Failure mechanisms and material degradation

processes at high temperatures in

ammonia synthesis
J. Korkhaus*
Ammonia has been manufactured on an industrial scale for almost 100 years. Nevertheless, this
process still presents a challenge to the materials involved and to the material engineers who are
responsible for the selection of materials. This is due to the temperatures and the media handled.
Failure mechanisms that have been known in ammonia plants since the industrial production of
ammonia started are hydrogen attack, creep and embrittlement. Since the new generation of
plants characterised by optimised heat recovery have been in service, metal dusting has
emerged as a relatively common problem in ammonia plants following the secondary reformer. In
the present study, the wide range of failure mechanisms and material degradation processes
observed in ammonia plants is illustrated by a number of examples, some of which relate to the
historical development of the process.
Keywords: Ammonia plants, Failure, Hydrogen attack, Materials degradation, Metal dusting

Introduction to this problem and probably also for the realisation of

The widespread industrial production of ammonia
started with the introduction of the Haber-Bosch
process in September 1913. At that time, the first plant
went into service at BASF Aktiengesellschaft in
Ludwigshafen-Oppau with a daily output capacity of
30 t of ammonia.
From the time Fritz Haber first approached BASF to
seek support for his ideas to the start-up of the industrial
plant, an interval of only about 5 years was needed. This
was to the credit of Carl-Bosch and his team at BASF,
who were charged with responsibility for solving the
basic problems involved with the process on an
industrial scale.
The main challenge the team had to solve was that the
reactors of the pilot plant were made of carbon steel
running at 400–500uC at a pressure of about 200 bars
with a gas atmosphere consisting of H2, N2 and
ammonia and failed after a short time of service.
Figure 1 shows a failed reactor bundle and a contact
tube from a pilot plant.
Bosch, who not only studied chemistry but also had
an excellent knowledge of metallurgy, conducted metal-
lographic failure analyses and found that the carbon
steel exhibited decarburisation combined with internal
fissuring. As is now known, these are the typical features
of hydrogen attack. Figure 2 demonstrates these metal-
lographic findings. It was the breakthrough with respect
BASF Aktiengesellschaft Werkstofftechnik, WLE/AC – L 443, 67056
Ludwigshafen, Germany
*Corresponding author, email juergen.korkhaus@basf-ag.de
the process on an industrial scale that Bosch found a
solution. Based on his observations he concluded that
iron free of carbon would not show this kind of failure
mechanism. The reactor construction was changed by
introducing a soft iron liner within the pressure bearing
shell. Hydrogen diffusing through the liner was led out
through so-called Bosch holes. These were holes in the
pressure bearing shell, which did not degrade its pressure
bearing capacity. In this way, the carbon steel of the
shell could be protected from hydrogen attack.
Figure 3 shows a simplified flow diagram for a coke-
based ammonia plant from the 1930s.1 In principle, the
ammonia process, although approaching its 100th
anniversary, is still the same today. Its efficiency and
energy consumption, however, have been optimised
dramatically, as indicated in Fig. 4. In the following
paragraphs, some examples of failures and material
degradation occurring at high temperatures in ammonia
plants are presented which demonstrate that the
ammonia process itself still represents a challenge for
the materials involved and the materials engineers
although the product is nowadays regarded as a
commodity.
Modern steam-reforming ammonia
process
Figure 5 shows BASF’s youngest ammonia plant, in
Antwerp, having an annual capacity of 650 000 tons,
which is more than 10 times the Ludwigshafen capacity
in 1921.
In Fig. 6, a block diagram is presented which indi-
cates the different steps of a modern steam reforming

ß 2005 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Accepted 26 July 2005
204 Corrosion Engineering, Science and Technology 2005 VOL 40 NO 3 DOI 10.1179/174327805X66245
 Korkhaus
1 Failure by hydrogen attack in ammonia pilot plant in
1910
2 Hydrogen attack in catalyst tube of ammonia pilot
plant in 1910
3 Simplified flow sheet of coke-based ammonia plant in
1930s
4 Specific energy consumption in ammonia plants
ammonia process, together with the gas temperatures.1
Temperatures above 400uC are involved in the reform-
ing part – primary and secondary reformer, subsequent
steam production, the CO-shift reactor, ammonia
synthesis and the process gas cooler. In any of the
adjacent components, failures have been observed in the
past.
Primary and secondary reformer
The primary reformer consists of a tube furnace, where
the feed of methane and steam is converted to a mixture
of CO/CO2 and hydrogen at temperatures of about
Corrosion Engineering, Science and Technology
Failure mechanisms and materials degradation in ammonia synthesis
5 Ammonia plant in Antwerp
6 Block diagram and gas temperature profile for steam
reforming ammonia plant in Antwerp
7 Inner view of primary reformer
800uC and a pressure of 30 bars. The vertical tubes are
filled with a NiO catalyst. The tubes are externally
heated by natural gas burners. Figure 7 gives an
impression of the internal appearance of a primary
reformer. The vertical tubes are centrifugally cast and
consist of austenitic steels such as GX-40 NiCrSiNb 35-
25 (1.4852) and GX-10 NiCrNb 32-20 (1.4859). Failures
occurring here are usually caused by creep, which is
critical because the combination of membrane stresses
due to internal pressure and the high heat flow leads to
maximum stresses at about one-third of the wall
thickness from the inside. This means that classical field
metallographic methods to check for initiating creep are
not applicable. Furthermore, the coarse microstructure
of the cast material does not favour regular methods of
non-destructive testing. Determining the remaining life
of tubes is, therefore, quite difficult and needs specialised
testing methods. Figure 8 shows a cross-section of a
failed tube from a primary reformer.
2005 VOL 40 NO 3 205
Korkhaus Failure mechanisms and materials degradation in ammonia synthesis

10 Relaxation cracking in Alloy 800 H outlet header;

cracking in longitudinal weld

8 Creep damage in reformer tube

The hot gas leaving the primary reformer is led

through a bricked transfer line to the secondary
reformer. The secondary reformer, having the highest
temperatures of the process, and the transfer line to the
boiler, are bricked as well. Compressed air is fed into
the secondary reformer together with the gas from the
primary reformer. In this way, nitrogen is introduced
into the process. 11 Relaxation cracking in Alloy 800 H outlet header;
In the bricked reactor and the adjacent transfer lines, cracking near pipe-to-tube connection welds
high temperature failures have occurred in the past
because of failures of the refractory as the outer shells
consisting of low alloyed or carbon steels cannot resist
the high temperatures in combination with a pressure of
about 30 bars.

Process air line and air preheater

In the modern steam reforming ammonia process, the
preheating of compressed air to high temperatures
makes the selection of austenitic materials necessary.
Design temperatures of more than 600uC are common.
This was the case in BASF’s Antwerp ammonia plant.2
The air preheater coil and the headers are therefore
made out of Alloy 800 H. Figure 9 shows the air
preheater coil and the headers in a sketch. In the outlet
header, cracking was experienced after 2 years of service.
The outlet header (see right-hand side of Fig. 9) has a
diameter of 508 mm, a length of 4720 mm and a wall
thickness of 34.5 mm. The operating temperature is
about 600uC (design temperature 630uC). The header
was manufactured out of solution annealed Alloy 800 H
plate material, which was sequentially cold bent into a
cylindrical shape and then longitudinally welded with an
Alloy 600 Ni-base filler.
Following manufacture, no further heat treatment
was performed. After leakage was detected in the outlet
header, extensive dye-penetrant testing was conducted
9 Air preheat coil and outlet header
12 Metallographic appearance of relaxation cracking in
Alloy 800 H outlet header
which revealed cracking close to the pipe-to-tube
connection weld in the pipe material and near the
longitudinal weld. The crack in the pipe material close to
the pipe-to-tube connection welds followed part of the
circumference of the connection weld, then crossed over
into the longitudinal direction to the next pipe-to-tube
connection weld, where it again followed part of the
connection weld, etc. In the vicinity of the longitudinal
weld, cracking was found in the longitudinal direction in
the heat affected zone and in the transverse direction
crossing the weld. Figures 10 and 11 show cracking in a
segment which was cut out of the header.
The metallographic examination of cross-sections
revealed intergranular cracking starting from the outside
in all cases. On the crack surfaces, oxide layers were
found which contained metallic filaments rich in nickel
(Fig. 12). These are indications of relaxation cracking.
Relaxation cracking in materials like Alloy 800 H is
caused by high residual stresses from fabrication (cold
deformation, welding, etc.) or by cyclic deformation
during service at temperatures in the range of 550–
760uC.3 In this temperature range, the critical nucleation
radius for carbide precipitation is very small. Fine
carbides (mainly chromium carbides) are precipitated
within the grains at dislocations after short periods of

206 Corrosion Engineering, Science and Technology 2005 VOL 40 NO 3

 Korkhaus
13 Microstructural constitution of Alloy 800 H after ser-
vice at about 550–760uC
time leading to strengthening of the grains (Fig. 13). At
the grain boundaries, coarse chromium carbides are
present, leading to chromium depletion in the vicinity.
Consequently, precipitation-free zones of low strength
occur beside the grain boundaries. Because of the
relative difference in strength between the grains and
the grain boundaries, deformation under relaxation
conditions will take place at the soft grain boundaries
leading to crack formation at relatively low overall
deformations. A similar mechanism was proposed to
explain the stress relief cracking in microalloyed steels.
Crack formation starts in a stepwise manner on both
sides of the grain boundaries in the weakened zones,
producing a metal filament in the middle, which by
oxidation processes becomes rich in Ni. Because of
the comparatively high dislocation density and the
existence of high residual stresses, the heat affected
zones of weldments are the most critical areas for crack
formation.
Practically all of the austenitic and Ni-base materials
usually applied at elevated temperatures are more or less
susceptible to relaxation cracking if they contain carbon
in an amount considerably above the solubility limit. A
remedy for this kind of cracking is to undertake a final
heat treatment, which in the case of Alloy 800 H should
be near 950uC. At this temperature, the carbide
precipitates are coarser and, therefore, the difference in
strength between the grain boundaries and the grain
interior is reduced. In the course of fabricating the
replacement header, a two-stage heat treatment was
performed. After cold bending a heat treatment at 950uC
was performed followed by a heat treatment at 850uC
after welding.
Another way to handle relaxation cracking problems
is to make use of the austenitic steel 1.4910, X 3
CrNiMoN 17-13, which has a low carbon content and is
14 Location of metal dusting found in outlet portion of
waste heat boilers
Corrosion Engineering, Science and Technology
Failure mechanisms and materials degradation in ammonia synthesis
15 Superheater of NH3 plant at BASF Antwerp
nitrogen alloyed. This has also proved to be a good
remedy in other cases where relaxation cracking has
occurred.
Waste heat recovery units following
secondary reformer
Figure 14 is a schematic drawing of the waste heat
recovery units downstream of the secondary reformer.
First there is a waste heat boiler which in some modern
plants is followed by one or two superheaters. In the
boiler, the hot gas from the secondary reformer is led
through the tubes; the boiler feedwater is on the outside.
In many cases, the superheaters consist of U-tube
bundles.
In both plant items, the gas consisting of CO, CO2, H2
and N is cooled down, passing through non-equilibrium
conditions where the carbon activity considerably
exceeds unity. Therefore, metal dusting has been
experienced in the areas indicated in boilers and super-
heaters.4 In BASF’s ammonia plant in Antwerp, a
serious case of metal dusting occurred in the first
superheater after the waste heat boiler, which was also
affected by metal dusting in the outlet area.2
Figure 15 shows a schematic drawing of the super-
heater with its U-tube bundle and a photograph of the
pulled U-tube bundle, together with the service condi-
tions. As a result of the design temperatures of 650uC,
the U-tube bundle and also the liner were initially made
of Alloy 800 H.
After about 9 months in service, heavy coking was
observed on the U-tube bundle and liner. After removal
of the coke, a heavy pitlike metal dusting attack was
observed. Figure 16 shows an attacked part of the
bundle together with metallographic sections through
pits indicating the heavy carburisation in the pitted area.
In the area not attacked, no carburisation was observed.
16 Metal dusting at superheater of NH3 plant at BASF
Antwerp
2005 VOL 40 NO 3 207
Korkhaus Failure mechanisms and materials degradation in ammonia synthesis
17 Failure mechanism by metal dusting
The 800 H liner was also attacked by metal dusting,
while the Alloy 600 weld of the liner was undamaged.
In Fig. 17, the mechanism of failure by metal dusting
is shown in principle, together with a simple quantitative
relationship for estimating the carbon activity. Metal
dusting is a form of attack which requires a carbon
activity in excess of 1. For austenitic steels and Ni-
base alloys, it has been found that temperatures of
about 600–650uC are the most critical ones in syngas
atmospheres.
The surface of the material is, for the most part,
protected from gas phase carburisation by an oxide film.
At defects like cracks, etc., which may arise in the oxide
layer, contact between the bare metal surface and a gas
phase having a carbon activity above 1 leads directly to
carburisation and the formation of stable and unstable
carbides. Since the bare metal surface also acts as an
active site for coke deposition from the gas phase, coke
deposits will form, which lead to a dramatic change in
the thermodynamics of the system. As a consequence,
carbides that are only stable when in equilibrium with
the gas phase will decay into graphite and metal. Owing
to the higher specific volume of the graphite, disintegra-
tion of the material into metal particles and graphite
takes place. In the specific case of the superheater
bundle, the tubes made of Alloy 800 H lost about
0.9 mm within 9 months, which is about one-third of the
total wall thickness. This indicates the high rate of the
attack. The observation that weld metal of an Alloy 600-
type was not attacked gave a first indication of the
remedy. However, since the first bundle, experience with
several others using Alloy 600 and Alloy 601 has
demonstrated that Alloy 600 is obviously an appropriate
material choice for this application. Alloy 601 was
considerably worse and in another Alloy 600 replace-
ment bundle, other failures occurred. One of the main
problems when looking at many processes in the
petrochemical industry is that all of them are running
under conditions where the gas phase has a carbon
activity well in excess of 1. Although several research
programmes on metal dusting have been run, there are
still problems in predicting the criticality of the gases
when attempting to select materials in an economically
and technically appropriate manner. What has been
established in a research programme at TNO5 is the
ranking of materials shown in Fig. 18, which appears to
be reproducible. However, surface treatment is also
important. Ground and sandblasted surfaces seem to be
superior compared with those produced using other
surface treatment methods.
208 Corrosion Engineering, Science and Technology 2005
18 Metal dusting resistance of materials (according to
TNO5)
Ammonia reactors
In ammonia reactors, there is potential for nitridation of
materials in long term service. Temperatures in the
reaction zone are normally about 520uC. Figure 19
shows a thermowell tube made out of the austenitic steel
1.4541 (X 6 CrNiTi 18-10), which failed due to
nitridation. Normally these tubes, which are pushed
through the different catalyst layers, are changed at
regular intervals. This tube was missed, so that the
nitridation reached a critical extent. In the external dark
area, the nitridation was so heavy that practically all of
the chromium contained in the material was consumed.
Because of the residual stresses combined with the
formation of such a zone, which is brittle in nature,
multiple equidistant cracks had formed, leading to
locally deeper nitridation. Finally, the remaining cross-
section was no longer sufficient and rupture occurred.
At BASF in Ludwigshafen, one of the ammonia
plants operates with hot-walled reactors. These are
reactors where the pressure-bearing wall is heated by the
hot inlet gas to a temperature of about 400uC. Figure 20
shows the process scheme for the conversion consisting
of two reactors in series where the ammonia content is
increased in stages, reaching 16% of the stream at the
outlet of the second reactor. The material of construc-
tion was a 2JCr–1Mo steel. Figure 21 demonstrates
where the operating conditions of the two reactors lie
with respect to temperature and hydrogen partial
pressure on the Nelson diagram. After 8 years of
operation, a leak was observed within a 175 mm thick
girth weld, the closing seam of the second reactor, which
contained the higher ammonia concentration. Extensive
ultrasonic testing and metallographic examinations
revealed a considerable amount of cracking over the
19 Fracture of thermowell tube due to nitridation
VOL 40 NO 3
 Korkhaus
20 Process scheme, NH3-IV-Plant, BASF Ludwigshafen;
part of conversion
21 Operating limits of steels in hydrogen service to
avoid decarburisation and fissuring
22 Converter C 702
whole circumference of the weld.6 Figure 22 shows a
sketch of converter C 702 and the position of the closing
seam, which was cut out in the course of the repair work.
Figure 23 indicates the depth of cracking attained over
the circumference of the weld. Metallographic cross-
sections of the weld revealed the very distinctive
appearance of the microstructure along the cracks
(Fig. 24). The cracking was intergranular and the cracks
were accompanied by a band indicative of decarburisa-
tion.7 Obviously, the cracking was assisted by hydrogen
attack. The mechanism responsible for the damage is
demonstrated in Fig. 25. The initial stage in cracking is
nitridation by ammonia. Since the chromium carbides in
the steel, which protect it from hydrogen attack, are less
stable than chromium nitrides, chromium carbonitrides
are formed and a certain amount of carbon is released.
This carbon forms methane in combination with the
hydrogen dissolved in the material. In the case of low
mechanical stresses, a nitrided zone is formed in which
Corrosion Engineering, Science and Technology
Failure mechanisms and materials degradation in ammonia synthesis
23 Converter C 702 – crack path and partition of crack
welded seam
24 Converter C 702 – failed closing seam
25 Damage by synthesis gas
cracking by hydrogen attack occurs parallel to the
surface, as shown in the upper part of Fig. 25. The
decisive factor for the cracking perpendicular to
the surface was that, in the closing seam, high residual
stresses were present after fabrication, because this seam
was locally heat treated. Under the action of these high
stresses, cracking by hydrogen attack no longer occurs
parallel to the surface but perpendicular to it, as
indicated in the lower section in Fig. 25.
The plant management subsequently decided to
replace the reactor. Again 2JCr–1Mo steel was
selected. The wall thickness, however, was adjusted to
comply with an ASME design code. Furthermore, it was
decided that final heat treatment had to be conducted in
a furnace. Nevertheless, during regular shut downs, the
girth welds of the reactors are inspected with a highly
sophisticated ultrasonic testing program. Up to now, no
cracks have been detected in the new reactor.
As indicated in the process scheme in Fig. 20, heat
recovery is conducted in the conversion by preheating
the synthesis gas (W 721, W 723) and by steam
production (W 722). As the vessels are charged with
ammonia and hydrogen-containing gas at high
2005 VOL 40 NO 3 209
Korkhaus Failure mechanisms and materials degradation in ammonia synthesis
26 Inlet part of process cooler in ammonia plant
temperatures, there is always potential for nitridation,
hydrogen attack and embrittlement. As a result of the
high pressures involved, conventional low alloyed Cr–
Mo steels are applied, having excellent strength at the
service temperatures. In order to handle the problems of
nitridation, hydrogen attack and embrittlement, intelli-
gent designs have been developed which make it possible
to operate heat exchangers made from these materials
under such critical conditions in long term service.
Figure 26 demonstrates an example of such a design for
a boiler directly heated with hot gas having a high
ammonia concentration.
For pressure and temperature reasons, the tube sheet
of the gas cooler has a thickness of more than 400 mm.
The hot gas is led through the tubes. To protect the
tubesheet from direct contact with hot gas at a
temperature of more than 410uC, there is high tempera-
ture insulation on the tube sheet. The hot gas is led
through Alloy 600 H type ferrules in this area.
The shape and length of the ferrules is chosen in such
a way that they act as insulation against the hot gas in
the region of the tubesheet, where no cooling due to heat
exchange occurs. The tubesheet itself is weld-overlaid
with Alloy 600 material. Here the tubes made of Cr–Mo
steel are welded in. The design makes it possible to
perform repairs because the Ni-base material is resistant
to nitridation and hydrogen attack under the service
conditions. As can be appreciated, this kind of
intelligent design takes into consideration possible
material degradation in the hot product gas stream
210 Corrosion Engineering, Science and Technology 2005
and makes it possible to use conventional Cr–Mo steels
under such critical conditions.
Summary
Although ammonia itself is a widely used commodity
nowadays, its production still remains a challenge for
the materials involved. As demonstrated by several
examples, a wide variety of high temperature corrosion
processes and mechanisms of material degradation may
occur in an ammonia plant during service. Material
concepts for modern plants are mostly driven by the
wish to increase the energy efficiency of the process.
Therefore, temperatures exceeding 600uC are common
locally, which necessitates the use of austenitic steels.
This step is combined with surprises in the form of
unexpected failure mechanisms as has been shown by
experience with Alloy 800 H, which has failed due to
relaxation cracking and metal dusting. Although the
mechanism of the multi-stage metal dusting process is
quite well understood, it in particular remains an
unsolved problem insofar as it is still not possible to
predict with certainty whether or not it will occur.
There is still a need for further research.
References
1. M. Appl: ‘Ammonia: principles and industrial practice’; 1999, New
York, Wiley VCH-Weinheim.
2. J. Dejaeger, L. Guns and J. Korkhaus: ‘Experiences with Alloy 800
H in ammonia plants’, AIChE, Technical Manual, Ammonia Plant
Safety, Vol. 35, 1994.
3. TNO-Research Project: ‘Prevention of relaxation cracking by
material selections and/or heat treatment’, Final Report,
Apeldoorn, November 2000 – unpublished.
4. T. Shibasabi, K. Takemura, T. Mohre and H. Hashimoto:
‘Experiences with metal dusting in H2/CO/CO2/H2 atmosphere’,
AIChE, Technical Manual, Ammonia Plant Safety, Vol. 37, 1996.
5. TNO-Research Project: ‘Prevention of metal dusting in chemical
production plants’, Final Report, Apeldoorn, October 2003 –
unpublished.
6. A. Heuser: ‘Repair of a thick-walled ammonia synthesis converter
containing a leak’, AIChE, Technical Manual, Ammonia Plant
Safety, Vol. 32, 1993.
7. G. H. Wagner, A. Heuser and G. Heinke: ‘Hydrogen attack in
2JCr–1Mo steel below Nelson’s curve’, AIChE, Technical
Manual, Ammonia Plant Safety, Vol. 3, 1991.
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