of

Fire in
After seven years of smooth operation of an ammonia plant, an explosion occurred in
the synthesis section. This paper analyzes the likely causes of the accident and
describes the actions taken for rehabilitation of the plant along with remedial
measures taken to prevent recurrence of the accident.

A.K. Mukhopadhyay and P.P. Singh

Krishak Bharati Cooperative Ltd., Gujarat, India

INTRODUCTION; section in this plant is partially

modified compared to other
KRISHAK BHARATI COOPERATIVE LIMITED, 'Conventional Kellogg' plants. Instead
(KRIBHGO) operates a fertilizer of mixing the compressed make up gas
complex at Hazira, near Surat city in with converter outlet gas from gas to
India, consisting of two Amnonia gas exchanger (121C) at the inlet of
Plants of 1350 MIPD each and four Urea water cooled exchanger (124C), here
(Prilled) plants of 1100 MIPD each on another water cooled exchanger (156C)
natural gas as feed stock. The basic has been introduced at the 3rd stage
engineering for Amnonia and Urea discharge of the syn gas compressor
Plants were supplied by M.W.Kellogg, and the syn gas is further cooled by
USA and Snamprogetti, Italy anmonia in a second exchanger (140C)
respectively. before mixing with converter outlet
All the above plants were ccnmissioned gas. It has been specifically
during Nov/Dec.1985 and operated designed this way to be able to send a
consistently at capacities well over part of cooled syn gas to an adjacent
100%. Based on the excellent processing plant. Syn gas return from
operating experiences in terms of this plant is also mixed up with
design energy norms, capacity converter effluent prior to separation
utilisation and high on stream days, of MHL in Anmonia separator and
energy optimisation retrofit /debottle sending the gas to recirculator.
-necking of these Anmonia Plants have Converter in this plant is a bottle
been planned in phased manner. shaped, three bed, axial flow catalyst
reactor with inter bed quenches
PROCESS DESCRIPTION; (ref.simplified PFD Fig.l).

Process flow in Anmonia Synthesis

171
 TO tOt,.C

115.C

I22X
TO »3-E

105-0
SYN.CONVtH

FIG-1 PROCESS FLOW

DIAGRAM OF AMMONIA SYNTHESIS

TO NHj
REFRIG

There are two vent headers, one in the as cold vent which connects the
front end upto CO? removal referred to discharges of all relief valves and
as hot vent which connects all the control process gas vents of synthesis
discharges of relief valves and few section and releases in the atmosphere
control process gas vents and releases through a silencer located at the top
in the atmosphere through silencer of Œ>2 stripper (réf. P&I of cold vent
located at the top of steam drum header Fig.2).
structure. The other is referred to
-00-££— DRAIN FROM VENT
HEADER

0450
Seh .40 WPt 200,
woo
.
2-0
i SILENCER GATED
ASIDE STRIPPER TOP

GOO

DRAIN TO HUB

^rrt
rtuT" ~fr5 i "P
"

MODIFIED DRAINS WITH WATER SEAL

«s AT GRADE
PROVIDES
SEAL LOOP

FIG-2 P&I COLD VENT

HEADER WITH MODIFICATIONS

172

BACKGROUND OF THE INCIDENT;
The incident occurred on 26th
September 1991 at 0117 hours when the
Airmonia Plant (Unit-II) was running
normally at around 117% load.
However, a few minutes earlier to the
occurrence of incident, operating
staff in the control room acknowledged
an alarm on the annunciator panel due
to "low steam flow to reformer."
While the operators were busy in
analysing the cause of the alarm, a
loud explosion was heard in the
synthesis section, opposite to the
control room. A large flame was
noticed in the area on 3rd stage
discharge pipeline of synthesis gas
compressor (103J) where a relief valve
(RV 156C) with lead pipe was found
knocked off from the pipeline.
During dépressurisâtion of the plant
and venting the process gas through
cold vent header through valve PIC4(V)
the hydrogen rich gas also came back
through the sheared off tail pipe of
the same safety valve (RV 156C) and
caused a secondary source of fire in
the nearby area.
Fire was controlled within about one
hour when the supply of process gas
LOCATION OF
RV 156 G LEAD
PIPE ON SYN
GAS PIPING
Photo-1
173
totally cut off. Anmonia plant Unit-I
was isolated but continued to run.
Isolation of gas also became difficult
as the motorised actuators of the
valves were burnt and could not be
approached for manual closure.
OF DAMAGE:
During the outbreak of fire, the main
power supply and plant lighting cables
got burnt off and power supply was
disrupted within about three minutes.
Hence, extent of damage was assessed
partly on the following morning and
balance after two days when the
compressor house and pump bay area
could be approached after airmonia
liquid drain, due to rupture of
anmonia line, could be controlled and
debris was cleared off from the area.
The general observations made are as
follows :-
1) The pilot operated relief valve
RV156C was uprooted from its
existing position on the pipeline
(réf. Photo 1). The discharge tail
pipe was knocked out of position
and a portion immediately after the
tail pipe with expander 4"x8" was
found sheared and blown open (réf.
Photo 4,5 & 6).
 Due to intensity of explosion the located after two days. The pilot
relief valve was thrown off to the valve of this relief valve was also
nearby pipe rack and could be found detached and lying on the
ground.

PHOTO -4 BURST OPEN PORTION OF TAIL PIPE

PHOTO-5 RV-156C WITH SHEARED OFF INLET LEAD PIPE & PORTION OF TAIL
74 PIPE
2) Nearby exchangers like 120C,130C 3) Cold insulation of expanded
and 117C (réf.plot plan of polysterene of almost all the other
synthesis section Fig.3) got exchangers/pressure vessels
directly exposed to flame coming including above in the nearby area
out from the opening created due to got burnt off (réf.Photo 7). Cold

PHOTO-6

SHEARED OFF
PORTION OF
TAIL PIPE
CONNECTED TO
R.V.

detachment of the RV 156C. The insulation on the long multishell

shells of the exchangers were amnonia separator (110F,112F etc.)
heated to red condition and also got burnt off.
simultaneously subjected to water
spray during fire fighting.

N r} t
'

t
K •

\\
J

jt a
;r
ir ti 123-C
1 1

J
1 > i
105. D
X f
o;
^ i TI 122-d
u
C!
<n .XI
to "• rhrii
» 5 »I o: 111l ES
«•—S
<TU»
II * 102-B

I AREA.B AREA.A
l

CONTROL ROOM

FIG-3 PLOT PLAN OF SYNTHESIS SECTION

175
4) Mstorised actuators of valves were
found burnt.
5) Many power cables, lighting cables,
instrument cables and tube found
severely damaged alongwith their
supporting trays.
6) Concrete foundations of two
exchangers developed cracks and
structural members of a few pipe
supports found twisted/bent.
7) Almost all the low pressure pipes
PHOTO-7 AMMONIA SYNTHESIS SECTION AFTER ACCIDENT
found damaged in the nearby area
particularly in anrnonia
refrigeration section including
cold anmonia pump discharge which
resulted in draining of anmonia in
the pump bay behind the synthesis
section. The cold vent header on
the pice rack where the tail pipe
of the RV 156C is connected, found
badly damaged and moved towards the
open vent on the rack by nearly one
metre (réf.Fig.4).
8) Another relief valve (RV 104F) on
the suction to syn gas compressor
knock out drum was also found
damaged. The discharge tail pipe
of this valve is also connected to
the cold vent header.
176
9) With the waves of explosion which
could be heard about four k»m.aways
control roan window panes and
frames were shattered, false
eel ings had given way« Seme
annunciator panels and instruments
were dislodged but fortunately no
major human injury was caused
(ref.Fhoto 9).
10)20 control valves were damaged in
varying degrees. Two pumps with
their drive motors were found
partially burnt.
OBSERVATIONS:
Inspection on the integrity of the
fire affected plant equipments and
piping were carried simultaneously
with the rehabilitation of the plant
on top priority. Separate specialist
group were formed inhouse as well as
outside experts from other operating
plants and engineering consultants®
The process licencer and detailed
engineering consultants were also
contacted. The aims were two fold»
i) To find out the probable cause of
 DETAILS:
COLD VENT HEADER
DON. PRESS : 21 Kg/cm 2
DON. TEMP : 120*C
DAMAGED AND
MATERIAL :C.S. (A53.B SML) SHIFTED TOWARDS
THICKNESS :8". STD. NORTH AFTER EXPLOSION
WISTD.
i^" «CM tn
INSUL. THK. : 40 MM

FIG-4 PIPING DRAWING OF COLD VENT HEADER

accident. the basis of different hypothesis on

ii) To work out remedial measures to the causes of the accident and also
avoid recurrence of similar the recccrmendation made to avoid
accident in future. More so as recurrence of similar incident.
the second plant of identical
design was under operation with OBSERVATION:
potential for similar hazard.
a) The pilot operated relief valve RV
Investigating groups had examined 156-C popped in 1986, when the
physically the failed pieces of piping discharge pipe got dislodged from
and relief valve attachments, damaged the cold vent header. The
vent header, process licencer's supporting system was modified and
technology transfer document, recorder a drain line was added at tail pipe
chart of operating parameters during (réf. fig. 5) to drain out
the time the accident happened, intermittantly the condensate
visited accident site and also likely to get accumulated.
discussed with operating and b) The RV 156-C again popped in 1988.
maintenance staff. This time also it caused seme
On delibration the following
observations were made which formed
177
 damage to the discharge tail pipe.
c) Quite a few deviation had been
noted in the execution of cold vent
header with reference to P&I.
Discharge leg of the RV 156C and a
few other connections were found to
have no self draining provisions.
To drain the header fron the likely
condensate accumulation, float
traps are provided but were
reportedly not functioning
properly.
d) The vent headers are provided with
purging steam connection at the end
of headers which are used only
during start up and shutdown of
plant and for extinguishing fire at
the vent silencer, but due to lack
of seat tightness small amount of
steam always passes through.
e) The header is designed for
atmospheric pressure but
simultanaeous blowing of more than
one R.V. can build?up back pressure
to around 12 kg/cm g.
f) The subject RV 156C is having 'J'
size orifice (réf.API RP-520),
which is just adequate for 100%
capacity of plant operation, but
since the plant is normally
operated above 110% capacity the
'J' orifice is found undersized.
g) All the four pilot operated RVs in
synthesis section had escaped the
attention and had not been tested
since conmissioning of the plant.
h) The supporting of RV 156C was found
inadequate having overhung
unsupported length of nearly two
metre from the main pipe.
i) The P&I of synthesis section had a
specific cannent for RV 156C to
locate the same as close as
possible to the cooler 156C,
probably leading to the existing
piping configuration of both lead
pipe and discharge pipe of RV.
j) During physical check it was found
that in other unit of Atrmonia
plant, appreciable vacuum is felt
at the end of the drain pipe on RV
tail pipe if the drain valve is
opened, due to natural draft. It
suggests that ingress of air
through this line is possible if
178
this valve is left accidentaly open
or not shut tightly.
Observations on operating conditionsi
1) The plant was running normal at an
average load of over 115% for
around 100 days prior to accident.
2) A few minutes before the accident,
steam to carbon (S/C) ratio to
primary reformer dropped to about
3.3 with alarm indication on the
panel (alarm set at 3.35 and trip
at 3.10).
3) Apparently there had been no
increase of H.P. steam to syn gas
drive turbine.
4) No increase in temperature to
synthesis converter catalyst bed.
5) At the adjacent plant where syn gas
is sent for processing, a pressure
increase of 1.2 kg/cm g was
recorded.
6) Pressure recorder on the third
stage discharge was not functioning
hence actual pressure developing by
the compressor during accident
could not be ascertained.
Observations on Mechanical failure;
1) Inlet lead pipe 3" NB Sch.140 was
sheared off fron the parent pipe
10" NB Seh. XXS (réf. Photo 4). It
may be seen that 3" branch was
taken directly on 10" NB with a
reinforcement pad.
2) The failure took place at the HAZ
of welding whereas there had been
no apparent damage to the parent
pipe or welding.
3) Sheared edges of the branch pipe
clearly indicates reverse slant
fracture which is usually
associated with internal explosion.
4) Above 1.5 metre portion of RV tail
pipe (8" NB Sch.std.wt. smls)
sheared off and ripped open (réf.
photo 4)). Opening of the pipe is
on the bottom where the drain pipe
was connected. The drain pipe
could not be located.
5) The vertical support on exhaust
pipe near RV 156C was pulled out of
foundation.
 6) Pilot valve of RV 156C got detached Micrographs clearly indicates that
and fell on the ground. failure at first location was purely
mechanical indicating a ductile
Failure analysis; fracture (réf.photo 10, 11), where
samples at other two locations
Metallographie investigations were indicated decarburisation and
carried out at three locations of the overheating (photo 12,13,14 & 15).
ruptured pipes connected to RV 156C. Thus the investigation proved that
explosion had taken place inside the
1) at the inlet lead pipe at the point discharge tail pipe of the RV.
of detachment.
2) at the point where the drain line
was attached to the discharge tail
pipe.
3) at the end of the ruptured tail
pipe.

FIG-1Î MICROGRAPH OF LOCATION-1

FRACTURE : ABSENCE OF
DECARBURISÂTION-DEFORMED PEARLITE

FIG-10 LOCATION 1 FRACTURE

/ Jf

^V
f

/ , •*?
>

^f**?
A
f

'à *
'

^
"""

*w#f
€^
i ^J* tty $& ' **'

r** /*-*^
-f^>^
v
V - *' ^ *
i- % v
k
\& é ^ ^* -îfej*?' * .aw

FIG-13 MICROGRAPH OF LOCATION-2

EVIDENCE OF DECARBURISATION AND
OVERHEATING

FIG-12 LOCATION 2 FRACTURE

FIG-15 MICROGRAPH OF LOCATION-3

EVIDENCE OF DECARBURISATION AND
FIG-14 LOCATION 3 FRACTURE OVERHEATING
179
Probable causes of accident and Causes for blowing of Relief Valve (RV
analysis; 156G);
Based on the above observations, 1) Due to existing trip logic of syn
following probable causes emerged:- gas compressor, there was
possibility of discharge MOV's
1) EKplosive mixture can be formed in closing without tripping of the
the vent system/tail pipe due to; compressor either due to low
governor oil pressure or due to
a) passing of RV 156C or other RV tripping of back end of plant.
and valves connected to this Since the compressor is not
vent system. provided with unloading facility to
b) Popping of RV 156-C. minimum governor speed, with the
2) Accumulation of condensate in the closure of discharge MOV's the
vent header/tail pipe of RV 156C pressure in the compressor system
due to passing of steam purging shall rise causing RV 156C to blow.
valve and popping of RV 156C Similar incident of RV blowing had
resulting in severe water hatrmer occurred earlier also. But in this
and consequent mechanical failure. particular case there had been no
3) Mechanical failure of the branch indication of compressor unloading
inlet pipe of RV 156C during due to process upset.
popping due to inadequate 2) Possibility of speed fluctuation of
supporting arrangement. With the the turbine was also looked into
failure at RV inlet, flamable gas but in absence of speed recording
rushing out may cause explosion and no positive clue was available.
fire due to friction. After the rehabilitation of the
4) Popping of RV 156C with discharge plant, during reconmissioning, the
of IrL, rich syn gas entering the syn gas turbine speed was found to
vent systen and forming explosive fluctuate uncontrollably between
mixture with 0 from air ingress 8200 and 9700 rpm due to
through the drain on the tail pipe malfunctioning of the governing
(réf. fig.5). Due to high velocity system.
of discharged gas and expansion, On a check up after shutdown of the
temperature of PL shall rise (due turbine the pilot piston was found
to inverse ïïoules Thompson not moving freely.
Phenomena) and spark may be
generated by friction in contact It may, therefore, be inferred that
with weld metal etc. inside the during the accident the turbine
pipe in presence of C^ already under high operating load might
present. have experienced similar speed
fluctuation due to governor
Analysing the probable causes it manfunctioning leading to over
appears that the strongest possibility pressurisation of the system
exists for popping of RV 156C causing momentarily causing blowing of
explosive mixture in the vent coupled relief valve. In absence of
with ingress of air (O^) from the' pressure and speed recording it
drain on the tail pipe efae to valve went unnoticed. The pressure
being left partially open accidentaly setting of RV 156C was 219.05
after manual draining of condensate or kg/cm g against a normal operating
not shut tight. Spark for ignition pressure of the third stage
might have been provided by friction discharge of around 180 kg/cm g»
in the pipeline at uneven welding Since the same was not tested for a
penetration and rise in temperature long time, the change of its
due to hydrogen gas expansion. popping at lower than the set
pressure cannot be ruled out.
180
Circumstantial evidence in the form of f) Optical boroscopy inside the tubes
pressure rise at the adjacent plant of the exchangers to check for
where part of syn gas is sent for defect/deformation.
their process requirement through one g) Soundness of concrete foundation.
kilometre long piping, and less M.P.
steam flow to reformer (syn gas Fortunately no damage to equipments
turbine extraction being the only and high pressure piping was notified.
source of MP steam) give credence to Damaged insulation of around 2500 M
this theory. area was redone after removal of burnt
out material by polyurethane foam with
Assessment of damages and external cladding by G.I. sheets in
rehabilitation; place of expanded polysterene. Prior
to start up pressure testing was
Separate groups were organised with carried out in stages to identify
properly identified job responsibility deficiencies. Plant started anmonia
and by and large all jobs were production merely after 24 days of
simultaneously started through shutdown between production to
following major groups:- production as a result of meticulous
planning, monitoring, control, quick
1) L.P.piping and structural supports resource mobilisation and work
2) H.P.Piping distribution. All the jobs were
3) Instrumentation repair, new carried out round the clock under
installation and cabling close supervision.
4) Electrical repair, modification and Remedial measures taken:
cabling.
5) Remaking of civil foundation for 1) Location of RV 156C - changed from
equipments and piping present position to the pipe rack
6) Equipment isolation, purging and with proper supporting. New R.V.
handing over for inspection, with 'K' orifice was installed in
insulation etc. place of 'J' orifice valve.
7) Inspection and redesign of piping, Supports of similar RVs like 105D
supports etc. and 103J were strengthened. This
8) Repair of relief valves, was also checked from the process/
developments of H.P. testing and engineering consultant (réf.fig.6).
certification.
For assessment of damages of
equipments and piping, following NOT
methods were employed:-

a) Thorough visual inspection

b) Dye penetrant and MPI of affected
areas and other vulnerable areas
inside the exchangers and vessels
particularly at the saddle support
and plates, corner radius of forged
tube sheets, curbed surface of
bends and pipe supporting shoes,
nozzle connections etc.
c) Hardness survey of all affected
areas FIG-6 MODIFIED PIPING OF RV 156C
d) Insitu metallography to study the AFTER REHABILITATION
changes in the grain structure in
2) Synthesis gas compressor was
the worst heat affected areas. prov ided wi th : -
e) Ultrasonic flaw detection in
selected areas
181

a) high pressure trip at 205kg/orug
with a prealarm at 195 kg/cm g
to avoid blowing of RV 156C»
b) earlier logic of unloading of
compressor at a low governor oil
pressure was found unsafe and
modified to trip.
c) Considering normal operating
speed of the compressor even
with 120% load at around 10,300
rpm trip setting was reduced to
10,700 rpm from 12,430 rpm with
a prealarm at 10,430 rpm.
3) Continuous purging of cold vent
system with NL has been implemented
(réf.fig.3) to ensure blanketing of
combustible, if any, inside the
header.
4) To prevent ingress of air inside
the vent header during manual
draining, water seal pots have been
introduced on drain lines.
5) Power cables to the plant have been
rerouted behind the control room
burying them underground.
6) Opening to the control room
(particularly glass windows) have
been practically removed leaving a
few smaller openings to watch the
plant through blast proof glass.
Blast wall is also provided at the
entrance of the control room.
7) Approach of synthesis area improved
by relocating the general lighting
tower. Additional fire fighting
monitors have been installed.
8) For self draining of the hot and
cold vent headers, improvements in
layout as far as practical, have
been carried out.
As a long term measure, study of
entire vent systems with relief valves
has been initiated, involving the
process consultants. All
modifications shall be implemented as
far as practicable looking into the
safe operation of the plants taking
into account the retrofit of the plant
for higher operating load.
CONCLUSION:
After the incident, a number of
182
operating plants using similar
technology all over the world were
contacted. The feedback showed that
almost all the operators of similar
plants till date were quite unaware of
the potential hazard that exists in
the cold vent system.
It was also noted during discussion/
personal visits to some of these
plants that except for one plant in
UK, none had used continuous purging
by N to control combustible mixture
in tne vent header that may form due
to passing of any of the relief or
control valves connected to the
header. Even the vent header and
connecting relief valves supports were
not adequate and properly designed for
actual operating (blowing of relief
valves) condition.
Further the ends of manual drains have
also been left open in most of the
plants without any kind of sealing
arrangement to prevent ingress of air
in the system.
The accident brought out another fact
that the significance of the built in
safety vtfiich was envisaged in the P&I,
was not reflected properly during
detailed engineering and execution of
the project. It overlooked an
intrinsic unsafe condition which was
otherwise avoidable. After the
accident during discussion with the
original process designer in USA and
co-consultant in India, it was also
found that there had been a
communication gap between the
consultant and co-consultant with
respect to interpretation of the P&I
resulting in deviations in detailed
engineering.
On overall analysis, it may be
suggested that after gaining
sufficient experience of the plant
operation, a detailed HAZOP analysis
should be carried out in the plant by
experienced consultant with thorough
knowledge of the process and with
involvement of the plant operating
personnel, so that the potential
hazard situation like above may be
avoided for safe operation of the
plant.
***@@@***
P.P. Singh A.K. Mukhopadhyay

183