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1
Fires and Explosions at
TPC Group Port Neches Operations Facility
Port Neches, Texas
|
Incident Date: November 27, 2019
|
No. 2020-02-I-TX
U.S. Chemical Safety and
Hazard Investigation Board
Factual Update
October 29, 2020
Incident Summary
•
On November 27, 2019, a major loss of containment event occurred, resulting in multiple fires and explosions at
the TPC Group (TPC) Port Neches Operations (PNO) facility in Port Neches, TX. The TPC PNO facility
manufactured 1,3-butadiene and raffinate-1 [1].
a
The incident occurred in the
facility’s South Unit
(
Figure 1
).
The initial explosion resulted in injuries to two TPC employees and a security contractor and caused significant
damage to the facility.
Following the incident, county officials issued a mandatory four-mile radius evacuation
order [2] which remained in effect until 10:00 a.m. on November 29, 2019.
Figure 1
.
TPC PNO facility prior to the incident.
(Credit:
Google Maps)
•
Because of the incident, TPC has decided to transition to a “terminal and services” operation
while they evaluate
and plan to rebuild [3].
As part of this transition, TPC terminated the employment of multiple workers and
a
Raffinate-1 is a byproduct of 1,3-butadiene and is a chemical building block used in the manufacture of methyl tertiary butyl ether (MTBE) and
diisobutylene (DIB) [15].
2
Fires and Explosions at
TPC Group Port Neches Operations Facility
Port Neches, Texas
|
Incident Date: November 27, 2019
|
No. 2020-02-I-TX
U.S. Chemical Safety and
Hazard Investigation Board
supervisors.
Marsh JLT Specialty reported the property damage loss resulting from the incident to be $500
million [4].
Background
•
The South Unit is used to produce 1,3-butadiene, which is primarily used to manufacture synthetic rubber and
resins [5, p. 4]. Because 1,3-butadiene is a flammable liquid with a flashpoint below 100 °F,
a
and because the
TPC PNO facility maintains an onsite quantity of 1,3-butadiene greater than 10,000 pounds, the production of
1,3-butadiene at the TPC PNO facility is regulated by the requirements of the Occupational Safety and Health
Administration
’s (OSHA) Process Safety Management (PSM) standard
, 29 CFR 1910.119 [6].
Also, 1,3-
butadiene is a regulated substance under section 112(r) of the Clean Air Act; as such, the process is subject to the
Environmental Protection Agency
’s (EPA) Risk Management Plan (RMP)
Rule [7].
•
In addition to its flammability, 1,3-butadiene is also highly reactive, with several undesirable reactions.
In the
presence of oxygen, butadiene readily reacts to form a butadiene peroxide.
Butadiene peroxides, which are
denser than 1,3-butadiene, will separate out and form a second liquid phase.
If enough butadiene peroxides
become concentrated, a critical mass is achieved which can initiate a fire or explosion [5, p. 30].
Another
potential undesirable reaction that can occur between oxygen and 1,3-butadiene is the formation of popcorn
polymer.
Popcorn polymer, if left uninhibited, grows exponentially [8, p. 4]. When popcorn polymer growth is
left unabated inside process equipment, the accumulated material can generate very high pressure inside the
equipment and can ultimately lead to equipment rupture [9, p. 240].
•
Figure 2
shows a block flow diagram of the butadiene production process at TPC PNO.
Crude butadiene ranging
from 35 to 75 percent purity proceeds through multiple production phases.
After the final fractionation phase, the
1,3-butadiene is at 99.8 percent purity, where it is sent to storage tanks for shipping.
The loss of containment
occurred in the final fractionation phase.
Figure 2
.
Block flow diagram of the butadiene production process at TPC PNO.
The highlighted area shows where
the loss of containment occurred.
(Credit:
CSB)
a
The flashpoint of 1,3-butadiene is
–
105
o
F [9, p. 239].
3
Fires and Explosions at
TPC Group Port Neches Operations Facility
Port Neches, Texas
|
Incident Date: November 27, 2019
|
No. 2020-02-I-TX
U.S. Chemical Safety and
Hazard Investigation Board
•
A simplified process flow diagram of the TPC PNO butadiene post-fractionation process is shown in
Figure 3
.
Indicated on the process flow diagram by the red ellipse is the area of interest as the potential origin of the
flammable vapor release.
a
Figure 3
.
Simplified process flow diagram of the TPC PNO butadiene post-fractionation process at the time of the
incident.
(Credit:
CSB)
Preliminary Incident Timeline
•
During the night shift that began on Tuesday, November 26, 2019, the unit was reportedly operating normally.
•
At 12:54 a.m.,
b
a loss of containment event occurred, causing the liquid level in the final fractionator A to drop
rapidly from its operating level. The CSB calculated the liquid volume at the time of the initial level drop to be
a
The likely location of release is based on data from the final fractionator A level controller and eyewitness accounts.
As of this update, the CSB
has not been able to visually confirm the failure location due to the extensive damage at the site.
b
Time obtained from correlating external time-stamped video to TPC PNO process data, using the initial loss of multiple alarms as the time of
the explosion.
Since the TPC PNO timestamp from their process control system was found to be four minutes and thirteen seconds ahead of the
time stamp from the video, the CSB subtracted four minutes and thirteen seconds from the TPC PNO timestamp.
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4
Fires and Explosions at
TPC Group Port Neches Operations Facility
Port Neches, Texas
|
Incident Date: November 27, 2019
|
No. 2020-02-I-TX
U.S. Chemical Safety and
Hazard Investigation Board
approximately 6,000 gallons.
The liquid, which was primarily butadiene,
a
emptied from the fractionator in less
than a minute (
Figure 4
).
The liquid vaporized upon release
b
and formed a vapor cloud. Three workers were in
the unit at that time. Two of them were facing toward the final fractionator A, and they both told the CSB after
the incident that they saw a pipe rupture. Of these two workers, one of them identified the release point (circled
in red in
Figure 3
)
to be in the suction piping of the final fractionator A to B transfer pump.
The third worker,
who turned toward the sound of the release after the release occurred, also believed it was the suction piping into
the final fractionator A to B transfer pump that failed.
The
workers’
observations are consistent with the
unit’s
recorded process data.
The CSB has not yet visually confirmed the failure location due to the extensive damage
and unstable structural conditions at the site.
•
Immediately following the loss of containment, the three workers quickly departed the unit.
•
At 12:56 a.m., the vapor cloud ignited, resulting in an explosion that created a pressure wave that heavily
damaged the site and caused damage to buildings, including houses, offsite.
Thermal imagery
c
provided by TPC
shows multiple fires following the explosion
(Figure 5
).
Figure 4
.
Process data trend graph showing the liquid level (in percent) in the final fractionator A dropping from its
operating level to zero in less than a minute.
The estimated liquid quantity in the fractionator at the time of the release
was 6,000 gallons (30,000 pounds).
d
(Credit:
CSB)
a
The composition of the contents at the bottom of the final fractionator A was not analyzed on-line; however, the design specification of the feed
into the final fractionator from the methyl acetylene removal tower was 98.00 wt.% 1,3-butadiene minimum.
b
The normal boiling point of 1,3-butadiene is 24.1
o
F [5, p. 7].
c
Thermal imaging devices measure infrared (thermal) radiation and translate the data to images.
In this instance, the colors progress from black
(least amount of radiation) to white (greatest amount of radiation).
d
Volume calculated based on the final fractionator A dimensions and liquid level of six feet.
The weight in pounds was calculated using an
assumed density of 38.75 pounds per cubic feet liquid butadiene.
5
Fires and Explosions at
TPC Group Port Neches Operations Facility
Port Neches, Texas
|
Incident Date: November 27, 2019
|
No. 2020-02-I-TX
U.S. Chemical Safety and
Hazard Investigation Board
Figure 5
. Thermal drone imagery of the TPC PNO facility South Unit taken the morning after the initial explosion.
(Credit:
TPC)
•
At least two additional explosions occurred following the initial blast.
At 2:40 a.m., a cell phone recording
captured an additional explosion (
Figure 6
).
That afternoon at 1:48 p.m., another explosion propelled one of the
facility’s
towers into the air (
Figure 7
). The tower landed within the confines of the TPC PNO facility.
In
addition to the propelled tower (later identified as an out-of-service debutanizer), four additional towers (
Figure
8
) fell as a result of the blast and/or fires: the final fractionator A, an extractive distillation absorber, an out-of-
service water wash tower, and the depentanizer.
6
Fires and Explosions at
TPC Group Port Neches Operations Facility
Port Neches, Texas
|
Incident Date: November 27, 2019
|
No. 2020-02-I-TX
U.S. Chemical Safety and
Hazard Investigation Board
Figure 6
.
Explosion at 2:40 a.m. on
Figure 7
.
Explosion at 1:48 p.m. on November 27, 2019 which
November 27, 2019 captured by cell
propelled one of the South Unit towers.
(Credit:
Huntsman
phone video (Credit:
TPC)
Corporation)
•
The explosion heavily damaged piping and equipment in the unit.
Some of the resulting ruptured portions of
piping could not be isolated. For instance, the area of interest indicated in
Figure 3
lies between the final
fractionator A and the final fractionator A to B transfer pump, and no remotely actuated isolation valve
a
existed
on that piping section upstream of the area of interest as the potential origin of release.
Flammable process fluid
continued to release from damaged equipment, and the fires burned for over a month. At 10:09 a.m. on January
4, 2020, the TPC Incident Command confirmed that all fires were out.
•
At 6:08 p.m. on Wednesday, December 4, 2019, the Port Neches Fire Chief issued a shelter-in-place order for the
City of Port Neches “out of an abundance of caution.”
At 10:00 p.m. that evening, the Jefferson County Judge
issued a voluntary evacuation order for the City of Port Neches.
At 12:29 p.m. on Thursday, December 5, 2019,
the Jefferson County Office of Emergency Management said that the shelter-in-place and voluntary evacuation
orders were lifted due to improved conditions.
•
Port Neches schools were also impacted.
Although Port Neches schools were closed for Thanksgiving break on
November 27, 2019, schools did not reopen until December 3, 2019, because school officials needed additional
time to clean debris, complete structural inspections, and repair school buildings [10].
After returning to school
for two days, the schools were closed again, and they ultimately reopened on December 9, 2019.
a
A manual isolation valve existed on this piping section downstream of the likely release point.
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7
Fires and Explosions at
TPC Group Port Neches Operations Facility
Port Neches, Texas
|
Incident Date: November 27, 2019
|
No. 2020-02-I-TX
U.S. Chemical Safety and
Hazard Investigation Board
Figure 8
.
Overhead depiction of TPC PNO South Unit showing the locations of the fallen towers.
(Credit:
TPC)
Popcorn Polymer
•
A solid substance called “popcorn”
polymer
a
(
Figure 9
) can form in process vessels containing a high
concentration of butadiene. Popcorn polymer is a hard, porous, opaque material created when oxygen reacts with
butadiene in various areas of a butadiene production plant [11, p. 830].
Popcorn polymer formation involves two
phases:
initiation (seed formation) and propagation to polymer chains (seed growth) [11, p. 830].
Oxygen reacts
with butadiene to form peroxides; butadiene peroxides react with butadiene to form popcorn polymer [8, pp. 8-9].
a
Popcorn polymer is so called because it is pyrophoric and makes a popping sound when exposed to air [14, p. 29]; it also has a physical
appearance resembling popcorn [5, p. 32]
8
Fires and Explosions at
TPC Group Port Neches Operations Facility
Port Neches, Texas
|
Incident Date: November 27, 2019
|
No. 2020-02-I-TX
U.S. Chemical Safety and
Hazard Investigation Board
Figure 9
.
Popcorn polymer in a manhole from another undisclosed butadiene unit, published in the Butadiene
Popcorn Polymer Resource Book.
(Credit:
International Institute of Synthetic Rubber Producers Inc. [12, p. 261])
•
High internal strain inside the popcorn polymer chains causes them to rupture and form new polymer seeds,
thereby increasing the total volume of popcorn polymer as the process repeats [8, pp. 8-9]. This large increase in
volume can produce enough pressure to swell or crack steel equipment.
Throughout the industry, the buildup of
popcorn polymer historically has caused equipment ruptures leading to loss of containment.
Figure 10
shows a
pipe rupture caused by the buildup of popcorn polymer in another butadiene unit at the Lavera petrochemical
complex located in Martigues, France in 2000 [12, pp. 154-159].
Figure 11
shows another pipe rupture, which
occurred at the PNO facility in 1999.
a
a
In 1999, the PNO facility was owned by Huntsman Corporation.
9
Fires and Explosions at
TPC Group Port Neches Operations Facility
Port Neches, Texas
|
Incident Date: November 27, 2019
|
No. 2020-02-I-TX
U.S. Chemical Safety and
Hazard Investigation Board
Figure 10
.
Pipe rupture caused by popcorn polymer in a butadiene unit in the Lavera petrochemical
complex.
(Credit:
French Ministry of the Environment [12, p. 157])
Figure 11
.
On July 29, 1999, a section of pump suction piping ruptured at the Huntsman PNO facility.
Huntsman Corporation owned the facility until TPC acquired it in 2006.
(Credit:
TPC)
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10
Fires and Explosions at
TPC Group Port Neches Operations Facility
Port Neches, Texas
|
Incident Date: November 27, 2019
|
No. 2020-02-I-TX
U.S. Chemical Safety and
Hazard Investigation Board
•
A piping segment that is open to the process but that does not have flow through it, for example due to a closed
valve in the segment preventing flow, is known as a “dead leg”
[13, p. 1].
Dead legs are known by the industry to
promote popcorn polymer formation [12].
a
•
From September 6, 2019 through the date of the incident (at least 82 days), the final fractionator A to B transfer
pump was out of service.
The suction piping into this pump was open to the process during this period but with
no flow through it, and was therefore a “dead leg.”
As discussed above, this is the piping segment that workers in
the unit observed to have ruptured.
•
Popcorn polymer was known to form in the South Unit before the incident.
Figure 12
shows a heat exchanger
bundle pulled from one of the methyl acetylene removal tower reboilers on or around September 10, 2019.
A
TPC employee also noted that the emergency pressure-relief valve
on this bundle “was plugged solid
with
popcorn and polymer.”
Figure 13
shows multiple locations where the TPC PNO facility has experienced
polymer fouling problems since July 2019.
Figure 12
.
Polymer found on methyl acetylene removal tower reboiler bundle pulled on or around September 10,
2019.
(Credit:
TPC)
a
The Butadiene Popcorn Polymer Resource Book contains numerous examples of popcorn polymer incidents attributed to the existence of dead
legs.
11
Fires and Explosions at
TPC Group Port Neches Operations Facility
Port Neches, Texas
|
Incident Date: November 27, 2019
|
No. 2020-02-I-TX
U.S. Chemical Safety and
Hazard Investigation Board
Figure 13
.
Simplified process diagram showing locations of recent polymer fouling (all dates shown are from 2019).
(Credit:
CSB)
•
On November 19, 2019
, TPC installed temporary filters on the liquid outlet of the final fractionator B to “catch
any popcorn polymer chunks before they reach the downstream piece of equipment.”
On November 25, 2019,
TPC collected a sample of polymer obtained from these temporary filters for analysis.
The CSB and OSHA
requested that TPC perform an analysis to determine the characteristics and activity level of this butadiene
polymer sample. The test characterization results indicated that the polymer collected was butadiene-based
popcorn polymer.
Also, those portions of the sample that were tested for activity level all experienced limited
growth (between 5 and 19 percent weight increase) over a six-day period.
Investigation Path Forward
•
The CSB is continuing to conduct its investigation of this incident. CSB investigators analyze a wide range of
aspects relating to incidents, including:
o
Equipment and system design;
o
Regulations, industry standards, and guidance;
12
Fires and Explosions at
TPC Group Port Neches Operations Facility
Port Neches, Texas
|
Incident Date: November 27, 2019
|
No. 2020-02-I-TX
U.S. Chemical Safety and
Hazard Investigation Board
o
Training, operations, and procedures;
o
Human and organizational factors;
o
Safety management systems; and
o
Historical and event data.
At the conclusion of the investigation, the CSB will publish a final investigation report discussing the facts,
conditions, and circumstances of the event; the cause(s) or probable cause(s); and may issue safety
recommendations to prevent the recurrence of similar incidents.
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13
Fires and Explosions at
TPC Group Port Neches Operations Facility
Port Neches, Texas
|
Incident Date: November 27, 2019
|
No. 2020-02-I-TX
U.S. Chemical Safety and
Hazard Investigation Board
References
[1]
TPC Group, "Contact," TPC Group, 2019. [Online]. Available: https://www.tpcgrp.com/contact. [Accessed 28
November 2019].
[2] J. R. Branick, "TPC Incident Related Documents and Declarations," 27 November 2019. [Online]. Available:
https://co.jefferson.tx.us/documents/TPC%20Incident%20Docs/tpcdocs.htm.
[3] TPC Group, "Port Neches Response - Situation Update," 25 February 2020. [Online]. Available:
https://portnechesresponse.com/port-neches-response-situation-update-2/. [Accessed 16 October 2020].
[4] Marsh JLT Specialty, "100 Largest Losses in the Hydrocarbon Industry," Marsh JLT Specialty, 2020.
[5] American Chemistry Council (ACC), "Butadiene Product Stewardship Guidance Manual," 2019. [Online].
Available: https://www.americanchemistry.com/Butadiene-Product-Stewardship-Guidance-Manual.pdf.
[Accessed 3 December 2019].
[6] Occupational Safety and Health Administration, "Process Safety Management of Highly Hazardous Chemicals,"
29 CFR 1910.119, Subpart H, 2020. [Online].
[7] "List of Regulated Substances under the Risk Management (RMP) Program," Environmental Protection Agency,
2020. [Online]. Available: https://www.epa.gov/rmp/list-regulated-substances-under-risk-management-plan-rmp-
program. [Accessed 3 April 2020].
[8] S. J. Korf and S. S. Seifert, "The identification of butadiene popcorn polymer," in
AiChE Spring National
Meeting
, San Antonio, 2013.
[9] Center for Chemical Process Safety, Guidelines for Safe Storage and Handling of Reactive Materials, New York:
American Institute of Chemical Engineers, 1995.
[10]
"Jefferson County officials cancel evacuation following TPC Group plant e," YouTube, 29 November 2019.
[Online]. Available: https://www.youtube.com/watch?v=yZj4KQQ0_eE. [Accessed 3 April 2020].
[11]
M. S. Kharasch, W. Nudenberg, E. V. Jensen, P. E. Fischer and D. L. Mayfield, "Inhibition of Polymerization:
Laboratory and Plant Control of Popcorn Polymer Growth,"
Industrial & Engineering Chemistry,
vol. 39, no. 7,
pp. 830-837, 1947.
[12]
International Institute of Synthetic Rubber Producers Inc., Butadiene Popcorn Polymer Resource Book, 2006.
[13]
A. Sloley, "Watch Out For Dead Legs,"
Chemical Processing,
pp. 1-6, 27 September 2011.
[14]
K. Kolmetz, A. Sloley, T. Zygula, W. K. Ng and P. Faessler, "Design Guidelines for Distillation Columns in
Fouling Service," in
The 16th Ethylene Producers Conference
, New Orleans, 2004.
[15]
Shell Chemicals, "Mixed C4s Product Stewardship Summary," 2017.
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Using the enthalpy of reaction for two reactions with ozone, determine the enthalpy of reaction for the reaction of chlorine
with ozone.
(1) CIO(g) + O,(g) → Cl(g) + 20,(g) AHxn = -122.8 kJ
AHn = -285.3 kJ
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(3)°O + (3)OIƆ (3)1Ɔ+(3)*o (£)
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12 22
Sucrose (C₁₂H₂₂O₁) is combusted in air according to the following
reaction:
C₁₂H₂₂O₁(s) + O₂(g) → CO₂(g) + H₂O(1)
12 22
11
How many moles of carbon dioxide would be produced by the
complete combustion of 21.7 grams of sucrose in the presence of
excess oxygen?
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A chemical is sprayed onto a lawn at a rate of 0.90 kg active ingredient per hectare. The chemical has a half-life of 30 days at 20C. A storm event occurs 15 days after application and causes 3.5% of the material present in the 25 hectare field to be lost (total losses). If average temperatures during the 15-day period were 17C, how much material (mass) was lost during the storm?
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If a chemical substance is produced at a rate of au(ẞ-u) per unit volume due to a chemical
reaction, derive the equation that the concentration of the chemical pollutant u(x, t) satisfies.
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- the kinetics of the reaction given were studied... etc Please provide an answer to part D. Thanks!arrow_forwardO Macmillan Learning The 1995 Nobel Prize in Chemistry was shared by Paul Crutzen, F. Sherwood Rowland, and Mario Molina for their work concerning the formation and decomposition of ozone in the stratosphere. Rowland and Molina hypothesized that chlorofluorocarbons (CFCs) in the stratosphere break down upon exposure to UV radiation, producing chlorine atoms. Chlorine was previously identified as a catalyst in the breakdown of ozone into oxygen gas. Using the enthalpy of reaction for two reactions with ozone, determine the enthalpy of reaction for the reaction of chlorine with ozone. (1) CIO(g) + 03 (g) → Cl(g) + 2O₂(g) (2) 203(g) 30₂(g) (3) 03(g) + Cl(g) →→→ ClO(g) + O₂(g) ▲Hixn = AHxn ▲Hixn AHixn = = -122.8 kJ = -285.3 kJ = ? kJarrow_forwardProf. Neiman and Prof. James were first to discovered in 1973 that chlorofluorocarbons (CFCs) were depleting the Earth’sozone layer when released into the atmosphere. Once they reach the stratosphere, Clis released from the CFCs molecules by interaction with UV light. Free Cl atoms areable to react with ozone in a catalytic cycle that converts O3into the more stable O2.It is estimated that a single Cl atom is able to react with∼100000 O3molecules.Although CFCs production was banned in 1996, there are still a substantial numberof motor vehicle air conditioners (MVACs) that use CFC-12 (CF2Cl2) as refrigerant.The average CFC-12 emission rate from operating MVACs has been estimated tobe 59.5 mg per hour per vehicle (Zhang et al.Environ. Sci. Technol. Lett.2017).How much chlorine, in kg, is added to the atmosphere in a year due to 100 millionMVACs using CFC-12 as refrigerant?arrow_forward
- hello maam/sir, kindly help me with this numbers please... kindly provide complete solution.. I PROMISE to give 5 star rating directlyarrow_forwardHere is a graph of the pressure of iodine (I,) in a reaction vessel during a certain chemical reaction. Use this graph to answer the questions in the table below. 30- olo 25 Ar 20.541)- atm 15- 10- 5- 50 100 150 200 250 300 seconds created destroyed Is 1, being created or destroyed by the chemical reaction? neither created nor destroyed If 1, is being created or destroyed, what is the rate atarrow_forward3. The decomposition of N2O5 in the gas phase was studied at constant temperature, 2N2O5 (g) → 4NO2 (g) + O2(g) The following results were collected: find nature) N2O5] 0.1000 Ln[N2O5] -2.30 2.65 2.99 -3.69 -4.38 -5.08 a. Complete the table. Using the data and graph paper, plot the [N2O5] versus time and Time (s) 10g. (LN) 0.0707 0.0500 50 0.0250 100 0.0125 200 0.00625 300 400 Ln[N2O5] versus time. Determine the value of k. Which graph did you use? graph *b. On your graph of [N2O5] versus time, highlight the times it takes for each halving of the reactant concentration. What is the half-life? Using this half-life calculate k. design experiments to find the activation energy,arrow_forward
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