Oa. Asbjornsen et M. Hillestad, REACTION INVARIANCE AND STABILITY IN CATALYST PARTICLES FOR PRODUCTION OF METHANOL, AIChE journal, 43(4), 1997, pp. 1082-1090
Industrial practice requires immediate and adequate responses to simpl
e questions asked. For example, does a catalyst particle show any tend
ency to thermal oscillations in the form of a limit cycle? The root to
such cycles is found in the eigenvalues of the Jacobian matrix to the
reaction rate vector, applying the concept of reaction invariance, a
direct consequence of Avogadro's stoichiometric principle for homogene
ous stirred tank reactors. However, this concept does not generally ap
ply to heterogeneous reactor dynamics, because it is found in the hete
rogeneous transports of heat, reactants and products. The transport is
an irreversible phenomenon that usually contributes to shifting the e
igenvalues to the left and hence increases the stability. Still, effec
ts of transport mechanisms, both internally and externally, on the cat
alyst particle are important to assess in such industrial analyses. A
practical industrial reactor for methanol production was the subject f
or stability studies, which concluded that thermal oscillations are no
t likely to occur. During this study, a number of interesting details
were examined such as rank deficiency of the reaction matrix and root
loci for the temperature dependence of the Jacobian matrix eigenvalues
. A practical consequence of eventual thermal cycling of the catalyst
particles is a long-term degradation of the catalyst efficiency, as se
en in the ammonia synthesis.