Lux, λ= 254 nm Systems Kinetics kbk.AZOs Ratio R -1 equations kUV/kwithout UV (minute ) ZVI/PS/MO y=-0.0454x 0.0454 0.9878 ZVI/PS/MO/UV y=-0.1122x 0.1122 0.9925 ZVI/PS/AY y=-0.0419x 0.0419 0.9985 ZVI/PS/AY/UV y=-0.0828x 0.0828 0.9886 ZVI/PS/BT y=-0.0306x 0.0306 0.9977 ZVI/PS/BT/UV y=-0.0558x 0.0558 0.9934 17 2.47 1.97 1.82 Appendix 18 Results of color analysis before and after treatment of textile dyeing wastewater of Duong Noi, La Phu and Van Phuc villages 18 ... of AZOs in 39 systems: ZVI/AZOs, PS/AZOs, ZVI/PS/AZOs and ZVI/AZOs /UV, PS/AZOs /UV, ZVI/PS/AZOs /UV 2.4.2 Survey of factors affecting on the degradation efficiency of 40 AZOs in systems: ZVI/PS/AZOs... %) and ZVI/PS/AZOs /UV (HAZOs .UV %) Table 3.3.Results of effecting of [AZOs] on the decomposition efficiency 68 of AZOs in systems ZVI/PS/AZOs (HAZOs %) and ZVI/PS/AZOs /UV (HAZOs ,UV %) Table 3.4.Results... of 72 AZOs in systems ZVI/PS/AZOs (HAZOs %) and ZVI/PS/AZOs /UV (HAZOs ,UV %) Table 3.5.Results of effecting of temperature on the decomposition efficiency of AZOs in systems ZVI/PS/AZOs (HAZOs