Ammonia Synthesis Theory and Operation

948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 1
Information contained in this publication or as otherwise supplied to Users is believed to be accurate and correct at time of going to
press, and is given in good faith, but it is for the User to satisfy itself of the suitability of the Product for its own particular purpose.
Johnson Matthey gives no warranty as the fitness of the Product for any particular purpose and any implied warranty or condition
(statutory or otherwise) is excluded except to the extent that exclusion is prevented by law. Johnson Matthey accepts no liability for
loss or damaged (other than that arising from death or personal injury caused by Johnson Matthey’s negligence or by a defective
product, if proved), resulting from reliance on this information. Freedom, under Patent, Copyright and Designs cannot be assumed.

948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 2
1 Introduction

Ammonia Synthesis is an important part of any ammonia plant. As such the importance of the good
operation, monitoring and maintenance of the ammonia synthesis loop can not be under-stated.

The purpose of this paper is to,

• Detail some fundamentals about the chemistry of ammonia synthesis,

• Detail the principles of the operation of ammonia synthesis,
• Discuss some common operating problems.

948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 3
2 Ammonia synthesis theory

2.1 Chemistry

The following reaction details the reaction that converts nitrogen and hydrogen to ammonia,

3H2 + N2 Ù 2NH3 ∆H = -52.1 kJ/kmol

2.2 Optimal pressure

Since there is a large volume decrease associated with the synthesis of ammonia (4 volumes to 2
volumes), the synthesis reaction is favoured by high pressures.

Older ammonia plants required pressures between 300 and 600 bara, however with modern catalysts and
converter designs, the synthesis loop pressure has been reduced to 100-300 bara. Furthermore, the
Johnson Matthey Catalysts AMV and LCA process operate at an even lower pressure, typically 80 - 100
bara.

2.3 Optimal temperature

An analysis of the thermodynamics equilibrium for the synthesis reaction shows that the highest possible
yield is achieved at the lowest possible temperature as illustrated in the figure below,

Figure 1 – Maximum rate line

40

Equilibrium

30
Max Rate
Ammonia content %

20

10

0
300 350 400 450 500 550 600 650
Temperature °C

948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 4
However, balanced against this is the reaction rate, which is related to the operating temperature by a
classic expression as below,

d[NH3]  − ∆E 
∝ exp
dt  R × T 
So at high temperature, the reaction rate of ammonia synthesis will be high whilst at low temperatures,
the reaction rate will be lower.

Considering both factors above, there is a balance between the equilibrium and reaction kinetics. The
operating temperature range for synthesis catalyst is 350 – 520°C, constrained by kinetics at low
temperature and sintering at high temperature. There is a limited temperature range between the
minimum strike temperature of synthesis catalyst and the equilibrium temperature required for a high
conversion per pass. To satisfy these temperature constraints it is necessary to cool the converter, and
various cooling arrangements are used.

• Addition of cold quench gas,

• Transfer of heat from the catalyst bed to colder feed gas,
• Cooling between beds by transfer of heat within heat exchangers to a medium such as steam.

3 Poisons

The most common poison for ammonia synthesis catalysts is oxygen in the form of oxygenated
compounds such as water, carbon monoxide and carbon dioxide. Under ammonia synthesis conditions,
oxygenates are converted to water and this is considered to be the active poison.

Carbon oxides should be converted in the methanation stage of the front end of the plant, and excessively
high carbon oxides are only a problem if the methanator fails to perform correctly.

Water should be removed in the knock out pots prior to the carbon dioxide removal system and between
stages of the synthesis gas machine.

Poisoning of ammonia synthesis catalysts can be either temporary or permanent.

3.1 Temporary poisoning

Loss of activity from exposure to oxygen compounds is normally reversible provided that the partial
pressure of the oxygenate is low and the period of exposure has been restricted to a few days. Under
these circumstances the catalyst can normally be reactivated by following a reduction procedure. Some
permanent damage is likely to take place even during temporary poisoning due to thermal sintering and
reorganization of the iron surface. However, this is not normally seen as a loss in production.

3.2 Permanent poisoning

Exposure to oxygenates for several weeks normally results in permanent deactivation of the ammonia
synthesis catalyst. Activity does not completely recover when pure synthesis gas is re-introduced or the
catalyst is re-reduced. When the reduced catalyst is exposed to moderate partial pressures of water
vapour, partial and reversible surface oxidation takes place. However, the transient oxidic phases do not
contain alumina in solid solution. Hence during re-reduction there is no support-precursor phase present
to prevent sintering of the iron crystallites. It is also thought that this oxidation/ reduction mechanism

948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 5
could result in the reorganisation of the crystal faces, decreasing the population of the highly active
Fe(111) faces.

Other compounds will affect the catalyst irreversibly. These poisons include sulphur, chlorine, arsenic
and phosphorous. Sulphur remains on the catalyst surface as bulk iron sulphide. Catalysts in operating
plants that have lost activity as a result of poisoning have been found to contain less than 0.1% sulphur.
Chlorine compounds are also severe poisons because the metal chlorides are relatively volatile and their
transient formation can lead to irreversible sintering and hence loss of activity.

In addition to chemical poisoning of the iron surface, ammonia synthesis catalysts are also susceptible to
loss of activity due to the physical covering of the active sites by an otherwise inert material. Compressor
lubrication oil leaking into the process will result in cracking of the hydrocarbons to form carbon, which will
act as a physical barrier. This poisoning can be partly reversible provided that the problem is recognized
quickly, however permanent damage sometimes occurs.

4 Catalyst

4.1 Promoters

Ammonia synthesis catalysts have been traditionally been based on magnetite along with a range of
specialised promoters. It is the addition of these promoters that gives the difference between the various
commercially available ammonia synthesis catalysts and this is illustrated below,

Table 1 – Catalyst composition

Parameter Units 35-4/S6-10 74-1

Magnetite % 94 94.5
K2O % 0.5 0.6
CaO % 2.5 1.5
Al2O3 % 3.0 2.1
SiO2 % n/a <0.2
MgO % n/a n/a
Co % n/a 1.0

It is these promoters that define the initial activity and stability of the catalyst.

4.1.1 Effect of promoters

There are a range of promoters that are added to magnetite catalyst; the effects of these promoters are
as detailed below,

• Alumina (Al2O3) – This functions are a structural promoter, enabling the production and
preparation of an open and porous structure. During the initial catalyst activation, reduction starts
on the outside of the irregular particles, and the dissolved alumina separates out of the solid
solution within the pores forming between the iron crystallites. This minimises further crystallite
growth during the catalyst reduction and future operation.
• Potash (K2O) – This component is an electronic promoter, functioning by considerably increasing
the intrinsic activity if the high surface area iron particle produced on reduction.
• Calcium Oxide (CaO) – This promoter (as well as other basic promoters), react with silica
impurities in the raw materials to form glassy silicates, which themselves can enhance the

948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 6
 thermal stability of the reduced iron. The main benefit is to minimise any neutralisation of the
potash promoter which would reduce it effectiveness.

There is a considerable interaction between the many components of the catalyst which can radically
affect both the initial reducibility and level of initial activity and long term activity stability. A through
understanding of these interactions is vital in order to optimise the performance of the catalyst.

4.2 Catalyst size

A key feature of all ammonia synthesis catalysts is that there is a diffusion limitation. The catalyst size is
important since the smaller the catalyst pellet, the higher the surface area per unit volume and hence
there is more surface area within the converter to catalyse the ammonia synthesis reaction. The following
figure illustrates the effect of size on catalyst activity.

Figure 2 – Effect of catalyst size on activity

120
100
Relative Activity

80
60
40
20
0
0 2 4 6 8 10 12 14
Particle Diameter (mm)
However, if a smaller catalyst size is used to maximise the activity if the catalyst, then this will increase
the pressure drop across a bed. Therefore, in order to offset this effect, modern practice is to use radial
(or axial-radial) flow through the catalyst beds.

Due to the unique manufacturing route that is used to produce ammonia synthesis catalyst, there is no set
catalyst size, but rather a set of size ranges. The industry accepted ranges are detailed in the table
below,

Table 2 – Effect – size ranges

Size Grade Size Range

Units mm
A 1.5-3.0
B 3.0-4.5
C 3.0-6.0
D 6.0-10.0
G 14.0-20.0

948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 7
5 Converter schemes

As noted above, the exothermic nature of the ammonia synthesis reaction, the effect of catalyst size,
contractor choice and the option for retrofits have defined the nature of the various converter designs that
have been historically available and presently available. The various converter types include,

• The Kellogg Axial Quench Converter design,

• The Kellogg horizontal Converter,
• The Johnson Matthey Catalysts Quench Cooled Converter
• The Johnson Matthey Catalysts Tube Cooled Converter (and similar TVA converters),
• Axial radial designs as offered by Ammonia Casale,
• Haldor Topsøe Radial Flow Converter,
• Uhde Radial Flow Converters.

5.1 Kellogg quench type converter

The following illustrates a Kellogg Quench Converter with 4 axial flow beds and inter-bed cooling by
addition of quench gas,

Figure 3 – Kellogg quench converter

Outlet

Inlet

948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 8
5.2 Kellogg horizontal converter

The following figure illustrates the Kellogg Horizontal Converter, This design uses downward flow in beds
installed in a horizontal pressure shell. The objective is the same as in radial flow designs, i.e. low
pressure drop with small catalyst particles,

Figure 4 – Kellogg horizontal converter

Inlet

Bed 2B Bed 2A Bed 1

Outlet

5.3 Johnson Matthey quench cooled converter

The following figure illustrates the Johnson Matthey Quench Cooled Converter. The ‘lozenge quench’
system was designed to simplify catalyst loading and discharge.

Figure 5 – Johnson Matthey quench

948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 9
5.4 Johnson Matthey tube cooled converter

The following figure illustrates the Johnson Matthey Tube Cooled Converter as used in LCA ammonia
plants. An adiabatic section is included at the exit of the catalyst bed to optimise the temperature profile,

Figure 6 – Johnson Matthey Catalysts TCC

5.5 Haldor Topsøe radial flow converter

Haldor Topsøe’s radial flow converters have been installed in a range of configurations, e.g. S-100 2-bed
with quench cooling, S-200 2-bed with interchanger cooling and S-300 3-bed with interchanger cooling.
The following figure illustrates a S-200 design,

Figure 7 – Haldor Topsøe S-200

Inlet

Cold Outlet
Bypass

948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 10
5.6 Uhde’s three bed radial flow converter

Uhde’s radial flow converter technology is available in a range of configurations to suit the application.
The following figure illustrates the loop lay out for an Uhde three bed radial flow converter in a large-scale,
high conversion per pass application,

Figure 8 – Uhde ammonia loop flowsheet

HP steam

Refrigeration
Purge

C.W.
NH 3
( liquid )
BFW
Make-up gas

Syngas compressor

The following illustrates the design of the first double bed converter and the design of the third and final
bed converter,

Figure 9A/B – Uhde converters

Gas inlet
Start up gas

First bed

Second bed Third bed

Gas inlet
Gas outlet Gas outlet

948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 11
6 Control parameters

On initial inspection, there would appear to be a large number of control parameters including,

• Loop pressure,
• Gas composition,
• Circulation rate,
• For temperature control within the converter, the quench rates and / or bypass valve positions.

However, in reality, ammonia synthesis loops are very stable and do not require constant attention. The
principal control parameters are as follows:

6.1 Loop pressure

Loop pressure increases as the inert level in the synthesis loop increases. The pressure is controlled by
varying the loop purge rate; some plants use cascade control with the purge flow setpoint re-set by the
pressure, in many cases a simple flow controller is adequate with manual control of the setpoint. Loop
pressure tends to increase slowly with time because of an increase in methane from the front-end and
because of loss of activity of the synthesis catalyst.

6.2 Gas composition

As mentioned above, the methane content of the make-up gas tends to increase slowly as a result of
catalyst die-off. The other main variable in the circulating gas composition is the H2:N2 ratio. This depends
on the air rate to the secondary reformer, and is usually controlled manually although some plants do
have automatic control of H2:N2 ratio. The optimum ratio is believed to be around 2.8 under most
conditions, although the effect on loop performance is small over quite a wide range.

6.3 Circulation rate

The circulation rate is not a control parameter since on the majority of plants, the synthesis gas machine
and circulator are on the same shaft and therefore the speed and hence the circulation rate is determined
by the speed of the synthesis gas machine. However, some compressors have guide vanes on the
circulator to give independent control of the compression and circulation duties. When guide vanes are
fitted, they are usually controlled manually.

6.3.1 Converter temperature control.

For quench based converters, the quench flows to the individual beds can be varied in order to optimise
the temperature profile through the converter. Control of quench flow rates is usually manual (by HICs)
because the rate of die-off of ammonia synthesis catalyst is very slow. The inlet temperature to the first
catalyst bed is a particularly sensitive control parameter and in some plants this temperature is on
automatic control (by varying the bypass flow) because this stabilises the operation of the entire
converter.

For converters with inter bed cooling by heat exchangers, the bed temperatures are controlled by heat
exchanger bypasses rather than by quench flow rates.

948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 12
7 Monitoring

7.1 Production rate

The ammonia production rate should be monitored as an overview check on the performance of the plant
as a whole. Reduction in the production rate indicates that there is the potential for a problem in one of
the upstream unit operations.

7.2 Loop pressure

The loop pressure should be monitored as this is a good general indication of a loss of efficiency in the
synthesis loop. An increase in loop pressure may be caused by many factors including high inerts
concentration, loss of catalyst activity or low circulation rate. Further investigation will be required to
identify the problem.

7.3 Gas composition.

The circulating gas composition should be monitored for inerts concentration and for hydrogen to nitrogen
ratio. The exit composition should be monitored for ammonia because this is a good indicator of converter
performance.

7.4 Pressure drop

The pressure drop across the converter should also be monitored to determine if there is attrition of the
catalyst or failure of the internals within the converter basket. Note that a reduction in pressure drop may
indicate a reduction in flowrate through the converter, e.g. because of a partial bypass due to an internal
leak.

7.5 Converter temperature profile

The temperature profile within the converter should be monitored in order to ensure that the ammonia
production rate is maximised. Furthermore, if there is a leak within the loop interchanger, this will be
reflected in a heat imbalance within the converter and hence an unusual temperature profile within the
converter.

8 Common problems

Modern ammonia synthesis loops are generally very reliable, although there are many problems that can
occur; below is a brief discussion of some of the more common problems. If as an operator you believe
that you have a problem, then you should consult your catalyst vendor.

8.1 Poisons

As noted above, oxygenates are the most frequent form of poisons for the synthesis catalyst. Common
sources are carbon oxides from a poorly performing methanator ( or from a leaking methanator
interchanger), water from carryover in the make-up gas separators, or oxygen from impure nitrogen

948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 13
during a plant overhaul. The first indication of a poisoning problem is usually a reduction in converter
performance as indicated by a high loop pressure or low conversion to ammonia.

Note that in extreme circumstances, e.g. ingress of air during an overhaul, oxidation of ammonia
synthesis catalyst can generate an exotherm of up to 1600°C.

8.2 Leaks

Internal leaks sometimes occur in synthesis loops; these can be in the loop interchangers, in the
converter internal interchangers, or in expansion bellows.
In many cases, Johnson Matthey Catalysts can identify leaks from evaluation of operating data, and
TRACERCOTM techniques can be used to confirm the leak.

Loop boilers and steam preheaters normally run at a lower pressure than the loop so leaks lead to
hydrogen/nitrogen in the steam rather than water on the synthesis catalyst. During shut-downs there is
the potential for the driving force to be the other way resulting in deactivation/oxidation of the synthesis
catalyst due to the ingress of water into the synthesis loop.

9 Conclusions

In conclusion, this paper has illustrated some of the key features of the ammonia synthesis loop, most
notably,

• The fundamentals of ammonia synthesis,

• The key control parameters,
• The common problems that can occur.

948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 14
948M/113/0/AMOG
© Johnson Matthey Group 2003 Page 15