L. D.

COLLEGE OF ENGINEERING

Case study: FLIX BOROUGH DISASTER

Prepared by:
From enrollment number 1
to 22
 CONTENT
Introduction (180280126001 Bhavsar sarthak)
Plant information (180280126013 Maniya Rutvik )
Conversion from benzene to nylon 6 (180280126003 Chhotala Santosh)
Oxidation Process at flixborough (180280126022 shaikh aman)
Events occurred prior to accident (180280126008 Hadiyal Mehul)
Accident occurred (180280126020 Sarvaiya Darshan)
Cyclohexane properties (180280126005 Dhola Naimish)
Properties of nylon-6 (180280126018 Radadiya Yash)
Uses of nylon-6 (180280126011 Karena Nikunj)
Cyclohexane toxicology (180280126009 Halpati Manav)
Precautions & Cyclohexane effect on environment and ecology (180280126006 Kelvin
Gajera)
Consequences (180280126012 Kukadiya Keval)
Human errors (180280126019 Rudatala Mahesh)
Steps taken by government (180280126021 Savaliya Kevin)
What do we learn form this disaster (180280126007 Gediya Prajesh)
What is safety culture (180280126015 Patel Harsh)
What is HZOAP (180280126014 Nada Jenil)
Other accidents (180280126004 Dhariyaparmar Gautam)
 INTRODUCTION
On 1st June 1974, the worst disaster in UK’s history took place, it was also one of a serious
explosion occurred during the 1970’s in both Europe and the USA.
Plant location: on the east bank of river Trent near flixborough village, Scunthorpe, England
Cause of disaster:
The explosion at Nypro chemical plant was due to leakage of large amount of flammable
cyclohexane vapors 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.
“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
Some quotes related to safety:
“Safety isn’t expensive, it’s priceless.”
“Carefulness costs you nothing. Carelessness may cost you your life.”
MASTER PLAN OF NYPRO PLANT

N
 PLANT INFORMATION
year Event

1938 It had been established for the manufacture of fertilizer, as a subsidiary of Fisions Ltd.

1960s – 70s Chemical industries experiencing exponential growths and demand for new material is on
peak
1964 It starts production of caprolactam (for nylon-6) in participation with Dutch mines

1967 It was re-organized with participants: DSM (45%), British National Coal Board (45%),
Fisons Ltd. (10%)
1967 The 20,000 tons/year of caprolactam was made from phenol

1972 The process was revised to include the oxidation of cyclohexane (capacity: 70,000
tons/year)
1974 It was the sole manufacturer of caprolactam in Great Britain
 CONVERSION FROM BENZENE TO NYLON-6

Beckmann
Beckmann
oxidation
oxidation applications
applications
• benzene • cyclohexanone rearrangement
rearrangement • Caprolactam
• cyclohexane • Cyclohexanone- • Nylon-6
oxime

Ring
Ring opening
opening
hydrogenation
hydrogenation NH
NH22OH
OH polymerization
polymerization
1. Hydrogenation of benzene:

The hydrogenation of benzene in presence of metal (nickel, platinum, pallidum) gives

cyclohexane.
2. Oxidation of cyclohexane:

Temperature: 150℃ & pressure : 8.8 bar

Separation of mixture: fractional distillation
3. Cyclohexanone to cyclohexanone-oxime:

In this reaction there is a nucleophilic attack at the π-bond of carbonyl group (C=O) 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
 OXIDATION PROCESS AT FLIXBOROUGH

The oxidation of cyclohexane is done on series of 6 reactors in sequence, each unit having a
capacity of 45 m3 (while each reactor contains 25 m3 of liquid) and made of mild steel with
rustproof plating (of 3mm) internally. The safety valves being calibrated at 11 bar. The
reactors are also equipped with stirring rod.
Oxidation condition:
Temperature : 155℃, Pressure : 8.8 bar
The air (mixture of N2 & O2) is injected through perforated gradient on the top.
The following is plant process flow chart
Why we use high pressure and temperature ?
It is difficult to obtain cyclohexanone as a major oxidized product when reaction parameters
are not controlled

When the concentration of product (cyclohexanone) increases, it will tends to oxidize further
and give more side products like adipic acid, CO2 etc.

This can be prevented by maintaining low concentration of product

From the above we can conclude two things:
a) Low oxidation conversion will give high yield
b) High temperature will increase reaction rate

The high pressure is used to condense it into liquid form (because it’s boiling point is 80.7℃)
How can we control reaction rate and avoid reaction?
The most popular catalyst for this reaction is cobalt stearate. It’s mechanism is as follow as:

The catalyst is mostly added up to 0.06 %mole, cobalt stearate after reaction converted to cobalt
adipate which can be easily removed.
The copper stearate catalyst is used to slow down 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).
 EVENTS OCCURRED PRIOR TO ACCIDENT:

On 27th march, the small amount of cyclohexane was found leaking from reactor no. 5, the
production was shut down. On 28th march director found vertical 2m long crack from the
internal casing.
Immediate meeting was held on that day, after 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.

The crack formed in reactor no. 5 is due to corrosion of mild steel by nitrates containing water
 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.
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.
The above given is combustion reaction of cyclohexane
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.
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
 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 colorless liquid, posses chloroform like odor sometimes irritating odor.
• It is highly flammable and highly volatile (like gasoline!)
• It’s vapor is heavier than air and liquid is lighter than water in terms of density
• It posses flash point -18.3℃
• 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 oxidizing 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 minor 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
• 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℃ and undergoes thermo-oxidative degradation at 190℃
• It is susceptible to hydrolytic attack, when immersed in water at 25℃ it drastically loses its mechanical
properties
• It undergoes yellowing on slight degradation
 USES OF NYLON-6
• They are used as reinforcement in
conveyor belt, v-belt, hoses.
• Nylon cords are also used in rubber tires
• It used in ropes, fishing nets, and
parachutes
• Men’s socks
• They are used as fine filaments in lady’s
saree
• They are best carpet fiber
 TOXICOLOGY OF CYCLOHEXANE

On acute exposure it can cause,

• Nausea
• Headache
• Dizziness
• shortness of breath
• Gastrointestinal disturbance
• Lung irritation
• chest pain
• pulmonary edema (wet lungs)
• It is skin irritant, mild eye irritant and throat irritant.
• 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 exposure:
• It is non-carcinogenic as classified by IARC, NTP, ACGIH, OSHA.
• It is non-mutagenic when exposed, this is verified by Ames test. It is also non-
mutagenic when ingested or inhaled into body, it is verified by cytogenetic test 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.
The chronic exposure tests were done for weeks (mostly 5 weeks)
 FIRST AID MEASURES
If inhaled
• Then go to open environment and inhale more and more fresh air. If a person can’t able to breath then give him
artificial respiration and consult a physician

If exposed to skin
• Wash that exposed area with soap and water, rinse carefully with for 15-20 min. if irritation continuous then consult a
physician

If exposed to eye
• Then wash eye thoroughly for 15 to 20 min and call specialist

If swallowed
• Then rinse mouth with water, don’t induce vomit, don’t drink water or alcohol beverages
 PRECAUTIONS

• It must be stored in closed container under high pressure in presence of inert gas (mostly N2).
It must be stored away from oxygen or any other oxidizing agents (nitrates, chlorates).
• 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.
• 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.

Hand protection:
Handle cyclohexane with gloves. Use proper glove removal technique (without touching
glove's outer surface). Dispose of contaminated gloves after use. Wash and dry hands. Use of
low permeable nitrile gloves are preferred.
Eye protection:
Use face shield and safety glasses Skin
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 but it does not bio-accumulate.
• 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.
 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 (which is nearly 7 crore
INR), and it took 180 million USD (1326 crore INR) for reconstruction.
• All buildings within a radius of 600 meters 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 epicenter 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
• 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 chalk, 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 license 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 tons of
caprolactam but in reality, it produced only 47,000 tones 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 authorize a 48 per cent increase in the price of caprolactam. This
authorization was refused. In other words, Nypro was subject to serious economic and
commercial pressure and this explain why it led them to this disaster.
 STEPS TAKEN BY GOVERNMENT
Flixborough is one of several landmark process safety events which has led to both
management and legislative changes. Following are some efforts taken by government in order
to increase safety at workplace:
• 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.
• 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 led to amendment of “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.
 SAFETY CULTURE
A safety culture is an organizational culture that places a high level of importance on safety
beliefs, values and attitudes—and these must be shared by the majority of people within the
company or workplace. It can be characterized as ‘the way we do things around here’. A
positive safety culture can result in improved workplace health and safety (WHS) and
organizational performance.
Following are some ways to generate positive safety culture within a industry:
1. Demonstrate leadership
2. Personalize safety outcomes
3. Engage and own safety responsibilities and accountabilities
4. Increase hazard/risk awareness and preventive behaviors
 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 analyzing 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:
 OTHER EXPLOSIONS

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.
Causes:
Some said leak had occurred in tanks, some
said spark generated inside tank, while some
said it was work of Germans. However,
investigator never found proper cause for
explosion.
Aftermath:
It killed nearly 131 people among which 22 were never identified. The flames destroyed
many people homes, this led to withdrawn people’s saving from banks and many banks
had failed during the impact of great depression. However, company had also
financially aided many people
After this incident, east Ohio company begin to store their natural gas underground.
2. Piper alpha disaster:
Piper alpha was oil platform in north sea 190
km away from north-east of aderbaan. It
occurred on 6th July 1988.
Causes:
One of two pumps stopped working to prevent
costly shutdown, they used another pump
whose maintenance was not done (they were
unaware about this). The gas started to leak
and exploded.
Consequences:
167 men lost their life but 61 men were
survived by jumping into from rig.
Some facts:
It produced 3,00,000 barrels of oil a
day! Which account for 10% of north
sea oil production.
It was a worst off-shore oil disaster in
the world.
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.
Causes:
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.
Casualties:
It killed 6 people and over 30 were injured
 REFERENCES:
• An Assessment of Industrial Disasters by Dr. PATRICK LAGADEC
• The oxidation of cyclohexane by I.V. BEREZIN · E.T. DENISOV AND N. M. EMANUEL
• Manufactured Fiber Technology by V.B. Gupta and V.K. Kothari
• Safety under scrutiny — Flixborough 1974 by Matthew Jenson, Callum Lawford, Alex Norman, Elizabeth
Ogden
• Understanding safety culture by work place health and safety Queensland
• Flixborough: Lessons which are still relevant today by Robin Turney
• Material safety data sheet by SIGMA-ALDRICH
• The Risk Assessment of: CYCLOHEXANE by Scientific Committee on Toxicity, Ecotoxicity and the
Environment (CSTEE)
• Safety data sheet by chevron Phillip
• Some authenticate internet sources:
• https://www.independent.co.uk/news/uk/this-britain/true-cause-of-flixborough-to-be-revealed-after-26-years-2
81640.html
(introduction)
• https://www.bbc.com/news/uk-england-humber-48483691 (introduction)
• https://www.cpchem.com/what-we-do/solutions/aromatics/products/cyclohexane (cyclohexane)
• https://studylib.net/doc/12540555/cyclohexanone-oxime-synthesis-notes (cyclohexanone to cyclohexanone-
oxime)
• https://byjus.com/chemistry/nylon/ (nylon)
• https://www.graphicproducts.com/articles/what-is-hazop/ (what is HZOAP)
• http://ohiohistorycentral.org/w/East_Ohio_Gas_Company_Explosion (East Ohio Gas Company Explosion)
• https://www.bbc.com/news/uk-scotland-22840445 (piper alpha)
• https://www.firstpost.com/india/bhilai-steel-plant-6-killed-30-injured-after-gas-leak-1568573.html#:~:text=Si
x%20people%2C%20including%20two%20Deputy,district%20of%20Chhattisgarh%20on%20Thursday
. (Bhilai steel plant gas leak)
Thank you