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Flixborough disaster

        By:


        Paradigma Carlo
        Giovanni
Introduction
• Largest peacetime explosion ever to occur in the UK
• Date: Saturday, 1 June 1974
• Location: Flixborough chemical plant owned by Nypro
  (UK) Ltd
• Deaths of 28 workers on the site
• Widespread damage to property within a 6 mile radius
  around the plant
• 1967: 20,000 TPA caprolactam plant built by DSM at the
  Flixborough site using process involving the hydrogenation
  of phenol
       C6H5OH + 2 H2 → (CH2)5CO

• 1972: 70,000 TPA ; new process used

• New process based on oxidation of cyclohexane

• Posed much greater hazard than phenol process
Description of the cyclohexane
                 process
• Process operates by injecting compressed air into
  liquid cyclohexane at a working pressure of about 9
  bar and temperature of 155°C
• Cyclohexanone and cyclohexanol produced
• Conversion is low and it is necessary to recirculate
  the cyclohexane continuously through a train of six
  large SS-lined reactors
C6H12 + O2 → (CH2)5CO + H2O
Cyclohexane   Cyclohexanone




Caprolactum                   Nylon6
Simplified flow diagram of cyclohexane oxidation plant
       before March 1974 (Whittingham, 2005)
Events leading to the accident
2.   Miners overtime ban of Nov, 1973

•    Resulted in the government passing legislation to restrict
     the use of electricity by industry to 3 days a week

•    Was not possible to operate the process on this basis

•    Was decided to utilize existing emergency power
     generation on-site
• Major electricity user: 6 stirrers in the cyclohexane
  reactors

• Primary purpose: disperse compressed air that was
  injected into each reactor via a sparger

• Also ensured that droplets of water formed within
  the reactor system were dispersed into the
  cyclohexane
1. The No. 5 reactor problem

•   Jan, 1974:normal electricity supply resumed

•   Was found that the drive mechanism for the stirrer
    in the No. 4 reactor had been subject to severe
    mechanical damage

•   No reason was found for this. It was therefore
    decided to continue to operate the plant with the
    No. 4 reactor stirrer shutdown.
• Cyclohexane reactors were MS vessels fitted with an
  inner SS lining to resist corrosion

• March,1974: Cyclohexane found leaking from 6 feet
  long vertical crack in the MS shell of the No. 5 reactor

• Due to technical problems experienced earlier and the
  effects of the 3-day week, the plant owners were keen
  to make up lost production

• Therefore decided to remove No. 5 reactor for
  inspection and continue operation with the remaining
  five reactors
1. Installation of 20” bypass pipe

•   This pipe connected together the existing 28 inch
    bellows on the outlet of reactor No. 4 and the inlet of
    reactor No. 6

•   Dog-leg shape of pipe

•   Company did not have qualified mechanical engineer
    on site to oversee design and construction

•   No hydraulic pressure testing of pipe carried out,
    except for a leakage test using compressed air.
Simplified flow diagram of cyclohexane oxidation plant
        after March 1974 (Whittingham, 2005)
1. Resumption of production
•   Plant restarted and operated normally, with occasional
    stoppages, up until the afternoon of Saturday, 1 June 1974

•   Previous day: plant had been shut down for minor repairs

•   Early hours of 1 June: plant in process of being restarted

•   Start-up involved charging system with liquid cyclohexane to
    normal level and then recirculating this liquid through a heat
    exchanger to raise the temperature.
• The pressure in the system was maintained with nitrogen
  at about 4 bar until the heating process began to raise the
  pressure due to evaporation of cyclohexane.

• The pressure was then allowed to rise to about 8 or 9 bar,
  venting off nitrogen to relieve any excess pressure. The
  temperature in the reactors by then was about 150°C.
• On 1 June this procedure was followed except it was noted
  by the morning shift that by 06.00 hours the pressure had
  reached 8.5 bar even though the temperature in the No. 1
  reactor had only reached 110°C

• Was not realized at the time that this discrepancy might
  have indicated the presence of water in the system

• The start-up continued until, at about 16.50 hours, a shift
  chemist working in the laboratory close to the reactors
  heard the sound of escaping gas and saw a haze typically
  associated with a hydrocarbon vapour cloud.
The accident
• 16.53 hours on 1 June 1974: massive aerial explosion
  occurred with a force later estimated to be about 15 to
  45 tonnes of TNT equivalent
• Explosion heard up to 30 miles away and damage
  sustained to property over a radius of about 6 miles
  around the plant
• 28 plant workers killed with no survivors from the
  control room
• All records and charts for the start-up destroyed
• Following the explosion, 20 inch bypass assembly was
  found in a ruptured condition
The Public Inquiry
•   Following the disaster, public inquiry
    conducted under the chairmanship of Roger
    Parker QC
•   To establish the causes and circumstances of
    the disaster
•   To identify lessons to be learnt from the
    disaster
Conclusions of the inquiry
• The immediate cause of the main explosion
  was the rupture of the 20 inch bypass
  assembly between the No. 4 and No. 6 reactor
• Two main theories to explain
The 20 inch pipe theory
• The 20 inch bypass assembly failed due to its
  unsatisfactory design features
• However, the assembly had survived 2 months of
  normal operation.
• A number of independent pressure tests were
  commissioned to determine unusual conditions
• The normal working pressure = 8 bar
• practice during start-up to allow the pressure to
  build up to about 9 bar.
• The safety valves for the system, were set to
  discharge at a pressure of 11 bar
• At pressure above 11 bar, squirming motion
  which distorted the bellows.
• Even when the assembly squirmed, no rupture
  until pressure crossed 14.5 bar, a pressure not
  achievable in reactors.
• Inquiry concluded that a rupture of the 20 inch
  bypass due to pressure, temperature conditions
• Report conceded ambiguity in the hypothesis
• Simulation tests could not replicate failure at
  similar conditions
The 8 inch hypothesis
• Alternative theory
• 50 inch split in an 8 inch line connected to
  separator below bypass
• this failure led to a smaller explosion causing
  failure of the main 20 inch bypass
• Zinc embrittlement had caused the split
• Small lagging fire at a leaking flange causing zinc
  to drip onto the 8 inch pipe
• Brittle failure – Vapour release – Explosion – 20
  inch failure
• Inquiry Report had devoted discussion of this
  two-stage theory
• Finally dismissed as being too improbable
• No other theories considered by them to explain
  failure of 20 inch bypass pipe
The water theory
• Another alternative theory
• Not considered by the Inquiry
• Much of scientific work after Inquiry closed
• Examined the effects of not operating the No. 4
  reactor stirrer during the start-up at a time when
  water may be present
• More probable explanation
• Cyclohexane and water are normally immiscible
• Azeotrope forms due to the limited solubility of
  water in cyclohexane.
• This azeotrope has lower boiling point than
  either water or cyclohexane
• Unstable interfacial layer may form
• Under certain conditions can boil and erupt
  violently ejecting cyclohexane and superheated
  water from the reactor.
• Normally impossible for water layer to form due to
  dispersion of water by air distribution
• During start-up, the air to the reactors shut off
• If stirrers running during start-up, no water layer
• If stirrer stops, a layer of water could form, together
  with the unstable azeotrope.
• As temperature of reactor increases, boiling
  point of azeotrope is reached
• Possibility of a sudden violent eruption from the
  reactor and ejection of slugs of liquid reactant
• Slugs exert high mechanical forces on the bypass
  assembly, loosely supported by scaffolding
• Causes bypass assembly to fail without the high
  static pressure in the reactors
Alternative event sequence
• Most credible explanation
• Explains failure of 20 inch bypass
• Also provides an explanation for the whole
  sequence of events
• Unexplained failure of drive mechanism of No. 4
  reactor
• Crack developing in the lining and shell of No.
  5 reactor
• Failure of the 20 inch bypass assembly.
• Any/all failures caused by violent eruption of
  reactor contents due to presence of water
• Committee failed to see common thread
• Drive mechanism failure for No. 4 reactor
  unexplained
• Thought to be irrelevant
• Crack in the shell of the No. 5 reactor due to
  stress corrosion
• Proposed by plant owners but not credible
• The failure of the bypass concluded by Inquiry
  due to reactors being over-pressurized
• Implies human error, not verifiable
• Greatest failing of Inquiry was not taking
  account of all the events 6 months prior to the
  disaster
• Issue of non-operation of the reactor stirrers
  ignored
Conclusions
•  Human error analysis
  Table gives causes against the different types of
  error that occurred.
• Direct cause
  Failure of the 20 inch bypass pipe led to huge
  release of inflammable cyclohexane vapour
  which ignited
• Root causes
  A badly designed 20 inch bypass pipe installed
  rather than finding reasons for the crack in the
  No. 5 reactor
  Why bypass failed ?
(Whittingham, 2005)
Safety considerations
• Learnings
• Low inventory especially of flashing fluids
• Before modifying process, carry out systematic
  search for possible cause of problem
• Carry out HAZOP analysis
• Construct modifications to same standard as
  original plant
• Use blast-resistant control rooms and buildings
THANK YOU

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Flixborough disaster

  • 1. Flixborough disaster By: Paradigma Carlo Giovanni
  • 2. Introduction • Largest peacetime explosion ever to occur in the UK • Date: Saturday, 1 June 1974 • Location: Flixborough chemical plant owned by Nypro (UK) Ltd • Deaths of 28 workers on the site • Widespread damage to property within a 6 mile radius around the plant
  • 3. • 1967: 20,000 TPA caprolactam plant built by DSM at the Flixborough site using process involving the hydrogenation of phenol C6H5OH + 2 H2 → (CH2)5CO • 1972: 70,000 TPA ; new process used • New process based on oxidation of cyclohexane • Posed much greater hazard than phenol process
  • 4. Description of the cyclohexane process • Process operates by injecting compressed air into liquid cyclohexane at a working pressure of about 9 bar and temperature of 155°C • Cyclohexanone and cyclohexanol produced • Conversion is low and it is necessary to recirculate the cyclohexane continuously through a train of six large SS-lined reactors
  • 5. C6H12 + O2 → (CH2)5CO + H2O Cyclohexane Cyclohexanone Caprolactum Nylon6
  • 6. Simplified flow diagram of cyclohexane oxidation plant before March 1974 (Whittingham, 2005)
  • 7. Events leading to the accident 2. Miners overtime ban of Nov, 1973 • Resulted in the government passing legislation to restrict the use of electricity by industry to 3 days a week • Was not possible to operate the process on this basis • Was decided to utilize existing emergency power generation on-site
  • 8. • Major electricity user: 6 stirrers in the cyclohexane reactors • Primary purpose: disperse compressed air that was injected into each reactor via a sparger • Also ensured that droplets of water formed within the reactor system were dispersed into the cyclohexane
  • 9. 1. The No. 5 reactor problem • Jan, 1974:normal electricity supply resumed • Was found that the drive mechanism for the stirrer in the No. 4 reactor had been subject to severe mechanical damage • No reason was found for this. It was therefore decided to continue to operate the plant with the No. 4 reactor stirrer shutdown.
  • 10. • Cyclohexane reactors were MS vessels fitted with an inner SS lining to resist corrosion • March,1974: Cyclohexane found leaking from 6 feet long vertical crack in the MS shell of the No. 5 reactor • Due to technical problems experienced earlier and the effects of the 3-day week, the plant owners were keen to make up lost production • Therefore decided to remove No. 5 reactor for inspection and continue operation with the remaining five reactors
  • 11. 1. Installation of 20” bypass pipe • This pipe connected together the existing 28 inch bellows on the outlet of reactor No. 4 and the inlet of reactor No. 6 • Dog-leg shape of pipe • Company did not have qualified mechanical engineer on site to oversee design and construction • No hydraulic pressure testing of pipe carried out, except for a leakage test using compressed air.
  • 12. Simplified flow diagram of cyclohexane oxidation plant after March 1974 (Whittingham, 2005)
  • 13. 1. Resumption of production • Plant restarted and operated normally, with occasional stoppages, up until the afternoon of Saturday, 1 June 1974 • Previous day: plant had been shut down for minor repairs • Early hours of 1 June: plant in process of being restarted • Start-up involved charging system with liquid cyclohexane to normal level and then recirculating this liquid through a heat exchanger to raise the temperature.
  • 14. • The pressure in the system was maintained with nitrogen at about 4 bar until the heating process began to raise the pressure due to evaporation of cyclohexane. • The pressure was then allowed to rise to about 8 or 9 bar, venting off nitrogen to relieve any excess pressure. The temperature in the reactors by then was about 150°C.
  • 15. • On 1 June this procedure was followed except it was noted by the morning shift that by 06.00 hours the pressure had reached 8.5 bar even though the temperature in the No. 1 reactor had only reached 110°C • Was not realized at the time that this discrepancy might have indicated the presence of water in the system • The start-up continued until, at about 16.50 hours, a shift chemist working in the laboratory close to the reactors heard the sound of escaping gas and saw a haze typically associated with a hydrocarbon vapour cloud.
  • 16. The accident • 16.53 hours on 1 June 1974: massive aerial explosion occurred with a force later estimated to be about 15 to 45 tonnes of TNT equivalent • Explosion heard up to 30 miles away and damage sustained to property over a radius of about 6 miles around the plant • 28 plant workers killed with no survivors from the control room • All records and charts for the start-up destroyed • Following the explosion, 20 inch bypass assembly was found in a ruptured condition
  • 17. The Public Inquiry • Following the disaster, public inquiry conducted under the chairmanship of Roger Parker QC • To establish the causes and circumstances of the disaster • To identify lessons to be learnt from the disaster
  • 18. Conclusions of the inquiry • The immediate cause of the main explosion was the rupture of the 20 inch bypass assembly between the No. 4 and No. 6 reactor • Two main theories to explain
  • 19. The 20 inch pipe theory • The 20 inch bypass assembly failed due to its unsatisfactory design features • However, the assembly had survived 2 months of normal operation. • A number of independent pressure tests were commissioned to determine unusual conditions
  • 20. • The normal working pressure = 8 bar • practice during start-up to allow the pressure to build up to about 9 bar. • The safety valves for the system, were set to discharge at a pressure of 11 bar • At pressure above 11 bar, squirming motion which distorted the bellows.
  • 21. • Even when the assembly squirmed, no rupture until pressure crossed 14.5 bar, a pressure not achievable in reactors. • Inquiry concluded that a rupture of the 20 inch bypass due to pressure, temperature conditions • Report conceded ambiguity in the hypothesis • Simulation tests could not replicate failure at similar conditions
  • 22. The 8 inch hypothesis • Alternative theory • 50 inch split in an 8 inch line connected to separator below bypass • this failure led to a smaller explosion causing failure of the main 20 inch bypass • Zinc embrittlement had caused the split • Small lagging fire at a leaking flange causing zinc to drip onto the 8 inch pipe • Brittle failure – Vapour release – Explosion – 20 inch failure
  • 23. • Inquiry Report had devoted discussion of this two-stage theory • Finally dismissed as being too improbable • No other theories considered by them to explain failure of 20 inch bypass pipe
  • 24. The water theory • Another alternative theory • Not considered by the Inquiry • Much of scientific work after Inquiry closed • Examined the effects of not operating the No. 4 reactor stirrer during the start-up at a time when water may be present • More probable explanation
  • 25. • Cyclohexane and water are normally immiscible • Azeotrope forms due to the limited solubility of water in cyclohexane. • This azeotrope has lower boiling point than either water or cyclohexane • Unstable interfacial layer may form • Under certain conditions can boil and erupt violently ejecting cyclohexane and superheated water from the reactor.
  • 26. • Normally impossible for water layer to form due to dispersion of water by air distribution • During start-up, the air to the reactors shut off • If stirrers running during start-up, no water layer • If stirrer stops, a layer of water could form, together with the unstable azeotrope.
  • 27. • As temperature of reactor increases, boiling point of azeotrope is reached • Possibility of a sudden violent eruption from the reactor and ejection of slugs of liquid reactant • Slugs exert high mechanical forces on the bypass assembly, loosely supported by scaffolding • Causes bypass assembly to fail without the high static pressure in the reactors
  • 28. Alternative event sequence • Most credible explanation • Explains failure of 20 inch bypass • Also provides an explanation for the whole sequence of events
  • 29. • Unexplained failure of drive mechanism of No. 4 reactor • Crack developing in the lining and shell of No. 5 reactor • Failure of the 20 inch bypass assembly. • Any/all failures caused by violent eruption of reactor contents due to presence of water • Committee failed to see common thread
  • 30. • Drive mechanism failure for No. 4 reactor unexplained • Thought to be irrelevant • Crack in the shell of the No. 5 reactor due to stress corrosion • Proposed by plant owners but not credible
  • 31. • The failure of the bypass concluded by Inquiry due to reactors being over-pressurized • Implies human error, not verifiable • Greatest failing of Inquiry was not taking account of all the events 6 months prior to the disaster • Issue of non-operation of the reactor stirrers ignored
  • 32. Conclusions • Human error analysis Table gives causes against the different types of error that occurred. • Direct cause Failure of the 20 inch bypass pipe led to huge release of inflammable cyclohexane vapour which ignited • Root causes A badly designed 20 inch bypass pipe installed rather than finding reasons for the crack in the No. 5 reactor Why bypass failed ?
  • 34. Safety considerations • Learnings • Low inventory especially of flashing fluids • Before modifying process, carry out systematic search for possible cause of problem • Carry out HAZOP analysis • Construct modifications to same standard as original plant • Use blast-resistant control rooms and buildings