High‐temperature kinetics of the homogeneous reverse water–gas shift reaction

AICHE Journal - Tập 50 Số 5 - Trang 1028-1041 - 2004
Felipe Bustamante1, Robert M. Enick1, A.V. Cugini2, R.P. Killmeyer2, Bret Howard2, K.S. Rothenberger2, Michael V. Ciocco3, Bryan D. Morreale3, Sharmila Chattopadhyay4, Shuang Shi5
1National Energy Technology Laboratory–Research Associates, Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261
2U.S. Department of Energy, National Energy Technology Laboratory, Pittsburgh, PA, 15236
3National Energy Technology Laboratory–Support Contractors, Parsons Project Services Incorporated, Library, PA 15129
4Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA, 15261
5Fluent Incorporated, Morgantown, WV 26505

Tóm tắt

AbstractThe high‐temperature rate of reaction of the homogeneous, reverse water–gas shift reaction (rWGSR) has been evaluated in quartz reactors with rapid feed preheating under both low‐ and high‐pressure conditions. The form of the power‐law rate expression was consistent with the Bradford mechanism. The Arrhenius expressions for the reaction rate constant, corresponding to the empty reactor, were in very good agreement with the low‐pressure results of Graven and Long, but yielded rate constants roughly four times greater than those obtained in our packed reactor and those reported by Kochubei and Moin and by Tingey. Reactor geometry was not responsible for these differences because computational fluid dynamics simulations revealed similar residence time distributions and comparable conversions when the same kinetic expression was used to model the rWGSR in each reactor. Most likely, the empty NETL reactor and the Graven and Long reactor did not attain an invariant value of the concentration of the chain carrier (H) at low reaction times, which led to an overestimation of the rate constant. Conversions attained in an Inconel® 600 reactor operating at comparable conditions were approximately two orders of magnitude greater than those realized in the quartz reactor. This dramatic increase in conversion suggests that the Inconel® 600 surfaces, which were depleted of nickel during the reaction, catalyzed the rWGSR. © 2004 American Institute of Chemical Engineers AIChE J, 50: 1028–1041, 2004

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AICHE Journal

Tập 50 Số 5

1028-1041

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