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00 Institution of Chemical Engineers 2005

Carbon bed adsorbers: An overview of incidents and measures for safe operation
Dr Helen James Health and Safety Executive, Hazardous Installations Directorate, Bootle, UK

Introduction
Carbon bed adsorbers are being used increasingly to remove, and sometimes recover, volatile organic compounds (VOCs) from effluent streams, off-gases and tank venting. Units range from small disposable drums to large multi-bed systems with airflow capacities in excess of 100,000 m3 h1. Carbon is a very good thermal insulator, so heat losses in an adsorber bed can be low enough to approach adiabatic conditions. As a result, the bed temperature can rise very quickly if a hot spot is formed. If there is sufficient airflow and remedial action is not taken sufficiently quickly, a hot spot can be fanned into a fire.

Failure of reactor cooling had led to more methanol building up in the adsorber than usual. The fire occurred when an air intake was opened.

The grade of carbon is changed and the new grade has a lower thermal stability
Example 2:
A carbon bed adsorber was severely damaged by a fire that was attributed to the change of use to wood-based carbon and prolonged steaming because of plant problems. The fire occurred when cooling air was introduced to the bed. There was no solvent on the bed at the time: the exotherm was entirely due to the fresh carbonthe new grade of carbon had a lower thermal stability than the coal-based carbon used previously.

Incident history
The Health & Safety Executive (HSE) has received reports, worldwide, of a number of serious incidents involving fires and explosions in carbon bed adsorbers, mainly located in chemical and petrochemical plants. These amount to about one serious incident per year over the past twenty years. This in itself does not give undue cause for concern. However, there is significant anecdotal evidence of fires that have not been reported to HSE1, some no doubt because the incident did not fall within the scope of the reporting regulations (for example if there were no reportable injuries and the plant was able to re-start normal production within 24 hours). These unreported incidents have become more common over the last few years. The following are typical factors involved in incidents.

Introduction of air into the adsorber, for example on start-up, fans a hot spot into a fire
Example:
A carbon bed adsorber unit used for acetone recovery had been routinely shut down for the weekend. When it was restarted, it was immediately apparent that one of the three beds was very hot. The plant was put out of action for approximately 36 hours. No one was injured.

The adsorber is overloaded with effluent vapour, leading to the formation of hot spots
Example:
A fire occurred in a carbon bed adsorber used for scrubbing venting gases from a process plant.

Hot particles from a carbon bed adsorber ignite flammable vapours

Example 3:
Drums of activated carbon were used for deodorizing emissions from tanks of crude sulphate turpentine. The system design permitted backflow of air through the drums. Exothermic activity in the bed led to a fire that ignited flammable

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vapours in the headspaces of the tanks. The fire and explosion burned for three days and damaged other storage tanks, resulting in the release of toxic gases. Over 2,000 residents were forced to evacuate. This incident occurred in the USA in 1995. It is also worth mentioning that the atmosphere in a sealed vessel containing activated carbon can become oxygen depleted. This led to the deaths of two workers in a water filtration tank in Australia in the mid-1990s.

Safe operation: measures to consider Small-scale thermal stability testing

Various small-scale tests have been used to attempt to quantify the onset temperature for exothermic activity and specify maximum safe operating temperatures. Although not essential for safe operation, this information can help to reduce the likelihood of hot spot formation and bed fires. Suitably competent personnel who take care to ensure that the tests accurately model plant conditions, including likely airflows, must carry out small-scale tests. Great care and expertise is needed to analyse the results and apply suitable scale-up factors in order to apply the results meaningfully to plant conditions. Carbon suppliers sometimes quote carbon ignition temperatures as measured in the ASTM test4. These test results should only be used for comparative purposes, as they do not indicate the temperature at which ignition will occur under operating conditions. This is because the test is highly non-adiabatic (the sample size is only 35 ml). This is stated in the standard, but is often overlooked.

sensitive than temperature monitoring and can detect the onset of combustion during its very early stages. However, CO monitoring is more expensive and is not often used in practice. CO monitors may need to be used off-line because the CO concentration during the early stages of hot spot growth may be too low when measured on-line. Infra-red-type monitors are more reliable than pellister-based ones because materials such as silicones, organo-lead compounds, halogenated hydrocarbon, and materials containing sulphur can poison the latter. Some substances, such as formic acid, can give false readings because they decompose to give carbon monoxide. In practice, carbon bed adsorbers are often not provided with means for hot spot detection. Suppliers may consider that the risk of hot spot formation is sufficiently low not to fit detection, based on their assessment of the application and, in particular, the type of VOC adsorbed (for example, hydrocarbons and alcohols tend to be regarded as low risk). The author would be interested to hear of fires that have occurred in these cases. Alarms and monitors should be tested and calibrated at suitable intervals and properly maintained. In addition to CO or temperature monitoring, the exterior of the adsorber unit should be visually checked at least daily for signs of overheating.

Mitigation systems for hot spots and fires

Advice on dealing with hot spots is given in guidance5 produced by the Energy Institute (formerly the Institute of Petroleum). Strictly, this applies only to vacuum swing desorption units handling gasoline. However, it contains useful advice that can be applied to other systems, in particular on action temperatures for: increased frequency of temperature monitoring; isolating the inlet from the process; and use of mitigation systems such as water flooding.

Location of new units

It is important to take the fire risk into account when positioning new units. Carbon beds should preferably be located outdoors in an easily accessible position. The area around the bed should be kept free of hazardous substances and flammable or combustible materials such as packaging and wooden pallets.

Detection of hot spots

Differential temperature monitoring using probes on the inlet and outlet can provide an indication of hot spot formation. Hot spots can also be detected by carbon monoxide (CO) monitoring on the bed outlet. This is much more

Operating personnel should be provided with suitable training and written instructions to assist with remedial action in the event of a fire. Logic diagrams can be useful here. If a hot spot or fire is detected, any lagging around the carbon bed should be removed, if it is safe and practicable to do so. This will help the bed to cool down faster. The bed should not be opened up because this can introduce oxygen that will fuel the combustion. As with means of hot spot detection, suppliers often do not provide carbon bed adsorbers with hot spot mitigation systems. Again, the author would be interested to hear of incidents that have occurred in these cases. Flooding with water or nitrogen are the most common methods for dealing with a bed fire. Flooding

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with water is preferable because it can effectively stop the combustion reaction and also dissipate the heat. An action temperature of 150C is suggested in the Energy Institute guidance5. To minimize pressure build-up resulting from steam generation, water should be added in a controlled manner and the outlet valve should be fully open during water flooding. So far these measures appear to have been sufficient to prevent damaging overpressures. Eventual flooding of the bed will quench the hot spots. The adsorber should be left, typically for at least 24 hours after flooding with water, before any further remedial action is taken. Hydrogen and carbon monoxide can be formed by the water gas reaction between steam and carbon above approximately 1000C. However, to date it appears that no incidents have been attributed to this mechanism.

How are hot spots detected? Have there been any previous incidents involving hot spots or fires in this type of application? What mitigation systems are provided? What criteria are used for their initiation? For example, there may be water deluge or nitrogen flooding systems in place. What information and training have operators received on how to deal with a hot spot or bed fire?

Acknowledgements
The author would like to thank Drs Andrew Fowler and Ralph Rowlands of HSE who carried out earlier work on carbon bed adsorbers, Mark Hoyle of AstraZeneca in Macclesfield, and Aidan Foley of Macfarlan-Smith in Edinburgh for their help and advice.

Risk assessment
The Dangerous Substances and Explosive Atmospheres Regulations 2002 (DSEAR)6 require a detailed assessment of fire and explosion risks. The carbon bed adsorber should be included in the risk assessment of the plant and process. Care should be taken to include the effects of nearby plant and operations, particularly where flammable, combustible or toxic materials are involved. The scope should include consideration of measures to minimize the formation of hot spots and fires, and to mitigate the consequences should a hot spot or fire occur. One of the key factors affecting the control measures needed is the type of VOCs adsorbed. The following list contains some questions that can be used to help compile the risk assessment: Are any of the components in the incoming air-stream flammable? If so, what is the flammable range of the mixture at the operating temperature? Bear in mind that flammable limits tend to widen as the ambient temperature increases. How is the percentage of flammables controlled to prevent a flammable atmosphere? Usually the concentration of flammables should not exceed 25% of the lower flammable limit of the mixture. Further information on vent collection systems can be found in Ref 7. Is the exterior of the unit visually checked at least daily? Is the unit located outdoors? It should be in an easily accessible area, well away from flammable or combustible materials? What VOCs are adsorbed? How do they affect the thermal stability of the carbon? How critical is the grade of carbon used in preventing the formation of hot spots? If a new grade or supplier is used, there may be significant differences in the thermal stability between grades. This should be subject to the usual plant change procedures.

References
1. Further information on the Reporting of Injuries, Diseases and Dangerous Occurrences Regulations 1995 is given in RIDDOR explained, downloadable from the HSE Books website at http://www.hse.gov.uk/pubns/hse31.pdf and A guide to the Reporting of Injuries, Diseases and Dangerous Occurrences Regulations 1995, reference L73, HSE, 1999, 7.95, obtainable from HSE Books http://www.hsebooks.com/Books/default.asp 2. Carbon bed adsorber fire, GR Astbury, Loss Prevention Bulletin 134, pp. 79. 3. Hazard Information Bulletin: fire hazard from carbon adsorption deodorizing systems, OSHA, http://www.osha.gov/dts/hib/hib_data/hib199707 30.html 4. Standard test method for ignition temperature of granular activated carbon, ASTM D 346676, 1988. 5. Vapour recovery unitsguidance on preventing and controlling temperature excursions in carbon beds, Energy Institute (formerly Institute of Petroleum), January 2001, 47.00, http://ein.powerweb.co.uk/ dbtw-wpd/exec/dbtwpub.dll 6. Further information on DSEAR is given in Fire and explosionhow safe is your workplace? downloadable from the HSE Books website at http://www.hse.gov.uk/pubns/indg370.pdf and Dangerous substances and explosive atmospheres approved code of practice and guidance, reference L138, HSE, 2003, 15.50, obtainable from HSE Books http://www.hsebooks.com/Books/default.asp 7. The safe use of vent collection systems for potentially flammable atmospheres, HSE. This guidance is currently in preparation.

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