The AIChE Ammonia Safety Symposium

50 Years of Shared Experiences

ABSTRACT

It has been 50 years since the first AIChE ammonia safety symposium was held and a
comprehensive review was made of more than 1200 papers that were presented over the last 49
years. This review includes various topics such as accidents, fires, explosions, safety
developments, benchmark studies, technological advances, and process and maintenance
improvements.

The paper also highlights the key lessons learned by the ammonia and syngas industries across
the globe from past experiences.

Venkat Pattabathula, Incitec Pivot Ltd

Gibson Island Works, Brisbane, Australia

Bhaskar Rani, Terra Industries

Courtright, Ontario, Canada

And

D.H. Timbres, Agrium, Inc.

Fort Saskatchewan, Alberta, Canada
In the 50 years of the Symposium there have been
INTRODUCTION
more than 1200 papers presented. The titles alone
of many of the papers reflect the advances in the
The AIChE organisation has played an important
technology used in our industry. Others reflect
role in providing the platform, which has no doubt
lessons learned the hard way through accidents
improved the safety of our plants, and saved lives
and near misses. In this paper, we will review what
and expense. The symposium also prevented many
we consider to be some of the most important
similar incidents from ever happening due to
developments and lessons learned from the past.
people being aware of what has happened
elsewhere. Over the last 50 years, the global ammonia
industry has grown ten folds from about 14 million
The first AIChE Safety in Ammonia Plants and
tonnes per year to 140 million tonnes per year
Related Facilities Symposium was held in 1956.
today.
At that time, the symposium was called Safety in
Air and Ammonia Plants. This year, we are
PLANT SAFETY PERFORMANCE
celebrating the 50th anniversary of the Symposium,
which has become the premier forum for sharing Fires, Lost Time Injuries, Explosions and
experiences in the nitrogen fertiliser and syngas Ruptures in Ammonia Plants
chemicals industry. Plant Surveys International (PSI) and others have
Through the papers presented at these conducted ammonia plant benchmarking surveys
Symposiums we have been able to make our for many years. The surveys demonstrate that fires
industry safer and more efficient. Knowledge of or incidents in ammonia plants have been
the bad experiences has helped others to avoid significantly reduced over the last 30 years.
them. Knowledge of the positive experiences and
design improvements has contributed to a more
efficient industry.

AMMONIA TECHNICAL MANUAL 12 2005

 Figure 1 shows that ammonia plants reporting no L o st T i m e
fires have increased from 7% to 42% over the last
30 years and it has been held at 42% since 1998. 2 0 0 0 -0 1 35%

1 9 9 7 -9 8 32%
No Fire s
1 9 9 4 -9 6 39%

2000-01 42% 1 9 8 2 -8 5

1997-98 42% 1 9 7 8 -8 1

1 9 7 3 -7 6
1994-96 41%
0% 10% 20% 30% 40% 50%
1982-85 30%

1978-81 23% Figure 3. Ammonia Plants reporting Lost Time

1973-76 7%
Ex plosion/Rupture s
0% 10% 20% 30% 40% 50%

2000-01 7%

1997-98 18%
Figure 1. Ammonia Plants Reporting No Fires
1994-96 14%
Figures 2, 3, and 4 show the trend of Fatalities,
1982-85
Lost Time Injuries (LTI) and Explosions/Ruptures
reported for benchmarking survey periods. This 1978-81
information is limited to the plants that 1973-76
participated in the surveys and it does not reflect
the whole ammonia industry. However, the survey 0% 5% 10% 15% 20%

was wide ranging and plants represented were

from all the regions of the world. Figure 4. Ammonia plants reporting
Explosion/Ruptures
Fa ta litie s
Major Safety Incidents
2000-01 2%
All the safety incidents that include fires,
1997-98 1% explosions, and equipment failures reported at
1994-96 1% most of the AIChE symposiums since 1956 are
1982-85
listed in Table-1.
1978-81 We consider the most significant incidents from
1973-76
290 reported over the last 49 years are as follows:

0% 1% 2% 3% 4%
Figure 2. Ammonia plants reporting Fatalities
One fatality was reported in each benchmarking
survey period.
In 2000-01 survey, a contractor’s employee
accidentally fell through a plastic sky light on the
roof of the compressor house. He fell 15 meter and
died from his injuries the following day. Work on
the roof was authorised and the work area was
defined by taping. The incident occurred outside of
the authorised work area.
In 1997-98 survey, a contract employee died when
he fell in to a high temperature shift reactor while
loading catalyst in to the vessel.
In 1994-96 survey, a welder died from burns
received while working inside a steam boiler.
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5%
1. Compressor explosion during a routine shop
test killed 6 people.
A major disaster occurred during a routine shop
test of a centrifugal compressor at the Ingersoll-
Rand Phillipsburg, N.J. plant. The accident killed
6 people and hospitalised 6 more for varying
periods of time.
The reference for this example provides an
external view of the building and gives an idea of
the damage done. The investigation team
identified the probable cause was the ignition of an
oil-air mixture that occurred in the compressor as
air was used for testing the compressor.
To prevent a recurrence, it was recommended to
use only inert gas in all future testing of
compressors.
2. One person killed in an explosion while
breaking in a compressor.
13 AMMONIA TECHNICAL MANUAL
 An explosion on the fourth stage synthesis gas
compressor discharge killed one person.
The cause of the accident was the use of air to
lubricate the compressor at higher pressures,
which increased the air temperature.
It was suggested to use only nitrogen to lubricate
compressors.
3. Suffocation of workers in CO shift converter
killed 3 people.
The accident occurred on 17 December 1960 at
Asahi Chemical Industry Co. Ltd, Japan. Three
people died from suffocation due to lack of oxygen
in the CO shift converter.
One person entered the shift converter without
knowing that the vessel was being purged with
nitrogen after a catalyst change out. Two other
workers also died from suffocation as they tried
rescuing the first worker.
New safety measures were implemented for
confined space entry.
4. Many failures were reported on front-end
waste heat boilers.
A) Cause of damage and repair of reformed
gas fire tube boiler
The secondary reformer waste heat boiler was
damaged due to the high pH level of boiler water
at Jianfeng Chemicals, Fuling, Sichuan, Peoples
Republic of China.
The boiler was repaired in-situ in 115 days and the
repaired unit achieved the design heat transfer rate.
B) Experience with metal dusting in waste
heat boilers
Metal dusting was reported to occur in ammonia
plant 3 of DSM Fertilisers, The Netherlands. In
ammonia plants metal dusting can occur in the
process equipment between the secondary
reformer outlet and the inlet of the high
temperature shift converter.
Modern ammonia plants generally operate at low
steam/carbon ratios and higher front end pressures.
Both conditions will increase the CO-content in
the process gas leaving the secondary reformer and
will therefore increase the temperature range over
which the formation of carbon can happen.
The metal dusting process can be slowed or even
halted by:
- The prevention of carbon formation.
- the prevention of carbon adsorption, and
AMMONIA TECHNICAL MANUAL
- The formation of a less stable intermediate
carbide.
C) Failures in waste heat boilers
Thielsch Engineering presented a paper in 1994
with case histories of waste heat boiler failures and
the remedial actions taken to restore those boilers
for continued service.
The failures were caused by various factors
including design deficiencies; defects introduced
during manufacturing or fabrication, service-
related deterioration and/or upset plant operating
conditions.
D) Failure and repair of two primary make
gas boilers
ICI Chemicals and Polymers Ltd, Billingham plant
in England reported tube failure of primary waste
heat boilers.
The principal damage had occurred as a
consequence of ferrule failures and subsequent
loss of refractory. The importance of ferrules and
refractory cannot be over emphasised. The choice
of material should be taken into consideration both
from mechanical and corrosion resistance aspects.
The total duration of the inspection and repair
including the replacement of ferrules was 35 days
and involved approximately 4,000 man-hours.
Another lesson learned from this failure is that
prolonged operation with serious tube leaks should
be avoided, as it will almost inevitably lead to
severe boiler damage.
E) Repair and retubing of reformed gas boiler
Tube leaks were detected on the reformed gas
boiler after 600 days of plant operation at
Rashtriya Chemicals & Fertilisers Ltd (RCF))
ammonia plant in India. The leaks were found
from the cracks behind the tube-to-tubesheet weld
joint on the hot compartment of the boiler.
On some occasions the water level in the boiler
was very low while the plant was still in operation.
About 33 tubes were leaking badly and half of the
tubes collapsed within one-meter distance from the
inlet. Some tubes had pits up to 2 mm diameter
and 1-2 mm deep.
Also, a whitish layer of phosphate deposit was
noticed on the tube surfaces with a possible
accumulation of sludge and sediments inspite of
continuous and intermittent boiler blow down.
In-situ retubing of the boiler was completed in
about 34 days.
14 2005
 F) Failure of a waste heat boiler after
debottlenecking process air compressor
In November 1991 BASF’s ammonia plant No.3 in
Ludwigshafen, Germany had an emergency
shutdown caused by an untypical failure of the
waste heat boiler downstream from the secondary
reformer. The high-pressure steam generating
system had a sudden loss of water due to a ruptured
tube in one of the boilers. Upon inspection, one
hole, several small leaks, and erosion on the tubes
were noticed.
The complete boiler was replaced by a new one in a
4-week shutdown period.
With the debottlenecking of the process air
compressor, the ammonia plant capacity was
increased and this contributed to a higher thermal
load on waste heat boiler, which caused two-phase
flow in the boiler tubes and hence eroded tubes.
G) Failure of a waste heat boiler downstream
of secondary reformer
Waste heat boiler failures were experienced at
Krishak Bharati Cooperative Ltd (KRIBHCO)’s
ammonia plant in India.
The most likely cause was the sludge deposits that
were left in during initial chemical cleaning, as
there was no means of cleaning the shell side. No
intermittent blow down was operated on the boiler
side. The boiler was planned to be replaced with a
new design and a new blow down installed on the
existing boiler after its repairs.
H) Failure and repair of a primary waste heat
boiler
A rupture occurred in the bottom-dished head of the
primary waste heat boiler at P.T.Pupuk Kalimantan
Timur, Kaltim ammonia plant in Indonesia.
Localised refractory failure and subsequent
overheating resulted in a short-term high
temperature stress rupture. There was no evidence
of hydrogen damage.
The head was replaced with a new one and the skirt
was cleared of all debris.
I) Failure and repair of the shell of a primary
waste heat boiler
A primary waste heat boiler shell on an 1100-tpd-
ammonia plant failed at Fertilisers of Trinidad &
Tobago Limited.
Analysis of the failure revealed an extensive surface
cracking pattern on the OD surface of the waste
heat boiler shell, extending downward to the centre-
line of the process gas outlet nozzle.
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The failure mechanism clearly involved localised
corrosion, aggravated by periodic mechanical
stress. The cracking involved a slow step-like
progression and was not restricted to the water
jacket portion of the shell. Thermally induced
surface stresses due to liquid level fluctuation,
local boiling or splashing within the water jacket
was also accepted as the failure mechanism.
To prevent a recurrence of similar failures, the
level in the water jacket was increased by 51 mm,
a coating to the exposed shell area and, use of an
oxygen scavenger were also considered.
J) Failure, repair and replacement of a waste
heat boiler
A double compartment designed waste heat boiler
downstream from the secondary reformer failed at
Fauji Fertiliser Co. Ltd in Pakistan.
The main cause of the failure was the loss of water
level in the steam drum and subsequent steam heat
up of the waste heat boiler from steam flow
through the process air coil while the pressure
control on the steam drum remained in the manual
mode.
The observed defects were visible cracks in the
tube-to-tubesheet ligaments; microcracks on the
tube-to-tubesheet weld; tube holes; ligaments and
welding lips.
A partial retubing was carried out on the WHB
with the replacement of 101 tubes in the upper
portion. This repair lasted for only nine months.
Finally, the WHB was replaced with an improved
design boiler.
K) Failure of a boiler pressure shell
The primary waste heat boiler shell failed at an
ammonia plant of Commercial Solvents Corp.;
Sterlington, LA.
The probable cause of the failure was deterioration
of refractory, which allowed the wall temperatures
to exceed the design limits. This deterioration was
aided by having to hammer the shroud slip joints
to facilitate installation of the tube bundle.
A section of shell was replaced and separate flow
meters were installed to each of the three water
jackets. The new refractory was superior to the
original installation for this type of service.
L) Failure of a primary waste heat boiler
A pressure shell of primary waste heat boiler
suddenly ruptured at Terra Chemicals ammonia
plant in Sioux City, Iowa.
15 AMMONIA TECHNICAL MANUAL
 A metallurgical examination of the rupture area
revealed that the failure was due to a short time
high temperature stress rupture.
The vessel was repaired and a new low silica (less
than 0.1%) bubbled alumina refractory was
installed.
M) Waste heat boiler failure and modifications
Two horizontal fire tube waste boilers failed at an
ammonia plant of Petrochemical Industries Co,
Kuwait.
The boilers had long tubes with thick tube sheet
design, which is very sensitive to thermal shocks.
Both waste boilers were replaced with a double
compartment design after repairing and operating
the old boilers for a few months until the new
boilers arrived at the site.
N) Fire in secondary reformer outlet line to
waste heat boiler
A fire occurred on the pressure shell-
interconnecting pipe between the secondary
reformer and primary waste heat boiler at
KRIBHCO’s ammonia unit-2 in India.
The interconnecting pipe bulged and water jacket
burst open. All electrical and instrument cables in
that area were damaged.
The reasons for the failure of the pressure shell
could have been hydrogen attack or creep of the
pressure shell. The refractory failure may have
been due to thermal cycling of the transfer line.
To avoid hydrogen embrittlement, the shroud
material was changed to Inconel-601. Jacket water
level indications were brought on to DCS and four
thermocouples were provided on each jacket of the
interconnecting pipe to the waste heat boiler.
O) Catastrophic failure of tubesheet in fire
tube reformed gas waste heat boiler
The reformed gas waste heat boiler failed after
nine years in service at Terra Nitrogen’s,
Courtright plant in Canada.
A drop in gas temperature at the inlet to the boiler
indicated evidence of a leak. Inspection of the
boiler revealed two failures. One was a tube failure
just behind the tubesheet to tube weld joint and the
other was a failure at the tubesheet to shell forging
weld joint.
The cause of the failure was attributed to departure
from nucleate boiling, initiated by an increase in
plant rates earlier in the year.
A new front section of boiler was designed for
AMMONIA TECHNICAL MANUAL
higher plant rates and with more equitable
distribution of the heat load between the two
sections of the boiler. A new riser design was also
required in view of the increased steam flow and
also to mitigate the formation of regions of
stable/semi stable pockets of steam.
The new boiler design included the installation of
larger diameter tubes in the front section to keep
the heat flux below the critical value. This
increased the heat flux to the second section, but
care was taken to have the heat flux within the
critical values. The new design necessitated an
increase in the diameter of the shell and the new
section was installed in October 1996.
P) Ammonia process primary waste heat
boiler shell failure experience
Canadian Fertilisers Ltd at Medicine Hat have
experienced shell failures on ammonia plant
primary waste heat boilers. The failure was two
types at shell plate cracks and ruptures, and shell
nozzle attachment weld cracks.
The pressure shell of the waste heat boiler failed
due to thick-lip stress rupture (creep). The damage
was due to prolonged exposure of the shell
material, in the temperature range of 480-620oC.
No evidence of hydrogen related damage or
cracking was noted in the samples examined.
The stainless steel internal shrouds and refractory
were removed from the vessel. The entire shell
section was “baked out” to remove hydrogen prior
to attempting any welding. The vessel was
repaired and returned to operation after 15 days of
production interruption.
CFL felt that the use of 1.25 Cr-0.5Mo or higher
alloy shell material would offer the increased
margin of protection that may avoid shell failures
due to overheating. Both the resistances to
hydrogen attack and creep resistance of 1.25 Cr-
0.5Mo material in this temperature range is
substantially better.
Q) Remedial actions to reformer waste heat
boilers
Several repeated failures were experienced on
reformer waste heat boilers in two Asmidal
Ammonia Plants, at Arzew in Algeria.
Localised refractory failures and subsequent
overheating resulting in short-term high
temperature caused the failures.
Partial repairs were carried on one ammonia plant
boiler whereas as the boiler was replaced on other
ammonia plant.
16 2005
 R) Failure of a secondary waste heat boiler
A secondary waste heat boiler (102C) failed in one
of the ammonia plants at KRIBHCO, India.
The main cause of the failure was sludge formation
and accumulation due to lower circulation rate that
resulted from reduced heat load than design. Also,
there was no intermittent blowdown for the initial
four years; conventional solid treatment till 1998
and improper tube expansion contributed to the
failure.
Sleeves were inserted in the weakened tubes and
this helped to prolong boiler life. Also, new
coordinated phosphate treatment, and continuous
blowdown of boiler were implemented. Finally, a
new exchanger with modified design was procured
and installed.
5. Ammonia storage bullet failure killed 18
people.
A pressure storage ammonia bullet failed on 13 July
1973 at AE&CI Ltd, Potchefstroom, South Africa.
An estimated 30 tonnes of anhydrous ammonia was
released which caused the deaths of 18 people.
The failure resulted from the brittle fracture of a
dished end of the bullet. The vessel was not stress
relieved after manufacture and strain aging had
weakened the metal of the vessel.
6. Synthesis converter start up heater failures
damaged plants.
A) During start up of the synthesis loop, a violent
explosion occurred at about 8 P.M. on 9 December
1973 at Shellstar Ltd Ince, ammonia plant in
England.
The temperature imbalance in 2-parallel coils and
nitriding of coils caused the failure.
B) A fire occurred on 6 February 1979 at Monsanto,
Luling, LA ammonia plant that resulted from a
rupture in one of the two-synthesis start up heater
coils. The rupture of the coil was primarily caused
by an inadequate flow of process gas through the
coil.
Following the accident, new interlocks were
provided to trip fuel gas to heater on low synthesis
gas flow. Also, the coil material was upgraded
from 2.25 Cr-0.5Mo to TP304H.
C) A fire occurred on start up heater on 25
November 1983 at BASF Ludwigshafen plant in
West Germany.
The damage of coil was caused by hydrogen
induced cracks from too high hardness and
condensing of moisture on the tube outer surface.
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The coil was repaired and later on, its material was
upgraded. New thermocouples were installed to
measure coil wall temperatures during operation.
D) At Standard Oil Chemical Co. Lima, OH, a
tube in converter start up heater ruptured on 9 July
1985 resulting in a fire and plant shutdown. The
rupture occurred during the refractory dry out. One
damaged coil was removed, and the converter was
heated with three coils.
Stresses from thermal cycling and continued
nitride formation during subsequent start-ups
propagated the crack to a depth where
circumferential stress from the tube internal
pressure together with the stress intensification of
the crack caused a ductile failure through the
remaining wall.
The coil was replaced with a new material of 9%
Cr-1% Mo to provide a somewhat greater
resistance to diffusion of nitride layer.
7. Fatal accident in CO2 removal section killed 9
people.
On 22 June 1974, at Madras Fertilisers Ltd (MFL)
in India, a fatal accident took place when a 400
mm (16-inch) elbow ruptured and sprayed hot
potassium carbonate solution into the control
room, killing nine operators and seriously injuring
the tenth operator.
Of 10 persons in the control room at the time, 8
died almost instantaneously, one died after 5 hours
in the hospital; and one recovered after long
hospitalisation.
The root cause of the incident was the erosion by
impingement of a high velocity stream of liquid
from a faulty control valve upstream elbow. The
hydrogen gas from the absorber that escaped
through the ruptured elbow caught fire. MFL
contacted other ammonia producers in Europe and
the USA and received many suggestions on
improved materials of construction.
MFL replaced the carbon steel elbow with an SS
lined elbow as a quick fix and then changed to a
complete SS material. Glass panels in the control
room were reduced in size although retained to
maintain some visibility.
8. Two people killed when NH3 loading line
ruptured.
A serious accidental rupture of a rubber hose
unloading anhydrous ammonia from a tanker to a
quayside storage sphere caused two deaths at
Supra Aktiebolag facilities in Sweden.
17 AMMONIA TECHNICAL MANUAL
 Time elapsed between the rupture to closure of the
valve on board was 50 minutes and about 180 tons
of ammonia leaked out on to the quay. Two people
were drenched in liquid ammonia, which resulted
in edema of the lungs. They had been standing
close to the rubber hose when it ruptured and had
then run in to vapour cloud.
The cause of the hose rupture was wrongly
specified polyester hose, which was destroyed by a
form of hydrolysis resulting from the reaction of
ammonia.
After the accident, the hose was replaced and new
procedures were put in place to improve ammonia
ship loading operations.
9. Accident in Lithuanian plant killed 7 people.
On 20 March 1989, an accident took place in a
Lithuanian fertiliser plant, which destroyed a
10,000 tonne ammonia storage tank.
The whole ammonia tank was dislodged from its
foundation, smashed with great force through the
surrounding wall of reinforced concrete and finally
landed about 40 meters from the foundation.
Devastation around the tank was enormous and
liquid ammonia around the plant site was 70 cm
deep. Large quantities of ammonia evaporated, the
ammonia gas caught fire and the whole plant area
was engulfed in flames.
About 32,000 people were evacuated from a
nearby town, the rescue operation continued for
three days and the total fatalities were 7 with 57
people injured.
It was reported that ammonia tank over pressured
due to roll over of its contents resulting from the
warm ammonia being supplied to the bottom of the
tank while at the same time, tank refrigeration
compressors were out of service.
10. Explosion of ammonia separator led to a major
plant outage.
Hans-Dieter Marsch of Uhde GMBH presented a
paper in 1990 symposium on explosion of a
multishell ammonia separator that had been in
operation for ten years. The vessel exploded into at
least 80 fragments in a 1000-tpd ammonia plant.
The most likely cause was the presence of
mercury, which affected steel properties and
formed explosive compounds.
The average mercury (Hg) content of the feed gas
was 150-180 microgram/cu.m and it was
equivalent to 60-72 kg of mercury per year.
Experts estimated that 1 kg of mercury is
AMMONIA TECHNICAL MANUAL
equivalent to approximately 2 kg of TNT or 9.2
MJ. Assuming 10 kg of Hg was present at the time
of rupture at the bottom of separator, it would have
been a charge of 92 MJ in addition to the stored
energy of 473 MJ in the gas.
The paper message was, if mercury is detected in
the feed gas, it should be removed to the lowest
possible level.
11. Failure of ammonia injector in urea plant
killed 2 people.
In July 1989, the casing of a high-pressure
ammonia injector in the urea plant operated by ICI
Chemicals and Polymers at Billingham, U.K.
failed catastrophically without any warning. The
release of ammonia resulted in the deaths of two
employees who were close to the injector.
The crankshaft had fractured allowing plungers to
come out of the cylinders thus causing an
uncontrolled release of ammonia.
The crankshaft fracture was due to a fatigue crack.
Also, the initial design of the machine should have
ensured that the plungers do not come out of the
cylinders in the event of crankshaft failure and loss
of containment could have been minimised by
better process plant design.
ICI developed an extensive list of improvements to
prevent a recurrence of this incident, which
included design changes to the urea injector pumps
and modified emergency and operating
procedures.
12. Explosion and fire in synthesis section
damaged plant.
A loud explosion followed by a large fire occurred
on 26 September 1991 at 0117 hours, in Ammonia
Unit 2 of Krishak Bharati Cooperative Limited
(KRIBHCO), India.
Due to the intensity of the explosion, one of the
relief valves was thrown off to the nearby pipe
rack.
The synthesis loop exchangers were exposed to
flames and shells of the exchangers were over-
heated. Cold insulation on syngas chillers and
ammonia separator burnt off. Motorised actuators
burned off, many instruments and power cables
were damaged. Control room window panels and
frames shattered, a false ceiling gave way and
instrument panels were dislodged. A relief valve
on the suction of the syngas compressor and about
20 control valves were damaged.
The most probable cause of the incident was
popping of one of the relief valves in the synthesis
18 2005
 loop causing an explosive mixture in the vent
header with ingress of air from the drain line on
the tail pipe due to a valve being left open after
manual draining of condensate. The spark for
ignition might have been provided by a friction in
the pipeline at uneven welding penetration and a
rise in temperature due to hydrogen gas expansion.
Many remedial actions were taken to prevent the
recurrence of the incident: - new location of the
relief valve with proper support of the tail pipe;
new RV with K orifice; high pressure trip of
syngas compressor; continuous purging of the cold
vent with nitrogen; new water seals on vent header
drain lines; and reduction of glass window panels
on the control room.
13. Many failures reported on Synthesis loop heat
exchangers.
A) Brittle fracture of an ammonia synthesis
heat exchanger
On 19 March 1970, an explosion occurred at
Typpi Oy ammonia plant in Finland due to the
failure of the forged steel chamber in one of the
effluent water coolers in the synthesis loop.
The syngas, at a pressure of 235 bar escaped and
caught fire and the height of the flame was about
30 m. The force of the explosion threw the
exchanger cover weighing 250 kg horizontally
about 100 m and bounced another 100 m. In
addition windows were broken within a radius of
hundreds of meters around the centre of the
explosion.
The explosion also damaged the multilayer
ammonia reactor. The hydrogen flame partly
loosened the outermost layer, which was repaired
by the vessel manufacturer.
The basic reasons of the failure are the selection of
material, too light forging and defective heat
treatment. The method of heat treatment used
resulted in a bainitic structure, which is brittle.
B) Failure of ammonia converter feed/effluent
exchanger
About 15% of production loss was estimated from
an internal leak of the converter feed/effluent
exchanger (121C) at Sherritt Gordan Mines
Limited, ammonia plant in Canada.
Both shell and tubes were designed for a pressure
of 15,169 kPa and the tube sheets were designed
for a maximum differential pressure of 2,069 kPa.
Finite element stress analysis was carried out after
a third failure and it was decided to install a
packed gland at the cold end.
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The gland and gland follower were prefabricated
and they were installed in a 15-day outage. The
repaired heat exchanger was hydrotested at 16,680
kPa. The synthesis loop performed well after
fixing the internal leak in 121C.
C) Further cracking in converter Effluent
BFW exchanger
A 1993 inspection of the ammonia converter
effluent boiler water exchanger revealed more
cracks than those discovered previously at ICI
Chemicals and Polymers Ltd, Billingham plant in
England. The primary cause was identified as
hydrogen embrittlement of a locally hardened
region.
A Fitness For Purpose assessment was carried out
and operating limitations and inspection
requirements were defined until a replacement
vessel could be installed.
The limitations included an external ultrasonic
examination prior to any cold start up and also a
maximum pressure of 100 bar was imposed until
the converter outlet gas temperature reached 200C.
D) Stress corrosion cracking in syngas heat
exchangers
In October 1982 severe damage was discovered in
two synloop feed/effluent heat exchangers at a
UKF ammonia plant in Geleen, The Netherlands.
When the problem of gas pocketing in leaking
water coolers was solved by making a vent in the
outlet cooling water nozzle, a fine mist of cooling
water escaping from this vent wetted the insulation
material of other equipment including the feed-
effluent exchanger. The wall temperature of the
steel pressure shell underneath the insulation of the
exchanger was in the temperature range likely to
cause stress corrosion.
Due to ammonia leakage into cooling water, more
nitric acid had to be added to control the pH at the
desired level, resulting in a higher nitrate content
than is usual in the cooling water. Stress corrosion
occurs even in stress relieved equipment such as
this exchanger.
The counter measures were- protective painting
underneath insulation material and avoiding
unnecessary wetting by watertight insulation
sheeting especially at nozzles
E) Repair of a waste heat boiler in synloop of
ammonia plant
Damage to the synloop waste heat boiler was
reported at the BASF AG, Ludwigshafen ammonia
plant in Germany.
19 AMMONIA TECHNICAL MANUAL
 The leak occurred because of the failure of the heat
protection shield. 71 boiler tubes were removed,
repaired and re-installed. The design of the heat
protection shield was changed to avoid this kind of
damage in the future.
F) Tube failure in a waste heat boiler in
ammonia synthesis section
A tube failure occurred in an 1800 tpd ammonia
plant at BASF Antwerp in Germany.
The damaged tubes were plugged. The pore in the
leaking plug weld seam was ground away and
rewelded.
The reason for the damage was inadequate design
of the product steam lines not considering the
fluctuating pressure drops in the separate product
steam lines upstream the common steam line due to
load changes.
These fluctuating pressure drops resulted in large
fluctuations in the steam drum level, which dropped
below the local level glass gauge for some time.
The drop of level below the lower level glass gauge
led to a collapse of the water circulation in the
vessel, which resulted in local superheating/cooling
down, of the tube wall. This also led to a continued
loss of protective magnetite layers and thinning of
tube wall. Finally the remaining tube wall failed.
Counteractions were installation of orifice plate in
the product steam line and installation of level
indication with alarm.
14. Significant incidents reported on reformer tube
dissimilar weld failures.
A) Abu Qir Fertilisers Co., Egypt reported
dissimilar metal weld failures on the reformer
tube to outlet manifold.
The mechanism of hydrogen induced crack
formation was considered to be the most probable
cause of the weld failures. The counter measure to
this type of failure is to increase the temperature
above dew point at the dissimilar weld. This was
achieved by adding outside surface insulation and
the installation of windshields on 3 sides of the
furnace.
B) ICI Chemicals and Polymers Ltd, Billingham,
England also reported dissimilar weld cracking on
reformer tube outlet headers.
The reformer tubes were fitted with both inlet and
outlet pigtails in Incoloy 800H sub-headers. In turn
these sub-headers were connected to larger diameter
carbon steel refractory lined headers via sixteen
transition cones. Each of these transition cones
incorporated a dissimilar weld at the change of
material.
AMMONIA TECHNICAL MANUAL
The explanation for the cause of cracking was that
the wall temperature had dropped below the process
dew point which resulted in the condensation and
hence corrosion. This corrosion then lead to
hydrogen liberation which diffused into the hard
fusion zone of the weld causing hydrogen induced
cracking on subsequent cooling down. The action
taken was to fit a local windshield and local
lagging.
C) Agrium Borger (TX) Nitrogen Operations also
reported dissimilar metal weld failures, on reformer
tube top transition pieces between cast tube and
P11. This was identified from a new inspection
technique using electromagnetic testing (EMT). A
new tube design was developed with a transition
piece of SS304H and all the tubes that had weld
failures were replaced with the new design top
transition pieces.
15. Explosion of Benfield and aMDEA storage
tanks.
A) At 11.40 A.M. on 4 April 1984, a violent
explosion occurred in the Benfield storage tank at
Farmland Industries, Pollock, LA plant, completely
destroying the tank and causing extensive damage
to synthesis gas piping.
At the time of the explosion, Benfield solution was
being transferred from the stripper to the tank. The
explosion sent the tank roof and side walls some 37
meters in to the air expelling an estimated 114 cu.m
of solution in to the process area.
Although standard operating procedures were
followed, hydrogen accumulated inside the storage
tank with sufficient oxygen, which, with a static
charge or auto ignition, caused the explosion.
Damages to process piping caused by the explosion
were repaired and a new tank was designed and
built to prevent any ingress of hydrogen from the
process system with an air induced purge system.
A new operating procedure for pumping out the
Benfield system to the storage tank was prepared
with emphasis on not allowing any gas to enter the
storage tank or solution sump.
B) In August 1999, an explosion occurred in
aMDEA storage tank at Alaska Nitrogen Products
plant in Kenai, Alaska. The explosion propelled the
MDEA storage tank off of its base and in to the air.
The tank landed on an adjacent air-cooled heat
exchanger, which was also filled with synthesis
make up gas. The impact of the tank on the air-
cooled heat exchangers initiated a second explosion
and fire. Three operators were treated for minor
injuries.
20 2005
 The reverse flow phenomena caused process gas
ingress into the MDEA storage tank, which was
ignited by some unknown source.
As a result of this incident, check valves were
installed in the MDEA system and the storage tank
was equipped with inert gas blanketing system.
Process Hazard Analysis (PHA) was conducted on
the aMDEA system and operating procedures were
revised to improve the focus on reverse flow and
other start up/shutdown conditions.
16. Explosion of H2 in CO2 line.
On 13 April 1997, the transfer pipe for carbon
dioxide gas from the ammonia plant exploded at
Hydro Agri, Prosgrunn facilities in Norway. There
were no injuries, but 850 meters of the line was
totally destroyed and a large number of glass
windows on nearby buildings were broken.
The line was temporarily out of service and the
investigation team concluded that the trip system
had been disabled prior to the explosion, hydrogen
rich gas had entered the pipeline, the nitrogen
purge had not been effective, allowing air leakage
into the line and forming an explosive mixture,
which ignited.
The trip system was modified and separate
sampling lines with block valves were installed for
each analyser in order to eliminate a common
mode failure caused by, for example, freezing in
the wintertime. A new analyser was also installed
for use in the reformer section for the start up.
17. Reformer tubes burn out, a big impact on
business.
The Agrium Fort Saskatchewan Nitrogen
Operations experienced a massive reformer failure
on 16–17 November 1998 during start up after a
short maintenance outage.
The incident happened during the reformer start up
when the reformer furnace was fired harder while
observing the process gas outlet temperature rather
than flue gas temperature, when there was no
steam flow through the radiant tubes.
It was noted that the flue gas temperature had
reached a maximum value of 1071oC. The tube
melting point is typically quoted at about 1343oC
and complete melting will be finished at 1400oC.
It’s probable that the localised flue gas
temperatures were much higher than the
temperatures reported by thermocouples at the
outlet of the radiant box. Uneven firing or the
relatively high air leakage rate at low firing rates
could cause this.
2005
Approximately 50% of the tubes had completely
failed and the tube failures were observed mainly
at welds. No risers failed, but overheating was
evident.
All the reformer radiant tubes were replaced in just
39 days after the damage to the furnace occurred.
Russian built cargo planes were used to transport
radiant tubes from the U.K. to Canada.
An automatic shutdown system was installed to
protect against overheating during start up.
Operating procedures were modified to reflect
changes in communication between the shifts.
18. Failure of a molecular sieve dryer.
At 11.30 P.M on 24 May 2000, a molecular sieve
vessel failed catastrophically at CF Industries
Donaldsonville, Louisiana, Ammonia plant 3.
Vessel fragments were projected throughout
Ammonia plant 3, Urea plant 2 and the adjacent
offsite operating areas causing extensive damage
to equipment in the fragments’ path. The resulting
fire from escaping process gas caused burn injuries
to several personnel working in the local area.
The failure resulted from a delayed hydrogen
crack that originated at the toe of a repaired fillet
weld. The crack propagated into the vessel head to
a critical flaw and then fast-fractured through the
shell thickness. The vessel shell continued to fast-
fracture from the origin into approximately forty
fragments in less than one-tenth of a second.
Minimising the weldment hardness and residual
welding stress would have increased the critical
flaw size preventing this type of failure.
19. Failures on ammonia synthesis converters
A) Failure and repair of ammonia converter
basket
The Shahpur Chemical Co., ammonia plant in Iran
experienced failure of ammonia converter basket,
which led to plant shutdown.
Hot spots appeared on the converter pressure shell
and upon inspection, vertical cracks were observed
on the basket. The repair of the basket was
accomplished by lining the inside with two layers
of 6.5-mm (¼ in) thick plates. A liner was welded
to the grid at the bottom of each bed.
The cause of the basket failure attributed to
chloride stress corrosion cracking as the basket
materials were made of 304SS. Records showed
that water used for the final pressure test of the
shell with the basket insulation in position
contained 11 ppm of chlorides.
21 AMMONIA TECHNICAL MANUAL
 Lessons from this failure that hydrostatic testing
should be carried out with water containing less
than 1-ppm chlorides. The use of moisture
retaining insulation for the basket to be avoided
and the insulation should not contain chlorides.
B) Ammonia converter basket failure
Agrico Chemical Co., Donaldsonville, La also
reported ammonia converter basket failures caused
by stress corrosion. A series of hot spots were
noticed even after repairs made to basket and the
basket was finally replaced with a new one.
The main cause of the failure appears to be high
chloride levels in the basket insulation material i.e-
spun rock wool. The catalyst, insulation and
hydrotest water also had chlorides in varied
ranges.
Construction and shipping photographs indicated
the side of the vessel was cracked during
hydrotesting and shipping.
Good design with the right equipment materials of
construction is not enough to prevent stress
corrosion cracking. Particular attention must be
given to water, which comes in contact with the
materials of construction. Analysis of insulating
materials, which do not include tests for particular
contaminants such as chlorides in the 0 to 500-
ppm range, should not be accepted.
C) Damage and repair of a 1000 tpd horizontal
ammonia converter
In March 1984, the diaphragm and impeller of the
high-pressure case of the synthesis gas compressor
failed, resulting in a plant shutdown at the Sheritt
Gordan Mines ammonia plant in Canada.
The basket internals suffered significant, but
readily repairable damage. Catalyst plugging of
the Bed2A distributor grids caused a high-pressure
drop across the converter resulting in a reduction
in plant capacity. Damage was also found in
downstream exchangers 120C, 121C and 123C.
Repairs and modifications made to converter
basket allowed the plant to operate the plant at full
capacity.
D) Failure and novel repair of thick wall
synthesis converter forgings
During a routine ultrasonic inspection, severe
cracks were discovered in the 5-Cr converter
bottom forgings at an ammonia plant of Arcadian
Corporation, Augusta, GA.
The investigations concluded that low cycle
thermal fatigue was a key element in initiation of
AMMONIA TECHNICAL MANUAL
the cracking of the Inconel 182 overlay at the I.D.
of the forgings. Once cracking had progressed
through the In-182 there was considerable
evidence to indicate that propagation within F-5
forging material was enhanced and possibly
accelerated by the nitriding effect of the process.
Repairs were made by selecting an alternate design
that improved vessel safety and integrity. The key
lesson from this is that any users of vessels with
thick wall components subject them to periodic
examination.
E) Inner basket failure of ammonia booster
reactor
A major failure involving the inner basket of the
ammonia booster reactor after a scheduled
turnaround caused an additional down time of 31
days at ABF Bintulu’s ammonia plant in Malaysia.
In August 1997, the inner basket of the booster
reactor had partially failed and leaked catalyst,
resulting in plugging of downstream synthesis loop
high-pressure equipment and piping.
The possible cause of the failure was the missing
bolts on catalyst basket and strips, which were
replaced, reinforced after unloading the catalyst.
The numerous trips coupled with the defective
valves caused the failure of the bolts and thus the
catalyst leak. The booster reactor internals can be
improved to increase their robustness.
F) Ammonia converter leakage and repairs
The centre screen on 2nd bed failed in ammonia
converter basket at Fauji Fertiliser Co. Ltd in
Pakistan.
The main cause of the failure suspected to be the
weaker design of the centre screen to bear the
actual compression stresses caused by the
combined action of thermal expansion of the
screen and the opposite forces resulting from
friction of catalyst and/or expansion bellows.
The entire catalyst was removed and a new
modified design, centre screen was installed and
new catalyst charge was loaded.
G) Ammonia converter weld joint failure
On 25 April 1995, at Tata Chemicals Ltd ammonia
plant in India, a fire was noticed at the joints of the
insulation cladding close to the location of the first
circumferential site weld joint from the bottom of
the second ammonia converter. Immediately after
the incident the plant was shutdown, as they
couldn’t extinguish the fire with dry chemical
powder.
22 2005
 Various tests carried out have established the root
cause of the failure as hydrogen induced cracking
due to unsatisfactory PWHT on the original P22
converter shell.
The failed joint was repaired in-situ in the
following steps:
- The entire defective portion was removed by
gouging, drilling and grinding.
- The stresses developed were relieved by
heating the entire seam to 700 oC with a
soaking period of 1 hour and 45 minutes.
- Hardness was measured after stress relieving
and was found within 185 Hv.
- Surface preparation followed by dye penetrate
check was done.
H) Failure of internals of ammonia converter
In 1999, Ammonia converter internals failed at
PTPK ammonia plant in Indonesia.
The sliding expansion joint of the gas return pipe
in bed no.3 and 4 and the screen of the support
thermowell on the inner collector of the fourth bed
were found broken.
The sliding expansion joint was repaired and the
support of the thermowell was relocated.
The possible causes of the internal damage to the
ammonia converter include:
- The design of the expansion joint did not absorb
the thermal expansion leading to the expansion
joint collapse on the wire mesh and catalyst filling
the gas return pipe.
- The internal damage occurred during the
ammonia plant start-ups and shutdowns. When the
temperature changes produced excessive
differential growth and movements of the gas
return pipe may have caused deformation of the
centre pipe.
- The support of the thermowell pipe and wire
screen of the inner collector was not strong enough
to support this pipe, so the wire screen and catalyst
spilled from the basket.
20. Failures on ammonia storage tanks
A) Overflow of an ammonia storage tank
On 16 November 1970, Gulf’s refrigerated
ammonia storage tank at Blair, Nebraska
overflowed, causing considerable concern to
residents of the community but, fortunately, no
serious injuries. About 150 tonnes of ammonia
were lost to atmosphere and three city firemen
were treated for fume inhalation.
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The tank high level alarm and shutdown system
did not work which resulted in to this incident.
Lessons from this incident that tanks equipped
with overflow systems like this tank should have
the relief valve and block valve separated by
sufficient distance to allow closing the block valve
when relief is open. At Blair, the block valve was
directly below the relief and showered with liquid
ammonia during an overflow. There should be
back up level indications on the tank.
B) Partial collapse of an ammonia storage tank
On 13 November 1978, a 6,349 tonne atmospheric
ammonia storage tank located at J.R. Simplot’s
Pocatello plant, partially collapsed when a vacuum
developed in the tank.
The tank, which was approximately one third full
at the time partially collapsed on the one side and
developed a small rupture near the top portion of
the tank, well above the liquid level. The tank was
subsequently drained, cleaned and repaired before
decommissioning.
The cause of the tank collapse was the result of
several conditions. The initial failure was
precipitated by the failure of the pressure
transmitter following the power outage. It was
believed that moisture in the instrument air froze
during the power outage and caused the failure.
The only other pressure indicator in the tank was a
gauge, which received a signal from the same
transmitter, as did the controller. A manometer on
top of the tank had been allowed to fall into
disrepair and the regular operator checks on the
manometer were not conducted.
The ultimate cause of the tank collapse was the
failure of the vacuum relief valves.
The controller failure and lack of any warm
ammonia from the plant following power failure
coupled with the cold weather and atmospheric
conditions were sufficient to create vacuum in the
tank. With no vacuum relief on the tank, the tank
collapsed when the structural design conditions
were exceeded.
Several preventive measures were taken to exclude
any recurrence of the tank collapse. An additional
pressure indicator was installed on the tank, using
an electronic transmitter and sensor. The pressure
recorder-controller and auxiliary pressure indicator
remain a pneumatic system.
The nitrogen blanketing of ammonia storage tank
shall be avoided. Sub-cooling of the ammonia in
the tank, which results in temperatures well below
the design of the tank steel and foundations.
23 AMMONIA TECHNICAL MANUAL
 C) Damage to ammonia storage tank
foundation
M.W.Kellogg reported a foundation damage on an
ammonia storage tank at the Asmidal plant in
Algeria. This was caused by freezing and heaving
leading to movement, tilting, tearing, cracking,
bending and fracture.
The integrity of the tank was not affected and the
tank foundation was repaired to modern design.
It was concluded that the most probable scenario
of events was damage due to ground movement of
the 19 April 1981 earthquake to the foundation
insulation system. This damage was spreading and
slight tilting of the segments, failure of anchor
bolts, breaking of the cork insulation, tearing of
the water proofing and outer fabric and local
punching failure of the vermiculite insulating
concrete. Water then entered the foundation
system both from above and laterally, increasing
the conductivity of the thermal system, and froze.
The soil below also froze. The expansion forces of
frozen vermiculite concrete, soil and ice in the
joints further acted to distort and fail other
elements.
Much attention must be placed on details of design
especially in the area of water proofing and
peripheral drainage to the concentrated
compression forces caused by the rocking action
of tanks especially when they are in a near full
condition subject to earthquake induced sloshing
action.
D) Stress corrosion in an ammonia storage tank
BASF Chemicals Ltd, Middelesbrough in England
reported stress corrosion cracking of 12,000 tonne
ammonia storage tank during first inspection after
nine years in operation.
The material used and the weld procedures
adopted on site produced microstructures
susceptible to both stress corrosion cracking and
hydrogen cracking.
All the defects were repaired and tank was
recommissioned.
It was recommended that wherever possible cleats
be made on the outside of tanks and proper weld
procedures employed for those inside the vessel. It
was also recommended that where practicable
consideration should be given to limiting the
parent metal to lower yield strength steels when
constructing new tanks.
E) Failure of inner shell on double integrity
ammonia storage tank
AMMONIA TECHNICAL MANUAL
A 5,000 tonne ammonia storage tank which was
originally commissioned in 1998, needed to be
decommissioned and repaired due to the failure of
the inner shell of the double wall tank at
Coromandel Fertilisers Ltd, India.
Ammonia liquid level was noticed in annulus area
of the two tanks and hence, a decision was made to
decommission the tank for inspection as they
thought inner cup failed.
The liquid level in the annular space of the tank
was measured by a level transmitter, which had
high level alarm. But, level transmitter was
reading zero since “as built” drawings were wrong
to which the annulus level transmitter connected
to.
No action was initiated to drain annulus area as
they thought it did not have high level whereas it
actually had 6.5 m of level. It appeared that some
ammonia had started collecting in the annulus due
to splashing from the inner cup during ship
unloading at high levels.
The inner cup was drained to 0.813 mm for
decommissioning and then failure occurred due to
hydrostatic head of ammonia in annulus acting
below the bottom plate, ultimately resulting in the
fracture of the bottom side plates as well as the
circumferential weld.
The tank was repaired and it involved the repair of
the concrete kerb, removal and refilling of bottom
sand layer, repair of and replacement of shell
courses, bottom plate renewal, and other
modifications.
Following actions were taken to prevent
recurrence of the incident:
- The tank was derated to, 4,865 Te and setting
of alarms and trips changed accordingly so as
to provide a minium 500 mm of free board
between maximum allowable liquid level and
overflow level.
- A separate recording instrument to record tank
inner cup and annulus levels. A parallel
independent level indication was also provided
for the annulus.
- All indicators were changed to fail-safe.
- A temperature indicator to monitor annulus
temperature, with a low temperature alarm.
- Interlock to trip the ammonia pumps if annulus
level reaches 400-mm level.
- The annulus drain line permanently connected
to the drain pot and routine of draining the
24 2005
 annulus into the drain pot every weekend was
initiated.
- The siphon breaking on the liquid inlet line
into the tank was modified, so that the top
most hole of the dip pipe is above the
maximum liquid level in the tank.
- All documents have been updated to reflect
“as built” conditions.
ENVIRONMENTAL ISSUES
Some plants have installed continuous emission
monitoring system (CEMS) on the primary furnace
stack. This system monitors O2, NOX and CO
emissions. It has become a useful tool to indicate
deviation from optimum combustion conditions
within the furnace. CEMS eliminates the need to
estimate or calculate the emissions of NOX and
CO from the reformer furnace and it can easily
determine the total quantity of each pollutant
emitted during the calendar year for reporting
purposes.
Process condensate from a few ammonia plants is
reused by putting it back into the reforming system
through natural gas saturators. In some plants,
process condensate is purified by HP or LP stage
stripping.
NOISE
Noise has been defined as unwanted sound. Its
undesirable effects can be temporary or permanent
hearing loss, inability of personnel to
communicate effectively and reduction of
efficiency.
The potential sources of noise are commissioning
blow-offs, relief valve blow offs, suction silencers,
fans, ducts, pressure reducing stations etc. It’s far
more preferable to design noise control systems
into the plant rather than wait until an aroused
public compels remedial action.
Noise levels in ammonia plants have been reduced
by improving the design of Greenfield sites
(largely by World Bank legislation) and by
installing acoustical insulation, barriers, energy
absorption devices and implementation of ear
protection in the operating plants.
PLANT OPERATION PERFORMANCE
Plant on stream performance is summarised for the
benchmarking surveys conducted by Plant Surveys
International, Inc. (PSI) in Table 2.
2005
There have been a total of 8 benchmarking
surveys, the first beginning in 1969. The first 3
surveys were limited to North America. Since
then, all the surveys have been worldwide
although plants in Russia and China have not
participated.
The poor operating factor in Survey No. 5 was due
to excessive inventory control downtime. The
service factor is more representative of plant
performance since service factor downtime
excludes business-related downtime (inventory
control, feedstock curtailment, loss of utilities,
etc.).
There has been a steady increase in ammonia plant
service factor over the years from 87% to 92%.
DESULFURIZATION
In the earlier days of desulphurisation, activated
carbon drums were used to remove sulfur
compounds. Later on, Sulfatreat (iron sponge) and
molecular sieve dryers were also used to remove
low-level sulfur compounds.
The hot desulphurisation process using Ni-Mo or
CoMo with ZnO has now become the industry
standard in removing sulfur compounds from feed
gas. This has increased catalyst life of both the
primary reformer and the LT shift converter.
CO2 REMOVAL SYSTEM
Different solvents were used over the years. These
included:
• Physical solvents such as Selexol, Fluor 1 and
Rectisol (methanol);
• Chemical solvents such as MEA, TEA, and
Sulfinol;
• Alkaline salts like Benfield (vanadium as
corrosion inhibitor), Catacarb (organic borate
and vanadium as corrosion inhibitor);
Vetrocoke (arsenic as corrosion inhibitor),
and Giammarco Vetrocoke (glycine and
vanadium pentoxide as corrosion inhibitor).
• Alkanolamines such as Dow GasSpec,
UCARSOL and BASF aMDEA.
BASF aMDEA has become one of the most
popular solvents in modern ammonia plants.
25 AMMONIA TECHNICAL MANUAL
 PROCESS TECHNOLOGY
DEVELOPMENTS
Prereforming technology
Many plants have installed prereformers to
increase production rates and also to meet
fluctuations in feed gas compositions.
Prereformers can easily be integrated into existing
plants.
Pressure drop improvements on shift converters
Johnson Matthey developed a new catalyst support
system for shift converters, which is known as
StreamLine.
Haldor Topsoe has developed a new catalyst
support grid, which was applied on the vessels that
had elephant stools in original design.
Ammonia Casale have installed axial-radial flow
baskets on shift converters.
All three systems have reduced the pressure drop
across the shift converters by about 50%.
Catalyst loading technology
Norsk Hydro developed the Unidense loading
system for primary reformers. The technique to
load other reactors was known as Densicat.
Haldor Topsoe developed the SpiraLoad catalyst
loading method, another dense loading technique
that is used mainly for primary reformer tube
catalyst loading.
It has become a standard practice to use these
dense loading systems in place the old sock
loading system. The advantage for primary
reformer furnaces is the tubes can be loaded with a
very uniform range differential pressure (dP)
which reduces the likelihood of hot tubes during
operation.
Low energy accelerated startups
Hays Mayo suggested this well-known accelerated
ammonia plant start up technique in eighties that
many North American plants have implemented.
Typical start up times are about 12 hours and
consume only 12 giga joules of energy.
Hydrogen recovery from purge gas
Three types of hydrogen recovery systems were
installed in different plants. Those are: membrane
separators, cryogenic separation using a cold box
and pressure swing absorption systems.
Each has advantages and disadvantages and all
these have improved ammonia plant efficiency and
increased plant production rates by about 6%.
AMMONIA TECHNICAL MANUAL
Selectoxo process
A new process was developed which selectively
oxidises CO, and this has increased plant yield by
3-5% and extended LTS catalyst life. Some plants
installed this system in the early years of the
industry and those plants are still in operation.
KAAP, KRES, KBR Purifier process
M.W.Kellogg developed large-scale single train
ammonia plants using centrifugal compressors in
the 1960’s. Also, in the 1960’s C.F.Braun
developed the Purifier process. M.W.Kellogg
along with BP developed the Kellogg Advanced
Ammonia Process (KAAP). After the merger of
Dresser and Halliburton in 1998, Kellogg and
Brown & Root (KBR) was formed; combined
Kellogg and Braun ammonia technologies. KBR
now offers many different processes including
Purifier, KAAP+Purifier, and KAAPlus with a
Kellogg Reforming Exchanger System (KRES)
and KAAP reactors.
The Purifier plants use mild primary reforming
conditions, excess air in the secondary reformer,
cryogenic purifier, horizontal synthesis converter
and unitized refrigerant chiller. KBR claims the
designs are now available to build large scale new
plants up to 5000 tpd using their latest
technologies.
Haldor Topsoe plants
Many plants were built over the years using this
technology up to 2000 tpd. Various synthesis loop
designs and converter arrangements such as S200,
S250 and S300 have been employed in Topsoe
plants.
ICI AMV process: has a feed gas saturator, milder
reforming conditions, excess air in the secondary
reformer, an electric driven syngas compressor,
and a cryogenic purifier. Some plants are in
operation using this technology in Canada and
China.
Leading Concept Ammonia (LCA) process
Originally developed by ICI, LCA incorporates
low temperature catalysts for pre-treatment, gas
heated reforming, feed gas saturator, single
isothermal shift reactor and syngas purification.
The plants built in the UK with LCA process have
been in operation for more than 20 years.
Ammonia Casale
Developed axial-radial baskets for ammonia
synthesis converters and these were installed in all
types of converters. This has helped many
26 2005
 ammonia plants to upgrade plant capacities and
also to improve plant efficiencies.
Linde Ammonia Concept (LAC) This process has
an air separation plant, primary reforming,
isothermal high temperature (HT) shift reactor,
and CO2 removal by Pressure Swing Absorption
(PSA) and back-end with Ammonia Casale
technology.
Uhde Dual Pressure process
Uhde and Synetix developed a new process for
large capacity ammonia plants to overcome the
bottlenecks of standard piping and to reduce the
compressor demands.
This process employs a once through ammonia
synthesis converter located at an intermediate
pressure level, upstream of the main synthesis
converter. The new flow sheet delivers a capacity
of 4000 tpd using well-proven equipment.
Megammonia process
Lurgi developed this process with an Ammonia
Casale back-end loop. The main features of the
process are catalytic partial oxidation, a high
temperature shift reactor, and CO2 removal using
Rectisol solvent, liquid N2 wash unit and 200-bar
synloop. Lurgi would offer 4000 tpd plants using
this technology.
Process simulation
Computer simulation models were developed to
investigate optimum operating conditions and
evaluate potential projects for existing ammonia
plants. The well known process simulation
packages are AspenTech, HYSIS, and SIMSCI.
Training simulator
This is an advanced training tool with excellent
capabilities for providing hands-on experience in a
true-to-life environment. It’s useful for training
new operators, for refresher training, and also for
developing appropriate corrective strategies to
minimise process upsets, thereby improving the
reliability and safety of the plant. The dynamic
simulator is also a significant tool in carrying out
process studies to evaluate alternative process
control schemes and operating parameters.
Training simulators can also be used to optimise
the control strategy, to test the trip logic, and to
develop detailed start up instructions.
PROCESS CONTROL
Over the years, ammonia plants have replaced the
old pneumatic control systems with distributed
computer control systems (DCS). They have
2005
advantages like consistent and smoother operation;
good response to unusual conditions, provide snap
shots and trend charts, and generate process logs
and management reports.
With the DCS systems, the process variables such
as feed flow determination, catalyst tube
temperature control, CH4 slip control, flue gas
temperature control, S/G ratio control, H/N ratio
control, purge flow and synthesis reactor control
have improved significantly. DCS systems have
increased productivity and improved plant
efficiency.
In the 21st century, advanced process control
systems came into place and increased yield,
extended catalyst life and provided better on-
stream time.
Some plants have installed multi-variable
advanced control systems and have increased
production rates by 0.6% and reduced energy
consumption by 1.5%.
Another type of advanced process control system
was known as Adaptive Technologies. This was
originally based on neural networks and then
encompassed fuzzy logic and non-linear multi-
variable dynamic control.
HAZOP STUDIES
Hazard and operability (HAZOP) studies have
been introduced in eighties to ammonia plants. The
methodology can be applied in all plant
modifications as well as to new plant design. The
same studies have been used for DCS projects.
Some plants have installed stand-alone
computerised emergency shutdown systems and
this is widely used in the industry on modern
ammonia plants.
AMMONIA STORAGE TANKS
Many surveys have been reported on ammonia
storage tanks at AIChE symposiums.
There are essentially three different types of
storage tanks, namely Horton spheres [design
conditions of 413 kPa, 1.1 oC (60 psig, 34 oF)],
high-pressure bullets [1723 kPa, 93 oC (250 psig,
200 oF)] and atmospheric storage tanks [6.9 kPa, -
33 oC (1 psig, -28 oF)].
The atmospheric storage tanks are designed to
three different types; single wall tanks with
external insulation, double wall tanks with perlite
insulation between the tanks and double integrity
tanks with cup in tank and external insulation. The
atmospheric storage tanks are built per the API
620 Code.
27 AMMONIA TECHNICAL MANUAL
 About 60% of installed tanks have flares to
dispose of ammonia vapours in the event of
pressure build up.
Different types of secondary containment systems
are available - separate steel structure dikes
combined with conventional earthen dikes,
reinforced concrete dikes backed by earthen fill,
and conventional earthen dike.
Many tanks have been decommissioned, inspected
and recommissioned. There is a trend to using
non-intrusive inspection methods for tank integrity
utilising acoustic emission testing and risk based
inspection techniques. Such methods can reduce
the cost considerably versus intrusive inspection
methods and have the advantage of keeping
oxygen out of the system, which can contribute to
stress corrosion cracking.
Studies have also shown that a small amount of
water is effective as a corrosion inhibitor in
ammonia service, and it prevents stress corrosion
cracking.
COMBUSTION OF AMMONIA
In the symposium of 1961 the combustion
properties of ammonia were first addressed. In that
meeting combustion of ammonia had been of
interest for a long period of time but the available
combustion properties have been inadequate to
explain fully the anomalous behaviour of ammonia
or to permit satisfactory evaluation of the potential
hazards of ammonia in industrial operations.
Historically W. Henry in the 1809 Philosophical
Transactions first published the flammability
limits of ammonia in oxygen and was apparently
the oldest recorded for any combustibles.
By 1914 German investigators established definite
flammable limits for ammonia in air.
A compilation of flammable-limit data shows
seven additional published studies were presented
between 1922 and 1949.The pressures developed
by ammonia-air explosions were measured in
1923.
In spite of this evidence, and apparently as late as
1951 ammonia was indicated to be non-
combustible and experiments were cited as “rough
proof that ammonia does not support combustion
or burn.”
In the 1961 AIChE proceedings it was reported
this misconception was fairly wide spread, even
among people associated with the ammonia
operations in part because historical incidences of
fires or explosions attributed to ammonia was low.
AMMONIA TECHNICAL MANUAL
This fact could be explained by the observed
difficulty of igniting ammonia, and by the low
speed of flame propagation in ammonia-air
mixtures.
The work by Buckley and Husa lead to
confirmation of the combustion properties of
ammonia and in defining the boundaries between
flammable and non-flammable mixtures of
ammonia and air at 16 to 27% at OoC and 15.5 to
28% at 100oC.
Even though ignition is difficult and flame
propagation proceeds with little vigor the work is
recognised and well respected in the ammonia
industry today to ensure safety in operations.
COOLING WATER TREATMENT
Many plants have changed over their cooling
water treatment from the heavy metal based
chromate to a phosphate-based treatment. The
non-chromate treatment program meets the new
environmental standards and provided industry
with protection approaching that of chromate
based treatment.
BOILER WATER TREATMENT
Boiler water systems for the nitrogen industry
mainly consists of make up water (demineralised
water) preparation, handling of condensate returns,
condensate polishing, and chemical treatment to
prevent corrosion, strong alkali attack, and
hydrogen damage.
Steam systems operating at 100 bar or higher
require high purity make up and consistently
uncontaminated condensate return.
There are mainly two types of treatments for high-
pressure boiler water systems and these are
coordinated phosphate (an internal treatment) and
an all volatile zero solids treatment which requires
precision control. Plants are using both the
systems.
Periodic chemical cleaning of the steam generation
equipment must be considered inevitable. Every
possible step should be taken to maintain clean
waterside surfaces in high-pressure boilers in order
to minimise corrosion potential.
Depending on the contamination type, amount and
frequency, the internal treatment prerequisite is a
thorough examination of the system prior to
choosing the program. Once the program is
selected, meaningful testing and monitoring of the
BFW and boiler water system is necessary.
28 2005
 METALLURGICAL IMPROVEMENTS
The reformer tube materials have changed over the
years from HK-40, to HP Nb modified, to HP
micro-alloys. Inlet pigtails have changed from 1-
1/4Cr-1/2 Moly to stainless steel. Hot outlet
manifolds and weldolets use Alloy 800H or
800HT materials and there is a trend towards using
cast equivalent materials instead of wrought
materials.
Many changes have been made to the mechanical
design and fabrication of reformer tubes. Besides
upgrades in metallurgy to improve creep rupture
life, the new alloys have allowed thinner wall
enabling higher rates and better heat transfer.
Great strides have been made in welding
technology for reformer tubes such that very few
reformer tubes fail at the weld or heat affected
zone areas.
New designs have been developed using internal
refractory lining systems to solve problems of
failures at outlet headers and transfer lines in
reformer furnace service.
The reformer tube inspection and life assessment
have also improved over the years. Various
techniques are employed such as eddy current,
ultrasonic, laser profilometry, tube thickness and
tube diameter measurements. All these systems
have their own merits, but the salient point is they
have to be used on a frequent basis to monitor tube
life. The inspection advances have proven highly
beneficial to operators in delineating tube
retirement schedules and removed the uncertainty
of early or unexpected tube ruptures.
Brittle failure/rupture has been troublesome for the
industry for years. Most will remember or read
about the numerous instances of ships breaking in
half during World War II. Great strides have been
made in understanding the combined presence or
actions of several factors, of which temperature is
very important consideration in influencing the
brittle fracture behaviour of ferritic steels. There
are many interconnecting factors affecting brittle
failure, namely alloy content, deoxidation practice,
microstructure, thickness and heat treatment to
name a few. Other issues, and much harder to
define, include defect size and shape, fabrication
methods, welding practices, post weld heat
treatment, and rate of loading. Rigorous
mathematical analytical methodologies have
unfolded over the years in an attempt to quantify
material load carrying capacity with known or
perceived defects.
Many embarrassments have occurred to operators
2005
on existing equipment and to fabricators for new
equipment where catastrophic failure has occurred
to fabricated vessels following repairs or during
the final acceptance stage of hydro testing with
media at low ambient temperatures.
Industry has taken heed of these incidents and now
incorporates for the most part safe guards to
mitigate against such embarrassing occasions.
Huge advances have been made in the inspection
of serpentine piping coils in process heaters
utilising intelligent pigs. Corrosion and/or erosion
effects can be tracked on successive outages
providing management with a tool for scheduling
repairs and replacement, without forced outages.
Many advances have occurred in inspection and
testing for ammonia and urea plant equipment. To
name a few, automated ultrasonic, time of flight
diffraction, advanced ultrasonic backscatter
technique, electromagnetic acoustic transducers,
acoustical emission, alternating current field
measurement, laser profilometry, remote field
eddy current, real time radiography, various tank
inspection tools [tank climber and magnetic flux
exclusion (MFE)], video imaging, real time
radiography, and thermography to list a few.
Likely there are others that are missed, but suffice
to say, many tools have come to the assistance of
plant operators to help improve plant reliability.
Many failures were reported on front-end waste
heat boilers (WHB) downstream of the secondary
reformer. Those were addressed by replacing them
with alternative designs. However, failures are still
reported for various reasons, such as overheating,
lack of continuous water supply, loss of refractory,
fabrication issues, metal dusting and improper
operating conditions. Some designers have offered
alternative WHB designs with removable bundles.
The latter provide a means of removing the failed
bundle in a controlled and scheduled manner
permitting the plant to get back on stream without
the uncertainty in repair time.
New designs with thin tube sheets for horizontal
WHB and for a close coupling to the converter
outlet have proved to be reliable.
Improvements to eliminate metal dusting have
been made with a clear understanding of the
mechanism and the development of materials to
resist metal dusting. This new knowledge is being
incorporated in newer plants and as retrofits in
older operating plants.
Ammonia synthesis equipment is also prone to
failures and design of such equipment must be
done considering the possibilities of hydrogen
29 AMMONIA TECHNICAL MANUAL
 attack and nitriding. Major advances have been
made in understanding the process of nitriding,
and in materials to lessen this effect in operation.
More information is being developed on the
understanding of high temperature hydrogen
attack. The API recommended practice 941 is in
its 6th revision since inception in 1970 due to new
and continued damage cases found in industry.
The ammonia industry, petroleum refining and
petrochemical industry is indebted to George
Nelson for first proposing the “Nelson Curves” on
high temperature hydrogen attack at Shell in 1949.
Complimenting API 941 is data incorporating time
at operating temperature, operating temperature
and hydrogen partial pressure in assessing risk to
high temperature hydrogen attack.
Of particular concern is the issue with C + 0.5 Mo
materials where serious damage has been cited in
the past 20 years. With respect to Mn + 0.5 Mo
materials API 941 6th edition reports no hydrogen
attack history below the C + 0.5 Mo line,
especially when normalised, quenched and
tempered material is used. However the writer’s
have first hand experience with hydrogen attack in
Mn + 0.5 Mo in a horizontal ammonia converter
below the C+ 0.5 Mo line.
Many older plants have considerable equipment
made of C + 0.5 Mo with High Temperature
Hydrogen Attack (HTHA) a major issue.
Thick section 2 ¼ Chrome + 1 Mo steel plates
used in ammonia pressure vessel equipment at
high operating temperatures experienced many
temper embrittlement failures until the extensive
research found ways to avoid such a phenomenon
by controlling impurity levels and altering
fabrication processes.
Stress corrosion cracking continues to be an issue
in the ammonia industry and continues unabated.
Failures occur due to lack of attention on hydro
testing, wet insulating materials, and oxygen
entrainment in the case of carbon steel ammonia
storage tanks.
Thermal fatigue in the ammonia industry is a
major concern. Thermal fatigue or thermal stress
fatigue results in the deterioration of alloys due to
temperature cycles in which stresses from
expansion or contraction and from differential
expansion of various phases without external
loading eventually lead to cracking, resulting in
premature failures and safety hazards. Many
incidences of thermal fatigue have been discussed
at various symposiums and failures continue even
today in the industry.
AMMONIA TECHNICAL MANUAL
Urea plant information started to be addressed by
N.H Walton in the proceedings in 1964. Data first
listed the many alloys that had been tested in urea
carbamate mixtures. Material issues in the form of
corrosion were interesting and unpredictable.
A listing materials examine ranged from austenitic
stainless steels, nickel alloys all the way up to the
more exotics like titanium, tantalum and
zirconium. Samples of lead were included. 316SS
was the workhorse alloy at the time. Many
materials corroded away quite obviously. It is
quite interesting to note the high nickel alloys did
not due well in urea carbamate mixtures.
Such information was confirmed later in 1975
works of DSM in The Netherlands where nickel
content was shown to have a negative influence on
the corrosion resistance of austenitic stainless
alloys and has lead to the work on developing the
duplex stainless steel alloys for urea service. Much
work continues on these alloys today.
Ferritic content was also broached at this time
wherein lower ferritic was better, and upper limits
are now imposed by all urea licensors.
Even in 1964 zirconium was noted to have a very
low rate of corrosion in urea carbamate mixtures,
although it was difficult to obtain components in
zirconium at that time. Such is not the case today.
Titanium has been used for years in urea
carbamate service and continues to be used today
in some plants, although its major drawback is low
erosion resistance.
Great strides have been made in alloy development
for urea service and today the Moly modified
310SS is one of the main staples. As well,
zirconium alone and in combination with stainless
steel is used very extensively in urea service, but
corrosion issues with this combination have
surfaced in other locations.
New developments are considering combinations
of Zr/Ti to overcome corrosion and erosion issues.
SUMMARY
1. All the incidents since the early years of
the symposium were listed including the
root causes and remedy actions taken.
2. Major safety incidents were discussed in
brief.
3. Plant operational performance over the
years was reviewed.
30 2005
 4. Major process technology developments
were highlighted.
5. New process technologies for building
large-scale new ammonia projects were
briefed.
6. Various developments on ammonia
storage tanks, desulphurisation and CO2
removal systems were described.
7. Maintenance or metallurgical
improvements carried out over the years
were elaborated.
Authors’ Acknowledgment
The paper is dedicated to all those of past and
present who spared their valuable time in
organising the symposiums, writing, reviewing
and presenting papers.
Also thanks to all the current AIChE ammonia
safety committee members and our friend Walter
Benson for their very valuable input and
suggestions to this paper.
REFERENCES
[1] Safety Performance in Ammonia, Methanol
and Urea Plants, 1999-2001 Surveys
Gerald P. Williams
Vol 44 AIChE Symposium, 2003
[2] Failures of Secondary Waste Heat Boilers
Jagmohan Singh, S.L.Verma and B.M.Patel
Vol 44 AIChE Symposium, 2003
[3] Failure of a Molecular Sieve Vessel Resulting
from a Defective Weld Repair
Michael Picou
Vol 43 AIChE Symposium, 2002
[4] Fire in Secondary Reformer Outlet Line to
Wastle Heat Boiler
Jagmohan Singh, P. Basu, and B.M. Rao
Vol 42 AIChE Symposium, 2001
[5] Primary Reformer Failure
D.H. Timbres and Mark McConnell
Vol 42 AIChE Symposium, 2001
[6]Failure of Inner Shell of Double Walled
Atmospheric Ammonia Tank
K.A.Nair and N.V.Jagan Mohan
Vol 42 AIChE Symposium, 2001
[7] Explosion of MDEA Storage Tank
Russell R. Peterson, David C. Haring, Timothy G.
Johnson, and James M. Senn
Vol 41 AIChE Symposium, 2000
[8] Explosion of Hydrogen in a Pipeline for CO2
2005
John Oscar Pande and JanTonheim
Vol 41 AIChE Symposium, 2000
[9] Failure of Internals of Ammonia Converter
Dadang Heru Kodri, Handiono, and Didiek P.
Vol 41 AIChE Symposium, 2000
[10] Safety Performance in Ammonia Plants 1997-
1998 Survey
Gerald P. Williams
Vol 41 AIChE Symposium, 2000
[11] Ammonia Converter: Weld Joint Failure
C.P.Chhabra and Ashok J.Gupta
Vol 40 AIChE Symposium, 1999
[12] Experience of Ammonia Converter with
Catalyst Leakage and Repairs
Muhammad Aleem Khan and Jorgen Juul
Ramussen
Vol 40 AIChE Symposium, 1999
[13] Safety Performance in Ammonia Plants:
Survey VI
Gerald P. Williams
Vol 39 AIChE Symposium, 1998
[14] Ammonia Process Primary Waste Heat Boiler
Shell Failure Experience
Colin P.Jackson
Vol 39 AIChE Symposium, 1998
[15] Inner Basket Failure of Ammonia Booster
Reactor
Kamarudin Zakaria and Lau Nai Tuang
Vol 39 AIChE Symposium, 1998
[16] Cause of Damage and Repair of Reformed
Gas Firetube Boiler
Zeng Zhong Quan and Mark A. Holderman
Vol 37 AIChE Symposium, 1996
[17] Catastrophic Failure of Tubesheet in Fire
Tube Reformed Gas Waste Heat Boiler
Harry van Praag, Bhaskar Rani and Harvey M.
Herro
Vol 37 AIChE Symposium, 1996
[18] Remedial Actions to Reformer Waste Heat
Boilers
M.Boumaza and M.El Ketroussi
Vol 37 AIChE Symposium, 1996
[19] Failure, Repair and Replacement of Waste
Heat Boiler
Shahid Ahmed and Zaheer Anwar
Vol 37 AIChE Symposium, 1996
[20] Dissimilar Weld Cracking and Repairs on
Primary Reformer Exit Header
Andrew Walker and Neil Mackenzie
Vol 36 AIChE Symposium, 1995
31 AMMONIA TECHNICAL MANUAL
 [21] Failure and Repair of Two Primary Make Gas
Boilers
Philip Bailey and John MacDonald
Vol 35 AIChE Symposium, 1994
[22] Tube Failure in a Waste Heat Boiler in
Ammonia Synthesis Section
Reinhard Michel and Hans-Dieter Marsch
Vol 35 AIChE Symposium, 1994
[23] Failures in Waste Heat Boilers
Helmut Thielsch, Florence Cone, and Jonathan
Freeman
Vol 35 AIChE Symposium, 1994
[24] Experience with Metal Dusting in Waste Heat
Boilers
R.J. Gommans and T.L. Huurdeman
Vol 35 AIChE Symposium, 1994
[25] Repair and Retubing of Reformed Gas Boiler
Anil Bhaskar Tipnis, Dilip Deshmukh, and Nirmal
Chandra Bandopadhyay
Vol 34 AIChE Symposium, 1993
[26] Repair of Waste Heat Boiler in Synloop of
NH3-Plant
Wolfgang Bickel, Maximilian Walter, and Konrad
Nassauer
Vol 34 AIChE Symposium, 1993
[27] Further Cracking in Converter Effluent/BFW
Exchanger
Philip J. Bailey and John G. MacDonald
Vol 34 AIChE Symposium, 1993
[28] Failure of Waste-Heat Boiler after
Debottlenecking Process Air Compressor
Edgar Lebold, Joerg Reininghaus, and Roland
Schober
Vol 33 AIChE Symposium, 1992
[29] Causes and Prevention of Explosion and Fire
in Synthesis Section
A.K. Mukhopadhyay and P.P. Singh
Vol 33 AIChE Symposium, 1992
[30] Failure of Waste Heat Boiler Downstream of
Secondary Reformer
S.K. Mukherjee, S.R. Ghosh, and S. Chatterjee
Vol 32 AIChE Symposium, 1991
[31] Failure and Novel Repair of Thick-Wall
Synthesis Converter Forgings
James D.Campbell and Robert L. Rawlinson
Keith C.Wilson
Vol 32 AIChE Symposium, 1991
[32] Major Incident Following the Failure of an
Ammonia Injector on a Urea Plant
P.J. Nightingale
Vol 31 AIChE Symposium, 1990
AMMONIA TECHNICAL MANUAL
[33] March 20, 1989 Accident in Lithuanian
Fertiliser Plant
Bengt Orval Andersson
Vol 31 AIChE Symposium, 1990
[34] Explosion of Synloop Ammonia Separator
Hans-Dieter Marsch
Vol 31 AIChE Symposium, 1990
[35] Stress Corrosion in a 12-ltonne Fully –
Refrigerated Ammonia Storage Tank
J.R.Byme and F.E.Moir
R.D. Williams
Vol 29 AIChE Symposium, 1988
[36] Failure and Repair of a Primary Waste Heat
Boiler
V. Sitaraman, Eko Santoso, and S. Sathe
Vol 28 AIChE Symposium, 1987
[37] Damage to and Replacement of an Ammonia
Storage Tank Foundation
O.A.Martinez, S.Madhavan, D.J.Kellett and
H.Hamrouni
Vol 27 AIChE Symposium, 1986
[38] Failure of Ammonia Converter Start-Up
Heater Tube
R.J. Mack and J.T Shultz
Vol 27 AIChE Symposium, 1986
[39] Failure of Ammonia Converter/Feed
Exchanger
S. Karkhanis and W.H. Van Moorsel
Vol 27 AIChE Symposium, 1986
[40] Investigation of Damage and repair of a 1000
MTD Horizontal Ammonia Converter
Subir Rao, R.C.A. Wiltzen and Wesley Jacobs
Vol 26 AIChE Symposium, 1985
[41] Failure and Repair of the Shell of a Primary
Waste Heat Boiler on a 1,100 ton/d Ammonia
Plant
A.F. Pariag, I.E. Welch, and G.E. Kerns
Vol 26 AIChE Symposium, 1985
[42] Explosion of a Benfield Solution Storage
Tank
J.T. McDaniel
Vol 26 AIChE Symposium, 1985
[43] Rupture of the Start-Up Heater Coil in the
Synthesis Loop of the New Ammonia Plant
Wolfgang Rall and Heinz Spaehn
Vol 25 AIChE Symposium, 1984
[44] Stress Corrosion Cracking in Syngas Heat
Exchangers
H.G. Orbons and T.L. Huurdemann
Vol 25 AIChE Symposium, 1984
32 2005
 [45] Failure of Dissimilar Metals Weld in [59] Explosion During Breaking-in of a
Reformer Tubes Compressor
Osama El Ganainy S. Strelzoff
Vol 25 AIChE Symposium, 1984 Vol 6 AIChE Symposium, 1963
[46] Waste Heat Boiler Failure and Modifications [60] Compressor Explosion
M. Lufti El-Migharbil and E.M. Hasaballah C.W. Gibbs
Vol 22 AIChE Symposium, 1979 Vol 2 AIChE Symposium, 1959
[47] Partial Collapse of an Atmospheric Ammonia
Storage Tank
Bruce H.Winegar
Vol 22 AIChE Symposium, 1979
[48] Synthesis Start-Up Heater Failure
F.G. Kokemor
Vol 22 AIChE Symposium, 1979
[49] Ammonia Loading Line Rupture
R. Hakansson
Vol 19 AIChE Symposium, 1976
[49] Ammonia Loading Line Rupture
R. Hakansson
Vol 19 AIChE Symposium, 1976
[50] Ammonia Plant Converter Basket Failure
R.L. Thompson and J.B. Brooks
Vol 19 AIChE Symposium, 1976
[51] Fatal Accident in CO2 Removal System
T.R. Visvanathan
Vol 18 AIChE Symposium, 1975
[52] Failure and Repair of Ammonia Converter
Basket
A.Kusha and D.Lloyd
Vol 18 AIChE Symposium, 1975
[53] Failure in Start-Up Heater Tube
J. Mitcalf
Vol 17 AIChE Symposium, 1974
[54] Ammonia Tank Failure - South Africa
H. Lonsdale
Vol 17 AIChE Symposium, 1974
[55] Failure of a Boiler Pressure Shell
W.W. Patterson
Vol 15 AIChE Symposium, 1972
[56] Ammonia Storage Tank Repair
J.G.MacArthur
Vol 14 AIChE Symposium, 1971
[57] Brittle Fracture of an Ammonia Synthesis
Heat Exchanger
H.K. Karinen
Vol 13 AIChE Symposium, 1970
[58] Suffocation of Workers in a CO Converter
R.K. Simms
Vol 7 AIChE Symposium, 1964

2005 33 AMMONIA TECHNICAL MANUAL

 Table – 1: Incidents / Fires / Explosions/ Failures
All of these are covered in papers printed in the AIChE Ammonia Technical Manuals and using the “year reported” the source paper can be located
in the “Ammonia Technical Manual.”

Item Year Incident Root Cause Remedy Action Taken

Reported
1. 1959 Compressor explosion during a Ignition of oil air moisture Inert gas used for testing compressors.
routine shop test killed 6 people

AMMONIA TECHNICAL MANUAL

& injured 30
2. 1959 Oxygen plant re-boiler Co-crystal formation of acetylene & New design, where solids do not accumulate
explosion, no injuries, no nitrous oxide built up at the bottom of re- adopted.
ruptures boiler
3. 1960 Oxygen plant vaporiser Accumulation of hydrocarbon in the Additional instrumentation; simplified cold box design with
explosion vaporiser SS piping.
4. 1960 Oxygen plant explosion Hydrocarbon concentration in main Unit was rebuilt with a recirculation pump on main condenser
condenser & silica gel trap.

34
5. 1960 Heat exchanger explosion at a Accumulation of nitrous oxides Systems put in place to reduce nitrous oxide accumulations.
nitrogen wash unit
6. 1960 Rupture of carbon steel piping on Heavy thermal shock resulting from low Carbon steel piping replaced; provided additional
nitrogen wash unit temperatures instrumentation.

7. 1961 Hydrogen fire from reverse flow Check valve on pump discharge failed Flow control valve installed on discharge of each pump.
on pump
8. 1961 Oxygen trailer fire Leaking hose on the trailer Procedure to stop liquid oxygen transfer in case of any leaks.
Remote isolation on liquid discharge lines
9. 1961 Air fractionation plant explosion Wooden structures on oxygen plant Wooden equipment removed from the cold box shell after
maintenance work.
10. 1962 Oil separator explosion in an Air Oil mixed with O2 rich waste gas New O2 analyser installed.
Separation plant.
11. 1962 Hydrogen compressor cylinder Interchangeable valves on compressor Installed non-interchangeable suction & discharge valves.
explosion
12. 1962 Nitrogen compression system Electrical failure led to hydrocarbon New alarms, safety instrumented system, O2 analyser
explosion contamination

2005
2005
Item Year Incident Root Cause Remedy Action Taken
Reported
13. 1963 Failure of primary reformer High temperature stress rupture in 304SS Replaced outlet piping with incoloy 800 material.
outlet piping piping resulted in weld seam failure due to
brittleness at 787oC
14. 1963 Explosion in after cooler of a Combustion on the compression cylinder Changed the cooler design.
compressor using synthetic created shock pressure wave that led to
lubricant explosion
15. 1963 Explosion during breaking of a Air used to test synthesis gas compressor Do not use air for compressor testing at higher pressures, use
compressor incident killed one at higher pressures that increased air only N2 pressures.
person temperature.
16. 1963 Air heater explosion Oversized heating element installed as part New thermocouples installed to monitor temperatures on air
of earlier modification. heater. Heaters protected by circuit breakers.
17. 1963 Air separation plant fire Trapped oil accumulation on liquid O2 Eliminated liquid O2 pump.
reflux pump
18. 1963 Oxidising salt explosion Mixing of oxidising & reducing materials Seals/gaskets made of non-combustible materials.
19. 1964 Catastrophic oxidation on Localised formation of molybdenum oxide Avoid using 316 SS
primary reformer outlet piping rich slag.
20. 1964 Suffocation of workers in a CO Confined space entry in “CO” atmosphere Stringent procedures developed for confined space entry.

35
converter, 3 people killed
21. 1964 Explosion in N2 gas compressor O2 Contamination of N2 compressor Installed dual range O2 analyser and trip system to S/D O2
compressor.
22. 1964 Explosion of condenser in an O2 Hydrocarbon caused combustion of Installed a recycling absorber. Installed a trap to drain liquid
plant material in condenser O2.
23. 1965 Explosion in expander discharge Oil accumulation in expander piping New analytical equipment installed.
piping
24. 1965 Liquid O2 disposal vessel Hydrocarbon contamination New heating procedures incorporated.
explosion
25. 1965 Nitric oxide explosion Reaction with hydrocarbons New method of removing NO from the gas stream developed.
26. 1965 Oxygen fire HP Oxygen pump seals failed Dereming and replacement of silica gel carried out. Seal was
redesigned.

AMMONIA TECHNICAL MANUAL

 Item Year Incident Root Cause Remedy Action Taken
Reported
27. 1965 Ammonia Tank Leak Missing weld on tank floor during Tank emptied out, repaired & put back in service.
construction.
28. 1966 Liquid O2 pump failure Bearing failed, Impeller of the pump came Locking device installed at the end of the shaft. Setscrew
in contact with the pump casing, O2 material changed to SS.
booster pump exploded
29. 1966 Loss of insulation on an Expansion joints installed incorrectly in Tank insulation rebuilt completely.
ammonia storage tank original installation

AMMONIA TECHNICAL MANUAL

30. 1966 Insulation fire on a Storage Space heaters used during construction Vessel sandblasted & reinsulated.
Sphere
31. 1966 Brittle fracture of ammonia No final heat treatment done Vessel replaced.
converter during hydrotest at the
shop
32. 1966 Reforming system failure Stress corrosion cracking resulted from Repair work done.
chloride in activated carbon.
33. 1966 Tube & piping failure Localised overheating resulted in rupture Change of piping metallurgy, periodic inspection &

36
of air piping & subsequent fire additional instrumentation
34. 1966 Distance piece explosion A loose piston nut & slipper failure on Using only two bolts on the distance piece.
reciprocating compressor
35. 1966 Methanol plant explosion Rupture of oil blowdown line allowed Changes made to control room building.
compressor synthesis loop to depressure
in a reverse flow direction
36. 1966 Nitric acid plant explosion Accumulation of ammonium nitrite during Changes made to plant startup procedures.
a prolonged startup.
37. 1967 Air separation plant incident Reaction in hydrocarbon Liquid dump from the column separated. Dead leg
absorber eliminated.
38. 1967 High speed coupling failure Misalignment, poor control & assembly Long bolts, good tolerance & assembly controls
procedures.
39. 1968 Reformer manifold cracking Oxidation & magnetism Cracks repaired.
40. 1969 Rupture of ammonia tanker Stress corrosion cracking Ceased using TI built tankers.
41. 1969 Transfer line failure Higher water boil off than anticipated Improved insulation on jacket water.

2005
2005
Item Year Incident Root Cause Remedy Action Taken
Reported
42. 1969 Failure of primary waste heat Silica carry over from refractory Refractory was replaced with low silica refractory.
boiler
43. 1970 An ammonia tank car Hole on the tanker following a collision Tanker repaired, new procedures put in place.
emergency with another tanker.
44. 1970 Failure of low temperature NH3 Free thaw cycle between the pipe sleeve Seal between the sleeve and the pipe made more
line & the pipe watertight.
Non freezing solution added to the sleeved portion of the
line.
45. 1970 Explosion in feed gas section Ignition of a mixture of O2, H2 and N2 Continuous on stream analysis. Trip system provided.
46. 1970 Brittle fracture of an ammonia Materials, light forging & defective heat Right materials heat exchanger selected.
synthesis heat exchanger treatment
47. 1970 Explosion in the feed gas Cracks developed during welding, poor Preheat on welding attachments controlled carefully
section heat treatment. when making main seam.
48. 1971 Ammonia tank overflow Failure of high level alarm and S/D Installed reliable additional high-level alarms/trip
system systems.

37
49. 1971 Catalyst fusion in secondary Loss of natural gas feed and continued Trip system checked thoroughly.
reformer airflow
50. 1971 Failure of an exchanger Corrosion in hot MEA, floating heat New corrosion inhibitor installed.
exchanger.
51. 1971 Failure of ammonia loading Sudden pressure build up in hose due to Do not drag hose over docks or decks. Do not roll hose
hose failed switch on ship. more than one revolution. Avoid sharply bent, curved or
twisted hoses
52. 1971 Failure of reformer outlet header Creep rupture resulted from extensive Bulge monitoring devices installed regular optical
intergranular cracking. pyrometer surveys of the tubes, pigtails, and tube
supports.
53. 1971 Hydrogen damage to a Hydrogen attack on ammonia converter Replaced carbon steel forgings with 2-1/4CR. – 1Mo
converter. alloy steel.
54. 1971 Nitriding in an ammonia plant Nitriding on synloop WHB Repairs made on cracks.

AMMONIA TECHNICAL MANUAL

 Item Year Incident Root Cause Remedy Action Taken
Reported
55. 1971 Leak of an ammonia tank Leakage on floor of the tank through Tank emptied out, repairs carried out.
storage tank numerous pinholes, resulted from
construction & testing activities in cold
winter months.
56. 1971 Primary reformer transfer header Creep rupture caused with rapidly Transfer header repaired.
failure increasing temperature due to low level on
water jacket.

AMMONIA TECHNICAL MANUAL

57. 1972 Cracking & blistering in the Materials of construction Repaired vessels, stress relieved, materials changed.
shift converter
58. 1972 Failure of boiler pressure shell. Deterioration of the refractory wall aided Vessel repaired, replaced water jacket.
by hammering of the shroud slip joints.
59. 1972 Failure of ammonia separator Emergency S/D caused shocks, resulting Vessel repaired.
in massive failure.
60. 1973 Corrosion in CO2 removal Stress corrosion cracking resulted from Repaired damaged vessels by welding an external band
tower electro chemical reaction. of steel plates.
61. 1973 Explosion in a water treatment Pressure build up, decomposition of Standard operating procedures modified. Copper

38
unit ammonium nitrate & oxidisation of resin. sulphate discontinued as algicide.
62. 1973 Failure of ammonia storage tank Freeze thaw cycle on foam glass 85% of the insulation replaced with urethane.
insulation insulation
63. 1973 Steam generating tube failure Accumulation of boiler chemicals & low Increased circulation rate, change over of water
circulation treatment program
64. 1973 Steam reformer tube failure Water carry over in steam drum Horizontal perforated baffle plates installed above
steam/water inlets. Secondary separator installed
between steam drum & superheater.
65. 1973 Expansion joint failure Heat treatments at wrong temperatures Stringent procedures adopted at the shop.
66. 1973 Explosion in vent stack Reverse flow of burning gas Vent heater drain lines provided with water seals.
Continuous N2 purge. Ruptured 24” elbow replaced.
67. 1973 Air steam coil failure Relief valve failed to lift. PSV relocated, properly designed and braced.
68. 1974 Secondary reformer air inlet Intergranular cracking of weld joints Repairs done using new type of welding rods.
nozzles failure

2005
2005
Item Year Incident Root Cause Remedy Action Taken
Reported
69. 1974 Waste heat boiler failure Downcomer drain lines ruptured. Loss of Letdown valves replaced with high-pressure rating.
circulation in WHB
70. 1974 Explosion in Urea Plant Presence of oil traces & H2 gas in CO2 Operating procedures changed to keep scrubber off gas
feed out of explosion limits.
71. 1974 Ammonia Tank failure in South Brittle fracture of dished end of pressure Undefined
Africa, 18 people killed storage bullet. The vessel not stress
relieved
72. 1974 Ammonia reformer freeze up Reverse flow water from leaking WHB Avoid cold weather shutdowns. Keep reformer warm
freeze up on reformer tubes, resulted into during S/D & pay attention to draining liquid
rupture of tubes
73. 1974 Coupling failure between Misalignment of LP case of syngas Misalignment corrected using optical alignment.
compressors compressor. Extreme care taken in tightening coupling bolts.
74. 1974 Explosion of ammonia liquor Internal overpressure due to combustion New operating procedures/codes developed.
tank of NH3, H2, methane gas above the liquor
75. 1974 Failure in secondary reformer Failure of refractory lining on the vessel. Monolith refractory lining replaced with a two-phase
vessel. system. Installed thermal siphons & water jacket.

39
76. 1974 Failure of start up heater tube. Nitriding of heater coils and temperature Undefined
imbalance on coils
77. 1975 Corrosion in the Naphtha Wrong outlet materials of construction Repaired outlet pigtails.
reformer
78. 1975 Failure & repair of ammonia Chloride stress corrosion cracking from Vessel repaired.
converter basket insulation
79. 1975 Fatal accident in CO2 removal Rupture of CS elbow in CO2 CS elbows replaced with SS, glass panels reduced in the
system, 9 people killed. removal system caused by erosion with control room.
impingement of high velocity stream of
hot liquid.
80. 1975 Rupture in ammonia shift Corrosion resulted from poor water Distributor tray provided, pH measured at more points.
conversion unit distribution & lack of good pH control. Corrosion probes installed in the loops.
81. 1976 Ammonia converter basket Stress corrosion cracking from chlorides Converter basket was replaced.
failure in hydrotest water, insulation.

AMMONIA TECHNICAL MANUAL

 Item Year Incident Root Cause Remedy Action Taken
Reported
82. 1976 NH3 loading line ruptured., Two Wrong hose specified. Hose replaced and new procedures put in place.
people killed
83. 1976 Ammonia pipeline rupture External corrosion of the pipeline Line repaired by replacing 30 m of the pipe.
84. 1976 Ammonia shift converter failure Hydrogen cracking on the vessel weld A small reactor used as a temporary HTS converter.
resulted from weld electrodes.
85. 1976 Ammonia tank floor and Improper welding during construction. Floor & foundation repaired.
foundation failure.

AMMONIA TECHNICAL MANUAL

86. 1976 Catastrophic failure in process Carbonic acid corrosion on carbon steel. Line replaced with SS pipe.
gas line.
87. 1976 Explosion in ammonia Nitriding of the austenitic materials. Converter repaired.
converter.
88. 1976 Failure of ammonia plant air Poor detail design & fabrication of inter Damage to compressor motor repaired, inter stage
compressor. stage coolers. coolers repaired.
89. 1976 Failure of ammonia plant Severe corrosion damaged riser castable Shroud changed to SS.
transfer line coating
90. 1976 Major field repairs to ammonia Hydrogen damage on lower CS outlet Vessel forging renewed.

40
converter forging
91. 1976 Replacement of ammonia Chloride attack resulted from insulation, Basket replaced.
converter basket hydrotest water & catalyst.
92. 1977 Corrosion of ammonia plant Hydrogen attack. Exchanger was repaired & heat-treated per procedure.
heat exchanger
93. 1977 CO2 stripper explosion. H2 gas or natural gas dissolved in solvent. Wash trays & demisting pads replaced.
94. 1977 Tube damage in NH3 plant Vibration damage. Baffle design modified from double-segmented, baffle
exchangers thickness doubled.
95. 1977 Problems with waste heat boiler. Excessive fouling resulted from high Low silica alumina balls installed. Catalyst changed in
silica support balls. secondary reformer.
96. 1978 Ammonia separator accident. Nozzle failure on multi layer vessel. Vessel was repaired.
97. 1978 Ammonia storage vent accident Refrigeration compressor tripped out, Flare was relocated; emergency manway vent replaced
released NH3 vapours, ignited by the flare with a standard relief vacuum breaker.
on top of the tank.

2005
2005
Item Year Incident Root Cause Remedy Action Taken
Reported
98. 1978 Failure at the inlet nozzle of Hydrogen embrittlement at the location of A new nozzle with the upgraded material installed on
ammonia converter. forging LAP converter inlet.
99. 1978 Reformer riser pressure shell Gas leaks on transfer header and riser Replaced transfer header, modification made to risers.
leak. tube.
100. 1978 Start up damage to a CO2 Internal explosion resulted from Control circuits for air trip valve modified.
absorber combustible gas mixture.
101. 1978 Stress corrosion cracked Corrosion by ammonium nitrate. The syngas line was repaired.
synthesis gas line.
102. 1978 Urea reactor failure. Plugged weep holes & corroded liner Weepholes increased, automatic and reliable monitoring
shell. system installed.
103. 1979 Cracking in ammonia converters High thermal stress from many cycles Cracks repaired.
caused cracking on multi wall converter.
104. 1979 Partial collapse of an Failure of vacuum relief valves. Tank was repaired.
atmospheric storage tank
105. 1979 Stress corrosion cracking in Inadequate purging of air before Welding repairs done on tank.
ammonia storage. introducing liquid NH3,

41
106. 1979 Synthesis startup heater failure. Localised overheating due to low flow. New interlocks provided and coil material upgraded.
107. 1979 Urea reactor bottom failure. Micro cracking in the lap weld joint due Welding repairs carried out.
to stress from thermal expansion &
contracting of lining sleeves.
108. 1979 Waste heat boiler failure. Thick tube sheets and long tubes, New double compartment design developed.
sensitive to thermal shocks.
109. 1980 Failure of superheated steam Overheating, overstressing distortion. Weld repairs done on failed piping.
header.
110. 1980 Small leak caused a big leak. Ignition of a pigtail leak initiated catalyst Leaks repaired.
tube flange leaks.
111. 1980 Temperatures run away of a Thermowell temperatures were lower than All thermocouples made horizontal.
methanator. gas temp. Gas temp lower than that of
bulk gas.
112 1981 Failure of process air line Back flow of process gas in to air line and Operating procedures changed and modified surge
failure of check valve control system.

AMMONIA TECHNICAL MANUAL

 Item Year Incident Root Cause Remedy Action Taken
Reported
113 1981 Vent silencer failure Water and steam ingress in to vent header Silencer and tail pipe repaired and installed.
due to WHB failure
114 1981 Pump and motor failure in hot Back flow due to check valve failure Improved instrumentation on pump discharge control
potassium carbonate system valves.
115 1981 Ammonia separator failure Metallurgical failure of the vessel New vessel fabricated.
116 1981 Urea autoclave failure Corrosion of weld overlay from Permanent repairs made to autoclave.
carbamate solution

AMMONIA TECHNICAL MANUAL

117 1981 High pressure heat exchanger Hydrogen diffusion through the crystal Weld repairs on tube sheet retaining ring.
ignition structure of the metal
118 1982 Sudden pressure increase in a Nickel based foil on vent silencer holes Use of natural gas for heating up LT shift converter.
vent header
119. 1983 Failure of a 100 bar steam line. Rupture from high temperature & stress, Piping was replaced.
wrong material.
120. 1983 Fire in a compressor house Vibration induced by the pumping system. Lube oil console was installed outside the building.
121. 1983 Primary reformer riser liner Deposit of carbonaceous material resulted Reformer operating procedure modified.
collapse from high sulfur in feed gas.

42
122. 1983 Reformer pigtail cracks. Movement caused by thermal expansion. Bearing rollers installed on process gas line to pigtails.
123. 1983 Secondary reformer catalyst Explosion in secondary reformer. New temporary catalyst support installed.
support dome failure
124 1983 Shell rupture of a secondary Overheating near the steam water New lining and refractory installed. Repairs done on the
reformer interface. vessel.
125 1984 Cracks in the outlet section of Presence of water in condensed form. Damaged tubes replaced.
the steam reformer tubes
126 1984 Failure of dissimilar welds in Hydrogen induced crack formation. Leaking tubes repaired. External insulation applied on the
reformer tubes weld.
127. 1984 Fire in primary reformer Riser rupture & gas leak. Riser tube repaired.
penthouse.
128. 1984 Rupture of startup heater coil. Hydrogen induced cracks; condensing of Coil repaired, new thermocouples installed on the coils
moisture on the tube outer surface.
129. 1984 Stress corrosion cracking in Corrosion from contaminated water of Protective painting underneath insulation material.
syngas heat exchanger. wetting the insulated equipment.

2005
2005
Item Year Incident Root Cause Remedy Action Taken
Reported
130. 1984 NH3, Storage tank roof rupture. Deficiency in the roof to wall weld Weld was properly repaired.
connection, resulted into high stress low
fatigue.
131. 1985 Corrosion in CO2 Carbonic acid impingement. Repairs done to absorption tower.
absorption tower.
132. 1985 Damage at syngas turbine by Defect in control system, loss of process New trip system on steam superheat control.
excessive steam superheating air.
133. 1985 Explosion of a Benfield solution Hydrogen gas ingress into storage tank, New tank designed with no ingress of H2. New operational
storage tank ignition by static charge. procedures adopted.
134. 1985 Explosion in cold storage kills Ignition of a hazardous accumulation of Undefined
fire fighter NH3 gas
135. 1985 Extra low S/C ratio caused over Malfunction of steam flow control. Tight shut off valves were provided on impulse line drain
reduction of HTS catalyst. valves.
136. 1985 Failure & repair of primary Thermally induced stresses due to liquid Coating the upper exposed area of the shell and use of
waste heat boiler. level fluctuation. oxygen scavengers in BFW.
137. 1985 Failure of high-pressure Severe hydrogen attack. Converter inlet piping changed to right material.
synthesis pipe.

43
138. 1985 Firebox explosion in a primary Leaking reformer tube. Reformer tube replaced.
reformer
139. 1985 Damage & repair of a horizontal Reverse flow from syngas compressor due Internal repairs made to basket.
ammonia converter. to diaphragm failure.
140. 1985 Leak in ammonia plant reformer Overheating of pre-heat coils. Part of pre-heat coil replaced
convection section natural gas
preheat coil.
141. 1985 Major fire in a steam methane Weld quality, shortening of pigtails. Furnace rebuilt with new tubes.
reformer furnace.
142. 1985 Multiple cracking & leakage of Incorrect heat treatment, and nitriding All cracks were repaired.
hot synthesis gas pipe
143. 1985 Severe carry over phenomena in Incomplete seal welds and cracked welds Steam drum internals modified.
methanol plant due to strain and high temperatures.
144. 1985 Tube failure on the synthesis gas Flow induced tube vibration. Cross baffle design modified.
compressor after cooler.

AMMONIA TECHNICAL MANUAL

 Item Year Incident Root Cause Remedy Action Taken
Reported
145. 1986 Damage of syngas compressor. Failure of anti-surge control valve due to Changed zero point dislocation of the flow measurement.
faulty flow measurement.
146. 1986 Damage of ammonia storage Ground movement from earthquake. Tank foundation replaced.
tank foundation.
147. 1986 Failure of the feed gallery & Impingement plate breaking away from Repair work performed on feed gallery.
pressure shell of CO2 the wall, surge of gas.
regenerator.
148. 1986 Failure of ammonia converter Stiffening effect caused by the repair ring Repairs made to tubesheet.

AMMONIA TECHNICAL MANUAL

feed exchanger. added to the original kit.
149. 1986 Failure of ammonia startup Nitriding & stresses induced by thermal Tube material changed.
heater. cycling.
150. 1986 Fire at Semilean pump by Defective check valve. Pump discharge gate valves replaced by motor operated
reverse motion. valves – check valve replaced with a reliable one.
151. 1986 Auxiliary boiler explosion Gas leaks through leaking fuel valves. Provided double block & bleed valves on fuel gas header.
152. 1986 Syngas compressor train failure. Localised high stress resulting in high New design coupling installed.
cycle fatigue failure.

44
153. 1986 Overheating of syngas Rag in compressor suction line. Removed rag.
compressor.
154. 1987 Piping failure in a high pressure Localised thermal strain due to Piping design modified to hold temperature and eliminate
steam system accumulation of condensation. condensation.
155. 1987 Failure and repair of a primary Localised refractory failure, subsequent The bottom head was replaced.
waste heat boiler overheating, and high temperature stress
rupture.
156. 1987 Pipe rupture caused by Improper safety valve, piping layout and Safety valve inspection program enforced to minimise future
vibrations of a safety valve supports. risks.
157. 1987 Weld cracking in reformer outlet Difference in mechanical and physical Repairs carried out on weld failures.
parts properties of base and weld metal.
158. 1987 Synthesis gas compressor failure Unconventional repairs, due to lack of Diameter of balancing drum reduced. Quick closing NRV
spare diaphragm assembly. was modified.
159. 1987 Failure of secondary reformer Insufficient combustion zone. Catalyst hold-down layer of alumina balls was reduced.
catalyst and air burner

2005
2005
Item Year Incident Root Cause Remedy Action Taken
Reported
160 1987 Corrosion in hot potassium CO2 Failure of corrosion inhibition system. Bottom section of the shell was SS overlaid, stress relieved
absorber and passivated.
161. 1987 Stress corrosion cracking in Presence of oxygen. Post weld heat treatment carried out.
field ammonia storage tanks
162. 1988 Rupture of HTS exit process gas Rapid temperature rise. Provided high temperature alarms and second gas flow
line meter.
163. 1988 Explosion that occurred during a Inadequate isolation procedures and Process isolation procedures modified.
welding operation monitoring techniques.
164. 1988 Synthesis gas compressor Fatigue initiation. Clean lubrication system.
coupling corrosion fatigue
failures
165. 1988 Severe cracking of CO2 Stress corrosion cracking. Cracks repaired.
absorber exit line
166. 1988 Stress corrosion in a 12,000 Material used and weld procedures All defects repaired.
tonne ammonia storage tank adopted susceptible to SCC and H2
cracking.
167. 1988 Problems in a process gas cooler Poor BFW quality. Cooler leaks were repaired.

45
168. 1988 Explosion in a nitric acid tail gas Difficulty in obtaining even H2 Two bellows replaced. Piping modifications carried out.
duct distribution, leakage of gas compressor
discharge valves.
169. 1989 Anhydrous ammonia release Buckling of tank floor due to deterioration Storage tank decommissioned, mothballed.
of foam glass insulation.
170. 1989 New cases of SCC in ammonia SCC in O2 atmosphere. Cathodic polarisation.
storage tank
171. 1989 Near failure of 50 bar nitrogen Brittle fracture failure due to reverse flow. Installed an inverted ‘U’ tube in N2 line.
supply line
172. 1989 Explosion in synthesis gas Backflow of synthesis gas through Additional safety valves were installed.
compressor compressor recycle lines.
173. 1989 Structural integrity of 12,000 Signs of stress corrosion cracking. Tank integrity monitoring put in place.
tonne ammonia tank in the
presence of SCC

AMMONIA TECHNICAL MANUAL

 Item Year Incident Root Cause Remedy Action Taken
Reported
174. 1989 Cracking in HP syngas pipe Thermal cycling resulted from mixing of Condensate reboiler shell size was increased.
wet and dry steam.
175. 1989 Magnetite layer in primary Boiler leaked due to corrosion. Boiler water pH lowered, blowdown rates increased.
WHB and auxiliary boiler
176. 1989 Severe damage to the rotor of a Collision between stationery and rotating Various parts of compressor were modified or
syngas compressor parts. redesigned.
177. 1990 Accident in Lithuanian fertiliser Ammonia storage tank rollover. Undefined

AMMONIA TECHNICAL MANUAL

plant, 7 people killed
178. 1990 Explosion of synloop ammonia Mercury affected steel properties, formed Mercury removal system installed.
separator explosive compounds.
179. 1990 Effect of mercury in ammonia Corrosion and forming of explosive Monitor mercury levels in feedgas.
plants mixture.
180. 1990 Leak in ammonia storage tank Crack on overlapping plates. Tank decommissioned, leaks repaired.
181. 1990 Major incident following the Crank shaft failure on ammonia injection Equipment isolation procedures improved.
failure of ammonia injector in pump due to a fatigue crack.
urea plant, 2 people killed

46
182. 1990 Failure of syngas compressor Improper design and operation of anti- Surge control system was redesigned.
surge system.
183. 1990 Failure of LTS exit process gas SS line ruptured and exploded due to Piping was replaced with new liner and nozzle.
line thermal cycle stress fatigue along seam
weld.
184. 1990 Failure of process air preheat Coil deformed due to thermal expansion. Coil redesigned with a two-piece tube support system.
coil
185. 1990 Cracking in ammonia converter Hydrogen embrittlement. Cracks were grounded and repaired.
effluent BFW exchanger
186. 1991 Failure and novel repair of thick Low cycle thermal fatigue initiated Modified design for converter forging.
wall synthesis converter forging cracking.
187. 1991 Crack formation in welds in the Hydrogen induced static fatigue. Sections of piping replaced.
outlet lines of an ammonia
converter.

2005
2005
Item Year Incident Root Cause Remedy Action Taken
Reported
188. 1991 Catalyst tubes failure following High temperature stress, thermal shock, Operating temperatures lowered. Eddy current inspection
furnace fire inside surface carbonisation employed.
189. 1991 Failure of secondary reformer High thermal stress between tube to tube Routine intermittent blow down restored.
waste heat boiler sheet joints.
190. 1991 Failure of two 100 bar BFW High flow velocities caused erosion in BFW piping was repaired.
lines BFW piping.
191. 1991 Failure of two CO2 regenerators Vacuum formation. Operating procedures changed.
192. 1991 Explosion in Purge Gas Missing of gasket during original Damaged tail gas line was replaced along with the jacket
Recovery (PGR) unit cold box installation. water line.
193. 1991 Weld failure in 2 -1/4 Cr- 1 Mo Use of agglomerated flux in conjunction Undefined
ammonia converter with a LTPLHT.
194. 1991 Steam system contaminated by Using steam condensate as pump seal Catacarb pump seal flush system modified.
Catacarb solution flush water
195. 1991 Leak in thick walled synthesis Undefined Cracked weld seam was cut out and completely re-
converter welded.
196 1991 Hydrogen attack in 2-25 Cr – Formation of nitrides/carbonitrides out of

47
1Mo steels below Nelson curve the pre-existing carbides, led to hydrogen Undefined
attack.
197. 1992 Timely detection of damaged Carburisation and plastic deformation due New gas distributor installed.
gas distributor avoided failures to overheating.
198. 1992 Impeller failure of a process air Fatigue failure. Improvements made on anti-surge control system.
compressor
199. 1992 Failure of WHB after Malfunction of water circulation in boiler WHB repaired.
debottlenecking air compressor tubes, resulted two-phase flow.
200. 1992 Explosion and fire in synthesis Explosive mixture in vent tail pipe from Vent header drain system modified. PSV’s relocated.
section passing drain valves and lifting of PSV. Provided continuous purging of N2 air vents
201. 1992 Incident on motive steam raising Crevice corrosion promoted by chlorides. New design cooler installed.
gas cooler

AMMONIA TECHNICAL MANUAL

 Item Year Incident Root Cause Remedy Action Taken
Reported
202. 1992 Foundation failure on 20,000 Cyclic freezing damage. Repairs done on tank foundation.
tonne ammonia storage tank
203 1993 Cracking of steam reformer Strain assisted inter-granular oxidation. Use of centrifugal cast 20/32+Nb with matching fillers.
bottom manifold
204. 1993 Failure of synthesis waste heat Nitriding, wrong material for the ferrules. Undefined
boiler by rotating ferrules
205. 1993 Failure of WHB in synloop Failure of heat protection shield inlet to 71 tubes removed, repaired and reinstalled.

AMMONIA TECHNICAL MANUAL

the boiler.
206. 1993 Further cracking in converter Hydrogen embrittlement. Cracks were repaired.
effluent BFW exchanger
207. 1993 Process gas exit temperature Trapped steam between liner and Transition assembly of 8th row riser was replaced
fluctuations in primary reformer refractory led to buckling of outlet header. completely.
208. 1993 Inefficient moisture separator Moisture eroded interstage labyrinths. New peerless in line separator installed.
damages air compressor
209. 1993 Secondary reformer air mixer Loss of steam flow caused burner tip New burner installed, catalyst replaced.
failure failure.

48
210. 1993 Retubing of reformed gas boiler Boiler water deposits caused build-up on Insitu replacement done of all tubes.
tubes.
211 1994 Stress corrosion in ammonia High O2 content of 10 ppm. Maintain water content of about 0.2%.
storage tanks
212 1994 Tube failure in Synloop WHB Lack of water circulation. Leaking tubes plugged, repaired.
213. 1994 Creep damages in outlet Creep cracking after 25 years in Full manifold was replaced.
manifolds and primary reformer operation.
214. 1994 Failure of two primary make gas Loss of BFW flow, brittle fracture of Boiler tubes repaired, replaced, plugged.
boilers ferrules.
215. 1994 Failures in waste heat boilers Design deficiencies, defects during Repairs carried out on WHB’s.
fabrication, plant upsets.
216. 1994 Ammonia waste heat boiler Boiler ran dry. New boiler of floating head type was installed.
replacement

2005
2005
Item Year Incident Root Cause Remedy Action Taken
Reported
217. 1994 Weld zone cracks in repaired 2- Manufacturing defects, hydrogen attack. Cracks repaired.
1/4-1 Mo ammonia converter
218. 1994 Metal dusting in waste heat Carbon deposition, wrong materials. Avoid carbon formation, use refractory liners.
boilers
219 1994 Heavy corrosion problem in Failure of Benfield solution quality. The system was shutdown, cleaned, passivated and
Benfield CO2 removal system restarted.
220. 1994 Severe leakage in CO2 stripper Failure of floating head gasket. Gasket replaced and new shell of SS ordered.
reboiler
221. 1994 Failures in urea strippers Stress corrosion cracking in ammoniacal Bottom channel heads replaced.
solution.
222 1995 Dissimilar weld cracking & Low temperature created aggressive A heater installed on dissimilar metal weld (DMW) joint
repairs on primary reformer environment with carbonic acid. for S/D purpose - new temperature monitoring system
outlet header installed.
223. 1995 Vibration problems with Contamination of the compressor with CS suction lines replaced with SS.
revamped air compressor corrosion products.
224. 1995 Catastrophic failure of Pre-ignition of air/ammonia mixture by Mixer pipe was replaced.

49
ammonia/air mixer catalyst, rust.
225. 1995 Failure of CW circulation pump Malfunction of overspeed trip device and New vibration monitors installed. Thrust wear trip
governor of turbine. provided.
226. 1995 Problematic LTS catalyst Incorrect operation of vent valve on Careful planning improved catalyst reduction systems.
reduction corner gas line.
227. 1995 Nitriding in ammonia reactor Nitriding caused by failed protection Materials resistant nitriding installed.
tubing.
228. 1995 Fatigue cracking of absorber on Defect from hydration propagation. Crack was repaired.
hydrogen plant PSA unit
229. 1995 Repairs on CO2 absorber. Corrosion by CO2 attack on MEA system. Organic coating employed on MEA absorber.
230. 1995 Failures in urea reactors Defects during fabrication, plant upsets, Repairs carried out on liners
operating condition.
231. 1995 Crack formation in welds in Low cycle thermal fatigue. Welds were repaired.
converter outlet lines

AMMONIA TECHNICAL MANUAL

 Item Year Incident Root Cause Remedy Action Taken
Reported
232. 1995 Ammonia release during barge Vacuum build-up in the tank, failure of Undefined
unloading vacuum breaker.
233. 1995 Synthesis gas coupling failure Torsional impact on the coupling to rotor Coupling was replaced.
shaft.
234 1996 Damage of reformed gas fire High pH boiler water. Boiler was repaired.
tube boiler
235. 1996 Catastrophic failure of tube High heat flux and departure from Boiler front section replaced.

AMMONIA TECHNICAL MANUAL

sheet in fire tube waste heat nucleate boiling.
boiler
236. 1996 Failure of BFW pump turbine Pump ran without lubrication. A second non-return valve installed.
following site power failure
237. 1996 Failure of waste heat boiler Localised refractory failures and Boiler head was replaced.
subsequent overheating.
238. 1996 Failure of expansion bellows of Hydrogen attack, fatigue loading Expansion bellows repaired by installing a sleeve with
synloop hot heat exchanger packing rings and gland.
239. 1996 Failure and repair of waste heat Loss of water level in steam drum. Design improvements made, repairs done on WHB.

50
boilers
240. 1996 Replacement of NH3 storage Did not meet any standards for tanks. A new tank was built.
tank
241. 1996 Corrosion assisted cracking in SCC, stress, media Vessel scrapped.
CS wall of urea reactor
242. 1996 Contamination of Benfield CO2 Organic acids produced in ‘CO’ shift Process condensate treatment system installed.
removal system reactor.
243. 1997 Repair of CO2 stripper column Chloride stress corrosion caused by wet Repaired CO2 stripper - revised operating controls.
insulation.
244. 1997 Weld cracks in NH3 converter Hydrogen induced cracks Welds repaired.
245. 1997 Defects with NH3 plant stacks Localised internal combustion overheated Deformed bend was cut out and replaced.
base of the stack.
246. 1998 Shroud failures of process air High stress levels on the shrouds. Shrouds and blading modified.
compressor turbine

2005
2005
Item Year Incident Root Cause Remedy Action Taken
Reported
247. 1998 Explosion in primary reformer Explosive gas mixture in reformer Burner management system modified.
furnace.
248. 1998 Pressure relief valve piping Inadequate support for pressure relief Developed new piping support criteria.
failures and fire in synthesis piping.
loop
249. 1997 Stress corrosion of Nb Caustic produced from hydrolysis Spare parts should be kept in dry condition.
containing cast alloys reaction.
250 1998 Plugging of bayonet/scabbard Power failure caused damage to boilers. Leaking tubes plugged.
tube WHB
251. 1998 Inner basket failure of NH3 Numerous plant trips. Failure of bolts and Basket internals were repaired.
booster reactor trip valves/check valves.
252. 1998 Damage of electric motor of Reverse rotation of pumps from failed NRV piping sizing increased to minimise flow induced
Benfield solution pump Non Return Valves’ (NRV). vibrations.
253 1998 Primary WHB shell failure Hydrogen attack, creep rupture, Use of 1¼Cr-½ Mo for WHB shells.
mechanical, thermal cyclical stress.
254. 1999 Strain-age cracking of Alloy 601 Stress relaxation cracking. Extensive repairs made to reformer outlet piping.

51
tubes at 600oC.
255. 1999 Catalyst leakage in ammonia Restriction in thermal expansion of screen Centre screen was repaired.
converter wires caused excessive compressor stress.
256. 1999 Failure of aMDEA line Instrument failure led to flow induced Failed piping was replaced.
vibrations of piping.
257. 1999 Natural gas feed preheater fire Flame impingement led to overheating. Trip system was modified.
258. 1999 Ammonia converter joint failure Hydrogen induced cracking due to poor Converter was repaired.
PWHT.
259. 1999 Failure of Benfield flash drum Fatigue failure of upper baffles. Repairs made to flash drum, PWHT also done.
260. 1999 Corrosion in CO2 removal Arsenic based vetrocoke system. Solvent system replaced with a new one.
section
261. 1999 Air and refrigeration machine Failure of refrigeration compressor seals - Many hardware modifications implemented.
oil console fire resulted to the breakage of oil line.
262. 1999 Air compressor inter cooler Vibrations of tubes on ‘U’ tube design. U tubes provided with supports. Velocity increased in
leakage tubes.

AMMONIA TECHNICAL MANUAL

 Item Year Incident Root Cause Remedy Action Taken
Reported
263. 1998 Failures in CO2 removal system Inadequate mechanical design, fabrication A new distributor and support arrangement provided.
defects.
264. 2000 Secondary reformer burner Wrong modifications, operation at higher Burner design modified.
failure rates.
265 2000 Failure of synthesis loop BFW Incomplete fusion on interface buttering, Nozzle was repaired.
exchanger (123C) inlet nozzle hydrogen embrittlement.
266. 2000 Explosion of aMDEA storage Reverse flow of gas from absorber. Check valve installed; Process Hazard Analysis (PHA)
tank and Standard Operating Procedures (SOP) reviewed.

AMMONIA TECHNICAL MANUAL

267. 2000 Internal failures of ammonia Expansion joint did not absorb thermal Design improved for converter internals.
converter expansion.
268. 2000 Explosion of hydrogen in a CO2 H2 enriched gas entered the pipeline, Trip system modified. Separate sampling system
pipe line formed explosive mixture. installed.
269. 2001 Failure of natural gas Sticking of main trip valve and nozzle Trip valves replaced. Trip matrix modified.
compressor valves.
270. 2001 Failure of inner shell of double Hydrostatic head of ammonia in the Instrumentation was improved on the tank, repairs done
walled storage tank annulus acted on bottom plate led to on tank bottom.
plastic deformation.

52
271. 2001 Natural gas line failure Corrosion resulted from carbonic acid. Gas line replaced with upgraded material.
272. 2001 Fire in secondary reformer Hydrogen attack, thermal cycling. Damaged portion of piping replaced with Inconel 601.
outlet line to WHB
273. 2001 Primary reformer failure Overheating at no steam flow condition. New trip system installed for start-up operation.
274. 2002 Auxiliary boiler failures Poor water quality. Not properly cleaned All the BFW and steam system chemically cleaned.
steam system.
275. 2002 Failure and repair of secondary Hydrogen assisted cracking. Repairs made on all cracks.
reformer
276. 2002 Burst before leak failure of High Strain ageing. Leaks were repaired.
temperature shift effluent WHB
277. 2002 Failure of molecular sieve dryer Delayed hydrogen attack. Undefined
278 2002 Failure and damage of High Excessive heat generated from air Catalyst was replaced. Air valve repaired.
temperature shift converter oxidation of catalyst
279. 2002 Hot spot and ruby formation in Dehydration and deposition of ruby. Upper part of catalyst replaced - alumina tiles replaced
secondary reformer with hexagonal bricks.

2005
2005
Item Year Incident Root Cause Remedy Action Taken
Reported
280. 2002 Explosion in air line to Contamination in process air line due to Start-up procedures modified. Trip valve replaced with
secondary reformer backflow. ball type.
281. 2002 Liner cracks in a gas phase area Cyclic thermal stresses. Relining done.
of urea reactor
282. 2002 Cracks in ammonia converter Hydrogen embrittlement, poor weld repair Cracks repaired.
during fabrication.
283. 2003 Synloop waste heat boiler exit High transient stress and strain. Repairs done on failures.
line failure
284. 2003 Explosion of auxiliary boiler Leaking fuel gas valves. Reliability of safety trip system improved.
285. 2003 Secondary reformer WHB Sludge deposits and corrosion under Exchanger design modified to allow intermittent
failure sludge. blowdown.
286. 2003 Embrittlement in cast reformer Formation of niobium rich silcide Undefined
outlet manifold components intermetallics.
287. 2003 Lifting of inner cup of NH3 Earthquake. Inner cup was lifted, levelled the cup.
storage tank
288. 2003 Axial flow air compressor Loose blade in inner ring. Second row blades made stronger.

53
failure
289. 2004 Steam explosion in ammonia Overfilling of steam drum, passing valves Repairs made to waste heat boiler.
plant in BFW lines.
290. 2004 Failure of Catacarb solution Reverse rotation of pump, failed check Changed check valve design. Installed remote operated
pump valves. discharge valves.

AMMONIA TECHNICAL MANUAL

 Table – 2 History of Ammonia Plant Benchmarking Surveys

Operating Service
Survey No. No. Factor Operating Total Factor
No. Years Survey Period Plants % Factor dpy spy %

1 2 1969 - 1970 22 86.3% 50.0 9.5

AMMONIA TECHNICAL MANUAL

2 2 1971 - 1972 27 87.5% 45.5 8.5
3 4 1973 - 1976 30 86.4% 49.5 10.8
4 5 1977 - 1981 88 84.9% 55.2 9.3 87.2%
5 4 1982 - 1985 93 80.8% 70.1 8.3 89.4%
6 3 1994 - 1996 82 91.9% 29.5 5.7 92.4%
7 2 1997 - 1998 95 91.5% 31.1 6.0 92.7%

54
8 2 2000 - 2001 55 89.6% 37.8 5.7 91.5%

Average 87.4% 46.1 8.0 90.6%

Operating factor (On stream factor) = Uptime/Total time; Service factor = Uptime/ Demand time;
Operating factor, days per year, dpy = All down time days/No.of years (survey period); spy = shutdowns per year

Plant Surveys International, Inc. (PSI) was established in 1996 and conducted Surveys 6, 7, and 8. These were fee-based multi-client benchmarking studies.

2005