Loss Prevention Bulletin 275 October 2020 | 19
Process safety essentials: Hazards of nitrogen
The hazards of nitrogen
Dr J Bond, BP Chemicals
Published in LPB063, 1985
on something inside. While kneeling down, trying to
Introduction disentangle the rope, he was overcome by nitrogen.
Nitrogen is available as a high purity material and generally Afterwards he admitted that if necessary he would have
complies to a specification which in the UK is contained in entered the vessel.1
the British Standard 4366:1968. It is available as a gas or a • Case history 2
liquid. A man was working near an open manhole of a vessel
It is an inert gas and prevents combustion of most containing inert gas and was about to replace the manhole
chemicals and therefore is similar to the inert gas cover when he fell in and died before he could be
generated from oil-fired equipment. However, nitrogen recovered.3
differs significantly from oil-fired inert gas in a number
of properties; particularly, it has no smell, and therefore • Case history 3
presents a significant additional hazard. A ship carried a bulk supply of soya bean oil to Melbourne,
Nitrogen presents three principal hazards: Australia. After it had been unloaded, a man was sent into
the tank to clean it out. He was found unconscious and two
• Asphyxiation other men entered the tank to rescue him. They were also
• Low temperature if in liquid form asphyxiated and all three died. Nitrogen had been used
• Overpressurisation to pad the ullage space above the soya bean oil to prevent
oxidation and maintain quality but had not been removed
Nitrogen has been reported as killing more people than
before entry.4
knowledge and
any other single substance.1 Its use must therefore be
competence
restricted to those systems where it is vital and unlikely to • Case history 4
cause great harm. Nitrogen is sometimes termed an inert In the course of cleaning a tank a man was asphyxiated and
gas but ‘inert’ is not to be taken as meaning ‘ died due to a hose being connected to a nitrogen supply
without hazard’. instead of an air supply.5
• Case history 5
Hazards Inert gas leaked into a double bottom tank from a known
defect in the bulkhead separating the tank from the void
Asphyxiation hazard space. Three crewmen died when inspecting the tank.
This incident it is believed, occurred with oil fired inert
If a man enters an atmosphere containing only 6-10% oxygen it
gas and not nitrogen, but demonstrates the problem of
has been reported2 that he is affected as followed:
interconnecting tanks.6
‘….. he may be wholly unaware that anything is wrong. • Case history 6
Then his legs give way leaving him unable to stand, walk
or even crawl. This is often the first and only warning and it An experienced supervisor climbed about 24 metres
comes too late. He may realise that he is dying but does not to the top manhole platform of a column. He went to
greatly care. It is all quite painless. Even if resuscitation is investigate whether there was an adequate flow of water
possible, permanent damage to the brain may result.’ from a hosepipe into the column through the open
manhole. Sodium nitrate solution in the column was
Oxygenated blood takes only 10 seconds to reach the brain. being roused with nitrogen so the column had a nitrogen
When a man enters an atmosphere of pure nitrogen there is no atmosphere. Shortly afterwards the man was found with
smell or feeling of distress or warning symptoms, he can lose his head and shoulders inside the manhole. He had died of
consciousness in as little as 20 seconds. asphyxiation.7
Due to these properties nitrogen has been the cause of many • Case history 7
asphyxiation deaths in industry. The following case histories
A reactor was being water tested prior to examination by
illustrate the asphyxiation hazards:
a vessel inspector. Because the water was taking so long
• Case history 1 to empty after the test a discussion was held between the
A member of a cleaning squad decided to recover a works personnel and the examiner from the authorities and
rope which was half inside a vessel and was caught up it was agreed that nitrogen should be used to speed the
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20 | Loss Prevention Bulletin 275 October 2020
emptying of the reactor. When the reactor was empty the overcome by the gas and died. A third person who tried to
works personnel went to a passenger lift 10 metres away rescue the two men was also affected but recovered.8
leaving the examiner alone at the reactor. While waiting • Case history 9
for the lift to come, they saw the examiner climbing into
The fire brick lining of a combustion chamber seemed to be
the reactor. He took no notice of shouted warnings and
damaged and the chamber was being prepared for entry.9
collapsed immediately. A fitter took a deep breath and
went in also but collapsed immediately. A second fitter The day before the accident, analysis of the air in the
threw in a welding torch containing oxygen and called for chamber had shown 20.8% oxygen. At 6.40 a.m. on the
help. The Emergency Team brought both men out but the day of the accident another sample was analysed and again
examiner died and the fitter recovered only after being in the oxygen content was normal.
intensive care for several days.7 Pipes leading to the chamber had been spaded.
• Case history 8 At approximately 8.00 am the assistant plant manager and
Two men were working in a pit and using nitrogen to a shift supervisor, both very reliable men with long years of
freeze a water pipeline prior to making a repair. They were experience, went out to the plant to check the preparations
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Loss Prevention Bulletin 275 October 2020 | 21
that had been made before issuing the Permit to Enter. used and all finished offloading at the same time. The rush
of nitrogen into the tank was too great for the relief valve to
At 8.35 am a man passing the plant noticed an arm
handle and the tank roof was lifted about six inches. 12
hanging out of the manhole and discovered the two men
lying inside the chamber. Immediately he called help but • Case history 2
attempts to revive the men were in vain. While blanketing a cargo tank with nitrogen from a shore
A new air sample had an oxygen content of less than 2%. installation, an error was made by the operator. Instructions
required pressure to be raised to 0.6 bar. The operator
A post accident investigation revealed the following facts: interpreted this as 6 bar and consequently over-pressurised
– One pipe leading to the chamber had not been spaded; the tank. The relief valve could not cope with the flow.13
– A nitrogen hose had been attached to this pipe the day • Case history 3
before to inert the rest of the apparatus. Consequently While blowing lines clear after offloading a parcel chemical
200 m3/hr of nitrogen had streamed into the chamber. tanker, a mistake at the shore installation caused the ship’s
– The first air sample had been taken before the nitrogen tank to be overpressured and rupture. 14
valve had been opened and the second sample whilst
an air blower was running and blowing fresh air into Other hazards
the chamber. If liquid nitrogen is spilt onto water there is a rapid phase
– When the men were found, the air blower was transition due to transfer of heat from the water to the liquid
stopped. Apparently they had stopped it themselves nitrogen. The gas generated expands rapidly, 1 lb giving rise
before entering, because the strong stream of air to about 13 cu. ft., and can give the effect of an explosion in
coming out of the manhole had hindered them. certain circumstances throwing liquid nitrogen over a wide
– The company had strict regulations for entering a area. The behaviour of cryogenic material spilt onto water is
vessel. An observer with a walkie-talkie had to be still the subject of testing and its behaviour is uncertain.
present and rescue gear including breathing apparatus
had to be standing by. The two men were responsible Conclusions
for issuing the permit to enter and everybody agreed
Nitrogen can be used successfully for providing an inert
that they would never have permitted anybody else
atmosphere but great care has to be exercised in controlling
to enter without such a permit and only when all the
entry into tanks. Its advantages have to be weighed carefully
necessary precautions had been carried out. However,
against the disadvantages found in the industry from the above
they did not apply these rules to themselves.
examples.
Low temperature hazards
Liquid nitrogen is stored in cryogenic tanks at about -200oC.
References
If the tank is overfilled, liquid nitrogen can be ejected from 1. Nitrogen – our most dangerous gas. T A Kletz, 3rd
the relief valve causing adjacent equipment to be cooled to International Symposium on Loss Prevention and Safety
this low temperature. Similarly if the vaporisation equipment Promotion in the Process Industries. Basle, 15-19
fails causing liquid nitrogen or cold gas to be passed to a tank, September 1980, Session 11, Vol.4, p 1518
embrittlement of the steel can occur with disastrous results.
2. Noxious Gases. Y. Henderson and W.H. Haggard.
• Case history 1
3. Private Communication
A 1000 ton liquid nitrogen storage tank was ruptured
causing cold liquid to fall onto other pipework which 4. Melbourne Herald, Friday 15th May 1981.
fractured due to embrittlement. The released material from 5. Safety Division, Industrial Location and Environmental
the pipework was oxygen which drifted in a cloud into Protection Bureau, Ministry of International Trade and
another works where three men were very badly burnt Industry, Japan, February 1976.
and died.10
6. Merchant Shipping Notice No. M910. Department of
• Case history 2 Trade, UK
A carbon steel line carrying hydrogen at 325 psig was
7. Private communication
suddenly subjected to liquid nitrogen temperatures causing
it to rupture violently.11 8. The Guardian, London, 25th June 1982
Overpressurisation hazards 9. Loss Prevention Bulletin
Liquid nitrogen boils at -196 C and has a vapour pressure
o 10. Chemical Week, 8th February 1978
of some 30 bars at -148oC. If vents or relief systems become 11. Nitrogen Wash Incident. Ammonia Plant Safety,
blocked the pressure which can be generated is more than AIChE 3, 1961
sufficient to rupture a tank.
12. Private communication
• Case history 1
13. Private communication
Acrylonitrile was being loaded into a ship by pressurising
road tankers with nitrogen. Three road tankers were being 14. Private communication
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22 | Loss Prevention Bulletin 275 October 2020
Loss Prevention Panel comment • A vessel contained a catalyst bed that had been agitated
with nitrogen. The catalyst had been left standing for a time
This article, by the late John Bond, first published in Loss
and a crust had formed on its surface. A man entered the
Prevention Bulletin in 1985, and reproduced herein, is as
vessel in full protective clothing but when he broke into
relevant to the prevention of loss now, as it was then. The
the crust, pressure was released and this was sufficient to
principal hazards presented by asphyxiation, exposure to liquid
damage the vessel and kill him. This tragically illustrates the
nitrogen and overpressurisation, continue to result in a tragic
danger that a sudden release of trapped nitrogen (or other
litany of serious accidents and fatalities. The following more
recent examples starkly illustrate this1. gas) pressure can present.
Nitrogen plays an important and vital part in our everyday lives.
• A student was found dead on the floor of an underground
dry area where he had been filling a Dewar flask from a Without its presence in the air that we breathe, there would
cylinder containing liquid nitrogen. A sudden evaporation be an increased risk of uncontrollable fires and rusting of steel
of the liquid had resulted in lowering of the oxygen structures. It is a component of ammonia, which is essential to
concentration in his breathing zone to a level that would not the production of synthetic fertilisers without which, modern
support respiration. The normal concentration of oxygen day demands for many foodstuffs and crops could not be met.
in the air that we breathe, is about 21%. In confined spaces However, we must never forget that it is also potentially a silent,
such as that present in this case, a local reduction to about odourless killer if not properly controlled. A lowering of oxygen
10% or less can easily occur if there is a sudden release of concentration in a person’s breathing zone, from the normal
nitrogen. This would result in a high probability of death. level of about 21%, to 16% by displacement with nitrogen, will
• A technician fell through the open manhole into a reactor result in asphyxiation. Liquid nitrogen, at a temperature of
whilst trying to retrieve a roll of tape. The reactor contained -1960C, will cause “cold burns” and frostbite on contact with skin
an atmosphere of nitrogen that had been used to purge it. and other tissue, and can crack steel equipment.
He lost consciousness. A colleague entered the reactor to I am both pleased and honoured to have been invited to
try to rescue him. Both men died from nitrogen suffocation. support the re-publication of this article by John Bond, one of
The lessons here are that the atmosphere inside a vessel the foremost loss prevention practitioners of our times.
that has been purged with nitrogen may well not support Tony Fishwick
respiration, that open manholes should be made safe by
fitting of a locked-on cover between essential entries, and
Reference
that rescue of anyone in distress inside a vessel or confined
space should never be attempted unless the rescuer first 1. BP Process Safety Series – Hazards of Nitrogen and Catalyst
puts on the specified protective clothing. Handling. ISBN 0 85295 469 7
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