Research

1. Introduction:
The chemical explosion occurred 46 years ago (1st June 1974) near
flixborough village, Scunthorpe, England. The explosion at Nypro
chemical plant was due to leakage of large amount of flammable
cyclohexane vapours into atmosphere. The fire raged with flames
rising up to 70-100 metres and the impact of blast was seen up to 50
km which devastated 24 hectares of land of company. Flixborough
was not only the most serious incident to have occurred in the UK’s
history, but it was also one of a serious explosion occurred during the
1970’s in both Europe and the USA.
“it was a still, warm, sunlit afternoon. One moment, a blast of
nightmarish intensity as the giant plant blew up and blotted out the
sun” – Humberside police report
“Safety isn’t expensive, it’s priceless.”
“Carefulness costs you nothing. Carelessness may cost you your life.”

2. Plant information:
Initially the factory was a subsidiary of Fisons Ltd; it had been
established in 1938 for the manufacture of fertilizer.
In the 1970s the chemicals industry was experiencing a period of
exponential growth. The primary focus of most companies was to
develop advanced chemical processes to fulfil the demand for new
materials following the scientific revolution that began after the 2nd
world war.
One of these new materials were polyamides called “nylons”. Most
nylons have a good chemical and thermal resistance with a range of
applications from textiles to insulating electrical wires.
So, in 1964 it passed to the Nypro company which had been formed
with the participation of Dutch State Mines (DSM) with a view to the
manufacture of caprolactam, an intermediary product in the
manufacture of nylon. In 1967 Nypro was reorganised with the
following participants: DSM (45%), British National Coal Board (45%),
Fisons Ltd. (10%). In August 1967, the 20,000 tonnes/year of
caprolactam was made from phenol. In 1972 the process was
revised to include the oxidation of cyclohexane, a highly
flammable and toxic hydrocarbon, which in turn increase
productivity up to 70,000 tonnes/annum. In 1974 the Nypro
company was the sole manufacturer of caprolactam in Great Britain.
3. Conversion from benzene to nylon:

benzene

hydrogenation

cyclohexane

oxidation

cyclohexanone

NH2OH

Cyclohexanone-oxime
 Beckmann
rearrangement

caprolactam

Ring opening
polymerization

Nylon-6

1. Benzene to cyclohexane:

The hydrogenation of benzene in presence of metal (nickel,

platinum, pallidum) gives cyclohexane
2. oxidation of cyclohexane:

The oxidation of cyclohexane in presence of catalyst at 150℃

temperature and 9 bar pressure, gives mixture of cyclohexanol and
cyclohexanone. This mixture is then separated by fractional
distillation
3. conversion from cyclohexanone to cyclohexanone-oxime:
The cyclohexanone is converted to cyclohexanone-oxime by reaction
of hydroxylamine (NH2OH) and HCl
In this reaction there is a nucleophilic attack at the π-bond of
carbonyl group in cyclohexanone. But here quaternary salt of
hydroxyl amine & HCl is not a good nucleophile, so NaOH is added to
make it strong nucleophile whose mechanism is shown below:
4. Beckmann rearrangement:

The cyclohexanone-oxime is converted into caprolactam in presence

of acid & ammonium sulphate at 300 to 350℃
5. Preparation of nylon-6:

Nylon-6 is obtained by ring opening polymerization of

caprolactam in presence of water at higher temperature

Process :
 the oxidation of cyclohexane is done on series of six reactors in
sequence, each unit having a capacity of 45 m3 and made of
mild steel (13mm) with rustproof plating (3mm) internally. The
safety valves being calibrated at 11 bar.

The reactors are equipped with a central stirring rod. The oxidizing
reaction of the cyclohexane is accomplished with a catalyst at 155° C
under 8.8 bars of pressure by means of air injection with the help of
a perforated gradient. Each reactor contains 25 m3 of liquid. The
throughput circulating from one reactor to the next through piping
systems of 28 inch diameter is 250-300 m3 h-1.

Why we use high temperature & pressure during oxidation?

It is more difficult to select the conditions for the production of
cyclohexanone as the major product in the oxidation of cyclohexane.
The cyclohexanone is more readily oxidized compared to
cyclohexanol & adipic acid.

But it also give rise to many by products after high oxidation

conversion. Thus, we need to maintain low concentration of
cyclohexanone and this can be done by connecting reactors in series.

Thus, we can conclude from above graph that at low oxidation

conversion it will give high yield of cyclohexanone (because high
concentration of cyclohexanone will promote secondary products)
and high temperature tends to increase reaction rate. The high
pressure is used in reaction because it’s boiling point is 80.7℃, so at
155℃ in order to condense it into liquid phase high pressure must
be required
How can we control reaction rate and avoid reaction?
The reaction rate can be increased by catalysts and most popular
catalyst here is cobalt stearate. The catalyst converts cyclohexane
into free radical by abstracting H-atom, whose mechanism is as
follow as:

The catalyst is mostly added up to 0.06 %mole. The cobalt stearate

after reaction converted to cobalt adipate which can be easily
removed

The copper stearate catalyst is used to slow down reaction. While

catalysts also absorbs reaction.
Whenever some accident occurred during process, the oxidation
reaction can be stopped by adding some inhibitor like α-naphthol,
hydro-quinone they are just radical quenchers (i.e. they stabilizes
radical formed during reaction)

Events occurred prior to accident:

On the morning of March 27th it was discovered that cyclohexane
was escaping from reactor No. 5. Investigation showed a vertical
crack in the outer casing of the reactor; a small quantity of
cyclohexane escaped from this crack; this indicated that the internal
casing was also defective. The production engineer on duty
telephoned the director for zone 2 and they agreed that the
installation would have to be closed down, depressurised and cooled
while a complete inspection was to take place.
Why does the crack on reactor No 5 formed?
After the accident the investigation took place and it was found
that crack was formed due to corrosion of mild steel (from
which material reactor was made) by the nitrates containing
water. The water is used for cooling or temperature controlling.
At that time this problem was not recognized but now a day
this corrosion of mild steel by nitrates is very popular
phenomenon.
On March 28, the director inspected the crack and found that it was
about 2 m long. This indicated a serious situation and immediate
meeting was held. During this meeting, they had decided to remove
reactor No. 5 and to continue oxidation with remaining 5 reactors by
connecting reactor No. 4 and 6 via temporary by pass which was
supported by jack knife
The by pass pipe was made from mild steel having dog-legged shape
and 28 inches diameter, expansion bellows were applied on both
sides and it was supported by poles
On April 1st production was restarted and it was functioned normally
up to 29th may.
The following are some series of leakage and repair works from 29th
may to 1st June:
A. On Wednesday, May 29th, a leakage was discovered which
forced a stoppage. The process was restarted in the early hours
of Saturday after repairs and escape tests.
B. At 4 am a new leakage occurred; the process was stopped and
at about 5 am operations were restarted.
C. Shortly afterwards the process was stopped again because of a
leakage. Repairs could not be carried out immediately because
the necessary special tools were not available.
D. The process was restarted at 7 am on Saturday morning. At this
time they had also reported that they doesn’t have sufficient N2
gas, which sufficient to prevent accident.

Accident occurred:
At 4:53 pm on 1st June 1974, the by pass pipe was broken down
because the expansion bellows can not be able to withstand
excessive pressure, the pipe broke and fell down on the ground. At
large amount of hot cyclohexane was leaked from reactor No 4 & 6
(which looks like a massive cloud!) and within 25 to 35 seconds
combustion occurred, followed by fire. This killed all the people in
control room and destroyed all the instruments

The enthalpy of combustion of cyclohexane is -3920 kJ mole-1 (this

can be compared to -285 kJ mole-1 which is enthalpy of combustion
for hydrogen)
Causes:
The geometry of pipe is such that it had created a turbulence in flow
of cyclohexane fluid which in turn increased the pressure on the
which it wouldn’t be able to sustain.
Some moment before accident they had reported that they doesn’t
have sufficient quantity of nitrogen which acts as inert medium and
control the oxidation reaction. Instead of nitrogen, they had added
water which is undesirable.
Properties of cyclohexane:
Cyclohexane is a cycloalkane and volatile organic chemical. It occurs
naturally in petroleum crude oil, volcanic gases, but Nearly all
industrial cyclohexane is produced by benzene hydrogenation.

It’s chemical formula is C6H12 and molecular weight is 84.16

gm/mole.
Physical properties:
• It is colourless liquid, posses chloroform like odour sometimes
irritating odour
• It is highly flammable and highly volatile (like gasoline!)
• It’s vapour is heavier than air and liquid is lighter than water in
terms of density (which common in most of hydrocarbon
solvents)
• It posses flash point -18.3℃ (due to this it is stored in closed
vessel in inert gas at high pressure)
• It’s melting point is 6.5℃ and boiling point is 80.7℃
• It’s auto ignition temperature is 260℃
Chemical properties:
• It readily reacts with oxygen and strong oxidising agent like
nitrates, chlorates, peroxides etc
• It is soluble in hydrocarbon solvents, natural oils, fats, and
waxes; but insoluble in water (because of it’s polar nature).

Properties of nylon-6:
Here we have described about nylon-6, because majority of
cyclohexane is used in production of nylon-6. However, there are
also other uses of cyclohexane such as an industrial solvent, in
adhesives & paints, glues and printing inks.
• it is lustrous, tough, elastic fiber
• it posses high tenacity (due to this it can be used where high
strength at low weight is required)
• It posses high abrasion resistance and resistant to damage by
oils
• It is insoluble in common organic solvents but soluble in phenol
and formic acid
• It’s glass transition temperature is 50℃
• It undergoes thermo-oxidative degradation at 190℃
• It is susceptible to hydrolytic attack, when immersed in water
at 25℃ it drastically loses its mechanical properties (water
destroys secondary hydrogen bonding between amide groups)
• It undergoes yellowing on slight degradation which is
unacceptable for commercial application

Uses of nylon-6:
The nylon-6 has wide range of application form apparel wear to
industrial sector
• Men’s socks
• They are used as fine filaments in lady’s saree
• In light weight, sheer garments
• They are used as reinforcement in conveyor belt, v-belt, hoses
• Nylon cords are also used in rubber tyres
• It used in ropes, fishing nets, and parachutes
• They are best carpet fibres because of their stability, durability
& price advantage
Toxicology of cyclohexane:

Acute (short term) exposure:

It is skin irritant (because it is fat soluble), mild eye irritant and throat
irritant. It can also cause nausea, headache, dizziness, shortness of
breath, Gastrointestinal disturbance, Lung irritation, chest pain,
pulmonary edema (wet lungs). It also affect central nervous system
above 250 ppm as this level is described by OSHA. If swallowed in
significant amount it can cause pneumonia. The safe exposure level
prescribed by OSHA, AIGH is 300 & 100 ppm respectively.

Chronic (long term) exposure:

It is non-carcinogenic as classified by IARC (international agency for
research on cancer), NTP (national toxicology program), ACGIH
(American conference of governmental industrial hygienists), OSHA
(Occupational Safety & Health Administration)
It is non-mutagenic when exposed (this is verified by Ames test
which is done on Escherichia coli). It is also non-mutagenic when
ingested or inhaled into body, it is verified by cytogenetic test (in this
test defective chromosomes of the cell are measured) on bone
marrow of rat and it was found that it is non-mutagenic up to 10141
ppm.
It does not show any Teratogenicity up to 7000 ppm (which means it
does not cause any birth defects). The chronic exposure tests were
done for weeks (5 weeks).
First aid measures:
1. If inhaled accidently, then go to fresh air & inhaled more and
more pure air. If person can’t be able to breath the give him
artificial respiration and consult a physician
 2. If skin gets accidently exposed to cyclohexane, then wash the
affected area with soap and water. Rinse/flush carefully the
exposed area with water for 15 to 20 minutes and if irritation
continuous then consult a physician. Remove all contaminated
clothes and wash them
3. If eye gets exposed then wash eye thoroughly with water for 15
to 20 minutes and call specialist
4. If accidently swallowed, then rinse mouth with water and do
not induce vomit and don’t drink alcoholic beverages or milk.
Don’t give anything to mouth to unconscious person.

Precautions:
It must be stored in closed container under high pressure in presence
of inert gas. It must be stored away from oxygen or any other
oxidising agents.
While working with cyclohexane do not drink water or eat food or
smoke cigarette.
Prevent build-up of electrostatic discharge either in atmosphere or
in container, because electric spark might be sufficient to ignite
organic vapours of cyclohexane. In case of container apply anti-static
coating on the interior.
Alcohol resistant foam, dry chemical powder or CO2 are appropriate
fire suppressing media. In case of laboratory, follow fire suppressant
procedure. Don’t use water because it might be ineffective to bring
down chemical below it’s flash point.
In case of spill, collect liquid using vaccum collector or by absorbing
with suitable absorbents
For personal protection:
Respiratory protection:
It doesn’t required under normal working condition. Wear NIOSH
approved respirator while working under harmful exposure level.
Use positive pressure air supplying respirator, when there is
uncontrollable release of cyclohexane (in case of accident).
Hand protection:
Handle cyclohexane with gloves. Gloves must be inspected prior to
use. Use proper glove removal technique (without touching glove's
outer surface) to avoid skin contact with this product. Dispose of
contaminated gloves after use in accordance with applicable laws
and good laboratory practices. Wash and dry hands. Use of low
permeable nitrile gloves are preferred.
Eye protection:
Use face shield and safety glasses
Skin and body protection:
Wear flame retardant and anti-static protective clothing. Worker
should wear anti-static footwears.

environmental impacts:
cyclohexane is readily biodegradable. It is toxic to many aquatic
species with long lasting effects. Cyclohexane is also released from
cigarette but it is readily decomposed in air. However, it should not
thrown along with house-hold garbage, do not allow cyclohexane to
reach sewage or open waters. Consult federal state/provisional or
local regulations for proper disposal. It does not bio-accumulate
which means it cannot enter into food chain (cannot cause mercury
Minamata like diesease)

Consequences:
The explosion was very massive it’s impact is similar to 15 – 45 tons
of TNT, some people after visiting devasted site compared this
disaster to minor atom bomb.

Among the 72 people present at the site 28 died (of whom 19 were
in the control room), 36 others were injured. Outside the factory 53
injured were counted; hundreds more suffered minor injuries which
were not officially registered. The fire was so gigantic that it took 2
and half to reach principle source of fire by fire fighters.
Economic impacts:
The estimated material damage of factory was 10 million USD, and it
took 180 million USD for reconstruction. All buildings within a radius
of 600 metres were destroyed and more than 2,450 houses were
damaged in the vicinity. Windows were shattered within a radius of
13 km. The estimated increase in pressure at epicentre is 2 bar.
It destroyed 72 houses out of the 73 at Flixborough (800m away), 73
out of 79 at Amscott, 644 out of the 756 at Burton (3.5km) were
damaged to various degrees. Some large pieces of projection were
also found 6km away from factory.
Fortunately, the accident occurred away from urban centre and it
does not occur on busy day, otherwise it might resulted in much
larger casualties.
Human errors:

At the beginning of 1974 the maintenance engineer left the factory

for personal reasons, and by June 1974 the company had not yet
found a replacement. None of the other engineers, even though they
were graduates, had a little knowledge in mechanics. The duties of
the maintenance engineer, especially coordination, were given
provisionally to a subordinate (a person who had a technician’s
diploma and who had completed his training). This technician had
spent ten years of his career in the public electricity supply service
and four years in maintenance. His qualification was insufficient for
the job given to him temporarily and also insufficient for the
detection of certain design anomalies in connection with important
modifications of the equipment.
After the meeting on 28th march, they concluded to install bypass
pipe in between reactor no. 4 & 6, and restart production as soon as
possible.
Following are main problems they had done:
• Before restarting production they haven’t check other reactors
whether the crack is formed or not.
• No stress analysis was done on pipe
• They had just draw pipe on board with chain, no engineering
drawing of pipe was made.
• All of the technicians working there were from chemical
background, and 1 technician was there was but he does not
have sufficient knowledge and credentials.
• The haven’t done fluid flow analysis inside bypass pipe.
• They haven’t designed jack knife for that much force.
• There was poor social environment at the plant, there was lack
of communication between senior managers and junior safety
officers.
• On June 1st, 1974 Nypro stocked : 3,30,000 gallons of
cyclohexane, 66,000 gallons of naphtha, 11,000 gallons of
methyl benzene, 26,400 gallons of benzene, 450 gallons of
gasoline. While they had licence issued only for 7,000 gallons of
naphtha, 1,500 gallons of gasoline under Petroleum
(Consolidation) Act of 1928.
• The caprolactam factory of Nypro was programmed for a
production of 70,000 tonnes of caprolactam but in reality, it
produced only 47,000 tonnes at the time of the accident. Dutch
State Mines as well as the National Coal Board had also
requested the government's Price Commission to authorise a
48 per cent increase in the price of caprolactam. This
authorisation was refused. In other words, Nypro was subject
to serious economic and commercial pressure and this explain
why it led to this disaster.
Steps taken by government:
On 27th June 1974, government send investigation team under
Section 84 of the Factories Act 1961 to hold a formal investigation to
establish the causes and circumstances of the disaster and to point
out any lessons which we might consider were immediately to be
learned therefrom.
Flixborough is one of several landmark process safety events which
has led to both management and legislative changes. Following are
some rules amended by government in order to increase safety at
workplace:
• The most widely recognized change is Management Of Change
(MOC) which states that modifications must be subject to the
same protocols, standards, and testing used in the initial
design of the plant.
• This disaster also influenced The Pressure Systems and
Transportable Gas Containers Regulations 1989, SI 1989/2169
15 years later. This describes essential procedures for safely
handling, processing & disposing hazardous volatile liquids.
• Government also conducted research and development for
understanding vapour cloud explosion
• At the time of the disaster many process safety management
tools (that are commonly used today) were in their early
stages of development. Most notably the Hazard and
Operability study method (HAZOP).
• Some research is done in computational fluid analysis models.

What do people learn from this disaster?

One of the positive thing regarding flixborough incident is that not
only government but people are also concerned about industrial
safety. Following are some of significant changes seen throughout
the country regarding industrial safety:
• When implementing designs, hazard and risk analysis became
a core consideration
• It was not permissible to allow engineers, operators, or
contractors to work unaware of the potential dangers in their
workplace.
• It was also encouraged that engineers learned a wide breadth
of skills like a chemical engineer must have some basic
knowledge regarding mechanical and electrical branch.
• It was also recommended that, where possible, control rooms
and administrative facilities should be placed away from the
chemical process in order to reduce risks of life.
• A guide for “how to design and place buildings around a
chemical process” was published in the late 1970s. It continues
to be updated, with a 3rd edition being printed in 2010 and a
4th edition due to be published at the end of 2019.

What is safety culture?

A safety culture is an organisational culture that places a high level of
importance on safety beliefs, values and attitudes—and these are
shared by the majority of people within the company or workplace. It
can be characterised as ‘the way we do things around here’. A
positive safety culture can result in improved workplace health and
safety (WHS) and organisational performance.
Following are some ways to generate positive safety culture within a
industry:
1. Demonstrate leadership
2. Personalise safety outcomes
3. Engage and own safety responsibilities and accountabilities
4. Increase hazard/risk awareness and preventive behaviours
1. Demonstrate leadership:
Act to motivate and inspire others to work towards achieving a
particular goal or outcome by sending clear and consistent messages
about the importance of work health and safety.
Leading from the top down can be demonstrated by:
• seeking staff engagement and participation when developing
‘safety’ tools (e.g. checklist inspections, safe work method
statements, job safety analyses)
• wearing personal protective equipment when on-site
• conducting periodic checklist inspections
• conducting periodic risk assessments
• conducting periodic toolbox talks.
2. Personalise safety outcomes:
Make work health and safety more obvious, relevant and emotional
for the individual to personalise their role in preventing and
eliminating risks and hazards.
Managers can personalise the impact of an employee injury or death
by communicating:
• the personal impact of the risks of a process or distinct task when
an individual is injured or becomes ill; or if his or her actions (or lack
of them) cause injury, illness or death to a workmate
• why it is important to the individual and the project that employees
ensure their own safety and health and that of others
• the behaviours your company expects everyone to consistently
adopt.
The impact of an injury or fatality can be personalised by relating
that incident is not just an anonymous statistic reported in annual
workers’ compensation reports, but a workmate who has a name, a
partner, children, parents and siblings.
3. Engage and own safety responsibilities and accountabilities:
Increase input, actions and involvement in the safety management
process by individuals.
At a safe workplace people will:
• look for hazards proactively and manage risks before they cause
harm
• take care of hazards themselves without needing policing
• believe they are responsible and accountable for making sure that
they and their workmates remain healthy and safe
• follow workplace rules.
Engaging employees:
• Obtaining employee input into safety management on a daily basis
— not just through work health and safety committees or other
formal means.
• Reducing the ‘us’ versus ‘them’ mentality through building trust.
• Involving all workplace management in the planning process.
• Sharing the information with workers.
Building relationships:
• Creating a sense of belonging through team building.
• Providing opportunities for people to meet socially (e.g. BBQs).
• Having regular conversations at a social level (e.g. enquiring about
things important in colleagues’ lives).
• Generating conversations about safety — subtle weaving of safety
into general conversation
• providing good amenities that promote interaction and show that
management cares for the well-being of the workplace.
4. Increase hazard/risk awareness and preventive behaviours:
Increase the individual’s understanding of the work health and safety
outcomes associated with their decisions, behaviours and actions.
Effective communication should:
• be clear and direct
• be relevant to those receiving the message
• avoid blame (as this is likely to create defensiveness and the
message will not be heard)
• emphasise the personal impact of the action or decision.

What is HZOAP?
HAZOP, or a Hazard and Operability Study, is a systematic way to
identify possible hazards in a work process. The task of analysing
hazards in a workplace or system can be difficult. However, without
an effective analysis, potential hazards may not be discovered before
they result in injuries and loss. The cost of an accident is often many
times greater than the cost of the analysis that could have stopped
it. It’s the old proverb: “An ounce of prevention is worth a pound of
cure.”
HAZOP is a common hazard analysis method for complex systems. A
Hazard and Operability Study systematically investigates each
element in a process. The goal is to find potential situations that
would cause that element to pose a hazard or limit the operability of
the process as a whole. There are four basic steps to the process:
Some other gas explosion accidents:
1. East Ohio gas explosion:

On October 20, 1944, a natural gas storage tank at the East

Ohio Gas Co. plant in Cleveland, Ohio, exploded. Although
 investigators never discovered a cause for the explosion,
witnesses stated that a leak in one of the tanks occurred. Some
spark must have then ignited the gas, although, with World
War II currently raging, some residents initially suspected a
German for this accident.
It killed nearly 131 people among which 22 were never
identified. For the people who survived, most lost everything.
The flames destroyed several blocks of homes. Many of these
people also had withdrawn their savings from banks during the
Great Depression (however it was ended in 1939), as numerous
banks had failed.
After this incident, east ohio company begin to store their
natural gas underground.

2. Piper alpha:

It was world’s worst offshore oil disaster, occurred on 6th July

1988. One of two pump located under main body of platform
stopped working. Failure to restart pump within 30min would
mean complete shutdown (while piper alpha rig account for
10% of north sea oil and gas production).
 To prevent a costly shutdown the 2nd started but it was also
faulty. The control room was unaware that maintenance work
on that pump was not completed. Gas started to leak and then
exploded. (the platform was built to withstand fire not
explosion)
Within 2 hours, 167 men lost their life but 61 men were
survived by jumping into from rig.
It produced 3,00,000 barrels of oil a day!

3. Bhilai Steel Plant Gas Leak:

On June 2014, poisonous gas was leaked in Steel Authority of
India's Bhilai Plant in Durg district of Chhattisgarh.
The pump House No 2 which supplies water to the Gas
Cleaning Plants (GCP) of blast furnaces suddenly ruptured
which resulted in loss of water pressure, due to this the release
of toxic blast furnace gas from the scrubbers entered the water
pipeline.
It killed 6 people and over 30 were injured