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AmmoniA operAtions

Understanding the basic principles of catalytic reactor operation in an ammonia plant can
help to avoid costly performance and operating problems. M. Anderson, and S. Osborne
of Clariant Corporation (formerly Sd-Chemie) focus on three particular topics that have
a significant impact on production performance: 1) chemistry, consequences and avoidance
of carbon formation in the steam reformer; 2) proper flow distribution in catalytic reactors,
and 3) the impact of improper plant operation on catalyst and equipment.

he ammonia industry has seen significant change in recent decades as

high turnover, leaner organisational
structures, and new operations have shifted
the demographics of the operations and
technical personnel staff. These changes
have resulted in a loss of long-term operational knowledge and can lead to incidents
of equipment and catalyst damage during
operation and upset conditions.
As catalyst technology continues to
improve, the products high performance
are best enabled when accompanied by a
thorough understanding of the chemical and
physical principles of catalytic reactions1.

affect the catalysts performance and can

lead to costly equipment failure.

Primary reformer reactions

The main reactions in the primary reformer
Steam reforming of hydrocarbons
CnH2n+2 + n H2O

n CO + (2n+1) H2
H > 0
Steam reforming of methane
CO + 3 H2
CH4 + H2O
H = 88700 Btu/lb-mole
(206 kJ/mol)
Water-gas shift
CO2 + H2
CO + H2O
H = -17,600 Btu/lb-mole
(-41 kJ/mol)

Carbon formation in
primary reformers
An important step in the ammonia manufacturing process is steam reforming; the
conversion of hydrocarbons into hydrogen.
The primary reformer is the main piece of
equipment for this and represents the largest expenditure in terms of capital and ongoing energy costs. Optimum performance
of the reformer and the installed reforming
catalyst is critical to ensuring high plant
productivity and efficiency. Poisoning, fouling or incorrect operation can adversely

Overall, the process is endothermic. A lower

CH4 leakage is favoured by higher exit temperature, higher steam-to-carbon ratio, and
lower exit pressure.
The standard primary reformer system
is comprised of a tubular furnace where
the feed stream passes over a catalyst
packed in multiple banks of externally
heated tubes. With improvements in tube
metallurgy, primary reformers operate at
pressures up to 6,000 kPa and tube wall

Nitrogen+Syngas 321 | January - February 2013 

temperatures up to 1010C. The average heat flux may be as high as 94,000110,000 W/m2.
Firing is usually controlled such that
tube wall temperatures are maintained at
values that will give a reasonable tube life.
By design and industry practice, maximum
allowable tube wall temperatures give an
in-service life of about 100,000 hours.

Carbon formation reactions

With no steam present and at normal
reformer operating temperatures, all hydrocarbons will decompose into carbon and
hydrogen via the following reaction:
Thermal cracking

C + 2 H2

Cracking reactions are favoured thermodynamically at high temperature. In the presence of steam, gasification reactions also
occur over the primary reformer catalyst as:
C + H2O

CO + H2

Operating the reformer at conditions that

drive this reaction can prevent the accumulation of carbon deposits. When conditions
exist that favour hydrocarbon cracking,
the heavier hydrocarbons in the feed will

AmmoniA operAtions

Fig 1: Comparative average TWT

surveys of two charges of
catalyst at a 1200 STPD
ammonia plant


temperature, F

crack first. As this occurs, the active sites

of the catalyst become masked, resulting
in less reforming reaction and higher gas
temperatures, which further increases the
tendency for cracking and coke deposition.
Common causes of carbon formation
and deposition are low steam/gas ratio
operation, heavy hydrocarbons in the feed,
sulphur poisoning, and temperature excursions resulting from poor firing control.
Higher catalyst activity can reduce carbon
formation potential by lowering gas temperature when methane concentration is high
enough for cracking, thereby reducing the
carbon formation potential.
The overall effect of carbon formation on
the primary reformer is reduced conversion,
increased pressure drop and increased tube
wall temperatures which, if severe, can be
seen as hot bands on the tubes. Not only
does the carbon deposit block active sites,
its formation within the pores of the catalyst
can cause catalyst breakage.




months on stream

Fig 2: IR thermographic image of a

row of reformer tubes

Monitoring program
During routine operation of a primary
reformer, a monitoring program assists in
optimising the catalysts performance as
well as providing early detection of issues
that can lead to catalyst or tube failure.
Three performance parameters are typically
trended during operation; calculated CH4
approach to equilibrium (ATE), tube wall temperatures (TWT), and relative pressure drop.

Approach to equilibrium
Reformer catalyst activity is commonly
expressed as CH4 ATE, which is the difference between the measured catalyst outlet
temperature and the calculated equilibrium
temperature for the observed methane
leakage. An increased ATE or methane slip
from the front-end results in a higher purge
rate from the synthesis loop and increased
energy consumption for the plant. While
operating the primary reformer at higher
exit temperature can mitigate this effect,
the cost of increased fuel requirements
and the impact of hotter tube wall temperatures must be considered when choosing
to operate in that non-optimal mode.

Fig 3: Plotted TWT surveys showing

the heat distribution across the
top level: surface profile










top level: top profile





temperature F

Pressure drop
The impact of increasing primary reformer
pressure drop is reduced plant efficiency,
caused by the lowering of the suction pressure at the synthesis gas compressor, and
the resulting higher horsepower requirements to maintain the desired loop pressure. Depending on pressure relief valve
set-points, a higher reformer P may also
require reduction of plant operating rates if
near those limits.

Using Clariants proprietary Cat-Trends

program, calculated ATE and relative
pressure drop can be trended over time.
Carbon deposition on the catalyst will
manifest itself as increasing ATE, increasing relative pressure drop and increasing
TWTs. In severe cases, visual hot bands
on the tubes will also become evident.

Operational control factors for

minimising carbon formation

Tube wall temperatures

Tube costs are a significant item in the
overall economics of a reforming plant.
The goal is to operate the reformer under
conditions that result in the lowest possible tube wall temperatures (TWTs) consistent with satisfactory reformed gas quality.
Even a slight increase in the tube wall

temperature F

temperatures will have a drastic impact on

the tube life. A TWT increase of as little as
10oC may result in up to a 30% shortened
life-time of the reformer tubes.
The use of a high activity/shape optimised reforming catalyst results in lower
tube wall temperatures and a significant
cost and efficiency advantage to an operator. As an example, a 1,200 short t/d plant
in North America was able to realise such
an advantage by installing the high activity

ReforMax reforming catalyst from Clariant.

The Kellogg-designed primary reformer of
this plant was initially designed to produce
600 short t/d of ammonia. After several
expansions, the reformer now operates at
a high heat flux of around 110,000 W/m2.
Figure 1 shows that the mean TWT is 55C
cooler with catalyst from Clariant than with
the previous competitor charge.
Additionally, the maximum tube wall
temperature was also lowered and the
number of tubes with TWTs exceeding the
temperature limit of 927C was cut from
five to zero, significantly reducing the risk
of potential tube failure.
Effective monitoring of the TWTs and
balancing of the firing of the reformer furnace can extend the life of the tubes and
optimise the performance of the catalyst
(Figures 2 and 3).


To prevent carbon formation, a minimum

steam-to-carbon (S/C) ratio must be maintained at all times. This value is contingent
on the composition of the feed gas, firing
rates, operating pressure and incoming
feed temperature. Most carbon formation

Nitrogen+Syngas 321 | January - February 2013

AmmoniA operAtions

Fig 4: The impact of sulphur

concentration in feed gas on
the tube wall temperature
in the reformer
increase in tubewall temp, F

incidents occur, however, during transient

conditions such as start-up, operating trips
or shutdowns. Modern operating plants
typically have a low S/C trip interlock
that cuts out the feed-gas to protect the
reformer during upset conditions. Additionally, a properly installed minimum stop on
the steam valve ensures that steam continues to flow through the reformer in an
emergency trip to sweep all feed-gas out
of the reformer. Complete isolation of the
feed-gas valve during a trip or shut-down is
necessary before steam cut-out.
Controlled start-up and shutdown procedures and emergency interlocks are
designed to avoid carbon formation. The
objectives are to:
l Prevent over-firing and thus temperature excursions during rate changes.
This typically considers the following
operating parameters: fuel flow, fuel
pressure, flue-gas temperature, process gas pressure, steam flow, feed-gas
flow, combustion air flow, exit process
gas temperature and the number and
location of burners lit. Often a manual
start-up rate guide is used and in some
cases an algorithm with interlocks
guides the operator during the start-up.
l Maintain a high S/C ratio during rate
changes. This is typically achieved by
increasing the steam flow before the feedgas on start-up and reducing the feed-gas
before the steam on shutdowns.
l Ensure sufficient and even flow distribution throughout the entire reformer.
Before feed gas is introduced to the
reformer during start-up, the steam
flow should be sufficient to ensure



sulphur in feed, ppmv


that all tubes have similar operating

conditions i.e. even flow and even heat
through all tubes.
l Ensure sufficient steam flow exists for
adequate mixing of steam and feed-gas
well before the tube inlet manifold.
Visual monitoring of the tubes and burners
is critical to detect any issues during the
start-up process.

Sulphur poisoning as root cause for

carbon formation
Sulphur has an adverse impact on reforming catalyst activity as it reacts with the
reforming catalysts active nickel component and forms an equilibrium condition
over the active sites of the catalyst:
Ni + H2S

NiS + H2

The sulphur must be removed from the

feed-gas in an upstream desulphurisation

step to levels less than 0.1 ppmv. Sulphur
is not a permanent poison for short-term
exposures and when removed from the
feed, the catalyst can regain the original
activity. However, sulphur poisoning can
deactivate the catalyst to the extent that
less reforming is done and elevated gas
temperatures cause high tube wall temperatures. Even small amounts of sulphur
in the feed can significantly influence the
tube wall temperatures as shown in Fig. 4.
If the temperature rises to the point
where carbon formation occurs, pressure
drop will increase and catalyst performance will be further compromised.
In a 600 short t/d design ammonia plant,
the desulphurisation unit was bypassed due
to vessel design concerns. During this time,
the high performance ReforMax primary
reformer catalyst was exposed to inlet sulphur levels of up to 3 ppmv for nine months.
As expected, catalyst poisoning occurred
which resulted in activity loss in the 30-40%
top inlet tube location.
The plant was subsequently brought
down and a successful steam-air regeneration procedure was done with the assistance
of Clariant technical support. On re-start, the
reformer experienced full recovery to pre-incident performance levels and tube wall temperatures; visual success of the decoking
procedure is reflected in Fig. 5.
The ReforMax catalyst withstood the
intense conditions during this high sulphur
exposure time-frame and continued to provide the full expected design life-time.
Given the impact of sulphur poisoning
on the performance of the reformer, the

Fig 5: The reformer tube appearance before and after a decoking procedure

Nitrogen+Syngas 321 | January - February 2013 

AmmoniA operAtions

Fig 6: Secondary reformer exit

methane slip over time

Table 1: Impact of changes in performance of selected front-end catalysts on

energy costs and lost production in a 1,500 short t/d ammonia plant
with membrane purge gas recovery

Change in energy
cost ($/annum)

Lost production


5.6C increase in ATE




5.6C increase in ATE




1% increase in CO leakage




0.1% increase in CO leakage



Flow distribution in reactors

The design of a catalytic reactor considers
effective flow and distribution of the feedgas through the catalyst bed volume. Poor
distribution of gas flow can lead to bypassing/channeling within the catalyst bed and
ineffective utilisation of the loaded catalyst volume. This manifests itself in higher
calculated ATE in primary and secondary
reformers, higher CO leakage in HTS and
LTS reactors, higher COx from methanators and reduced conversion from ammonia
converters. The impact of these non-optimal conversions is less efficient and more
costly operation of the NH3 plant.



Fig 7: Photo of the surface of the secondary reformer showing mixing of catalyst
and inert balls and bed disruption

choice of high activity desulphurisation

catalyst should not be under-estimated.
Proper monitoring of the total sulphur slip
from the pre-treatment section ensures
that the reforming catalyst is protected.

CH4 leakage, %

Change in performance

Using the results of a study carried

out to examine the impact of such operation, the cost impacts can be converted
to dollar values to demonstrate the large
impact they can have on overall plant profitability. This study was based on a 1,500
short t/d ammonia plant with membrane
purge gas recovery2. Assuming a production rate of 1,500 short t/d, $2.70 per
MMBtu natural gas and $450/t ammonia,
the table above shows the results in terms
of potential costs.
As shown in Table 1, the increase in
costs associated with lost production and
if the lower production can be compensated
by a higher energy input in energy costs
can be significant for these different scenarios. It is clear that proper initial design,
procedures and operation is imperative to
ensure stable and optimal catalyst performance from start of run (SOR) to end of run
(EOR). The potential causes of poor flow in a

10 14 17 19 25 34
time on-stream, months

catalyst bed include gas distributor issues,

vessel design issues, movement of catalyst
during operational upsets and initial loading
Movement of catalyst at the top of a bed
caused by poor feed distributor designs,
burner issues in a secondary reformer or
plant upsets can create flow or channeling
issues, and result in changes in performance. Such an event was experienced
recently in a 1,750 short t/d ammonia plant.
During operation, the secondary reformer
experienced an increase in methane leakage from around 0.3% to over 0.5% (Fig. 6).
On shutdown it was found that there was
mixing of the catalyst and inert balls which
were pushed up toward the walls of the vessel (Fig. 7). The root cause was traced back
to an operational upset that caused high
gas velocities and bed movement creating
unevenness/flow distribution issues in the
bed which subsequently compromised the
overall performance.
The purpose of any initial loading of catalyst and support media is to achieve a uniform density throughout the bed to ensure
proper flow distribution. In fixed beds crosssectional uniformity is also desired.
The primary reformer is one of the most
intensive and time-consuming reactors to
load and carries severe penalties if tubes
are loaded improperly. With no physical
means for balancing the feed gas flow
through tubes, catalyst with non-uniform
loaded density results in non-uniform flow
rates which in turn cause some tubes
to operate hotter than the average tube
temperatures. Additionally, catalyst bridging can occur when particles interlock to
form a bridge across the tube crosssection. These voids within the catalyst
layer result in localised overheating of the
tube. Hot tubes fail prematurely and can
be very costly. It has been estimated that

Nitrogen+Syngas 321 | January - February 2013

AmmoniA operAtions

Fig 8: Photo of reduced particle size of HTS catalyst after

exposure to extreme temperatures caused by air
introduction to the HTS reactor

a 2.5% lower than average tube flow rate

can result in an 4-6C hotter tube wall temperature3. Further experience has shown
that tube wall temperatures in the area of
a catalyst void are about 16-28C hotter
than the surrounding area of the tube.

The impact of plant operations on catalyst

Many catalyst failures are the result of
poor operation or operational upsets. To
illustrate the significant potential negative
impacts, a number of different examples
for various catalytic services are discussed
Reduced/pyrophoric catalyst
Catalysts are often in the reduced metal
state during operation in HDS, HTS, LTS,
methanator and ammonia synthesis reactors. Exposure to air can result in spontaneous ignition with extremely high localised
temperatures causing catalyst failure,
fusing and equipment damage. For turnarounds and longer shut-down periods,
ensuring a continuous positive pressure
inert blanket is one routine monitoring item.
Discharging of pyrophoric catalyst without
first oxidising it must be done under nitrogen with precautions taken to avoid ingress
of air to the vessel by a chimney effect. In
cases where repair work is required around
vessels without adequate isolation, the risk
is particularly high and continuous nitrogen
purge is necessary. It should be noted that
without flow through the catalyst bed, temperature measurements do not accurately
represent the bed temperatures nor do
they detect localised peak temperatures.
They can, however, give some indication or
warning of an issue.

Fig 9: Photo of fused inert ball, floating screen and catalyst

removed from the HTS following exposure to air and
extreme temperatures

Complete isolation of the air flow to the

secondary reformer is required in a secondary reformer trip to protect downstream
catalysts. In one incident at a 1,700 short
t/d ammonia plant in North America, the
HTS catalyst performance was greatly
affected following an upset during start-up
of the secondary reformer. A high pressure air flow condition resulted in air to
the HTS for a short duration. The event
occurred relatively fast and other events
were occurring so it was not even noticed
by the operations team.
Shortly after stabilising plant rates,
however, the performance of the charge in
terms of CO leakage, while acceptable to
allow operation, was higher than expected.
After approximately a year on-stream, the
decision was made to unload the catalyst
during a shut-down. Inspection of the reactor showed that the overall outage from the
manway had increased by over 0.9 m and
that in a particular area of the bed the catalyst particle size was reduced from 6x6
mm to roughly 3x3 mm. The support balls
were also found fused to melted screen
pieces which in turn were fused to catalyst. For this level of shrinkage and fusion
to occur it is estimated that temperatures
must have exceeded 870C. It is important
to note that despite this significant temperature exposure, the Clariant catalyst was
still able to achieve an acceptable level of
performance with no pressure drop issues.
(Figs 8 and 9)
Impact of water on catalyst
Water can affect the integrity of all catalysts and in some cases can lead to catastrophic incidents. Water entrainment

Nitrogen+Syngas 321 | January - February 2013 

during start-up of the primary reformer can

lead to instantaneous flashing at the hot
catalyst releasing enough energy to rupture
reformer tubes. Water entrainment can
occur when low point drains are plugged
or not used during shutdown and start-up.
HTS and LTS are particularly at risk due to
their location downstream of the HP boiler,
quenches and temperature controls. When
water comes in contact with catalyst, catalyst breakage and increased pressure drop
results from water vaporising out of the catalyst pores at a faster rate than the porosity
of the catalyst will allow. The HTS catalyst is
very susceptible to leaks from the upstream
HP boiler which are almost inevitable during

a plants life. Clariants HTS ShiftMax catalyst was able to survive major boiler leaks
at the 1,600 short t/d Terra plant4. In this
case, the HTS was flooded with water from
a major boiler failure and a dry out procedure was successfully implemented under
the direction of Clariant. Besides the effect
of wetting the catalyst, accumulated boiler
solids from boiler leaks can also increase
the catalysts pressure drop and create poor
gas distribution issues. The impact of water
and boiler solid carryover can be minimised
by using a high voidage inert top layer.
During operational upsets, temperature
controller swings can lower the inlet temperature of the shift converters below the
dew point and wet the catalyst. Operating
the LTS at an inlet temperature 17-22C
above dew point can reduce this potential.
Boiler feed water quenches are normally
installed upstream of shift converters in
order to control inlet temperature as well
as lower the CO equilibrium. Atomisation
is critical to prevent wetting the catalyst

AmmoniA operAtions

and proper design and maintenance of

the quench valve/nozzles is imperative.
Quench valves also require complete isolation during a shutdown to prevent water
buildup in low point piping areas that can
be entrained onto the catalyst on restart.
Water treatment
The steam quality in an ammonia plant is
typically monitored to ensure protection of
rotating equipment. However it is also an
important consideration for reforming catalyst. Carry-over and deposition of silica and
sodium on reforming catalyst can act like a
permanent poison by physically covering the
active sites of the catalyst. This can cause
poor reformer performance, increased pressure drop and increased TWTs at the top
of the tubes. These contaminants can also
be introduced to the process via boiler feed
water quenches upstream of the reformer.
A well controlled and monitored water treatment program is necessary for effective
catalyst performance.
LTS reduction
LTS reduction is a procedure required to
activate the catalyst and is typically performed every 3 to 4 years. It is a process
that can have catastrophic consequences
if not done carefully. The infrequency of
the procedure requires a thorough review
before performing the procedure.
The CuO in the LTS catalyst is reduced
to copper metal by an exothermic reaction. To effect the reduction, hydrogen is
carefully and precisely added to a carrier
gas (natural gas or nitrogen) and the bed
temperatures are closely monitored. Measures taken to achieve adequate control of
hydrogen include:
l complete isolation/blinding of any
potential sources of hydrogen other
than reduction gas especially when at
higher pressure than the carrier gas;
l gas composition analysis of the reduction and carrier gases (Note: natural
gas carrier gas should be free of hydrogen recycle);
l reliable supply of reduction and carrier
gas flows, including reduction gas flow
meter calibration at constant conditions
of carrier gas flow and back pressure;
l Gas testing schedule of inlet and outlet
hydrogen concentrations.
Caution statements in a procedure describe
reducing or removing reduction gas at certain peak temperatures. Achieving optimum
catalyst performance and preventing tem-


perature run-away are both considered.

Studies have been done to understand
what happens at elevated temperatures
that cause run-away. In the case of a natural gas carrier, CuO reacts with methane at
246C via the following reaction5:
CH4 + 4CuO 4Cu0 + CO2 + 2H2O
This is also exothermic creating even
higher bed temperatures. At temperatures
near 370oC, hydrogen can be produced by
hydrocarbon cracking, which can lead to
temperature run-away. Under such circumstances vessel design temperatures can
be exceeded.
Methanator operation
Methanator operations are seldom given
much attention and COx concentrations are
typically not measured. However upstream
conditions affect its performance and can
have an adverse effect on plant efficiency,
production and even equipment.
During start-up, the front end of the
plant is brought up and the synthesis gas
is introduced into the synthesis loop. The
inlet temperature of the methanator is typically controlled by available steam and the
feed/effluent exchanger. The introduction
of low temperature make-up gas to the loop
can introduce higher levels of COx. These
higher concentrations increase the potential for ammonium carbamate formation
within the loop that fouls equipment and
increases the loop pressure drop, which
in turn increases the energy requirements
of the plant. In addition to ammonium carbamate formation, ammonia synthesis
catalyst is temporarily poisoned by oxygenates and this will adversely impact plant
production and loop performance. Once
the COx levels are returned to normal,
production rates can take quite some time
before recovering. If ammonia synthesis
catalyst is exposed to high COx levels for
long periods of time, the poisoning affects
can be permanent.
In addition to operating conditions at
the methanator, upsets at the upstream
LTS reactor that cause increased inlet CO
to the methanator can overload the available capacity of the catalyst and lead to
higher COx leakage.
Upsets at the CO2 removal unit tend to
be more frequent and can have a greater
impact on the methanator. Also CO2 is
more difficult to methanate than CO, so
higher levels can overwhelm the methanator and result in premature COx leakage. In
cases where the CO2 increases to such an

extent that the resultant exotherm elevates

the methanator temperature to equipment
design limits, process gas should be immediately shut off or vented upstream.
The operation and control of the CO2
removal system is critical to maintaining
the inlet levels to the methanator. Plants
that have been revamped or are running at
higher than design throughputs can push
the CO2 removal system to maximum load.
At these conditions, small fluctuations can
lead to gross carryover of solution and CO2
breakthrough. Some solutions can poison
and permanently deactivate the methanator catalyst, or leave deposits on the top
of the bed which reduces catalyst activity
by blocking active sites and also leads to
increased pressure drop. Severe liquid
carryover of all solutions can also cause
physical damage of the catalyst further
increasing the pressure drop. A skim of the
catalyst is can sometimes be performed to
correct the situation.

In summary, understanding the basic principles of catalytic reactor operation in an
ammonia plant can help to avoid costly performance and operating problems. Operations and technical crews should routinely
review and analyse process monitoring
systems and procedures to ensure that the
consequences of mal-operation are understood and best available procedures and
technology are in place. Understanding the
impact on catalyst and process equipment
from a safety perspective and an operational cost standpoint is important so that
potential adverse situations are avoided
or minimised in magnitude. With this complete knowledge and understanding, high
performance catalysts can achieve their full
utilisation and maximise the efficiency and
productivity of the plant.

1. Gebert S., Cai Y,. and Kniep B.: Continuous
improvement in ammonia catalysts Nitrogen + Syngas (Jan-Feb 2012).
2. Rice D.: The value of catalyst performance
in ammonia plants AIChE 2002.
3. Rice D.: Loading of primary reformer catalyst tubes AIChE 1993.
4. Borzik K., Howerton R. and Archer T.: Successful recoveries from major WHB failures
experience AIChE 2007.
5. Richardson J., Wagner J., Drucker R., Rajesh
H.: Understanding hydrocarbon reactions
during LTS catalyst reductions AIChE 1996.

Nitrogen+Syngas 321 | January - February 2013