Study on activated persulfate by zero valent iron and uv to produce dual oxidation system to degrade some azo dyes in water

4 HOOC-CH 2 -CH 2 -(NH) 2 -COOH HOOC-CH 2 -CH 2 -CH-COOH HOOC-CH 2 -CH 2 -CH 2 -COOHCOOH OH CO 2 NO3H O SO4 HO SO 4 * *;+ * * * * *;+ + + *;+*;+ * * * * * * * * + + 2 2 *;+ * + + + (I) (II) (III) (IV) (V) Figure 3.43. Diagram of the expected BT decomposition mechanism. 118 3.5. Application of the activated persulfate system with UV to treat azo- contaminated wastewater from some textile dye villages. The above research results have shown that: the activated persulfate systems by ZVI with UV to decompose MO, AY and BT have high efficiency, in a short time. This oxidation system was applied to treat textile dye wastewater in traditional villages of Duong Noi, La Phu and Van Phuc. Researching on wastewater treatment of textile dyeing villages focuses only on monitoring the mineralization of organic substances of azo dyes by determining the COD and color index. Basis for calculating the amount of PS and ZVI are added in the wastewater samples: Based on the COD determination of the initial solution of MO 0.1mM is 50 mgO/L. Treating solution of MO 0.1mM on photochemical equipment Fig 2.1 with PS concentration of 1.0 mM and ZVI of 0.5 g/L. Treatment time is 16 minutes, the COD of solution after treatment is 8 mgO/L. Thus, the COD of the initial MO solution decreased by 6.25 times compared to the COD after treatment with time of 16 minutes. Taking the ratio of CODwasterwater/CODMO 0.1mM is the ratio to add the needed amount of PS and ZVI to each specific wastewater. Calculating the needed amount of PS, ZVI for 800 mL of wastewater solutions of all kinds according to Table 3.13: Table 3.13. The needed amount of PS and ZVI to wastewater solutions of the textile dyeing villages Wastewater Duong Noi La Phu Van Phuc CODwasterwater/CODMO 0.1mM 20.4 8.8 58.0 [PS] (mM) 20.0 8.8 58.0 [ZVI] (g/L) 10.0 4.4 29.0 Based on the initial pH measurement results of the wastewater samples from the textile dyeing villages (Table 3.14). It was found that the pH ranges from 6.0 to 8.0. When PS is added to waste water, then the pH is in the range of 4.8 to 5.6. As it is analyzed above, when PS dissolves in water, the pH of the solution will be lower. As such, there is no need to adjust the initial pH of the wastewater and take that pH as an input condition for treatment. The experiments are carried out at room temperature 25  C ± 2. 119 Results of wastewater treatment for textile dyeing villages are shown in Table 3.14: Table 3.14. Results of pre-treatment and post-treatment analysis of textile dye wastewater in villages of Duong Noi, La Phu and Van Phuc [23], [24]. Wastewater Characteristics Unit QCVN40:2011 /BTNMT Pre- treatment Post- treatment A B Duong Noi, after 2h treatment Color Pt/Co 50 150 1860 75 COD mg/L 75 150 1020 130 pH - 6-9 5.5-9 7.9 5,5 TDS mg/L - - 551 28 La Phu, after 1h treatment Color Pt/Co 50 150 395 22 COD mg/l 75 150 440 110 pH - 6-9 5.5-9 7.6 5.0 TDS mg/L - - 462 24.7 Van Phuc, after 3h treatment Color Pt/Co 50 150 5662 55 COD mg/l 75 150 2900 140 pH - 6-9 5.5-9 6.2 4.8 TDS mg/L - - 1317 39.5 Figure 3.44. Decreasing of COD over time of Duong Noi, La Phu and Van Phuc wastewater treatment. 0 500 1000 1500 2000 2500 3000 3500 0 30 60 90 120 150 180 COD (mg/L) t (phút) Dương Nội La Phù Vạn Phúc 120 Pre-treatment Post-treatment after 2 hours Precipitated by PAC Figure 3.45. Photos of Duong Noi wastewater before and after treatment Pre-treatment Post-treatment after 1 hours Precipitated by PAC Figure 3.46. Photos of La Phu wastewater before and after treatment Pre-treatment Post-treatment after 3 hours Precipitated by PAC Figure 3.47. Photos of Van Phuc wastewater before and after treatment. From Table 3.14 and Fig 3.44 to Fig 3.47, the ZVI/PS/Wastewater/UV system has strong oxidation activity. When applying this system treats the textile dyeing wastewater of Duong Noi, Van Phuc and La Phu villages, the mineralization efficiency is as follows: Waste water from Duong Noi village after treatment of COD index decreased by 87.25%, color index decreased from 1860 Pt/Co to 75 Pt/Co after 2 hours of treatment, Appendix 18. 121 Wastewater from La Phu village after treatment of COD index decreased by 75%, color index decreased from 395 Pt/Co to 22 Pt/Co after 1 hour of treatment, Appendix 18. Wastewater from Van Phuc village after treatment of COD index decreased by 95.17%, color index decreased from 5662 Pt/Co to 55 Pt/Co after 3 hours of treatment, Appendix 18. After treatment, wastewater from Duong Noi, La Phu and Van Phuc villages has COD index and color level meeting standard of the B wastewater type according to QCVN 40: 2011/BTNMT. Results of the application of the ZVI/PS/Wastewater/UV systems for textile dyeing wastewater treatment in this study compared with some other results of textile dyeing village wastewater treatment by Fenton- electrochemical, Fenton, methods flocculation - catalyst oxidation in documents [6], [8], [13], this ZVI/PS/Wastewater/UV system gives the best results on COD treatment rate. This proves that the ZVI/PS/Wastewater/UV system has produced free radicals SO4  ,  OH, these free radicals strongly decompose the pigments in wastewater. The above results show that the oxidation system ZVI/PS/Wastewater/UV is a potential system in the application of organic pollutants in water environment. 122 CONCLUSION * The thesis has solved the following issues: 1. Studying on persulfate activation by chemical method was carried out based on the results of comparing the AZOs decomposition efficiency of systems without UV (ZVI/AZOs, PS/AZOs, ZVI/PS/AZOs) and with UV (ZVI/AZOs/UV, PS/AZOs/UV, ZVI/PS/AZOs/UV). Research results have indicated that for activated persulfate systems by ZVI, UV produced a dual oxidation system of free radicals (  OH, SO4  ). These free radicals decompose strongly AZOs in the water samples. Systems of ZVI/PS/AZOs and ZVI/PS/AZOs/UV have the best AZOs decomposition performance: + The ZVI/PS/AZOs system: after reaction time of 30 minutes HMO= 73.65 %; HAY= 71.42 %; HBT= 58.94 %. + The ZVI/PS/AZOs/UV system: after reaction time of 30 minutes HMO,UV= 95.89 %; HAY,UV= 90.99 %; HBT,UV= 79.85 %. 2. Studying the effect factors (ZVI, PS, AZOs, pH and temperature) on the activated persulfate systems by ZVI without UV and with UV (ZVI/PS/AZOs and ZVI/PS/AZOs/UV) was performed in detail. Research results of effect factors have shown optimal conditions to decompose AZOs best in the ZVI/PS/AZOs and ZVI/PS/AZOs/UV systems are: [ZVI]= 0.5 g/L; [PS]= 3.0 mM; [AZOs] = 0.05 mM; pH = 2.54.5; t = 55 C. 3. Studying the AZOs decomposition kinetics in the activated persulfate systems by ZVI without and with UV was carried out. Research results have indicated that the AZOs decomposition in the ZVI/PS/AZOs and ZVI/PS/AZOs/UV systems follows the rules of the pseudo first order reaction kinetics. These are based on the graph ln(C/C0)= f(t) to calculate the pseudo first order rate constants: The ZVI/PS/AZOs system (kMO= 0.0454 minutes -1 ; kAY= 0.0419 minutes -1 ; kBT=0.0306 minutes -1 ) and ZVI/PS/AZOs/UV system (kMO,UV= 0.1122 minutes -1 ; kAY,UV= 0.0828 minutes -1 ; kBT,UV= 0.0558 minutes -1 ). 4. Calculating thermodynamic parameters for the AZOs decomposition reaction in systems includes ZVI/PS/AZOs and ZVI/PS/AZOs/UV according to Arrhenius equation as Ea,MO= 37.413 kJ/mole; Ea,AY= 32.040 kJ/mole; Ea,BT= 28.095 kJ/mole; Ea,MO,UV= 123 18.239 kJ/mole; Ea,AY,UV= 20.288 kJ/mole; Ea,AY,UV= 22.787 kJ/mol. According to Eyring equation, free activation energy as G#MO = 90.705 kJ/mole; G # AY= 90.946 kJ/mole; G#BT= 91.613 kJ/mole; G # MO,UV = 88.574 kJ/mole; G # AY,UV= 89.377 kJ/mole; G#BT,UV= 90.251 kJ/mole. Calculation results and analysis of thermodynamic parameters show that the Eyring model is more suitable than Arrhenius in this study. 5. Studying the qualitative determination of free radicals SO4  ,  OH was based on the difference of the reaction between free radicals SO4  ,  OH with ETA and BTA. The results indicate that there are two free radicals SO4  ,  OH in the ZVI/PS/AZOs system. The mathematical model has been established to determine the concentration of free radicals SO4  ,  OH and the reaction rate constants of reaction between free radicals  OH, SO4  and AZOs (k17(HO,AZOs), k18(SO4,AZOs)) in systems: ZVI/PS/AZOs and ZVI/PS/AZOs/UV. Calculation results are quite consistent with the experimental decomposition efficiency of AZOs and the kinetics model of the pseudo first order reaction. 6. Calculating quantum parameters, molecular structure of MO, AY and BT by HyperChem software. It is based on the characteristics of AZOs molecular structure and free radicals SO4  ,  OH, which has proposed the mechanism of the AZOs mineralization decomposition of MO, AY and BT according to the five stages in systems: ZVI/PS/AZOs and ZVI/PS/AZOs/UV. 7. Application of the activated persulfate system by ZVI with UV (ZVI/PS/wastewater/UV) to treat textile dyeing wastewater of La Phu, Duong Noi and Van Phuc villages through COD and color reduction was carried out. The COD results are quite good compared to previous studies. * New contributions of the thesis: 1. The thesis has built method of activating persulfate by zero valent iron powder combined with UV to decompose some azo dyes MO, AY and BT in water. 2. The thesis has provided a pseudo first order reaction kinetic model and calculated some thermodynamic parameters of the AZOs decomposition in the ZVI/PS/AZOs and ZVI/PS/AZOs/UV systems. 124 * Further research directions: 1. Study and experiment with other methods to determine free radicals  OH, SO4  to compare with the quantitative mathematical models as presented in this thesis. 2. Study to clarify intermediate products during the AZOs mineralization process of AZOs reacting with free radicals  OH, SO4  . From that results to build a suitable decomposition mechanism of reaction AZOs with  OH, SO4  is more explicit. 3. Study to compare the AZOs decomposition efficiency by AOPs based persulfate with other AOPs such as: Fenton, Fenton/UV, O3/UV... From that researches to evaluate the economic efficiency and to apply for the actual treatment of organic waste water in general and the pollution of azo dyes in particular. 125 LIST OF PUBLISHED SCIENTIFIC WORKS 1. Nguyen Thanh Binh, Do Ngoc Khue, Tran Van Chung (2017),"Persulfate activation by zero valent iron to decomposing methyl orange in water" Vietnam Journal of Catalysis and Adsorption, Vol.6, No. 1, pp.73-78. 2. Nguyen Thanh Binh, Do Ngoc Khue, Tran Van Chung, Dao Duy Hung, Vu Quang Bach (2017), "Studying degradation of methyl orange contaminated by radicals SO4  and  OH," in Analytica Vietnam Conference, 5th, March, Hanoi, 2017, pp. 182-189. 3. Nguyen Thanh Binh, Do Ngoc Khue, Tran Van Chung (2017), "A novel study on degradation of methyl orange by dual oxidation system," International Jounral of Development Research, Vol. 07, No. 05, pp. 12896-12900. 4. Nguyen Thanh Hoa, Nguyen Thanh Binh, Do Ngoc Khue, Vu Duc Loi (2018), "Application of BoX-Behnken designs in parameters optimization of AOPs combined persulfate and H2O2 activated by Fe 0 under UV light for treating dye waste water” Reports at the National Conference on High Technology Application in practice 2018, Journal of Military Science and Technology, 8 th August 2018, Hanoi. 5. Nguyen Thanh Binh, Do Ngoc Khue, Tran Van Chung, Nguyen Thanh Hoa, Doang Song Quang (2019), "Kinetic modeling of degradation for alizarin yellow R by the activated persulfate by FeO (ZVI) under UV light", Vietnam Journal of Chemistry, Vol. 57, No. 1, pp. 46-51. 6. 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Reactive Red 120. Dyes pigments 60, pp. 1-7. 89 Zongping Wang, Miaomiao Xue, Kai Huang and Zizheng Liu (2011). Textile Dyeing Wastewater Treatmen. Huazhong University of Science and Technology China. 90 Zheng H. Lin; S. M. Lin, Henry J. Eyring; (1980), Basic Chemical Kinetics, John Wiley & Sons Inc., USA. 1 APPENDIX Appendix 1. List of carcinogenic amines follow Technischen Regeln für Gefahrstoffe 905 (TRGS 905) [59] Name’s Amin CAS numbers TRGS905 (a-b) 67/548/EEC 4-Amino biphenyl [92-67-1] Carc. Cat. 1 Benzidine [92-87-5] Carc. Cat. 1 4-Chloro-o-toluidine [95-69-2] Carc. Cat. 1 2-Naphthylamine [91-59-8] Carc. Cat. 1 o-Aminoazotoluene [97-56-3] Carc. Cat. 2 5-Nitro- o-toluidine [99-55-8] Carc. Cat. 3 p-Chloroaniline [106-47-8] Carc. Cat. 2 4-Methoxy-m phenylenediamine [615-05-4] Carc. Cat. 2 4,4 -Diaminodiphenylmethane [101-77-9] Carc. Cat. 2 3,3 -Dichlorobenzidine [91-94-1] Carc. Cat. 2 3,3 -Dimethoxybenzidine [119-90-4] Carc. Cat. 2 3,3 -Dimethylbenzidine [119-93-7] Carc. Cat. 2 4,4 -Methylendi-o-toluidine [838-88-0] Carc. Cat. 2 6-Methoxy-m-toluidine [120-71-8] Gef StV 4,4 -Methylenebis(-2- chloroaniline) [101-14-4] Carc. Cat. 2 4,4 -Oxydianiline [101-80-4] Carc. Cat. 2 4,4 –Thiodianiline [139-65-1] Carc. Cat. 2 o-Toluidine [95-53-4] Carc. Cat. 2 4-Methyl-m-phenylendiamine [95-80-7] Carc. Cat. 2 2,4,5-Trimethylaniline [137-17-7] Carc. Cat. 2 o-Anisidine [c] [90-04-0] Carc. Cat. 2 4-Aminoazobenzene 60-09-3 Carc. Cat. 2 4-Amino-3-fluorophenol [d] 399-95-1 Carc. Cat. 2 6-Amino-2-ethoxynaphthalene [d] GefStV [a] Technische Regeln für Gefahrstoffe (German Technical Law on hazardous substances). [b] TRGS 905 List only substances that do not correspond according to other provisions of law. [c] Azo dyes are prohibited dyeing on carpets. [d] Azo dyes are decomposed amines those suspected carcinogens 2 Appendix 2. Results of the MO decomposition in the systems: 1.ZVI/MO, 2.PS/MO and 3.ZVI/PS/MO. Systems t (minute) [MO] (10 -2 mM) H (%) C/C0 ln(C/C0) 1. ZVI/MO (Conditions: CZVI = 0.5 g/L, CMO= 0.1 mM, pH= 4.5, t= 25  C) 0 10.0000 0.00 1.0000 0.0000 5 9.9750 0.25 0.9975 -0.0025 10 9.9508 0.49 0.9951 -0.0049 15 9.9210 0.79 0.9921 -0.0079 20 9.8986 1.01 0.9899 -0.0102 25 9.8810 1.20 0.9880 -0.0121 30 9.8641 1.36 0.9864 -0.0137 2. PS/MO (Conditions: CPS= 1 mM, CMO= 0.1 mM, pH= 4.5, t= 25  C) 0 10.0000 0.00 1.0000 0.0000 5 9.6115 3.89 0.9612 -0.0396 10 9.3758 6.24 0.9376 -0.0645 15 9.0500 9.50 0.9050 -0.0998 20 8.8312 11.69 0.8831 -0.1243 25 8.4517 15.48 0.8452 -0.1682 30 8.1950 18.05 0.8195 -0.1991 3. ZVI/PS/MO (Conditions: CZVI = 0.5 g/L, CPS= 1 mM, CMO= 0.1 mM, pH= 4.5, t= 25  C) 0 10.0000 0.00 1.0000 0.0000 5 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 3 Appendix 3. Results of the AY decomposition in the systems: 1.ZVI/AY, 2.PS/AY and 3.ZVI/PS/AY. Systems t (minute) [AY] (10 -2 mM) H (%) C/C0 ln(C/C0) 1. ZVI/AY (Conditions: CZVI = 0.5g/L,CAY=0.1mM, pH= 4.5, t=25  C) 0 10.0000 0.00 1.0000 0.0000 5 9.9626 0.37 0.9963 -0.0037 10 9.9563 0.44 0.9956 -0.0044 15 9.8622 1.41 0.9862 -0.0139 20 9.8121 1.88 0.9812 -0.0190 25 9.7910 2.09 0.9791 -0.0211 30 9.7611 2.39 0.9761 -0.0242 2. PS/AY (Conditions: CPS= 1 mM, CAY= 0.1 mM, pH= 4.5, t= 25  C) 0 10.0000 0.00 1.0000 0.0000 5 9.7721 2.28 0.9772 -0.0231 10 9.4770 5.23 0.9477 -0.0537 15 9.1551 8.45 0.9155 -0.0883 20 8.7524 12.48 0.8752 -0.1333 25 8.4193 15.81 0.8419 -0.1721 30 8.0123 19.88 0.8012 -0.2216 3. ZVI/PS/AY (Conditions: CZVI = 0.5 g/L, CPS= 1 mM, CAY= 0.1 mM, pH= 4.5, t= 25 C) 0 10.0000 0.00 1.0000 0.0000 5 8.2461 17.54 0.8246 -0.1929 10 6.7203 32.80 0.6720 -0.3974 15 5.4005 46.00 0.5401 -0.6161 20 4.3404 56.60 0.4340 -0.8346 25 3.4023 65.98 0.3402 -1.0781 30 2.8576 71.42 0.2858 -1.2526 4 Appendix 4. Results of the BT decomposition in the systems: 1.ZVI/BT, 2.PS/BT and 3.ZVI/PS/BT. Systems t (minute) [BT] (10 -2 mM) H%) C/C0 ln(C/C0) 1. ZVI/BT (Conditions: CZVI= 0.5g/L,CBT= 0.1 mM, pH= 4.5, t= 25 C) 0 10.0000 0.00 1.0000 0.0000 5 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 2. PS/BT (Conditions: CPS= 1 mM, CBT= 0.1 mM, pH= 4.5, t= 25  C) 0 10.0000 0.00 1.0000 0.0000 5 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 3. ZVI/PS/BT (Conditions: CZVI= 0.5 g/L, CPS= 1 mM, CBT= 0.1 mM, pH= 4.5, t= 25 C) 0 10.0000 0.00 1.0000 0.0000 5 8.5198 14.80 0.8520 -0.1602 10 7.2918 27.08 0.7292 -0.3158 15 6.1987 38.01 0.6199 -0.4782 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 5 Appendix 5. Results of the MO decomposition in the systems 1. ZVI/MO/UV, 2. PS/MO/UV and 3. ZVI/PS/MO/UV. Systems t (minute) [MO] (10 -2 mM) H%) C/C0 ln(C/C0) 1. ZVI/MO/UV (Conditions: CZVI = 0.5 g/L, CMO= 0.1 mM, pH= 4.5, t= 25  C. I= 785 Lux. = 254 nm) 0 10.0000 0.00 1.0000 0.0000 5 9.7550 2.45 0.9755 -0.0248 10 9.4508 5.49 0.9451 -0.0565 15 9.1701 8.30 0.9170 -0.0866 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 2. PS/MO/UV (Conditions: CPS= 1 mM, CMO= 0.1 mM, pH= 4.5, t= 25  C. I= 785 Lux. = 254 nm) 0 10.0000 0.00 1.0000 0.0000 5 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 3. ZVI/PS/MO/UV (Conditions: CZVI = 0.5 g/L, CPS= 1 mM, CMO= 0.1 mM, pH= 4.5, t= 25  C. I= 785Lux. = 254 nm) 0 10.0000 0.00 1.0000 0.0000 5 5.2934 47.07 0.5293 -0.6361 10 3.0955 69.05 0.3095 -1.1727 15 1.7177 82.82 0.1718 -1.7616 20 0.9319 90.68 0.0932 -2.3732 25 0.5915 94.08 0.0592 -2.8276 30 0.4108 95.89 0.0411 -3.1921 6 Appendix 6. Results of the AY decomposition in the systems: 1. ZVI/AY/UV, 2.PS/AY/UV and 3.ZVI/PS/AY/UV. Systems t (minute) [AY] (10 -2 mM) H%) C/C0 ln(C/C0) 1. ZVI/AY/UV (Conditions: CZVI = 0.5 g/L, CAY= 0.1 mM, pH= 4.5, t= 25  C, I= 785 Lux, = 254 nm) 0 10.0000 0.00 1.0000 0.0000 5 9.6780 3.22 0.9678 -0.0327 10 9.4410 5.59 0.9441 -0.0575 15 9.2850 7.15 0.9285 -0.0742 20 9.1704 8.30 0.9170 -0.0866 25 9.0704 9.30 0.9070 -0.0976 30 8.9026 10.97 0.8903 -0.1162 2. PS/AY/UV (Conditions: CPS= 1 mM, CAY= 0.1 mM, pH= 4.5, t= 25  C, I= 785 Lux, = 254 nm) 0 10.0000 0.00 1.0000 0.0000 5 7.8143 21.86 0.7814 -0.2466 10 6.3697 36.30 0.6370 -0.4510 15 5.3262 46.74 0.5326 -0.6299 20 4.4980 55.02 0.4498 -0.7990 25 3.8055 61.95 0.3805 -0.9661 30 3.0546 69.45 0.3055 -1.1859 3. ZVI/PS/AY/UV (Conditions: CZVI=0.5 g/L, CPS= 1 mM, CAY= 0.1 mM, pH= 4.5, t= 25  C, I= 785Lux, = 254 nm) 0 10.0000 0.00 1.0000 0.0000 5 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 7 Appendix 7. Results of the BT decomposition in the systems: 1.ZVI/BT/UV, 2.PS/BT/UV and 3.ZVI/PS/BT/UV. Systems t (minute) [BT] (10 -2 mM) H%) C/C0 ln(C/C) 1. ZVI/BT/UV (Conditions: CZVI = 0.5 g/L, CBT= 0.1 mM, pH= 4.5, t= 25 C, I= 785 Lux, = 254 nm) 0 10.0000 0.00 1.0000 0.0000 5 9.7240 2.76 0.9724 -0.0280 10 9.5448 4.55 0.9545 -0.0466 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 2. PS/BT/UV (Conditions: CPS= 1 mM, CBT= 0.1 mM, pH= 4.5, t= 25  C, I= 785 Lux, = 254nm) 0 10.0000 0.00 1.0000 0.0000 5 8.3993 16.01 0.8399 -0.1744 10 7.4015 25.99 0.7401 -0.3009 15 6.7067 32.93 0.6707 -0.3995 20 6.1721 38.28 0.6172 -0.4825 25 5.7084 42.92 0.5708 -0.5607 30 5.4093 45.91 0.5409 -0.6145 3. ZVI/PS/BT/UV (Conditions: CZVI = 0.5 g/L, CPS= 1 mM, CBT= 0.1 mM, pH= 4.5, t= 25  C, I=785 Lux, = 254 nm) 0 10.0000 0.00 1.0000 0.0000 5 7.3145 26.85 0.7315 -0.3127 10 5.5092 44.91 0.5509 -0.5962 15 4.1093 58.91 0.4109 -0.8893 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 8 Appendix 8. 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 system, t  C changes t (minute) [MO] (10 -2 mM) H%) C/C0 ln(C/C0 1. t= 25  C 0 10.0000 0.00 1.0000 0.0000 5 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 2. t= 35  C 0 10.0000 0.00 1.0000 0.0000 5 6.5715 34.29 0.6572 -0.4198 10 4.1823 58.18 0.4182 -0.8717 15 2.7952 72.05 0.2795 -1.2747 20 1.9561 80.44 0.1956 -1.6316 25 1.4168 85.83 0.1417 -1.9542 30 1.0921 89.08 0.1092 -2.2145 3. t= 45 C 0 10.0000 0.00 1.0000 0.0000 5 4.6739 53.26 0.4674 -0.7606 10 2.5746 74.25 0.2575 -1.3569 15 1.5141 84.86 0.1514 -1.8878 20 0.7595 92.41 0.0759 -2.5777 25 0.4057 95.94 0.0406 -3.2047 30 0.2053 97.95 0.0205 -3.8858 4. t= 55  C 0 10.0000 0.00 1.0000 0.0000 5 3.8171 61.83 0.3817 -0.9631 10 1.5980 84.02 0.1598 -1.8338 15 0.6624 93.38 0.0662 -2.7145 20 0.2585 97.41 0.0259 -3.6554 25 0.1025 98.98 0.0102 -4.5806 30 0.0622 99.38 0.0062 -5.0805 9 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= 1 mM , pH= 4.5, CAY= 0.1 mM The ZVI/PS/AY system. t  C changes t (minute) [AY] (10 -2 mM) H%) C/C0 ln(C/C0 1. t= 25 o C 0 10.0000 0.00 1.0000 0.0000 5 8.2461 17.54 0.8246 -0.1929 10 6.7203 32.80 0.6720 -0.3974 15 5.4005 46.00 0.5401 -0.6161 20 4.3404 56.60 0.4340 -0.8346 25 3.4023 65.98 0.3402 -1.0781 30 2.8576 71.42 0.2858 -1.2526 2. t= 35 o C 0 10.0000 0.00 1.0000 0.0000 5 6.9319 30.68 0.6932 -0.3665 10 4.8097 51.90 0.4810 -0.7320 15 3.3946 66.05 0.3395 -1.0804 20 2.3723 76.28 0.2372 -1.4387 25 1.9013 80.99 0.1901 -1.6601 30 1.6205 83.80 0.1620 -1.8199 3. t= 45 o C 0 10.0000 0.00 1.0000 0.0000 5 5.5815 44.19 0.5582 -0.5831 10 3.2440 67.56 0.3244 -1.1258 15 1.9821 80.18 0.1982 -1.6184 20 1.2028 87.97 0.1203 -2.1179 25 0.8534 91.47 0.0853 -2.4611 30 0.7154 92.85 0.0715 -2.6375 4. t= 55 o C 0 10.0000 0.00 1.0000 0.0000 5 4.1482 58.52 0.4148 -0.8799 10 2.0901 79.10 0.2090 -1.5654 15 1.1725 88.27 0.1173 -2.1434 20 0.5901 94.10 0.0590 -2.8300 25 0.3192 96.81 0.0319 -3.4444 30 0.2071 97.93 0.0207 -3.8771 10 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= 1 mM , pH= 4.5, CBT= 0.1 mM. The ZVI/PS/BT system, t  C changes t (minute) [BT] (10 -2 mM) H%) C/C0 ln(C/C0 1. t= 25 o C 0 10.0000 0.00 1.0000 0.0000 5 8.5198 14.80 0.8520 -0.1602 10 7.2918 27.08 0.7292 -0.3158 15 6.1987 38.01 0.6199 -0.4782 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 2. t= 35 o C 0 10.0045 0.00 1.0000 0.0000 5 7.2901 27.04 0.7290 -0.3161 10 5.5212 44.70 0.5521 -0.5940 15 4.3087 56.80 0.4309 -0.8419 20 3.4125 65.74 0.3413 -1.0751 25 2.7970 71.89 0.2797 -1.2740 30 2.4262 75.59 0.2426 -1.4162 3. t= 45 o C 0 10.0251 0.00 1.0000 0.0000 5 6.3657 36.27 0.6366 -0.4517 10 4.4271 55.62 0.4427 -0.8148 15 3.2608 67.26 0.3261 -1.1206 20 2.3844 76.00 0.2384 -1.4336 25 1.8268 81.57 0.1827 -1.7000 30 1.5121 84.71 0.1512 -1.8891 4. t= 55 o C 0 10.0251 0.00 1.0000 0.0000 5 5.7002 42.91 0.5700 -0.5621 10 3.4502 65.37 0.3450 -1.0642 15 2.3014 76.83 0.2301 -1.4691 20 1.7078 82.76 0.1708 -1.7674 25 1.1390 88.43 0.1139 -2.1724 30 0.8509 91.31 0.0851 -2.4641 11 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= 1 mM , pH= 4.5, CMO= 0.1 mM , I= 785 Lux, = 254 nm. The ZVI/PS/MO/UV system, t  C changes t (minute) [MO] (10 -2 mM) H%) C/C0 ln(C/C0 1. t= 25 o C 0 10.0000 0.00 1.0000 0.0000 5 5.2934 47.07 0.5293 -0.6361 10 3.0955 69.05 0.3095 -1.1727 15 1.7177 82.82 0.1718 -1.7616 20 0.9319 90.68 0.0932 -2.3732 25 0.5915 94.08 0.0592 -2.8276 30 0.4108 95.89 0.0411 -3.1921 2. t= 35 o C 0 10.0000 0.00 1.0000 0.0000 5 4.1906 58.09 0.4191 -0.8697 10 2.1818 78.18 0.2182 -1.5224 15 1.1810 88.19 0.1181 -2.1363 20 0.5561 94.44 0.0556 -2.8894 25 0.3680 96.32 0.0368 -3.3023 30 0.1721 98.28 0.0172 -4.0623 3. t= 45 o C 0 10.0000 0.00 1.0000 0.0000 5 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 4. t= 55 o C 0 10.0000 0.00 1.0000 0.0000 5 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 12 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= 1 mM , pH= 4.5, CAY= 0.1 mM , I= 785 Lux, = 254 nm. The ZVI/PS/AY/UV system, t  C changes t (minute) [AY] (10 -2 mM) H%) C/C0 ln(C/C0) 1. t= 25 o C 0 10.0000 0.00 1.0000 0.0000 5 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 2. t= 35 o C 0 10.0000 0.00 1.0000 0.0000 5 4.8319 51.68 0.4832 -0.7273 10 3.1090 68.91 0.3109 -1.1683 15 1.9016 80.98 0.1902 -1.6599 20 1.1232 88.77 0.1123 -2.1864 25 0.7301 92.70 0.0730 -2.6171 30 0.4513 95.49 0.0451 -3.0983 3. t= 45 o C 0 10.0000 0.00 1.0000 0.0000 5 4.4194 55.81 0.4419 -0.8166 10 2.4124 75.88 0.2412 -1.4220 15 1.2012 87.99 0.1201 -2.1193 20 0.7003 93.00 0.0700 -2.6588 25 0.4047 95.95 0.0405 -3.2072 30 0.2515 97.48 0.0252 -3.6827 4. t= 55 o C 0 10.0000 0.00 1.0000 0.0000 5 3.5835 64.17 0.3584 -1.0262 10 1.4993 85.01 0.1499 -1.8976 15 0.6725 93.28 0.0673 -2.6993 20 0.3101 96.90 0.0310 -3.4734 13 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= 1 mM , pH= 4.5, CBT= 0.1 mM, I= 785 Lux. = 254 nm The ZVI/PS/BT/UV system, t  C changes t (minute) [BT] (10 -2 mM) H%) C/C0 ln(C/C0 1. t= 25 o C 0 10.0000 0.00 1.0000 0.0000 5 7.3145 26.85 0.7315 -0.3127 10 5.5092 44.91 0.5509 -0.5962 15 4.1093 58.91 0.4109 -0.8893 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 2. t= 35 o C 0 10.0000 0.00 1.0000 0.0000 5 6.5012 34.92 0.6501 -0.4306 10 4.1248 58.63 0.4125 -0.8856 15 2.8376 71.48 0.2838 -1.2596 20 2.0110 79.73 0.2011 -1.6040 25 1.4093 85.74 0.1409 -1.9595 30 1.1232 88.59 0.1123 -2.1864 3. t= 45 o C 0 10.0000 0.00 1.0000 0.0000 5 6.1383 38.54 0.6138 -0.4880 10 3.5142 64.73 0.3514 -1.0458 15 2.1369 78.47 0.2137 -1.5432 20 1.2625 87.20 0.1263 -2.0695 25 0.8186 91.63 0.0819 -2.5027 30 0.5724 94.09 0.0572 -2.8605 4. t= 55 o C 0 10.0000 0.00 1.0000 0.0000 5 5.2372 47.53 0.5237 -0.6468 10 2.6230 73.62 0.2623 -1.3383 15 1.2495 87.33 0.1250 -2.0798 20 0.6902 92.91 0.0690 -2.6733 25 0.3690 96.12 0.0369 -3.2995 30 0.2253 97.55 0.0225 -3.7929 14 Appendix 14. Results of the MO decomposition in the systems: 1.ZVI/PS/MO, 2.ZVI/PS/MO+ETA, 3. ZVI/PS/MO+BTA, 4.MO. Conditions: CZVI= 0.5 g/L, CPS= 1 mM, CMO= 0.1mM, CETA=100mM, CBTA= 100 mM, pH= 4.5, t= 25  C. Systems t (minute) [MO] (10 -2 mM) H%) C/C0 ln(C/C0) 1. ZVI/PS/MO 0 10.0000 0.00 1.0000 0.0000 5 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 2. ZVI/PS/MO+ETA 0 10.0000 0.00 1.0000 0.0000 5 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 3. ZVI/PS/MO+BTA 0 10.0000 0.00 1.0000 0.0000 5 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 15 Appendix 15. Results of the AY decomposition in the systems: 1.ZVI/PS/AY, 2.ZVI/PS/AY+ETA, 3. ZVI/PS/AY+BTA, 4. AY. Conditions: CZVI= 0.5 g/L, CPS=1 mM, CAY= 0.1 mM, CETA= 100 mM, CBTA=100 mM, pH= 4.5, t= 25  C. Systems t (minute) [AY] (10 -2 mM) H%) C/C0 ln(C/C0) 1. ZVI/PS/AY 0 10.0026 0.00 1.0000 0.0000 5 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 2. ZVI/PS/AY+ETA 0 10.0159 0.00 1.0000 0.0000 5 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 3. ZVI/PS/AY+BTA 0 10.0170 0.00 1.0000 0.0000 5 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 16 Appendix 16. Results of the BT decomposition in the systems: 1.ZVI/PS/BT, 2.ZVI/PS/BT+ETA, 3. ZVI/PS/BT+BTA, 4. BT. Conditions: CZVI= 0.5 g/L, CPS= 1 mM, CBT= 0.1 mM, CETA= 100 mM, CBTA=100 mM, pH= 4.5, t= 25  C. Systems t (minute) [BT] (10 -2 mM) H(%) C/C0 ln(C/C0) 1. ZVI/PS/BT 0 10.0000 0.00 1.0000 0.0000 5 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 2. ZVI/PS/BT+ETA 0 10.0000 0.00 1.0000 0.0000 5 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 3. ZVI/PS/BT+BTA 0 10.0000 0.00 1.0000 0.0000 5 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 17 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= 1 mM , pH= 4.5, CAZOs= 0.1 mM, I= 785 Lux, = 254 nm. Systems Kinetics equations kbk.AZOs (minute -1 ) R 2 Ratio kUV/kwithout UV 1. ZVI/PS/MO y=-0.0454x 0.0454 0.9878 2.47 2. ZVI/PS/MO/UV y=-0.1122x 0.1122 0.9925 3. ZVI/PS/AY y=-0.0419x 0.0419 0.9985 1.97 4. ZVI/PS/AY/UV y=-0.0828x 0.0828 0.9886 5. ZVI/PS/BT y=-0.0306x 0.0306 0.9977 1.82 6. ZVI/PS/BT/UV y=-0.0558x 0.0558 0.9934 18 Appendix 18. Results of color analysis before and after treatment of textile dyeing wastewater of Duong Noi, La Phu and Van Phuc villages