Reaction Engineering and Design

Safety Module 2b: Synthron Runaway Reaction1†

Problem Statement:
On January 31, 2006, a vapor cloud explosion killed one worker and injured fourteen people at the
Synthron, LLC facility in Morganton, NC. The explosion destroyed the facility and damaged
buildings in the nearby community. Following investigation, the CSB issued a final report (found
below) which explains how a runaway reaction caused the explosion1.

The product that was being manufactured at the time of the incident was a liquid acrylic polymer
industrially known as Modarez MFP-BH. In planning for the polymerization of the MFP-BH batch,
managers at the facility made several changes in reaction conditions that increased the potential
for a dangerous runaway reaction. The customer ordered 12% more MFP-BH than was
polymerized in a standard reaction, and Synthron decided to scale up the recipe to produce a single
batch rather than running two half-batches. This decision was made to save time and effort, but
the changes in conditions increased the total amount of monomer in the reactor by 45%, increased
the concentration of the monomer by 27%, and increased the atmospheric boiling point of the
mixture of the mixture by almost 5oC. These changes were a result of modified solvent amounts,
and they combined to increase the heat output from the reaction to at least 2.3 times greater than
the standard recipe.

Although the chemists, manager, and superintendent on-site all reviewed the changes in solvent
quantities and the potential changes in boiling point that would result, they did not recognize the
impact that increased monomer could have on the reaction rate or total rate of heat release. This
oversight proved deadly, as a runaway reaction occurred, which resulted in the vapor cloud release
and eventual explosion.

Synthron Video: (https://www.youtube.com/watch?v=sRuz9bzBrtY) Note: Only 2:00-7:00 is

relevant for this problem.
Synthron Incident Report: (https://www.csb.gov/file.aspx?DocumentId=5619)

Synthron polymer reaction

1†
Adapted from the problem by Ronald Willey, Seminar on a Nitroaniline Reactor Rupture. Prepared for SAChE,
Center for Chemical Process Safety, American Institute of Chemical Engineers, New York (1994). Also see
Process Safety Progress, vol. 20, no. 2 (2001), pp. 123–129. The values of ΔHRx and UA were estimated from the
plant data of the temperature–time trajectory in the article by G. C. Vincent, Loss Prevention, 5, 46–52.
1
“The First Responder,” Volume 12, Issue 1. Jan 31, 2008.
<https://www.aristatek.com/Newsletter/JAN08/JAN08ts.aspx>
1
Reaction Engineering
(a) It is important that chemical engineers understand what the accident was, why it happened
and how it could have been prevented in order to ensure similar accidents may be prevented.
Applying a safety algorithm to the accident will help achieve this goal. In order to become
familiar with a strategy for accident awareness and prevention, view the Chemical Safety
Board video on the Synthron explosion and fill out the following Safety Algorithm for the
incident. See definitions on the last page. If necessary, view the Synthron incident report.

Safety Analysis of Synthron Incident

Activity: _________________________
_________________________
Hazard: _________________________
_________________________
Incident: _________________________
____________________________________________________
Initiating Event: _________________________
____________________________________________________
Preventative Actions and
Safeguards: _________________________
_________________________
Contingency Plan/
Mitigating Actions: _________________________
_________________________
Lessons Learned: _________________________
_________________________________________

For parts (b) through (e), download the following files based off software preferences. Wolfram,
Polymath, and MATLAB code can be found at the following link:
http://www.umich.edu/~elements/5e/13chap/live.html

Note: Due to the complexity of the problem, it is advised to use Wolfram or MATLAB, so the
proper graphs are already provided. If Polymath is your preferred method, please be sure to read
the notes at the top of the file to avoid confusion.

For more information on the derivations, definitions, and calculations used in the plots for this
incident, please review the Synthron Safety Module Case Study from the Elements of Chemical
Reaction Engineering website here.

2
Reaction Engineering
Sample temperature-time trajectory using Wolfram:

b.) Describe and discuss the original recipe temperature-time trajectory.

c.) What is the critical initial volume of reactants (Vo) above which the reactor will explode?
For the sake of simplicity, assume the reactor will explode if the contents of the reactor
remain above 350 K at 500 s after the start of the reaction, as the lack of cooling will result
in an unsafe pressure increase.

d.) Vary two parameters of your choice that you think will have the most effect on the
explosion and describe what you find.

e.) Write a set of conclusions after completing the previous questions.

Parts (f)-(h) are based on industry practices used to assess process safety. For more information
on process safety and its importance in chemical engineering, please visit the University of
Michigan SafeChE website here. It is recommended that professors only assign 1-2 of the
following parts due to the similar nature of the questions.

f.) Review the explanation of the components of a BowTie diagrams found here. After
reviewing the information, create a BowTie diagram for the Synthron reaction incident.

g.) A HAZOP study is structured analysis of process design to identify potential vulnerabilities
in a facility. Review the background on how to conduct a HAZOP study here before
completing one for the following system. It is important to note that not all guidewords and
parameters will be relevant for different systems. Some information is given here for
guidance:

3
Reaction Engineering
 System to consider: The semi-batch reactor vessel and the heat exchanger used to cool the
vapor that was allowed to leave the reactor.

Process Parameters to Consider: Temperature, Pressure, Level, Composition, Heat

Exchanger Flow ______

(i) Fill out the HAZOP chart as shown in the tutorial. Some information has been filled out
here for you.
Guideword + Parameter = Causes Consequences Safeguards Recommendations
Deviation
______ Level Charging more
feed from the
original recipe
than usual
Other Composition Than Changing usual
Usual feed recipe
and/or feeding
all at once rather
than
continuously
______Temperature 1.High reaction
rates due to high
initial
concentrations
2. Insufficient
heat exchange
due to fouling
_______Pressure

Less (or No) Heat

Exchanger Coolant Flow

4
Reaction Engineering
 (ii) When conducting a HAZOP, you will often find combinations of guidewords and
parameters that describe a possible situation for the system that is not hazardous. For the
given process parameters, give an example, explain why the situation is not hazardous, and
describe another consequence that could occur. HINT: Consider process efficiency

(iii) Write a short conclusion on some takeaways from completing a HAZOP for this
system and recommendations you would make.

h.) A Layers of Protection Analysis (LOPA) is a semi-quantitative study to identify available

safeguards and determine if the safeguards sufficiently protect against a given risk. Review
the background on how to conduct a LOPA study here before filling the table out for the
system described in this module. Some information is given for guidance:
• Assume that the plant can only accept a moderate risk
• Assume that the reaction involved in this process is carried out 100 times per year
• Per the incident report, the explosion killed one worker, injured 14 more, and
bankrupted the company

LOPA Study for Synthron Runaway Explosion

Cause: Operator error (charging more feed than usual)

Initiating Event
Consequence: Unexpected heat release leading to reaction
runaway and dangerous pressure increase inside the
reactor

FOIE:

Description of IPL1, IPL2, ... Pressure relief valve

IPL(s)
PFD = PFD1 x PFD2 x ...

MCF = FOIE x PFD

MCF
Category of MCF:

Impact: Killed a worker and injured 14 more. Damages

Severity were severe enough to bankrupt the company

Category:

Type of risk:
Risk
Acceptable / Unacceptable?

If risk evaluated above is unacceptable, please continue below:

Description of P-IPL1, P-IPL2, ...

Proposed IPL(s)
(P-IPL(s)) P-PFD = P-PFD1 x P-PFD2 x ...

5
Reaction Engineering
 MCF = FOIE x PFD x P-PFD
MCF
Category of MCF:

Type of risk:
Risk
Acceptable / Unacceptable?

i.) Describe what was the most unsettling to you about this incident.

6
Reaction Engineering
 Definitions

Activity: The process, situation, or activity for which risk to people, property or the environment
is being evaluated.

Hazard: A chemical or physical characteristic that has the potential to cause damage to people,
property, or the environment.

Incident: What happened? Description of the event or sum of the events along with the steps that
lead to one or more undesirable consequences, such as harm to people, damage to property, harm
to the environment, or asset/business losses.

Initiating Event: The event that triggers the incident, (e.g., failure of equipment, instrumentation,
human actions, flammable release, etc.). Could also include precursor events, (e.g., no flow from
pump, valve closed, inadvertent human action, ignition). The root cause of the sum events in
causing the incident.

Preventative Actions and Safeguards: Steps that can be taken to prevent the initiating event from
occurring and becoming an incident that causes damage to people, property, or the environment.
Brainstorm all problems that could go wrong and then actions that could be taken to prevent them
from occurring.

Contingency Plan/ Mitigating Actions: These actions occur after the initiating event. They are
steps that reduce or mitigate the incident after the preventative action fails and the initiating event
occurred.

Lessons Learned: What we have learned and can pass on to others that can prevent similar
incidents from occurring

BowTie Diagram: A qualitative hazard analysis tool through which potential problems and
consequences associated with a hazard are studied through a pictorial representation. Necessary
preventive and mitigating barriers are determined to reduce the process safety risk.

Hazard and Operability Study (HAZOP): A qualitative hazard analysis tool that uses a set of
guide words to determine whether deviations from design or operating intent can lead to
undesirable consequences. The existing safeguards are evaluated and if required, actions are
recommended to mitigate the consequences.

Layer of Protection Analysis (LOPA): A semi-quantitative study that determines initiating event
frequency, consequence severity, and likelihood of failure of independent protection layers (IPLs)
to calculate the risk of a scenario. If the existing risk is intolerable, then additional IPLs are
suggested to bring down risk to an acceptable level.

i
In collaboration with Zach Gdowski, University of Michigan

7
Reaction Engineering