4.5.

SIMULATION OF UNIT OPERATIONS 171

Conversion Reactor (Stoichiometric Reactor)

A conversion reactor requires a reaction stoichiometry and an extent of reaction,
which is usually specified as an extent of conversion of a limiting reagent. No reaction
kinetics information is needed, so it can be used when the kinetics are unknown
(which is often the case in the early stages of design) or when the reaction is known to
proceed to full conversion. Conversion reactors can handle multiple reactions, but
care is needed in specifying the order in which they are solved if they use the same
limiting reagent.

Equilibrium Reactor
An equilibrium reactor finds the equilibrium product distribution for a specified set of
stoichiometric reactions. Phase equilibrium is also solved. The engineer can enter the
outlet temperature and pressure and let the reactor model calculate the duty needed to
reach that condition, or else enter a heat duty and let the model predict the outlet
conditions from an energy balance.
An equilibrium reactor solves only the equations specified, so it is useful
in situations in which one or more reactions equilibrate rapidly, while other reactions
proceed much more slowly. An example is the steam reforming of methane to
hydrogen. In this process, the water-gas-shift reaction between water and carbon
monoxide equilibrates rapidly at temperatures above 4508C, while methane conver-
sion requires catalysis even at temperatures above 8008C. This process chemistry is
explored in Example 4.2.
In some simulation programs, the equilibrium reactor model requires the designer
to specify both liquid and vapor phase products, even though one of the streams may
be calculated to have zero flow. If the real reactor has a single outlet, then the two
product streams in the model should be mixed back together.
Gibbs Reactor
The Gibbs reactor solves the full reaction (and optionally phase) equilibrium of all
species in the component list by minimization of the Gibbs free energy, subject to the
constraint of the feed mass balance. A Gibbs reactor can be specified with restrictions
such as a temperature approach to equilibrium or a fixed conversion of one species.
The Gibbs reactor is very useful when modeling a system that is known to come to
equilibrium, in particular high-temperature processes involving simple molecules. It is
less useful when complex molecules are present, as these usually have high Gibbs
energy of formation; consequently, very low concentrations of these species are
predicted unless the number of components in the model is very restricted.
The designer must specify the components carefully when using a Gibbs reactor
in the model, as the Gibbs reactor can solve only for specified components. If a
component that is actually formed is not listed in the component set, then the Gibbs
reactor results will be meaningless. Furthermore, if some of the species have high
Gibbs free energy, their concentrations may not be properly predicted by the model.
An example is aromatic hydrocarbon compounds such as benzene, toluene, and
xylenes, which have Gibbs free energy of formation greater than zero. If these