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

CoMo/γ-Al₂O₃촉매상에서 VO-TPP의 수소 첨가 탈금속반응에 관한 연구

Hydrodemetallation(HDM) of VO-tetraphenylporphyrin(VO-TPP) was studied over $CoMo/{\gamma}-Al_2O_3$ catalyst at emperatures between $300^{\circ}C$ and $400^{\circ}C$, the total pressure between $15{\times}10^5$ and $30{\times}10^5$ 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 $350^{\circ}C$ 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.

$CoMo/{\gamma}-Al_2O_3$ 촉매상에서 $300{\sim}400^{\circ}C$의 온도와 $15-30{\times}10^5$ 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. $350^{\circ}C$ 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.