Practical approach to prediction and prevention of runaway reactions

Vinayak Vishvanath Londhe * and Kalpana S. Deshmukh

Department of Chemical Engineering, School of Engineering and Applied Sciences, University of Mumbai (Kalyan Sub
Center) Mumbai, India.

World Journal of Advanced Research and Reviews, 2022, 16(02), 139–144

Publication history: Received on 23 September 2022; revised on 01 November 2022; accepted on 04 November 2022

Article DOI: https://doi.org/10.30574/wjarr.2022.16.2.1137

Abstract
A chemical reaction that becomes uncontrollable and escapes may cause a major event involving people, property and
the surrounding area. Temperature runaway can be observed as a result of accidents such as overcharging, cooling
water failure, pipe obstruction, and excessive initial heating. They can devise various techniques to avoid temperature
runaway as a result of events, as well as advise on operational and technical improvements to the process to make it
more robust to component failures and accidents. Exothermic methods used in the chemical industry have the potential
to cause runaway reactions, resulting in fatalities and damage to infrastructure. Traditional approaches to prevention
and prediction of runaway reactions are costly and unsuited to Ministry of Micro, Small & Medium Enterprises (MSME)
units. Consequently, we often see incidents in MSME units caused by runway reactions. To reduce such mishaps, a no-
cost theoretical prediction system and convenient preventative strategies are recommended.

Keywords: MSME; Incident; Exothermic reaction; Temperature Runaway; Precaution

1. Introduction
Reactive compounds can release massive amounts of potentially harmful energy under certain conditions, resulting in
massive pressure rises. Such risky combinations can result in reactions that vary from the fundamental process
reactions, primarily in their pace of progression. Annually, reactive chemicals are implicated in numerous industrial
mishaps that endanger people, property, and the environment. The vast majority of chemical reactions in the industry
are exothermic. Chemical process industries have substantially helped society throughout the years. Nevertheless,
chemical processes can result in accidents such as fires, explosions, and poisonous substance releases. One of the most
serious hazards in chemical processes such as polymerization, nitration, sulfonation, epoxidation, and so on This is
owing to the exothermic nature of these reactions, which creates considerable heat in the processes. Because of the
increased pressure, such a runaway reaction will result in the boiling over of poisonous compounds and their discharge
into the atmosphere, as well as the bursting and splintering of reaction vessel fragments.

The MSME segment is estimated to account for 25- 30% of the sector and is critical to domestic chemical manufacturing
and job creation. But frequently everyone has witnessed similar catastrophes in MSME chemical process firms, resulting
in enormous property losses and injuries or the loss of human life. These units cannot forecast and, as a result, give
preventive measures to avert such harmful interactions. It is therefore critical to foresee and avoid such catastrophes
caused by runaway reactions using methods available to MSME units. This necessitates the use of simpler heat
generation and heat removal prediction algorithms. Modern advanced predictive experimental calorimetric techniques
for the determination of heat generation are very costly and also time-consuming, generally suitable for newly
developed molecules. Reaction processes carried out in MSME units are usually known and prediction of heat


Corresponding author: Kalpana S. Deshmukh
Department of Chemical Engineering. School of Engineering And Applied Sciences, University Of Mumbai (Kalyan Sub Center)
Mumbai, India.
Copyright © 2022 Author(s) retain the copyright of this article. This article is published under the terms of the Creative Commons Attribution Liscense 4.0.
 World Journal of Advanced Research and Reviews, 2022, 16(02), 139–144

generation can also be made by evaluating the thermal kinetics of the reaction theoretically. The heat removal capacity
of the cooling system can be calculated with detailed engineering design data calculations or with simple experiments.
It is important to remember that perhaps the linkage of mass and energy balance necessitates the solution of
complicated differential equations. This resolution is time intensive and may lengthen the time to act in the event of a
runaway. Hence, in the case of rapid response rates, it is critical to reducing this energy balance equation to an analytical
formula. In the present paper, the application of reaction heats to process safety analysis and simple and reliable
methods of computation of heat generation and heat removal by a combination of theoretical estimation and simple
experiments are presented that can be easily implemented by MSME units.

2. Runaway Reaction
The heat created by an exothermic reaction raises the temperature of the reaction mass in proportion to the amount of
heat generated. This temperature rise may trigger the thermal exothermic breakdown of reaction constituents, raising
the temperature even higher. Runaway occurs when the total temperature of the reaction mass surpasses a particular
limit. The following temperature characteristic values are related to the runaway reaction:

2.1. MTT: Maximum Temperature for Technical Reason

This is the temperature of the boiling point of reaction mass constituent in an open system or the temperature of
maximum permissible pressure in a closed system. If the reaction mass exceeds this temperature, MTT, runaway will
occur either in the form of the release of boiling hazardous chemicals in the atmosphere in an open system or the case
of a closed system, leading to rupture of the reaction vessel and splintering of fragments of reaction vessel along with
the release of hazardous chemicals in the atmosphere.

2.2. ΔTad: Adiabatic Temperature Rise

The Adiabatic Temperature Rise is a property calculated for any given reaction to indicate the potential severity of a
cooling failure or other processes upset. It is determined by the entire amount of energy released (reaction enthalpy),
the total mass of the reaction mixture, and the specific heat capacity of the system. This is particularly crucial to
determining if it can bring the reaction mixture to a temperature where a secondary reaction or decomposition reaction
can eventuate. The adiabatic temperature rise is easily calculated using a Reaction Calorimeter to provide simple 'worst-
case' evidence of the temperature rise. This is the increase in temperature of reaction mass only due to the heat of
reaction under adiabatic conditions, meaning no heat is given or taken from the reaction mass. This ΔTad can be
calculated by the following Equation:

ΔTad = Qr / Cp………………….. (1)

Qr is a heat of reaction generally expressed in the unit of Kilo Joules (KJ) or Kilo Calories (KC) per mole of reactant and
Cp is the specific heat capacity of reaction mass generally in the unit of Joules/ gm °C or Calories / gm °C.

High ΔTad generally means high energies that result in fast runaway or thermal explosion. Assessment of the severity
of a runaway reaction based on ΔTad is presented in Table 1.

Table 1 Classification of the Severity of Decomposition Reactions According to the Corresponding Adiabatic
Temperature Rise (Assuming a Cp of 2 J/(g K))

∆H(J/g) ∆ Tad (0C) Severity

Less than -500 >250 High
-500<∆H <-50 25<∆ Tad<250 Medium
More than -50 <25 Low

2.3. MTSR: Maximum Temperature of Synthetic Reaction

One of the pillars of process safety in a semi-batch reactor is the Maximum Temperature of the Synthesis Reaction
(MTSR). It describes the temperature evolution following a cooling failure as a result of the amount of non-reacted
material existing at the time of the cooling failure. MTSR is calculated by initiating with the Process Temperature and
determining the maximum temperature that the reaction mixture will reach assuming that all of the reaction energy

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remains in the reactor (i.e. The system is or becomes adiabatic). The Reaction Calorimeter is an essential tool for the
measurement of the heat of the reaction, the reagent accumulation, and MTSR. This is the temperature a synthetic
reaction will reach in case of cooling failure and is expressed as

MTSR = Tp + (Xac*ΔTad) , ……………………. (2)

Where;
Tp is reaction process temperature,
Xac is the unconverted fraction of reactant at the time of cooling failure
ΔTad is the adiabatic temperature rise of the reaction.

In the worst scenario, MTSR at maximum level will be when cooling failure is at start time and Xac equal to one

MTSR = Tp + ΔTad…………………. (3)

Tb: Boiling Point of the Reaction Mass

Td: Temperature at which rate of decomposition of reaction mass constituent becomes hazardous.

3. Application of Reaction Heats to Process Safety Analysis

Stoessel has described the risk associated with chemical processes using five scenarios as shown in Fig. 1. Risk is
analyzed concerning the relationship between the desired process temperature, Tp, adiabatic temperature rise ΔTad
for the reaction, boiling point of reaction mass, Tb, the temperature of hazardous decomposition, Td, and maximum
temperature of the synthetic reaction, MTSR. The potential hazard increases from left to right [2].

In scenario A, even if all the heat is released instantaneously, the temperature will reach MTSR, which is below the
boiling point of reaction mass, Tb, and hazardous decomposition temperature, Td. So, this is a thermally safe process.
In scenario B also MTSR is below Tb and Td, though Tb is higher than Td. This is also a thermally safe process unless
the input of extra heat in the reaction mass leads to decomposition.

Figure 1 Five scenarios that depict the relative risk associated with chemical processing [2]

In scenario C, MTSR exceeds boiling temperature Tb, and there is the possibility of overpressure in the reactor due to
boiling vapor pressure. However, there is no risk of hazardous decomposition since Td is above MTSR. Controlling
reaction rate by measures such as controlled dosing of a reactant may suffice to bring MTSR below Tb.

In the case of scenario D, MTSR exceeds both Tb and Td. Hazardous decompositions leading to higher temperature and
pressure may take place. Some evaporative cooling may take place since Tb is lower than MTSR. However, reaction
controls and protection are necessary. In scenario E, MTSR exceeds Td but not Tb. In the event of loss of control,

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significant decomposition will take place leading to the hybrid pressure effect of gaseous decomposition and high-
temperature vapor pressure.

3.1. Prediction and Prevention of Runaway Reaction

As seen above, the risk assessment prediction of runaways can be made if Tp, Tb, Td, and MTSR, are known. Tp is desired
reaction temperature and Tb is known from the reaction experiment. Td can be found from data banks for known
reaction ingredients or determined by simple Differential Scanning Calorimetry (DSC) experiment of the reaction
mixture. MTSR is determined from Equation (3) by calculation of ΔTad from Equation (1). To calculate ΔTad, the heat
of reaction Qr and specific heat capacity Cp should be known. Cp values are readily available from data banks or
generally assumed 2.0 joules/ gm K for organic compounds. Thus, if the heat of reaction, Qr, is assessed, ΔTad, MTSR,
and thereby severity of runaway reaction can be predicted from the Stoessel diagram.

Once the severity of the exothermic reaction is known, one needs to mitigate the severity by removing heat from the
process to keep the temperature of the reaction within safe limits of preventing boiling over, decomposition, and
pressurization. To prevent runaway reactions, therefore, the cooling capacity of the process needs to be assessed. And,
if this cooling capacity is not adequate, measures to boost the cooling capacity need to be provided for the existing
system.

3.2. Prediction of Runaway Reaction

As seen above, the severity of the runaway reaction can be assessed if reaction heat, Qr, is known.

Two methods are used to determine this reaction heat, Qr.

 Calorimetric experimental determination.

 Theoretical estimation from thermal data of reaction

Modern advanced predictive calorimetric experimental techniques for the estimation of heat generation are very costly
and time-consuming, generally suitable for newly developed reactions. Reactions carried out in MSME units are usually
known and the heat of the reaction can be estimated theoretically from the thermal kinetics of the reaction. Both
techniques have some limitations and can be considered with a safety margin. Theoretical estimation techniques are
more suitable for MSME units and considered here.

3.3. Theoretical Estimation of Heat of Reaction, Qr, and Assessment of Severity

Theoretical estimation of heat is long known and is part of textbooks now. It is calculated as the Sum of the Heats of
Formations (ΔHf ) of Products of reaction minus that of reactants. Heats of formations, ΔHf, of compounds are readily
available from data banks.

For better understanding, we will now work out the theoretical estimation of Qr and assessment of reaction runaway
severity with a case example of the heat of epoxidation of Butene Diol with hydrogen peroxide.

Butene Diol + Hydrogen Peroxide ―› Epoxy Butane Diol + Water

C4H8O2 (88) + H2O2 (34) ―› C4H8O3 (104) + H2O (18)

ΔHf= -342.6 + ΔHf= -187.8 ―› ΔHf= -436.3 + ΔHf= -285.4 KJ / M

Therefore, Heat of Reaction, Qr, will be = -436.3 -285.4 + 342.6 +187.8 = -191.3 KJ / M.

A negative sign means that heat will be generated in the reaction.

Thus, 191.3 KJ (45.72 KC) of heat will be produced by epoxidation of one mole, that is 88 gms, of Butene Diol, for a
reaction mass of 122 gms.

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3.4. Runaway Risk Analysis for above example

Calculation of ΔTad once the heat of the reaction is known, ΔTad can be calculated from Equation (1). Assuming Cp for
diol of 2 joules / gm K and that of water is 4.182 joules / gm K, specific heat capacity of reaction mass will be (104*2) +
(18*4.182) / (104 +18) = 2.322 J / gm K. Therefore,

ΔTad = (191.3 * 1000) / (122 * 2.322) = 675.3 K

That is with no heat provided to or removed from the reaction mass, the temperature of reaction mass will increase by
675.30C, assuming a reaction temperature of 250C, MTSR will be

MTSR = 675 + 25 = 7000C

From the criticality class Table 1 and Stoessel diagram, it is a catastrophic reaction falling under Scenario D of the Stossel
diagram. All preventive measures such as efficient cooling controlled dosing etc. need to be provided.

4. Prevention of Runaway Reaction

Scientists can model runaway reaction scenarios and determine the best reaction procedure by analyzing reaction
dynamics. Measuring, calculating, and comprehending the parameters are critical for assessing and avoiding risk in a
chemical process. This enables scientists to forecast temperature and dosing profiles, concentrations, and maximum
operating temperatures. Once the severity of the runaway reaction is known, the first step to prevent it is to provide for
efficient cooling of reaction mass so that all heat produced in the reaction mass is removed and the temperature of the
reaction is maintained at desired process temperature, Tp. This may be achieved by circulating cooling media along the
reaction container surface area to remove heat from the reaction by heat transfer from the reaction mass.

The quantification of this heat transfer is provided in the following equation (4).

Q = U*A*ΔTlm = m*Cp*(T2 – T1) ………………………….. (4)

Where;
Q is heat transferred under a steady state from the reaction vessel, KJ/sec
U is the overall heat transfer coefficient, KJ/( sec*m²* °C)
A is an area available for heat transfer, m2
Δ Tlm is log mean temperature difference = °C
T is the temperature of reaction mass in the vessel, °C
T1 is the inlet temperature of the cooling fluid, °C
T1 is the outlet temperature of cooling fluid, °C
M is the mass flow rate of cooling fluid, kg/sec
Cp is a specific heat capacity fluid, KJ/Kg °C

5. Conclusion
Researchers have regularly observed comparable disasters in MSME chemical process enterprises, resulting in massive
property damages, injuries, and sometimes the loss of life. It is therefore vital to anticipate and avoid such runaway
responses utilizing technologies available to MSME units. The severity of runaway reactions can be assessed if reaction
heat, Qr, is known. Two methods are used to determine this reaction heat, Qr. Calorimetric experimental determination
and Theoretical estimation from thermal data of reaction. The reaction between Butene Diol and Hydrogen Peroxide
can be used as a model system for thermal runaway reactions. The required cooling area for the exothermic reaction
can be calculated from Equation 4 and if it is adequate, no runaway will occur. However, if the available cooling area is
less, a runaway reaction is predicted and other measures such as cooling media at lower temperature or modifications
to the process with reaction mass dilution with high Cp solvent, control dosing of reactant, etc. may be considered to
prevent the runaway reaction.

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Compliance with ethical standards

Acknowledgments
The author is thankful to Dr. Deepak Patil Director of Beekey Finochem Pvt Ltd, Mumbai for providing necessary
facilities and full support of this research.

Disclosure of conflict of interest

The authors have no conflicts of interest to declare

References
[1] Barton J and Rogers R., Chemical Reaction Hazards, Institution of chemical engineers: Rugby UK, 1996.
[2] Stoessel F. What is your Thermal Risk Chem. Eng. Prog., 1993; Volume 89 (10):68-75.
[3] US Chemical Safety and Hazard Investigation Board, Hazard Investigation: Improving Reactive Hazard
Management, 2001, http://www.csb.gov, accessed in May 2005.
[4] Y Iwata, H Koseki, Decomposition of hydroxylamine/water solution with added iron ion, Journal of Hazardous
Materials 2003; 104: 39-49.
[5] A. Benuzzi, JM Zaldivar, Safety of Chemical Batch Reactors and Storage Tanks, Kluwer Academic Publishers,
Boston 1991.
[6] T Yoshida, Safety of Reactive Chemicals, Elsevier, New York 1987.
[7] PF Nolan, JA Barton, Some lessons from thermal-runaway incidents, Journal of Hazardous Materials 1987; 14:
233-239.
[8] G. Joseph, Recent reactive incidents and fundamental concepts that can help prevent them, Journal of Hazardous
Materials 2003; 104: 65-73.
[9] TCHo, YS Duh, JR. Chen, Case studies of incidents in runaway reactions and emergency relief, Process Safety
Progress 1998; 17: 259-262.
[10] T Grewer, DJ. Frurip, B. Keith Harrison, Prediction of thermal hazards of chemical reactions, Journal of Loss
Prevention in the Process Industries 1999; 12:391-398.

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