SMALL CHANGES BRING MAJOR HEADACHES

At a plant producing intermediate organic synthesis compounds, a runaway reaction coupled with an explosion (approx. 1 kg of TNT equivalent) took place in the 3.5-m high glass column overlooking a 3,000- litre reactor. The explosion triggered a fire outbreak inside the unit. A 110-kg cloud of hydrochloric acid (HCl) hovered over the site before dispersing after a few minutes due to a favourable wind. The noise alerted the technical staff, who promptly placed the installation in safe operating mode and launched the internal emergency plan. The staff began to fight the fire using the resources at hand, and were then joined by fire-fighters who brought the blaze under control within twenty minutes. One employee sustained loss of hearing due to the explosion and property damage amounted to €700,000. 

On the day of the accident, a batch production had been underway involving the addition of 1,000 kg of a cold liquid ethylene compound along with 750 kg of a highly flammable and volatile silyl (hydrosilane). The homogeneous mix was then supposed to be poured into a 2nd reactor at 100°C in the presence of a catalyst to form the final product. The hydrosilylation reaction was maintained under control by gradually introducing the mix. However, in this incident, a sudden rise in mix temperature caused a pressure surge and a pneumatic burst of the column. The hydrosilane was hydrolyzed into HCl upon coming into contact with humid air and then decomposed into the hydrogen that triggered this fire. 

The investigation revealed that in order to compensate for the loss of catalyst activity (this was the seventh consecutive batch), which would have necessitated an extended batch time, a technician took the initiative to insert around 10g of new catalyst into the reactor at the same time as the raw materials. Data studies and laboratory tests actually indicated that the reaction could not have started in the low temperature reactor (5-20°C), since deviation from the temperature required for synthesis (at 90°C) appears to safeguard the reaction safety of this modification, i.e. now deemed to be minor. Nonetheless, the tests conducted by the operator following the accident revealed that at these temperatures, an exothermic hydrosilylation reaction could arise following an induction period lasting several hours in the presence of trace alcohol amounts. Since the catalyst had been placed in solution with a ketone, an infinitesimal quantity of ketone (in the order of 0.01%) was found in the mix inside the reactor and subsequently reduced to alcohol by the hydrosilane. Despite an extensive process of analysing reaction risks plus the synthesis of 36 batches without an accident in six years, the accident occurred on the only batch for which the process had been slightly modified. 

The operator reminded plant technicians that: 1. this modification should have been rated as significant and undergone an in-depth, collective analysis prior to implementation; and 2. any modification to a process must be justified and accompanied by compensatory safety measures.

Source:Aria database

DO YOU HAVE BACK UP POWER TO SAFETY CRITICAL EQUIPMENT?

A transformer caught on fire at 7:45 pm on a production building’s basement floor at a pharmaceutical plant. The building’s electrical power was cut, causing shutdown of the reactors’ stirring and cooling mechanisms. An exothermic reaction that was taking place at the time became uncontrollable. The reactor’s rupture disc, calibrated at 4 bar, broke, and the explosion vent opened to protect the structural integrity of the reactor. A quantity of the reaction mix at 70°C, composed of several hazardous products, projected onto one employee and six fire-fighters in the vicinity and formed a 60-m² puddle on the floor. 

The plant operator activated the internal emergency plan and the facility was evacuated. The safety report conducted on-site had not identified any comparable scenario. No backup source had been allocated to ensure the continued operations of critical equipment. Activities assigned to the damaged building and associated solvent storage zone were suspended until the safety systems (fire detection control, both post and automatic extinction) were once again operational. A diagnostic assessment of all site electrical installations was performed, along with a study, on the backup power supply for critical equipment, dedicated to exothermic reactions, i.e.: cooling, stirring, temperature and pressure probes.

Source:Aria database

LIGHTNING STRIKE DAMAGES CARD

A thunderstorm struck in the vicinity of a flammable liquid storage facility protected by an early streamer emission lightning rod. The indirect effects of the lightning damaged one of the 4 computer interface cards. This particular card had interfaced with the bus network responsible for relaying high-level safety alarms from the storage tanks. The facility operator detected the malfunction via the depot supervisor, who had indicated the communication breakdown. The operator did not possess a backup card and was unable to perform a quick replacement. He decided to inform the entire operating staff and requested extra vigilance when monitoring the performance sheets. Operations continued in this manner for 5 days before the interface card could actually be replaced. The damaged card had not been protected against indirect lightning effects. Following this accident, the operator kept on hand an additional card as a backup and implemented the recommendations issued in the study on indirect lightning effects conducted in April 2006. These recommendations focused on the protection, mainly by lightning rod, of the supervisor’s computer, alarm relay units, sensors, utility rooms, fire pumps serving 3 depots, and the electric generating sets for 2 sites.

 Source: Aria ACCIDENT ANALYSIS OF INDUSTRIAL AUTOMATION

AMMONIA RELEASE DUE TO LACK OF DIAGNOSING THE PROBLEM

 On a tubular exchanger, a disc broke over ¼ of its cross-section at 4:50 am during a pressure surge in the liquid ammonia (NH3 ) circuit connecting NH3 storage cells to a urea workshop operating under stable conditions. NH3 was partially led to a 100-m high degassing stack. Given stable weather conditions, a foul-smelling cloud drifted towards the city. The release occurred unbeknownst to control room operators, who had incorrectly interpreted several alarms that had tripped. Once the diagnosis rendered, the device was isolated at 6:25 am. The plant operator only became aware of the severity of the event at 8 am; two and a half hours were then needed to fully determine the origin and likely causes. The 10 tonnes of NH3 release was due to a succession of physical, organisational and human malfunctions: - Lack of anomaly detection and automatic safety systems: information made available to control room operators was inadequate; - Poor diagnosis / decision-making process lacking adequate verifications despite several precursors; - Incomplete safety recommendations, insufficient monitoring procedures and inspection plans. This poor diagnosis would explain the delay required to isolate the deficient circuit and the potential impact of this release. Long periods elapsed between the onset of the accident, the alarm and activation of the internal emergency plan, source identification, causes and circumstances of the discharge, and then a definitive quantification.

Source: Aria ACCIDENT ANALYSIS OF INDUSTRIAL AUTOMATION

DOMINO EFFECTS DUE TO POWER NON AVAILABILITY NOT CONSIDERED DURING DESIGN

 In a Seveso chemical plant, a fire broke out at 12:59 pm in a substation supplying a hydrazine hydrate unit. An electrical fault on a cooling water pump caused a generalised short circuit on an electrical tower. The fire alarm was triggered at 1.00 pm. The fire spread to the other towers of the panel through the subfloor. The 400 V circuit breaker located upstream was blocked and did not function. The fault current passed through the 13,000 / 400 V transformer, there was overpressure and an oil leak followed by a primary side homopolar fault causing the 13 kV circuit breaker to trip. The absence of voltage caused the diesel generator set to stop but the switchover to the emergency system failed as the automatism was damaged by the fire. The smoke spread to the UPS room whose door remained opened. The UPS stopped when a high temperature (> 40 °C) was reached causing the loss of control and command on the process. The component switched over to safety mode. Due to the lack of power supply, the cooling system, agitation and the internal and external emergency plan siren were no longer functional. Since the ongoing reaction was exothermic, the reactor temperature and pressure increased. Several measures are taken such as designing an emergency cooling circuit, improving circuit breaker maintenance, sectoring UPS system, electric boards, generator sets, etc.

Source: Aria ACCIDENT ANALYSIS OF INDUSTRIAL AUTOMATION