Boreskov Institute of Catalysis of the Siberian Branch of Russian ...

PP-I-9The increase in pressure, in the concentration of sulphur trioxide in oleum and in thetemperature cause a raise of the methane esterification rate. Therefore the reaction rate (r)consists of the function of the sulfur trioxide concentration, function of the methane partialpressure, function of the temperature (equation [a]).dCdtE= r = f (T) ⋅ f (C ) ⋅ f (p )[a]01SO23 CH 4C E , C SO – methyl bisulfate, sulfur trioxide concentration [mol⋅dm–3 3]p CH 4– methane partial pressure [MPa]f 0(T) – function of the temperaturef31(CSO) – function of the sulfur trioxide concentration2(pCH) – function of the methane partial pressuref4We have found that the theoretical equation of the reaction rate for methane to esterconversion can be defined by equation [b]:n 2⎡⎤n ⎛ 0.00082T ⋅C⎞1Er = k ( − + ) ⎢⎜ −+⎟TC0SO2C a p0.10C + b⎥3 E0 CH4E[b]⎢⎣⎝ 0.15 − 0.0043CE ⎠ ⎥⎦T – the temperature of the process [K]k T – the reaction rate constant at the temperature Tp0CH 4– initial methane partial pressure [MPa]C0SO 3– initial sulfur trioxide concentration [mol⋅dm –3 ]a, b, n 1 , n 2 – empirical factorsOn the base of the experimental work the empirical factors and reaction rate constant atdifferent temperatures were determined. The relationship of the logarithm of the reaction rateand the inverse temperature was the straight line. The activation energy was calculated.AcknowledgmentA financial support from the Polish Scientific Research Committee (Research Project 2053705 33) is gratefully acknowledged.References1. Periana R. A., Taube D. J., Evitt E. R., Löffler D. G., Wentrcek P. R., Voss G., Masuda T., Science, 1993,259, 340 – 343.2. Gang X., Birch H., Zhu Y., Hjuler H. A., Bjerrum N. J., J. Catal., 2000, 196, 287 – 292.3. Periana R. A., Taube D. J., Gamble S., Taube H., WO 98/50333, 1998.4. Michalkiewicz B., Kałucki K., Sośnicki J.G, J. Catal., 2003, 215, 14–19.5. Gang X., Zhu Y., Birch H., Hjuler H.A., Bjerrum N.J., Appl. Catal. 2004, 261, 91–98.6. Periana R.A., Mirinov O., Taube D.J., Gamble S., Chem. Commun., 2002, 2376–2377.228