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Located at Geleen in The Netherlands, OCI Nitrogen operates two ammonia plants (Figure 1), each with a nameplate
capacity of 1,360 MTPD of ammonia. Till July 2010 these plants
were owned by DSM Agro. One plant (AFA-2) was designed
and constructed by Bechtel; the plant was commissioned in
1971. The other plant (AFA-3) was designed and constructed by
M.W. Kellogg based on Kelloggs reduced energy ammonia
technology; the plant was commissioned in July 1984. Current
capacity of both plants is 1,500 MTPD each.
This article will show the importance of continuously performing Hazop and SIL studies. Safety studies are important
for plants being built but also for older plants that are in
operation for a long time.
Risk Assessment at the Time of Commissioning
Check of the As-build Plant
For a new chemical plant, it is almost invariably the practice to invoke some form of a safety audit in the design
phase. The audit will normally include a process hazard analysis (PHA). In the United States, the occupational safety and
health administration (OSHA), made the use of PHAs mandatory.
2011 American Institute of Chemical Engineers
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Figure 2. Are you sure not having explosives getting into your
sewer? [Color gure can be viewed in the online issue, which is
available at wileyonlinelibrary.com.]
properly. The hydrogen rich process gas can form an explosion and this was classied as a SIL-1 scenario.
To improve this situation and get all system and the
equipment SIL-1 level classied, the small degassing vessel
was removed. In this way the coupling between the are system and the sewer removed. A separate low level switch was
installed in the separator coupled to a separate open/close
valve. An end contact is installed on the open/close valve to
guarantee that under normal conditions the valve is closed.
The open/close is only opened when the level control valve
opens the drain valve to reduce the liquid level in the separator. It is situated in series with the level control valve
(Figure 4).
Ammonia Storage Sphere: Blowing of a Pressure Relief
Valve Causing a SIL-1 Scenario
OCI Nitrogens ammonia plants have a storage facility
with two atmospheric ammonia storage tanks of 25,000 m3
and one pressure sphere. The pressure sphere has a volume
of 2,200 m3 and operates at 4 bar (Figure 5). The scenario of
overpressurizing the sphere and having a leak in the sphere
is classied as SIL-2. This scenario is protected by three Pressure Relief Valves (PRVs) located in top of the sphere that
have sufcient high capacities to remove and the excess ammonia causing the overpressure. In the ammonia sphere the
governing case of the PRVs results in a release of 108 ton
h21 (30 kg s21) of ammonia. This ammonia release will result
in ashing of the pressurized ammonia forming an ammonia
vapor cloud of 13 ton h21. The remaining liquid ammonia is
streaming down the sphere and partly evaporating and for a
signicant par contributing to the vapour cloud (Figure 6).
So when one of the PRVs of the sphere has to open a
very large ammonia release with vapor cloud is formed. As
such this release can also be classied. Primarily because of
the large amount of ammonia, we came to the conclusion
that blowing PRVs are a SIL-1 scenario. The sphere already
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March 2012 85
has one electronic high pressure switch (HPS) that closes the
feed to the sphere when a certain pressure level is passed.
During the design and construction verication it was found
that one HPS was not enough to guarantee a SIL-1 level.
Therefore a second HPS was installed. It is of course important to make sure that this second HPS is operating independent from the rst one. So it should be on another line,
and preferable be based on another measuring principle.
Ever since the design of the older ammonia plants much
new knowledge has become available on the problem of ammonia stress corrosion cracking in ammonia spheres, atmospheric ammonia storage tanks, and even other equipment in
contact with ammonia. See Refs 14. This know-how must
be incorporated in the Hazop studies.
Protecting a Primary Reformer Against an Explosion
During Start-Up: a SIL-2 Scenario
On April 1, 2003 an explosion occurred in a gas-red furnace in the melamine plant of OCI Nitrogen (at that time
DSM Melamine) in Geleen. Three people sadly lost their lives
during the accident. The gas-red furnace at which the accident occurred generates heat for the melamine process and
is installed next to this plant as a separate unit. The explosion occurred during start-up of the furnace after a short
maintenance stop. A detailed root cause analysis was done
and the conclusions of this are also applicable to other parts
of the chemical industry.
After this accident new hazard and operability (Hazop)
safety analyses were performed on all gas-red equipment of
OCI Nitrogen. The focus was for a major part on the ammonia plants where gas is red in the primary reformer, the
auxiliary boiler, the start-up furnaces and the gas turbine
(Figure 7).
The perception is often that natural gas is not a dangerous
gas and therefore the risks of operating a gas-red apparatus
are not always recognised. There is clearly the effect of habituation using natural gas in the plant.
The dedicated Hazop OCI Nitrogen performed for the fertiliser plants resulted in a lot of potential improvement. With
regards to instructions and procedures one has to make sure
that clear instructions are present and that work is exactly
done according to these instructions. Operators not following
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Before a start-up one relies on block-in valves like pneumatically operated XPVs or electrically operated XEVs to be
tight. However this is not always the case. Block-in valves
are not always 100% close and they can leak. This is especially the case with very large valves like for example in the
fuel gas line to the burners of a world-scale ammonia plant
consuming tens of thousands of m3 natural gas per hour.
Leaking valves can cause the rebox to be lled with gas
forming an explosion mixture. To prevent this from happening one should use top class valves and preferably install
two valves in series with a bleed system in between, a so
called block-and-bleed system. Experience has shown that
even two valves (without a bleed in between) were not
100% close anymore after many years of operation. It is also
advised to always purge the re box before start-up and
preferably continuously so that no gas can be building up in
the furnace.
Gwyn [1] describes a system that provides a reliable, positive method of testing to assure that there are no leaking
valves and that conditions are safe for lighting the gas burners. OCI Nitrogen uses more or less the same system.
The system basically functions by injecting natural gas
through a by-pass valve into the header piping to establish a
positive pressure in the main fuel gas header down stream of
the main gas supply valve. The gas is injected for a predetermined time or until the header reaches a certain pressure.
On attaining the correct pressure the by-pass valve is closed,
Process Safety Progress (Vol.31, No.1)
and the header is required to hold a given pressure for a certain time.
This test must be done in two different modes. First the
pressure in the header must be chosen low (almost atmospheric). With this mode one can test the closeness of the main
fuel gas valve. If this valve leaks the pressure will increase. A
leaking main fuel gas valve is also a very dangerous situation
when stopping a furnace. A furnace like a primary reformer
has a lot of manual plugcock valves and operators need some
time to close them when the equipment is stopped. A leaking
main gas valve is then a potential risk for an explosion.
The second mode of the pressure test is to do the test at a
high pressure (max. feed gas pressure). With this mode one
can check if all the (manual plugcock) valves at the burners
are tight. When the burner valves are not close one must
look in the eld which one is leaking and close/repair this
one. An ultrasonic device can be used to detect the valves
with excessive leakage.
Upon the header holding the required pressure, and completion of the purge cycle, the system will allow resetting
and opening of the main gas valve. While the system certainly can be built using conventional relays and hardware,
the application favors using a P.L.C. Also, another medium
can be used for pressuring the main gas header; however,
this medium would then have to be purged from the system
to get natural gas to the burners.
Overlling an Ammonia Rail Tank Car:
A SIL-2 Scenario
Overlling an ammonia rail tank car (RTC) can result in
one of the most dangerous loss of containment scenarios.
This is the scenario where the tank of the RTC can burst
under the thermal expansion pressure of the liquid ammonia.
This situation could occur when an RTC is overlled to such
an extent that there is too little gas space left, above the liquid, to accommodate the thermal expansion of the liquid ammonia. During the time the ammonia is in the RTC, the ammonia can become warmer due to ambient conditions, especially during extreme hot summer days. For that reason the
legally allowed maximum ll level of the RTC in Europe is
limited to 0.53 kg ammonia/litre of effective tank volume
(Figure 8). If a RTC contains more than this legally allowed
quantity the RTC must be regarded as overlled and immedi-
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checked off line on an independent and ofcially calibrated scale or weighing bridge.
The lling weight of the railway tank wagon is continuously monitored during the lling process on a weighing
bridge. The lling automatically ends when the predetermined maximum is reached.
The mass ow into the tank is monitored continuously
during the lling operation. The lling automatically ends
when the predetermined maximum is reached.
Before transporting the weight of the RTC is additionally
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