Removal of Nitrate-Nitrogen in Pickling Acid Wastewater from Stainless Steel Industry Using Electrodialysis and Ion Exchange Resin

전기투석과 이온교환수지를 이용한 스테인레스 산업의 산세폐수 내 질산성 질소의 제거

  • Yun, Young-Ki (Department of Environmental Engineering, Kyungpook National University) ;
  • Park, Yeon-Jin (Department of Environmental Engineering, Kyungpook National University) ;
  • Oh, Sang-Hwa (Department of Environmental Engineering, Kyungpook National University) ;
  • Shin, Won-Sik (Department of Environmental Engineering, Kyungpook National University) ;
  • Choi, Sang-June (Department of Environmental Engineering, Kyungpook National University) ;
  • Ryu, Seung-Ki (POSCO Technical Research Laboratories)
  • Published : 2009.06.30


Lab-scale Electrodialysis(ED) system with different membranes combined with before or after pyroma process were carried out to remove nitrate from two pickling acid wastewater containing high concentrations of $NO_3\;^-$(${\approx}$150,000 mg/L) and F($({\approx}$ 160,000 mg/L) and some heavy metals(Fe, Ti, and Cr). The ED system before Pyroma process(Sample A) was not successful in $NO_3\;^-$ removal due to cation membrane fouling by the heavy metals, whereas, in the ED system after Pyroma process(Sample B), about 98% of nitrate was removed because of relatively low $NO_3\;^-$ concentration (about 30,000 mg/L) and no heavy metals. Mono-selective membranes(CIMS/ACS) in ED system have no selectivity for nitrate compared to divalent-selective membranes(CMX/AMX). The operation time for nitrate removal time decreased with increasing the applied voltage from 10V to 15V with no difference in the nitrate removal rate between both voltages. Nitrate adsorption of a strong-base anion exchange resin of $Cl\;^-$ type was also conducted. The Freundlich model($R^2$ > 0.996) was fitted better than Langmuir mode($R^2$ > 0.984) to the adsorption data. The maximum adsorption capacity ($Q^0$) was 492 mg/g for Sample A and 111 mg/g for Sample B due to the difference in initial nitrate concentrations between the two wastewater samples. In the regeneration of ion exchange resins, the nitrate removal rate in the pickling acid wastewater decreased as the adsorption step was repeated because certain amount of adsorbed $NO_3\;^-$ remained in the resins in spite of several desorption steps for regeneration. In conclusion, the optimum system configuration to treat pickling acid wastewater from stainless-steel industry is the multi-processes of the Pyroma-Electrodialysis-Ion exchange.


  1. Lee E. G., Moon S. H., Chang Y. K., Yoo I. K., Chang H. N., 1998, Lactic acid recovery using two-stage electrodialysis and its modelling, J. Membr, Sci., 145, 53-66
  2. Gain E., Lahorie S., Viers P., Rakib M., Hartmann D., Durand G., 2002, Ammonium nitrate wastewaters treatment by an electromembrane process, Desalination, 149, 337-342
  3. Schmidt B., Wolters R., Kaplin J., Schneiker T., Lobo-Recio M. A., Lopez F., Lopez-Delgado A., Alguacil F. J., 2007, Rinse water regeneration in stainless steel pickling, Desalination, 211, 64-71
  4. Yeon K. H., Moon S. H., 1999, Removal of Nitrate from Drinking Water by Electrodialysis or Electrodeionization, J. KSEE., 21, 87-99
  5. Strathmann H., 2004, Ion-Exchange Membrane Separation Processes, Elsevier, 305-307
  6. Sim J. H., Seo H. J., Seo J. H., Kim D. H, 2006, Comparative Study on Recovery of Nickel by Ion Exchange and Electrodialysis, J. KSEE., 28, 640-647
  7. Marafion E., Suarez F., Alonso F., Fernandez Y., Sastre H., 1999, Preliminary study of iron removal from hydrochloric pickling liquor by ion exchange, Ind. Eng. Chern. Res., 38, 2782-2786
  8. Lee Y J., Min J. H., Kim J. H., Kim H. S., 2006, Comparison on the Removal Characteristics of Nitrate by Ion Exchange and Nanofiltration Membrane, Abstracts of Proceedings of the KSWW & KSWQ
  9. Clifford D. A., 1990, Ion exchange and inorganic adsorption, In: Water Quality and Treatment, 5th ed.AWWA, McGraw-Hill. Inc., 1248pp
  11. Kim E. S., 2007, Desalination and fouling characterization in Electrodialysis with pulsed electric fields for wastewater reclamation, Master. Dissertation, Dept of Enviromental Engineering Kyungpook national University, Deagu
  12. Min J. H., Kim H. S., 2008, The removal of Nitrate-nitrogen from ground water by electrodialysis, J. KSWW., 22, 307-314
  13. Kim J. O., Jung J. T., Chung 1., 2007, Treatment performance of metal membrane microfiltration and electrodialysis integrated system for wastewater reclamation. Desalination, 202, 343-350
  14. Gregory T., Chelsey L. K., Shimizu K. D., 2005, A critical examination of the use of the Freundlich isotherm in characterizing molecularly imprinted polymers (MIPS). Anal. Chim. Acta, 528, 107-113