Thermal Safety Case Study- Lesson 1

•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 1 is a step by step procedure to allow a
preliminary evaluation of both severity and probability
using simple experimental techniques (SCREENING).
 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 : The following is a short description
of an actual manufacturing
Batch reaction procedure for the substitution of
para-chloro-nitrobenzene:

Lesson 1 A quantity of 1-chloro-4-nitrobenzene is

charged in a reactor with ammonia
(27% by weight in water).
The autoclave is then heated in about 3
hours to 195°C and maintained at this
temperature for 5 hours. The pressure
finally reaches 41-42 atms.
After this time, the reaction mass is
colled down to room temperature.
Reaction scheme

Cl NO2 + 2 NH3

H2N NO2 + NH4Cl

 Process data
Lesson 1
Charge

The results of lesson 1 Compound Mass kmol Molar ratio

(kg)
should be summarized in
risk analysis forms 1 and 2. 1-Chloro-4-
nitro-benzene 423 2.7 1
Ammonia 27% 2024 32.1 12
Using these forms fill in the (pure NH3)

headings and the “BATCH Total 2447

SIZE” section of form 1 for
the process data shown Reactor data

opposite. Stage Reaction mass Approximate

(kg) volume (m3)

Initial 2447* 2.6

Final 2447* 2.6

*In a batch process, the initial and final

reaction mass are the same.
Case study : Batch reaction
Case study : Batch reaction
Thermal
ThermalData
DataofofReaction
Reaction
BASIC DATA FOR RISK ANALYSIS
BASIC DATA FOR RISK ANALYSIS
FORM
FORM11
Product:
Product: Batch
Batchreaction
reaction Ident
IdentNo:
No:
Location:
Location: Case
Casestudy
study Proc.
Proc.dated:
dated:
Author
Author of risk analysis: ( (Your
of risk analysis: Yourname
name) ) Date:
Date: ( (actual
actualdate
date) )
DESCRIPTION
DESCRIPTIONOF
OFSYNTHESIS
SYNTHESISREACTION
REACTION (USE ONE SHEET PER STEP)
(USE ONE SHEET PER STEP)

BATCH
BATCHSIZE
SIZE 2.7
2.7 kmol
kmol
atatthe
thestart
start 2.6
2.6 mm3 3 2447
2447 kg
kg
atatthe end
the end 2.6
2.6 mm3 3 2447
2447 kg
kg
Case study : Batch reaction
Case study : Batch reaction
Thermal
ThermalStability
Stability
BASIC DATA FOR RISK ANALYSIS
BASIC DATA FOR RISK ANALYSIS
FORM
FORM0h 0h
Product:
Product: Batch
Batchreaction
reaction Ident
IdentNo:
No:
Location:
Location: Casestudy
Case study Proc. dated:
Proc. dated:
Author
Authorofofrisk
riskanalysis:
analysis: ( (Your
Yourname
name) ) Date:
Date: ( (actual
actualdate
date) )
CHARACTERISTIC
CHARACTERISTICDATA
DATAOF
OFDECOMPOSITION
DECOMPOSITIONREACTIONS
REACTIONS
(USE SEVERAL SHEETS IF NECESSARY)
(USE SEVERAL SHEETS IF NECESSARY)
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 Lesson 1
Case study :
Batch reaction In order to obtain a preliminary
evaluation (SCREENING) of the
Lesson 1 severity of the chemical process
under study, one should
Assessment of severity determine the following data:

Heat of the desired

reaction
Heat of the
decomposition reaction
Specific heat capacity of
the reaction mixture
 Overall potential thermogram:
Lesson 1 Quantitative differential thermal analysis of a
mixture of the starting materials.
In order to evaluate the heat of the desired
2 Heat release rate ( W·g-1)
reaction and the heat of the decomposition
1.5 -750 kJ·kg -1
reaction two thermograms were supplied by Baselines
the thermal safety laboratory. 1

0.5

A linear temperature ramp from 23°C to 450°C 0

was used in both measurements (scan rate -0.5 +30 kJ·kg -1

4°C·min-1). -1
50 100 150 200 250 300 350
scan rate: 4°C·min -1 Temperature (°C)
The overall potential thermogram shows an
endothermic signal (fusion of the product) and Final reaction mixture thermogram:
two overlapping exothermic signals. The first Quantitative differential thermal analysis of the
signal equals a potential of +30 kJ·kg-1 and the final reaction mixture.
second ones a total potential of -750 kJ·kg-1. 1.2 Heat release rate (W·g-1)
1 -500 kJ·kg-1
A sample of the reaction mixture after 0.8
0.6
completing the desired reaction (final reaction 0.4
mixture thermogram) shows, excepted the 0.2
endotherm, only one peak of -500 kJ·kg-1. This 0
-0.2
energy is in the same temperature range of the -0.4
+30 kJ·kg-1
second exothermic peak of the overall potential -0.6
thermogram. 0 100 200 300 400
scan rate: 4°C·min-1 Temperature (°C)
 Overall potential thermogram:
Quantitative differential thermal analysis of a
Answer this question:
mixture of the starting materials.
According to the results of
2 Heat release rate ( W·g-1)
experimental
1.5 -750 kJ·kg -1
measurements, what is the Baselines
1
heat of the desired
0.5
reaction?
(Units should be kJ·kg-1) 0

-0.5 +30 kJ·kg -1

-1
50 100 150 200 250 300 350
scan rate: 4°C·min -1 Temperature (°C)
Final reaction mixture thermogram:
Quantitative differential thermal analysis of the
final reaction mixture.
1.2 Heat release rate (W·g-1)
1 -500 kJ·kg-1
0.8
0.6
0.4
0.2
0
-0.2
-0.4
+30 kJ·kg-1
-0.6
0 100 200 300 400
scan rate: 4°C·min-1 Temperature (°C)
 Overall potential thermogram:
Quantitative differential thermal analysis of a
Answer this question:
mixture of the starting materials.
According to the results of
2 Heat release rate ( W·g-1)
experimental
1.5 -750 kJ·kg -1
measurements, what is the Baselines
1
heat of the desired
0.5
reaction?
(Units should be kJ·kg-1) 0

-0.5 +30 kJ·kg -1

-1
50 100 150 200 250 300 350
Right answer: scan rate: 4°C·min -1 Temperature (°C)
The heat of the desired Final reaction mixture thermogram:
reaction is Quantitative differential thermal analysis of the
250 kJ·kg-1 final reaction mixture.
1.2 Heat release rate (W·g-1)
1 -500 kJ·kg-1
0.8
0.6
0.4
0.2
0
-0.2
-0.4
+30 kJ·kg-1
-0.6
0 100 200 300 400
scan rate: 4°C·min-1 Temperature (°C)
 Overall potential thermogram:
Quantitative differential thermal analysis of a
Answer this question:
mixture of the starting materials.
According to the results of
2 Heat release rate ( W·g-1)
experimental
1.5 -750 kJ·kg -1
measurements, what is the Baselines
1
heat of the decomposition
0.5
reaction?
(Units should be kJ·kg-1) 0

-0.5 +30 kJ·kg -1

-1
50 100 150 200 250 300 350
scan rate: 4°C·min -1 Temperature (°C)
Final reaction mixture thermogram:
Quantitative differential thermal analysis of the
final reaction mixture.
1.2 Heat release rate (W·g-1)
1 -500 kJ·kg-1
0.8
0.6
0.4
0.2
0
-0.2
-0.4
+30 kJ·kg-1
-0.6
0 100 200 300 400
scan rate: 4°C·min-1 Temperature (°C)
 Overall potential thermogram:
Quantitative differential thermal analysis of a
Answer this question:
mixture of the starting materials.
According to the results of
2 Heat release rate ( W·g-1)
experimental
1.5 -750 kJ·kg -1
measurements, what is the Baselines
1
heat of the decomposition
0.5
reaction?
(Units should be kJ·kg-1) 0

-0.5 +30 kJ·kg -1

-1
50 100 150 200 250 300 350
Right answer: scan rate: 4°C·min -1 Temperature (°C)
The heat of the Final reaction mixture thermogram:
decomposition reaction is Quantitative differential thermal analysis of the
500 kJ·kg-1 final reaction mixture.
1.2 Heat release rate (W·g-1)
1 -500 kJ·kg-1
0.8
0.6
0.4
0.2
0
-0.2
-0.4
+30 kJ·kg-1
-0.6
0 100 200 300 400
scan rate: 4°C·min-1 Temperature (°C)
 Lesson 1
Case study :
Batch reaction In a preliminary evaluation
(SCREENING) of the severity of
Lesson 1 the chemical process under study
the following data are already
Assessment of severity known:

Heat of the desired reaction

QR = 250 kJ·kg-1
Heat of the decomposition
reaction
QD = 500 kJ·kg-1

These results are summarized in

the risk analysis forms 1 and 2.
Case
Casestudy
study: :Batch
Batchreaction
reaction Thermal
ThermalData
DataofofReaction
Reaction
BASIC
BASIC DATA FOR RISKANALYSIS
DATA FOR RISK ANALYSIS FORM
FORM11
POTENTIAL
POTENTIAL
Heat
Heatofofreaction
reaction Specific
Specificheat
heatcapacity
capacity Adiabatic
AdiabaticTemperature
TemperatureRise
Rise
(Ratio
(RatioQQRR/ /Cp)
Cp)

QQR ==250
250 kJ/kg
kJ/kg Cp
Cp== kJ/kg/K
kJ/kg/K ∆Tad==
∆Tad °C
°C
R

Highest
Highesttheoretical
theoreticalattainable
attainabletemperature
temperatureinincase
caseadiabatic
adiabaticconditions
conditionsoccur:
occur: °C
°C
Total gas evolution:
Total gas evolution: l/kg
l/kg l/batch
l/batch
Source of data:
Source of data:
Consequences
Consequencesofofallowing
allowingadiabatic
adiabaticreaction
reaction (Check
(Checkappropriate
appropriateboxes)
boxes)

Harmless
Harmlesstemperature
temperaturerise
rise

Boiling
Boiling(Bp
(Bp== °C)
°C)

Gas
Gasrelease
release


Critical temperature rise
Critical temperature rise

Decomposition
Decomposition

Pressure
Pressurebuild
buildup
up


Other
Other: :
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Case
Casestudy
study: :Batch
Batchreaction
reaction Thermal
ThermalStability
Stability
BASIC
BASIC DATA FOR RISKANALYSIS
DATA FOR RISK ANALYSIS FORM
FORM22

Severity:
Severity:
Energy
Energypotential
potentialof
ofrelevant
relevantdecomposition
decompositionreactions:
reactions: 500
500 kJ/kg
kJ/kg
Specific heat capacity of reaction mass:
Specific heat capacity of reaction mass: kJ/kg/K
kJ/kg/K
Adiabatic temperature rise:
Adiabatic temperature rise: °C
°C
Boiling
Boilingpoint
pointofofreaction
reactionmass
mass(if(ifrelevant):
relevant): °C
°C
Gas evolution:
Gas evolution: mm3/batch
3/batch
Known
Knowndecomposition
decompositionproducts:
products:
Source of data:
Source of data:
Assessment
Assessmentofofseverity:
severity:

Low
Low

Medium
Medium

High
High

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 Lesson 1
Case study :
Batch reaction In a preliminary evaluation
(SCREENING) of the severity of
Lesson 1 the chemical process under study
the following data are already
Assessment of severity known:

Heat of the desired reaction

QR = 250 kJ·kg-1
Heat of the decomposition
reaction
QD = 500 kJ·kg-1

The next step of lesson 1 is to

estimate the specific heat
capacity of the reaction
mixture.
Lesson 1 Example

A rough estimate of the specific heat
capacity of the reaction mixture can be
obtained by addition of the heat capacities of
its components.
Estimate of the specific heat capacity of a mixture
of 2000 kg of an organic compound in 2500 kg of
ammonia (27% by weight) in aqueous solution.
Table of data

The table below shows approximate values Compound Cp M M·Cp

(kJ·kg-1·K-1) (kg) (kJ·K-1)
of specific heat capacities for different
compound classes. The example shows how Organic
to calculate the specific heat capacity of a compound 1.8 2000 3600
Ammonia
mixture of 2000 kg of an organic compound
27% by wt. 3.9 2500 9750
in 2500 kg of ammonia (27% by weight) in
aqueous solution. Total 4500 13350
Specific heat capacity calculation
Compound Specific heat capacity
(kJ·kg-1·K-1) Σ Mi·Cpi 13350
Cp = = = 3.0 kJ·kg-1·K-1
MR 4500
Organic 1.8
Inorganic 1.0 Cp Specific heat capacity of the reaction mixture
Ammonia 27% 3.9 (kJ·kg-1·K-1)
Mi Mass of a compound (kg)
Water 4.2 Cpi Specific heat capacity of a compound
(kJ·kg-1·K-1)
MR Total mass of the reaction mixture (kg)
 Process data
Answer this question:
Charge
According to process data
shown opposite, what is the Compound Mass kmol Molar ratio
specific heat capacity of the (kg)
reaction mixture?
(Units should be kJ·kg-1·K-1) 1-Chloro-4-
nitro-benzene 423 2.7 1
Ammonia 27% 2024 32.1 12
(pure NH3)

Total 2447

Remember the following approximate

values of specific heat capacities for
different compound classes:

Compound Specific heat capacity

(kJ·kg-1·K-1)

Organic compounds 1.8

(fused or in solution)
Inorganic 1.0
Ammonia 27% 3.9
Water 4.2
 Process data
Answer this question:
Charge
According to process data
shown opposite, what is the Compound Mass kmol Molar ratio
specific heat capacity of the (kg)
reaction mixture?
(Units should be kJ·kg-1·K-1) 1-Chloro-4-
nitro-benzene 423 2.7 1
Ammonia 27% 2024 32.1 12
(pure NH3)

Total 2447
Right answer:
The specific heat capacity
of the reaction mixture is Remember the following approximate
3.5 kJ·kg-1·K-1 values of specific heat capacities for
different compound classes:

Compound Specific heat capacity

(kJ·kg-1·K-1)

Organic compounds 1.8

(fused or in solution)
Inorganic 1.0
Ammonia 27% 3.9
Water 4.2
 Remark
Lesson 1
The following procedure is suggested for estimating the
specific heat capacity of the reaction mixture.
In a preliminary evaluation
Table of data
(SCREENING) of the severity of the
chemical process under study the Compound Cp M M·Cp
(kJ·kg-1·K-1) (kg) (kJ·K-1)
following data are already known:
1-Chloro-4- 1.8 423 761.4
nitro-benzene
Ammonia 27% 3.9 2024 7893.6
Heat of the desired reaction
QR = 250 kJ·kg-1 Total 2447 8655

Heat of the decomposition

reaction Specific heat capacity calculation
QD = 500 kJ·kg-1 Cp =
Σ Mi·Cpi
=
8655
= 3.5 kJ·kg-1·K-1
2447
Specific heat capacity of the MR

reaction mixture Cp Specific heat capacity of the reaction

Cp = 3.5 kJ·kg-1·K-1 mixture (kJ·kg-1·K-1)
Mi Mass of a compound (kg)
These results are summarized Cpi Specific heat capacity of a compound
(kJ·kg-1·K-1)
in risk analysis forms 1 and 2. MR Total mass of the reaction mixture (kg)
Case
Casestudy
study: :Batch
Batchreaction
reaction Thermal
ThermalData
DataofofReaction
Reaction
BASIC
BASIC DATA FOR RISKANALYSIS
DATA FOR RISK ANALYSIS FORM
FORM11
POTENTIAL
POTENTIAL
Heat
Heatofofreaction
reaction Specific
Specificheat
heatcapacity
capacity Adiabatic
AdiabaticTemperature
TemperatureRise
Rise
(Ratio Q / Cp)
(Ratio QR / Cp)
R

QQR ==250
250 kJ/kg
kJ/kg Cp
Cp==3.5
3.5 kJ/kg/K
kJ/kg/K ∆∆Tad
Tad== °C
°C
R

Highest
Highesttheoretical
theoreticalattainable
attainabletemperature
temperatureinincase
caseadiabatic
adiabaticconditions
conditionsoccur:
occur: °C
°C
Total gas evolution:
Total gas evolution: l/kg
l/kg l/batch
l/batch
Source of data:
Source of data:
Consequences
Consequencesofofallowing
allowingadiabatic
adiabaticreaction
reaction (Check
(Checkappropriate
appropriateboxes)
boxes)

Harmless
Harmlesstemperature
temperaturerise
rise

Boiling
Boiling(Bp
(Bp== °C)
°C)

Gas
Gasrelease
release


Critical temperature rise
Critical temperature rise

Decomposition
Decomposition

Pressure
Pressurebuild
buildup
up


Other
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 Lesson 1
Lesson 1
The adiabatic temperature rise of a reaction is calculated by
dividing the heat of reaction by the specific heat capacity of
In a preliminary evaluation (SCREENING) of the reaction mixture.
the severity of the chemical process under
study the following data are already known: Example

The adiabatic temperature rise of a high exothermic

Heat of the desired reaction decomposition reaction having a heat of reaction of
2000 kJ·kg-1 in a reaction mixture with 2 kJ·kg-1·K-1 specific
QR = 250 kJ·kg-1 heat capacity is:
Heat of the decomposition reaction
QD = 500 kJ·kg-1 QR 2000
∆Tad = = = 1000 °C
Specific heat capacity of the reaction Cp 2
mixture ∆Tad adiabatic temperature rise (K or °C)
Cp = 3.5 kJ·kg-1·K-1 QR heat of reaction (kJ·kg-1)
Cp specific heat capacity (kJ·kg-1·K-1)
Remember
The adiabatic temperature rise of the
decomposition reaction will be For the process under study, the following data are already
known:
determined in the next step of
lesson 1. Heat of the desired reaction
QR = 250 kJ·kg-1
Heat of the decomposition reaction
QD = 500 kJ·kg-1
Specific heat capacity of the reaction mixture
Cp = 3.5 kJ·kg-1·K-1
 Lesson 1

Answer this question: The adiabatic temperature rise of a reaction is calculated by

What is the adiabatic dividing the heat of reaction by the specific heat capacity of
the reaction mixture.
temperature rise of the
decomposition reaction? Example
(Units should be K)
The adiabatic temperature rise of a high exothermic
decomposition reaction having a heat of reaction of
2000 kJ·kg-1 in a reaction mixture with 2 kJ·kg-1·K-1 specific
heat capacity is:

QR 2000
∆Tad = = = 1000 °C
Cp 2

∆Tad adiabatic temperature rise (K or °C)

QR heat of reaction (kJ·kg-1)
Cp specific heat capacity (kJ·kg-1·K-1)
Remember

For the process under study, the following data are already
known:

Heat of the desired reaction

QR = 250 kJ·kg-1
Heat of the decomposition reaction
QD = 500 kJ·kg-1
Specific heat capacity of the reaction mixture
Cp = 3.5 kJ·kg-1·K-1
 Lesson 1

Answer this question: The adiabatic temperature rise of a reaction is calculated by

What is the adiabatic dividing the heat of reaction by the specific heat capacity of
the reaction mixture.
temperature rise of the
decomposition reaction? Example
(Units should be K)
The adiabatic temperature rise of a high exothermic
decomposition reaction having a heat of reaction of
2000 kJ·kg-1 in a reaction mixture with 2 kJ·kg-1·K-1 specific
heat capacity is:

Right answer: =
QR
=
2000
= 1000 °C
∆Tad
The adiabatic temperature Cp 2
rise of the decomposition ∆Tad adiabatic temperature rise (K or °C)
reaction is QR heat of reaction (kJ·kg-1)
143 K Cp specific heat capacity (kJ·kg-1·K-1)
Remember

For the process under study, the following data are already
known:

Heat of the desired reaction

QR = 250 kJ·kg-1
Heat of the decomposition reaction
QD = 500 kJ·kg-1
Specific heat capacity of the reaction mixture
Cp = 3.5 kJ·kg-1·K-1
 Lesson 1
Answer this question:
What is the severity of a The adiabatic temperature rise of the
potential incident? decomposition reaction is a direct measure
(Type HIGH, MEDIUM or LOW) of the severity of a possible incident.

As a guideline, the following values can be

used

Severity Adiabatic temperature rise

HIGH ∆Tad > 200 °C

MEDIUM 50 °C < ∆Tad < 200 °C
LOW ∆Tad < 50 °C(1)

(1) where the boiling point is not reached

Remember

In the previous step of lesson 1 the adiabatic

temperature rise due to the decomposition
reaction was calculated. Its value is 143 °C.

Answer this question:
What is the severity of a
potential incident?
(Type HIGH, MEDIUM or LOW)
Right answer:
The severity of a potential
incident is
MEDIUM
Lesson 1
The adiabatic temperature rise of the
decomposition reaction is a direct measure
of the severity of a possible incident.
As a guideline, the following values can be
used
Severity Adiabatic temperature rise
HIGH ∆Tad > 200 °C
MEDIUM 50 °C < ∆Tad < 200 °C
LOW ∆Tad < 50 °C(1)
(1) where the boiling point is not reached
Remember
In the previous step of lesson 1 the adiabatic
temperature rise due to the decomposition
reaction was calculated. Its value is 143 °C.
 Lesson 1
Lesson 1
The severity of a possible
The conclusion of the incident in the process is
initial steps of lesson 1 MEDIUM due to the amount
is that the severity of a of energy which can be
released by the
possible incident in the decomposition reaction. The
process is MEDIUM. adiabatic temperature rise is
a direct measure of this
energy potential.

Data used for the

assessment of severity are
summarized in risk analysis
form 2.
Case
Casestudy
study: :Batch
Batchreaction
reaction Thermal
ThermalStability
Stability
BASIC
BASIC DATA FOR RISKANALYSIS
DATA FOR RISK ANALYSIS FORM
FORM22
Severity:
Severity:
Energy
Energypotential
potentialofofrelevant
relevantdecomposition
decompositionreactions:
reactions: 500
500 kJ/kg
kJ/kg
Specific heat capacity of reaction
Specific heat capacity of reaction mass: mass: 3.5 kJ/kg/K
3.5 kJ/kg/K
Adiabatic
Adiabatictemperature
temperaturerise:rise: 143
143 °C
°C
Boiling
Boiling point of reaction mass(if(ifrelevant):
point of reaction mass relevant): °C
°C
Gas evolution:
Gas evolution: mm3/batch
3/batch
Known
Knowndecomposition
decompositionproducts:
products:
Source of data:
Source of data:
Assessment
Assessmentof ofseverity:
severity: Low
Low Medium
Medium High
High

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 Case study : Lesson 1
Batch reaction
The conclusion of the initial
Lesson 1 steps of lesson 1 is that the
severity of a possible
Rough estimate of incident in the process is
probability MEDIUM.

The next step of lesson 1 is

to make a rough assessment
of the probability of
triggering the decomposition
reaction in the event of loss
of control of the desired
reaction.
 Lesson 1 Lesson 1

Use the equation below to calculate the

To give a rough estimate of the adiabatic temperature rise of the desired
probability of triggering the reaction.

decomposition reaction in the The parameters which are already known are
event of loss of control of the given.
desired reaction, the following
data should be determined: QR
∆Tad, R = Cp

∆Tad, R adiabatic temperature

∆Tad, R adiabatic temperature
rise of the desired rise of the desired
reaction (°C). reaction (K or °C)
Tmax, R maximum attainable QR heat of the desired
temperature if the reaction ( 250 kJ·kg-1)
desired reaction occurs Cp specific heat capacity of
the reaction mixture
under adiabatic
( 3.5 kJ·kg-1·K-1)
conditions (°C).
 Lesson 1
Answer this question:
What is the adiabatic Use the equation below to calculate the
temperature rise of the adiabatic temperature rise of the desired
desired reaction? reaction.
(Units should be K)
The parameters which are already known are
given.

QR
∆Tad, R = Cp

∆Tad, R adiabatic temperature

rise of the desired
reaction (K or °C)
QR heat of the desired
reaction ( 250 kJ·kg-1)
Cp specific heat capacity of
the reaction mixture
( 3.5 kJ·kg-1·K-1)

Answer this question:
What is the adiabatic
temperature rise of the
desired reaction?
(Units should be K)
Right answer:
The adiabatic temperature
rise of the desired reaction
is
71 K
Lesson 1
Use the equation below to calculate the
adiabatic temperature rise of the desired
reaction.
The parameters which are already known are
given.
QR
∆Tad, R = Cp
∆Tad, R adiabatic temperature
rise of the desired
reaction (K or °C)
QR heat of the desired
reaction ( 250 kJ·kg-1)
Cp specific heat capacity of
the reaction mixture
( 3.5 kJ·kg-1·K-1)

Answer this question:
What is the maximum
attainable temperature if the
desired reaction runs under
adiabatic conditions?
(Units should be °C)
Lesson 1
Use the equation below to calculate the
maximum attainable temperature if the
desired reaction occurs under adiabatic
conditions.
The parameters which are already known are
given.
Tmax, R = Tp + ∆Tad, R
Tmax, R maximum attainable
temperature if the
desired reaction occurs
under adiabatic
conditions (°C)
Tp process temperature
(195°C)
∆Tad, R adiabatic temperature
rise of the desired
reaction ( 71°C)

Answer this question:
What is the maximum
attainable temperature if the
desired reaction runs under
adiabatic conditions?
(Units should be °C)
Right answer:
The maximum attainable
temperature if the desired
reaction runs under
adiabatic conditions is
266°C
Lesson 1
Use the equation below to calculate the
maximum attainable temperature if the
desired reaction occurs under adiabatic
conditions.
The parameters which are already known are
given.
Tmax, R = Tp + ∆Tad, R
Tmax, R maximum attainable
temperature if the
desired reaction occurs
under adiabatic
conditions (°C)
Tp process temperature
(195°C)
∆Tad, R adiabatic temperature
rise of the desired
reaction ( 71°C)
 Case study : Lesson 1
Batch reaction To give a rough estimate of the
probability of triggering the
Lesson 1 decomposition reaction in the
event of loss of control of the
Rough estimate of desired reaction, the following
probability data are already known:
∆Tad, R: adiabatic temperature rise
of the desired reaction (71°C).
Tmax, R: maximum attainable
temperature if the desired
reaction occurs under adiabatic
conditions (266°C).
These results should be
summarized in risk analysis
form 1.
Case
Casestudy
study: :Batch
Batchreaction
reaction Thermal
ThermalData
DataofofReaction
Reaction
BASIC
BASIC DATA FOR RISKANALYSIS
DATA FOR RISK ANALYSIS FORM
FORM11
POTENTIAL
POTENTIAL
Heat
Heatofofreaction
reaction Specific
Specificheat
heatcapacity
capacity Adiabatic
AdiabaticTemperature
TemperatureRise
Rise
(Ratio
(RatioQQRR/ /Cp)
Cp)

QQR ==250
250 kJ/kg
kJ/kg Cp
Cp==3.5
3.5 kJ/kg/K
kJ/kg/K ∆∆Tad
Tad==71
71°C
°C
R

Highest
Highesttheoretical
theoreticalattainable
attainabletemperature
temperatureinincase
caseadiabatic
adiabaticconditions occur:266°
conditionsoccur: CC
266°
Total
Totalgas
gasevolution:
evolution: l/kg
l/kg l/batch
l/batch
Source of data:
Source of data:
Consequences
Consequencesofofallowing
allowingadiabatic
adiabaticreaction
reaction (Check
(Checkappropriate
appropriateboxes)
boxes)
Harmless
Harmlesstemperature
temperaturerise
rise Boiling
Boiling(Bp
(Bp== °C)
°C) Gas
Gasrelease
release
Critical temperature rise
Critical temperature rise Decomposition
Decomposition Pressure
Pressurebuild
buildup
up
Other
Other: :

Lesson
Lesson11
Use
Userisk
riskanalysis
analysisforms
forms11and
and22to
tosummarize
summarizethe
theresults
results
 Case study : Lesson 1
Batch reaction In the event of loss of thermal
control of the desired reaction,
Lesson 1 the temperature will rise until
266°C.
Rough estimate of
probability The next step in making a rough
estimate of the probability of
triggering the decomposition
reaction, is to determine if at this
temperature (266°C) the
decomposition reaction is active
enough to produce an incident,
in a time too short to take
counter-measures.
Lesson 1 Lesson 1

In the final reaction mixture thermogram,

Taking account of the signal corresponding to the
decomposition reaction is detected at
experimental conditions, one 235°C.
can assume that if the trace Remark: This assumption depends
of the decomposition on the sensitivity of the measuring
reaction shows an instrument (10 W·kg-1) and the scan
rate (4°C·min-1).
observable signal at 266°C,
then at this temperature this Final reaction mixture thermogram:
reaction is active enough to Quantitative differential thermal analysis of final
reaction mixture.
produce an incident in a time 1.2 Heat release rate (W·g-1)
1 -500 kJ·kg-1
too short (minutes) to take 0.8
0.6 235°C Tmax,R=266°C
counter- measures. 0.4
0.2
0
-0.2
-0.4
+30 kJ·kg-1
-0.6
0 100 200 300 400
scan rate: 4°C·min-1 Temperature (°C)
Lesson 1
A rough estimate indicates that at
the maximum temperature
attainable on loss of control of
the desired reaction (266°C) , the
decomposition reaction will give
rise to an incident in a very short
time (minutes).
This means that in a preliminary
approximation (SCREENING), the
probability of triggering the
decomposition reaction is HIGH.
Lesson 1
Remark
Morever, the overlapping signals
of the heat of the desired reaction
and the heat of the
decomposition reaction in the
final reaction mixture thermogram
gives a clear evidence that the
PROBABILITY of triggering the
decomposition reaction is HIGH.
 Case study : Lesson 1
Batch reaction Pressure build up related to the

Lesson 1 process...

The pressure build up caused by

Pressure build-up uncontrolled heat release of the desired
and decomposition reactions is an
important risk especially in industrial
synthesis reactions performed under
pressure.

To assure a safe design of the process

and the plant including the choice of an
appropriate pressure relief system, it is
indispensible to know the maximum
pressure that can be reached in the event
of a failure.
We will study it later in lesson3.
Lesson 1 Lesson 1

Maximum Temperature for Potential at the Maximum

Technical reasons (MTT)... Temperature for Technical
reasons (MTT)...
In order to complete the consequences of
loss of thermal control of the desired
reaction, we must consider if the As the process temperature is 195°C,
Maximum Temperature for Technical
only 5°C of the 71°C adiabatic
reasons (MTT) could be reached in the
temperature rise of the desired
event of a failure.
reaction is needed to reach the
The Maximum Temperature for Technical Maximum Temperature for Technical
reasons is the temperature at which the reasons (MTT = 200°C).
pressure reaches the maximum
permissible value. Consequently, the remaining energy
In the case under study, the reactor is potential of the desired reaction will be
equipped with a safety valve. The safety still high at this point.
limit of this valve will be attained if the
temperature of the reactor attains 200°C.
Lesson 1
The results
According to the results of a
preliminary evaluation of the thermal
risks of the process under study
obtained in
(SCREENING), the consequences of a
loss of thermal control over the lesson 1
synthesis reaction may lead to a
critical situation: should be
- the Maximum Temperature for
Technical reasons (MTT) will be
summarized in
reached
- at this point, the potential of the risk analysis
desired reaction is still high: there
exists a risk of pressure build up
- the decomposition reaction will be
forms 1 and 2.
triggered.
Case
Casestudy
study: :Batch
Batchreaction
reaction Thermal
ThermalData
DataofofReaction
Reaction
BASIC
BASIC DATA FOR RISKANALYSIS
DATA FOR RISK ANALYSIS FORM
FORM11
POTENTIAL
POTENTIAL
Heat
Heatofofreaction
reaction Specific
Specificheat
heatcapacity
capacity Adiabatic
AdiabaticTemperature
TemperatureRise
Rise
(Ratio Q / Cp)
(Ratio QR / Cp)
R

QQR ==250
250 kJ/kg
kJ/kg Cp
Cp==3.5
3.5 kJ/kg/K
kJ/kg/K ∆∆Tad
Tad==71
71°C
°C
R

Highest
Highesttheoretical
theoreticalattainable
attainabletemperature
temperatureinincase
caseadiabatic
adiabaticconditions occur:266°
conditionsoccur: CC
266°
Total
Totalgas
gasevolution:
evolution: l/kg
l/kg l/batch
l/batch
Source of data:
Source of data:
Consequences
Consequencesofofallowing
allowingadiabatic
adiabaticreaction
reaction (Check
(Checkappropriate
appropriateboxes)
boxes)

Harmless
Harmlesstemperature
temperaturerise
rise Overpressure
Overpressure(MTT
(MTT==200°C)
200°C) Gas
Gasrelease
release
Critical
Criticaltemperature
temperaturerise
rise Decomposition
Decomposition Pressure
Pressurebuild
buildup
up
Other
Other: :
Lesson
Lesson11
Conclusions
Conclusions
Case
Casestudy
study: :Batch
Batchreaction
reaction Thermal
ThermalStability
Stability
BASIC
BASIC DATA FOR RISKANALYSIS
DATA FOR RISK ANALYSIS FORM
FORM22
Severity:
Severity:
Energy
Energypotential
potentialof
ofrelevant
relevantdecomposition
decompositionreactions:
reactions: 500
500kJ/kg
kJ/kg
Specific heat capacity of reaction mass:
Specific heat capacity of reaction mass: 3.5 kJ/kg/K
3.5 kJ/kg/K
Adiabatic temperature rise:
Adiabatic temperature rise: 143
143°C
°C
Maximum Temperature for Technical reasons (MTT):
Maximum Temperature for Technical reasons (MTT): 200 °C
200 °C
Gas evolution
Gas evolution mm3/batch
3/batch
Known
Knowndecomposition
decompositionproducts:
products:
Source of data:
Source of data:
Assessment
Assessmentof ofseverity:
severity: Low
Low Medium
Medium High
High

Lesson
Lesson11
Conclusions
Conclusions