촉매성 산화물 전극에 의한 암모니아의 전기 화학적 분해 특성

Electrochemical Decomposition Characteristics of Ammonia by the Catalytic Oxide Electrodes

  • 투고 : 2004.06.23
  • 심사 : 2004.11.19
  • 발행 : 2005.02.28

초록

본 연구에서는 전기화학적 방법에 의한 암모니아의 질소화 분해 특성을 파악하기 위하여 여러 암모니아 전해 실험 변수에 대하여 조사하였다. $IrO_2$, $RuO_2$, Pt 양극에서 암모니아의 분해에 대한 pH 및 염소 이온의 영향이 상호 비교되었으며, 전해 반응기에서의 분리막의 존재 유무, 전류밀도, 암모니아 초기 농도 등의 변화에 따른 암모니아의 전기화학적 분해 특성이 조사되었다. 산성이나 알칼리 조건에서 암모니아의 분해에 대한 전극의 성능은 전체적으로 $RuO_2{\approx}IrO_2>Pt$ 순으로 나타났다. 암모니아의 분해는 전극에 공급되는 전류 밀도가 $80mA/cm^2$에서 가장 높았으며 그 이상의 전류 밀도에서는 산소발생에 의해 암모니아의 전극 흡착이 영향을 받아 오히려 감소되었다. 암모니아 용액에 존재하는 염소 이온의 농도가 증가할수록 암모니아의 분해는 증가하나 10 g/l 이상에서는 분해율 증가가 크게 둔화되었다. pH 7의 전해 반응의 경우 전극 표면에서 OH 라디칼이 생성되어 암모늄 이온의 분해가 이루어지는데, 이 OH 라디칼은 $RuO_2$ 전극에서 가장 많이 생성이 되었다.

In order to know the electrochemical decomposition characteristics of ammonia to nitrogen, this work has studied several experimental variables on the electrolytic ammonia decomposition. The effects of pH and chloride ion at $IrO_2$, $RuO_2$, and Pt anodes on the electrolytic decomposition of ammonia were compared, and the existence of membrane equipped in the cell and the changes of the current density, the initial ammonia concentration and so on were investigated on the decomposition. The performances of the electrode were totally in order of $RuO_2{\approx}IrO_2>Pt$ in the both of acid and alkali conditions, and the ammonia decomposition was the highest at a current density of $80mA/cm^2$, over which it decreased, because the adsorption of ammonia on the electrode surface was hindered due to the evolution of oxygen. The ammonia decomposition increased with the concentration of chloride ion in the solution. However, the increase became much dull over 10 g/l of chloride ion. The $RuO_2$ electrode among the tested electrodes generated the most OH radicals which could oxidized the ammonium ion at pH 7.

키워드

참고문헌

  1. Feng, C., Sugiura, N., Shimada, S. and Maekawa, T., 'Development of a High Performance Electrochemical Waste Water Treatment System,' Journal of Hazardous Materials, B103, 65-78 (1992)
  2. Bae, S. K. and Park, S. C., 'The Study on the Removal of Ammonia in Wastewater by Electrochemical Method,' J. of Kor. Soc. Env. Engs., 6(1), 1044-55(1984)
  3. Lin, S. H. and Wu, C. L., 'Electrochemical Removal of Nitrate and Ammonia for Aquaculture,' Wat.Res., 30(3), 715-721(1996) https://doi.org/10.1016/0043-1354(95)00208-1
  4. Bouwer, E. J. and Crowe, P. B., 'Biological Process in Drinking Water Treatment,' J. AWWA, 80(9), 82-93(1988)
  5. Grimm, J., Bessarabov, D. and Sanderson, R., 'Electro-Assisted Method for Water Purification,' Desalination, 115, 285-294(1998) https://doi.org/10.1016/S0011-9164(98)00149-0
  6. Trasatti, S., 'Physical Electrochemistry of Ceramic Oxides,' Electrochimica Acta, 36(2), 225-241(1991) https://doi.org/10.1016/0013-4686(91)85244-2
  7. Trasatti, S., 'Electrode of Conductive Metallic Oxides,' Part A, Elsevier Sci. Pub. Co., Amsterdam(1980)
  8. Kim, K. W., Lee, E. H., Kim, J. S., Shin, K. H. and Kim, K. H., 'Study on the Electroactivity and Non-Stochiometry of a Ru-based Mixed Oxide Electrode,' Electrochimica Acta., 46, 915-921(2001) https://doi.org/10.1016/S0013-4686(00)00674-5
  9. Kim, K. W., Lee, E. H., Kim, J. S., Shin, K. H. and Chung, B. I., 'A Study on Performance Improvement of Ir Oxide-Coated Titanium Electrode for Organic Destruction,' Electrochimica Acta., 47, 2525-2531(2002) https://doi.org/10.1016/S0013-4686(02)00129-9
  10. Kim, K. W., Lee, E. H., Kim, J. S., Shin, K. H. and Chung, B. I., 'Material and Organic Destruction Characteristics of High Temperature-Sintered $RuO_2$ and $IrO_2$ Electrodes,' J. Eectrochem. Soc., 149, D187-D192(2002) https://doi.org/10.1149/1.1515280
  11. Kim, K. W., Kim, Y. J., Kim, I. T., Park, G. I. and Lee, I. H., 'Electrolytic Decomposition Mechanism of Ammonia to Nitrogen at $IrO_2$ Anode,' Korean, Chem., Eng. Res., 42(5), 524-531 (2004)
  12. Echigo, S., Yamada, H., Matsui, S., Kawanishi, S. and Shishida, K., 'Comparison Between $O_3/VUV, O_3/H_2O_2$, VUV and $O_3$ Processes for the Decomposition of Organophosphoric Acid Trimesters,' Wat. Sci. Tech., 34, 81-88(1996)
  13. Floyd, R. A. and Soong, L. M., 'Spin Trapping in Biological Systems. Oxidation of the Spin Trip 5,5-Dimethyl-1-Pyrroline-1-Oxide by a Hydroperoxide-Hematin System,' Biochem. Biophy. Res. Commun., 74(1), 79-84(1977) https://doi.org/10.1016/0006-291X(77)91377-8
  14. Vooys, A. C. A., Santen, R. A. and Veen, J. A. R., 'Electrocatalytic Reduction of $NO_3$ -on Palladium/Copper Electrode,' J.Molecular Catalysis A: Chemical, 154, 203-215(2000) https://doi.org/10.1016/S1381-1169(99)00375-1
  15. Pintar, A., Batista, J., Levec, J. and Kajiuchi, T., 'Kinetics of Catalytic Liquid-Phase Hydrogenation of Aqueous Nitrate Solutions,' Applied Catalysis B: Environmental, 11, 81-98(1996) https://doi.org/10.1016/S0926-3373(96)00036-7
  16. Bryabt, E. A., Fulton, G. P. and Budd, G. C., 'Disinfection Alternatives for Safe Drinking Water,' Van Nostrand Reinhold, N.Y. (1992)
  17. Sasaki, K. and Hisatomi, Y., 'Oxidation and Adsorption of Ammonia on a Platinized Platinum Electrode,' J. Eectrochem. Soc., 117(6), 758-762(1970) https://doi.org/10.1149/1.2407624
  18. Boodts, J. F. C. and Trasatti, S., 'Effect of Composition on the Electrocatalytic Acitivty of the Ternary Oxide $Ru_{0.3}Ti_{(0.7-x)}SnO_2$,' J. Eectrochem. Soc., 137(12), 3784-3789(1990) https://doi.org/10.1149/1.2086301
  19. Trasatti, S., 'Electrocatalysis in the Anodic Evolution of $O_2$ and $Cl_2$,' Electrochimica Acta, 29, 1503-1512(1984) https://doi.org/10.1016/0013-4686(84)85004-5
  20. Comninellis, C., 'Electrocatalysis in the Electrochemical Conversion/Combustion of Organic Pollutants for Waste Water Treatment,' Electrochimica Acta, 39, 1857-1862(1994) https://doi.org/10.1016/0013-4686(94)85175-1
  21. Kim, K. W., Lee, Kim, E. H., Kim, Y. J., Lee, M. H., Kim, K. H. and Shin, D. W., 'A Relation Between the Non-Stochiometry and Hydroxyl Radical Generated at Photocatalytic $TiO_2$ on 4CP Decomposition,' J. Photochem. Photobio. A: Chemistry, 159, 301-310(2003) https://doi.org/10.1016/S1010-6030(03)00186-2