CoMo/Υ-Al<SUB>2</SUB>O<SUB>3</SUB> 촉매상에서 Ni-TPP의 수소첨가탈금속 반응에 관한 연구

강상윤; 구헌서; 최기섭; 김경림

HWAHAK KONGHAK, Vol.29, No.1, 11-18, February, 1991

Export Citation

CoMo/Υ-Al₂O₃ 촉매상에서 Ni-TPP의 수소첨가탈금속 반응에 관한 연구

A Study of Hydrodemetallation of Ni-TPP Catalyzed by CoMo/Υ-Al₂O₃

강상윤, 구헌서, 최기섭, 김경림

초록

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 30×10⁵Pa 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]

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[5] Ware RA, Wei J, J. Catal., 93, 122 (1985)

[6] LePage JF, "Applied Heterogeneous Catalysis," Technip (1987)

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[10] Newson EJ, Ind. Eng. Chem. Process Des. Dev., 14, 27 (1975)

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[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)