황화 CoMo/γ-Al<sub>2</sub>O<sub>3</sub> 촉매상에서 수첨탈질반응과 수첨탈산소 반응의 상호작용

김학수; 박해경; 김경림

Journal of the Korean Industrial and Engineering Chemistry, Vol.2, No.2, 108-118, June, 1991

황화 CoMo/γ-Al₂O₃ 촉매상에서 수첨탈질반응과 수첨탈산소 반응의 상호작용

Interactions between Hydrodenitrogenation of pyridine and Hydrodeoxygenation of m-Cresol over sulfided CoMo/γ-Al₂O₃ Catalyst

김학수, 박해경, 김경림

초록

황화 CoMo/γ-Al₂O₃ 촉매를 사용하여 473∼723K 의 온도와 10∼15×10⁵Pa의 압력 그리고 접촉시간 0.0125∼0.03g-cat hr/ml-feed 범위에서 pyridin의 수첨탈질반응과 m-cresol의 수첨탈산소 반응의 상호작용 및 그 속도론에 관하여 연구하였다. Pyridin의 수첨탈질반응과 m-cresol의 소첨탈산소 반응의 상호반응을 저지억제하였으며, pyridin에 의한 m-cresol의 수첨탈산소반응의 억제효과는 m-cresol에 의한 pyridin의 수첨탈질반응의 억제효과보다 더 컸으나 반응성은 m-cresol이 더 높았다. Pyridin의 수첨탈질반응 속도식 및 m-cresol의 수첨탈산소반응 속도식을 LHHW 모델을 이용하여 구한 결과 γ_HDN=k_HDN·K_pC_p / (1+K_cC_c+K_pC_p) γ_HDO=k_HDO·K_cC_c/(1+K_cC _c+K_pC_p)였다. 각 온도에서 반응속도상수 및 흡착평형상수를 구하여 Arrhenius plot 과 Van't Hoff plot을 행하여 구한 활성화 에너지값은 pyridin과 m-cresol이 각각 16.21 Kcal/mole, 13.83 Kcal/mole이었고, 흡착열은 각각 -6.458 Kcal/mole, -5.045 Kcal/mole이었다.

Interactions between pyridine hydrodenitrogenation (HDN) and m-cresol hydrodeoxygenation(HDO), and the kinetic analysis were studied over sulfided CoMo/γ-Al₂O₃ catalyst at the range of temperatures between 473 K and 723 K, the total pressures between l0 × 10⁵ Pa and 50×10⁵ Pa, and the contact times between 0.0125 g-cat. hr/ml-feed and 0.03g-cat. hr/ml-feed. HDN of pyridine and HDO of m-cresol were inhibited by each other and the inhibition effect of HDO by pyridine is higher than that of HDN by m-cresol. But reactivity of m-cresol is higher than that of pyridine. The rate equations of pyridine and m-cresol were given to be γ_HDN=k_HDN·K_pC_p/(1+K_cC_c+K_pC_p) andγ_HDO=k_HDO·K_cC_c/(1+K_cC_c+K_pC_p)c in terms of Langmuir-Hinshellwood-Hougen-Watson model. At each temperature, reaction rate constants and adsorption equilibrium constants were determined and activation energies of pyridine HDN and m-cresol HDO are 13.83kcal/mol, respectively and the heat of adsorption are -6.458 and -5.045kcal/ mol, respectively.

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[2] Knishnamurthy S, Panvelken S, Shah YT, AIChE J., 27(6), 994 (1981)

[3] Bartsch R, Taniellian C, J. Catal., 3, 353 (1974)

[4] Aubert C, Durand R, Geneste P, Moreau C, J. Catal., 97, 169 (1986)

[5] Wikens JA, Ind. Eng. Chem. Process Des. Dev., 19, 154 (1980)

[6] Weitsz PB, Prater CD, Adv. Catal., 6, 143 (1954)

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[10] Singhal GH, Espino RL, Sobel JE, J. Catal., 57, 446 (1981)

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[20] Modell M, Ind. Eng. Chem. Process Des. Dev., 29, 296 (1980)

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