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0260-9576=03=$17.63 C 0.00 # Institution of Chemical Engineers 2003

A re whilst charging a batch reactor

Tony Fishwick

Summary
Diethyl oxalate was manufactured in a batch process by charging a reactor with ethanol and cyclohexane, then, whilst stirring, adding oxalic acid from polypropylene sacks. This had been done many times over a period of years without incident. However, on this occasion an ignition occurred while the contents of a sack were being charged and ames erupted from the reactor. Although no major items of plant were damaged, the operator was burned about the face, arms and chest. He was treated in hospital but discharged on the same day.

temperature. The stirrer and dust extraction system had been switched on and oxalic acid charging had commenced in the standard manner. About two-thirds of the prescribed amount of oxalic acid had been added and the nal contents of a bag were being shaken into the reactor when ignition occurred. Flames erupted from the manway and burnt the operator. The ames quickly died back into the reactor and were readily extinguished by closing the manway cover. There was no damage to the reactor or its immediate ancillaries, but the exible hose and ducting of the ventilation system were broken.

Description of the incident

The process was an esterication, carried out in a stainless steel reactor equipped with a paddle stirrer, charging port=manway and associated equipment and process pipework. During charging of the oxalic acid, a stainless steel hood connected to a dust extractor system was tted to the manway (see Figure 1). Following completion of the previous batch, ethanol and cyclohexane had been charged at ambient

Investigation of the incident

The following relevant points were established: The ethanol=cyclohexane mixture would form a ammable vapour in the space above the liquid in the reactor, ash points of ethanol and cyclohexane being 12 C and 17 C respectively. The temperature of the contents at the time of the incident was estimated to be 1520 C. The 1% lower explosive limit boundaries were 300 mm below the rim of the manway with the extraction system on, and 300 mm outside the manway with the system off. All electrical equipment was in good working order and earth bonding on the reactor and associated equipment was satisfactory. The oxalic acid used was of two distinct physical typeseither damp, crystalline and clinging or dry, ne and free owing. Various electrical measurements were made as follows: resistance between reactor and metal ooring was zero ohms; resistance to earth of an operator wearing the shoes as in the incident was within the acceptable range for antistatic footwear; vigorous shaking of an empty oxalic acid bag by an operator wearing the same gloves and footwear as in the incident produced a maximum charge transfer of 60 nC between the inner plastic liner of the bag and the detector probe; emptying a full bag of normal moist oxalic acid produced a maximum charge transfer of C 40 nC

FIGURE 1: TRADITIONAL CHARGING METHOD

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from the bag, and only 10 nC from the powder itself; emptying a full bag of dry oxalic acid produced a maximum charge transfer of C 200 nC from the bag, and only 120 nC from the powder. Attempts to simulate a dust explosion using dry oxalic acid were unsuccessful. A charge transfer value of 75 nC is normally considered hazardous. The only operation to produce a charge in excess of this value was emptying a full bag of dry oxalic acid powder. NB: The unit nC is a nano Coulomb, i.e. 1 10 9 Coulombs. A Coulomb is the electric charge which passes a given point when 1 amp of current ows for 1 second.

when not in good electrical contact with the manway rim, a possibility but not a strong one. the plastic sack of oxalic acidcharge transfer values well in excess of the non-hazardous value of 75 nC were measured, the strongest possibility. Thus, the most likely sequence of events was ignition caused by electrostatic discharge from the plastic bag to either the reactor or its stirrer. Ignition of the ammable vapours in the reactor would then cause the eruption of ame through the manway and into the dust extraction system.

Discussion
Possible sources of fuel for the re were ethanol= cyclohexane vapour in the reactor and (much less likely) oxalic acid dust in the ventilation system. The most likely source of ignition was considered to be electrostatic discharge. Possible charge collectors for subsequent discharge were: PVC ducting on the extract systemthis had low capacity, high surface resistance and was electrically isolated from the reactor, therefore unlikely. the operatorfootwear was anti-static, therefore unlikely. the manway extraction hoodthis was not positively attached to the manway and was electrically isolated from the extract system, but it could conceivably accumulate electrical charge from oxalic acid particles

Modications made to prevent a recurrence

A screw conveyor was installed so that bag opening and emptying is carried out remotely from the reactor. The powder is tipped into a hopper, which feeds the conveyor. The hopper and conveyor are earthed so that any charge on the powder or bag is discharged remote from any ammable mixture. This also enables the operator to work away from the ammable zone. The new arrangement is shown in Figure 2. All operators were issued with antistatic footwear. The manway extraction hood is positively earthed. The dust extraction system is connected to the manway hood and the conveyor feed hopper. Tests show that it is not possible to form ammable mixtures in the conveyor itself.

FIGURE 2: MODIFIED CHARGING METHOD

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Authors note on toxicity of oxalic acid

No mention was made of the operator being required to wear any protective clothing to guard against the toxic effects of oxalic acid. Apart from acute effects, such as vomiting, collapse and even death by ingestion of a large quantity (highly unlikely in this case), there can be quite signicant chronic effects due to regular exposure to smaller amounts. These can be due to either inhalation or by subcutaneous means, and can include eye and respiratory tract irritation, weight loss, general weakness and nervous system complaints such as loss of sensation at nger ends and other extremities. The effect of oxalic acid is to remove calcium from the blood. Respiratory protection and=or absolute dust extraction are generally recommended for operations involving the manual handling of large quantities1 . There have even been

reported cases of `heroic consumers of rhubarb, which contains oxalic acid, suffering such effects!!

Reference
1. N. I. Sax, Dangerous Properties of Industrial Materials, 8th edn. Van Nostrand Reinhold, New York, USA, 1992.

LEARNING FROM THE PAST The Accident Database contains: 22 records of res that occurred during reactor charging.

An uncontrollable reaction
During the rst full-scale operation of a new polymerization process the reaction became uncontrollable, pressure built up in the reaction vessel faster than the ability of the vent line to dissipate it and a lid joint and the stirrer gland packing eventually gave way discharging ammable, mildly toxic, vapour into the process building and its immediate surrounding. The building, which was equipped to ameproof standards, was quickly evacuated, the re brigade was called and the emergency procedure was carried out. No persons were injured, no re resulted from the incident, the vapours were damped down with `high pressure fog by the Fire Brigade and the situation was rapidly brought under control. Although suitable breathing apparatus was used, four of the remen were slightly affected by the nauseous smell of the vapour by which they had been affected before donning the breathing apparatus. the reaction rate was slower than the addition rate of monomer leading to a concentration of unreacted monomer which eventually reacted at a rate beyond the control capabilities of the plant.

Prevention precautions
It is clear that a HAZOP would have laid down the operating parameters of the process and warned the plant technicians of the instability of the initiator. The incident caused the company to speed up the introduction of a system of control on all new processes or plant and on all modications of process or plant to ensure that full HAZOP studies are carried out before implementation. The reaction vessels will be modied to afford safer dissipation of any such uncontrolled reaction by using larger vents and a surge tank to contain vapours or liquids. The emergency procedures will be modied in co-operation with the local emergency services to improve the effectiveness of the actions. Included in the modied procedure is a system of trafc control on the arrival of emergency vehicles and a system to cordon off areas where vapours may affect personnel.

Cause
The incident occurred because the thermally unstable initiator had been charged to the vessel, heated to reaction temperature and then a delay of one hour ensued before the monomer addition was started. The subsequent reduction in the effectiveness of the initiator meant that

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