Search / Korean Journal of Chemical Engineering
HWAHAK KONGHAK,
Vol.29, No.1, 11-18, 1991
CoMo/Υ-Al2O3 촉매상에서 Ni-TPP의 수소첨가탈금속 반응에 관한 연구
A Study of Hydrodemetallation of Ni-TPP Catalyzed by CoMo/Υ-Al2O3
CoMo/γ-Al2O3 촉매상에서 250-450℃의 온도와 30×105-60×106Pa의 압력 그리고 접촉시간 0.009-0.034gcat.hr/ml feed 범위에서 Ni-tetraphenylporphyrin(ni-TPP)의 pyridine 존재시 수소첨가탈금속반응에 관하여 연구하였다. Ni-TPP의 수소첨가탈금속반응은 pyridine양이 증가함에 따라서 전화율 감소가 발생하므로 pyridine은 수소첨가탈금속반응을 억제한다. 350℃ 이상의 온도에서 Ni-TPP의 반응은 외관상 1차로 진행하였으며 그것으로부터 Arrhenius plot을 하여 구한 활성화 에너지는 약 10kcal/mole이었다. Fresh 촉매와 aged(숙성) 촉매의 흡착 탈착 isotherm을 구해 보고 pore size distribution을 측정해 본 결과 촉매의 macropore에서 pore mouth-plugging 현상이 일어난 것을 알 수 있었다.
Hdyrodemetallation(HDM) of Ni-tetraphenylporphyrin(Ni-TPP) was studied over CoMo/Υ-Al2O3 catalyst at temperatures between 250℃ and 450℃, the total pressure between 30×105 Pa and 60×105Pa, the contact times between 0.009gcat.hr/ml feed and 0.034gcat.hr/ml feed, and pyridine concentrations between 3.6mole% and 16.7mole%. HDM of Ni-TPP was inhibited by pyridine because the increase of pyridine concentration caused the decrease of HDM conversion. The reaction rate of Ni-TPP was found to be apparently 1st order over 350℃ and its activation energy was determined to be about 10kcal/mole by Arrhenius plot. Pore mouth-plugging phenomena were shown by ad/de-sorption isotherm and pore size distribution of fresh and aged catalysts.
[References]
  1. Ronald H, Ind. Eng. Chem. Res., 26, 1945, 1987
  2. Oleck SM, Sherry HS, Ind. Eng. Chem. Process Des. Dev., 16(4), 525, 1977
  3. Hung C, Wei J, Ind. Eng. Chem. Process Des. Dev., 19, 250, 1980
  4. Ware RA, Wei J, J. Catal., 93, 100, 1985
  5. Ware RA, Wei J, J. Catal., 93, 122, 1985
  6. LePage JF, "Applied Heterogeneous Catalysis," Technip, 1987
  7. Toulhoat H, Plumail JC, Martino G, Symposium on Development in Hydrodemetallation, Miami Beach Meeting, April 28-May 3, 1985
  8. Fleish TH, Meyers BL, Ott GL, J. Catal., 86, 147, 1984
  9. Chang CD, Silvestri AJ, Ind. Eng. Chem. Process Des. Dev., 15(1), 161, 1976
  10. Newson EJ, Ind. Eng. Chem. Process Des. Dev., 14, 27, 1975
  11. Hughes R, "Deactivation of Catalysts," Academic Press, 1985
  12. Ware RA, Wei J, J. Catal., 93, 135, 1985
  13. Hung C, Wei J, Ind. Eng. Chem. Process Des. Dev., 23, 515, 1984
  14. Agrawal R, Wei J, Ind. Eng. Chem. Process Des. Dev., 23, 505, 1984
  15. Satterfield CN, "Heterogeneous Catalysis in Practice," McGraw Hill, 1985
  16. Corrigan TE, Chem. Eng., 199, 1955
  17. Chen H, Massoth FE, Ind. Eng. Chem. Res., 27, 1629, 1988