Characteristics of Cyanide Decomposition by Hydrogen Peroxide Reduction

과산화수소에 의한 시안의 분해특성

  • 이진영 (한국지질자원연구원, 자원활용연구부) ;
  • 윤호성 (한국지질자원연구원, 자원활용연구부) ;
  • 김철주 (한국지질자원연구원, 자원활용연구부) ;
  • 김성돈 (한국지질자원연구원, 자원활용연구부) ;
  • 김준수 (한국지질자원연구원, 자원활용연구부)
  • Published : 2002.04.01

Abstract

The characteristics of cyanide decomposition in aqueous phase by hydrogen peroxide have been explored in an effort to develop a process to recycle waste water. The self-decomposition of $H_2O$$_2$at pH 10 or below was minimal even in 90 min., with keeping about 90% of $H_2O$$_2$undissociated. On the contrary, at pH 12 only 9% of it remained during the same time. In the presence of copper catalyst at 5 g Cu/L, complete decomposition of $H_2$O$_2$was accomplished at pH 12 even in a shorter time of 40 min. The volatility of free cyanide was decisively dependent on the solution pH: the majority of free cyanide was volatilized at pH 8 or below, however, only 10% of it was volatilized at pH 10 or above. In non-catalytic cyanide decomposition, the free cyanide removal was incomplete in 300 min. even in an excessive addition of $H_2$$O_2$at a $H_2$$O_2$/CN molar ratio of 4, with leaving behind about 8% of free cyanide. On the other hand, in the presence of copper catalyst at a Cu/CN molar ratio of 0.2, the free cyanide was mostly decomposed in only 16 min. at a reducedH202/CN molar ratio of 2. Ihe efnciency of HBO2 in cyanide decomposition decreased with increasing addition of H2O2 since the seu-decomposition rate of $H_2$$O_2$increased. At the optimum $H_2$$O_2$/mo1ar ratio 0.2 of and Cu/CN molar ratio of 0.05, the free cyanide could be completely decomposed in 70 min., having a self-decomposition rate of 22 mM/min and a H$_2$$O_2$ efficiency of 57%.

본 연구에서는 시안 성분을 제거함에 있어 처리수의 재활용이 가능한 과산화수소에 의한 시안분해 특성을 규명하기 위한 실험을 수행하였다. 수용액중의 과산화수소의 자가분해반응은 pH와 금속촉매(Cu) 유무에 크게 좌우된다. pH 10 이하에서는 자가분해반응은 미미하여 90%이상의 과산화수소가 잔류하지만 pH 12에서는 90경과시 잔류 과산화수소가 9%이하로 낮아졌다. 금속촉매 첨가(5 g Cu/L)한 경우 pH 12에서도 40분 경과후 대부분의 과산화수소가 분해되었다. 유리시안의 휘발성은 용액의 pH에 크게 좌우된다. 동일한 240분 경과시 pH 8이하에서 대부분의 시안이 휘발하는데 반하여 pH 10이상에서는 10%미만이 휘발하였다. 비촉매반응에 의한 과산화수소의 시안분해실험에서는 $H_2$$O_2$/CN 몰비 4까지 과다하게 증가하여도 8%가량의 시안이 잔류하였다. 그러나 구리촉매반응에 의한 과산화수소의 시안분해 실험에서는 과산화수소 및 구리 첨가량이 증가함에 따라 분해속도가 증가하였다. 그러나 일정량 이상 첨가시 과산화수소의 자체분해 반응에 의해 $H_2$$O_2$의 시안분해 효율이 감소하며 과산화수소와 구리의 적정투입량은$ H_2$$O_2$/CN 몰비 2, Cu 몰비 0.05로서 이때의 분해속도는 22 mM/min, $H_2O$$_2$효율은 57%이었다. 또한 이러한 적정조건에서 70분 반응시 완전제거가 가능하였다.

Keywords

References

  1. V. Padiyar & V. S. Mishra : 'Cyanide detoxification a review', Trans I Chem E, Vol. 73, Part B, Feb. (1995)
  2. 국제환경문제연구소편 : '환경관계법규', 동화기술, 서울, 3-82 (1996)
  3. Zeevalkink, J. A. et al.: 'Mechanism and kinetics of cyanide ozonation in water', Water Res., Vol. 14, 1375-385 (1979) https://doi.org/10.1016/0043-1354(80)90001-9
  4. Frederick, E. B.: 'Cyanide detoxification using adsorption and catalytic oxidation on granular activated carbon', Jour. of WPCF, 45(2), 221-231 (1973)
  5. Murphy, R. S. and Nesbitt, J. B. : 'Biological Treatment of Cyanide Wastes', Engineering Research Bull B-88, The Renn. State Unib. (1964)
  6. 佐藤完ニ : 'シアン 含有 廢水の處理 方法', 公開特許公報 51-67672(1976)
  7. Muller, K. R. et al : 'Chemical waste handling and treatment', 231-241 (1986)
  8. Bhakta D., Shukla S. S., Chandrashekharaiah m. S. and Margrave J. L.: 'Detoxification of cyanide wastes', Environ Sci Technol, 26(3), 625-626 (1992) https://doi.org/10.1021/es00027a029
  9. Kolb M. and Schulz W.: 'Halogenated organic compounds in solutions of sodium hypochlorite for the detoxification of cyanide', Korresp Abwasser, 37(1), 67-68 (1990)
  10. Schwarzer H., and Nakagawa S. : 'Prevention of organohalogen containing wastewater and liquid wastes by replacing hypochlorite by hydrogen peroxide in cyanide detoxification', Stullg Ber Abfallwirtsch, 39, 173-189 (1979)
  11. Bakes M. and Daude L. M. C.: 'Elimination of cyanides in wastewater by a hydrogen peroxide-sodium hypochlorite system', Rev Alum, 463, 293-296 (1978)
  12. Laws B. C., Fournier L. B. and Mathre 0. B. : 'A peroxygen system for destroying cyanide in zinc and cadmium electroplating wastewaters', Plating, 60 (1973)
  13. Knorre H. and Fisher H. : 'Detoxification of hydrocyanic acid containing exhaust gases from blast furnaces and other high temperature processes', Fachber Huettenprax Metallweiterverab, 26(10), 937-938, 940-941 (1988)
  14. Baxendale J. H., Westcott D. T. : 'Kinetics and Equilibria in Copper(II)-cyanide Solution', J. Chem. Soc., B 2347, (1989)
  15. James K. Beattie, G. A. Blyblank : 'Copper-Catelysed oxidation of cyanide by peroxide in alkaline aqueous solution', Aust. J. Chem., 48 (1995)
  16. 오동규 : '펜턴 시약을 이용한 폐수중 유기물의 산화처리', 박사논문, 인하대 (1993)