CoMo/y-Al<sub>2</sub>O<sub>3</sub> 촉매상에서 VO-TPP의 수소 첨가 탈금속반응에 관한 연구

심현섭; 박해경; 고을석; 김경림

Journal of the Korean Industrial and Engineering Chemistry, Vol.4, No.4, 701-708, December, 1993

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CoMo/y-Al₂O₃ 촉매상에서 VO-TPP의 수소 첨가 탈금속반응에 관한 연구

A Study of Hydrodemetallation of VO-TPP over CoMo/γ-Al₂O₃ Catalyst

심현섭, 박해경, 고을석, 김경림

초록

CoMo/γ-Al₂O₃ 촉매상에서 300∼400℃의 온도와 15-30×10⁵ Pa의 압력 그리고 접촉시간 0.008-0.020 gcat.hr./ml feed 범위에서 VO-TPP(VO-tetraphenylporphyrin)의 수소 첨가 탈금속반응에 관하여 연구하였다. VO-TPP의 수소 첨가 탈금속반응에서 pyridine 농도 4mole%까지는 농도가 증가함에 따라 전화율의 감소가 나타났으므로 pyridine은 수소 첨가 탈금속반응을 억제한다. 350℃ 이상의 온도에서는 VO-TPP의 외관상 반응차수가 1차였으며, Arrhenius plot에서 얻은 활성화 에너지는 약 23kcal/mole이었다. Fresh 촉매와 aged 촉매의 pore size distribution과 흡착, 탈착 isotherm으로부터 pore mouth-plugging 현상을 확인할 수 있었다.

Hydrodemetallation(HDM) of VO-tetraphenylporphyrin(VO-TPP) was studied over CoMo/γ-Al₂O₃ catalyst at emperatures between 300℃ and 400℃, the total pressure between 15×10⁵ and 30×10⁵ Pa and the contact times between 0.008 and 0.020gcat. hr./ml teed. HDM of VO-TPP was inhibited by pyridine because the increase of pyridine concentration(up to 4mole%) caused the decrease of HDM conversion. The reaction rate of VO-TPP was found to be apparently 1st order over 350℃ and its activation energy was determined to be about 23kca1/mo1e by Arrhenius plot. Pore mouth-plugging phenomena were shown by ad/desorption isotherm and pore size distribution of fresh and aged catalysts.

[References]

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[2] Hung C, Wei J, Ind. Eng. Chem. Process Des. Dev., 19, 250 (1980)

[3] Ware RA, Wei J, J. Catal., 93, 100 (1985)

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

[5] Nelson WL, Oil Gas J., 72(Nov.), 15 (1976)

[6] Nelson WL, Oil Gas J., 247(Mar.), 2 (1977)

[7] Kim KL, Choi KS, Int. Chem. Eng., 27, 340 (1980)

[8] Yen TF, "The Role of Trace Metals in Petroleum," Ann Arbor Science (1975)

[9] Prash BD, Gabriel GA, Ma YH, Ind. Eng. Chem. Process Des. Dev., 17, 266 (1978)

[10] LePage JF, "Applied Heterogeneous Catalysis," Technop (1987)

[11] Agrawal R, Wei J, Ind. Eng. Chem. Process Des. Dev., 23, 515 (1984)

[12] Toulhoat H, Plumail JC, Martino G, Symposium on Development in Hydrodemetallation, Miami Beach Meeting, April 28-May 3 (1985)

[13] Corrigan TE, Chem. Eng., April, 161 (1955)

[14] Anderson JB, Chem. Eng., April, 199 (1955)

[15] Mears BC, Ind. Eng. Chem. Process Des. Dev., 10, 541 (1971)

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[17] Chen H, Massoth FE, Ind. Eng. Chem. Res., 27, 1629 (1988)