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Process Safety Guide

Understanding the Risks


Safe Chemical Processes at Scale

In the chemical and pharmaceutical industry, most processes are carried out in batch
or semi-batch mode. The hazard potential and risk of chemical processes are related
to reactivity and toxicity of chemicals involved and the process design itself.

While the toxicity of the reagents cannot be influenced, the appropriate design of a
process is essential to keep the reaction under control at any given time. As there is
no steady-state in batch and semi-batch operation, the process dynamics becomes an
important factor too and needs to be assessed carefully. Consequently, striving for an
intrinsically safe process is thus the goal of process development.

Contents

1 Thermal Risks in Chemical Production

2 Runaway Scenarios

3 Data Requirements

4 Evaluating the Risk and Criticality of a Process

5 Striving for Intrinsic Safety – Design Safe Processes

6 Study of a Semi-Batch Nitration Reaction: An Example

7 Developing Safer Process Designs

8 Conclusion
1 Thermal Risks in Chemical Production
Process Safety Guide

The risks and hazard potential of chemical processes are affected by a number of
different parameters, such as:
• Heat transfer
• Effect of mixing
• Kinetics and heat generation rate
• Overall heat balance
• Heat removal capacity of the reactor
• Accumulation of reagents and energy
• Physical properties and stability of the reagents and the reaction mass

Thermal runaway scenarios in a


chemical plant can be ultimately Power
related to conditions in which the
heat generation of an ongoing Stable
reaction exceeds the heat Operating
dissipation capacity of the process Point
um
equipment. A number of cases can
M edi
g
olin
be identified:
1. Generally, during a chemical C o
Unstable
process the reactor is in an Operating
unstable equilibrium state Point
(Figure 1), where the desired
reaction releases heat. In
case of reactant accumulation Temperature
and a simultaneous failure of Starting Temperature
the cooling system, the heat of Cooling Medium
production rate persists and
Figure 1. Heat balance diagram. A typical semi-batch is run at the unstable
whatever energy potential is operating point
present at this moment will be
released adiabatically.
2. The predominant hazard in the manufacturing process however, is loss of control of the
desired reaction, e.g. due to reactant accumulation, high sensitivity to impurities, problems
with initiation (long induction time), wrong kinetic assumptions etc.
3. The energy balance is dominated by a low heat dissipation capacity and subsequent
accumulation of energy. In this case, even very weak undesired reactions can run away.
4. Furthermore, undesired operational conditions may lead to insufficient mixing, wrong or too
high feed rates, wrong temperatures etc.
5. The runaway of the desired reaction can also be the reason for secondary undesired
events. First, it causes an intermediate temperature level to be reached by the runaway of
the desired reaction. It is called MTSR (Maximum Temperature of the Synthesis Reaction =
maximum achievable temperature based on the amount of accumulated reagent) or MAT
(Maximal Attainable Temperature = maximum achievable temperature in the worst case
assuming 100% accumulation of reagents). Starting from MTSR, further events, particularly
decomposition reactions, can be triggered which may ultimately lead to an explosion.
6. Finally, undesired reactions may occur rapidly if reactive compounds are mixed acciden-
tally, e.g. if cooling water penetrates into the reaction mass

2 Chemical Process Safety Guide


2 Runaway Scenarios

In order to evaluate potential


runaway scenarios, data to Running
predict their progress needs to be Process ΔtR ΔtDec
evaluated including thermodynamic
and kinetic analysis of the reacting
system. Because it is not feasible Desired Reaction Secondary Reaction
to completely model the reaction
in practice, the analysis can be

Temperature
reduced to a number of basic
properties and relatively easy-to- ΔTad,Dec
obtain data. Based on these data,
the risk can be presented as a
'Runaway Graph' (Figure 2).
MTSR
The data used in the graph are
determined by answering the
following questions: ΔTad,R
1. What is the heat evolution rate of
the process as a function of time Tp
[qR(t)] with which the equipment tx (Cooling Failure)
has to cope?
2. What temperature will be reached
when the desired process runs
away, assuming adiabatic Time
conditions for a cooling failure Figure 2. Runaway graph from iC Safety™ software
(MTSR or MAT)?
3. When is MTSR maximal? (most critical instance for a cooling failure)
4. In what time, ΔtDec(T0), will a runaway decomposition reaction develop, given the initial
temperature T0 (in this case, T0 is typically equal to MTSR)? This time can be either related
to the heat production rate at T0 by assuming zero order kinetics (Time to Maximum Rate
or TMR) or by explicitly integrating isothermally measured heat production rates as a
function of time.
5. In what time, ΔtR(Tp), will MTSR be reached?
6. What is the order of magnitude of an adiabatic temperature increase (ΔTad, Dec) caused by
the runaway of secondary reactions and what are the consequences?

MTSR: Maximum Temperature of the ΔtR: Time in which MTSR is reached


Synthesis Reaction
ΔtDec: Time to runaway at a
MAT: Maximum Attainable Temperature given temperature
MTT: Maximum Technical Temperature qR(t): Heat evolution rate
TMR: Time to Maximum Rate Tr: Reactor temperature
ΔTad, R: Adiabatic temperature increase Tj: Jacket temperature
of desired reaction
Tp: Process temperature
ΔTad, Dec: Adiabatic temperature increase
TD24: Temperature at which TMR is 24h
caused by secondary reaction

Chemical Process Safety Guide 3


3 Data Requirements
Process Safety Guide

From the previous questions it becomes evident that data related to the energy potential of
the reaction mass as well as data related to the reactant accumulation and heat evolution
characteristics need to be determined.

The most appropriate tool to


obtain information of the desired
reaction is the Reaction Calorimeter
RC1e® which allows a chemical
reaction to be run under conditions
representative of a specific process.
The measurement of the heat flow
serves as a direct indicator of the
reaction rate and provides the basic
data required [qR(t), ΔtR(Tp)].

The accumulation of reactants dur-


ing the process is calculated from
the addition and the conversion as
a function of time. The accumula-
tion of energy is obtained by the
integration of the heat flow curve,
Figure 3. Diagram of the High Performance Thermostat RC1e® enabling fast
from which ΔTad, MTSR and MAT heating and cooling precisely
can be derived.

The energy potential of the reaction mass can be determined by micro-thermal analysis
(e.g. Differential Scanning Calorimetry, DSC), where typically the mixture of the starting
materials and samples from intermediate process phases are investigated. A comparative
evaluation of the results indicates which signals correspond to the desired and
undesired reactions.

The data of the heat evolution dynamics of secondary reactions an be obtained from either
isothermally or dynamically measured heat evolution rates, typically using DSC techniques
or adiabatic calorimetry, e.g. ARC. Adiabatic experimental techniques require a careful
selection of the experimental regime and are less adequate for modeling reactions with
complex kinetics.

Apart from these basic data, physical properties such as boiling points, heats of vaporization,
vapor pressures, etc. and data related to process equipment are used to assess the
consequences of a thermal runaway.

4 Chemical Process Safety Guide


4 Evaluating the Risk and Criticality of a Process

The risk of a process depends on


the severity and probability of its
occurrence. The criticality of the TD24 - Temperature at which TMR is 24 hours
runaway can thus be evaluated MTT - Maximum Technical Temperature
using the relative levels of the MAT/MTSR - Maximal Attainable Temperature
different temperatures attained or Maximum Temperature of Synthesis Reaction
if the desired reaction and the Tp - Process Temperature
decomposition reaction proceed
under adiabatic conditions.

The probability can be estimated


using the time scale. If there is
enough time left to take emergency
measures before the runaway Temperature
TD24 TD24 TD24 TD24 TD24
becomes too fast after the cooling
failure, the probability of the run-
away will remain low. MTT

The criticality of a reaction MTT MAT/MTSR MAT/MTSR


presenting a thermal potential
overall can be estimated by looking
at the following four temperatures:
MTT MAT/MTSR MTT
• Tp (process temperature)
• MTSR (Maximum Temperature of
the Synthesis Reaction) MAT/MTSR MAT/MTSR MTT
• TD24 (temperature at which the
Time-to-Maximum-Rate (TMR) is Tp Tp Tp Tp Tp
24 hours)
• MTT (Maximum Technical
1 2 3 4 5
Temperature, e.g. boiling point,
maximum allowed pressure, Criticality Class
material, etc) Figure 4. Criticality Graph from iCSafety™ software

The graphical representation of these temperature levels (Figure 4) allows the classification
of a process from non-critical to highly critical. Depending on the allocated criticality class a
process might be safe and not require any modifications at all. However, it also may require
slight or considerable modifications, or a complete re-work of the entire process.

Chemical Process Safety Guide 5


5 Striving for Intrinsic Safety
Process Safety Guide

Design Safe Processes


In process development normal operating conditions are assumed. However, when
developing a safe process, deviations from the normal operating conditions must be
considered by asking questions like "What happens if...?".

The integration of risk analysis into process design at an early stage of the development
provides the opportunity to design an inherently safe process. Used correctly, risk analysis
becomes an iterative procedure accompanying the process development.

The rules for improving process safety by an appropriate design are almost trivial:
• Know your chemistry: Are there dangerous side reactions? Which conditions favor them?
Which parameters may have an influence on the reaction rates of the main reaction? Can
initiation be a problem?
• Avoid unnecessary accumulation of exothermally reacting compounds
• Maximize heat transfer capacities per unit of reactor volume
• Avoid external sources which trigger runaways

As mentioned earlier, most of the processes in the chemical and pharmaceutical industry are
run in batch or semi-batch mode.

The batch-mode however, is strictly acceptable for non-hazardous reactions only (moderate
ΔTad, no exothermic decompositions at the MTSR). If these conditions are met, batch or
adiabatic batch reactions are a safe and cost effective way of operation. If they are not
met, running the process in semi-batch operation, where the addition of one or more of the
reactants is controlled, is preferred.

Typical heat accumulation problems occur if the heat producing effects and the heat
dissipation rate are not in equilibrium, e.g. the heat production is larger than heat removal
even if the heat production is only very small. This may particularly be the case in highly
viscous liquids or reaction masses with high solid contents.

In case of fast or very fast reactions, continuous operation (flow or plug flow reactors) is the
most effective way to run a process. This is of particular importance for the production of
thermally unstable products (e.g. explosives), but also has its limitations.

Even though chemical manufacturing should be intrinsically safe, classical defensive safety
measures must not be abandoned or neglected. Emergency control, such as emergency
and evaporation cooling, quenching, dumping, controlled depressurization or pressure
relief will remain an important function of the process control systems or even a regulatory
requirement.

6 Chemical Process Safety Guide


6 Study of a Semi-Batch Nitration Reaction

The following experiment describes a nitration reaction run in sulfuric acid. The traditional
process was run in the semi-batch mode where mixed acid (with a 67% excess) is added
continuously at 80°C isothermally to an aromatic substrate dissolved in sulfuric acid over a
ten hour period.

The process presents various difficulties with respect to thermal process safety:
• The reaction is rather slow. Therefore, a continuous reactor is not the preferred solution as
the mean residence times would be unrealistically long.
• A highly exothermic decomposition reaction is able to take place very slightly above the
process temperature
• The solvent does not provide any capacity for evaporation cooling

Based on this example, the thermal hazards assessment procedure and the development of
an optimal semi-batch process are explained.

6.1 Information from Differential Scanning


Calorimetry (DSC)
Sample size: 10-20mg
Heating rate: 4°C/min
At first, the mixture of starting materials was
investigated by DSC showing the slow behavior of the Results Derived Data (Adiabatic
desired reaction (blue curve, Figure 5). Looking at the Heat of desired reaction: temperature increase)
-175kJ/kg Desired reaction: 135°C
energy potential, an adiabatic temperature increase Heat of decomposition: Decomposition reaction:
of 135K is calculated which results in a maximum -1300kJ/kg 1000°C
cp: 1500kJ/kgK (corrected for equimolar
temperature of the desired reaction (MAT) of 215°C. (other source) mass)

However, the reaction mixture also shows a highly


exothermic decomposition above 200°C which is a
concern for two reasons (green curve, Figure 5): Decompostion
Heat Evolution (w/kg)

Reaction
a. If a cooling failure occurs once the full amount of 6000
reagent is added the adiabatic reaction would in-
Desired
crease the process temperature to a maximum of 4000 Reaction
215°C (MAT) which is beyond the onset temperature
of the highly exothermal decomposition reaction 2000
x10

b. With an onset temperature of about 200°C it can


30 100 200
be assumed that the decomposition reaction has
Temperature (°C)
already initiated while the desired reaction is ending.
In order to estimate runaway times as a function of Figure 5. Micro-Thermal Analysis (DSC) of reactant mixture of an
example reaction
initial temperatures, further analysis and additional
quantitative data on the runaway dynamics of the
decomposition reaction are required.

Chemical Process Safety Guide 7


)
/kg
(w
6.2 Runaway Dynamics
Process Safety Guide

iont
olu
Ev
For simplicity reasons data of the

at
dynamics of runaway reactions

He
are acquired by means of isother-
mal DSC runs. These are more
adequate than those obtained by
100
attempting to simulate adiabatic

Heat Evolution (w/kg)


conditions. In Figure 6 a series of 180°C
isothermal experiments of the final
reaction mixture are shown rep- 50 170°C
resenting the behavior at different
160°C
temperatures.
150°C
The heat evolution signals as a
10 20 30
function of time show an increas-
Time (hours)
ing trend with time passing through
two maxima. Figure 6. Isothermal Micro-Thermal Analysis (DSC) of reaction mixture

The maximum heat evolutions as a function of the set temperatures of the isothermal experi-
ments follow the Arrhenius Law in an astonishingly simple manner (Figure 7).

Even though this formally autocatalytic behavior is not mechanistically clear, it can be used
to model adiabatic runaway curves (TMR at respective temperature; Figure 8). Subsequently,
the runaway times of the decomposition reaction at various temperatures can be estimated.

200 T0 = 140°C
100 T0 = 130°C

50 180
Heat Evolution (W/kg)

Temperature (°C)
ak
Pe

170
nd

20
T0 = 120°C
co

160
k
ea
Se

10
P
st

150
Fir

5
140

2 130

1 120
100 120 140 160 180 0 10 20

Temperature (Scale 1/T [K]) Hours

Figure 7. Peak heat production rate from isothermal experiments Figure 8. Adiabatic runaway curves. Calculated from curves
of Figure 6. Values extrapolated to 120°C: first peak: 1W/kg, shown in Figures 6 and 7.
second peak: 2.4 W/kg

Based on these results and supposing a runaway time of around 10 to 20 hours is


accepted, MTSR must be limited to less than 120°C (often a time of 24 hours is assumed
also called TD24).

8 Chemical Process Safety Guide


6.3 Dynamics of the Desired Reaction
As the process temperature is 80°C and the maximum

Heat Evolution Rate [W/mol]


tolerable temperature of the synthesis reaction is
below 120°C, we can only tolerate a maximum energy
2
potential equivalent to 40K to be accumulated at any A
time. This corresponds to a fraction of about 30% of 1
accumulated reactant.
0 5 10
Time (Hours)
In order to find the actual degree of accumulation, Feed
investigations using the Reaction Calorimeter RC1e Equimolar Feed
were run (Figure 9).

Curve A is the heat evolution obtained when running Total Energy: 175 [kJ/kg]
100
the reaction according to the original process in the

Relative Energy (%)


reaction calorimeter. A balance between input and 80 C
B
output of reactive potential – measured in units of 60
energy – is calculated next, where:
• Curve C is proportional to the actual feed and 40

corresponds to the overall heat of reaction (input)


20 D
• Curve B is the integration of the experimental curve A
and represents the conversion (output)
0 5 10
• Curve D is the difference between the input (C) Time (Hours)
and the output (B) and thus, represents the Figure 9. Measured heat evolution curve (A). Its integral (B) is
accumulation as a function of time opposed to the reactant input (C); (D = C – B)

To obtain MTSR(t) it simply must be divided by the heat capacity (Figure 10).

From the calculations explained


above and the trends in Figure 10
Temperature (°C)

(left), it is clear that the reactant 160 160

accumulation is higher than 50%.


140 140
As a consequence MTSR becomes
155°C which is clearly above the
120 120
maximum tolerable.

100 100
It is evident, that an adiabatic
cooling failure in the moment of 80 80
equimolar feed would give rise to 0 5 10 15 0 6 7.5 10 30
a runaway of the desired reaction, Time (Hours) Time (Hours)
immediately followed by a run- Figure 10. Curve indicating Maximum Attainable Temperature by runaway of the desired
away decomposition. reaction (MTSR, left). Calculated runaway profiles at different cooling failure times (right).

Responses to cooling failures occurring at different times in the process have been calculated
from the model. Figure 10 (right) confirms that if a cooling failure occurs at a time of around
six hours, the temperature rapidly increases due to the nitration reaction. As the temperature
is above the limit of 120°C it is followed by a runaway due to decomposition leading to a
thermal explosion with severe consequences.

In this domain the process has a «built-in» potential for a catastrophic runaway where safety
uniquely depends on the reliability of the cooling system. It is obvious, that the primary cause
of such an incident is the loss of control of the desired reaction. The high severity, however, is
mainly due to the high decomposition energy.

Chemical Process Safety Guide 9


7 Developing Safer Processes
Process Safety Guide

The process described is far from intrinsically safe and


the question arises: How could it be improved?
140 157

Apart from more basic procedure changes, such as 130 151


changing reaction media, reversing the additions, etc.,

Temperature (°C)
the systematic variation of concentrations, tempera- 120 147

ture and feed profiles can give rise to a large number 159 150 144 141 138
110
of different processes with distinctly different hazard
potentials. 100 145

151
90 147
An overview for the MTSR’s based on the variation of
1.5
the temperature and feed time is shown in Figure 11. 80 153

2.5 5 7.5 10 12.5 15


While the MTSR seems to be optimal at a process
Feed Time (Hours)
temperature of around 110°C and an increasing feed
time, the goal of an MTSR of not more than 120°C Concentration (mol/kg)
cannot be met. On the other hand, the MTSR curve in Figure 11. MTSR values as a function of process
design parameters
Figure 12 shows a distinct maximum. Therefore, the
problem of MTSR being too high can be bypassed by
choosing a variable feed rate. Figure 13 shows a
(°C)

feed profile adjusted so that the MTSR of 120°C is MTSR


120
never exceeded.
Temperature

100
(°C)

MTSR
Process Temperature
120
The process now consists of three different stages: 80
Rate (W/kg) Temperature

• In the first stage, the reactant is added as fast as the 100


0 5 10 15
cooling capacity allows until the acceptable MTSR- Process Temperature
80 Time (Hours)
value is reached
Figure 12. MTSR
• The second stage involves decreasing the feed rate 0 5 10 15
to a level maintaining the MTSR-value Time (Hours)
4 100
• Towards the end of the process the MTSR-value
Rate (W/kg)

drops and any excess of reactant can be added


Feed (%)Feed (%)
3
Heat Evolution

quickly 4 100
2 50

3
Heat Evolution

1
2 50

1 0 5 10 15
Time (Hours)

0 5 10 15
Time (Hours)
Figure 13. Semi-batch procedure with feed rate adapted to
MTSR-limitation of 120°C

10 Chemical Process Safety Guide


8 Conclusions

Crucial for the development of a safe manufacturing process is the availability of information
describing the process, the toxicity and stability of the individual raw materials, intermediates
and final products.

Careful examination of the process with respect to


accumulation, the maximum attainable temperature
in the reactor, and possible decomposition reactions
are very important. The analysis of the dynamics of
the reaction, as well as the subsequent decomposition
reaction may allow scientists to model runaway
scenarios and establish the ideal reaction procedure.
One of the key components in the risk assessment of
the example was the availability of kinetics data and
reliable MTSR information. The knowledge gained was
used to make predictions about the temperature pro-
Figure 14. RC1e® Reaction Calorimeter
files, maximum operating temperature, concentration,
and feed rate or feed profiles.

In the example discussed, the proposed process


parameters were applied to experiments in the
reaction calorimeter, which resulted in a nitration
process allowing to manufacture the product with
an acceptable risk.

With the RC1e® Reaction calorimeter (Figure 14),


iControl™ and iC Safety™ software (Figure 15)
and the Differential Scanning Calorimeter DSC 1,
METTLER TOLEDO provides the toolbox to support Figure 15. iC Safety™ software
comprehensive process safety studies.

Chemical Process Safety Guide 11


Sources and References
[1] F. Stoessel, Thermal Safety of Chemical Processes, Wiley-VCH, Weinheim, (2008).
[2] Dr. R. Gygax, Chemical Reaction Engineering for Safety, ISCRE 10 (1988), Basle,
Switzerland.
[3] H. Fierz, P. Finck, G. Giger, R. Gygax, The Chemical Engineer 400, 9, (1984).
[4] F. Brogli, P. Grimm, M. Meyer, H. Zubler, Prep. 3rd Int. Symp. Safety Promotion and Loss
Prevention, Basle, 665, (1980).
[5] P. Hugo, J. Steinbach, F. Stoessel, Chemical Engineering Science, 43, 2147, (1988).

Additional Resources
Webinars
- Francis Stoessel: Avoiding Incidents at Scale-up: Is Your Process Resistant
Towards Maloperation?
- Stephen Rowe: Safe Scale-up of Chemical Processes: Holistic Strategies Supported
by Modern Tools
- Kevin Drost: Safe Process Scale-up with iC Safety™ - A Case Study of Nitroalkane
Chemistry by WeylChem
To watch the webinars, please visit: www.mt.com/process-safety

Brochures and Data Sheets


- Process Safety Brochure
- RC1e® Process Safety Workstation Brochure
- iC Safety™ Datasheets
To download brochures or datasheets, please visit: www.mt.com/process-safety

Websites
- Process Safety Application Website (www.mt.com/process-safety)
- RC1e® Process Safety Product Page (www.mt.com/RC1e)

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www.mt.com/process-safety
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