QD438 : Application of hybrid advanced oxidation method in the presence of nano-catalysts for photocatalytic degradation of some water-soluble agricultural pesticides
Thesis > Central Library of Shahrood University > Chemistry > PhD > 2023
Authors:
[Author], Ghadamali Bagherian Dehaghi[Supervisor], [Advisor]
Abstarct: In this study, the advanced hybrid oxidation process, the simultaneous action and synergistic effect of powerful and effective oxidants of peridate, persulfate and non-toxic and effective nanocatalysts of titanium dioxide (TiO2) and bi- and tri-mextallic spinels of ferrite oxide (Fe3O4, CuFe2O4, ZnFe2O4 and ZnCuFeO4) were used in the presence of different radiation sources of sunlight, visible, and ultraviolet ligthes (UV-A and UV-C) for degradation and mineralizing paraquat and pirimicarb as dangerous, long-lasting and high-consumption toxins. In each section, the radiation source was used baxsed on how to activate the oxidants, the band gap of the nanoparticles, and the least amount of electrical energy consumed. The effective factors in the advanced oxidation process on the degradation efficiency of the pollutants (paraquat and pirimicarb), such as the power and wavelength of the radiation source, the irradiation time, temperature, the initial concentration of pollutant solution, the initial pH of solution, the concentration of oxidants and catalystes, the mineralization, the electrical energy consumption and the degradation process kinetics were investigated. Also, the effect of the effective variables on the degradation process was optimized and modeled using experiment design using central compound design (CCD) of response surface methodology (RSM). UV-Vis spectrophotometer was used to determine the pollutants concentration and the calculation of degradation efficiency. Total organic carbon analysis (TOC) was used to determine the amount of pollutant mineralization. In the first section of this research, the UV-C radiation was used to activate TiO2 nanoparticles and peridate and persulfate oxidants for degradation and mineralization of 400 mL of 30 mg L-1 paraquat. The experiment design software suggested quadratic model for both UV-C ligth/TiO2 nanoparticles/periodate and UV-C ligth/TiO2 nanoparticles/persulfate hybrid oxidation process. In the first process, the optimal values of the concentration of periodate, the concentration of TiO2 nanoparticles and, initial pH of paraquat solution, were obtained 90 mg L-1, 125 mg L-1 and 6.5 at 25 °C and during of 40 min. In these optimum conditions, its experimental value of the degradation and its mineralization amount were equal 90 % and about 55%, respectively. In the second process, the optimal amounts of the concentration of persulfate, TiO2 nanoparticles and the initial pH of the paraquat solution were obtained equal to 400 mg L-1, 150 mg L-1 and 6.3 at 25 °C and during of 40 min. In these conditions, the experimental value of the degradation and mineralization were equal to 77 % and 32%, respectively. The kinetics of the paraquat degradation reaction for both processes during of 30 min followed pseudo-first order and the rate constant values for both processes were 0.0542 and 0.0445 min-1, respectively. Also, the electrical energy for these processes during of 60 min was about 266 and 324 kWh m-3 were consumed. In the second section of this research, the UV-C radiation was used to activate TiO2 nanoparticles and the oxidants of peridate and persulfate for the degradation and mineralization of 400 mL of 30 mg L-1 pirimicarb solution. The experiment design software suggested a quadratic model for the hybrid oxidation processes of peridate/TiO2 nanoparticles/UV-C ligth and persulfate/TiO2 nanoparticles/UV-C ligth. According to these models, in the first process, the optimal amounts of peridote, nanoparticles and the initial pH of the pirimicarb solution were obtained 30 mg L-1, 74 mg L-1 and 6.5, respectively. In these optimum conditions, the experimental value of the degradation efficiency was 85% at 25 °C and during 10 min and the mineralization efficiency was a bout 46 % during 60 min. In the second process, the initial optimum values of persulfate, TiO2 nanoparticles and the initial pH of the pirimicarb solution were equal to 30 mg L-1, 79 mg L-1 and 8, , respectively. In this optimum condition, the experimental value of the degradation efficiency of pirimicarb was 86% at 25 °C and during 10 min and the mineralization efficiency was a bout 35 % during 60 min. The reaction kinetics of the pirimicarb degradation for both processes during the time 30 min followed pseudo-first order and rate constant values for both processes were obtained 0.1365 and 0.1152 min-1, respectively. Also, the electrical energy was consumed about 125 and 106 kWh m-3 for these processes during 60 min, respectively. In the third section of this research, the first, Fe3O4, ZnFe2O4, CuFe2O4 and ZnCuFeO4 nanoparticles were synthesized. Then, their activation method was investigated. UV-C radiation was used for the activation of CuFe2O4 and ZnCuFeO4 nanoparticles and peridate oxidant. While, visible ligth and sunlight were used as the main source of radiation for the activation of Fe3O4 and ZnFe2O4 nanoparticles and persulfate oxidant. Finally, the hybrid advanced oxidation process of persulfate/ZnFe2O4 nanoparticles/visible ligth was selected for the degradation and mineralization of 400 mL of 30 mg L-1 paraquat and the factors affecting it were optimized. The experimental design software suggested a second-order model for this process. According to this model, the optimal amounts of persulfate, ZnFe2O4 nanoparticles and the initial pH of the paraquat solution were equal to 537 mg L-1, 501 mg L-1 and 6.8 at the temperature 25 °C and during the time of 4 hours. In this optimized condition, the experimental value of the degradation efficiency of paraquat was obtained 64% and the amount of its mineralization was about 63%. Tthe kinetics of its degradation reaction followed pseudo-first order and the rate constant value was 0.2378 h-1, which, the electrical energy for this process wae consumed about 60.55 kWh m-3 during 60 min.
Keywords:
#Hybrid advanced oxidation processes #Nanophotocatalyst #oxidant #Degradation and mineralization of agricultural toxins #Optimization #Experimental design using central composite method. Keeping place: Central Library of Shahrood University
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