Technical Process Safety Seminar – Singapore

Applying Functional Safety and Reaction Safety for Safety Cases

Chemical Reaction Safety Workshop

Shaik Salim/Paul Sharratt

19 Aug 2019
Chemical Reaction Safety Workshop

Introduction:
Seveso: Reaction Safety 3

Fundamentals of Chemical Reaction Safety 8

Chemical Reaction Risk Assessment:

Chemical Hazard Evaluation 19

Desktop Screening 23

Experimental Techniques & Stoessel 36

Criticality Class

2
 Seveso: Toxic release
•Saturday 9 July 1976 a bursting disc ruptured on a chemical reactor at the works of the Icmesa Chemical
Company at Meda near Seveso
•The start of the batch began at 16.00 on Friday 9 July. The batch process was interrupted prior to
finishing the final step of removal of ethylene glycol by distillation, due to an Italian law requiring
shutdown of plant operations over the weekend.
•This batch was stopped by isolating the steam, and turning off the stirrer.
•A runaway reaction occurred which led to the formation and release of tetrachlorodibenzodioxin (TCDD)
•A white cloud drifted from the works and some TCDD settled downwind.

Icmesa chemical plant at Seveso,

Italy. The vent pipe of the
trichlorophenol reactor Is shown
ringed 3
 Seveso: The Process
• the formation of small quantities of
TCDD as a by-product is unavoidable.
At a reaction temperature below 180C
tetrachlorobenzene trichlorophenol tetrachlorodibenzodioxin(TCDD) the amount formed would be unlikely to
exceed 1 ppm of TCP, but with
3.5bar
prolonged heating in the temperature
range 230±260C it could increase a
thousand-fold. The known
decomposition exotherm starts at about
280C
• There exists two (unknown) slow
exotherms. One starts at about 185C,
the other starts at about 255C
• The residual heat in the jacket then
heated the upper layer of the mixture
next to the wall to the critical
temperature (ca. 180°C), starting a
12bar/188C slow runaway decomposition, and after
seven hours a rapid runaway reaction
ensued when the temperature reached
230°C
• The relief valve eventually opened and
4
6 tonnes of material (1kg TCDD) were
distributed over an area of 18 km2
5
6
Seveso: Lessons
• Hazard of ultratoxic substances
• Hazard of undetected exotherms
• Hazard of prolonged holding of reaction mass
• Inherently safer design of chemical
processes
• Control and protection of chemical reactors
• Adherence to operating procedures

7
Fundamentals of
Chemical Reaction
Safety

8
Fundamentals of chemical reaction safety:

• When considering reaction hazards,

temperature is rarely a hazard on its
own. Overpressure due to
temperature rise on the system is Hr
much more important. The three
potential sources of overpressure
are:

• Gas Generation from the normal process

• Vapour pressure effects as a consequence of heat on the normal
process
• Secondary reactions at elevated temperature due to heat from the
normal process causing gas and/or vapour effects

9
Fundamentals of chemical reaction safety: Thermal Hazards

Examples of exothermic reactions and their severity

Reaction Severity Hr (cal/g) Reaction Severity Hr (cal/g)
Type Type

Oxidation Highly exothermic >300 Amination Moderately exothermic 20 to 100

Nitration Highly exothermic >300 Esterification Moderately exothermic 20 to 100

Halogenation Highly exothermic >300 Methylation Mildly exothermic <20

Organometallics Highly exothermic >300 Alkylation Mildly exothermic <20

Diazotization Highly exothermic >300 Hydrolysis Mildly exothermic <20

Hydrogenation Highly exothermic >300 Salt formation Mildly exothermic <20

Thermal Highly
decomposition exothermic/Exothermic 100 to >300 Reduction Slightly exothermic <20
Highly
Polymerization exothermic/Exothermic 100 to >300 Electrolysis Slightly exothermic <20
Exothermic/Moderately
Sulfonation exothermic 20 to 300 Isomerization Slightly exothermic <20
Exothermic/Moderately
Condensation exothermic 20 to 300 Cyclization Slightly exothermic <20

[CSB Safety Video: Reactivity Hazards] 10

Fundamentals of chemical reaction safety: Thermal Hazards
Thermal Runaway

Heat generation due to

exothermic process

Heat
removal due
to cooling

Heat generation > cooling capacity

 Runaway reaction

Temperature (K)
Critical temperature

11
Fundamentals of chemical reaction safety: Thermal Hazards
Thermal Runaway

Beware assuming simple

Desired Reaction  Heat of reaction kinetics for:
• Autocatalytic reactions
• Heat generation not a problem if vessel correctly designed and • Heterogeneous reactions
vented ‐ Mass transfer may be
• Safety systems will contain or allow controlled release of rate determining
pressure ‐ Phase transfer agents
may dictate rate
• Complex reactions (multi
steps/routes)

Secondary Decompositions  Heat of decomposition

• May be initiated at high temperatures Rapid, simple screening
methods can determine
• If not considered during vessel design may cause severity & likelihood of
overpresurisation problem

12
Fundamentals of chemical reaction safety: Thermal Hazards

Adiabatic temperature rise

• When a reactive system cannot exchange energy with its
surroundings, adiabatic conditions prevail.
• All energy released by the reaction is used to increase the system’s
temperature
• Adiabatic temperature rise is a commonly used criterion to assess the
severity of a reaction

Adiabatic temperature rise:

: Molar enthalpy, kJ/mol : specific energy, kJ/kg

: concentration, mol/m3 : specific heat capacity, kJ/kgK
: specific weight, kg/m3

13
Fundamentals of chemical reaction safety: Thermal Hazards
q Semenov Diagram qrx
qex1 qex2 qex3
I
=UA

qrx: heat release rate of reaction

C qex: heat removal by cooling system
S Tc: temperature of cooling system
T
Tc Tc,crit

Heat balance when qrx =qex (at S, I, C)

I is the instable point:
• If T  heat generation dominates and runaway condition develops
• If T  heat removal dominates and temperature decreases to point S

S is the stable point

C is the critical point
14
Fundamentals of chemical reaction safety: Thermal Hazards
q qrx
qex1
qex2
Semenov Diagram I

qex3

C
S
T
Tc

If heat transfer coefficient (U) or the surface area (A) of the cooling
system is changed, a similar shift to a critical point will occur.
This may happen due to fouling of the cooling system
If reactor is operated with a cooling medium temperature close to the
critical cooling medium temperature, small variations of Tc, U and A may
result in a runaway situation

15
Fundamentals of chemical reaction safety: Thermal Hazards
q qrx

Tcrit : critical temperature

E  4 RT0 
Tcrit  1  1  
2 R  E 

q0 qcrit
T
T0 Tcrit
2
E RT02  Tcrit 
Tcrit  Tcrit  T0   Tcrit  1  
E  T0 
2
RTcrit
For a given reaction characterised by its thermo‐kinetic constants (k, E, Qr)
processed in a given reactor and characterised by its heat exchange
parameters (U, A, T0) there is a minimum temperature difference required
for stable reactor performance: 2
RTcrit
Tcrit  T  T0 
E 16
Fundamentals of chemical reaction safety: Thermal Hazards

Time of No Return – TNR

• TNR: time required to reach the critical temperature Tcrit from the initial
temperature from which the thermal explosion develops T0.
• After this time has elapsed under adiabatic conditions, even if the cooling
system has recovered, it is impossible to cool the reactor
• TNR is an important feature of an emergency cooling system designed to
cope with an imminent runaway reaction – i.e. It has to be effective in a
time less than the TNR

: heat release rate at initial conditions T0, J/s

: activation energy, J/mol
cp’ : specific heat capacity of reaction mixture, J/gK
17
Fundamentals of chemical reaction safety: Thermal Hazards

Time frame of thermal explosion – TMRad concept

• TMRad: time to maximum rate under adiabatic conditions is the time a
thermal explosion takes to develop under adiabatic conditions

cp RT02
TMRad 
q0 E

• TMRad is a function of the reaction kinetics

• q0 is an exponential function of temperature thus TMRad decreases
exponentially with temperature and decreases with increasing activation
energy

cp RT02
TMRad T  
q0e  E RT0 E

18
 Chemical Reaction Risk
Assessment

• Chemical Hazard Evaluation

19
 Chemical Hazard Evaluation Flow Chart

Review & document

Desk Screening available
information
Tonset,, H
 d
vs T, P vs t
& T,
Adiabatic
Thermal Stability residual P
DSC/TGA Calorimetry (ARC,
Assessment APTAC)
Tonset,
Trange,
Hd

Reaction Rate gas

Desired Reaction Gas Evolution
Calorimetry evolved,
Assessment (RC1, APTAC)
Measurement
Rate vs T

Hrxn,
maloperation,
A foaming

20
 Chemical Hazard Evaluation Flow Chart
A

Q, rate of
Undesired Reaction Reaction Calorimetry
Q, T, Tonset,
Assessment (RC1, APTAC)
venting

if
YES Additional Material flammability,
required
Stability Testing explosivity

NO

Establish Basis of
Safety

21
Chemical Reaction Risk Assessment: Reaction Hazard Evaluation

Desktop screening

Screening test

Detailed test

22
Chemical Reaction
Risk Assessment

Reaction Hazard Evaluation

• Desktop Screening

23
Important physical and chemical properties for initial evaluation
Reaction Hazard Evaluation: Desktop Screening

24
Reaction Hazard Evaluation: Desktop Screening
Typical High Energy Molecular Structures

25
Reaction Hazard Evaluation: Desktop Screening

Typical High Energy Molecular Structures

26
Reaction Hazard Evaluation: Desktop Screening
U:internal energy of the system, T:absolute
G = U - TS + pV 1 temperature, S:entropy, p:pressure,
V:volume
for reaction at constant temperature and pressure:

Gr = Ur-T Sr + p Vr 2
Since the entropy change of an exothermic reaction is
small(0.1kJ/mol.C) relative to Ur, TSr can be omitted.

for reaction at constant pressure:

Hr = Ur + p Vr 4

Under isobaric conditions, a small amount of energy is consumed or released by expansion or

contraction of the system, and Hr is the observed (i.e., net) heat dissipated or absorbed.
The enthalpy released or absorbed in an isobaric process can be described
in a manner similar to Equation (3) for constant volume conditions

27
Reaction Hazard Evaluation: Desktop Screening
Worked Example
The reaction/combustion of methane gas in oxygen is represented by the reaction:

CH4 (g) + 2 O2 (g)  CO2 (g) + 2 H2O (g)

The calculation for the heat of reaction (combustion) for methane is then:
ΔH = Σ ΔHf,products - Σ ΔHf, reactants
ΔH = (ΔHf,CO2 + 2 ΔHf,H2O)- (ΔHf,CH4 + 2 ΔHf,O2)
ΔH = [ ‐393.5 kJ + 2x(‐241.8 kJ)] ‐ [‐74.8 kJ + 2x(0 kJ)]
ΔH = - 802.3 kJ

So, the heat of combustion, that is, the heat of reaction, is ‐ 802.3 kJ per mole of
methane.
Notice that the value is negative, so the reaction gives off heat as expected for a
combustion reaction.

Data Source: NIST Chemistry WebBook28

Reaction Hazard Evaluation: Desktop Screening
Oxygen balance
The oxygen balance is the amount of oxygen, expressed as weight
percent, liberated as a result of complete conversion of the material
CxHyOzNq to CO2, H2O, SO2, N2, and other relatively simple
oxidized molecules.
(Note: the nitrogen is assumed to evolve as N2)
X : number of atoms of carbon
Y : number of atoms of hydrogen
Z: number of atoms of oxygen
M: number of atoms of metal

• substance lacking sufficient oxygen has a negative OB value, and one containing excess oxygen
has a positive OB value
• the power of explosives increases as the OB increases and approaches a value of zero

OB
‐240 ‐120 0 80 160

29
Reaction Hazard Evaluation: Desktop Screening

 Criterion – hazard potential classification

 : energy release evaluation (ERE) value

Q: decomposition energy in kcal/g (with positive sign for heat
released),
MW: molecular weight
N: number of atoms in the composition.

30
Reaction Hazard Evaluation: Desktop Screening
10

Difference between heats of combustion and decomposition

9

Low Hazard Potential

|Hc ‐ Hd| (kcal/g)

4 Medium Hazard Potential

2
High Hazard Potential
1

0
2.0 1.0 0.7 0.3 0
Heat of decomposition Hd (kcal/g) 31
Reaction Hazard Evaluation: Desktop Screening

Criterion Energy Hazard Potential

Low Medium High
1 Hd > ‐1255J/g ‐2929 < Hd < ‐1255J/g Hd < ‐2929J/g
2 Refer to relationship between heats of combustion and decomposition
3 OB < ‐240 ‐240 < OB < ‐120 ‐120 < OB < 80
OB > 160 80 < OB < 160

4  < 30 30 <  < 110  > 110

32
Activity: Heat of Reaction
The OMEGA process is a process by Shell that is used to produce ethylene glycol
from ethylene. This process comprises two steps, the controlled oxidation of
ethylene to ethylene oxide, and the net hydrolysis of ethylene oxide to
monoethylene glycol (MEG) as follows:
(EO)
1. Formation of ethylene oxide: 2C2H4 + O2 → 2C2H4O

(EC)
2. Formation of ethylene carbonate: C2H4O + CO2 → C3H4O3

(MEG)
3. Formation of MEG: C3H4O3 + H2O → C2H6O2 + CO2

Calculate the various Heats of Reaction

33
Exercise 1: Desktop Screening - Reaction
Hazard Evaluation

nitrotoluene: C7H7NO2 Benzaldehyde: C7H6O Aniline: C6H5NH2

1. Determine the heat of combustion

2. Determine the heat of decomposition
3. Calculate oxygen balance
4. Calculate 
5. Classify compounds

34
Experimental Data

Sample DSC ‐ benzaldehyde

Similarly: Aniline = Hd = ‐ 820 J/g

Nitrotoluene = Hd = ‐ 3520 J/g
35
 Chemical Reaction Risk
Assessment

Reaction Hazard Evaluation

• Experimental Techniques
• Stoessel Criticality Class

36
Reaction Hazard Evaluation: Experimental Techniques
Comparison of different common calorimetric methods used in safety laboratories
Method Measuring principles Application range Sample Temperature Sensitivity
size range W kg-1
DSC differential Differential, ideal flux, or Screening, secondary
scanning calorimetry isoperibolic reactions 1‐50mg ‐50 to 500°C 2 to 10
Main and secondary
Calvet Differential, ideal flux reactions 0.5‐3 g 30 to 300°C 0.1
ARC accelerating rate
calorimeter Ideal accumulation Secondary reactions 0.5‐3 g 30 to 400°C 0.5
SEDEX sensitive
detector of Secondary reactions,
exothermal processes Isoperibolic, adiabatic storage stability 2‐100g 0 to 400°C 0.5
Screening, secondary
RADEX Isoperibolic reactions 1.5‐3 g 20 to 400°C 1
Ideal accumulation,
SIKAREX isoperibolic Secondary reactions 5‐50g 20 to 400°C 0.25
RC1 reaction
calorimeter Ideal flux Main reactions 300‐2000g ‐40 to 250°C 1
TAM thermal activity Secondary reactions,
monitor Differential, ideal flux storage stability 0.5‐3 g 30 to 150°C 0.01
Main reactions and
Dewar Ideal accumulation thermal stability 100‐1000g 30 to 250°C varies

37
Reaction Hazard Evaluation : Experimental Techniques
Reaction calorimetry - desired reaction

Reaction Calorimeter

38
Reaction Hazard Evaluation : Experimental Techniques
Adiabatic calorimetry – undesired reaction
APTAC New ARC

Vent Sizing package ‐VSP2 Design pressure +10% Max. accumulated

pressure
Design pressure

Set pressure +10% Relief pressure

Set pressure
Valve discharges full capacity &
pressure continues to rise at
reduced rate
Safety valve
starts to open
Pressure rise due to
Adiabatic Calorimeters runaway reaction 39
Reaction Hazard Evaluation : Experimental Techniques
Differential scanning calorimetry – undesired reaction
DSC measures the energy required to keep both the
reference and the sample at the same temperature
DTA measures the difference in temperature between
the sample and the reference

Heat flow (mW)

time

DSC/DTA: Differential Scanning Calorimeter/Differential Thermal Analyser 40

Chemical Reaction Risk Assessment: Reaction Hazard Evaluation
Hazards of side reactions

Case 1 Case 2 Case 3

Safe Harmless Difficult Safe Dangerous
but
feasible

P: primary reaction; S: secondary reaction; Tmax: maximum reactor temperature; TR: temperature of reactor; TS: 41
temperature at which secondary reaction occurs; Tad: adiabatic temperature rise
Chemical Reaction Risk Assessment: Stoessel Criticality Class

T This runaway scenario works

Tf as follows:
• if a cooling failure occurs
while the reactor is at the
process temperature (TP), It
(undesired)
(desired) reaches a level called the
maximum temperature of
the synthesis reaction
(MTSR)
• a secondary decomposition
reaction may then be
initiated and the heat
produced by this reaction
may lead to a further
The cooling failure scenario was developed for increase in temperature
the systematic assessment of thermal risks reaching the final
linked with exothermal chemical reactions temperature (Tf)
42
Chemical Reaction Risk Assessment: Stoessel Criticality Class

• Question 1: Can the process temperature be

controlled by the cooling system?
– The power of the cooling system must be sufficient to remove the
heat released in the reactor
• Question 2: What temperature can be attained after
runaway of the desired reaction?
– Upon cooling failure, unconverted reactants still present in reactor
will react uncontrollably leading to an adiabatic temperature rise
– The available energy is proportional to the accumulated
(unreacted) fraction, Xac
– Maximal Temperature of Synthesis Reaction (MTSR):

MTSR  Tp  X ac .Tad ,reaction

43
Chemical Reaction Risk Assessment: Stoessel Criticality Class

• Question 3: What temperature can be attained after

runaway of the secondary reaction
– If the MTSR is higher than the intended process temperature,
secondary reactions may be triggered
– A further runaway due to uncontrolled secondary reaction (e.g.
decomposition) will further increase the temperature

Tend  MTSR  Tad ,sec ondary

• Question 4: At which moment does the cooling failure

have the worst consequences?
– The worst instance is when accumulation is maximum and/or
thermal stability of reaction mixture is critical

44
Chemical Reaction Risk Assessment: Stoessel Criticality Class

• Question 5: How fast is the runaway of the desired

reaction?
– The duration of the main reaction runaway may be estimated using
the initial heat release rate and TMRad:

 2
c p RTp
TMRad 
qTp E

• Question 6: How fast is the runaway of the

decomposition starting at MTSR?
– If secondary reactions are triggered:
cp RTMTSR
2

TMRad 
q MTSR E

45
Chemical Reaction Risk Assessment: Stoessel Criticality Class
• Severity
– The adiabatic temperature rise can be calculated by dividing the energy
of the reaction by the specific heat capacity:
Q
Tad 
cp
– Q’ represents the specific energy of desired reaction or of the secondary
(decomposition) reaction.
– The higher the final temperature, the worse the consequences of the
runaway
– The temperature increase may cause components of the reaction
mixture (e.g. solvents) to vapourise or the decomposition may produce
gasses causing pressure increase

Simplified Extended Tad Q’ (kJ/kg)

High Catastrophic >400 >800
Critical 200‐400 400‐800
Assessment criteria
Medium Medium 50‐100 100‐400 for severity of a
Low Negligible <50 <100 runaway reaction
46
Chemical Reaction Risk Assessment: Stoessel Criticality Class
• Probability
– The probability can be evaluated using the time scale: If after a cooling
failure, there is enough time left to take emergency measures before the
runaway becomes too fast, the probability of the runaway will remain low
Case 2: fast  Case 1: slow 
high probability low probability
temperature

Time (hr)

Simplified Extended TMRad (hr)

High Frequent <1
Probable 1‐8
Medium Occasional 8‐24
Low Seldom 24‐50 Assessment criteria
for probability of a
Remote 50‐100 runaway reaction
Almost impossible >100 47
Chemical Reaction Risk Assessment: Stoessel Criticality Class

Risk Matrix for Reaction Hazard Assessment

48
Chemical Reaction Risk Assessment: Stoessel Criticality Class
Stoessel Criticality Class

low high
Risk

49
Chemical Reaction Risk Assessment: Stoessel Criticality Class
KEY PARAMETERS
• Process temperature (TP): The initial temperature in the cooling failure. For
non‐isothermal processes, the initial temperature will be taken at the instant
when cooling failure has the worst consequences. Defined by the mode of
operation.
• Maximum temperature of the synthesis reaction (MTSR): This temperature
depends on the degree of accumulation of unconverted reactants. Defined by
the accumulation of reactants and Tp.

50
Chemical Reaction Risk Assessment: Stoessel Criticality Class

• Temperature at which TMRad is 24h (TD24): the highest temperature at which

the thermal stability of the reaction mass is unproblematic. Defined by the
thermal stability of reaction mass.

TMRad
TD24

cp RTp2
TMRad 
qT p E TD24 is given at the point where
24 h TMRad is equal to 24 hours

T
Variation of TMRad as a function of temperature T

51
Chemical Reaction Risk Assessment: Stoessel Criticality Class
KEY PARAMETERS
• MTT: maximum temperature for technical reasons (e.g. construction
materials, reactor permissible design temperature and permissible design
pressure). Defined by the equipment.
– open reacting system, i.e. Operated at atmospheric pressure, the
boiling point is used
– closed system, operated under pressure, the temperature at which
the pressure reaches the set pressure of the pressure relief system or
a shutdown pressure for a protection system

52
Chemical Reaction Risk Assessment: Stoessel Criticality Class

53
Chemical Reaction Risk Assessment: Stoessel Criticality Class

• Criticality Class 1
– After loss of control of synthesis reaction
the technical limit (MTSR < MTT) cannot
be reached and decomposition cannot be
triggered (MTSR < TD24)
– Process presents a low thermal risk
– No special measures required but reaction
mass should not be held for a long time
under heat accumulation condition
Decomposition is not – Evaporative cooling (i.e. boiling point) or
triggered.
MTT is not reached emergency pressure relief could serve as a
safety barrier

54
Chemical Reaction Risk Assessment: Stoessel Criticality Class

• Criticality Class 2
– After loss of control of synthesis reaction the technical
limit (MTSR < MTT) cannot be reached and
decomposition cannot be triggered (MTSR < TD24)
– Situation similar to Class 1 but MTT > TD24, hence is
reaction mass held for long time under heat
accumulation condition decomposition can be triggered
and reach MTT
– Process presents a low thermal risk
– No special measures required if heat accumulation is
avoided
– Evaporative cooling or emergency pressure relief could
serve as a safety barrier
Decomposition is not – Boiling point could not serve as a safety barrier.
triggered.
MTT is not reached

55
Chemical Reaction Risk Assessment: Stoessel Criticality Class

• Criticality Class 3
– After loss of control of synthesis reaction the
technical limit will be reached (MTSR > MTT) but
decomposition cannot be triggered (MTSR < TD24)
– Safety of this process depends on the heat release
rate of the synthesis reaction at the MTT
– Risk reducing measures are required.
– Evaporative cooling, controlled depressurisation,
backup cooling, dumping of the reaction mass or
quenching may be used
– Alternatively a pressure relief system could also
serve as a safety barrier
Decomposition is not
triggered.
MTT is reached

56
Chemical Reaction Risk Assessment: Stoessel Criticality Class
• Criticality Class 4
– After loss of control of synthesis reaction the technical
limit will be reached (MTSR > MTT) and
decomposition could theoretically be triggered (MTSR
> TD24)
– Safety of this process depends on the heat release
rate of both the synthesis and decomposition reactions
at the MTT
– Risk reducing measures are required.
– This scenario is similar to Class 3 with the difference
being that if control measures fail, the secondary
reaction will be triggered
– Evaporative cooling or pressure relief system may
Decomposition could be
triggered.
serve as a safety barrier
MTT is reached

57
Chemical Reaction Risk Assessment: Stoessel Criticality Class
• Criticality Class 5
– After loss of control of synthesis reaction the
decomposition reaction will be triggered (MTSR > TD24)
and the technical limit will be reached during the runaway
of the secondary reaction.
– The heat release rate of the secondary reaction at MTT
may be too high resulting in a critical pressure increase.
– Thus there is no safety barrier between the main and
secondary reactions.
– In this case, neither evaporative cooling or pressure relief
system can serve as a safety barrier. Only quenching or
dumping can be used.
– Worthwhile to consider alternative process design (e.g.
change from batch to semi-batch)
Decomposition is triggered.
MTT is reached

58
Chemical Reaction Risk Assessment: Stoessel Criticality Class
Worked example
A ketone is to be hydrogenated to the corresponding alcohol at 30°C in an aqueous solution at a
concentration of 0.1mol/l and at a pressure of 2 barg in a reactor protected against overpressure
by a safety valve with a set pressure of 3.2 barg. The molecule presents no other reactive
functional groups.
Assess the thermal risks linked to this hydrogenation reaction
Data:
Similar reactions have an enthalpy of 200kJ/mol.
The specific heat capacity of the reaction mass is cp’ = 3.6 kJ/kgK
Solution:
This example shows that with only sparse thermal data it is sometimes possible to assess thermal risks.
This is possible due to the low concentration used in this hydrogenation. The reaction is performed in a
diluted aqueous solution. Thus, its density can be assumed to be 1000kg/m3. Then, the specific heat of
reaction is:

Therefore, the corresponding adiabatic temperature rise is:

Such a weak adiabatic temperature rise cannot lead to a thermal explosion. The
severity is low. In case of malfunction of the reactor cooling system, the reaction,
providing it is not stopped, will lead to an immediate temperature rise by 6 K
reaching the MTSR of 36°C. The thermal risk linked to this hydrogenation reaction is
low. 59
Activity: Grignard Reagent Formation

Reaction mixture density,  = ?? kg/m3

Specific heat capacity,, cp = 123 J/mol.K

Activation energy, EA = 9.7 kJ/mol

If initial concentration of R-Br is 2 moles, what is the adiabatic temperature rise?

60
Exercise 2: Thermal Hazard Assessment
Chemistry
• Reaction: A + B  P  S at process temperature = 80 C
• Where: A, B: reactants, P: desired product , S: decomposition product
Experimental Data – Reactants A & B

Figure 1: DSC Thermogram of Reactant A

NOTE: Reactant B shows no exotherm below 500°C 61

Experimental Data – Final Reaction Mass

Figure 2: DSC Thermogram of the final reaction mass (A+B+P but mostly P)

Further Information:
 The specific heat capacity of the reaction mass is 1.7 kJ/(kg.K)
 The boiling point of the reaction mass is below 200°C.
 No gases are formed during the reaction.
62
Experimental Data – Whole Reaction Mass

Both reactants A und B were mixed at the ambient in a pressure resistant gold
plated steel cell which was then heated linearly in the DSC apparatus.

Figure. 3: DSC Thermogram of the Cold Mixed Reactants (A+B)

63
Experimental Data – Kinetics
A series of isothermal DSC measurements at different temperatures allow determining the
maximum heat flow as a function of temperature. The analysis of the flow by using Arrhenius
law leads to the activation energy of the decomposition.

Figure 5: Isothermal DSC Thermograms of the Final Reaction Mass

Table 1: Maximum Heat Release Rates (from isothermal DSC experiments)

T (°C) 190 200 210 220
qmax (W/kg) 40 70 120 190
64
 Exercise 2: Thermal Hazard Assessment

QUESTIONS

A. Desired Reaction

i. Is Reactant A likely to decompose under normal process

conditions?
ii. What is the adiabatic temperature rise (Tad) of the primary
reaction?
iii. What is the final temperature?
iv. Can the decomposition temperature be triggered by the
desired reaction?
v. If so, what will be the final temperature?

65
 Exercise 2: Thermal Hazard Assessment

B. Undesired Reaction

i. Calculate the activation energy Ea of the secondary (undesired) reaction

based on the data in Table 1 and using:

ii. Determine TMRad using:

iii. What is the temperature when the time to maximum rate (TMRad) is
24hrs (i.e. TD24)
iv. What is the Stoessel Criticality Class?
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 Exercise 3: Reactor stability - critical temperature
q qrx

E  4 RT0 
Tcrit  1  1  
Tcrit : critical temperature 2 R  E 

T0 : coolant temperature
2
RTcrit
Tcrit  T  T0 
qcrit
E
q0
T

T0 = 15 C Tcrit = ?

1. What is the minimum temperature difference between the cooling medium

and reaction mixture required for stable reactor performance?
2. What is the maximum temperature of the cooling medium that will allow for
a stable reactor if the required process temperature is 80 C?

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End
Contact us

Paul Sharratt
Institute of Chemical & Engineering Sciences
Principal Scientist

Shaik Salim
Institute of Chemical & Engineering Sciences
Principal Specialist
Tel: +65-67963950
Email: shaik_salim@ices.a-star.edu.sg

69
Thank you