1.

Introduction

The spread or release of toxic chemicals with the intent to result in harm is known as
the chemical attack. During an accident, process equipment can release toxic materials
quickly and in-significant quantities to spread in dangerous clouds throughout a plant site and
the local community. In the chemical process industry, raw materials are converted into
commercial products. Exothermic chemical reactions can lead to a thermal runaway if the
heat generation rate exceeds the heat removal rate. A runaway reaction is a reaction that is out
of control because the heat generation rate from the reaction exceeds the rate at which the heat
is removed from the system by the cooling media and the surroundings (CSB, 2002). A
runaway reaction is also known as one of the common cause resulting in overpressure.
During runaway reactions, which tend to accelerate with rising temperature, extremely
high volumes of non-condensable with high energy can cause the internal pressure of a vessel
or pipeline to rise rapidly. Runaway reactions are continuing to be a problem in the chemical
industry. A recent study showed that 26% of our major chemical plant accidents are due to
runaways. Pressure build-up during the runaway is caused by an increase in vapour pressure
of liquid components and by the production of non-condensable gases. As a runaway reaction
proceeds, the increased generation rate of vapour increases the vapour velocity, the mass flow
rate, and the inlet temperature in the overhead condenser. Basically, pressure relief valves may
not provide adequate protection because of their relatively slow response time. In such a
situation, vapour depressuring systems, rupture discs and emergency vents are preferred.
In this paper, a detailed survey of the incidents caused by runaway reactions was
performed. The results of this study can be used to identify the source of risk, to improve
safety, to reduce loss, and to design safer operation procedures. In the end of the report, the
inherent safety (IS) index of the process are analysed using the Chemical and Exposure Index
followed by design modification that is proven safe through:
I.
II.

Re-calculation of the IS index, and

Analyse the consequence contour before and after the implementation of the IS principle
using PHAST software.

U.S. Chemical Safety and Hazard Investigation Board

The U.S. Chemical Safety and Hazard Investigation Board (CSB) is an
independent federal agency charged with investigating industrial chemical
accidents at fixed facilities. It is designed to conduct scientific investigations
as to the root cause of chemical accidents and is not an enforcement or
regulatory body. A thorough CSB investigation of an industrial accident can
take several months, even sometimes over a year due to the complexity of
the situation.

II.1

Literature Review

The U.S. Chemical Safety and Hazard Investigation Board (CSB) conducted a
comprehensive investigation of a runaway chemical reaction at MFG Chemical (MFG) in
Dalton, Georgia on April 12, 2004 that resulted in the uncontrolled release of a large quantity
highly toxic and flammable allyl alcohol and allyl chloride into the community. The U.S.
Chemical Safety and Hazard Investigation Board (CSB) finds out that the runaway chemical
reaction rapidly pressurized the reactor causing the manway seal to fail, and then activated the
overpressure safety device. Unable to contain the toxic vapour or stop the runaway reaction,
the release continued until the chemical reaction ceased. CSB concluded that this incident was
avoidable.
An attempt to manufacture a new product resulted in a runaway reaction that overpressurized the reactor, activated the emergency vent, and released toxic vapour into the
atmosphere, exposing and injuring facility employees, nearby residents, and emergency
responders. The release forced more than 200 families from their homes. One MFG employee
sustained minor chemical burns and 154 people received decontamination and treatment at the
local hospital for chemical exposure, including 15 police and ambulance personnel assisting
with the evacuation. The reactor continued venting toxic vapour for nearly eight hours and the
evacuation order lasted more than nine hours.

2.1

Background

On the night of April 12, 2004, during an attempt to make the first production batch of
triallyl cyanurate (TAC) at MFG Chemical, Inc. (MFG), at their Callahan Road facility in
Dalton, Georgia. a runaway chemical reaction released highly toxic and flammable allyl
alcohol and toxic allyl chloride into the nearby community. At approximately 9:30 PM, the
reaction went out of control and over-pressurized a 4000-gallon reactor. The runaway reaction
caused the release of highly toxic and flammable allyl alcohol vapour and toxic allyl chloride
vapour into the community. The dense vapour continued to escape from the reactor for more
than eight hours. Neither the Dalton Fire Department emergency responders nor MFG
personnel had the personnel protective equipment required to enter the process area safely to
attempt to stop the vapour release. The Dalton Fire Department promptly ordered an
evacuation of all residents and businesses within a one-half mile radius of the facility. The
Dalton Police Department then dispatched officers to the neighbourhoods to alert the residents
to evacuate.
In this business workforce, there are 3 companies involved. The relationship of these
companies is illustrated below:
Lyondell Chemical Company

Manufacturer of allyl alcohol

MFG Chemical Company

Issue a PO
GP Chemical

Client for TAC

Figure 1: Relationship between companies involved

2.2

Investigation of Incident

The incident likely involved hazardous chemical reactions. Therefore, the CSB
launched an investigation to determine the root and contributing causes of the incident. The
CSB team began the investigation with the MFG management and senior engineering
personnel responsible for chemical process development and followed by a detailed
examination on the process equipment, the chemical transport and storage tanker (isotanker)
and the reactor cooling system. The investigation team also contracted modelling of the
vapour cloud release. The key findings based on their investigation are presented below:

There was a runaway reaction at the MFG facility during the TAC synthesis.
The runaway reaction resulted when operators added the entire quantity of
each reactant, as well as the catalyst, to the reactor at once, and was then

unable to control the reaction rate.

MFG did not conduct an adequate evaluation of the reactive chemistry
hazards involved in manufacturing triallyl cyanurate before attempting the
first production batch. Readily available technical literature, including specific
TAC synthesis accident histories would have alerted them to the reactive

chemistry hazards involved.

Lyondell Chemical (the allyl alcohol manufacturer) did not clearly
communicate to MFG management or GPC (the allyl alcohol buyer) that MFG
would be required to implement the EPA Risk Management Program
regulation, including conducting appropriate design reviews and preparing
comprehensive emergency plans, before receiving the allyl alcohol shipment at

the MFG facility.

MFG did not provide a hazardous vapour/liquid containment system on the
reactor emergency vent. The runaway reaction released allyl alcohol and allyl

chloride into the atmosphere and into a nearby creek.

MFG did not develop the comprehensive process hazards analysis, prestartup review, and emergency response elements required by the OSHA PSM

standard and the EPA Risk Management Program regulation.

MFG and GPC did not apply industry best practices for toll manufacturing
where MFG did not share certain critical process safety information with
GPC, and GPC did not ensure that MFG had addressed all hazards
associated with the process before attempting to produce the first production

batch. This industry best practices are highlighted in Guidelines for Process
Safety in Outsourced Manufacturing Operations (CCPS, 2000).

2.3

MFG Studies in TAC Synthesis

MFG personnel only conduct a research to confirm there are no any restrictions
that could adversely affect their TAC production. However, they did not conduct detailed
literature research addressing the reactive chemistry hazards involved in the process. The
following chemical equation shows the synthesis of triallyl cyanurate by reacting cyanuric
chloride with allyl alcohol in the presence of a catalyst:
Allyl Alcohol + Cyanuric Chloride + Catalyst

TAC + HCl + Catalyst (1)

HCl is the by-product formed from this reaction. The complete conversion of the cyanuric
chloride is achieved by using an excess amount of allyl alcohol. The neutralization reaction
between caustic soda and HCl is exothermic. Therefore the synthesize of the fixed-volume
batch of TAC is carried out using a 4000-gallon reactor with an external cooling jacket.
However MFG disregard the reaction between allyl alcohol and cyanuric chloride which is
also highly exothermic which could lead to significant heat generation. The synthesis of TAC
is illustrated through the flowchart attached in the appendix of this report.

2.4

Figure 2: Basic TAC Process Diagram

Process Upset

A short time after loading the allyl alcohol, the operators noticed that the reactor
temperature had increased from 32F to about 72F, presumably due to the addition of the
warm allyl alcohol. Ten minutes later, the operators noted that the temperature had already
climbed to 103F. The temperature continued to increase rapidly to 118 F, well above the
peak temperature of about 100F that they expected. Unknown to the engineers and operators,
it was almost at the temperature at which the exothermic decomposition reaction occurs.
Rapidly increasing pressure in the reactor caused the manway gasket to blow out. Dense,
white vapour immediately began to spray out of the manway. The rupture disc blew open
about 30 seconds later, sending additional white vapour out of the end of the 4-inch vent pipe
near the base of the reactor. The last observed reactor temperature was 124F (51C). The
runaway chemical reaction incident in the TAC process involved two reactions: (1) the
desired synthesis reaction to form the products; and (2) an undesired decomposition reaction.
The heat produced by the undesired decomposition reactions raised the temperature and
pressure of the reactor as follows:
Property
Maximum exoterm temperature (0C)
Maximum exoterm pressure (bar)

High Thermal Inertia

424
103

The detailed timeline of the incident occurrence were attached in the Appendix of this
report.

3.0

Analyze Inherent Safety (IS) Index

For this project, the IS index that will be used is the Chemical Exposure Index (CEI),
because of the toxic release incident. Furthermore, the toxic had been release is in the form of
gas. The Chemical Exposure Index (CEI) provides a simple method of rating the relative
acute health hazard potential to people in neighboring plants or communities from possible
chemical release incidents. Therefore, to calculate the Airborne Quantity, the following
equation will be applied which is suitable for the gas release incident. The equation can be
seen as follow:
AQ =4.751 106 (D 2 )( Pa )

MW
T +273

Where:
Pa = Absolute pressure (Pg + 101.35)
Pg = Pressure gauge (kPa)
D = Diameter of the hole (mm)
MW = Molecular Weight of Allyl alcohol (MW = 58.1)
T = Temperature (C)

From the scenario, the value of pressure gauge is assume bigger than the set pressure
of rupture disc to blew down which is, 75 psig, because of poor monitoring system for
pressure. So, the assumption value for pressure gauge is P g = 80 psig. From the equation, the
parameter needed is absolute pressure. So, the calculation of Pa as follows:
1. Change the unit from psi to kPa
6.89475729 kPa
80 psi
1 psi
551.58 kPa

2. Calculate Pa
Pa=P g +101.35 kPa
Pa=551.58+101.35
Pa=652.93 kPa

Furthermore, since the reactant inside the reactor which is allyl alcohol is vaporize
from liquid to gas and escape to the environment, therefore, the temperature of the reaction is
also assume bigger than the boiling point of the allyl alcohol which is 97C. Therefore, as per
the calculated maximum exoterm temperature from the literature review, T =424 C
From the scenario, there are 2 source of leak, first from the 18-inch manway gasket
and 4-inch vent pipe. So, the value of Airborne Quantity (AQ) is equal to the total for both
leaks. So, the value of AQ must be calculated for leak at diameter of 4-inch and 18-inch,
respectively.
1. Calculation for 4-inch diameter.
Since the diameter is 4-inch, the size of the pipe that needs to be account is 2- inch
(50.8 mm)
Substitute the value into the equation:
2

AQ =4.751 106 ( 50.8 mm ) (652.93 kPa)

58.1
424+273

AQ =2.31 kg/ s
2. Calculation for 18-inch diameter.
Since the diameter is 18-inch, the size of the pipe that needs to be account is 20% of
cross section area.
CSA = 254.47 inch2
0.20 (254.47) = 50.89 inch2
4
D=
50.89=8.05 204.47 mm

Substitute the value into the equation:

2

AQ =4.751 106 ( 204.47 mm ) (652.93 kPa)

58.1
424+ 273

AQ =37.44 kg /s

Then, calculate the Chemical Exposure Index (CEI) value:

CEI=655.1

AQ
ERPG2

Allyl alcohol use AEGL instead of ERPG. Replace ERPG with AEGL in the equation.
Assume the duration for the exposure of the toxic is 15 minutes.
AEGL for Allyl alcohol is:

ppm
2.1
4.2
130

AEGL 1
AEGL 2
AEGL 3

mg/m3
5.37
10.7
333

Therefore:
1. 4-inch diameter
CEI=655.1

2.31
10.7

CEI=304.38

2. 18-inch diameter
37.44
CEI=655.1
10.7

CEI=1225.42
Since, CEI value more than 1000, therefore, CEI = 1000.
Then, calculate the Hazard Distance for both situations.
HD=6551

AQ
ERPG

1. 4-inch diameter
For AEGL 1;
2.31
HD=6551
5.37

HD=4296.62 m

For AEGL 2;
2.31
HD=6551
10.7

HD=3043.84 m

For AEGL 3;
2.31
HD=6551
333

HD=545.62m
2. 18-inch diameter
For AEGL 1;
37.44
HD=6551
5.37

HD=17297.70 m
Since, HD value more than 10 000, therefore, HD = 10 000.
For AEGL 2;
37.44
HD=6551
10.7

HD=12254.16 m
Since, HD value more than 10 000, therefore, HD = 10 000.
For AEGL 3;
37.44
HD=6551
333

HD=2196.61m
Therefore, further reviews as well as design modification need to be done on the process to
reduce the impact if the accident happens.

4.0

Sequence of Vapour Dispersion Modelling in PHAST

The flowchart below illustrates the procedure that leads to the Chemical Exposure Index
calculation starting from the scenario selection to PHAST toxic vapour release modelling.
This procedure is prior to the implementation of the design modification.

ScenarScenario: Reactant in warm condition & poor cooling system

Scenario:
Reactant in
warm condition
& poor cooling
system

cause runaway
reaction

Temperature of
the reaction
high
(exothermic)

Pressure
increase

Reactant change
to vapour

Higher than
boiling point of
Allyl alcohol

Cause manway
gasket burst and
rupture disc
blow down

PHAST

Figure 3: Procedure for CEI calculation before Design Modification

io: Reactant in warm condition & poor cooling system

Wind direction and speed, ambient temperature, mixing (discharge) height, and atmospheric
stability are typical inputs used to simulate vapour plume transport and dispersion. Since the
released occurred after sunset at approximately 9:30PM and with calm wind condition, a
slight stable atmosphere (Pasquill-Gifford class E) was chosen. There were two discharge
point involved in the release:
A leaking gasket on an 18-inch diameter reactor manway on top of the reactor.
Followed by discharge through a 4-inch diameter vent line after the reactor rupture
disc blew.
Based on the analysis shown below, the rupture disc vent pipe discharge was directed
downward, close to the ground. The hazard distance of the release is shown in map below:

Figure 4: Hazard Zone for Rupture Disk Release

Figure 5: Hazard Zone for Manway Gasket Release

ERPG/AEGL
ERPG/AEGL
ERPG/AEGL

5.0

Proposed

Design Modification

Minimize the
temperature of the
reactant;
moderate the
system (cooling
system)

Can control the

temperature and
pressure of reaction

Create new scenario

PHAST

Take standard
operating
parameters for the
process

Figure 6: Procedure for CEI Calculation after Design Modification

Moderate the size of the reactor

MFG should recalculate the ability of the reactor to remove access heat since the heat

removal capacity of a reactor equipped with an external jacket is directly proportional to the
ratio of the jacketed surface area to reactor volume. Thus, the engineers need to improvise the
calculations as the surface-to-volume decreases as the reactor volume increases.

Reduce the controlling temperature

Apart from moderating the reactor size, reducing the control temperature will reduce
the exothermic rate of reaction and also easy to control especially in large scale production
reactor. By reducing the temperature inside the reactor, the pressure will also reduce to a safer
level. Controlling an exothermic reaction depends on the interaction among the kinetics and
reaction chemistry; the plant equipment design; and the operating environment.

Rearrange the reaction process

The reaction intended is to synthesize triallyl cyanurate (TAC) by reacting cyanuric
chloride with allyl alcohol in the presence of a catalyst. However, the reaction produces
hydrogen chloride (HCl) as a by-product. In order to ensure complete conversion of the
cyanuric chloride, the procedure specified an excess amount of allyl alcohol and also adding
sodium hydroxide to neutralize HCl. The rearrangement reaction of TAC is carried out by
heat-treating TAC in the presence of a catalyst. In the preferred embodiment of the present
invention, the rearrangement reaction is carried out in a reaction solvent (for example, xylene)
in the presence of a copper catalyst.
Applying the American Institute of Chemical Engineers Center for
Chemical Process Safety, Guidelines for Process Safety in Outsourced
Manufacturing Operations (CCPS, 2000)
It is recognizable as an industry recognized best practice that provides comprehensive
guidance for safe tolling operations.

Recommends that the client become familiar with the tollers planned
CCPS endorses the client, which is the GP Chemical (GPC) to become familiar with
MFGs planned operation and audit the health, safety and environmental practices as part of
the clients product stewardship responsibilities. GPC should ensure MFG specifically
addressed the hazards of production-scale manufacturing of TAC.

 Ensuring training program

CCPS best practice guidelines recommend that the GPC ensure that the training
program at the MFGs facility meets process safety, and environmental risk management
training recommendations and requirements. GPC should request and review the MFG
employee-training program to make sure that adequate training addressing the hazardous
chemicals involved in TAC production.

Make audit during operations

The guidelines also mention regarding the client (GPC) should make audits during
ongoing operations in order to assure that operations are going as planned and obligations
are being met. GPC should visit the MFG facility more often, or actively participate in the
verification runs or the attempt to make the first full-scale production batch.

Evaluating good process safety

The guidelines recommend evaluating good process safety practices even, when a
candidate toller is not currently regulated by a governmental process safety requirement and
the proposed toll project will not trigger regulation. Actions need to be taken although the
raw materials are not regulated by the Risk Management Program (RMP) or Process Safety
Management (PSM).

Discuss and implement any changes made

CCPS best practice guidelines recommend that MFG share any techniques,
information or experience learned as part of the contractual agreement with the client. MFG
should discuss and agree on any changes made to the equipment, chemicals, technology or
procedure of the tolling arrangement with the client (GPC). MFG should share all process
information with GPC and also adhere to the procedures that have been made. The operators
also need to consider any actions that might increase the probability of a runaway reaction if
the full production quantity is added of each raw material to the reactor.

 Applying and implementing Management of Change (MOC)

CCPS guidelines recommend MFG to discuss and agree on any changes made to the
equipment, chemicals, technology or procedure of the tolling arrangement with GPC. If
covered under PSM or RMP, any deviation from the original design specifications is
considered a change. Any change requires MFG and GPC to address the hazards and risks
associated with the production process. Ensure the hazard evaluations address critical process
controls,

overpressure

protection,

alarms,

and

other

equipment

such

as

vent

collection/containment devices to minimize the possibility and consequences of a toxic or

flammable release.

Conduct process hazard analyses

The CCPS guidelines also mentioning for every new situation or changes, a process
hazard analysis should be conducted. All aspects (including human factors) should be
considered while performing PHA to identify potential problems caused by the scale-up.

Conducting intensify observation

Guidelines of CCPS recommend augmenting observation during scale up of the
critical process characteristics that were designed in pilot testing to take into account the
order-of-magnitude changes in vessel size and quantity of materials that may have been
engineered into the new process. MFG should adequately evaluate the hazards associated with
the scale-up of the process, such as evaluation of the heat removal capability of the production
reactor compared to the bench-scale testing.

Provide comprehensive emergency response

Create a comprehensive emergency response plan and provide equipment and training
that is appropriate to the duties assigned to employees in the event of an emergency.
A summarized version of the step-by-step layers are shown in the flowchart below:

 Mitigate all possible dangers identifed with the help of

results generated from SAL, RAL and EAL.

Possible worst-case scenarios in equipment units using

appropriate models.

Assesses the intended reaction, unintended reactions and

the reactivity of substances
If reactivity between substances exists or reactivity indices
are higher than acceptable limit, appropriate measures can
be taken

SafetyTechnology
Technology
Assessment
Layer

Equipment
Assessment
Layer (EAL)

Reactivity
Assessment
Layer (RAL)

Substance

Substance
All substances present in the process are assessed with the
Assessment
help of EHS method
Layer
Result in each category, i.e. potential of danger, is
obtained in the form of index in the range between zero
and one and physical value

7.0

Reference

Health and Safety Executive (HSE) [Online], 2007. Chemical Reaction Hazards and the Risk of
Thermal Runaway, www.hse.gov.uk/pubns/indg254.htm, London, UK: HSE.

CCPS. Inherently Safer Chemical Processes, A Life Cycle Approach, New York: AIChE, 2004.

Investigation Report on Toxic Chemical Vapor Cloud Release. April 12, 2014. U.S. Chemical Safety
and Hazard Investigation Board.

Booth, A.D. et. al. Design of emergency venting system for reactors - Part 1, Trans IChemE, vol. 58
(1980) 75-79.
Health and Safety Executive (HSE), 2000. Designing and Operating Safe Chemical Reaction Process,
Norwich, U.K., HSE Books, 2000.

8.0

Appendix

Figure 7: Overpressure rupture disc & vent pipe on top of reactor

Figure 8: 18-inch Reactor Manway

Figure 9: Toxic Vapour Release Timeline