REFINING

Catalyst catastrophes in
hydrogen plants
Processing mishaps can occur if catalyst is placed in abnormal conditions These
catastrophes include temperature runaways, the formation of toxic nickel
carbonyl, steam-reforming disasters, unplanned exotherms and side reactions
John R Brightling, Peter V Broadhurst and Mike P Roberts
Johnson Matthey Catalysts

A
catalyst normally performs the
reaction for which it was
designed without causing any
problems for the plant operator.
However, if subjected to abnormal
conditions, whether during normal
operation, start-up or shutdown, the
catalyst may perform other unplanned
reactions. These reactions can generate
large amounts of heat, produce toxic
materials or have other potentially
dangerous effects. In the worst cases,
there can be serious equipment damage
and a threat to personnel.
There have been many lessons
learned over the years from incidents in
which catalysts being used in hydrogen
plants and similar processes have
demonstrated unexpected behaviour as
a result of abnormal conditions that, in
general, have been outside those
specified in the operating procedures for
the catalyst in question.
The incidents include temperature
runaways, which have exceeded vessel Figure 1 Diagram of a steam reformer
design temperatures and even led to
vessel failure; catastrophic failure of opportunity, catalysts can also perform Frequency of incidents
steam reformer tubes; formation of the other unplanned and undesirable side- In addition to the safety, health and
extremely toxic nickel carbonyl; the reactions. Depending on the reactions, environmental implications of serious
effects of catalyst wetting; catastrophic these can generate large amounts of catalyst-related incidents, the plant
carbon formation in a steam reformer; heat, toxic materials or other phenom- operator can incur significant costs. The
hydration exotherms; catalyst milling ena, which present in the worst cases a cumulative costs of preventable
and reactor loading issues. In many danger to life, equipment or the incidents in the industry are not known,
cases, the analysis of these incidents environment. but it is likely that they amount to as
indicates that many occur during It should be remembered that there much as $10 billion. Paradoxically, a
infrequent procedures. An unfamiliar are significant potential hazards contributing factor to serious incidents
task assessment procedure and staff associated with the commercial-scale can be that plants, equipment and
training in the prevention and handling operation of most heterogeneous catalysts nowadays deliver incredible
of incidents should minimise incident catalyst systems. Considering the syngas reliability. This means there are much
frequency, especially at start-ups and industry, the catalytic stages of these longer periods of time between transient
shutdowns, which are becoming less processes operate between 200 and operations such as start-ups, shutdowns
frequent events as the reliability of plant 900°C (392 and 1692°F) and at pressures and the occurrence of serious problems,
systems improves. of 20–300 bara (290–4350psia). Many of which makes dealing with them less
Improvements in catalyst technology the process streams are flammable and frequent and more unfamiliar. It also
enable catalytic reactions to happen at explosive if mixed with air. Some presents the problem of retention of
ever-improving energy efficiencies, materials are noxious, such as ammonia, corporate knowledge that has been built
while also reducing their environmental amines and caustic compounds. Heat up over many years when there is staff
impact. For the most part, catalysts work management uses high-pressure steam turnover due to retirement, promotion
in a quiet, sustained way and perform systems and, in certain reactors, fired or job relocation.
the reactions required of them without heaters. Nitrogen is used to flush vessels All of the incidents described are
issue. This, however, can lead operators free of air or hydrocarbon and is an based on real events, which have
into a false sense of security. If given the asphyxiant. resulted in risk to personnel, major

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w w w. e p t q . c o m
 REFINING
plant equipment damage or irrecover-
able catalyst damage leading to a plant
1,2
outage. Although most examples
within the context of this discussion are
taken from syngas operations, the
lessons are more broadly applicable
across a wide range of catalyst
operations. However, each plant will
have individual circumstances and the
applicability of the lessons must be
reviewed in light of local operational
knowledge.
Steam-reforming disasters
For those unfamiliar with steam-
reforming technology, it lies at the heart
of most plants that make on-purpose
hydrogen in the oil refinery, as well as
those petrochemical facilities making H2
and H2/CO/CO2 mixtures for the
production of ammonia, methanol and
other petrochemicals. The catalysed,
strongly endothermic reaction of
hydrocarbon and steam produces a gas
rich in H2 and CO with some CO2 and
unreacted steam and methane. Thus,
the steam reformer is designed to pass
the process gas down many narrow
catalyst-filled tubes, which are
positioned inside a fired furnace. The
furnace provides the heat to drive the
reaction, and the narrow tubes provide a
large surface area between this heat
source and the process gas to enable
rapid heat transfer into the reacting gas.
The heat in the hot flue gas produced in
the furnace is recovered by heating the
incoming process streams (Figure 1).
The complex control and integration
of both the process and furnace side of
the steam reformer can lead to many
potential issues that could compromise
the operation. Examples of disasters that
can occur include:
— Tube failure during start-up due to
over-heating or thermal shock from
steam condensate carry-over
— Catastrophic carbon formation
causing pressure drop increase and
widespread catalyst damage
— Catalyst wetting leading to
widespread catalyst damage
— Nickel carbonyl formation.
Examples will be considered in these
areas, but it should be appreciated that
there are many other incidents that can
occur.
Tube failure on start-up
Throughout the world, there are one or
more steam reformers each year that
experience the failure of a significant
number, if not all, of their catalyst-filled
tubes. In the last 12 months, Johnson
Matthey Catalysts is aware of at least
seven such incidents, including one
complete reformer burndown.
As is invariably the case, the damage
was caused during a reformer transient,
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P T Q Q1 2006
either at start-up or, more commonly,
3
following a short trip. In most cases
following a trip-related outage, there is
pressure to bring the plant back on-line
as soon as possible. In these circum-
stances, some operators deviate from
the normal start-up procedures.
The heating duty for a modern, large
steam reformer is approximately
100–150MW (340–510mmBTU/hr). The
heat input is supplied by burners, each
of which liberates 1–2MW (3.4–6.8
mmBTU/hr). During normal operation,
the endothermic steam-reforming
reaction absorbs 50–60% of the heat. At
start-up, however, there is no reaction
occurring while the reformer is warming
up, where nitrogen is initially used until
the process steam reaches required
capacity. Also, at this stage, the flow
through the tubes is low, with only
40–50% of the normal operational
steam flow. Hence, the heat-transfer
coefficient and heat-transfer rate are
much lower than during normal
operation. This means the temperature
readings (for example, in the tube exits
and headers) that are reliable during
normal operation do not provide
representative readings. In addition, it is
imperative to limit the heat input to the
steam reformer to avoid excessive tube
skin temperatures and possible tube
failure. At 50% design steam flow, the
heat sink available is about 14%
compared to when the plant is
operating at 100% of design rate. The
same considerations exist during a
controlled plant shutdown or a plant
trip.
At this stage, the steam-reforming
catalyst is an “innocent bystander”. As
there is no hydrocarbon feed in the
process yet, there is no reaction to
catalyse and so the catalyst cannot
influence the temperature in the
furnace. The key points at start-up are:
— There is no substitute for visually
monitoring the tube appearance to
ensure that the tubes are not being
overheated
— Procedures to ensure that the correct
sequence for staged lighting of burners
must be adhered to at each stage of
start-up to maintain a uniform pattern/
heat generation.
Case study 1
Operating procedure deviations
In one recent incident, a plant tripped,
abruptly stopping hydrocarbon feed
flow to the steam reformer. There was
management pressure to re-establish
production and so a fast restart was
attempted. However, there were two key
deviations from standard operating
procedure: all burners remained firing at
full rate and the plant was maintained
at operating pressure (lowering the

pressure provides additional operating
margin for the tubes against failure).
Steam flow had been reduced in line
with procedure, but this action further
compromised the tubes’ integrity in
light of the full firing, as it reduced the
available heat sink further.
The temperature indications in the
control room did not show any
problems. However, a visual inspection
of the steam reformer a short time later
revealed that the tubes were white hot
and that there was wholesale tube
failure. There were also flames emerging
from the peepholes in the furnace wall
as the internal box pressure had become
positive. This would normally have
tripped the plant, but the furnace
pressure trip was by-passed, as was usual
during start-up. Lessons learned from
this case study include:
— Control of firing is essential during
start-up and shutdown, including trip
situations
— Light burners in a staged pattern
during start-up
— Visual inspection of the steam
reformer during start-up is essential to
monitor what is happening
— Do not deviate from standard
operating procedures without careful
consideration of the implications.
Carbon formation
There are a number of causes of carbon
formation on steam-reforming catalysts,
including catalyst poisoning or
operation at too low a steam-to-carbon
4
ratio. For example, catalyst poisoning
can occur due to sulphur compounds
slipping through the upstream
purification system at levels in excess of
what the steam-reforming catalyst
(typically 100ppbv) can tolerate, thus
lowering catalyst activity. This allows
local temperatures to rise, as the catalyst
is providing less endothermic steam
reforming in the poisoned zone. If the
temperature rises to the point where net
carbon deposition is favoured, carbon
builds up on (and in) the catalyst pellets.
Also, for a given catalyst type,
feedstock and operating temperature,
there is a limiting value of steam-to-
carbon ratio, below which net carbon
deposition is favoured. Johnson
Matthey Catalysts produces steam-
reforming catalysts that provide
protection against carbon deposition
and offer possible recovery from a
carbon-forming incident by steaming
5
the catalysts. Even so, plant upsets and
issues can still lead to operation outside
the advised limiting condition for the
steam-to-carbon ratio. There are various
ways in which a low steam-to-carbon
ratio can result. Some examples include:
— Errors in metering of either steam or
hydrocarbon flow
REFINING
Figure 2 Pyrolytic carbon on catalyst
pellet
— Mechanical failure leading to loss of
steam flow
— Inadequate purging, such as during a
plant trip, leading to trapped hydro-
carbon in the purification section,
which is flushed onto hot catalyst on
restart
— With heavier feeds, condensation of
hydrocarbon liquid in dead legs and
pipework low points, which is slugged
into the reformer on start-up.
It is well known that a serious carbon
formation incident can even lead to
catastrophic catalyst failure. Depending
on the cause, different carbon species
can be formed on the catalyst surface:
two of the most common are pyrolytic
and whisker carbon. Pyrolytic carbon is
typically formed at high temperatures
(>600ºC/1112°F) from the thermal
cracking of hydrocarbons, leading to the
deposition of carbon precursors on the
catalyst particle, as Figure 2 illustrates.
Such carbon formation results in
catalyst deactivation and increasing
pressure drop.
At lower temperatures (>450ºC/
842°F), it is well known that reactions
with hydrocarbons or carbon monoxide
over transition metals can lead to the
formation of carbon filaments. The
whiskers have a tubular appearance and
most have a Ni-particle at one end, as
highlighted in Figure 3. As the nickel
crystallites are not obscured or covered
during this carbon-forming process, the
rate of carbon formation can be
enormous in a steam-free atmosphere.
The whiskers formed within the
“Catalyst poisoning can
occur due to sulphur
compounds slipping through
the upstream purification
system at levels in excess of
what the steam-reforming
catalyst (typically 100ppbv)
can tolerate”
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Figure 3 Whisker carbon on Ni-reforming
catalyst
catalyst pores are very strong. As a result,
these can cause significant damage to
the structure of the pellet. If serious
enough, catalyst breakage can occur, and
if an attempt is made to remove the
carbon with steam, further breakage is
likely. In part, this is because the carbon
has caused the structure of the catalyst
pellet to crack, but acts as a binder while
still in place. Also, gasification of carbon
inside the pore structure may occur
faster than the gas can escape, causing
the pellets to shatter.
Case study 2
Reformer catastrophe
A plant using naphtha feed was
undergoing a restart following a plant
trip. The reformer was still relatively hot
and had a small steam flow, but it
needed to establish nitrogen circulation.
During the introduction of nitrogen, the
reformer pressure drop increased from
1.4–7 bar (20–101psi) in approximately
two minutes. Nitrogen addition was
stopped. A carbon-forming incident was
suspected and so the steam flow was
increased and the exit gas monitored for
carbon oxides. Two observations were
made. First, over a number of hours, the
pressure drop increased to a point where
continued steaming was no longer
tenable. Second, the analysis of evolved
carbon oxides suggested that 1.4 tonnes
of carbon was removed from the
approximately 10 tonnes of installed
catalyst.
Investigations showed that the
nitrogen line operating at a lower
pressure than the process had filled with
naphtha due to reliance on valve
isolation rather than fitting a blind (slip
plate). The feed line was 100mm (4in) in
diameter and around 1km (3300ft) long
and was capable of holding 10 metric
ton of naphtha. The plant operating
procedures stated that the nitrogen line
should be checked and confirmed free of
liquid before opening to the process
using a drain valve. However, on this
occasion, the valve was not opened
because it was seized.
The catalyst charge had to be
replaced, the discharged material having

F i g u re 4 Fused catalyst from steam
reformer subjected to wetting
been reduced almost to dust in the top
60% of the tube. The lessons from this
case study are as follows:
— Proper isolations should always be
used rather than relying on single
isolation valves
— Large slugs of liquid hydrocarbon
will destroy a charge of steam-reforming
catalyst due to catastrophic carbon
formation
— Standard operating procedures for
start-up such as draining down lines
must be followed.
Case study 3
Condensation on catalyst
Earlier papers explained how wetting
the catalyst is unusual but does not
1,4
always have catastrophic effects.
However, the actions that are taken
once you have a wet catalyst can have
serious consequences.
In a recently commissioned hydrogen
plant, insufficient nitrogen was
available due to compressor limitations
for the initial heating phase of start-up.
Using nitrogen, the inlet pipe work to
the steam reformer could only be heated
to about 80ºC (176°F). The remainder of
the warm-up was carried out with 420ºC
(788°F) steam introduced to a system
pressure with a dew point of 115ºC
(239°F). Therefore, during each start-up,
condensation occurred in the “cold”
and rather long pipe work between the
feed and steam mixing point and the
reformer tube inlet.
In addition, once steam was
introduced to the process, the heat-up
rate at the steam reformer inlet was
170–200ºC/hr (306–360°F/hr) at least
over the initial period after steam
introduction. This far exceeds the
normal heat-up rate for dry catalyst,
typically 50ºC/hr (90°F/hr), let alone
that of wetted material, which is half
this level with recommended holding
periods to enable controlled water
evaporation.
The plant was also susceptible to trip
shutdowns at very frequent intervals.
After around 20 start-ups from cold
conditions, there was an unacceptable
pressure drop, which necessitated
REFINING
catalyst renewal. There was a significant
degree of damage to the catalyst that
had resulted not only in the pressure
drop issue but also poor gas distribution
within the reformer and the subsequent
development of hot spots. The breakage
was primarily due to the rapid heating
of wetted catalyst and the catalyst
shattering as vapourising water built
pressure within the catalyst pellet faster
than it could be relieved by the escape of
steam through the pellet pore structure.
Breakage was also exacerbated by
crushing due to tube contraction in
each of the frequent trip shutdowns.
Figure 4 shows the agglomerated
nature of the catalyst, which had fused
together through wetting and
compaction of the broken catalyst —
both symptoms of a wetted catalyst that
has been dried too quickly. This had to
be mechanically broken up before it
could be vacuumed out.
Lessons learned from this case study
are as follows:
— Steam-reforming catalyst should be
heated a suitable margin above the dew
point before steam is introduced.
Generally, 50ºC/hr (90°F/hr) is advised
— Rapid drying generates high steam
pressures within pellets that can break
steam-reforming catalysts. Careful
drying will minimise catalyst damage
— Problems “designed” into a process
inadvertently have major consequences
in terms of plant operability and also
incur expense in terms of capex and
downtime to correct the problem.
Unplanned exotherms
There is a range of reactions that can
occur over catalysts and give rise to an
exotherm. If this is a feature of the
reaction that is being catalysed, the
reactor and control system are designed
appropriately. Situations do arise,
however, where conditions occur
inadvertently, outside the normal
operating regime for the catalysts. In
these situations, unexpected, significant
and substantial exotherms can occur. A
number of case studies will be discussed
in further detail. Although these relate
to specific types of catalyst reactors,
many of the underlying causes are
relatively generic, in that the same type
of incident could occur over many
different catalyst reactors if the same
initiators existed.
Case study 4
Self-heating
A major possible hazard when
methanation reactors in an olefins plant
are shutdown is the potential for self-
heating if the reduced catalyst is
exposed to air. The same is true of other
types of catalyst for which the active
form contains metal, metal sub-oxide
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and other phases that react
exothermically with oxygen.
In this case, the methanation reactor
had been shut down and purged with
nitrogen as part of a planned
turnaround. The inlet and exit valves
and thermocouples were removed for
repair. The open ends of the pipes were
covered with plastic sheet and the
catalyst, which was still in the reduced
state, was left without a nitrogen purge.
Later in the shutdown, the process of
reconnecting the thermocouples began.
A reading of 454ºC (1013°F) was
registered. To cool the vessel, a nitrogen
purge was established and later a
reading of 649ºC (1200°F) was obtained
when another thermocouple was
reconnected.
The plastic sheet was not an adequate
means of isolation and, without a purge
of nitrogen, air had entered the vessel,
allowing the reduced catalyst to react
with the oxygen. A chimney effect due
to the exotherm then drew in additional
air, which in turn allowed more reaction,
with the liberation of yet more heat.
In the absence of any gas flow and
with some thermocouples disconnected
even as the nitrogen purge was
established, there was no way to
determine the peak localised temper-
atures in the catalyst bed. Therefore, it
was impossible to ascertain the extent of
catalyst damage. The lessons from this
case study are as follows:
— Reduced methanation catalyst (and
other similarly reactive catalysts) can
become very hot when exposed to air
— Secure isolation and inert purge is
essential for maintenance on vessels
containing reduced catalyst
— With little or no gas flow,
thermocouples do not provide a reliable
measurement of the temperatures
throughout the bed.
Case study 5
Methanation
Methanation is a very exothermic
reaction, generating an exotherm of
74°C (133°F) for each percentage of CO
converted, and 60°C (108°F) for each
percentage of CO2 in a bulk hydrogen
stream. In normal operation, the
upstream water gas shift reactors and
wet CO2 removal systems deliver no
more than 0.5 mol% of each
component. Thus, with a typical inlet
temperature of 250–300°C (482–572°F),
the exit temperature should not exceed
350°C (662°F). Thus, the vessel design is
such that its operating temperature limit
at the prevailing process conditions is in
many cases around 450°C (842°F). Total
carbon oxides of approximately 3–4
mol% will produce this temperature at
the exit of the methanator, depending
on precise operating and design

temperatures. Hence, it may be possible
to run an ammonia or hydrogen plant
with a complete LTS failure or even
change a low temperature shift (LTS)
catalyst on-line if the total carbon oxide
burden on the methanator does not
exceed the vessel design limit. However,
a CO2 removal failure can lead to much
higher CO2 levels that are capable of
quickly putting the methanator at risk,
potentially producing methanation
temperatures of over 700°C (1292°F).
In the event of such an upset, it is
important to consider how quickly the
trip system will respond to changes in
bed temperature. There have been cases
where delays in heat transfer from the
catalyst bed to the thermocouple have
resulted in bed temperatures reaching
approximately 750ºC (1382°F) despite
the inlet temperature trip being set at
6
400ºC (752°F).
A hydrogen plant in North America
suffered a plant trip due to an electrical
problem, which was quickly reset. The
focus was to re-establish operation
quickly and to get the plant running
again. During the restart process, the
methanator pressure rocketed to over 60
bar (900psi) and there was failure of the
vessel. Analysis of the incident
concluded that the CO 2 absorber had
probably drained during the trip and did
not have time to establish normal hold-
up when the process gas was re-
established. The result was a very high
level of CO2 to the methanator, leading
to overheating and failure of the vessel.
The lessons from this case study are as
follows:
— Be aware of the potential for over-
temperature in a methanator should
upstream processes fail, leading to a
much higher CO level in the feed gas.
The same analysis should be applied to
other catalyst systems to understand
what may be possible
— Make sure CO2 removal and
methanator high-temperature trip
systems are working and the trip
thermocouples are located correctly
— Consider the need for proper
procedures in the restart of a plant
following a trip situation, such as
whether these constitute an unfamiliar
task that should be subject to an
appropriate review.
Case study 6
Absorbent-related exotherm
The previous cases all involve catalysts,
but it should be noted that absorbents
are also capable of unexpected
reactivity. In this case, an absorbent
based on copper and zinc oxides was
being used to remove trace levels of H2S
and mercaptans from a CO2 stream at
about 90ºC (192°F). The reactor had
been in operation on the current
REFINING
“Care is needed to ensure
that alumino-silicate
supports are not used in
pre-reformers, secondary
reformers or HTS, where
silica migration can be an
issue”
absorbent charge for a number of
months. An incident occurred in which
a massive exotherm developed over a
period of 20–30 minutes. Temperatures
rose to in excess of 1000ºC (1832°F) and
the vessel failed explosively, but
fortunately without the occurrence of
any injuries.
The incident analysis indicated that
the absorbent had been in contact with
oxygen at high temperature. The source
of the oxygen was identified at an
upstream compressor incorporating a
vacuum breaker that, if operated, broke
vacuum by allowing air into the process.
After the incident, this was found to be
stuck open.
The source of the heat was a reaction
of the oxygen with the absorbent. The
absorbent reacts to remove the H2S and
mercaptans by the formation of CuS and
ZnS. Even at benign conditions, the
dispersed CuS will react with O2 to form
CuSO4 and this reaction is strongly
exothermic. At the time the absorbent
vessel was designed and installed, the
potential hazard from this reaction had
been overlooked. The lessons from this
case study are as follows:
— Reactive phases can be formed in
absorbents as a result of the expected
chemical changes in removing
impurities from the process stream
— The potential for reaction of these
formed phases with air must also be
considered as part of the HAZOP study
prior to vessel commissioning
— Suitable vessel protection must be
installed in the form of bed thermo-
couples, trips, alarms and so forth.
Side reactions and other
phenomena
Nickel carbonyl, Ni(CO)4, is described as
an extremely toxic stable, colourless
liquid at ambient temperature, which is
reported to have a musty smell but a
very low boiling point (42.5°C at
1 atm).7 Thus, even at ambient temper-
ature and pressure, there is a significant
vapour pressure over a sample of the
liquid. The current OEL for nickel
carbonyl is 0.001ppm (1ppb) and is
therefore extremely toxic. The key rule
is to keep CO away from all nickel
catalysts below approximately 200°C
(392°F). At this temperature, even quite
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P T Q Q1 2006
low CO partial pressures can generate
Ni(CO)4 and the propensity for its
formation should be checked where
there is any possibility of contact
between a CO-containing gas stream
and a nickel-containing catalyst. The
reactor most at risk in the syngas
flowsheet is the methanator and, to a
lesser extent, the pre-reforming and
steam-reforming catalysts.
Thus, one of the main hazards when
methanation reactors are shut down is
Ni(CO)4 formation. Also, a relatively
recent and serious incident involved a
reformer on a methanol plant. This has
been reported elsewhere in detail and
provides some excellent background
information as well as a description of
8
the incident itself.
Support and hold-down media
Materials used as support and hold-
down media are an important part of
the overall loading of a catalyst or
absorbent reactor. It is important that
the support and hold-down materials
are properly selected and deployed
within the reactors so that physical or
chemical degradation cannot occur due
to a reaction with or movement by the
process gas. A variety of problems can
result if the wrong type of support
material is selected or if that material is
not stored or installed properly.
Examples of the problems that can
occur include:
— Selection of the wrong type of
material. For example, it is possible to
leach silica from alumino-silicate
materials at temperatures in excess of
300°C (572°F) in steam-containing
environments
— Wetting of support media with
subsequent rapid drying
— Excessive pressure drop in the zone
around the gas collector.
Thus, care is needed to ensure that
alumino-silicate supports are not used in
pre-reformers, secondary reformers or
HTS, where silica migration can be an
issue. In addition, wrong specification at
the time of purchase can be an issue if
the need to use high-purity alumina
balls in these reactors is not understood.
A recent enquiry associated with HDS
and HTS catalysts simply specified
“ceramic balls”.
Case study 8
Improper use of support media
A large plant was renewing a full charge
3 3
of 60m (2120ft ) LTS catalyst. This was
installed and reduced without apparent
problems. However, when it was
subsequently operated at full rate, the
start-of-run pressure drop was measured
at 2.1 bar (30psi) and rising, whereas the
previous charge had only been 1 bar
(14.5psi) at end of run.

A catalyst problem was suspected and
additional pressure tappings were added
to the catalyst drop-out pipe of the vessel
to help characterise the pressure drop in
different parts of the vessel. This
measurement showed that the pressure
drop was 0.3 bar (4psi) from the catalyst
bed and 1.8 bar (26psi) below the catalyst
bed. The pressure drop became serious
enough that the vessel was emptied and
a detailed investigation completed. The
investigation showed that a number of
different types of inert balls had been
used and that one of the types installed
had failed catastrophically.
The investigation also showed that
some of the balls had previously been
used in other reactors such as the HTS
and HDS. In addition, it was suspected
that the mode of storage could have
allowed at least some of the balls to
become wet. The cause of the failure,
therefore, was believed to be the rapid
drying of the balls, which had become
wet during long-term storage. However,
in subsequent investigations, it proved
difficult to simulate in tests the extreme
conditions of heat transfer and
depressurisation leading to the
vapourisation of trapped moisture
within a 25mm (1in) ball, as was
thought to have occurred within the
plant reactor. The failure of the support
material necessitated complete replace-
ment of the LTS catalyst charge, which
incurred a significant additional
expense for the plant in both catalyst
purchase costs and plant downtime to
change out the reactor. The lessons from
this case study are as follows:
— Select and store support media to
the same standard as catalysts
— Only use high-purity alumina
support above 300ºC (572°F) in a steam
environment
— Reuse of support balls is not
uncommon, but this incident highlights
the dangers inherent in using material
where the history is not clear.
Catalyst loading
As catalyst improvements have led to
longer run lengths for catalyst charges,
changing catalysts is becoming an
increasingly infrequent task. Changes in
personnel may mean that many of the
responsible staff have not conducted a
catalyst change before. In these
circumstances, a detailed understanding
of the design intent and arrangement of
the catalyst bed is important. This will
allow proper review or preparation of
the detailed procedures for the catalyst
change-out. Also, it is prudent to keep
detailed records of what was done as a
reference for loading in the future and
also to help troubleshoot performance
issues should these arise. Such records
should include the catalyst type, batch
REFINING
“Infrequent operations
around start-up and
shutdown present a higher
risk than routine plant
operation. In this, one must
also include actions taken in
an unplanned plant
shutdown, such as a trip
condition”
or drum numbers of the catalyst loaded,
the weight of the catalyst loaded and
the level in the vessel. The same detail
should be applied to the associated
support and hold-down materials.
Vessel internal arrangements should
also be checked, such as thermocouple
positions. Photographs are a useful aid.
Key learning points
In the vast majority of the catalyst
catastrophes discussed, the catalyst,
although often placed in the dock
accused of causing the problem, is
ultimately found not guilty. The
incident has usually been initiated by
exposure to conditions that are outside
those advised by the supplier. A general
message from many of these events is
that infrequent operations around start-
up and shutdown present a higher risk
than routine plant operation. In this,
one must also include actions taken in
an unplanned plant shutdown, such as a
trip condition.
A full understanding of the side
reactions that can occur is required and
should have been considered through a
process such as HAZOP or process
hazard review. It is not the usual
exposure to process fluids in line with
the advised procedures from the catalyst
and absorbent vendors that creates the
issues whether during reduction,
commissioning, normal operation and
shutdown. It is, however, the advent of
an unusual process fluid composition
that creates the possibility for serious
incidents. Where possible, plant design
should eliminate the potential for such
a problem.
Some of the incidents arise from
procedural issues in a number of ways.
First, the existing procedures may be
inadequate. Second, the operating
personnel may not follow the proce-
dures. This may either be due to
pressures to restore plant operation and,
therefore, to “cut corners”. Alternatively,
it may be due to inadequate training and
understanding of the procedures that
exist.
Equipment problems also play a part
in creating unusual conditions, and a
00
P T Q Q1 2006
strategy for covering the effect of
equipment issues will help, as will
preventative maintenance routines.
Also, some catalyst users take actions
based on a partial understanding of the
application of the catalysts and
associated factors (for example, support
and loading). It is important to realise
that the catalyst vendor has a wealth of
expertise and should be able to provide
advice based upon a much broader
experience of operation of the catalyst
products.
This article is based on a paper originally
presented at the recent ERTC in Vienna. The
authors have expressed that this publication
is intended to provide authoritative general
technical information on the subject covered.
It is not intended to provide technical or
professional advice to cover specific factual
situations. Appropriate technical and
professional input should be obtained to
address specific circumstances.
References
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John Brightling is ammonia marketing
manager with Johnson Matthey Catalysts
in Billingham, Cleveland, UK.
John.Brightling@matthey.com
Peter Broadhurst is syngas technical
manager with Johnson Matthey Catalysts
in Billingham, Cleveland, UK.
Mike Roberts is technical development
manager with Johnson Matthey Catalysts
in Billingham, Cleveland, UK.