Industry Alert

BUTADIENE POPCORN POLYMERIZATION

ACC SHARES THE FOLLOWING ALERT PROVIDED BY TPC:

Incident Overview

On November 27, 2019, at approximately 12:56 a.m., a vapor cloud explosion occurred in the
south processing area at the TPC Group (TPC) Port Neches facility (PNO). Resulting fires
occurred in the process area and adjacent areas at the facility. Three individuals on-site were
treated for minor injuries, and all were released. No fatalities resulted. The process unit and other
areas of PNO sustained catastrophic damage.

Within 24-hours, TPC established an off-site emergency operations center to oversee and
coordinate the response to the incident. More than 20 federal, state, and local governmental entities
ultimately became part of a Unified Incident Command (UIC) that coordinated response activities
at PNO for 65 days. TPC also retained CTEH, LLC (CTEH) to support the response to the incident
by performing real-time air monitoring. CTEH air monitoring and other sampling data show that
there was no adverse impact on public health in the community as a result of incident-related
emissions.

RCA Learnings

TPC convened a multi-disciplinary team of internal and external subject matter experts to conduct
a Root Cause Analysis (RCA) of the incident. The investigation team was composed of TPC
personnel with experience in operations and maintenance, process chemistry, engineering, and
safety. An employee union representative participated. TPC also used an external technical expert
with experience in investigating major incidents to provide an external perspective.

The RCA team has completed its investigation. TPC believes it is important to share learnings with
industry regarding the incident and potential 1,3-butadiene (BD) process hazards.

The RCA team determined that the primary loss of containment occurred in the BD purification
part of the process. See Figure 1 – Process Diagram. Specifically, it appears that an operational
dead leg (labelled as (1) in Figure 1) was established on a high purity (>99 percent) BD line

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coming off the bottom of a column (S4D4A)1. The operational dead leg was created when a pump
(S4G7) was not running while it was undergoing troubleshooting and repairs for an extended
period of time. This extended downtime prevented the primary mitigation strategy of routine pump
cycling. The hazard associated with the presence of an operational dead leg and the applicability of
a dead leg mitigation procedure were not recognized.

Figure 1 - Process Diagram

Several undesired reactions involving BD can occur during manufacture, storage, handling,
distribution and use2. BD “polymerization” is the process of reacting BD monomer molecules
together in a chemical reaction to form polymer chains. One such reaction involves the formation
of a highly crosslinked “popcorn” polymer. Once formed, popcorn polymer “seeds” can propagate

1
An operational or temporary dead leg means a section of normally “in use” process piping experiencing
intermittent or no process flow due to operating or maintenance activities.
2
Additional information regarding BD hazards may be found in the Butadiene Product Stewardship
Guidance Manual, American Chemistry Council (2019).

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on their own due to internal stresses which generate new free radical sites within the polymer
matrix. This propagation allows more monomer to then react which sets off a cycle of further rapid
polymerization.

The RCA team concluded that the operational dead leg created a circumstance of low or stagnant
flow. The chemical inhibitor which is added to the process to prevent polymerization was depleted
in the line because of the stagnant flow. There was sufficient time while the operational dead leg
was in place for popcorn polymer to grow to the point that it could fill a 5-foot long section of the
16-inch line. The polymer eventually exerted sufficient force to cause mechanical failure of the
line. The loss of containment resulted in a vapor cloud which subsequently ignited.

Permanent dead legs that may exist by design have been an area of focus within industry.
Temporary or operational dead legs also may warrant monitoring. Specifically, given the potential
for maintenance and repair activities to create operational dead legs, owners and operators who
manufacture, use, or store BD need to be cognizant of the hazards associated with the potential for
BD popcorn polymerization in areas of low or stagnant flow – even if chemical inhibitors are used.

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