Lessons from Flixborough

Lessons from
Flixborough
E-learning module
S. EGAN, HSE/PTS

Contents
• Chronology
• Description of accident
• Chemistry
• Process
• Installation
• Technical explanation
• Lessons
• Summary

1
Chronology
• 1967 Cyclohexanone production from phenol
• 1972 Cyclohexanone production from cyclohexane
• 1974 March 27th: leak on Reactor N° 5
• 1974 April: temporary by-pass
• 1974 June 1st: vapour cloud explosion kills 30 people

Description of accident
• Leak of about 50 metric tons of cyclohexane
• Formation of a cloud of cyclohexane vapor
• Explosion of vapor cloud
• Collapse of control room killing 18 people
• 10 other people died on site
• 1800 buildings within 3 mile radius were damaged
• Fire burnt for ten days
• Property damage estimated at $ 425 M

2
Chemistry
• Main reaction 1

Chemistry
• Main reaction 2

3
Chemistry
• At least twenty side reactions:
• Hydroperoxycyclohexane + oxygen (faster than cyclohexane + oxygen)
• Cyclohexanone + oxygen (faster than cyclohexane + oxygen)
• Formation of formic acid (corrosive)

• Problems:
• Need high ratio of cyclohexane to hydroperoxycyclohexane/cyclohexanone
• Reaction mixture is about 95 % cyclohexane + 5 % wanted products
• Big inventory of cyclohexane at 155 °C (boiling point of 80 °C)
• Water and formic acid cause corrosion

Installation
• Six reactors in series: carbon steel + stainless cladding

28 INCH CONNECTING LINE WITH EXPANSION BELLOWS

CRACK IN VESSEL WALL

4
Installation
• By-pass of reactor 5

20 INCH CONNECTING LINE WITH 2 BENDS AND EXPANSION BELLOWS

Technical explanation

1. Corrosion
• Nypro used a “wet process”
• Too much water and formic acid left in the recycle stream
• These impurities caused internal corrosion
• Water sprayed onto the leak contained impurities (nitrates etc.)
• These impurities caused external corrosion

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5
Technical explanation
2. Temporary by-pass
• No drawing or stress calculations on 20 inch by-pass line
• Shape of line drawn with on workshop floor
• Supported by scaffolding
• Vibration and mechanical stresses caused rupture of line

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Technical explanation
3. Formation of vapour cloud
• Release of about 50 tons of cyclohexane at 155 °C
• Atmospheric boiling boiling point of cylcohexane = 80 °C
• Cyclohexane vaporised
• A cloud of cyclohexane vapour formed

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6
Technical explanation
4. Vapor cloud explosion
• Cyclohexane AIT = 244 °C
• No immediate ignition source
• Vapor cloud formed inside explosivity limits 1.0 % to 8.0 % v/v
• Ignited by the hot furnace of the nearby hydrogen plant
• Blast flattened the control room
• Heard up to 30 miles away in Grimsby and Hull.
• Equivalent to 35 tons of TNT
• Certain experts consider that a “detonation” occurred

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Lessons
1. Chemistry:
• Impurities matter
• Water and formic acid in the cyclohexane – internal corrosion
• Nitrates in the water – external corrosion
• Side-reactions affect process safety
• Formation of water and formic acid – internal corrosion
• Oxidation of the wanted product faster than of cyclohexane: large inventory

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7
Lessons
2. Human and Organizational Factors
• Management of change
• The installation of the by-pass was not seen as a major change
• The effects of vibrations and stresses on the by-pass were not examined
• The engineers did not realize detailed design calculations were needed
• T. KLETZ : “They did not know what they did not know”.

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Summary
• Root causes
• The process used was not compatible with the materials of construction
• Corrosion led to 2 m long crack on reactor N° 5
• A temporary by-pass line was installed without the necessary study
• Failure of the by-pass released 50 tons of cyclohexane
• The cyclohexane formed a vapour cloud which exploded
• 28 people died and 36 were injured out of 72 on the site

• Main lessons
• Process chemistry and materials suitabililty
• Management Of Change (MOC)

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