Huang Li, Li Liang, Dong Wenbo, Liu Yan, Hou Huiqi
Department of Environmental Science and Engineering, Fudan University, Shanghai 200433, China.
Environ Sci Technol. 2008 Nov 1;42(21):8070-5. doi: 10.1021/es8008216.
Many advanced oxidation technologies have been developed to remove ammonia in wastewater. All these technologies have one common characteristic, that is, the removal processes involve OH radical (*OH). In this research work, H2O2 was selected as *OH precursor. The removal of ammonia under 253.7 nm irradiation from low-pressure mercury lamp in the presence of H2O2 was studied to investigate the ammonia removal efficiency by *OH. Results show that the *OH, generated by H2O2 photolysis, could oxidize NH3 to NO2- and further to NO3-. Removal efficiencies of ammonia were low and were affected by initial pH value and ammonia concentration. Laser flash photolysis technique with transient absorption spectra of nanosecond was used to investigate the oxidation pathway and kinetics of ammonia oxidation by *OH. Results illustrate that *OH could oxidize NH3 to form *NH2 with a second-order rate constant of (1.0 +/- 0.1) x 10(8) M(-1) s(-1) (20 degrees C). *NH2, the main product of *OH with NH3, would further react with H2O2 to yield *NHOH. Since *NHOH could not stay stable in solution, it would rapidly convert to NH2O2- and consequently NO2- and NO3-. The rate constants for these elementary reactions were also given. The low removal efficiency of ammonia by *OH was mainly due to the slow reaction rate constant
人们已经开发出许多高级氧化技术来去除废水中的氨。所有这些技术都有一个共同的特点,即去除过程都涉及羟基自由基(OH)。在这项研究工作中,选择过氧化氢(H₂O₂)作为OH的前体。研究了在253.7纳米低压汞灯照射下,在H₂O₂存在时氨的去除情况,以研究OH对氨的去除效率。结果表明,H₂O₂光解产生的OH能将NH₃氧化为NO₂⁻,并进一步氧化为NO₃⁻。氨的去除效率较低,且受初始pH值和氨浓度的影响。采用纳秒瞬态吸收光谱的激光闪光光解技术研究了OH氧化氨的途径和动力学。结果表明,OH能将NH₃氧化形成NH₂,二级反应速率常数为(1.0±0.1)×10⁸ M⁻¹ s⁻¹(20℃)。NH₂是OH与NH₃反应的主要产物,它会进一步与H₂O₂反应生成NHOH。由于*NHOH在溶液中不能保持稳定,它会迅速转化为NH₂O₂⁻,进而转化为NO₂⁻和NO₃⁻。还给出了这些基元反应的速率常数。*OH对氨的去除效率较低主要是由于反应速率常数较慢。