The hydrodenitrogenation of quinoline was carried out in a stirred batch reactor with red mud at 370°C and 450°C at 7.0MPa of hydrogen. It was shown that quinoline was decomposed via 1, 2, 3, 4-tetrahydroquinoline (1-THQ) to ammonia or hydrogenated to 5, 6, 7, 8-tetrahydroquinoline (5-THQ).
quinoline k
1 _??_ k
3 1-THQ k
2 → ammonia k
4 ↓ 5-THQ
The reaction rate constants of quinoline hydrodenitrogenation in hexadecane agreed closely with those obtained from 1-THQ.(K
1=1.83×10
-6, K
2=1.16×10
-7, K
3=3.24×10
-7 [mol dm
-3min
-1g
-1]). Wall effect was negligible.
The rate constant for hydrogenation of quinoline decreased with following order in hexadecane>in trans-decalin>in 1-methylnaphthalene. Equilibrium between quinoline and 1-THQ was rapidly attained at 450°C. Ratios of equilibrium adsorption constant, K (trans-decalin) /K (quinoline) and K (1-methylnaphthalene) /K (quinoline), were found to be 0.055 and 0.155 respectively.
Phenol moderately decreased the rate of hydrogenation and hydrogenolysis of quinoline, because phenol could be adsorped more strongly on the catalyst than quinoline. The ratio of adsorption equilibrium constants of phenol and quinoline was calculated to be 3 from hydrogenation rate constants.
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