Runaway reactions, their courses and the methods to

establish safe process conditions

J. Gustin

To cite this version:

J. Gustin. Runaway reactions, their courses and the methods to establish safe process conditions.
Journal de Physique III, EDP Sciences, 1991, 1 (8), pp.1401-1419. �10.1051/jp3:1991198�. �jpa-
00248666�

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J. Phys. III France 1 (1991) 1401-1419 Ao0T 1991, PAGE 1401

Classification
Physics Abstracts
80.00

Runaway reactions, their courses and the methods to establish

safe process conditions

J. L. Gustin

Rh6ne-Poulenc Industrialisation, Ddcines, France

Rksumk. La plus grande partie de la littdrature sur [es emballements therrniques traite des
consbquences de l'accident telles que [es effets mdcaniques, les dmissions toxiques et inflamma-
bles. Les travaux publids par le DIERS fournissent des mdthodes perrnettant le dimensionnement
d'dvents, ndcessitant des ddterminations expdrimentales. II y a
moins d'inforrnation sur la
manidre dont [es emballements thermiques peuvent survenir alors que ceux-ci peuvent avoir
diffdrentes causes. Le propos de
est decet article
ddcrire les ddrives de procddd qui diffdrentes
peuvent entrainer un thermique et de
emballement ddterrniner l'inforrnation expdrimentale
ndcessaire pour l'analyse des risques du procddd, le choix de conditions opdratoires s0res et la
rdduction des consdquences de l'emballement therrnique. Chaque dative de procddd dangereuse,
est illustrde par des exemples connus dans l'industrie chimique et par des donndes expdrimentales
obtenues dans des essais de laboratoire.
Les conditions procddd dangereuses prises en compte sont [es suivantes
de I) L'emballement
thermique homogbne d0 I une tempdrature excessive 2) L'emballement thermique homogdne
par introduction d'un catalyseur ou d'un rdactif contr61ant; 3) L'emballement therrnique
hdtbrogdne d0 I une tempdrature locale excessive 4) L'emballement therrnique hdtdrogdne db I
une faible conduction therrnique vers l'extdrieur 5) L'emballement therrnique d0 I un temps de
sdjour excessif I la tempdrature du procddd (Rdactions autocatalytiques) ; 6) L'emballement
thermique par accumulation de rdactifs. La vitesse d'introduction d'un rdactif contr61ant est
supdrieure I la vitesse de consommation de ce rdactif, parce que la tempdrature est trop basse ou
le catalyseur absent 7) L'emballement therrnique d0 I la pressurisation d'une enceinte par des
interrnddiaires gazeux oxydants (situation caractdristique des oxydations nitriques) 8) L'emballe-
ment therrnique d0 I la sdparation de phases contenant des espdces instables (liquides, solides)
par perte de l'agitation ou par refroidissement 9) L'emballement thermique par mdlange de
produits incompatibles, se trouvant prdcddemment dans des phases sdpardes 10) L'emballement
thermique d0 I un chauffage exteme ou I un feu.

Considdrant les diffdrentes situations conduisant I un emballement therrnique, l'intdrdt de

l'approche systdmatique suivante est examind

Information thdorique et expdrimentale ndcessaire pour ddterrniner les risques du procddd.

Choix de conditions opdratoires addquates.
Choix de mdthodes convenables pour le contr61e du procddd.
Information expdrimentale ndcessaire pour le calcul d'dvent.

Abstract. Much of the literature runaway

on reactions deals with the consequences such as

mechanical damage toxic and flammable release. The DIERS literature provides effective
methods for vent sizing where experimental information is requested. Thermal stability
measurements provide information on the onset temperature and kinetic data for chemical
reactions. There is less information on
the way the runaway reactions occur whereas the runaway
1402 JOURNAL DE PHYSIQUE III M 8

reactions may have different causes. The purpose of this paper is to describe the various process
deviations which can cause a runaway react16n to occur and to discuss the experimental
information necessary for nsk assessment, the choice of a safe process and the mitigation of the
consequences of the runaway reaction. Each possible hazardous process deviation is illustrated by
examples from the process industry and/or relevant experimental information obtained from
laboratory experiments.
The typical hazardous situations are
the
to befollowing: I) The homogeneous
considered
thermal runaway due to too high
2) The homogeneous
a temperature. runaway reaction by
unintended introduction of additional reactants or catalyst. 3) The heterogeneous runaway
reaction due to too high a local temperature. 4) The heterogeneous runaway reaction caused by
slow heat conduction to the outside. 5) The runaway reaction caused by excess residence time at
the process temperature (autocatalytic reactions). 6) The runaway reaction caused by reactant
accumulation. The controling reactant feed rate is higher than the consumption rate perhaps
because the temperature is too low, or the catalyst is absent. 7) The runaway reaction due to the
pressurization of the enclosure by gaseous oxidizing intermediates (typical of nitric oxidations).
8) The runaway reaction due to phase separation of unstable species (liquids, solids) by loss of
mixing or on cooling. 9) The runaway reaction on mixing of fast reacting chemicals in separate
phases. 10) The runaway reaction due to fire or external heating.
Considering the various runaway situations, the effectiveness of the following approaches'is
discussed

Theoretical and experimental information required for hazard assessment.

Choice adequate process
of conditions.
Choice of adequate methods for process control.
Experimental information required for vent sizing.

What is a Runaway reaction ?

A runaway reaction is the consequence of the loss of control of the temperature of a chemical
compound or a mixture, in an enclosure.
This phenomenon is also called Thermal Runaway or thermal explosion.
The consequences of the loss of control of the temperature are

. An increase of the rate of the chemical reactions.

. The occurrence of unwanted exothermic reactions which are not obtained in the normal
process conditions. Most of the time these reactions are decomposition reactions of the
reaction mixture.

. A pressure rise due to two phenomena :

An increase of the reaction mixture vapor pressure due to the temperature rise.
The production of non condensable decomposition gasses.
The pressure increase often causes the enclosure to burst. This explains the name thermal
explosion ».

WHAT ARE THE CONSEQUENCES OF A RUNAWAY REACTION?

This loss of containment results in the emission of a two phase mixture of gas and liquid to the
outside giving an aerosol.
If the reaction mixture is released in the open air, the aerosol can ignite due to the oxidation
of the hot gasses and droplets with air, or possibly to the occurrence of electrostatic sparks.
The ignition of the cloud gives a fire ball with a weak pressure effect at the ground level.
 Pt 8 RUNAWAY REACTION. HAZARD IN THE PROCESS INDUSTRY 1403

If the reaction mixture is released in a housing, the mixture of the gasses, droplets and air
can explode in this enclosed area. In this case a strong blast effect is produced causing the
destruction of the building and secondary fires.
Often the reaction vessel bursts with emission of projectiles to a distance of several hundred
meters.
The projectiles can damage other apparatuses and neighbouring storage causing again
secondary fires.
The loss of containment due to pressures ranging up to several tens of bars causes a short
range blast effect which pushes all the equipments and pipes within 5 to 15 m distance.
In addition to the mechanical and thermal effect, the emission hazard due to the release of
toxic compounds to the outside is to be considered. The immediate or
long term toxic hazard
is the most dangerous. The toxic release caused a severe
pollution of the environment in
Seveso and thousands of deaths in Bhopal.

WHAT ARE THE CAUSES OF THE RUNAWAY REACTIONS?

In the literature the causes of reaction not well investigated the

runaway are so as

consequences of the accidents. The reason is that the causes are often complex.
a big deviation,
Unless the incident is the result of process the determination of the causes
requires a level of knowledge of the chemistry and of the process which is only available for a
few people.
Most of the time, the occurrence of a runaway reactioi is an unexpected event for those
who are in charge of running the plants.
For this reason it is of interest to describe the various process deviations which can cause a

runaway reaction to happen, and to discuss the experimental information necessary for risk
assessment, the choice of safe process and the mitigation of the consequences of the runaway.
It is sometimes difficult to distinguish between a process deviation and an hazardous
process situation which could cause a runaway reaction. For this reason it is easier to describe
the hazardous situation of a process and then to mention the process deviation which initiates
the runaway reaction.
At the moment, ten dangerous situations or process deviations can be distinguished.
In some accident, two or- three of them could be present but any one of them could have
caused a runaway reaction.
We now consider these ten situations.

1. The homogeneous tbermal runaway due to too high a temperature.

It is the most famous runaway behaviour. It is represented by the Semenov theory and can be
described as follows

A condensed phase happens to react at some temperature, in an enclosure with no or not

enough vent area.

The reaction is exothermic. According to the Arrhenius law, the rate of the reaction and/or
the rate of heat production is an exponential function of the temperature :

~~=@~= V.Q.k° exp(- ~ .C~~exp(-£).

t RT

Whereas the cooling capacity is a linear function of the temperature

@~=h.S. (T-T~)~T
1404 JOURNAL DE PHYSIQUE III Pt 8

where

4G "
heat $roduced by the exothermic reaction (w)
4R "
heat by cooling (w)
removed
V =
volume of the condensed phase (m~)
Q "
heat of reaction ilmole)
k° =
constant factor of the Arrhenius law ((mole/m~)~ ~~/s)
S =
heat exchange area (m2)
T~ =
ambient or cooling fluid temperature (K)
C =
concentration (mole/m3)
n =
order of the reaction (dimensionless)
E =
activation energy j/mole)
h =
heat transfert coefficient (W/m2/K).
There is some limit temperature above which the heat produced by the reaction is greater
than the heat removed.
Above this limit temperature, the system temperature increases steadily causing the rate of
the chemical reaction to accelerate exponentially. ~

Figures I and 2 give two possible deviations by which the temperature control is lost

figure I by the decrease of the heat exchange coefficient or of the heat exchange area
figure2 by a too high temperature for the heat exchange fluid

in these figures T~ is the heat exchange fluid temperature or

the ambient temperature and
To is the stable temperature of the system.
This model of Semenov is a good representation for batch stirred reactors containing an
homogeneous reaction mixture where the reactions follow the Arrhenius law.
The process deviation is the loss of the cooling capacity or too high a temperature of the
heat exchange fluid.

~ i~

,
i

,
, i

,
,
,
~
1j G T~~j~j~ai Tiimit

Fig. I.-Semenov representation. Temperature control lost by the decrease of the heat exchange
coefficient or of the heat exchange area.
Pt 8 RUNAWAY REACTION HAZARD IN THE PROCESS INDUSTRY 1405

.
~li~
i~

,
,

,
,
i
,
i
,
,

~A ~critical~limit

Fig. 2.- Semenov representation. Temperature control lost by too high a temperature for the heat
exchange fluid.

Example in the process industry

The runaway reactions occurring this way are fortunately seldom because the Semenov
representation is well known. The basic design of any process would meet the minimum
requirements for a proper control of the bulk temperature.
Nevertheless there is still a typical process situation where runaway reactions occur in
conditions where the Semenov representation would apply.
This happens in the polyvalent plants with batch processes. The wanted product is obtained
in a solvent which has to be removed by a batch distillation with the requirement that a low
solvent concentration should be left in the final product.
Of course, a batch reactor is not a good design for this operation and it will take a long time
to reach a low concentration of solvent in the product. In many instances several steam

pressures are available for heating and one could use steam with too high a temperature to do
the job within a reasonable time.
For unstable chemical compounds, this is a very dangerous situation, a bad process and a
time consuming operation.
Should the runaway decomposition reaction be initiated, the reactor inventory is very high
and the consequences of explosion will be disastrous.
In any case the quality of the product will be poor because of the Arrhenius decomposition
of the product at such a high temperature over a long time of exposure.
When an unstable compound is processed, like a nitrocompound, an oxime... the solvent is
best removed in a continuous film evaporator with a low inventory.
Should the decomposition of the product occur, the inventory is low and the consequences
of the runaway unsignificant.
Experimental information requested for a safety study
The experimental effort is devoted to the obtention of the following information
Determination of the onset temperature for the reaction or decomposition.
1406 JOURNAL DE PHYSIQUE III Pt 8

Heat of reaction or heat release.

Kinetic behaviour (Arrhenius.like or autocatalytic reaction).
Rate of reaction (slow or fast reaction).
Pressure effect.
Characterization of the reacting system for vent sizing (DIERS Methodology).
To collect this information, the following methods are used
The thermal stability of the reactants, the products or the reaction mixtures is measured in
DTA or
DSC experiments in closed cells.
The pressure effect and system behaviour can be obtained from Autoclave experiments.
These basic determinations allow the detection of strongly exothermic or
fast reactions.
The Arrhenius behaviour of the reaction must be checked on temperature scanning DSC
experiments or by isothermal heat flux determinations with a
sensitive isothermal calorimeter.
The runaway behaviour can be measured using pseudo adiabatic calorimetry :

An ARC experiment will provide a

sensitive detection of the onset temperature and the
kinetics near
the onset.
Low phi factor closed Dewar and VSP experiments will provide information on the

runaway behaviour for vent sizing.

Check that the same Arrhenius behaviour is obtained with the various experimental
techniques at least near the onset temperature

Hazard assessment

If the reaction is not too fast and exhibits Arrhenius type kinetics, the safety level is
evaluated by comparing the bulk process temperature and the onset temperature of the
runaway reaction.
The bulk process temperature must be lower than the known onset temperature in any case
and the heat exchange capacity must exceed the expected heat production. Vent sizing using
the DIERS methods will provide an effective protection.-
If the reaction may become a «
fast reaction » see case 3 below.

2. The homogeneous runaway reaction initiated « by introduction ».

It is a runaway reaction initiated in an homogeneous reaction mixture by the unexpected

introduction of a reactant or a catalyst. A fast and exothermic reaction occurs immediatly
even though the mixture may be at the normal temperature.
In this case, the process deviation is not too high a tdmperature but an operation mistake.

Example in the process industry

A good example of this situation is the well known Phenol + Formaldehyde runaway reaction
(Ref. [I]).
In this semi-batch process, phenol is allowed to react with formaldehyde in the presence of
a catalytic amount of caustic soda to obtain a condensation product.
In this step phenol is loaded with the catalytic amount of caustic soda in a batch reactor and
formaldehyde is introduced slowly under temperature control (cooling) at 60 °C. In the next
step of the process a stoichiometric amount of caustic soda is added to obtain a phenate.
The process deviation is to forget the introduction of the catalytic amount of caustic soda in
the first step, not to detect the failure, and to start the addition of caustic soda in the second
step whereas all the charges of phenol and formaldehyde are present. A runaway reaction
then occurs which will pressurize and burst the reaction vessel and solidify the reaction
mixture.
 Pt 8 RUNAWAY REACTION HAZARD IN THE PROCESS INDUSTRY 1407

Experimental determinations

The proper control of a process prone to runaway reactions by introduction should include
safety devices to prevent the deviation and an emergency relief system. There is little or no
interest in the determination of the onset temperature of the runaway reaction which may be
well below
the process temperature.
The purpose of the experimental determinations is then to provide the information
necessary for vent sizing ; using the DIERS recommendations
characterization of the system behaviour (High vapor system, gassy reaction, Hybrid
system),
determination of data required
. Adiabatic heat rate and vapor pressure versus temperature relationship,
. non condensable gas production rate.

These determinations should be made in conditions close to the adiabatic in low phi factor
devices ~VSP and close Dewar flask). The Phi Factor should not exceed 1.2.
The experiments are usually made by loading cool the reaction mixture and rising slowly
the temperature to initiate the reaction.
Care should be taken if the measured onset temperature is well below the process
temperature. This has a strong effect on the reaction rate together with the phi factor.

c~ °

-loco/limp -loco/<
Fig. 3. VSP.
1408 JOURNAL DE PHYSIQUE III Pt 8

ARC I° 208 209 PHtNOL + FORMALDEHYDE RtACTION

DT/ot tdeg C/mini

t-'trim 1.~6

PHI- 1,2~7
~

&

(°1)
Fig. 4. ARC.

Figs. 3 and 4. Phenol + Formaldehyde runaway reaction with the recipe of reference [I], measured
in VSP and ARC. Note the difference in onset temperature and heat rate.

The measured kinetic data should be corrected to take into account the value of the Phi
factor and the difference in onset temperature. A convenient correction method for simple
Arrhenius kinetics has been given by H. G. Fisher (2).
Note that in many cases, a reaction which is complex when measured with a high phi factor
and a sensitive onset detection (in ARC) turns to a simple one step Arrhenius reaction when
measured phi
in a low factor device with a high onset temperature due to a high heat rate base
line ~VSP) (Figs. 3-4).
The process deviation is best represented by the introduction of the added reactant or
catalyst on the reaction mixture at the required process temperature. This can be done with a

pressure resistant syringe pump.

3. The beterogeneous runaway reaction initiated by too high a local temperature.

The condensed phase is not homogeneous but heterogeneous in temperature and/or

composition, due to a poor stirring or no stirring at all :

Liquid enclosed in a storage, a pipe, a valve.

Other examples include stirring which fails to maintain an homogeneous temperature due
to the presence of fast propagating reactions or deflagration.
M 8 RUNAWAY REACTION HAZARD IN THE PROCESS INDUSTRY 1409

In this case, safe conditions are not ensured by a bulk temperature well below the reaction
onset temperature but by considering any possible local temperature which could initiate a
fast propagating reaction

wall temperature
dead headed pump...
The establishment of safe conditions should include
The recognition of deflagrating compounds or compounds which could sustain fast
propagating reactions.
The use of heating fluids with a temperature well below the onset temperature of the
reaction exotherm.
To avoid any cause of mechanical heating.

Example in the process industry

Several accidents have been reported involving various aromatic nitro compounds or
nitric
esters.
These compounds are prone to deflagrate and the decomposition reaction, once initiated
on the reactor wall by too high a temperature, will instantaneously assume a
deflagrating
behaviour with a strong blast effect.

'
j
(
30P
emper~ture

i~0 4°0 ~°°

'

~~~er
; 1 ~~~
(2) DE 2j7°C/IJN
1410 JOURNAL DE PHYSIQUE III M 8

Experimental determinations

special
A attention is paid to the determination of the onset temperature of the fast
decomposition using DSC or DTA measurements.
A fast and highly exothermic reaction is usually obtained on the DSC thermogram. The
exotherm exceeds 250 cal/g.
The deflagrating behaviour of liquids and solids can be revealed using methods described
by Grewer [3]. The fast reaction is on a initiated sample enclosed in an autoclave, either by a

pyrotechnic ignition source or by temperature scan. The pressure and temperature are
recorded using fast computer data acquisition.
The reaction behaviour is then analyzed by plotting
I) The pressure in log. scale versus the temperature in reciprocal scale. See figure 5.

2) The rate of pressure rise in log. scale versus

the pressure in log. scale. See figure 6.

Figure 5 shows the production of non condensable decomposition gasses, when the reaction
is initiated by heating.
Figure 6 can show that the rate of pressure rise is a power function of the pressure. Tl1is is
considered as the proof of a deflagrating behaviour.
This is known for the deflagration of solid propellants in combustion chambers where the
deflagration rate follows a law by Belyaev [4]

r=k.P~

10°
~
Pr«««ion .~arl
Fig..6. -Deflagration of Ammonium Nitrate, curve dP/dt vs. P.
Pt 8 RUNAWAY REACTION HAZARD IN THE PROCESS INDUSTRY 1411

Rates of pressure rise as high as 10 000 bar/s have been measured at pressures below 500 bar.
Note that this behaviour is influenced _by the filling ratio of the autoclave and that some
reacting systems may assume the same behaviour, which are probably not true deflagrating
systems.
There is little interest in experimental determinations for vent sizing unless the deflagration
occurs after some initial pressurization due to a slow reaction.

4. The heterogeneous runaway reaction by lack of heat conduction.

If a stagnant solid or liquid with a low heat conductivity exibits an

exotherm, a non~uniform
temperature profile will appear.
For example, in a storage the temperature will rise at the center of the containers faster
than at the wall boundaries.
This phenomenon can cause a runaway reaction. Convenient models have been developed
by Frank Kamenetskii and Thomas. This representation is realistic for solid storage whereas
for liquids, convection will help to equalize the temperature quicker than by heat conduction.

Examples in the process industry

self-heating of large coal heaps or bulk storages is known. This is due to an oxidation
The
reactioninvolving the diffusion of air into the solid bulk. In this case the theoretical models
provide a good representation of the phenomenon. In the chemical industry the explosion of
drums or rail trucks is known.
If drums containing a cristallized solid exhibit a
self heating the solid may melt at the Center
of the drums.
The impurities of the product will concentrate in the liquid because the less pure product
melts first. This may cause the decomposition rate to accelerate faster than expected and the
drum to burst.
Heavy chemicals or tars are often loaded in rail trucks at temperatures above ambient, to
be transported to incineration facilities. Tl1ese products cristallize on the container walls,
lowering the heat exchange capacity of the container. Again the product that cristallizes first
is the purer and the impurities concentrate in the remaining liquid. A minor exotherm in the
liquid can cause the temperature to rise at the center of the truck and the container to
explode.

Rules of good practice

Never store unknown or unstable chemicals in huge containers.
Fuel oil is stored in several thousands tons containers but it is a
well known product which
have been stored for nearly one century. This is not the case for your last new chemical.
For storage above I ton of any new chemical or for unusual large bulk storage of any
substance, special care should be taken.
In the United States the S.A.D.T. is obtained from experiments on full scale drums. More
conveniently the adiabatic self-heat rate could be measured by laboratory determinations.
If significant adiabatic self heating is measured, the monitoring of the temperature in the
storage is necessary. Provision for cooling or emptying the storage should be made.

Experimental determinations
The adiabatic self heat rate for very slow exothermic reactions at ambient temperature is
obtained from heat flux measurements in isothermal calorimeters. The reason for this unusual
practice is that sensitive isothermal calorimeters provide a better detection of the exotherm
than pseudo adiabatic methods.
1412 JOURNAL DE PHYSIQUE III M 8

The Setaram C80.isothermal calorimeter is able to measure heat fluxes down to 10 mW/kg
which equivalent
is to a self-heat rate of 0.35 °C/day. This apparatus seems to be agood
compromise :
Ten times this self heat rate would be a hazardous situation for unattended storage. Self-
heat rates below 0.3 °C/day are of no interest for safety purposes.
Reaction kinetics obtained from DSC/DTA measurements at higher temperatures should
not be extrapolated downwards to ambient temperature. This is as unsafe as the extrapolation
of kinetics to higher temperatures.
At least 3 determinations at 3 different temperatures are necessary to ensure that the heat
release follows an
Arrhenius law. A plot of the heat flux or
self-heat rate in log. scale versus

the temperature in reciprocal scale, will give a straight line.

S. The runaway reaction due to extended reaction/cycle time. Autocatalytic reactions.

In some cases, runaway reactions appear after too long a reaction or cycle time. This is
probably due to an autocatalytic or self accelerating reaction.
An autocatalytic or
self accelerating reaction is a reaction which produces its own catalyst
or one of its controlling reactants. For this reason, the reaction can accelerate at constant

temperature for chemical reasons.

It is not necessary to rise the temperature to initiate the reaction. The reaction will appear
under a constant temperature exposure after some induction time.
The induction time in log. scale is usually a linear function of the reciprocal temperature.
In Kinetic theory, induction times refer to time to maximum rate. For Safety considerations,
the time to the onset of the reaction is best considered.

Example in the process industry

A good example of this behaviour is the radicals chain polymerizations like the vinylic
polymerizations :
acrylic acid,
various acrylates,
acrolein,
vinyl acetate.

A large of reacting systems showing

number autocatalytic behaviour are found in all fields
of organic chemistry.
In the case of vinylic polymerizations the reaction catalysts are organic peroxids. For a
given concentration of peroxids in the vinylic monomers, the induction time is only a function
of the temperature. This system is a rather precise chemical clock.
Another process deviation leading to a long exposure to the process temperature, is to
tolerate the presence of deposits in the reaction vessel. These deposits may last for a large
number of batches. If their decomposition is autocatalytic, it will appear at the end.

Experimental determinations

Autocatalytic runaway reactions can be detected by considering the unusual dissymmetric

shape of their DSC/DTA thermograms obtained by a temperature scan.

The autocatalytic behaviour can then be checked by constant temperature exposures using
DSC/DTA or other apparatuses like close Dewar, VSP or
ARC. The isothermal induction
time must be measured at least 3 times using different temperatures to obtain the plot of the
induction time versus temperature. See figure 7.
M 8 RUNAWAY REACTION HAZARD IN THE PROCESS INDUSTRY 1413

.m
<m
ii

QJ

-
~m
o_ i
f
LJJ
~

a
oo i iii iii i11 iii-i i iii I till iii iJ jot (i ii iJ

iifii iiN

Fig. 7.- Induction time of the polymerization of Vinyl Acetate initiated by a peroxide. VSP
measurement.

The laboratory determinations can also provide the experimental information necessary for
vent sizing. See figure 8.
The vinylic polymerization are often high vapor pressure systems as long as the monomers

are present.
There are some theoretical and practical difficulties in determining the heat rate at a given
set pressure or temperature, because this rate can assume different values depending on
the
thermal history of the reaction. Autocatalytic reactions can accelerate at constant tempera-
ture.
In addition the methods to correct the results to adiabatic conditions are not available for
autocatalytic reactions. Much work is needed in this field.

Rules of good practice

If possibility for an autocatalytic
there is a reaction to appear or if this behaviour has not
been the operation
excluded, time of a process should not be allowed to exceed the usual
duration or should be kept well below the known induction time of the autocatalytic reaction.
Emergency relief vents can be provided to protect the enclosures. They must be carefully
sized and are not absolutely reliable especially for vinylic polymerizations.
1414 JOURNAL DE PHYSIQUE III M 8

c,i

I"
1-
#
j- n
n

in-1

~=>
lo 50 1"1)
ijii to i lo So

Ii off-. blip !ll'fi /

Fig. 8. Heat rate of the polymerization of Vinyl Acetate initiated by a peroxide. VSP measurement.

6. The runaway reaction by accumulation due to too low a temperature.

In semi-batch processes the reaction is controlled by the slow introduction of a

controlling
reactant. In these processes, if the introduction of this reactant is interrupted the reaction
stops readily.
If the temperature of the reaction mixture is too low, the rate of consumption of the
controlling reactant is slower than the rate of introduction. Consequently the reactant
accumulates in the reactor.
Later on, a small increase in temperature or higher
the concentration in controlling reactant
will initiate the sudden reaction of the whole inventory. The
reactant heat production by the
exothermic reaction is then far above the cooling capacity of the reactor. The temperature
rises and the reactor pressurizes.
Example in the process industry
Let us consider again the condensation step of the phenol + formaldehyde process.
This
reaction is made under temperature control at 60 °C.
Above 60 °C the polycondensation (polymerization) reaction takes place with a
significant
rate.

Below 60 °C the rate of the condenshtion reaction is slow. It is very slow at ambient
temperature, The rate of formaldehyde consumption will be lower than the rate of
Pt 8 RUNAWAY REACTION HAZARD IN THE PROCESS INDUSTRY 1415

introduction. Formaldehyde will accumulate and react later exothermically, triggering the
polycondensation reaction.

Rules of good practice

In semi-batch processes,- the rate of introduction of the controlling reactant must be
adjusted to its rate of consumption. The batch temperature must be kept under control and
the cooling demand must be surveyed to make sure that the reactant is consumed.
The reactor can be equipped with an emergency safety vent.

Experimental determinations

The kinetics
reactioncan be obtained from DSC/DTA measurements and from pseudo
adiabatic techniques (ARC, VSP closed Dewar).
There is no particular interest in the precise determination of the onset temperature of the
reaction. Processes are normally operated at temperatures where the reaction is fast. Data for
vent sizing is obtained from V.S.P. and clbsed Dewar experiments.

7. The runaway reaction caused by the pressurization of an enclosure by an

oxidizing gaseous
intermediate.

This runaway situation is found in the nitric oxidation of organic compounds.

typical example is
A the nitric oxidation of organic diacids present in the manufacture of
adipic acid, a nylon intermediate.
In this reaction, the controlling reactants are the nitrogen oxides produced by the reaction
itself.

S5fExo
~~~~~ en verre

so

45

40

as

30

25

20

15

to

19S car./9.

-5

TEMPERATURE (Cl
40 SO eO too 120 140 160 iBO 200 220 240 260 2eO
_~~

Fig. 9. DSC measurement of the heat release of nitric solutions of organic diacids.
 1416 JOURNAL DE PHYSIQUE III M 8

As the reaction takes place in an enclosed area, nitrogen oxides are produced and
pressurize the vessel causing the reaction to speed up.
Depending on the concentrations of nitric acid, organic fuel and diluent (water) the
reaction can assume a more or less violent behaviour deflagrating or detonating.
The course of the runaway is influenced by the filling ratio.

Experimental determinations

The reaction characteristic can

be investigated considering two separate contributions
the heat release,
the production of non condensable decomposition gasses including NO~
The exotherm can be measured by DSC/DTA experiments. The heat release onset
temperature is usually found about 160 °C. The exotherm is Arrhenius-like near the onset.
See figure 9.
The non-condensable gas production can be measured using thermomanometry or
Autoclave experiments.
The onset temperature for gas production is influenced by the filling ratio and by the initial
concentration in NO~ in liquid phase.
the
Depending on the sensitivity of the experimental technique, gas production is detected at
temperatures as low as 60-70 °C. See figure10.

I
11
lai I : LO@
do d.cawa.itian m ac

~
~ i
u

eo

Fig. 10. -Dewar flask measurement of the production of non condensable gas by nitric solutions of
organic diacids.
 Pt 8 RUNAWAY REACTION HAZARD IN THE PROCESS INDUSTRY 1417

If the reaction is allowed to pressurize the enclosure, the reaction rate can speed up at such
low temperatures.
The deflagration behaviour of the reaction can be studied in autoclave experiments where
the reaction is initiated by heating. Rates of pressure rise as
high as 10000bar/s can
be
measured. The rate of pressure rise is a power function of the pressure. See figure11.
The detonation behaviour can be investigated in shock tubes. Detonations are found to
occur in high energy content compositions (high PEM compositions).

~
Preaalon ~arl

Fig. ll.-Deflagration behaviour of nitric solutions of organic diacids measured in an autoclave

experiment.

Rules of good practice

These solutions should never be enclosed in vessels, pipes or valves. The pressurization
should never be allowed. Rupture disks can possibly provide a relief vent in case of mistake.
Under runaway conditions the reaction behaves like hybrid or gassy systems.

8. The runaway reaction by segregation.

In this case, the reaction mixture splits in separate phases one of which is unstable.
Liquid phases can separate by loss of mixing.
A solid phase can separate by cooling.
1418 JOURNAL DE PHYSIQUE III Pt 8

Examples in the process industry

Runaway reactions segregation
by due to a loss of mixing are known in several processes.
In emulsion polymerizations the monomer phase can separate from the aqueous phase and
react with violence.
In nitration processes where two liquid phases are present, a
high energy content liquid can

separate and then decompose.

Runaway reactions by segregation due to cooling are quite common.
Several explosions have occurred due to the cristallization of sodium nitrophenate as
deposits on reactor walls during cooling.
Sodium nitrophenate is a very unstable and sensitive compound with a
high energy content
(PEM).
Other examples cited are

The cristallization performic acid needles

of from a
concentrated solution on cooling
and their subsequent decomposition.
The cristallization of sodium hypochlorite at temperatures below 15-17 °C from bleach
solutions at a concentration of100-105 chlorometric degrees. The solid is very unstable.

Safety considerations

The main problem is to be aware

that such unstable compounds can separate in a process
especially by cristallization. If the unstable nature of deposits is known, their
the formation
must be avoided. If not, the composition of any deposit or unexpected separate liquid phase
must be investigated and their energy content evaluated (PEM),'especially when strong
oxidizers and fuel are present in the bulk phase.
The appearance of unwanted unstable phase must be avoided by propper process control.

Experimental determinations

The thermal stability of any separated phase or deposit can be investigated using DSC/DTA
and Autoclave experiments.

9. The runaway reaction by mixing incompatible reactants, previously in separate phases.

The deviation causing the runaway is quite the opposite of the previous case, for mixing two
liquid phases.
From a
theoretical point of view the situation is the same as for the runaway reaction by
introduction » ; the reaction is immediately fast at the initial system temperature.
A common case in the process industry is the fast reaction of incompatible reactants with
water left in the process side after a cleaning operation.
Another example could be the reaction of water with acetic anhydride previously in
separate jhases, mixing. on

For the experimental study, the same methods as for the runaway reaction by introduction
can be followed.

10. The runaway reaction initiated by a fire or external heating.

The occurrence
of a fire can initiate a runaway reaction by raising the temperature. In this

case
the reaction rate is greatly increased by the external heating.
The reaction is faster than in adiabatic conditions.
This phenomenon was known long ago but it has recently been pointed out by M. G.
Grolmes [5] with some theoretical support.
M 8 RUNAWAY REACTION HAZARD IN THE PROCESS INDUSTRY 1419

The external heating can cause runaway reactions which would not appear in adiabatic
conditions. This phenomenon is relevant to the same explanation by Grolmes.
A good example is a runaway reaction which appeared in a pilot plant when every morning
the operators raised the temperature of a batch to the process value, to resume the normal
operation after a night long interruption. The process involving the reaction of caustic soda in
the presence of 1-2 dichlorethan as solvent would never
exhibit a runaway at a constant

process temperature but under fast heating conditions, the reactor is pressurized by a
reaction
producing vinyl chloride.

Safety considerations

When enclosures are protected for the fire case by pressure safety valves, the possible
occurrence
of a runaway reaction should be taken into account for vent sizing. The vent area

should not be based on the rate of the runaway reaction measured under adiabatic conditions
but on the rate of the reaction under external heating.
If the adiabatic rate of reaction is known, corrections should be made using Grolmes
method. Otherwise the reaction rate should be measured under extemal heating conditions
using a closed Dewar or
the VSP.

Conclusion.

Much effort is devoted to the control of homogeneous runaway reactions whereas most
incidents in the process industry dont happen this way.
In many cases
the situation is complex and involves several of the basic cases presented here
above.
existing
The theoretical basis can nevertheless provide useful guidelines for a careful
experimental investigation of any complex case.

In any case, methods are available either to prevent the occurrence or to mitigate the

consequences of runaway reactions.

Hopefully this presentation ,vill help to give a better understanding of these hazardous
situations.

References

[1] GUSTIN L., 6th Int. Syrup. Loss

J. Prevention and safety promotion in the process industry Oslo
Nonvay, June 19-22 (1989) paper n 75.
[2] FISHER H. G., sth DIERS Users Group Meeting, Seattle, E.U. May 1989.
[3] GREWER Th., KLAIS O., pressure rise during homogeneous decomposition and deflagration, Chem.
Eng. Symposium series n
102 (1987).
[4] BELYAEV A. F., Acia physicochim., URSS 8 (1938) 763.
[5] GROLMES M. A., KING M. J., emergency relief requirements for certain organic peroxides based on

DIERS Methodology.

JOURNAL DE PHYSIQUE III T I, N 8, AQOT (W( 54

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