Production of Activated Carbon from Waste Walnut Shell Using Phosphoric Acid and Its Adsorption Characteristics for Heavy Metal Ion

인산활성화제에 의한 폐호도껍질을 원료로 한 활성탄제조 및 이의 중금속 이온 흡착특성

  • 이고은 (이화여자대학교 환경학과) ;
  • 안주현 (이화여자대학교 환경학과) ;
  • 김동수 (이화여자대학교 환경학과)
  • Published : 2003.06.01

Abstract

The production characteristics of activated carbon from waste walnut shell have been investigated by taking activation temperature, activation time, amount of activating agent, and kind of activating agent as the major influential factors. The adsorption capacity of the activated carbon which was produced using phosphoric acid as the activating agent increased with activation temperature and showed its greatest value at about $550^{\circ}C$. Yield for activated carbon was observed to decrease continuously as the activation temperature was raised. The optimal activation time for the highest adsorption capacity was found to be about 2 hr, and as the activation time increased the yield for activated carbon was showed to decrease continuously. The increase in the amount of activating agent resulted in the increase of the yield for activated carbon, however, excessive amount of activating agent deteriorated its adsorption capacity reversely. The variations of the microstructure of activated carbon observed by SEM with several influential factors, correlated very well with its changes in the adsorbability with the same factors and the kind of activating agent was found to play an important role in the determination of the adsorption capacity of activated carbon. To investigate the adsorption characteristics of the produced activated carbon, the adsorption reactions of $Cu^{2+}$ ion were examined using the produced activated carbon as the adsorbent. In general, the kinetics of the adsorption of $Cu^{2+}$ ion was observed to follow a 2nd-order reaction and the rate constant for adsorption reaction increased as the initial concentration of adsorbate was diminished. The equilibrium adsorption of $Cu^{2+}$ was explained well with Freundlich model and its adsorption reaction was found to be endothermic. The activation energy for adsorption was calculated to be 13.07 kcal/mol, which implied that the adsorption reaction was very irreversible, and several thermodynamic parameters of adsorption reaction were estimated using van't. Hoff equation and thermodynamic relationships.

폐호도껍질을 원료로 활성탄을 제조하는 과정에서 활성화 온도, 활성화 시간, 활성화제의 양, 그리고 활성화제의 종류 등을 변수로 하여 활성화 특성을 조사하였다. 인산을 활성화제로 사용하여 제조된 활성탄은 그 흡착능이 온도가 증가함에 따라 증가하여 약 $550^{\circ}C$부근에서 최대 흡착능을 보였으며 그 수율은 온도 상승에 따라 지속적으로 감소하였다. 활성화 시간은 약 2시간 정도에서 최적의 조건을 보였으며 시간이 증가함에 따라 활성탄의 수율은 계속 감소하였다. 활성화제의 농도 증가에 따라 수율은 지속적으로 상승하였으며 흡착능 또한 증대되다가 약 1.5M $H_3PO_4$ 이상의 조건에서는 오히려 흡착능이 감소하였다. SEM으로 관찰한 조건에 따른 활성탄의 미세구조의 변화는 조건별 흡착능의 변화와 잘 일치되었으며 활성화제의 종류는 활성화 과정에서 중요한 영향을 미치는 것으로 조사되었다. 제조된 활성탄의 흡착특성을 파악하기 위해 $Cu^{2+}$ 이온을 흡착질로 하여 흡착반응을 조사한 결과, 흡착반응은 전체적으로 2차식을 따르는 것으로 관찰되었으며 흡착질의 초기 농도가 감소함에 따라 반응상수는 점차 증가하였다. 평형흡착량은 Freundlich Model 을 잘 따르는 것으로 나타났으며 온도별 흡착반응을 검토한 결과, 중금속 이온의 흡착은 흡열반응의 특성을 나타내었다. 흡착에 따른 Activation Energy는 약 13.07kcal/mol로 산출되었으며 van't Hoff Equation을 이용하여 흡착반응의 열역학적 인자들을 계산하였다.

Keywords

References

  1. Suzuki, M., 1990: Adsorption Engineering, Kodansha Ltd., Tokyo
  2. Walker, O. L., 1993: Chemistry and Physics of Carbon Marcel Dekker, New York
  3. Walker, G. M., and Weatherley, L. R., 1999: Kinetics of Acid Dye Ddsorption on GAC, Water Research, 33(8), pp. 1895-1899 https://doi.org/10.1016/S0043-1354(98)00388-1
  4. Galiatsatou, Metaxas, P. M., Arapoglou, D., and Kasselouri-Rigopoulou, V., 2002: Treatment of Olive Mill Waste Water with Activated Carbons from Agricultural Byproducts, Waste Management, 22(7), pp. 803-812 (2002) https://doi.org/10.1016/S0956-053X(02)00055-7
  5. Sirotkin, A. S., Koshkina, L. Y., and Ippolitov, K. G., 2001: The BAC-process for Treatment of Waste Water containing Non-ionogenic Synthetic Surfactants, Water Research, 35(13), pp. 3265-3271 https://doi.org/10.1016/S0043-1354(01)00029-X
  6. Ruixia, L., Hongxiao, T., and Baowen, Z., 1999: Removal of Cu(II), Zn(II), Cd(II) and Hg(II) from Waste Water by Poly(acrylaminophosphonic)-type Chelating Fiber, Chemosphere, 38(13), pp. 3169-3179 https://doi.org/10.1016/S0045-6535(98)00506-2
  7. Benaddi. H., Legras, D., Rouzaud, J. N., and Beguin, F., 1998: Influence of the Atmosphere in the Chemical Activation of Wood by Phosphoric Acid, Carbon, 36, p. 306 https://doi.org/10.1016/S0008-6223(98)80123-1
  8. 한국산업규격, 1998: 활성탄 시험방법, KS M 1802
  9. Tsai, W. T., Chang, C. Y., Lin, M. C., Chien, S. F., Sun, H. F., and Hsieh, M. F., 2001: Adsorption of Acid Dye onto Activated Carbons Prepared from Agricultural Waste Bagasse by $ZnCl_2$ Activation, Chemosphere, 45(1), pp. 51-58 https://doi.org/10.1016/S0045-6535(01)00016-9
  10. Girgis, B. S., Yunis, S. S., and Soliman, A. M., 2002: Characteristics of Activated Carbon from Peanut Hulls in relation to Conditions of Preparation, Materials Letters, 57(1), pp. 164-172 https://doi.org/10.1016/S0167-577X(02)00724-3
  11. Chen, X., Jeyaseelan, S., and Graham, N., 2002: Physical and Chemical Properties Study of the Activcited Carbon made from Sewage Sludge, Waste Management, 22(7), pp. 755-760 https://doi.org/10.1016/S0956-053X(02)00057-0
  12. Metcalf., and Eddy, 1991: Wastewater Engineering; Treatment, Disposal, and Reuse, 3rd ed., McGraw Hill, Inc., pp. 318-319
  13. 김동수, 표나영, 김경하, 1999: Cd 폐수 흡착처리제로서의 Garnet 용도개발 한국자원공학회지, 36(1), pp. 1-9
  14. Snoeyink, V. L., and Jenkins, D., 1980: Water Chemistry, John Wiley & Sons, Inc.. pp. 40-44
  15. Atkins, P. W., 1990: Physical Chemistry, 4th ed., Freeman, W. H., and Company, pp. 219-221