0260-9576=03=$17.63 C 0.

00
# Institution of Chemical Engineers 2003

www.ingentaselect.com=titles=02609576.htm

Batch reactor hazards and their control

Phillip Carson and Clive Mumford

inadequate corrective action by management following

previous government inspections;
inadequate follow-up inspections by government
agency;
lack of internal quality control=assurance system.

Introduction
Batch processes are used in many industries, such as
dyestuffs, pharmaceuticals, synthetic resins, in some
fermentation processes, and in speciality chemicals
production. Because of their unique problems, this
themed issue is dedicated to the hazards of, and safety
controls for, batch processes.
As with continuous processes, accidents with batch
operations may result in re, explosion, employee illhealth, property and environmental damage, nancial
and business loss, or harm to consumers.

Serious mishaps can occur throughout any stage of the

batch processing life-cycle, from laboratory through to
production-scale, and during any operations, such as
material storage, mixing, product isolation, drying etc.
However, this paper concentrates on batch chemical
reactions.

Example 2

Example 1

An explosion in a conical drier blender killed one man

and caused 1.75m damage. At the time of the explosion
about 1300 kg of poultry food additive had remained in
the closed drier for a period of 27 hr after the drying
process was completed at a temperature of 120130 C.
The explosion was caused by thermal decomposition,
although tests using differential thermal analysis had
shown it was safe at the drying temperature. Other tests
included shock sensitivity, ammability and
thermodynamic computations, all of which failed to
identify a potential hazard. Afterwards, accelerating
calorimetry showed that a typical batch could self-heat to
destruction if held under adiabatic conditions at 120
125 C for 24 hr2 . This incident is discussed in more detail
on page 25.

A 5% solution of dextrose infusion uid was

manufactured by a batch process and autoclaved. One
third of the bottles failed to reach sterilizing temperature
due to retention of air in the autoclave. Evidence of the
shortcoming was clear to the operators since the autoclave
thermometer failed to indicate a temperature rise. This
was ignored in contravention of the operating procedure,
not for the rst time, on the grounds that the recording
thermometers had a history of unreliable operation.
Quality control checks on the batch failed to show
bacterial contamination and the product was released for
sale. During the interval between manufacture and use,
the bacteria in the product multiplied to dangerous levels.
Five hospital patients treated with this infusion uid
during surgical operations died1 . Subsequent examination
indicated that the product was contaminated and a major
product recall exercise was instigated. Issues identied as
requiring attention included:
thermometer calibration and logs;
autoclave maintenance and logs;
inadequate procedures generally;
permitting unofcial procedures to develop;
inadequacy of procedures to cope with all eventualities;
inadequate equipment=poor use of existing equipment;
inadequate procedures for cleaning the autoclave;
poor monitoring of autoclave conditions;
lack of adequate training;
poor communication;

Table 1 lists the main causes of accidents with batch

reactions3 . An analysis of the basic reasons for such
incidents in the UK identied inadequacies in
understanding the process chemistry and
thermochemistry, in design for heat removal, in systems
and safety systems and in operational procedures
including training4 . This, together with the following
examples, plus those in the other papers all highlight the
need to fully understand:
the properties of all materials involved, including the
potential risks of thermal decomposition of all materials;
the kinetics and thermodynamics of the process
whether an exothermic reaction is a risk, the rate and

LOSS PREVENTION BULLETIN 171

13

TABLE 1: CAUSES
REACTIONS

OF INCIDENTS

Cause
Mischarging
Reaction chemistry or
thermochemistry
Temperature
control=cooling
Maintenance
Agitation
Material specication
Human factors

INVOLVING BATCH

approximately 100 C had been pumped at 30 hr and 14 hr

prior to the incident where it remained unagitated and
exposed to air via an open vent. Subsequent thermal
stability tests indicated this could cause an oxidizing
reaction sufcient to raise the temperature to 300 C. At
above 300 C a rapid exothermic reaction takes place
generating large volumes of gasthis was believed to be
self-sustaining until the kettle ruptured6 .
This reinforces the need to simulate plant conditions
when designing plant and operating exothermic
reactions.

Percentage of accidents
21
20
19
15
10
9
6

Example 5
A diazonium compound in sulphuric acid was left for
45 hr at ambient temperature in a closed, jacketed enamellined vessel. The agitator was started. After 25 minutes

the pressure was 2.8 kg cm 2 and rising fast and the

temperature was 160 C. The operator immediately
opened the vent valve and turned on cooling water to the
jacket but, within a minute, the chargehole cover was
blown off and the contents of the vessel blown out7 .
Diazo solutions of this type are stable at ambient
temperature and the mixture must be heated to at least
115 C before decomposition becomes spontaneous. At
higher temperatures decomposition becomes violent.
However, if contaminated by traces of water,
decomposition becomes spontaneous at 100 C. The
accident was attributed to rain water having entered the
vessel via a vent pipe during a violent thunderstorm and
forming an unmixed layer of water on the surface of the
vessel contents. On starting the agitator the heat of mixing
was sufcient to raise the temperature of the
contaminated solution to above 100 C.

quantity of energy release, and the rate and quantity of

any gas release are important considerations;
the design of the reaction process and associated
equipment.

Materials involved
The physico-chemical and toxicological properties of the
materials used must be fully understood and accounted
for in design and operation. Typical requirements are
listed in Table 2. Clearly, for hazardous or nuisance
materials charging is preferably enclosed, or partiallyenclosed with local exhaust ventilation; risk may also be
reduced by handling them in a different physical form.

Example 3
After a period of work at a plastics company mixing
batches of granules for subsequent processing, a man
developed nose and eye discomfort. This was associated
with chest tightness and wheezing, often delayed for
several hours. His level of physical tness reduced. The
cause proved to be exposure to dust from sacks of
anhydride cross-linking agent. The managers were aware
of the hazards of this class of substance but did not have a
material safety data sheet. Workers were not provided
with any information, instruction or training. The man
was diagnosed as suffering from occupational asthma and
advised to avoid further exposure. He remained
unemployed and physically unt after four years away
from exposure5 .

Example 6
A reactor exploded due to an unexpected exothermic
reaction during the manufacture of
2,4-diuoronitrobenzene from 2,4-dichloronitrobenzene
and potassium uoride in the presence of
dimethylacetamide solvent8 . The plant was partially
destroyed, with missiles and blast damage extending to
500 m and secondary res. Six operators were injured and
one subsequently died.
The runaway was caused by contamination of the
recycled solvent with acetic acid, formed by the reaction
of the solvent with water that passed into the tank in
which the reaction product was stored. The azeotrope of
dimethylacetamide and acetic acid has the same boiling
point as dimethylacetamide itself, and hence acetic acid
was recycled with recovered solvent.
On previous occasions water contamination had been
removed at the start of batch distillation, but this time the
amount was greater and it formed a separate layer,
favouring acetic acid production. Moreover, although the

Consideration must be given to both in-process

materials such as feeds, catalysts, intermediates, products,
by-products, contaminants (including water and
corrosion products), solvents, additives, and to processing
aids such as heat-transfer uids, recycles, ow-aids,
refrigerants, re-ghting chemicals.

Example 4
An explosion in a 3.1 tonne reactor resulted in it being
projected 300 m. A polyether-alcohol intermediate at

LOSS PREVENTION BULLETIN 171

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TABLE 2: INFORMATION REQUIRED FOR HAZARDOUS CHEMICALS

Name of chemical
other names
Supplier
Uses
General description of hazards
Range of incompatible chemicals. Any incompatibility with air, water
General description of precautions
Fire ghting methods
Regulations
Sources of advice on precautions
Characteristics: evaluate as appropriate under all process conditions
Formula (chemical structure)
Purity (identity of any contaminants), physical state, appearance, other relevant information
Concentrations, odour, detectable concentration, taste (analytical methods)
Physical properties
Molecular weight
Particle size, size distribution
Vapour density
Foaming=emulsication characteristics
Specic gravity
Critical temperature=pressure
Melting point
Expansion coefcient
Boiling point
Surface temperature
Solubility=miscibility (with water; in general)
Joule-Thompson effect
Viscosity
Caking properties
Corrosivity
Contamination factors (incompatibility); oxidizing or reducing agent; dangerous reactions
Flammability data
Flash point
Vapour pressure
Fire point
Dielectric constant
Flammability limits (LEL=UEL)
Electrical resistivity
Ignition temperature
Electrical group
Spontaneous heating
Explosion properties of dust
Toxic thermal degradation products in a re
Reactivity (instability) information
Acceleration rate calorimetry
Drop weight test
Differential thermal analysis (DTA)
Thermal decomposition test
Impact test
Self-acceleration test
Thermal stability
Card gap test (under connement)
Lead block test
JANAF
Explosion propagation with detonation
Critical diameter
Pyrophoricity
Toxicity information
Toxic hazard rating
Hygiene standard (OEL, TLV, MAC)
LD5 0
Biological properties
Exposure effects
Inhalation (general)
Respiratory irritation
Ingestion
Respiratory sensitization
Skin=eye irritation
Skin sensitization
Carcinogenicity
Mutagenicity
Teratogenicity
Radiation information
Radiation survey
Alpha, beta, gamma, neutron emission

LOSS PREVENTION BULLETIN 171

15

equilibrium in the acetic acid formation equation is well

to the left, any unconverted raw material acts as a
scavenger and by removal of the dimethylamine formed
with the acetic acid moves the equilibrium to the right.

which was designed for 1000 psi. (Connement tests

subsequently indicated that the side reactions could
develop pressures of 400600 psi). Thrusts of gases from
the manhole propelled the vessel downwards releasing
gases into the building, where combustion caused the
explosion11 .

CH3 CONMe2 C H2 O D CH3 COOH C HNMe2

In the runaway reaction itself potassium acetate is
formed initially by reaction of potassium uoride and
acetic acid. This reacts with the 2,4-dichloronitrobenzene
to form acetoxychloronitrobenzene which is unstable
under the reaction conditions and reacts further to
produce a ketene, carbon dioxide, polyaryl ethers and tars.

Example 10
A batch operation involved charging an aldehyde to a
solution of caustic, an aromatic solvent and a phenolic
compound. The operator anticipated a problem with
fumes so he altered the sequence of addition, adding the
aldehyde before the caustic. Whilst the solvent was being
vacuum-charged via a dip pipe the reactor contents
exothermed and the pressure reached 25 psig. The
ammable solvent splashed into the process area, and
onto the operator, fortunately without igniting9 .
A proper safety review would have revealed the
potential fume problem, cautioned against altering the
order of addition, and hence avoided the incident.

Incidents have occurred in batch operations either

because the incorrect material was added by mistake,
because of changes in material specication, or because
materials had been added in the wrong sequence.

Example 7
The wrong material was charged to a reactor because of
confusion over chemical names. Three operators who
were involved in moving and charging the material failed
to notice that it was not triethanolamine but
triethylamine9 .

Clearly, problems may also arise if the wrong

quantities of materials are used.

Example 11

Example 8

An inorganic salt was used as a buffer to control the pH of

a batch reaction. Lack of control would result in a violent,
exothermic side reaction. Due to a mistake in the
calculation of the weights of raw materials required,
insufcient buffer was added to one batch. The reactor
exploded.
Additional protective measures were incorporated on
the modied plant and the formulation changed to allow
for addition of twice the theoretical buffer requirements1 2 .

An explosion in a batch process in an agrochemical plant

destroyed a ve storey building in June 1999. Potassium
hydroxide, instead of potassium carbonate, was
mistakenly heated with 2-chloro-5-nitrotoluene and
dimethylsulphoxide.
The blast from the explosion caused a nearby house
and several roofs to collapse and resulted in a power cut
which disrupted rail transport for several hours. People
required treatment for eye and respiratory problems
following exposure to the cloud of black smoke. Damage
costs were estimated to exceed 38m1 0 .

Kinetics and thermodynamics of

the process

Example 9

The characteristics of chemical reactions resulting in

intermediates or nal products vary widely. They may
involve:
reaction in gas, liquid, (neat or in solution, suspension
or emulsion) or solid phase;
catalytic or non-catalytic;
exothermic, endothermic, or negligible heat loss=gain;
reversible or irreversible;
rst-order (with the rate directly proportional to the
concentration of reactants), second-order (with the rate
depending on two concentration terms) or complex
kinetics.
A thorough knowledge of the reaction kinetics and
thermodynamics of the processes is a prerequisite for safe
operation.

In a reaction of an aromatic amine with a chloronitro

compound, synthetic soda ash was used as an acid
acceptor to prevent the formation of ferric chloride, which
was known to catalyse exothermic side reactions. After 20
years of successful operation the synthetic soda ash was
replaced by natural soda ash. In the non-aqueous reaction
medium the difference in crystallinity of natural soda ash
rendered it less efcient as an acid acceptor. This allowed
the acid to build-up and ferric chloride formed from
reaction with the mild steel vessel. This catalysed
exothermic side-reactions and resulted in overpressurization of the reactor and a serious explosion. A
weakness in the manhole closure caused the cover to
blow-off despite operation of a relief valve on the reactor,

LOSS PREVENTION BULLETIN 171

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Chemical reaction rate is generally a function of

reactants concentration and temperature. For example,
with the reaction:
A C B D product

(1)

the reaction rate D kaabb

where a, b D concentration of reactants
k D rate constant
a,b D constants depending upon reaction
Usually
k D A exp ( E=RTr)

(2)

Where E D activation energy, specic to the reaction

Tr D absolute temperature of reactants
A D integration constant
Thus in the case of an exothermic batch reaction unless
the heat of reaction is removed an increase in temperature
may lead to `run-away conditions. (For most
homogeneous reactions, the rate doubles for every 10 C
rise in temperature). If the sole means of heat removal is
an external jacket or internal coil through which coolant
ows at temperature Tc, the rate of heat removal is
proportional to (Tr-Tc). Clearly the rate of reaction
increases exponentially with temperature, whereas the
rate of heat removal is only linear. Thus a critical value of
Tr will exist at which control is lost and temperature can
then rise rapidly. This may result in a boil-over of the
reaction mass, over-pressurization of the reactor due to
rapid gas generation, or violent boiling leading to an
explosion. Elevated temperatures may initiate secondary
runaway reactions or thermal decomposition.
Hence, temperature is an important process variable
and typical reaction rate versus temperature relationships
are shown in Figure 1. Many chemical reactions are
exothermic, and particular concern for safety arises with
those reactions characterized by, for example, (a) and (c).
Examples of exothermic processes are given in Table 3.
Careful selection of operating temperature and the
provision of reliable means for heat removal, plus
emergency back-up, are therefore needed. The removal of
heat from a batch reactor may be by a combination of:
an external jacket, an internal coil or array of tubes with
either a ow of cooling media or vaporization of a
refrigerant;
an external heat exchanger, with re-circulation of the
reactants;
reactants vaporization-cooling with a reux condenser.
Potential instabilities during operation need to be
identied. For example contaminants such as impurities
in the reactants or corrosion products may act as catalysts,
which may promote unexpected reactions or accelerate
the rate of the desired reaction. Alternatively, process
conditions may change for some reason during operation,
or reactants may accumulate in the system. Possible
implications of the lack of understanding of the chemical
kinetics are illustrated by the following case histories.

FIGURE 1: TYPES OF REACTION =TEMPERATURE CURVE.

(A) RAPID INCREASE WITH TEMPERATURE NORMAL
CHARACTERISTICS WHERE IS THE HEAT REMOVAL
RATE FOR A SPECIFIC COOLANT TEMPERATURE AND
THROUGHPUT; R IS THE POINT OF RUNAWAY. (B) SLOW
INCREASE IN RATE WITH TEMPERATURE
CHARACTERISITIC OF SOME HETEROGENEOUS REACTIONS.
(C ) VERY RAPID INCREASE AT ONE POINTTHE IGNITION
POINT IN AN EXPLOSION . (D) DECREASE IN RATE AT
HIGHER TEMPERATURE CHARACTERISTIC OF CATALYTIC
REACTIONS . (E) DECREASE IN RATE AT INTERMEDIATE
TEMPERATURE FOLLOWED BY AN INCREASE . (F) SLOW
DECREASE IN RATE WITH TEMPERATURE

Example 12
A compound was produced from N-substituted aniline
and epichlorohydrin. The reaction was carried out so that
an agitated mixture of these two reagents was heated to
60 C by means of an internal steam coil. When the
exothermic reaction started a switch was made to cooling
water to maintain the temperature at 60 C. On one
occasion1 3 an operating error allowed the temperature to
exceed 70 C and, even with full water ow, the
reaction continued to accelerate. The temperature
increased slowly over about 10 minutes so that a full
evacuation was possible before the ensuing explosion at
120 C.
While a pressure relief system may have avoided an
explosion, because of the relatively slow rate of pressure
rise, this example clearly illustrates how the controllable
range of an exothermic reaction is a function of Tr.

Example 13
A nitric acid charge was added during the nitration of an
intermediate. The reactant mass was agitated for 4 hr,
with cooling applied, to allow for complete reactant
consumption. The nal shift before the weekend had
nished so cooling was shut off with the agitation left on.
The temperature was approximately ambient. The
temperature rose linearly over the next 35 hr reaching
80 C by Sunday morning. That evening the batch
erupted. Subsequently, a series of adiabatic heat ow

LOSS PREVENTION BULLETIN 171

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TABLE 3: POTENTIALLY HAZARDOUS EXOTHERMIC PROCESSES

Materials

Subject to explosive reaction or detonation

Which react energetically with water or common contaminants
Subject to spontaneous polymerization=decomposition=combustion

Processes

Exothermic
Contain ammables and operated at high pressure or temperature, or both
In which intrinsically unstable compounds are present
Operating in, or near, the explosive range
Involving highly toxic ingredients
Subject to a dust, gas, mist or vapour explosion
With a large inventory of stored pressure energy

Examples

Hydrogenation (addition of hydrogen atoms to both sides of a double- or triple-bond)

Hydrolysis (reaction of a chemical with water)
Isomerization (rearrangement of atoms within a molecule)
Sulphonation (introduction of an SO3 H radial into an organic moiety e.g. by reaction with H2 SO4 )
Neutralization (reaction between acid and base)
Alkylation (addition of alkyl group to a compound)
Esterication (reaction between alcohols and acids)
Oxidation (combination of oxygen with substances)
Polymerizations (linking small molecules to produce large ones)
Condensations (joining together two or more molecules with elimination of water)
Halogenations (substitution of, for example, H atoms in organic molecules by halogen)

calorimeter experiments in which energy input from

agitation was measured conrmed that this had increased
the batch temperature into its decomposition range and
resulted in the incident1 4 .

the agitator began operation, a violent reaction occurred

and sufcient heat was generated to cause explosive
liquid boiling. About half of the reactor contents were
projected through the hinged lid onto the operator who
suffered extensive phenol burns1 6 .

If the consequences of failure include thermal

runaway, it is important to ensure by an appropriate
system of work reinforced by instrumentation=alarms
that the agitator is on when required during charging:
if layering of reactants due to differences in liquid
density or miscibility or temporary crust formation
occurs, as these may subsequently result in a hazardous
reaction; or
if agitation is necessary for effective heat removal via
a jacket or coil.

Example 16
Chalk slurry was used to neutralize acidic efuent in an
agitated tank. When an excess acidity was detected in the
discharge efuent an operator found that the agitator had
stopped. When it was restarted the resulting violent
reaction blew-off a manway cover and lifted the bolted lid1 7 .

Example 17

Example 14

In a routine batch operation chlorosulphonic acid was to

be charged to a kettle followed by 98% sulphuric acid. An
operator failed to switch on the agitator prior to charging
the sulphuric acid; when this was noticed the agitator was
started. The chlorosulphonic acid had formed a layer over
the sulphuric acid. Hydrogen chloride was produced
spontaneously on mixing and this ejected acid out of the
man-way1 8 .

600 kg of `dry xylene was charged to a reactor. The

moisture content was checked using the Karl Fisher
method, but due to inadequate agitation there was a layer
of water beneath the xylene. When almost 300 kg of
phosphorus oxychloride was added, a violent reaction
generated an internal gas pressure of 2 bar causing the
relief valve to lift. A number of joints leaked and
hydrogen chloride vented into the building1 5 .

In the case of heat removal via a jacket=coil, the

process side offers the major resistance to heat transfer
and, as is commonly the case, the overall heat transfer
coefcient depends upon the speed of rotation of the
agitator (for example, overall heat transfer rate is
approximately proportional to (speed)2 =3 , neglecting dirt

Example 15
An operator was preparing a mixture of phenol and
liquid caustic soda. The phenol was added without
agitation resulting in layering in the mixing vessel. When

LOSS PREVENTION BULLETIN 171

18

is criticalif reliance is placed upon a jacket for heat

removal the reactor volume increases with (diameter)3 but
the heat transfer area increases approximately with
(diameter)2 .
A comparison of some safety features with those for
continuous reactors is given in Table 4.

Example 18
A new product was prepared in a laboratory glass
reactor1 9 . The process involved a rapid strongly
exothermic catalysed isomerization. A modied version
of the reactor was used on a pilot plant scale and feed was
to be introduced in small increments after the initial
charge had reacted. The arrangement had approximately
5-litre volume beneath the isomantle, from which a
pumping stirrer drew liquid into the bulk. However the
10 litres required to provide a reasonable level was
considered too large. The base of the reactor was therefore
lled with glass beads to immobilize the stirrer.
A 5-litre charge of reactant to a level just above the
glass beads was warmed-up with catalyst by switching on
the lowest zone of the isomantle. When the vapour-space
temperature reached 60 C, an internal vapour explosion
occurred which pushed apart the reactor base ange.
The reactant had a ash point of 28 C and an
autoignition temperature of 250 C. The explosion was
caused by autoignition of vapour by the hot glass surface
above the liquid level. Subsequent modications which
proved successful involved use of a heal to ensure that the
liquid level completely covered the isomantle zones in use,
use of a stirrer, and monitoring of the liquid temperature2 1 .
Such isomantles may reach surface temperatures of
300 C and it is important that glass surfaces always
remain submerged.

FIGURE 2: SELECTED CAUSES OF RUNAWAY IN BATCH

REACTORS
factors) and agitator failure may result in local hotspots=thermal runaways.
Selected causes of runaway in batch reactors are given
in Figure 2.

Equipment design
Batch arrangements are exible since each reactor can be
used to produce different products and quality assurance
is simplied by the ability to identify a specic batch.
Design details are however critical. For example, the scale

TABLE 4: SAFETY FEATURES OF BATCH AND CONTINUOUS REACTORS

Continuous
smaller quantities of materials are held up in the system;
the scale of any potential re=explosion or toxic release hazard is reduced;
any hazardous intermediate products may be consumed as fast as they are produced, hence minimizing their hazard;
less requirement for cleaning=entering vessels or equipment;
any potentially hazardous intermediates can be processed without storage;
less start-up and shutdown operations; therefore less unsteady state operation;
steady-state operation aids automatic control;
the reactor is less subject to cyclical uctuations in pressure and temperature;
the probability of operator error is reduced*.
Batch
reactors may be isolated from one another, so spread of re can be minimized by the use of small, isolated parallel
units;
analytical control can be applied to each batch of raw materials, materials in process, and products before use or
transfer;
identication of material sources and process conditions assists in Quality Assurance.
*Computer control also reduces the potential for operator error with batch reactors as do detailed instructions=
operating procedures, training and supervisions

LOSS PREVENTION BULLETIN 171

19

Many processes involve a high degree of technology

and require equipment designed to rigid specications
coupled with sophisticated automatic control and safety
devices. With some reactions that are difcult to control it
is particularly important to provide protection against
failure of cooling media, agitation, control or safety
instrumentation etc. Obviously, the reactor itself and
associated pipework=agitator must be adequately
designed for the operating conditions of pressure,
temperature, corrosive environment etc.

poison TCDD (tetrachlorodibenzodioxin) would be

produced as a by-product. The reactor was listed as
working at atmospheric pressure and the bursting disc,
rated at 3.5 bar, was to protect it from over-pressure
during transfer of the contents using air pressure; it
vented directly to atmosphere just above the roof of the
single-storey, reactor building.
At about 6 am on the day of the accident, a Saturday,
the reactor was shut down before the acidication stage,
which released the trichlorophenol product. All external
power was shut off including the temperature recorder,
which indicated 160 C. The exact cause of the ensuing
exothermic reaction was unproven but the reactor
contents were estimated to have reached 300 C before the
bursting disc ruptured. Approximately half of the reactor
contents escaped in 20 minutes; an estimated 0.253 kg of
TCDD was released to the atmosphere.
Although no fatalities were directly attributable to the
incident the drifting poison cloud caused 750 people to be
evacuated from their homes, development of chloracne in
large parts of the exposed population, widespread
damage to crops, pollution of the Rivers Seveso and Po,
and the death of many domestic animals. More than
12 km2 were contaminated with TCDD at or above a
concentration of 5 mg=m2 .
In this case the safeguards against over-heating
included provision for cooling using the steam coils, for
dumping 3000 litres of cold water into the reactor and for
using the reux condenser. These all required manual
operation but even if they had been automatic they would
have remained inoperative with the power shut off.
Suppliers of the bursting disc advised the provision of a
second receiver tank to cover the discharge of materials of
high value or toxicity. No such tank was provided.

Example 19
In the production of benzyl formate, equal volumes of
benzyl alcohol and phosgene were reacted in an excess of
toluene at 1216 C. On one occasion the glass-lined kettle
ruptured due to an internal explosion during vacuum
distillation of the toluene. Corrosion of a ferrous alloy
valve by the phosgene had provided ferric ions, which
catalysed decomposition of the ester2 0 .

Example 20
A 0.45 m3 vessel was used to chlorinate an aromatic
monomer dissolved in carbon tetrachloride at 50 C. When
only 10% of gaseous chlorine had been added to one batch,
the top of the vessel was blown off and the polymer
solution was ejected over the working area2 1 . Iron
chlorides had entered the reactor via stainless steel feed
lines. These then catalysed a very rapid side-reaction
between monomer and the chlorine, or hydrogen chloride,
evolving gas and producing a polymeric residue.

Example 21
An exothermic, liquid-phase reaction was performed
batchwise in a 379-litre agitated pilot-plant reactor. The
vessel was provided with a steam jacket equipped with
isolation valves to allow for multi-purpose use. At the end
of the day the reaction was left to progress with isolation
valves closed. Thermal expansion of the water retained in
the jacket occurred during the night due to the predictable
temperature rise associated with the exotherm. This
caused the vessel wall to buckle inwards and fouled the
agitator2 2 .

Considerations for reaction process selection and

design include those listed in Table 5.

Example 23
In a batch reactor system glycerol was charged and
circulated through a heat exchanger, which served as
either a heater or a cooler2 4 . It was rst used as a heater
until the temperature reached 115 C at which point the
feed of ethylene oxide commenced; since the reaction was
exothermic, the heat exchanger was switched to cooling.
To start the ethylene oxide feed pump required:
Circulating pump operational
Temperature > 115 C (otherwise no reaction)
Temperature < 125 C (otherwise reaction rate
excessive)
On one occasion when the ethylene oxide feed
commenced, the reactor pressure increased indicative
of the ethylene oxide not reacting. The operator deduced
that the temperature point was probably reading low and
therefore adjusted the trip setting to provide more heat to
initiate the reaction. He allowed the indicated

These points are further illustrated by the Seveso

incident, described briey below (and in more detail
elsewhere2 3 ).

Example 22
In July 1976 a bursting disc ruptured on a reactor at a
chemical works near Milan. The reactor was in use to
manufacture trichlorophenol at a temperature of 170
185 C. It was heated by steam at 190 C. It had been
assumed that the reactants could not attain the runaway
temperature of 230 C, at which temperature the hyper-

LOSS PREVENTION BULLETIN 171

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TABLE 5: CONSIDERATIONS

IN

REACTION PROCESS SELECTION

AND

DESIGN

consider whether less-hazardous materials can be used;

investigate potentially unstable reactions and side reactions such as spontaneous combustion or polymerization;
consider the risk that poor mixing or inefcient distribution of reactants and heat sources may, by malfunction or due
to design error, give rise to undesirable side reactions, hot spots, reactor runaway, fouling etc.;
consider whether the reaction can be made less hazardous by changing the relative concentration of reactants or other
reactor operating conditions, such as having less unreactive material in the reactor;
assess whether side reactions produce poisonous or explosive material, or cause dangerous fouling;
investigate whether the materials absorb moisture from the air and then swell, adhere to surfaces, form toxic or
corrosive liquid or gas, etc.;
determine the effect of all impurities on chemical reactions and characteristics of process mixtures;
ensure that the materials of construction are compatible with each other and the chemical process materials;
allow for all aspects of catalyst behaviour, such as ageing, poisoning, disintegration, activation, and regeneration;
investigate whether hazardous materials can build up in the process (such as traces of combustible and noncondensable materials, toxic or explosive intermediates, or by-products);
consider whether any heating medium used should have a maximum temperature signicantly lower than that at
which decomposition of the reaction mixture may be initiated.

temperature to reach 200 C but still the pressure did not

fall. He suspected his theory was wrong and, on checking,
found that the valve at the bottom of the vessel was still
closed. He opened the valve and three tonnes of ethylene
oxide together with the glycerol passed through the
heater and catalyser. There was a violent runaway
reaction which ruptured the reactor; the escaping gases
exploded and two men were injured. (The indicated rise
in temperature was unreal. A pump was running with a
closed suction valve and the heat generated affected the
nearby temperature point. The ow indicator and lowow alarm were both out of order).

The vapour cloud ignited and the explosion disabled the

sprinkler protection. The reactor area and an adjoining
warehouse were destroyed by re2 5 .

Numerous measures may be applied to minimize any

hazard with exothermic reactors including:
If possible, avoiding operation in which all reactants are
initially mixed together and any catalyst and heat is
applied to the start of the reaction. (Experience shows
that dangerous runaway reactions are more likely with
such an arrangement.)
Limiting the size of reactor (this limits inventory and
can provide a more favourable ratio of heat transfer area
to volume). As noted earlier, this ratio becomes
increasingly unfavourable as the size of the reactor is
increased, and there may be a critical diameter of
practical use for any specic reaction. This means that a
reaction which is easily controlled in a laboratory or
small pilot-plant reactor may be hazardous on a large
scale unless additional control measures are introduced.
Operating with reactants diluted either as solutions,
suspensions or emulsions reduces the reaction rate as
per equation (1) and effectively increases the ratio of
heat transfer area to reactants volume.
Controlling the rate of addition of one component
according to the temperature of reactants i.e. using
semi-batch operation.
Providing efcient agitation to distribute reactants
homogeneously throughout the reactor volume to avoid
hot spots and to improve the reactor-side heat transfer
lm coefcient. (Without good agitation a radial
temperature gradient may exist. If, for example, the
temperature at some point in the reaction mixture were
10 C higher than at the wall the reaction rate at this
point could be twice that at the wall. This may result in
the production of a different chemical).

In general, depending upon the nature of the

reactants, the types of reactor, the reactor conguration
and the reaction conditions, typical events and operator
errors requiring consideration to ensure safety are listed
in Table 6. The consequences of wrong material
transfer may simply be a ruined batch, or be so serious as
to indicate a potential requirement for valve
interlocking. In some processes (such as those in Table 3)
it may be so serious as to necessitate emergency shut-off
of in-ows, perhaps as indicated in the N-substituted
aniline case history described earlier. If the feed system
itself incorporates any heat exchange facilities, such as
pre-coolers or pre-heaters, then the effect of their
failure possibly leading to unusually high or low
temperatures of the reactor must be considered.

Example 24
An unusual `runaway occurred in a resin manufacturing
plant when, because of sub-zero weather, steam was
applied to a catalyst weigh-tank associated with a batch
reactor. Excess temperature initiated the reaction in
the weigh-tank and, since it had no cooling provisions,
the exotherm caused a boil-over of the tanks contents.

LOSS PREVENTION BULLETIN 171

21

TABLE 6: BATCH REACTOR POSSIBLE EVENTS AND OPERATOR ERRORS

Event
agitator failure (mechanical or electrical);
instrument failure (pressure, ow, temperature, level or a reaction parameter such as concentration);
failure of instrument air or electricity;
loss of inert gas blanket;
failure of relief devices (for example, pressure relief valves or rupture discs);
restricted or blocked vent;
leakage of materials out (for example, due to gasket failure) or air inwards;
attainment of abnormal reaction conditions (over-pressure, over-temperature, segregation of reactants, excessive
reaction rate, initiation of side reactions, layering);
failure of coolant, refrigerant, or other utilities;
restriction of material ows in=out;
failure of high- or low-pressure alarms=cut-outs;
power failure affecting agitator, pumps, instruments;
emergency elsewhere on plant=site.
Selected operator errors
failure to clean, purge vessel or lines;
addition of wrong material or wrong quantities (more, less or zero);
failure to add catalyst or other material3 5 ;
addition of materials in incorrect sequence;
failure to add material (for example, short-stop or inhibitor) at correct stage;
error in valve, switch or associated equipment operation;
spillage of material;
improper venting to atmosphere;
failure to actuate agitation at the proper time or use of incorrect speed.
Providing a reux condenser to remove latent heat of
vaporization.
Ensuring all instruments for temperature, pressure, and
ow control are actuated by properly located,
uncontaminated, correctly adjusted sensors that are
highly reliable. Critical instruments may be duplicated.
Limiting the temperature difference between coolants
and reactants to, for example, a maximum of 10 C.
Providing concise, up-to-date operating instructions
and training.

Example 26
The agitator on a batch-operated nitration reactor stopped,
but the instrument provided to alarm and shut off acid feed
ow when the agitator ceased to rotate failed to operate.
An explosion occurred when the agitator restarted2 7 .

Example 27
After the laboratory had closed for the weekend, re
broke out in a 23-litre insulated pot containing ammable
liquid. The liquid was undergoing a test at elevated
temperature, maintained by a hot plate equipped with a
temperature control. Failure of the temperature control
was responsible for over-heating and ignition of the
liquid. Fortunately a watchman discovered the re in time
and it was extinguished2 8 .

Example 25
A nitration reaction involving substituted benzoic acid
had been run many times in the laboratory and once on a
50-gallon pilot plant scale. Fuming nitric acid was used as
the nitronium ion source and fuming sulphuric acid as
solvent at 8090 C. On a 200-gallon scale a runaway
occurred. The nitric acidsulphuric acid mixture was
being slowly added to the substituted benzoic acid when,
a few minutes in to the run, the temperature suddenly
increased and the rupture disc blew. The dome gasket also
ruptured as personnel evacuated the area. Subsequent
procedures for running reactions in the pilot plant were
reviewed by a Batch Record Review Board; they required
more information and instructions to be included in the
written batch record2 6 .

One reason that batch reactors may be preferred is

because the interval between batches is available for
cleaning procedures to ensure no deleterious
intermediates accumulate. However, this itself may pose
hazards due to inadequate preparation for cleaning,
inadequate cleaning procedures, or incomplete removal of
the liquids used for cleaning purposes.

LOSS PREVENTION BULLETIN 171

22

the stirrer stopped while the instrument was repaired. A

delay in shutting off the chlorine ow allowed high
temperatures to develop and the resulting decomposition
reaction caused an explosion in the reactor with eight
fatalities and extensive damage3 4 .

Example 28
The procedure for washing out a reactor after discharging
a batch of aluminium chloride melt into water involved
lling it with water. On one occasion, the wash water was
added before the vessel was completely empty, no
dipping or visual inspection having been performed.
There was a violent reaction and the hydrogen chloride
evolved ruptured the glass vent2 9 .

In some cases it is likely to be very difcult to regain

control.

Example 31

Example 29

To start a reaction in an agitated vessel the contents had to

be heated by steam in a jacket. At 60 C the steam should
have been isolated, the jacket purged, and cooling water
applied to remove the heat of reaction. This change-over
was the responsibility of the operator.
The operator was distracted at the crucial time. On his
return shortly afterwards the temperature was 70 C. He
switched to full cooling but the temperature continued to
rise. The building was evacuated and the reactor
ultimately exploded at 120 C.
This incident should not be dismissed as `operator
error. It could have been identied by some formalized
hazard evaluation technique, and a system of work or
automatic control introduced to minimize it.

A commercial cleaning solution was used to remove

polymer build-up from a 50-gallon reactor. Some uncured
material beneath the hard crust reacted with the solution
causing a pressure rise. The relief valve being blocked
with polymer solids impeded pressure relief and pressure
blew out a 5 cm glass elbow. Such an incident could have
been anticipated by prior testing of the cleaning agent and
reaction residue9 .
In addition to measures for the control of possible
events and errors such as those listed in Table 6,
consideration should be given to limiting their
consequences. In some circumstances this may involve
designing the plant to contain the maximum pressure that
could be developed as a consequence of a runaway.
Depending on the reaction, reactor type and
conditions, emergency measures include a combination of:
vent to blow-down facilities or other safe place. Detailed
advice is available on relief system design3 2 ;
emergency heat removal by supplementary cooling,
such as by pumping reactants through an external heat
exchanger loop or by the use of lower temperature
cooling medium;
dilution with compatible gas or liquid;
dumping contents (for example, into a ash drum,
reservoir, or quench tank containing an appropriate
quenching uid);
shut-off feed; increase off-take;
destroy catalyst (i.e. add inhibitor);
inert gas purging;
deluge reactants with compatible liquid (such as solvent
or water);
increased agitation provision, so increasing the rate of
heat removal. With a semi-batch operation an obvious
measure is to shut off the ow of reactants.
Detailed examples of these measures are provided in
reference 33. The selection of the correct combination of
emergency measures and their speed of response are
clearly important factors.

Conclusion
Accidents involving batch reactors can be costly in terms
of injuries to personnel, damage to property or the
environment, lost business=reputation and in settling
claims for compensation. Loss prevention requires a
strategy to:
Plan reactions (understand the chemistry; plan as semibatch; consider side reactions; collect data; conduct desk
screening; carry out laboratory studies and pilot-plant
trials; use HAZOPs prior to scale-up to production
mode, as discussed by Bickerton on page 10).
Control reactions (charging of the correct materials of
the right specication, in the correct order, in the correct
amount at the correct time and temperature;
provision of material and line labelling; provision of
reactor cooling, agitation, temperature and pressure
control; operator instruction, training and
supervision).
Plan for loss of control (provide detection and alarms,
reactor venting, additional cooling, crash cooling,
dumping, quenching; stop feed supply, stop catalyst
feed; add reaction inhibitor; train operators to recognise
major deviations and the action to take, and rehearse
emergency actions and area evacuations).
Further guidance and case histories are provided by
references 33 and 3642 and in an excellent video
entitled `Control of Exothermic Chemical Reactions,
produced by the UK Health and Safety Executive

Example 30
A batch chlorination reaction was controlled by automatic
regulation of the ow of chlorine. One day the
thermocouple failed. The coolant (brine) was shut off and

LOSS PREVENTION BULLETIN 171

23

19. Anon, Loss Prevention Bulletin, Institution of Chemical

Engineers, 1981, ( ), 21.

in conjunction with the Institution of Chemical

Engineers.

20. Anon, Loss Prevention Bulletin, Institution of Chemical

Engineers, 1979, (025), 12.

References

21. Anon, Loss Prevention Bulletin, Institution of Chemical

Engineers, 1977, (012), 4.2.

1. (a) C. M. Clothier, Report to the Committee appointed

to inquire into the circumstances, including the
production, which led to the use of contaminated
infusion uids in the Davenport Section of the
Plymouth General Hospital, 1972, HMSO.
(b) Anon, The Daily Telegraph, March 7th 1972, 1;
J. Owen, ibid, March 8th 1972.
(c) Anon, The Pharmaceutical Journal, 1972, 209, 1, 5.

22. P. A. Carson and C. J. Mumford, Loss Prevention

Bulletin, Institution of Chemical Engineers, 1989, (089),
1; ibid. 1989 (090) 3; ibid, 1990; (093), 5; J. Jones, et al,
Chemical Engineering, 1993, (April), 136.
23. Anon, The Economist, 17 June 1998, 101, V. C. Marshall,
The Chemical Engineer, 1980, 499.
24. R. Rushford, NE Coast Inst Eng Trans, 1977, 93, 117.

2. Health and Safety Executive, The Explosion at the Dow

Chemicals Factory, Kings Lynn, 27th June 1976, 1977,
HMSO.

25. F. A. Manuele, One Hundred Largest Losses, Loss

Prevention Bulletin, Institution of Chemical Engineers,
1984, (058), 1.

3. P. F. Nolan, Report to HSE on case histories of

Runaway Reactions.

26. R. N. Brummel, Plant Operations Progress, 1989, 8(4),

228.

4. J. A. Barton and P. F. Nolan, Hazards X: Process Safety

in Fine and Speciality Chemical Plants, Institution of
Chemical Engineers Symposium Series, No 115, 3

27. E. J. Fritz, Loss Prevention, 1969, 3, 41.

28. National Fire Protection Association, Occupancy Fire
Record: Laboratories, NFPA, Boston, 1958, 6.

5. Anon, Health and Safety Commission Newsletter, 1991,

(77) June, 9.

29. Anon, Loss Prevention Bulletin, Institution of Chemical

Engineers, 1980, (035), 2.2.2.

6. C. H. Vervalin, (ed), Fire Protection Manual for

Hydroprocessing Plants, 2nd edn, Gulf, Houston, Texas,
1973, p. 82

30. J. C. Etchells and J. Wilday, Workbook for Chemical

Reactor Relief System Sizing, HSE Contract Research No
136, HSE Books, 1998.

7. A. J. D. Jennings, Courses on Process Safety. Theory and

Practice, Institution of Chemical Engineers, University
of Durham, 1116 July 1982.

31. J. A. Barton and R. L. Rogers, Chemical Reaction

Hazards, 2nd edn, Institution of Chemical Engineers,
1997.

8. T. A. Kletz and J. Redman, The Chemical Engineer, 28th

Feb 1991, 15; T. A. Kletz, Loss Prevention Bulletin,
Institution of Chemical Engineers, 1991, (100), 21.

32. Anon, Manufacturing Chemists Assoc. Case History

1962, 1, case history 371.

9. M. A. Capraro and J. H. Strickland, Plant Operations

Progress, 1989, 8(4), 189.

33. T. A. Kletz, An Engineers View of Human Error,

Institution of Chemical Engineers, 1985, 114.

10. Anon, The Chem. Eng. 24th June 1999, 5.

34. T. Yoshida, Safety of Reactive Chemicals, Elsevier, 1987.

11. W. W. Russell, Loss Prevention, 1976, 10; Anon,

Manufacturing Chemists Assoc Case History, 1911.

35. Association of British Pharmaceutical Industry,

Guidance Notes on Chemical Reaction Hazard Analysis,
1989.

12. T. A. Kletz, An Engineers View of Human Error,

Institution of Chemical Engineers, 1985, 21.
13. Anon, Loss Prevention Bulletin, Institution of Chemical
Engineers, 1975, (001), 3.

36. L. Bretherick (ed), Brethericks Handbook of

Reactive Chemical Hazards, Peter Urben. 6th edn,
1999.

14. E. D. West, G. W. Gravenstone and T. F. Hoppe, Plant

Operations Progress, 1986, 5(3), 142.

37. National Fire Protection Association, Manual of

Hazardous Chemical Reactions, 1986, NFPA, Boston.

15. Anon, Loss Prevention Bulletin, Institution of Chemical

Engineers, 1975, (03), 3.

38. P. A. Carson and C. J. Mumford, The Safe Handling

of Chemicals in Industry Volumes 1 and 2, Longman,
1988.

16. Annual Report of HM Inspector of Factories, HMSO,

1967.

39. P. A. Carson and C. J. Mumford, The Safe Handling of

Chemicals in Industry Volume 3, Longman, 1996.

17. T. A. Kletz, An Engineers View of Human Error,

Institution of Chemical Engineers, 1985, 35.

40. P. A. Carson and C. J. Mumford, Hazardous

Chemicals Handbook, 2nd edn, Butterworth Heinemann,
2002.

18. Anon, Loss Prevention Bulletin, Institution of Chemical

Engineers, 1977, (013), 2.

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