Determination of kinetic parameters for the water–gas shift reaction on copper catalysts under realistic conditions for fuel cell applications
The kinetic parameters for water–gas shift reaction on Cu-based catalysts were measured under fuel reformer conditions for fuel cell applications (7% CO, 8.5% CO 2, 22% H 2O, 37% H 2, and 25% Ar) at 1 atm total pressure and temperature in the range of 200 °C. The rate per unit of Cu surface area at...
Saved in:
Published in | Journal of catalysis Vol. 217; no. 1; pp. 233 - 239 |
---|---|
Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
Amsterdam
Elsevier Inc
01.07.2003
Elsevier |
Subjects | |
Online Access | Get full text |
Cover
Loading…
Summary: | The kinetic parameters for water–gas shift reaction on Cu-based catalysts were measured under fuel reformer conditions for fuel cell applications (7% CO, 8.5% CO
2, 22% H
2O, 37% H
2, and 25% Ar) at 1 atm total pressure and temperature in the range of 200
°C. The rate per unit of Cu surface area at the stated concentrations was 0.8×10
−6 mol
m
−2
s
−1 at 200
°C. The overall reaction rate as a function of the forward rate (
r
f) is
r=
r
f(1−
β), where
r
f=
k
f[CO]
0.8[H
2O]
0.8[CO
2]
−0.7[H
2]
−0.8,
k
f is the forward rate constant,
β=([CO
2][H
2])/(
K[CO][H
2O]) is the approach to equilibrium, and
K is the equilibrium constant for the water–gas shift reaction. This expression indicates a strong inhibition on the forward rate by H
2 and CO
2. When ceria was added to the catalyst, it decreased the Cu surface area and did not increase the rate per unit of Cu surface area, suggesting that ceria is not a promoter. The addition of ZnO did not increase the rate per unit of Cu surface area either. Thus, Cu is the active site for catalysis. It was proposed that the kinetics can be explained based on the “Redox” mechanism with
CO∗+
O∗⇄
CO
2∗+
∗
as the rate-determining step. |
---|---|
ISSN: | 0021-9517 1090-2694 |
DOI: | 10.1016/S0021-9517(03)00050-2 |