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?
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
Summary of lessons 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 : Lesson 4

Batch reaction In lessons 1 to 3 only data

concerning the reaction system
were examined. No reference

Lesson 4 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 : Lesson 4
Batch reaction Statement

Safe operation of this

Lesson 4 process is only possible if
the heat can be dissipated
under any circumstances. It
Thermal is clear from our
investigations, that the
control of consequences of a runaway
situation in this case will be
the reaction 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)
(W/kg) Maximum -1 TT(C)
(C)
Maximumheat
heatrelease
releaserate
rateisisca.
ca.28
28W.kg
W.kg-1at
at3h.
3h.
35
35 200
200

30
30 190
190

25
25 180
180
Tprocess
Tprocess
20
20 170
170

15
15 160
160

10 Heat
Heat release
releaserate
rate 150
10 150

55 140
140

00 130
130
22 33 44 55 66 77
Time
Time(h)
(h)

Answer this question:
What is the maximum heat
release rate of the synthesis
reaction?
(Units should be kWbatch-1)
Lesson 4
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 2447
Final 2447
 Lesson 4
Answer this question:
What is the maximum heat
The heat release rate of the synthesis
release rate of the synthesis
reaction? reaction reaches a maximum of
(Units should be kWbatch-1) 28 Wkg-1 after 3 h of process time.
At this point, the reaction mass
corresponds to the initial and the final
Right answer: stage as is shown in the table below.
The maximum heat release
rate of synthesis reaction is
approx. 69 kWbatch-1.
Batch size

Stage Reaction mass

(kg)

Initial 2447
Final 2447
 Case study : Lesson 4
Batch reaction
The maximum heat
release rate of the
Lesson 4 synthesis reaction is
28 Wkg-1 corresponding
to ca. 69 kWbatch-1.
Thermal These results should be
control of summarized in risk
analysis form 1.
the reaction
 Lesson
Lesson 44
Thermal
Thermal control
control of
of the
the reaction
reaction

DYNAMIC
DYNAMICASPECTS
ASPECTS
Maximum
Maximumgas
gasevolution
evolutionrate:
rate: l/kg/hr
l/kg/hr l/batch/hr
l/batch/hr
Maximum
Maximumheat
heatrelease
releaserate
rate:: 28
28 W/kg
W/kg 69
69 kW/batch
kW/batch

Form
Form 11
 Lesson 4
Lesson 4
The cooling capacity of the reactor
can be calculated using the following
Under normal equation:

operating conditions, qflow = U A ( T - Tc)

the cooling capacity
qflow cooling capacity (kW)
of the reactor must be U Overall heat transfer
sufficient to remove coefficient (kWm-2C-1)
the heat release rate A Heat exchange area (m2)
T Reactor temperature
of the synthesis (195C)
reaction (69 kW). Tc Temperature of the
cooling system (C)
 Lesson 4
Case study :
Batch reaction Criticality of the cooling failure
scenario related to the process under
study was determined in lesson 3.
The combination of the desired and

Lesson 4 the decomposition reactions added to

the high pressure provide a very high
criticality class.

Safe plant design for the given

Measures process implies an autoclave and a
pressure relief system suitable for an

to avoid the overpressure of at least 100 bar.

As a last resort, controlled

runaway depressurisation could be
used.
Lesson 4 Lesson 4
Controlled depressurisation Controlled depressurisation

WHY ? WHAT ELEMENTS ?

A controlled depressurisation The depressurisation system

could be used to both cool the itself is composed of a control
reaction mass by evaporation valve placed on a vent line, of a
of one of the reaction partners. condenser and of a storage tank
located after the condenser.
Lesson 4
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.
Lesson 4
Controlled depressurisation
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
Controlled depressurisation
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.
Lesson 4
Recommendations
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 self-
heating 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
NH
NH3 3 55
Chloronitro
Chloronitro
benzene
benzene 11

Effluent
Effluent

22
11Tubular
Tubularreactor
reactor
22Heating/cooling
33 44
Heating/coolingcirculation
circulation Nitroaniline
33Flash vessel
Flash vessel Nitroaniline
44Crystallizer
Crystallizer
55Waste Caustic
Causticsodalye
Wastegas
gasscrubber
scrubber sodalye
66NH
NH3 distillationcolumn
distillation aqueous
3 column aqueousNH
NH3 3
 Case study : Conclusions
Batch reaction
For this case study we can
conclude that:
Conclusions
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.