S2S

A GATEWAY FOR PLANT AND PROCESS SAFETY

Proposal N°: CTC1 – 2001 – 43061

Contract N°: G1RT – CT – 2002 – 0594

Document Title: INTRODUCTION TO THE SYSTEMATIC ASSESSMENT

OF THERMAL RISKS OF CHEMICAL REACTIONS

Author(s): Dr. F.Stoessel, Swiss Safety Institute

Document number: D_WP2&3_T0_SWISSI05(1)

Synopsis of contents

This document presents a systematic approach to the assesment of themral risks related to
chemical reactions.

Contents

1. Thermal Risks.................................................................................................................................3
1.1 Foreword....................................................................................................................................3
1.2 Definition....................................................................................................................................4
2. Systematic assessment....................................................................................................................4
2.1 Runaway Scenario......................................................................................................................4
2.2 Severity.......................................................................................................................................6
2.3 Probability..................................................................................................................................7
2.4 Thermal Process Safety..............................................................................................................8
3. Criticality of Chemical Processes...................................................................................................8
3.1 Assessment of the Criticality......................................................................................................8
3.2 Description of the criticality classes:..........................................................................................9
3.3 Measures...................................................................................................................................10
4. Practical Procedure for the Assessment of Thermal Risks............................................................11
1 Thermal Risks
1.1 Foreword
The assessment of thermal risks inherent to chemical reactions is difficult because it involves
various skills and disciplines:
· Process design:
The mode of operation is a particularly important risk determining factor. Obviously, a
batch reaction, where all reactants are charged initially is more difficult to control than
a semi-batch operation, whereby one of the reactants is being charged progressively as
the reaction proceeds.
· Engineering:
Design and lay-out of plant/equipment and built-in controls play an important role in
mastering an exothermic process. The capacity of the heating/ cooling system is
especially important in this context.
· Chemistry:
The nature of the process and the behavior of products involved must be known, not
only under intended reaction conditions, but also in case of unintended deviations (e.g.
possibility of side-reaction, instability of certain compounds, tendency toward
decomposition).
· Physical-chemistry / reaction kinetics:
The dynamics of a chemical reaction and the thermo-physical properties of reaction
masses are of primary importance for any risk assessment.
The comprehension and interpretation of thermal data is not always easy. This document is
intended to render guidance in interpreting thermal data and in assessing thermal hazards by
taking a systematic and structured approach - i.e., by asking the relevant questions and by
finding the pertinent answers derived from selected thermo-analytical data.
Thus we use a selective approach which guarantees that all the necessary data are measured
and correctly interpreted. A new systematic methodology for the analysis of the thermal risks
was worked out in the central safety research laboratory. This methodology is based on a
powerful tool, i.e. the design of a runaway scenario i. This scenario will help to ask the right
questions and to determine the data required for the risk assessment.
The goal of this document is not to make turn the reader into a specialist in thermal safety, but
to guide those who perform risk analysis of chemical processes in their task, to help them
understand the thermal aspects of processes, and -finally- to develop a common and easily
understandable language between specialists and non-specialists.
The methodology presented in this paper is the result of long-time experience and concern
with the assessment of thermal risks in the chemical process industry gained in the Central
Safety Research Laboratories of Ciba. Therefore the author would like to thank his
colleagues: K. Eigenmann, F. Brogli, R. Gygax, H. Fierz B. Urwyler and
W. Regenass, who all participated in the development of the methodology and techniques
covered in this paper.
1.2 Definition
Traditionally, "risk" is defined as the product of the severity of a potential incident by its
Severity
probability of occurrence. Hence, risk assessment requires the
evaluation of both the severity and the probability. Obviously, the
HIGH results of such an analysis must be used to design measures for
RISK the reduction of the risk (Figure 1). The question which arises
now is: what do severity and probability mean in the case of
Measures
thermal risks inherent to a particular chemical reaction ?

Low
Risk

Probability

Figure 1: Risk Diagram

The thermal risk linked to a chemical reaction is the risk of the loss of control of the reaction
and the associated consequences (e.g. triggering a runaway reaction). Hence it is necessary to
understand how a reaction can "switch" from its normal course to runaway conditions. In
order to make this assessment, the theory of thermal explosion needs to be understood along
with the concepts of risk assessment. The theory of thermal explosion will be shortly
summarised. The risk assessment implies the knowledge of the severity and of the probability
of occurrence of a runaway.

2 Systematic assessment
2.1 Runaway Scenario
The behaviour of a chemical system during a runaway will be demonstrated by the example of
an exothermic batch reaction. A classical procedure is as follows: reactants are charged into
the reactor at room temperature and heated up under stirring to the reaction temperature and
held where cycle time and yield are optimised. After the reaction has been completed, the
reactor is cooled down and emptied (dashed line in Figure 2).
Let us now assume that, while the reactor is at the reaction temperature, a cooling failure
occurs (point 4 in Figure 2). If at this instant unconverted material is still present in the
reactor, the temperature will increase due to the completion of the reaction. This temperature
increase will be proportional to the amount of non reacted material. At the temperature
reached at the end of this period, a secondary decomposition reaction may be initiated. The
heat produced by this reaction may lead to a further increase in temperature (period 6 in
Figure 2).
The following questions will help us to develop the runaway scenario and to provide data for
the risk assessment.
1. Can the process temperature be controlled by the cooling system?
This is a typical question which should be answered during the process development. To
ensure the thermal control of the reaction, the power of the cooling system must be
sufficient to dissipate the heat produced in the reactor.
2. What temperature can be attained after runaway of the desired reaction?
The answer to this question necessitates a study of the kinetics of the reaction, in
order to determine the degree of accumulation in the reactor as a function of time.
The concept of MTSR (Maximal Temperature of the Synthesis Reaction) was
developed for this purpose.
3. What temperature can be attained after runaway by decomposition?
The thermal data of the secondary decomposition reactions allow one to calculate the
adiabatic temperature rise and to determine the final temperature starting from the
temperature level MTSR. This temperature gives a direct indication of the possible
consequences of a runaway.

A desired reaction
B decomposition reaction
1 normal process
2 ΔTad (desired reaction)
3 ΔTad (decomposition reaction)
4 Cooling failure

T (°C)
T
fin

3
A B T
ad
5
MTS R
6
T 2 TMRad
ad
Tp

1 4 T (h)

Figure 2: Runaway Scenario

4. At which moment does the cooling failure have the worst case consequences?
The amount of unconverted reactants and the thermal stability of the reaction mass may
vary with time. Thus it is important to know at which instant the accumulation, and
therefore the thermal potential, is the highest. This will be the worst case, and obviously
the safety measures have to account for it.

5. How fast is the runaway of the desired reaction?

 Generally, industrial reactors are operated at temperatures where the wanted
reaction is fast. Hence, a temperature increase above the normal process
temperature will cause a significant acceleration of the reaction: therefore, in most
cases, this period of time is very short (see period 5 in Figure 2).

6. How fast is the runaway of the decomposition starting at MTSR?

The dynamics of the decomposition reaction play an important role in the determination
of the probability of an incident. The concept of Time to Maximum Rate under adiabatic
conditions (TMRad) was developed for that purpose.

The questions mentioned in this scenario can be answered using the results of calorimetric
experiments which can be directly used in the determination of the characteristic temperature
levels: after a cooling failure they will give us first the temperature due to the runaway of the
desired reaction (MTSR in Figure 2) and then the temperature reached after the runaway of
the decomposition reaction (Tend). In case of a large temperature increase, some components
of the reaction mixture can be vaporised and therefore the pressure of the system will
increase. This may result in the rupture of the vessel and heavy damage.

2.2 Severity
Most reactions in the fine-chemicals industry are exothermic. The energy of reaction or of
decomposition is a direct measure of the severity, i.e. the potential of destruction, of a
runaway. Adiabatic temperature rise can be calculated easily by dividing the energy of
reaction by the specific heat capacity :
The following heat capacities can be used as a first
Q approximation: Cp
Tad  R (1) Water 4.2 kJ/kg/K
Cp Organic liquids 1.8 kJ/kg/K
with: Tad adiabatic temperature rise [K] Sulphuric acid 1.3 kJ/kg/K
QR energy of reaction [kJ/kg] Good and easy to remember 2 kJ/kg/K
Cp specific heat capacity [kJ/kg/K] (for organic material)

The adiabatic temperature rise is not only important in the determination of the temperature
levels, but also to assess the dynamics of a runaway. As a general rule, high energies result in
fast runaway or thermal explosion, while lower energies (adiabatic rise below 100 K) result in
slower temperature increase rates (Figure 3) given the same activation energy, the same initial
heat release rate and starting temperature.
600
(°C)
Tad= 400 K
500

400
Tad= 200 K
300

Tad= 100 K
200

100 Tad= 50 K
(h)

0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0

Figure 3: Adiabatic runaway curves with different Tad

As an example, for the assessment of the potential severity of a reaction, the following table
shows the effect of typical energies of a desired synthesis reaction and a decomposition
reaction:
Table 1: Example of typical energies and their effect
Reaction Desired Decomposition
Energy 100 kJ/kg 2000 kJ/kg
Adiabatic Temperature Rise 50 K 1000 K
Evaporation of Methanol per kg of 0.1 kg 1.8 kg
Reaction Mixture

It becomes obvious that while desired reactions, in many cases, are not by themselves
inherently dangerous, decomposition reactions may lead to dramatic effects. For example, if
the boiling point is reached during runaway, the amount of solvent evaporated can be
calculated. In the example above, it is unlikely that the energy from the desired reaction
would cause an effect in a properly designed industrial reactor. Nevertheless, a possible
secondary effect of the evaporation of solvents is the formation of an explosive vapour cloud,
which in turn can lead to a severe room explosion if ignited. The probability of this type of
occurrence must be assessed.

The severity of the runaway can thus be evaluated using the levels of
temperature attained if the desired reaction (Question 2) and the
decomposition reaction (Question 3) proceed under adiabatic conditions.

2.3 Probability
Presently there is no direct quantitative measure of the probability of occurrence of an
incident, or in the case of thermal process safety, of the occurrence of a runaway reaction. But
if we consider the runaway curves presented in , it is clear that in case (1) there is enough time
left to take measures to regain control of the reaction, whereas in case (2) the runaway
reaction takes a very fast course and there is very little time to take measures. If we compare
the probability of runaway in both cases, it becomes clear that the probability is higher in case
(2) than in case (1). Thus, while we cannot easily quantify probabilities, we can at least
compare them on a semi-quantitative scale.
T (°C)

(2)
(1)

t (h)

0 10 20
Figure 4: Time scale as a measure of probability
Our experience indicates that three levels of probability - low, medium and high - are
sufficient for the assessment of thermal risks. For chemical reactions on an industrial scale
(not for storage or transportation), we can consider a probability to be low if the time to
maximum rate of a runaway reaction under adiabatic conditions is longer than 1 day. The
probability becomes high if the time to maximum rate becomes less than 8 hours (1 shift).
These time scales are only orders of magnitude and are dependent on many factors, among
them the degree of automation, the training of the operators, the frequency of electrical power
failures, size of the reactor, etc. This scaling of probabilities is only valid if something is
being done due to cope with the known severity.

The probability can be evaluated using the time scale: If, after the cooling failure
(question 4), there is enough time left (questions 5 and 6) to take emergency
measures before the runaway becomes too fast, the probability of the runaway will
remain low.

2.4 Thermal Process Safety

The runaway scenario shows how the loss of control of the desired synthesis reaction leads
to a temperature level above the normal process temperature which may trigger a secondary
decomposition reaction. This observation has a significant impact on the assessment of the thermal
process safety of a chemical process: Both the desired synthesis reaction and the secondary or
unwanted decomposition have to be studied ii, iii. The concept of MTSR allows one to link desired and
decomposition reactions.
The study of the thermal hazards of a chemical process involves the knowledge of the thermal
data of the reactions (energies or thermal potentials) and of the kinetic data at different temperature
levels that could be reached during runaway.

3 Criticality of Chemical Processes

3.1 Assessment of the Criticality
For reactions presenting a thermal potential we can consider the relative position of four temperature
levels:
· The Process temperature (Tprocess): it is the initial temperature in the cooling failure
scenario. In case of non isothermal process, the initial temperature will be taken at the
instant when the cooling failure has the heaviest consequences (worst case)
· Maximum Temperature of Synthesis Reaction (MTSR) this temperature depends
essentially on the degree of accumulation of non converted reactants and therefore it is
strongly dependant on the process design.
· Temperature at which TMRad is 24 hr (TD24): this temperature is defined by the thermal
stability of the reaction mixture. It is the highest temperature at which the thermal stability
of the reaction mass is unproblematic.
· Maximum Temperature for technical reasons (MTT). In an open system it is the boiling
point. For a closed system it is the temperature at which the pressure reaches the maximum
permissible i.e. the set pressure of a safety valve or bursting disk.
These four temperature levels allow to classify the scenarios into 5 different classes going from the
least critical 1 to the most critical 5 iv Figure 5.
 T (°C)

MTT MTT
MTSR MTSR
TD24

MTT
MTT
MTSR MTSR MTSR
MTT
A

B 1 2 3 4 5

Figure 5: Criticality Classes of Scenario

A T process
B Criticality class

3.2 Description of the criticality classes:

1 After loss of control of the synthesis reaction, the MTT cannot be reached and the
decomposition reaction cannot be triggered. Only if the reaction mass is maintained for a
long time under heat accumulation conditions could the MTT be reached. Then the
evaporative cooling serves as an additional safety barrier. The process is thermally safe.

2 After loss of control of the synthesis reaction, the MTT cannot be reached and the
decomposition reaction cannot be triggered. The situation is very similar to the class 1,
but if the reaction mass is maintained for a longer time under heat accumulation
conditions, the decomposition reaction could be triggered and reach the MTT. In this
case, reaching the boiling point could be a hazard if the heat release rate at MTT is too
high. If the reaction mass is not kept for longer time under heat accumulation conditions,
the process is thermally safe.

3 After loss of control of the synthesis reaction, the MTT will be reached, but the
decomposition reaction cannot be triggered. In this situation, the safety of the process
depends on the heat release rate of the synthesis reaction at the MTT.

4 After loss of control of the synthesis reaction, the MTT will be reached and the
decomposition reaction could theoretically be triggered. In this situation, the safety of the
process depends on the heat release rate of both the synthesis reaction and the
decomposition reaction at the MTT. The evaporative cooling or the emergency pressure
relief may serve as a safety barrier.

5 After loss of control of the synthesis reaction, the decomposition reaction will be
triggered and the MTT will be reached during the runaway of the decomposition reaction.
It is very unlikely that the evaporative cooling or the emergency pressure relief can serve
as a safety barrier in this case. The heat release rate of the decomposition at the MTT
determines the thermal safety of the process. It is the most critical of all scenarios.

3.3 Measures
Depending on the criticality class of the scenario, different measures can be applied to avoid,
to control or to stop the runaway:

1 No special measure is required for this class of scenario, but the reaction mass should not
be held for longer time under heat accumulation conditions. The evaporative cooling or
the emergency pressure relief could serve as a barrier.
 2 No special measure is required. The reaction mass should not be held for longer time
under heat accumulation conditions. The evaporative cooling or the emergency pressure
relief could eventually serve as a barrier.

3 The first measure is to use the evaporative cooling or a controlled depressurisation to

keep the reaction mass under control. The distillation system must be designed for that
purpose and has to function even in the case of failure of the utilities.
A backup cooling system, dumping of the reaction mass or quenching could also be used.
Of course, these measures must be designed for that purpose and must be ready to
function immediately after the failure occurs.

4 Similar to class 3. The same measures apply here but the additional heat release rate due
to the secondary reaction has also to be taken into account.
5 In this class the MTT is very unlikely to serve as a safety barrier. Therefore only
quenching or dumping can be used. Since in most cases, the decomposition
reactions release very high energies, particular attention has to be paid to the
design of safety measures. It is worthwhile to consider an alternative design of the
process in order to reduce the severity or at least the probability. As an alternative
design, the following possibilities should be considered: reduce the concentration,
change from batch to semi-batch, optimise semi-batch operating conditions in
order to minimise the accumulation, change to continuous operation etc.

Remarks concerning the use of the boiling point as a safety barrier:

The distillation or reflux system must be designed for this purpose: open system, independent cooling
of the condenser. Effects like flooding of the vapour tube or swelling of the reaction mass have to be
considered in this design.

4 Practical Procedure for the Assessment of Thermal Risks

The six key questions described in the cooling failure scenario allow to characterize and to assess the
thermal risks of a chemical process. In order to ensure an economic assessment, meaning to be sure to
determine all the required data and not to measure tediously data which are not really needed for the
assessment, a practical step by step procedure was elaborated. This procedure bases on the separation
of severity and probability and takes into account the possibilities of the equipment of a safety
laboratory.

Determine Assess Control

Energy Potential of Reaction:
Accumulation
(MTSR)

Medium
Severity ?
or High
Assess Probability
Low
of Triggering
Decomposition
(TMRad)
Process presents
no thermal risks

Build Scenario

Figure 6: Required Data

The first steps part allows to build a failure scenario which is easy to understand and serves as
a base for the assessment (Figure 6). In a second step, based on the scenario, the criticality
index can be determined to help in the choice and in the design of risk reducing measures
(Figure 7).

Scenario :
Assessment of criticality

Criticality ?

1-2 3-4 5

Process is notcritical Process is critical Process is critical

No Measures Redesign
Design technical
are required Process
Measures

Figure 7: Assessment using the criticality index.

These points are summarized in the graphical form which allows a fast check of the nature of
thermal risks linked to a given process.

References:
i

R. Gygax; IUPAC; Safety in Chemical Production; Blackwell Scientific Publications 1991;

ISBN 0-632-03255-3
ii
ESCIS-Booklet 8 (1993),"Thermal Process Safety: Data, Assessment Criteria, Measures;
available from SUVA CH-6001 Lucerne
iii
K. Eigenmann, Chimia 30 (1976),12,545-546
iv
F. Stoessel; Chem. Eng. Progress 89, (1993), 10, 68-75