AIChE Paper Number 175267 ETHYLENE UNIT FIRE LESSONS LEARNED SUNOCO MARCUS HOOK, PA REFINERY

By Arthur Jensen Mechanical Reliability Specialist Sunoco, Inc.

Prepared for Presentation at the 2010 Spring National Meeting San Antonio, TX, March 21 – 25, 2010

AIChE and EPC shall not be responsible for statements or opinions contained in papers or printed in its publications

maintenance. and operational work practice areas for improvement to prevent a similar event in the future. Seven other process lines within the pipe rack in the vicinity of the initial release ruptured from short-term overheating within the first 10 minutes. There were no injuries from the fire or the emergency response activities. with the dimensions of the sleeve being almost identical to the size of the localized thin area. There was significant heat damage to facility piping and equipment in the vicinity of the initial release.m. This sleeve trapped moisture creating crevice corrosion between the sleeve and outside of the pipe. there was a sudden and large hydrocarbon release from a main process pipe in the Ethylene Unit at the Sunoco Marcus Hook. Pennsylvania Refinery. There was essentially no corrosion or thinning of the line outside of this sleeve crevice area during the 48-year service life. Fire fighting and process isolation efforts brought the fire under control. The initial release was from a pipe rupture 10” long by 7” wide on the bottom of the 10" diameter (60oF . Abstract At approximately 10:15 p. The release found an ignition source at an operating process furnace within 2 seconds. Inc. but it continued to burn for approximately 18 hours while process systems depressured. resulting in a fire. This sleeve also obscured the corrosion such that visual pipe inspections failed to detect the degradation.ETHYLENE UNIT FIRE LESSONS LEARNED SUNOCO MARCUS HOOK.475 psig) main process line. The investigation identified the physical causes of the failure as well as design. on Sunday. inspection. May 17. A loose steel quarter-sleeve was found under the pipe at the support location. and the event received media coverage and attention from regulatory agencies. . The cause of the failure was long-term localized external corrosion at a pipe support contact area. PA REFINERY By Arthur Jensen Mechanical Reliability Specialist Sunoco. 2009.

Within the first minute of the release the unit operators initiated the unit shutdown functions. The unit was built in 1961 by SunOlin Company with the process and design license from Lummus Technology. This reduced the pressure on various systems on the unit and also began to depressure systems through the flare stack. polyethylene. ethane. on Monday afternoon. ethylene. the fire was under control. 2009. the final systems had de-pressured and the fire was declared extinguished. The process first involves amine scrubbing to remove sulfur compounds and contaminants. What Happened At approximately 10:15 p.Background The ethylene unit at the Marcus Hook facility is a multi-step separation and distillation purification process to produce a high-purity ethylene product stream. there was a hydrocarbon release and fire on the ethylene unit at the Marcus Hook Refinery. Over the next 10 minutes there were additional releases in the same area of the pipe rack. and was purchased and subsequently operated by Sunoco in approximately 1990. The ethylene product is subsequently used by downstream units to produce ethylene oxide. May 17. There were no reported injuries from the fire or subsequent emergency response activities. hydrogen. May 18. but one or more systems continued to de-pressure and feed small fires on the unit. and equipment in the proximity of the fire. structures. Unit operations personnel and responders from Sunoco emergency response and outside volunteer fire companies began aggressive actions to fight the fire within the first 10 minutes. and these additional releases continued to fuel the fire. The feed stream to the ethylene unit is a mixture of light refinery gases including butane. steadily reducing the size and intensity of the fire through the night. By the morning of Monday.m. This was followed by a sustained fire in the area surrounding the initial release. This is followed by desiccant driers to remove any moisture from the process stream. By 4:30 p. sulfur compounds. providing water cooling to piping and equipment that stabilized the fire after the initial series of releases. The facility is constructed on a remote corner of the Sunoco Marcus Hook Refinery. The desiccant drying section of the unit is of particular importance. including emergency trip of the feed gas and recycle compressors. 2009. Intra-refinery piping systems that pass through this area of the ethylene unit were also .m. The distillation process is high pressure (400 to 500 psig) and very cold (down to -140oF). propane. carbon dioxide. May 18. on Sunday night. which would condense and freeze inside the cold distillation towers. and other contaminants. since this is the section where the pipe failure and fire occurred. Over the next several hours the fuel sources to the fire were blocked in and the systems depressured. or for ethylene product sales. There was damage to ethylene unit piping. methane.

and paper (process monitoring computer data. Both of these methodologies place a high importance on systematic evidence gathering and evaluation – including evidence from people (witness interviews to obtain observations and knowledge). Figure 1 includes two photographs which support these initial eyewitness observations: the photo on the left was taken between 30 seconds to 1 minute after the initial release. records. The photo on the right was taken the next day to orient and provide a reference for the eyewitness photo. The distance is approximately ½-mile from the ethylene unit. Boiler stack ~300 ft high Figure 1: The photo on left was taken from an eyewitness camera within one minute of the initial release and fire. There was television. the Delaware Fire Marshal’s Office. while the fire was being extinguished. and the Failsafe Latent Cause Analysis (LCA) methodologies. Witnesses reported the initial fire was very large and very intense: “300 feet high by 300 feet wide”. requiring other refinery units to be shut down or cut back until repairs were made or bypass systems installed. Evidence Summary: Physical Causes The investigation followed a combination of methodologies. and OSHA were started on Monday morning.). and newspaper coverage of the event. etc. including the United Steel Workers Triangle Of Prevention (TOP) System Of Safety (SOS) analysis.damaged. procedures. Investigations by Sunoco investigators. They turned to look in the direction of the noise. and within about one second reported seeing a large fire ball ignite at the ethylene unit. . similar to the sound made when a high-pressure boiler safety valve lifts. The following is a summary of the evidence the investigation team used toward the determination of the physical causes of this event: • Several witnesses in the refinery at the time of the release reported hearing a loud release noise. and the photo on the right was taken the morning after the fire to orient the location and scale of the fire. physical (photographs and analysis of plant components involved in the event). May 18. radio.

The process is routed through multiple interconnected piping. This was a main process gas line through the ethylene unit. suggesting the metal was very thin in this localized area. such that there was a large volume of high pressure gas in the system at the time of the failure. . Process monitoring data was reviewed after the event. The failure location was in the lower tier of a 3-tier main pipe rack through the unit. Within the first 10 minutes of the event witnesses reported hearing up to 6 additional ruptures and releases. and this showed the initial system pressure loss was in the area of the process that included the V210A and B process desiccant driers. The bottom of the line blew out in a manner similar to a rupture disk.• Physical evidence identified the initial failure was a 10” high-pressure (475 psig) process gas line that experienced a large (10” by 7”) rupture in the bottom of the line at the location of a pipe support. with numerous other process and utility lines in close proximity. The data showed other systems having sudden pressure loss several minutes and up to 8 minutes after the initial leak. The photo on the right is a close-up photo of the rupture. Figure 3 shows a simplified schematic of the process drier system with the relevant process pressure and flow data (at the upstream compressors and downstream deethanizer tower) highlighted. showing the 10” x 7” hole in the bottom of the pipe. vessel. Side view of initial 10” line leak. and distillation towers on the unit. on the common outlet line from the desiccant drier vessels. The evidence indicates that fire fighting and cooling water spray efforts were effective at preventing additional pipe failures after the first 10 minutes. exchanger. Pieces of the ruptured line are visible “folded back” on the line. Physical evidence after the event has shown that in addition to the initial 10” line rupture there were 7 other secondary line ruptures within the pipe rack from short-term overheat. Figure 2 shows photographs of this initial line rupture. consistent with the secondary pipe ruptures due to short-term overheating. Process data supports that these secondary ruptures took place between 3 minutes and 10 minutes after the initial release and fire. • • • This 10” pipe was a mixed-light-hydrocarbon main process line through the ethylene unit. with other pieces missing. Figure 2: The photo on left was taken from ground level.

This loose sleeve was found resting on top of the pipe support (under the failed pipe) the morning after the fire was extinguished. Figure 4 shows a photograph of the sleeve along with the approximate orientation where the sleeve was found. During the summer months the metal surface temperature of this uninsulated line would be below the . including process data from upstream and downstream equipment. . • • • The initial pipe rupture on the 10” process gas line was determined to be from external corrosion at the bottom of the pipe. A localized area of corrosion (approximately the size of the failure) resulted from the presence of a loose steel sleeve under the pipe where it crossed over the pipe support (approximately 18 feet above grade).m. A corrosion situation such as this would be accelerated due to the normal operating temperature of this process line.Pressure drops sharply with flow forward stop (reverse flow) Figure 3: Simplified schematic of the desiccant drier section of the unit.m. with the potential to increase the expected corrosion rate significantly. . A crevice between two metal components would create a localized galvanic corrosion cell. The presence of this sleeve could enable moisture to be trapped within the crevice space between the sleeve and pipe.Pressure drops sharply with large flow forward sudden increase 10:15 p. which was approximately 60oF year-round.Process Drier Simplified Schematic 10:15 p.

• • • . The metallurgical analysis verifies that the area within the sleeve had severe pipe wall thinning occurring over a long time period prior to the May 17 failure. there was no evidence indicating that this paint was a grade sufficient for a continuously wet marine-type environment. • • The sleeve is ~10 inches long and provided extended area of contact corrosion. Pipe and sleeve external corrosion (outside of the crevice area) was negligible over the 48-year service life of the pipe. The loose sleeve was found under the failure (resting on top of the pipe support) the morning after the fire. It is believed that a small amount of movement could be what initiated the pipe failure and loss of containment. with the physical metallurgical examination showing that 90% of the metal thickness had corroded away in the proximity of the failure area. Although this small movement is believed to be what “triggered” the failure. • Although there is evidence the pipe was originally painted. Figure 4: Loose steel sleeve found under the failed pipe the morning after the fire. This thermal transient and thermal growth of the piping could have caused a minor amount of pipe movement at the location of the failure. During the night of May 17 the 10” process gas line was going through a normal thermal transient due to the planned start of the regeneration of the V210B desiccant drier.daily dew point temperature. Within the crevice area the corrosion was significant. the ongoing and undiscovered corrosion at the failure location is the primary cause of this event. The large corrosion area explains the large initial “blowout” failure. such that the line would sweat and enable the moisture to be pulled into the crevice area between the sleeve and pipe.

along with a negative draft inside the heater during operation. . There were penetrations through the heater skin at the top of the fire box (approximately 20 ft above grade). and the large and rapid energy release will cause the fracture area to expand rapidly along the area of pipe thinning. With an initial small leak the gas will rapidly expand through the fracture. was determined to be the ignition source of the fire. The H-202 drier regeneration heater. The result (in this case) was a large “blowout” type of failure along the entire area of thin pipe.• • A contributing factor to the size of the initial rupture was also determined to be the highpressure gas service of this piping system. rather than the large blowout rupture. This would enable a flammable mixture to be drawn into the fire box where numerous hot surfaces provided ignition sources. then it would be more likely that the failure would have been a small fracture and much smaller leak. The ignited flammable mixture then flashed back outside the heater. Ignition source at top of H202 Heater Desiccant driers Initial 10” pipe failure Figure 5: Overhead photo of fire damage area within the ethylene unit. or the service was a non-expanding liquid. If the system pressure was much lower. which was operating at the time of the leak.

It is believed that this sleeve was installed during initial construction in 1961 or within the first few years of operation. Research of the design and construction standards in use by SunOlin and Lummus does not indicate that the use of loose sleeves was specified. As long as Sunoco Standards are followed (with new construction. and was purchased by Sunoco in approximately 1990. and improvements in work practices and Systems Of Safety that can prevent similar failures in the future: 1. It is not clear whether this installation was an exception to the standards in use at the time. This rapid ignition of the released gas greatly limited the size of the vapor cloud and limited the scale of resulting pressure wave. fiberglass. • The ethylene unit was originally owned and constructed by SunOlin Company with the process and design license from Lummus Technology. there was minimal pressure-wave damage found during the physical evidence examination. • Current Sunoco Piping Standards do not permit the use of this type of loose sleeve. equipment. field . • The microscopic and chemical analysis of the components indicates there may have originally been tar or a similar organic adhesive substance between the pipe and sleeve when it was installed. Figure 5 is an overhead photo of the fire scene showing heat damage in the area of the pipe rack. In the other locations that evidence of loose sleeves were found there was clear evidence of similar large-contact-area corrosion taking place in the crevice area between the sleeve and the pipe. and the volume of material in the system. not typical of refinery installations. but this material had degraded over the service life of the installation. Design and Engineering • The loose external sleeve at the bottom of this line is a unique configuration. and locations of equipment involved with the event. It was believed to have been installed as an abrasion protection for the pipe where it rested on the concrete and steel support beam. Current requirements include the use of welded pipe shoes or non-metallic wear materials (Teflon. the velocity of the leaking process gas was high. Almost all of the damage to the unit piping. Although witnesses at the time of the event reported hearing an “explosion”. Dispersion models estimated that the flammable vapor cloud reached the top of H202 fire box area and ignited within 1 to 2 seconds. and also do not permit piping (2” and larger) to be installed directly on steel or concrete pipe supports. • Examination of numerous pipe support locations throughout the ethylene unit identified only a couple of other locations where this type of loose steel sleeve was used. Figure 6 is a photograph of another 10” line on the unit where a loose sleeve had apparently been used. showing the thinned area at the bottom of the pipe.• Due to the operating pressure of the system (475 psig). and structures was consistent with overheating from the fire. or if a field modification was implemented at some point during or after initial construction. the size of the initial pipe rupture. or carbon fiber) to prevent contact between the pipe and support. Lessons Learned The following is a summary of what was learned from this event.

Figure 6: Another 10” pipe on the ethylene unit with external corrosion from extended contact area due to a loose sleeve at a pipe support. .stoprust. These half-rods will allow for reduced friction between the pipe and support. Under consideration is the addition of non-metallic half-round rods to be installed under piping at support locations. such that high compressive strength thermoplastic materials or equivalent must be specified to avoid crushing the rods. the Sunoco Engineering Services leadership team is reviewing these standards. as well as further minimize the contact (crevice) area for corrosion.com). Figure 7 includes some pictures of example rod installations (courtesy of www.modification. It is important to note that this configuration will increase the compressive load-bearing requirements of the half-round rods. or replacement projects). future piping installations will not be susceptible to this type of failure mechanism. • As an opportunity for continual improvement after review of the findings from this event.

. One reason for this is a lack of awareness for this type of corrosion and pipe failure potential. These inspections are in conformance with API-570 requirements. but no problems were noted during the 2005 inspection of this piping. with the most recent inspection in April of 2005. Thickness monitoring showed no measurable wall loss on the system due to either internal or external corrosion. 2. • There were two small-bore drain connections that had been replaced on this system several years ago. It is important to recognize that the location of corrosion was obscured by the presence of the large concrete pipe support and loose sleeve under the pipe. The inspection checklist included observations of pipe supports. • External visual inspections of this pipe were also conducted. would likely not have been able to detect the ongoing crevice area corrosion. avoid protective coating abrasion. including the use of a certified piping inspector. and make future inspections simpler. due to external corrosion that was found during planned inspections (the two drain lines were along the ground in contact with the soil and experienced localized corrosion).http://www. which are the typical practice for these visual pipe inspections. which conform to API-570 requirements. avoid creating a galvanic cell.htm Figure 7: The use of non-metallic half-round pipe supports will minimize contact area.com/6pipesupports. Walk-by observations. Maintenance & Inspections • The 10” process gas line that had the initial failure had undergone repeated inspections over the 48-year service life of the system. the lines were essentially at new original wall thickness at the time of the failure. did not detect the progressing corrosion damage under the pipe sleeve. • Standard piping inspection practices.stoprust.

5.stoprust. radiography. When investigated more closely. The primary consideration would be piping systems which could have areas of significant contact area corrosion and also have the potential for a large rupture type of failure (rather than a small leak). The following six screening criteria are one suggested way to identify systems that could have this large failure consequence potential: 1.A single layer of corrosion scale is visible at the edge of the crevice. 4. binoculars. borescopes. Piping with a service life of 20 years or longer.Corrosion products visible but no evidence of layered scaling. Carbon or low-alloy steel (12% chrome or less). 2.htm Figure 8: Example screening and prioritization criteria for visual inspection of pipe support locations.• • Visual inspection practices need to be more detailed and rigorous. http://www. short-range ultrasonics.corrosion product leaching and visible multi-layer corrosion scale is visible. This may involve: the use of ladders or high-reach devices to access elevated piping. or other visual examination aids. Figure 8 provides one suggested categorization method (courtesy of www. or other techniques). CC-H (Heavy Crevice Corrosion) . or the use of advanced NDE technologies to assess piping condition (long-range guided ultrasonics.stoprust. Gas. Operating pressure above 150 psig. where ongoing corrosion of this type may have been missed by previous routine inspections. 3. CC-M (Moderate Crevice Corrosion) .com). Contact Point Corrosion Crevice Corrosion CC-L (Light Crevice Corrosion) . Other challenges with visual inspections are effective screening criteria for categorization and prioritization of follow-up actions to conditions that are found. . Practices used in the offshore industry provide methodology that can be effective for this purpose. A visual guide is provided to assist in making the correct assessment. such that any obstructions must be overcome to assure that a positive observation of the pipe condition is achieved. or vaporizing liquid services. • One additional concern is whether to perform high-urgency retroactive inspections of certain ultra-high-risk piping systems. the CC-M and CC-H situations would be expected to show a wall loss at the deepest pit of >40%. Piping larger than 2” diameter. LPG.com/6pipesupports.

The efforts of the team and the value of the fire protection equipment to mitigate and prevent escalation of the event were effective. which is an area for improvement. . until block valves at the boundary limits of the other units could be isolated. It is recognized that many of the secondary isolation valves will be at upstream and downstream process units. materials of construction. 3. The rapid and effective response of the team prevented the fire from escalating. Past standard practices did not require clearly identified and maintained “secondary” emergency isolation devices for all process streams. Some of the aspects to consider in these reviews include: 1. but was not able to prevent the secondary line failures near the initial leak (which happened within 3 to 10 minutes of the initial release). Have design and operability reviews been done to be sure the correct valve design. 2. Mitigation Devices • The size of the initial fire (approximately 300 feet high by 300 feet wide) resulted in the unit boundary limit isolation valves (approximately 100 feet away) being within the initial hot zone. Process streams from upstream or downstream refinery process units at the refinery fed the initial and subsequent secondary line leaks. If all six criteria are met then the system has the potential risk of a large rupture failure from undetected contact area corrosion. Are the valve locations clearly identified and accessible. • The overall size and location of the fire did not increase above the initial approximately 300 feet high by 300 feet wide area. so that they could not isolate the ethylene unit from the refinery. it was found that a number of these valves were not identified as isolation valves or did not operate adequately – further impeding the isolation effort. This restricted the ability of the operators and initial emergency response personnel (who did not yet have full personnel protective equipment for aggressive hot-zone actions) from taking defensive actions and they could not apply adequate cooling water directly on the fire source within the first 3 to 10 minutes of the initial event.• 6. • It is recommended that facilities adopt a practice of identifying process unit primary (at unit boundary limit) and secondary (outside of unit boundary limit) emergency isolation valves. • The size of the initial fire also put the location of permanent fire monitors (also approximately 100 feet from the initial release) within the initial hot zone. • During the attempt to isolate the unit via alternate (secondary) isolation valves outside the boundary limits of the unit and at other process units. Operating temperature between 32oF to 80oF. and installation orientation is in place. • Once these valves are identified they should be further reviewed and managed to assure high reliability when needed. Operators were not able to get access to close these manual valves during the first couple of hours following the initial release. Once proper protective gear was put on and additional (long range and high volume) fire water spray equipment was brought on scene the team was able to stabilize the fire. Where unit inter-connecting piping branches there may be two or more secondary valves for each process stream. Even then the volume of material within the inter-connecting unit pipe lines was still available to sustain the fire. or operating between 80oF and 350oF and proximity to an ambient moisture source (such as a cooling tower). and would be a candidate for urgent inspection priority.

Cold-Eye Mechanical Integrity Review • The investigation into the causes of this line rupture and fire identified opportunities for Sunoco to improve mechanical integrity design. • Sunoco is currently working with one of these industry consultants (the Equity Engineering Group. • With this objective in mind it is important to consult with expertise from outside the company. 4. Many of the improvement actions being taken go above and beyond regulatory compliance or even above and beyond conformance with industry Recognized and Generally Accepted Good Engineering Practices (RAGAGEP). • This type of comprehensive assessment by an industry-experienced “outsider” will greatly enhance the ability to identify and implement improved practices proactively – and avoid having to learn future improvement lessons “the hard way”. to gain a broader industry-wide perspective and sharing of experiences. – www. With the benefit of retrospective learning following this event it is much easier to see the value and benefits of “going above and beyond” in these specific areas noted in this report. Inc. .3.com). with a focus more toward “industry excellence” rather than compliance and conformance.equityeng. Operational controls are considered (such as not to be used for throttling service – or a second valve in series is installed if throttling is required). maintenance.). etc. Is preventive maintenance appropriate (lubrication. 5. and operational practices. packing adjustment. • The greater challenge is to learn from others throughout industry. inspection. Are periodic operability checks considered (such as exercising the valves). 4. with one site assessment currently completed and numerous detailed recommendations being organized and improvement initiatives implemented.

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