Preventing
Runaway
Department Editor: Rebekkah Marshall
general considerations [1]
A process is considered to be thermally
safe only if the reactions can easily be
controlled, and if the raw material, the
products, the intermediates and the re-
action masses are thermally stable under
the considered process conditions. Check
into the process equipment, its design, its
sequence of operation and the control
strategies. In addition to the engineer-
ing aspects, get detailed information on
thermodynamic and kinetic properties
of the substances involved, such as the
reaction rates or heat-release rates as
a function of process conditions. Deter-
mine the physical and chemical proper-
ties, as well.
Understanding of thermal-hazard po-
tential requires knowledge of various
skills and disciplines [3]. These include:
Operating mode: The mode of opera-
tion is an important factor. For instance,
a batch reaction, where all the reactants
are charged initially, is more difficult to
control than a semi-batch operation in
which one of the reactants is charged
progressively as the reaction proceeds
(for more, see Design Options).
Engineering: Design and layout of the
plant and equipment and its built-in con-
trols impact the entire process. The ca-
pacity of the heating or cooling system
is important in this context. Process en-
gineering is used to understand the con-
trol of the chemical processes on a plant
scale. It determines which equipment
should be used and how the chemical
processes should be performed. In ad-
dition, take into account technical failure
of equipment, human errors (deviations
from operating instructions), unclear
operating instructions, interruption of
energy supply, and external influences,
such as frost or rain (for more, see De-
sign Options).
Chemistry: The nature of the process and
the behavior of products must be known,
not only under reaction conditions, but
also in case of unexpected deviations
(for example, side reactions, instability
of intermediates). Chemistry is used to
gain information regarding the reaction
pathways that the materials in question
follow.
Physical chemistry and reaction kinetics:
The thermophysical properties of the reac-
tion masses and the kinetics of the chemi-
cal reaction are of primary importance.
Physical chemistry is used to describe the
reaction pathways quantitatively.
data collection
The following data are especially rel-
evant in avoiding runaway reactions:
• Physical and chemical properties, ig-
nition and burning behavior, electro-
static properties, explosion behavior
and properties, and drying, milling,
and toxicological properties
• Interactions among the chemicals
• Interactions between the chemicals
and the materials of construction
• Thermal data for reactions and de-
composition reactions
• Cooling-failure scenarios
design options [2]
If a reaction is has the potential for
runaway, the following design changes
should be considered:
• Batch to continuous. Batch reactors
require a larger inventory of reac-
tants than continuous reactors do, so
the potential for runaway in continu-
ous systems is less by comparison
• Batch to semi-batch. In a semi-batch
reaction, one or more of the reactants
is added over a period of time. There-
fore, in the event of a temperature or
pressure excursion, the feed can be
switched off, thereby minimizing the
chemical energy stored up for a sub-
sequent exothermic release
• Continuous, well-mixed reactors to
plug flow designs. Plug-flow reactors
require comparatively smaller volumes
and therefore smaller (less dangerous)
inventories for the same conversion
• Reduction of reaction inventory via
increased temperature or pressure,
changing catalyst or better mix-
ing. A very small reactor operating
at a high temperature and pressure
may be inherently safer than one
operating as less extreme conditions
because it contains a much lower in-
ventory [3]. Note that while extreme
conditions often result in improved
reaction rates, they also present their
own safety challenges. Meanwhile, a
compromise solution employing mod-
erate pressure and temperature and
medium inventory may combine the
worst features of the extremes [3].
• Less-hazardous solvent
• Externally heated or cooled to inter-
nally heated or cooled
Reactions
Thermal Stability
Criteria [1, 4]
As a guideline, three levels are sufficient
to characterize the severity and prob-
ability of a runaway reaction, as shown
in the Table.
Defining high, medium
and low risk [1]
Severity Probability
High ΔTad > 200K TMRad < 8 h
Medium 50K < ΔTad < 200K 8 h < TMRad <
24 h
Low ΔTad < 50K and TMRad > 24 h
the boiling point
cannot be sur-
passed
Adiabatic temperature rise
The adiabatic temperature rise is calculated
by dividing the energy of reaction by
the specific heat capacity as shown in
Equation (1).
ΔTad = 1,000Qr/Cp (1)
where:
ΔTad = adiabatic temperature rise, K
Qr = energy of reaction, kJ/kg
Cp = heat capacity, J/(kg)(K)
Time to maximum rate (TMR)
TMRad (the time to maximum rate, adiabatic) is
a semiquantitative indicator of the probability
of a runaway reaction. Equation (2), defining
TMRad in hours, is derived for zero-order
reaction kinetics:
TMRad = CpRTo2/3,600qoEa (2)
where:
R = gas constant, 8.314 J/molK
To = absolute initial temperature, K
qo = specific heat output at To, W/kg
Ea = activation energy, J/mol
The TMR value provides operating personnel
with a measure of response time. Knowledge
of the TMR allows decisions to be based on
an understanding of the time-frame available
for corrective measures in case heat transfer
is lost during processing.
References
1. Venugopal, Bob, Avoiding Runaway Reac-
tions, Chem. Eng., June 2002, pp. 54–58.
2. Smith, Robin, ”Chemical Process Design,”
McGraw-Hill, New York, 1995.
3. Kletz, T. A., “Cheaper, Safer Plants,”
IChemE Hazard Workshop, 2d., IChemE,
Rugby, U.K., 1984.
4. Gygax, R., Reaction Engineering Safety,
Chem. Eng. Sci., 43, 8, pp. 1759–71, Au-
gust 1998.