www.optience.

com

Microkinetics of Ammonia Synthesis

Objective: To simulate an Ammonia Synthesis reactor with a microkinetic
model
In this example, we illustrate the simulation of an ammonia synthesis reactor with a microkinetic
model based on [1]. This is a differential conversion reactor with Cesium promoted Ruthenium
catalyst where the Ammonia concentration (in ppm) at the reactor exit is examined at several N2 to H2
ratios. You may download the rex file to view the model. These microkinetic models can be built in a
matter of minutes in REX.
You may view this introductory example for Detailed Catalyst model first.

Features Illustrated
● Building a microkinetic model
● View catalyst surface coverage along the reactor length
● Using derived quantities to calculate and report auxiliary variables.
● Auto-detection of near-equilibrium reactions

Reaction Model
The elementary steps for the Ammonia synthesis on Cs-promoted ruthenium catalyst are described
below.

First, Nitrogen and Hydrogen adsorb on the active sites of the catalyst:
N2 + 2 s ⇄ 2 N-s
H2 + 2 s ⇄ 2 H-s
where s represents the free active sites on the catalyst, and N-s and H-s are the Nitrogen and
Hydrogen atoms adsorbed in the catalyst surface.

The surface reactions leading to Ammonia formation are:

N-s + H-s ⇄ NH-s + s
NH-s + H-s ⇄ NH2-s + s
NH2-s + H-s ⇄ NH3-s + s

Finally, NH3 desorption as shown below:

NH3-s ⇄ NH3 + s

The rate constants for the simulation, namely the pre-exponential factors and activation energies, are
obtained from [1].
Setting up the REX Project

We first activate the microkinetic modeling feature by right-click on Chemistry node and then
selecting “Enable Special Models → Detailed Catalyst Model”. After executing that action, Catalyst
Node is shown in the Chemistry tree.

In Units Configuration node, we specify that the rate is calculated per mass of catalyst, and that
partial pressures are to be used as the concentration units.

After entering the compounds and reactions described in the previous section, we go to Catalyst
node and assign the The compounds that represent the free active sites and the adsorbed species
are selected as Catalyst and Catalyst Complex respectively:

In Kinetics → Parameters node, we set the reactions orders and load the preexponentials and
activation energies values from [1].

In this example, we simulate a differential conversion fixed bed reactor, and the experimental data for
NH3 is reported in ppm. Thus, we build auxiliary variables in the Derived Quantities node to calculate
ammonia concentrations in ppm.

This is done by first defining a derived quantity that totals the moles of all gas phase species:

Strategic Solutions through Optimization Science

A second auxiliary variable is defined to calculate NH3 in ppm:

Experimental Data
Approximate values of the experimental data are entered from the charts in [1]. In this example, we
simulate the model at these experimental conditions. Cases include H2/N2 feed of 3:1, 1:1 and 1:3,
each at temperatures of 500, 550, 600 and 650K. Pressure is fixed at 1 atm by adjusting the gas flow,
and catalyst mass is 0.138g for all sets. The only measured values are NH3 moles per million moles
of outflow (NH3ppm).

Simulation Results
You may run the model and see the simulation results. The Parameters node shows that with the
exception of Nitrogen chemisorption, all reactions are nearly at equilibrium. This is consistent with the

Strategic Solutions through Optimization Science

observation in [1] that the chemisorption of Nitrogen is the rate limiting step for this Ruthenium based
catalyst. The model predictions for ammonia can be seen using the parity plots for NH3ppm:

You can see the profile for NH3ppm by disabling parity charts:

Strategic Solutions through Optimization Science

You may also see the surface fractions for the free active sites and the adsorbed species below. This
chart for a 550 K experiment shows that adsorbed hydrogen consumes more than 90% of the active
sites at the reactor entry conditions. Chemisorption of Nitrogen increases along the length, and as the
N-s surface fraction increases, the surface fraction of adsorbed hydrogen (H-s) reduces. Since N2
chemisorption to N-s is the rate limiting step, in the beginning most of the N-s is rapidly consumed
leaving little on the surface. As NH3 increases, the reverse reactions promote the accumulation of N-s
on the surface. At sufficiently high catalyst mass, all profiles should reach constant values as
equilibrium is achieved.

Further Studies
You may set the near-equilibrium reactions (reported in the Results → Parameters node) as quasi-
equilibrium reactions in the Chemistry→ Reactions Node and compare the results. You may also use
this REX file as a template for additional parameter estimation studies if more experiments are
available. Since surface fraction measurements are not available, caution should be exercised in
estimating the surface reactions because the parameters can be non-unique. You may also use this
file as a template for constructing other microkinetic models.

References
1. Hinrichsen, O., Rosowski, F., Muhler, M., and Ertl, G., (1996) The Microkinetics of Ammonia
Synthesis Catalyzed by Cesium-Promoted Supported Ruthenium. Chem. Eng. Sci., Vol 51, 1683-
1690.

Strategic Solutions through Optimization Science