CASE STUDY VOLATILE ORGANIC COMPOUNDS EXPLOSION

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SUMMARY This case study describes an explosion which occurred at a Plant which traditionally had manufactured both water-based and solvent-based coatings. A solvent based process had been bought-in from another manufacturer, but because the plant equipment was different, the process was altered significantly. The Management had no appreciation of the new hazards inherent in the altered process they were operating. As the original process did not have a written basis of safety for freedom from fire or explosion, the consequences of the alteration were not anticipated. There are lessons to be learnt from this incident. Principally, the Management was ignorant of the implications of the change; there was no reference to any experts for advice on fire or explosion prevention; and there was inadequate reference to the existing public-domain information which would have revealed the hazards of the process change. A classic case of not knowing what they did not know. INTRODUCTION The incident which occurred involved a simple dissolving and blending operation to produce a solvent based coating. The original process involved the simple dissolution of slabs of wax, granules of hydrocarbon resin and beads of polyvinyl acetate resin in an aliphatic solvent, contained in an open vessel. The mixing vessel was fitted with a large, low-speed anchor type agitator, and to assist in the dissolution, the solvent was heated to a temperature of about 80C. This was above the melting point of the wax, so the dissolution of the large pieces of wax would be easier. As the boiling point of the solvent was about 110C, the vapour pressure of the solvent was very high, and there were considerable losses. Consequently, the process took the solvent losses into account, and an excess of solvent was added, knowing that the loss would bring the final concentration into specification. As the process had been developed in the 1960's, the solvent losses had not been considered to be problematic at the time, and had been tolerated on the site. However, eventually, the site was to be closed, and the process was moved to a new site. With the transfer to the new site, it was unacceptable to operate the old process where such large losses occurred, because of the restriction on allowable emissions of volatile

organic compounds (VOCs). Therefore a new process was developed at a lower temperature to make the same solution, but in order to dissolve the wax and resins in an acceptably short time, a high speed mixer/blender had been specified.

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The new process was introduced to the Plant, and as it was a simple blending operation, the Management decided that there were no chemical reaction hazards. As several of the previous processes in use on the new site were solvent-based, the use of flammable solvents was recognized as an existing known hazard. Therefore an area classification exercise was undertaken, and the appropriate certified electrical equipment was used. The Plant itself was earthed, and the Operators were issued with antistatic footwear. This was thought to be adequate to deal with any flammable solvents in use. Despite there being a Hazards Group within the Avecia organization, it was decided by the Site Management that the expertise on site and at the Headquarters Engineering Group was adequate for hazard assessment, so no contact was made to the specialist Hazards Group for advice. THE INCIDENT The process had been operated successfully for 23 batches without incident. On the 24th batch, there was a new Operator being trained in the manufacture of the product. The solvent had been added to the 2M3 vessel using a flexible hose from a solvent dispensing manifold. The agitator was running, and the vessel contents were warmed to about 3540C using hot water at about 60C. The temperature is manually set on a temperature controller, with no record of the temperature, so the temperatures quoted are those stated by the Operators. The first wax was added as a series of lumps broken from slabs. The pieces were nominally 100 mm to 150 mm in two dimensions, and the thickness of the slab (38 mm) in the other dimension. Once the first wax had been added, the hydrocarbon resin was added from a three-ply paper sack, by slitting the sack and tipping the contents into the vessel. At this point, the mixer was stopped, and the Operator went for a break. On returning, the mixer was started, and the temperature was still 35 - 40C. The polyvinyl acetate resin beads were then added from triple ply paper sacks, which had a thin plastic coating on the inside. The same method of addition was used, in that the sack was slit across the bottom, and part way up the centerline of the upper surface, using a knife. The

contents of the sack were then tipped in. Six bags were added without incident. The seventh bag was added, and as the last of the beads of resin were being shaken from the bag, the Operator saw an orange glow inside the vessel. He immediately turned away, but received superficial burns to the right side of the face as the flame rose out of the vessel. The Supervisor training the Operator saw a large flame rise from the vessel which rose almost to the roof, a distance of approximately 3 to 4 meters. This quickly subsided to burning around the manhole, and the Supervisor then decided to close the lid of the vessel. The building was evacuated, power was isolated from the area, and the Fire Service attended. The temperature within the vessel was about 35C at this time, and no flames or other apparent abnormalities were observed, so the power was restored. The vessel was cooled to about 20C, and the vessel was left overnight. Page 3

As the vessel still contained an apparently normal batch, it was decided to review the incident. The initial thoughts were that the incident had been caused by an electrostatic spark, so the earthing of all the major items was checked. This revealed that the fume extraction hood was not earthed, so this was earthed prior to continuing. Polythene sheeting had been wrapped around the vessel to prevent spillages of material dropping through the floor. As a precaution, this was removed to avoid any risk from a brush discharge from the surface of the plastic sheet. This is shown before removal in the photograph Figure 1 on page 11, taken shortly after the incident. As the polyvinyl acetate resin had been added directly from the paper sacks before, it was decided to empty the remaining sacks of resin into an earthed metal drum, and charge the resin from the drum, so as to prevent any possibility of ignition from the plastic lining of the sack. The temperature was still about 20C from the previous night. When the polyvinyl acetate resin had been added to the vessel, it sank to the bottom as discrete beads. The vessel lid was closed, and a short nitrogen purge was then used on the vessel. This was neither timed nor measured, but carried out with the intention of "increasing the safety". With the lid secured, the mixer was started. After a short period of time, thought to be about 30 seconds, an explosion occurred within the vessel. This was described as a dull "boom" rather than a "bang". An orange flame was seen through the sight glass, and to emanate from the edge of the vessel lid as a single short spurt. The mixer was then stopped, and the vessel left. When it was obvious by looking through the sight glass that there was no further combustion taking place, the vessel lid was opened and the vessel emptied through the bottom run off into earthed metal drums. The un-dissolved epoxy resin was left at the bottom, and was removed using a long wooden handled brush. A sample of the

liquid part of the batch was taken for analysis. The plant was then left and it was decided to review the incident in more detail. THE INVESTIGATION After the second explosion, a critical review of the incident was undertaken by the site Management. As the second explosion had occurred whilst there was no addition of material being undertaken, it was apparent that the source of ignition was not external to the vessel. Hence suspicion fell on the agitator, which apparently had been exhibiting a noisy bearing for some time. The mixer manufacturers were called in, who removed the mixer for examination. Their conclusion was that the mixer itself was working correctly, but the bearings were badly worn, which allowed some lateral movement of the shaft. The mixer manufacturer was adamant that the mixer was not the source of ignition. At this point, the Management decided that they were unsure of the cause of the incident, and sought help from the main Avecia Parent Group Safety Section at Huddersfield, who advised an approach to Avecia Hazards Group.

Page 4 The investigation started by confirming that all the equipment was earthed, and that the Operator had been earthed through his footwear. Samples of the solvent were taken for the electrical resistivity to be determined, as well as samples of the wax, resins and the sacks in which they were supplied. The results of the tests were that the solvent was electrically insulating with a resistivity of 1.2 x 1012 m; and the wax and resins all had bulk electrical resistivities of greater than 1012 m. The plastic coated paper sack used for the polyvinyl acetate resin beads was highly insulating, and gave rise to brush discharges capable of igniting a 0.2 mJ minimum ignition energy flammable atmosphere when tribocharged. The electrical equipment was inspected and found to be of a satisfactory standard for the conditions under which it was being used. The mixer shaft, bearing and seal were examined at the mixer manufacturer's premises. The mixer motor power output was 6.8 kW at 1450rpm. Although the bearing wear was excessive, there was no evidence of the shaft being heated to the auto ignition temperature of the vapours, which was 240-245C. The simple lip-seal on the shaft used to seal the vessel from the external atmosphere was in poor condition, with obvious signs of wear. It was considered that the seal had been worn for some time, and this had allowed the solvent vapours to pass into the bearing housing, dissolving the grease, and

hence causing the bearing to run with inadequate lubrication. However, the shaft and the edge of the lip seal did not show any of the characteristic oxidation colours that occur on steels when heated. Whilst this is a rather crude and inaccurate method of determining the temperature to which a surface has been heated, it is none the less useful where there is no other information available. As the lowest discernable temperature using colour is about 230C, it can be concluded that ignition of the vapour by the seal running hot was unlikely. Both the solvent and the resin solutions were electrically insulating, and the resin beads were in suspension, so electrostatic charging of the liquid is almost certain to occur. The power input was 3.4 kW M-3, and the resistivity was 1.2 x 1012 m, which are far higher than the maximum power of 0.37 kW M-3 and maximum resistivity of 1 x 109 m suggested by Walmsley to avoid hazardous levels of electrostatic charge from accumulating on the liquid. The conclusion is that an electrostatic discharge from the liquid provided the ignition source. There have been incidents in the past where the same mechanism occurred. However, whilst this explains the mechanism, it does not fully explain why 23 previous batches had been made without incident. The normal flash point of the resin solution was measured at 0C, and the upper flash point was measured at 24C, using the method of Hasegawa and Kashiki. Consequently, in a closed system, the vapour would only be flammable when it was between the temperatures of 0C and 24C. During normal processing, the solvent temperature was between 35C and 40C, so the atmosphere would be over-rich and would not support combustion. During the first explosion, the trainee operator was adding material at a much slower rate than was normal, so there was a greater chance of vapour is leaving the vessel, and air entering, upsetting the equilibrium between the solution and its vapour. This would allow a greater Page 5

concentration of air to be present, and hence the concentration of vapour would be lower, moving the atmosphere within the vessel into the flammable range. The flame was initially described as a "dull orange", which is typical of a rich mixture - hence only just enough air to support combustion. When the second explosion occurred, the vessel temperature was about 20C which is within the flammable range. As the ignition occurred about 30 seconds after starting the mixer, it would appear that electrostatic charging of the liquid was the cause. As the resistivity of the liquid was 1.2 x 1012 m, and its relative permittivity is about 2.0, the charging time constant is given by:

 = 0 1 . Where:

(1)

= charging time constant, seconds 0= relative permittivity of free space = 8.85 x 10-12 F m-1 1= relative permittivity of the liquid = liquid resistivity, m Substituting into Equation (1), the charging time constant is 8.85 x10-12 x 2 x 1.2 x 1012= 21.2 secs. As the charge will reach 63% of its equilibrium value in one time constant, and 95% in three time constants, it is clear that the equilibrium value had not been attained in the time between the starting of the mixer and the occurrence of the second explosion. Again, the flame was orange, suggesting that the combustion was fuel- rich, which would be the case if the solvent was at a temperature of 20C and the upper flash point was 24C. BASIS OF SAFETY When the original process was purchased, there was no defined Basis of Safety. The process had been operated for many years, so there was probably no formalized hazard study undertaken. As it had been operated using a low speed agitator, there would be little electrostatic charging, and it would have been recognized that solvent vapours were given off due to the high temperature. Hence it is probable that had a Basis of Safety been defined for the original process, it could be surmised to have been the avoidance of potential sources of ignition. This would have been relatively easy to achieve by the earthing of the Operators, and exclusion of ignition sources such as hot surfaces, welding sparks, frictional heating etc. The use of the appropriate electrical equipment would have eliminated this as a potential ignition source. The low speed agitation would have ensured that any electrostatic charge accumulation would have been well below a level which would be hazardous. When the new process was developed, the absence of a defined Basis of Safety would make it extremely difficult to know exactly what could be altered safely, and why. Hence this is the first information which was unknown. Process Page 6 temperature was lowered in an attempt to reduce the hydrocarbon losses, but as it was below the melting point of the wax, it was considered that it would be difficult to dissolve the wax. Therefore a high speed, high shear mixer was specified. The high shear was specified so that any lumps of wax would be broken up by the impact of the rotor blades, thus increasing the surface area, and speeding up the dissolution.

As no Basis of Safety had been specified originally, it was not apparent to the Management that it was necessary to define a Basis of Safety prior to operation of the modified process. As all their previous experience had been with simple blending operations, the use of solvents with a high speed mixer was new technology. Whilst general guidance on flammable solvents and static electricity, prepared by the Health and Safety Executive in the U.K., is readily available, it is difficult for inexperienced people to determine the subtle differences between an old process and a new one. In a superficial way, the processes are the same - the wax and resin are dissolved in a flammable solvent, so precautions must be implemented to prevent ignition. However, the difference is in the detail, and had a full literature search been undertaken, it would be apparent that high levels of electrostatic charge could be generated where a two-phase mixture in an insulating liquid is agitated with high power mixers. From the above it is apparent that where a high speed, high power mixer is used to dissolve suspended solids in insulating flammable solvents, safety cannot be based on the avoidance of potential sources of ignition. Had there been an existing Basis of Safety, which defined exactly the safe envelope for operation, then it would have been easy to make a decision as to whether that Basis of Safety was invalidated by the proposed process modifications or not. In the case described, the change from the slow-speed anchor type agitator to the high-speed high-shear mixer introduced a potential ignition source as the electrostatic charge generation rate was higher than the dissipation rate, and the excess charge eventually accumulated to the point at which a discharge occurred. Hence this would indicate that the original Basis of Safety was no longer valid, and a different Basis of Safety was required. In the event, the process was eventually re-started using an inert atmosphere for the vessel, and the solids were added via an inert gas purged tun-dish. The physical form of the wax had to be changed from blocks to pastilles. This allowed the solids to be added at an adequate rate whilst the inert gas purge diluted the air trapped in the interstices of the powder to an oxygen concentration below the minimum oxygen for combustion. The calculation for the required rate has been described before... The Basis of Safety was then defined and written as the avoidance of flammable atmospheres by the use of inert gas. LESSONS TO BE LEARNED There are several lessons to be learned from this incident, but these lessons are not specific to this incident alone. There are many instances where the lack of information, or Page 7

the inability to realize that the required information is available can result in a hazard being overlooked. Whilst a process may operate without incident for a period of time, it may still be inherently hazardous as was the case with this incident. Lesson 1 - The need to provide information Any process to be operated on a Plant should have a defined Basis of Safety which sets out exactly the philosophy behind the operation. This Basis of Safety should be written clearly, explaining all of the hazards that are present, and the control methods required to ensure that safe operation can be undertaken. In the case described, this had not been carried out, either when the process was originally developed, or when it was sold. There is a duty of care on the seller to ensure that adequate information is given on the hazards of the process. Whilst this may simply be the toxicity, flammability, and electrical properties of the raw materials, intermediates and final products, it is incumbent on the Operating Company to understand the information so that the appropriate precautions can be implemented to ensure safe operation of the process. Hence if the Operating Company is unaware of the implications of the hazard information, then expert help should be sought. In this case, the Management was unaware of the implications of the information, so "they did not know what they did not know". Whilst the Management was aware that there were potential electrostatic hazards, these were not identified clearly, so no specific precautions could be established for their control. Clearly, in the case of a bought-in process, it is essential to understand the information. If the relevance of a piece of information is not known, then it is clear that the information should not be ignored, but an effort should be made to understand why the information was provided. If this cannot be done within the confines of the immediate personnel involved, then it is necessary to seek assistance from experts. Lesson 2 - The need for a defined Basis of Safety When a process has no defined Basis of Safety, such as a process bought in for toll manufacture, then it should be assessed by an expert in Hazards. Where hazard assessment is undertaken by Manufacturing or Production personnel, there is generally a lack of awareness of the subtleties of the hazards, as could be seen by the case study above. Whilst it is sometimes difficult to contract out such assessment work, it is still necessary to undertake such a study, as not knowing is inherently hazardous - again not

knowing what they do not know. If there are changes to a process, it is possible for an experienced Production or Manufacturing Chemist or Engineer to obtain the Hazard Assessment and, understanding the Basis of Safety, decide whether the changes are still within the scope of the existing Basis of Safety. Whilst this is obvious for changes of material, such as the change to a flammable solvent from a non-flammable one, it is less obvious, as in the above case, where the type of agitator affected the Basis of Safety. Page 8 Where a clear Basis of Safety defines the reasoning behind its selection, then even the change of agitator should be adequately covered. Where unfamiliar technology is being used, there is a great tendency to consider only those hazards which are already familiar. However, this is the greatest area where a lack of knowledge is inherently hazardous. Clearly there was existing case history of previous incidents of dissolving solids in insulating solvents, but it would be necessary to know that this information existed for it to be useful. As the Management at the Site did not know that the information existed, it was a clear case of not knowing what they did not know. Lesson 3 - The need to understand whether the information is complete The information printed on the paper sack containing the polyvinyl acetate resin beads stated "UNUSUAL FIRE, EXPLOSION HAZARDS An electrostatic charge can potentially build up when pouring powder or pellets. Grounding of all equipment is recommended, especially when blending [Trade Name] with volatile combustible substances This warning is valuable, but unless it is understood in its implications, it is easy to misinterpret the information in that simply grounding (earthing) will prevent any incident. Hence although it does indeed cover the pouring of the beads from the bag, it does not warn of the implications of stirring a suspension of the beads in an insulating solvent. Hence it is necessary to understand the information available, and to be able to apply it correctly. Here the information on the paper sack referred specifically to the pouring of the beads from the sack - and nothing else. It was easy to misinterpret the information to cover the entire process, which was done in this case. Lesson 4 - The need for all the facts before investigating When the initial investigation was undertaken, not all the facts were known - particularly the resistivity of the solvents was not known, nor the potential mechanism of charge generation. The initial investigation after the first explosion concluded that the cause was the plastic coating on the paper sack for the vinyl acetate beads producing an electrostatic

discharge which ignited the solvent vapours. This was eliminated by using an earthed metal container for continuing the process, but when the second explosion occurred, there was an immediate reaction to adopt the methods of Sherlock Holmes, "It is an old maxim of mine that when you have excluded the impossible, whatever remains, however improbable, must be the truth.". Unfortunately, the investigators had unwittingly excluded some possible causes, leaving them with the wrong conclusion that the agitator was to blame. This problem of not knowing the facts has also been pointed out by Sherlock Holmes later in the same book, where he says "I have no data. It is a capital mistake to theorise before one has data. Insensibly one begins to twist facts to suit theories, instead of theories to suit". As they did not know that they did not have all the facts, they were partially correct in that the agitator was to blame to an extent, as its action was generating the high electrostatic charge on the liquid, rather than the agitator itself action as the source of ignition directly due to frictional heating.

Page 9 Lesson 5 - The need to recognize one's limitations Whilst it is very hard to acknowledge one's ignorance, in matters of safety it is essential to recognize that not everyone knows everything. Therefore it is necessary to be aware of one's own limitations, and be ready to seek expert help where necessary. However, it is also useful for Engineers, Chemists and the like to be aware of the potential nature of the hazards, even if they are unable to deal with them directly. Hence there is a need for experts to be available for advice, and the culture of the organization needs to be such that the admission of ignorance is not seen as a failing, but a virtue. It is necessary to have a culture that allows Engineers to have a wide general knowledge, so that whilst they are aware of potential problems, they do not need to know how to deal with them that is for the experts to do. Lesson 6 - The need to seek expert advice Having recognized that there is a hazard, it is necessary not only to understand it, but to understand what is needed to control or eliminate it. In this instance, the problem was the high electrostatic charging of the liquid resulting in the potential for a discharge from the surface to occur, igniting the flammable vapours. There are several approaches that could be used - lower the power input; increase the conductivity of the solvent; reduce the temperature to below the flash-point of the solvent; use a non-flammable solvent; or

remove the oxygen to make the atmosphere non-flammable. Any of these would be a perfectly safe option, but not all are practical, nor would be recognized until the hazard has been defined. Hence the discussion of the problem with an expert in the appropriate hazards will reveal an iterative process requiring two-way communication. The hazard expert does not know the process, only the hazards, so is in a difficult position to make recommendations without the input of the Management. Thus the expert is there to guide the Management to safe operation, not to dictate to them. Lesson 7 - The need to have a wide general knowledge From the above we have seen that the lack of knowledge led a comparatively safe process into an inherently hazardous one by several changes, all undertaken with the best intentions. Only when people recognize that there may be a problem can experts be consulted. Thus there is a need for everyone concerned with the design and operation of processes to be aware of the potential problems that can arise. Only then can they make the required contact with the appropriate experts to enable a process to be designed and operated safely. Whilst it would be unrealistic to expect a Chemical Engineer to fully understand all other disciplines such as chemistry, and civil, electrical and mechanical engineering, they should at least have some understanding of other disciplines to allow them to know that there is the potential for a problem. Thus an engineer's training should continue throughout their life, so that they do encompass the other fields in their routine Page 10 work. The current availability of many databases world-wide means that there is little excuse for not being able to identify potential hazards before they arise.

CONCLUSIONS

* 1. The incident occurred because the process was changed to one which was inherently hazardous. * 2. There was no written Basis of Safety for the process, so there was no definition of the hazards that were present, nor were there any defined measures necessary to avoid or control them.

* 3. Those making the changes to the process had no written Basis of Safety for reference, so that they were unaware that the changes would introduce a potential source of ignition. * 4 The initial investigation after the incident drew the wrong conclusions, as those investigating the incident did not seek out all the relevant data, nor did they have the relevant expertise to undertake the task. * 5. The need for Engineers to be aware of other disciplines is essential so that possible hazards can be referred to those with expert knowledge to decide on the most appropriate course of action. * 6. There is a wealth of existing data available in the public domain, and with availability of search engines, there is no longer any excuse to "not know what you don't know".