Thermal Safety Case Study- Lesson 4

This case study shows through an example of a batch

reaction how to systematically assess the thermal risk
related to runaway reactions.
It was prepared by R.Perrayon and P.Lerena based on
the knowledge of the Swiss Safety Institute (Basel,
Switzerland)
Lesson 4 analyzes the operating conditions required to
mantain the process under thermal control as well as the
measures that should be taken to prevent an incident from
occuring.

What is risk?

Summary of lessons

Traditionally the risk is defined as the product of the

severity of a possible incident times its probability of
occurrence. Hence the risk assessment requires the
evaluation of both the severity and probability.
The following lessons are a guide to a systematic
evaluation of the risks of a chemical process.
Lesson 1 is a step by step procedure to allow a
preliminary evaluation of both severity and
probability using simple experimental techniques
(SCREENING).
Lesson 2 expands the study through the use of more
data if the conclusion of the previous SCREENING is
that the thermal risks of the process are high.
Lesson 3 summarizes the results obtained in the
previous lessons through the construction of a
COOLING FAILURE SCENARIO and the assessment
of its CRITICALITY.
Lesson 4 analyzes the operating conditions required
to mantain the process under thermal control as well
as the measures that should be taken to prevent an
incident from occuring.

Case study :
Batch reaction

Lesson 4

Lesson 4
In lessons 1 to 3 only data
concerning the reaction system
were examined. No reference
was made to the equipment in
which the process will run.
The first step of lesson 4 is to
determine, at normal operating
conditions, if the desired
reaction will be under thermal
control.
The second step is to analyze
which measures can be taken in
the case of loss of control of the
process due to a failure.

Case study :
Batch reaction

Lesson 4
Thermal
control of
the reaction

Lesson 4
Statement
Safe operation of this
process is only possible if
the heat can be dissipated
under any circumstances. It
is clear from our
investigations, that the
consequences of a runaway
situation in this case will be
of high severity.

Lesson 4
Can the heat release of the
process be controlled by the
cooling system?
Under normal operating
conditions, to ensure thermal
control of the synthesis
reaction, the cooling capacity
of the reactor must be
greater to the heat release
rate of the process.

Lesson 4
Thermal control of the reaction
The heat release of the synthesis
reaction can be determined by
evaluation of the results of a reaction
calorimetry experiment.
The next screen will show a plot of
the heat release rate and the process
temperature against time of a
reaction calorimetry experiment of
the process under study.
This plot serves to measure the
maximum heat release rate of the
desired reaction and the time at
which it occurs.

Results
Resultsof
ofthe
thereaction
reactioncalorimetry
calorimetryexperiment
experiment
(W/kg)
-1
(W/kg) Maximum
Maximumheat
heatrelease
releaserate
rateisisca.
ca.28
28W.kg
W.kg-1at
at3h.
3h.

TT(
C)
(
C)

35
35

200
200

30
30

190
190

25
25

180
180
Tprocess
Tprocess

20
20

170
170

15
15

160
160
Heat
Heat release
releaserate
rate

10
10

150
150

55

140
140

00

130
130
22

33

44

55

Time
Time(h)
(h)

66

77

Lesson 4
Answer this question:
What is the maximum heat
release rate of the synthesis
reaction?
(Units should be kWbatch-1)

The heat release rate of the synthesis

reaction reaches a maximum of
28 Wkg-1 after 3 h of process time.
At this point, the reaction mass
corresponds to the initial and the final
stage as is shown in the table below.

Batch size
Stage

Reaction mass
(kg)

Initial
Final

2447
2447

Lesson 4
Answer this question:
What is the maximum heat
release rate of the synthesis
reaction?
(Units should be kWbatch-1)

Right answer:
The maximum heat release
rate of synthesis reaction is
approx. 69 kWbatch-1.

The heat release rate of the synthesis

reaction reaches a maximum of
28 Wkg-1 after 3 h of process time.
At this point, the reaction mass
corresponds to the initial and the final
stage as is shown in the table below.

Batch size
Stage

Reaction mass
(kg)

Initial
Final

2447
2447

Case study :
Batch reaction

Lesson 4

Lesson 4

The maximum heat

release rate of the
synthesis reaction is
28 Wkg-1 corresponding
to ca. 69 kWbatch-1.

Thermal
control of
the reaction

These results should be

summarized in risk
analysis form 1.

Lesson
Lesson 44
Thermal
Thermal control
control of
of the
the reaction
reaction
DYNAMIC
DYNAMICASPECTS
ASPECTS
Maximum
l/kg/hr
Maximumgas
gasevolution
evolutionrate:
rate:
l/kg/hr
Maximum
Maximumheat
heatrelease
releaserate
rate:: 28
28 W/kg
W/kg

69
69

Form
Form 11

l/batch/hr
l/batch/hr
kW/batch
kW/batch

Lesson 4
Under normal
operating conditions,
the cooling capacity
of the reactor must be
sufficient to remove
the heat release rate
of the synthesis
reaction (69 kW).

Lesson 4
The cooling capacity of the reactor
can be calculated using the following
equation:

qflow = U A ( T - Tc)
qflow cooling capacity (kW)
U
Overall heat transfer
A
T
Tc

coefficient (kWm-2C-1)
Heat exchange area (m2)
Reactor temperature
(195C)
Temperature of the
cooling system (C)

Case study :
Batch reaction

Lesson 4
Measures
to avoid the
runaway

Lesson 4
Criticality of the cooling failure
scenario related to the process under
study was determined in lesson 3.
The combination of the desired and
the decomposition reactions added to
the high pressure provide a very high
criticality class.
Safe plant design for the given
process implies an autoclave and a
pressure relief system suitable for an
overpressure of at least 100 bar.

As a last resort, controlled

depressurisation could be
used.

Lesson 4

Lesson 4

Controlled depressurisation

Controlled depressurisation

WHY ?

WHAT ELEMENTS ?

A controlled depressurisation
could be used to both cool the
reaction mass by evaporation
of one of the reaction partners.

The depressurisation system

itself is composed of a control
valve placed on a vent line, of a
condenser and of a storage tank
located after the condenser.

Lesson 4

Lesson 4

Controlled depressurisation

Controlled depressurisation

WHAT MODEL ?

A simulation program concerning

the binary system NH3-H2O has
been developed using the ASPEN
Model Manager. This industrial
process simulation software is
used for liquid/vapor systems and
allows the calculation of
parameters like the pressure,
temperature, surface gas velocity
and liquid mass.

WHAT RESULTS ?
Considering a 3 m3 batch reactor
equipped with a valve aperture
temperature of 200C and a DN 15 type
valve, one can estimate from a NH3
pressure simulation the following
results:
Pressure decreases after 30 mn from
53 bar to 28 bar, reactor temperature is
reduced from 200C to about 174C.
The surface gas velocity of about 5
mm/s does not imply the risk of
entrainment of the liquid phase.

Lesson 4

Lesson 4

Controlled depressurisation

Recommendations

CONCLUSION

As stated above, this sort of

countermeasure has to be
considered as a last resort,
when no other process variant
than the batch process is
feasible.
Its effectivity should be
confirmed by experiments,
preferably in a technical scale.

We recommend to use a different way of

synthesis or a different process.
In fact, in a batch reactor the course of the
reaction can only be controlled by the
heat exchange system.
A continuous process using a reactor
with a small volume and a high heat
capacity could be used.
It would have the advantage that a selfheating of the reaction mixture is not
possible because of the good heat
transfer to its mass.
The next screen will show an actual
manufacturing process of 4-nitroaniline
using a tubular reactor.

Manufacturing
Manufacturingprocess
processof
of4-nitroaniline
4-nitroanilineusing
usingaapiston
pistonreactor
reactor
Water
Water Off
Offgas
gas

66
55

NH
NH3 3

Chloronitro
Chloronitro
benzene
benzene

11

Effluent
Effluent

11Tubular
Tubularreactor
reactor
22Heating/cooling
Heating/coolingcirculation
circulation
33Flash
vessel
Flash vessel
44Crystallizer
Crystallizer
55Waste
Wastegas
gasscrubber
scrubber
66NH
distillation
NH3 distillationcolumn
column
3

22

33

44
Nitroaniline
Nitroaniline

Caustic
Causticsodalye
sodalye
aqueous
aqueousNH
NH3 3

Case study :
Batch reaction

Conclusions

Conclusions
For this case study we can
conclude that:
A loss of thermal control of this
process will surely lead to the
thermal explosion.
In order to avoid this problem, we
recommend to use a continuous
process.