Ammonia Synthesis

by
Mahek
Sarah Lipp
GJ Sequeira

Submitted to
Dr. Thomas Edison

Chemical Engineering 253M

McKetta Department of Chemical Engineering
Cockrell School of Engineering
The University of Texas at Austin

Fall 2014

Ammonia Synthesis
Abstract

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Contents
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your major headings, tables, and figures.]
Introduction

Methods

Safety

Sample Calculations

Results

Conclusions and Recommendations

Appendices [List appendices as subheadings below.]

[Appendix 1. (data)]
[Appendix 2. (questions)]
[Appendix 3. (supporting material)]

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[Your title]
Introduction
Ammonia synthesis is common in industrial applications. The basic reaction for
ammonia synthesis is described by the reversible reaction

This reaction favors formation of ammonia at high pressures and low temperatures. In
order to optimize the process, these two parameters must be manipulated. Most processes
utilize a syngas feed stream flowing into a catalytic converter bed. We used a three stage
ammonia synthesis process. The goal of simulating an ammonia synthesis process is to
find the optimum operating conditions for a three stage, adiabatic, plug flow reactor
(PFR). The optimum conditions will be determined by creating adiabatic and equilibrium
operating lines at three different pressures; the temperature and conversion of the
reactants will be determined based on an input feed temperature and constant feed flow
rate. In addition, to model realistic applications more closely, cold-shot cooling and interstage cooling between stages are simulated to maximize the conversion while minimizing
the amount of catalyst needed. No recycle stream is included in the simulations in for
ease of calculation. All cases will be compared and an optimal feed temperature, reactor
design, process design, and weight of catalyst will be determined.
The synthesis gas from the converter is composed of hydrogen, nitrogen,
ammonia, methane, and argon. Methane and argon are inert gases in the feed in order to
absorb heat. The composition of the feed is

Figure 1: Composition of Synthesis Gas Feed

Synthesis of ammonia requires large activation energies in order to occur
spontaneously. In order to decrease the activation energy, a triply promoted (K2O-CaOAl2O3) iron-oxide catalyst is used. The catalyst is granules about 6-10mm in diameter. Its
associated physical properties are

Figure 2: Physical Properties of Catalyst

It is important to note that the catalyst is deactivated at operating temperatures above

985F, which puts a constraint on the reactor design. Furthermore, the catalyst can be
poisoned by hydrocarbons, such as lubricating oils and olefins. These species can crack
and plug pores in the catalyst. The model used does not incorporate the influence of
poisons.
Although the overall reaction is presented, the rate of the reaction follows the
mechanism which consists of the adsorption of nitrogen and hydrogen, and the surface
reaction of intermediate NH, NH2, and H compounds in order to facilitate the desorption
of ammonia.

Figure 3: Reaction Mechanism

This mechanism influences the reaction rate, and consequently the amount of catalyst.
The reactor vessel design will be modeled similar to industrial applications, which
involves a reactor that is split into portions of catalyst and heat exchanger areas.

Figure 4: Reactor Vessel Design Basis

The rate and design equations associated with the vessel are used to calculate the weight
of catalyst and heat requirements at each temperature, pressure, and design specification.
These calculations are too rigorous to be performed by hand, so POLYMATH is used for
ease of calculation. We expect the direct contact quench will provide a better cooling
alternative than indirect (heat exchanger) cooling. A combination of the two may
improve conversion at each stage.

Methods
The base case design algorithm involved using the rate equation based on the
activities of each species

For the sake of preliminary calculations, the effectiveness factor is unity. The rate
equation is used to determine the equilibrium lines by setting the left hand side equal to 0.
The adiabatic operating lines for a single bed are determined by solving the design
material and energy balances simultaneously.

The specific heat capacities and enthalpy of reaction are assumed to be temperature
dependent. The heat capacities and enthalpy relations are provided in Appendix 1.
The inter-stage cooling method uses the same equations for each stage. However,
between stages, the stream temperature is cooled using a shell and tube heat exchanger
embedded in the reactor vessel. The heat consumption is governed by the equation

The heat lost from the incoming stream is a simple heat transfer equation

where the heat capacity is still the sum of the individual heat capacity multiplied by the
flow rate of each component. These heat capacities are still temperature dependent. The
inlet temperature to the next stage is input to a desired value.
The next design case involves cold shot cooling. The design equations remain the
same, but the temperature of the inlet to the subsequent stages changes based on the
outlet temperature of the preceding stage and the temperature of the cold shot stream.

The heat capacity dependency is still applicable; however, the inlet temperature to the
next stage is determined based on the fraction of initial feed taken from the initial feed
stream. In addition, the composition of the feed changes; this behavior differs from the
constant feed composition between stages in inter-stage cooling.

Relevant equations

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dimensions. What did you measure and how?]
Safety
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experiment you described above. There are some safety issues that are common to
several of the experiments and some that are unique to each. Both the general and
specific safety considerations should be described]
Sample Calculations
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Results
Three operating pressures are simulated. The three adiabatic and equilibrium lines
and their corresponding equations are presented below
Three Pressure Ad and EquilLines
At higher pressure, the conversion is greater. However, the heat required to operate the
vessel adiabatically is

Important points to consider:

The size of the reactor for a single vs three stage
What temperature do you want to go down to between stages
The heat transfer area needed for the exchangers
Inclusion of recycle and how it would affect the results
Why the conversion is so low- comment on thermodynamic limits and why 21%
conversion is the maximum amount possible

Each of the laboratories has some unique and important safety issues that need to be
considered and there are some safety issues that are common to several of the
experiments.
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Specify what data you are presenting, how you analyzed them, and what you concluded
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Remember to maintain consistency with the Methods section and the Sample calculations
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Conclusions/Recommendations
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Appendix 1.

Figure A1: Fugacity Coefficients

Figure A2: Effectiveness Factor

Figure A3: Enthalpy of Reaction

Figure A4: Heat Capacity of Ammonia

[Put your data in Appendix 1. Some experiments may require only one appendix for raw
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Appendix 2.
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response to those questions in Appendix 2.]

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Appendix 3.
[Appendix 3. any other supporting documentation for your report]

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References
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Appendices
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