4

REACTORS

4.1 INTRODUCTION
This chapter presents potential failure mechanisms for reactors and suggests
design alternatives for reducing the risks associated with such failures. The
types of reactors covered in this chapter include:

Batch reactors
Semi-batch reactors
Continuous-flow stirred tank reactors (CSTR)
Plug flow tubular reactors (PFR)
Packed-bed reactors (continuous)
Packed-tube reactors (continuous)
Fluid-bed reactors

This chapter presents only those failure modes that are unique to
reaction systems. Some of the generic failure scenarios pertaining to vessels
and heat exchangers may also be applicable to reactors. Consequently, this
chapter should be used in conjunction with Chapter 3, Vessels, and Chapter 6,
Heat Transfer Equipment. Unless specifically noted, the failure scenarios
apply to more than one type of reactor.
4.2 PAST INCIDENTS
Reactors are a major source of serious process safety incidents. Several case
histories are presented to reinforce the need for safe design and operating practices for reactors.

4.2. / Seveso Runaway Reaction

On July 10, 1976 an incident occurred at a chemical plant in Seveso, Italy,

which had far-reaching effects on the process safety regulations of many countries, especially in Europe. An atmospheric reactor containing an uncompleted
batch of 2,4,5-trichlorophenol (TCP) was left for the weekend. Its temperature was 1580C, well below the temperature at which a runaway reaction
could start (believed at the time to be 23O0C, but possibly as low as 1850C).
The reaction was carried out under vacuum, and the reactor was heated by
steam in an external jacket, supplied by exhaust steam from a turbine at 19O0C
and a pressure of 12 bar gauge. The turbine was on reduced load, as various
other plants were also shutting down for the weekend (as required by Italian
law), and the temperature of the steam rose to about 30O0C. There was a temperature gradient through the walls of the reactor (30O0C on the outside and
16O0C on the inside) below the liquid level because the temperature of the
liquid in the reactor could not exceed its boiling point. Above the liquid level,
the walls were at a temperature of 30O0C throughout.
When the steam was shut off and, 15 minutes later, the agitator was
switched off, heat transferred from the hot wall above the liquid level to the
top part of the liquid, which became hot enough for a runaway reaction to
start. This resulted in a release of TCDD (dioxin), which killed a number of
nearby animals, caused dermatitis (chloracne) in about 250 people, damaged
vegetation near the site, and required the evacuation of about 600 people
(Kletz 1994).
Ed. Note: The lesson learned from this incident is that provision should have
been made to limit the vessel wall temperature from reaching the known onset temperature at which a runaway could occur.
4.2.2 3,4-DichloroanHine Autoclave Incident

In January 1976, a destructive runaway reaction occurred during the operation of a large batch hydrogenation reactor used in the production of 3,4dichloroaniline. The process involved the hydrogenation of 3,4-dichloronitrobenzene (DCNB) under pressure in an agitated autoclave. The autoclave was
first charged with DCNB and a catalyst and then purged with nitrogen to
remove air. A hydrogen purge followed the nitrogen purge, after which steam
was applied to the reactor jacket and the temperature raised to within 2O0C of the
reaction temperature before additional hydrogen was admitted through a sparger.
The heat of reaction carried the temperature to the desired operating level.
During the early stages, the rate of reaction was limited by the heat
removal capacity of the autoclave cooling coil. This resulted in a relatively low

autoclave pressure. Later, when the hydrogenation rate fell off, the autoclave
pressure was allowed to increase. Based on field evidence and subsequent laboratory work the following conclusions were reached as to the cause of the incident (Tong 1977):
The primary cause was a sudden pressure increase due to runaway reaction at about 26O0C.
The reaction mass reached runaway temperature due to the buildup and
rapid exothermic disproportionation of an intermediate (3,4-diphenyhydroxylamine). The most likely trigger for this reaction was a 1O0C
increase in the reactor temperature set point (operator error).
Ed. Note: The lesson learned from this incident is that a, study should have been
made of exotherm potential and provision should have been made to limit temperature setpoint or an interlock provided to address this hazard. If possible a larger operating temperature margin should have been employed.

4.2.3 Continuous Sulfonation Reaction Explosion

During the startup phase of a continuous system (3 CSTRs in series) for the
sulfonation of an aromatic compound, a thermal explosion occurred in a
pump and recirculation line. Although the incident damaged the plant and
interrupted production, no personnel were injured.
Investigation revealed that, while recirculation of the reaction mass was
starting up, the pump and the line became plugged. This problem was corrected and line recirculation was restarted. Four hours later the explosion
occurred, resulting in the blow-out of the pump seal, which was immediately
followed by rupture of the recirculation line.
Investigation further revealed that during pipe cleanout some insulation
had been removed, leaving a portion of the line exposed and untraced. This
condition apparently led to slow solidification of the reaction mass and a deadheaded pump. Calculations based on pump data indicated that a temperature
of 6O0C above the processing temperature could be reached within 5 minutes
after dead-heading occurred. Previous studies had determined that the rate of
decomposition is considerable at this temperature and that the total heat of
decomposition (500 kcal/kg) is large (Quinn 1984).
4.3 FAILURE SCENARIOS AND DESIGN SOLUTIONS
Table 4 presents information on equipment failure scenarios and associated
design solutions specific to reactors. The table heading definitions are provided in Chapter 3, section 3.3.

4.4 DISCUSSION
4.4.1 Use of Potential Design Solutions Table

To arrive at the optimal design solution for a given application, use Table 4 in
conjunction with the design basis selection methodology presented in Chapter
2. Use of the design solutions presented in the table should be combined with
sound engineering judgment and consideration of all relevant factors.
4.4.2 General Discussion

Reactors may be grouped into three main types: batch, semi-batch, and continuous.
In a batch reactor, all the reactants and catalyst (if one is used) are charged
to the reactor first and agitated, and the reaction is initiated, with heat being
added or removed as needed. In a semi-batch reactor, one of the reactants is
first charged to the reactor, catalyst is also charged and the reactor contents are
agitated, after which the other reactants and possibly additional catalyst are
added at a controlled feed rate, with heat being added or removed as needed.
In a continuous reactor all the reactants and catalyst (if one is used) are fed
simultaneously to the reactor, and the products, side products, unconverted
reactants, and catalyst leave the reactor simultaneously. In some continuous
reactors, the catalyst is held stationary, either in tubes or occupying the entire
cross-section of the vessel.
Batch and semi-batch reactors are used primarily where reaction rates are
slow and require long residence times to achieve a reasonable conversion and
yield. This often means large inventories and, if the contents are flammable,
there is a potential for serious fires should a leak develop. Many of these reactors have agitators, and if there is an agitator failure (stoppage or loss of the
impeller), some reactions can run away (Ventrone 1969; Lees 1996).
Heat removal is also a concern for batch or semi-batch reactors conducting exothermic reactions. Since the external jacket may not be adequate to
remove the heat of reaction, it may be necessary to install an internal cooling
coil as well, or an external heat exchanger with recirculation of the reactor contents. These additional items of heat transfer equipment increase the potential
for leakage problems and may lead to a runaway if the coolant leaks into the
reactants.
Continuous reactors are considered to be inherently safer than batch or
semi-batch reactors as they usually have smaller inventories of flammable
and/or toxic materials. Tubular reactors are generally used for gaseous reactions, but are also suitable for some liquid-phase reactions. Gas phase reactors
generally have lower inventories than liquid-phase continuous reactors of

equal volumes, and thus are usually inherently safer. Long, thin tubular reactors are safer than large batch reactors as the leak rate (should a leak occur) is
limited by the cross-section area of the tube, and can be stopped by closing a
remotely operated emergency isolation valve in the line (Kletz 1990).
Continuous-flow stirred tank reactors (CSTR) are also considered to be inherently safer than batch reactors as they contain smaller amounts of flammable
or toxic liquids. Since they are agitated, however, they have the same agitator
failure hazard as batch reactors, and can experience runaways if this occurs.
Exhibit 4.1 is a comparison of different types of reactors from the safety perspective (CCPS 1995).
EXHI BIT 4.1
Comparison of Different Reactor Types from the Safety Perspective

Plug Flow Reactor

(PFR)

Continuous-Flow
Stirred Tank
Reactor (CSTR)

Batch

Semi-Batch

ADVANTAGES
Low inventory
Stationary
condition (steady
state operation)

Stationary
condition (steady
state operation)

Agitation provides
safety tool

Agitation provides
safety tool
Streams may be
diluted to slow
reaction

Controllable
addition rate
Agitation provides
safety tool
Large exotherm
controllable

DISADVANTAGES
Process
dependency
Potential for hot
spots
Agitation present
only if in-line
mixers are
available
Difficult to design

Large inventory
Difficult to cool
large mass
Difficult start-up
and shutdown
aspects
Precipitation
problems
Low throughput
rate

Large exotherm
difficult to control
Large inventory
All materials
present

Starting
temperature is
critical (if too low,
reactants will
accumulate)
Precipitation
problems

4.4.3 Special Considerations

Table 4 contains numerous design solutions derived from a variety of sources

and actual situations. This section contains additional information on selected
design solutions. The information is organized and cross-referenced by the
Operational Deviation Number in the table.
Overpressure due to Loss of Agitation (3)

Runaway reactions are often caused by loss of agitation in stirred reactors

(batch, semi-batch, and CSTR) due to motor failure, coupling failure, or loss
of the impeller. Agitation can be monitored by measuring the amperage or
power drawn by the agitator drive. Nevertheless, this has its drawbacks as the
"measurement" of agitation takes place outside of the reactor, and sometimes,
if the reactor contents are not viscous enough, the amperage or power draw
will not detect that the agitator impeller has fallen off or corroded away.
Wilmot and Leong (1976) present a method of detecting agitation inside a
reactor, which will detect the loss of the impeller by using an internal flow
switch. The flow switch, or a similar in-vessel detection device, can be interlocked to cut off feed or catalyst being added to a semi-batch reactor or CSTR.
If agitation is critical to the operation of a batch, semi-batch, or CSTR
reactor then an independent, uninterrupted power supply backup for the agitator motor should be provided. Alternatively, some degree of mixing can be
provided by sparging the reactor liquid with inert gas.
Failure of mechanical seals can act as a potential high-temperature source
initiating vapor phase ignition. Agitator mechanical seal failure is often caused
by a lack of seal fluid, and results in release of flammable or toxic vapors from
the reactor. A dry mechanical seal is now available which can sometimes be
used to replace the older type of mechanical seals which required a liquid seal
fluid. Dry mechanical seals use a gas such as air or nitrogen to provide the sealing barrier. If a liquid seal fluid is used, monitoring of the agitator mechanical
seal fluid supply reservoir should be implemented. Monitoring can be done
automatically, by installing a low-level switch and alarm in the seal fluid reservoir to alert the operator, or by administrative means such as requiring the
operator to check the reservoir level on a regular schedule (e.g., once per shift)
and recording the level on a log sheet.
Overpressure due to Addition of Incorrect Reactant (5)

The addition of a wrong reactant can result in a runaway reaction. To minimize this error, the following measures can be taken:
Provide dedicated feed tanks (for liquids) or feed hoppers (for solids)
for batch reactors.

 Have two operators check the drums or bags of reactants before they are
added, and then sign off on a log sheet.
Properly color-code and label all process lines so the operators know
what is in them.
If the risk of adding an incorrect reactant is still present, further protective
measures can be implemented, such as providing a temperature sensor to
monitor the reaction and shut off a valve in the feed line upon detection of an
abnormal temperature rise or rate of temperature rise.
Overpressure due to Inactive/Semi-Active or Wrong Catalyst Addition (8)
The addition of a semi-active or wrong catalyst to a reactor may result in a runaway either in the reactor or in downstream equipment. If the catalyst is fed
continuously or at a controlled rate to a semi-batch reactor, protection can be
provided by installing a temperature sensor in the reactor, interlocked with an
isolation valve in the reactant feed line, which will shut the valve when the
sensor detects an abnormal temperature rise. The temperature sensor could
also be interlocked with a valve to stop the catalyst feed. Administrative controls, such as procedures for verifying catalyst identity and activity, can also be
applied.
Overpressure due to Monomer Emulsion Feed Breaking during Feed
Leading to a Runaway Reaction (12)

In some semi-batch emulsion polymerization processes, a mixture of monomers emulsified in water is fed from an agitated storage tank to the reactor. If
the monomer emulsion feed breaks into separate oil and water phases, the
potential exists for a runaway reaction in the oil (bulk monomer) phase without the heat sink provided by the water. To guard against this, the monomer
emulsion feed can be sampled to determine that it remains stable to separation
for a predetermined period of time without agitation before the feed is begun.

4.5 REFERENCES
CCPS 1995. Guidelines for Chemical Reactivity Evaluation and Application to Process Design. New
York: American Institute of Chemical Engineers.
Kletz, T. A. 1990. Critical Aspects of Safety and Loss Prevention, p. 265. London :Butterworth &
Co. Ltd.
Kletz, T. A. 1994. What Went Wrong: Case Histories of Process Plant Disasters. 3d ed., pp. 309-310.
Houston, TX: Gulf Publishing Co.
Lees, F. P. 1996. Loss Prevention in the Process Industries. 2d ed. Woburn, MA: Butterworth Inc.
Quinn, M. E., Weir, E. D., and Hoppe, T. F. 1984. IChemE Symposium Series, no. 85:31-39.
Tong, W. R., Seagrave, R. L., and Wiederhorn, R. 1977. Loss Prevention Manual. 11: 71-75.
New York: American Institute of Chemical Engineers.

Ventrone, T. A. 1969. Loss Prevention Manual. Vol. 3, pp. 41-44. New York: American Institute
of Chemical Engineers.
Wilmot, D. A. and Leong, A. P. 1976. Another Way to Detect Agitation. Loss Prevention Manual.
Vol. 10, pp. 19-22. New York: American Institute of Chemical Engineers.
Suggested Additional Reading
CCPS 1993. Problem Set for Kinetics, Problem 16, Prepared for SACHE. New York: American
Institute of Chemical Engineers.
CCPS 1995. Guidelines for Process Safety Fundamentals in General Plant Operations. New York:
American Institute of Chemical Engineers.
Benuzzi, A., and Zaldivar, J. M. (eds.). 1991. Safety of Chemical Batch Reactors and Storage Tanks.
Kluwer Academic Publishers, Norwell, MA.
Burton, J. and Rogers, R. 1996. Chemical Reaction Hazards, 2ded. Institution of Chemical Engineers, London, UK.
DIERS 1994. Risk Considerations for Runaway Reactions. Design Institute of Emergency Relief
Systems, New York: American Institute of Chemical Engineers.
Gygax, R. W. 1988. Chemical Reaction Engineering for Safety. Chemical Engineering Science.
43(8), 1759-1771.
Gygax, R. W. 1990. Scaleup principles for Assessing Thermal Runaway Risks. Chemical Engineering Progress, February 1990, 53-60.
International Symposium on Runaway Reactions. 1989. Cooling Capacities of Stirred Vessel,
Unstirred Container, Insulated Storage Tank, Uninsulated 1 cu meter Silo, Uninsulated 25 cu
meter Silo: 65. Sponsored by CCPS, IChemE and AIChE, Cambridge, MA.
Maddison, N., and Rogers, R. 1.1994. Chemical Runaways: Incidents and Their Causes. Chemical Technology Europe, November/December, 28-31.
Noronha, J., Merry, J., Reid, W., and SchifFhauser, E. 1982. Deflagration Pressure Containment
for Vessel Safety Design, Plant/Operations Progress, 1(1), 1-6.
Noronha, J., and Torres, A. 1990. Runaway Risk Approach Addressing Many Issues-Matching the
Potential Consequences with Risk Reduction Methods, Proceedings of the 24th Loss Prevention
Symposium, AIChE National Meeting, San Diego, CA.
Wier, E., Gravenstine, G. and Hoppe, T. 1986. Thermal RunawaysProblems with Agitatioa
Loss Prevention Symposium. Paper 830: 142.

TABLE 4. FAILURE SCENARIOS FOR REACTORS

Potential Design Solutions

No.

Operational
Deviations

Failure Scenarios

Inherently Safer/Passive

Active

Procedural

Overpressure
(Batch, Semibatch, and Plug
Flow Reactors)

Overcharge of
catalyst resulting
in runaway
reaction

Use dedicated catalyst

charge tank sized to hold
only the amount of catalyst
needed
Vessel design
accommodating maximum
expected pressure
Use different type of
reactor

Emergency relief device

Pressure or temperature sensors
actuating bottom discharge valve
to drop batch into a dump tank
with diluent, poison or shortstopping agent, or to an
emergency containment area
Automatic addition of diluent,
poison, or short-stopping agent
directly to reactor
Limit quantity of catalyst added
by flow totalizer

Procedural controls on the

amount or concentration of
catalyst to be added
Manual activation of bottom
discharge valve to drop batch into
dump tank with diluent, poison,
or short-stopping agent, or to an
emergency containment area
Manual addition of diluent,
poison, or short-stopping agent
directly to reactor
Intermediate location for preweighed catalyst charges

Overpressure
(Batch and
Semi-batch
Reactors)

Addition of a
reactant too
rapidly resulting in
runaway reaction

Limit delivery capacity of

feed system to within safe
feed rate limitations (e.g.,
screw feeder for solids or
flow orifice for liquids)
Vessel design
accommodating maximum
expected pressure
Select feed system pressure
characteristic so that feed
cannot continue at reactor
overpressure
Use different type of
reactor

Temperature or pressure sensor

interlocked to a shutoff valve in
the feed line
Emergency relief device
Pressure or temperature sensors
actuating bottom discharge valve
to drop batch into a dump tank
with diluent, poison or shortstopping agent, or to an
emergency containment area
Automatic addition of diluent,
poison, or short-stopping agent
directly to reactor
Highflowshutdown alarm and
interlock

Manual addition of diluent,

poison, or short-stopping agent
directly to reactor
Manual shutdown on high flow
alarm
Manual activation of bottom
discharge valve to drop batch
into dump tank with diluent,
poison, or short-stopping agent,
or to an emergency containment
area
Procedural controls on
concentration of reactants

Potential Design Solutions

No.
3

Operational
Deviations
Overpressure
(Batch, Semibatch and
CSTR
Reactors)

Failure Scenarios

Inherently Safer/Passive

Active

Procedural

Loss of agitation
resulting in runaway reaction or
hot bearing/seals
causing ignition of
flammables in
vapor space

Vessel design
accommodating maximum
expected pressure

Agitator power consumption or

rotation indication interlocked
to cutoff feed of reactants or
catalyst or activate emergency
cooling

Operators to visually check

mechanical sealfluidon regular
basis
In-vessel agitation (velocity)
sensor with alarm

Uninterrupted power supply

backup to motor

Mechanical seal fluid reservoir

low level sensor with alarm

Emergency relief device

Speed or vibration sensor with

alarm

Use different type of

reactor (plug flow)
Alternative agitation
methods (e.g., external
circulation eliminates shaft
seal as a source of ignition
in vapor space)

Pressure or temperature sensors

actuating bottom discharge valve
to drop batch into a dump tank
with diluent, poison, or shortstopping agent, or to an
emergency containment area
Inerting of vapor space

Manual activation of bottom

discharge valve to drop batch
into dump tank with diluent,
poison, or short-stopping agent,
or to an emergency containment
area

Provide nitrogen buffer zone

around seal using enclosure
around seal

Manual activation of inert gas

sparging of reactor liquid to
effect mixing

Automatic agitator trip on low

agitation (velocity) sensor, low
sealfluid,or low shaft speed

Overpressure
(Batch and
Semi -batch
Reactors)

Overcharge or
overfeed of reactant resulting in
runaway reaction

Use of dedicated reactant

charge tank sized only to
hold amount of reactant
needed
Vessel design
accommodating maximum
expected pressure
Use of continuous reactor

Emergency relief device

Reactant feed charge interlocked
via feed totalizer or weight
comparison in charge tank
Pressure or temperature sensors
actuating bottom discharge valve
to drop batch into a dump tank
with diluent, poison, or shortstopping agent, or to an
emergency containment area
Automatic addition of diluent,
poison, or short-stopping agent
directly to reactor

Manual feed charge shutdown

via indication from feed totalizer
or weight comparison in charge
tank
Manual activation of bottom
discharge valve to drop batch
into dump tank with diluent,
poison, or short-stopping agent,
or to an emergency containment
area

5
(T)

Overpressure

Addition of
incorrect reactant
resulting in
runaway reaction

Use of dedicated feed tank

and reactor for production
of one product
Vessel design
accommodating maximum
expected pressure
Elimination of crossconnections
Use of dedicated hoses and
incompatible couplings for
reactants where hose
connections are used

Emergency relief device

Automatic feed shutdown based
on detection of unexpected
reaction progress (i.e., abnormal
heat balance)

Procedures to shutdown feed

based on indication of
unexpected reaction progress
Procedure for double checking
reactant identification and
quality
Dedicated storage areas/
unloading facilities for reactants

Potential Design Solutions

No.
6

Operational
Deviations
Overpressure

Failure Scenarios
Loss of cooling
resulting in
runaway reaction

Inherently Safer/Passive

Active

Procedural

Vessel design
accommodating maximum
expected pressure
Use of large inventory of
naturally circulating,
boiling coolant to
accommodate exotherm

Low coolantflowor pressure or

high reactor temperature to
actuate secondary cooling
medium via separate supply line
(e.g., city water or fire water)
Automatic isolation of feed on
detection of loss of cooling
Emergency relief device
Pressure or temperature sensors
actuating bottom discharge valve
to drop batch into a dump tank
with diluent, poison, or shortstopping agent, or to an
emergency containment area
(This approach may not be
effective for systems such as
polymerization reactions where
there is a significant increase in
viscosity.)
Automatic addition of diluent,
poison, or short-stopping agent
directly to reactor

Manual activation of secondary

cooling system
Manual activation of bottom
discharge valve to drop batch
into dump tank with diluent,
poison, or short-stopping agent,
or to an emergency containment
area
Manual addition of diluent,
poison, or short-stopping agent
directly to reactor

Overpressure

Overactive and/or
wrong catalyst
results in runaway
reaction

Vessel design
accommodating maximum
expected pressure
Use prediluted catalyst

Emergency relief device

Automatic isolation of catalyst
and/or feed based on detection
of unexpected reaction rate (i.e.,
abnormal heat balance)
Pressure or temperature sensors
actuating bottom discharge valve
to drop batch into dump tank
with diluent, poison, or shortstopping agent, or to an
emergency containment area

Passivate fresh catalyst prior to

use
Procedures for testing and
verification of catalyst activity
and identification
Manual isolation of catalyst
and/or feed based on detection
of unexpected reaction rate
Manual addition of diluent,
poison, or short-stopping agent
directly to reactor

8
(T)

Overpressure

Inactive and/or
wrong catalyst
leading to delayed
runaway reaction
in reactor or
downstream vessel

Reactor or downstream
vessel design
accommodating maximum
expected pressure

Emergency relief device

Automatic isolation of catalyst
and/or feed based on detection
of unexpected reaction rate (i.e.,
abnormal heat balance)

Procedures for testing and

verification of catalyst activity
and identification
Manual isolation of catalyst
and/or feed based on detection
of unexpected reaction rate

Overpressure

Underfeed of
diluent resulting
in insufficient heat
sink

Vessel design
accommodating maximum
expected pressure

Automatic feed isolation on

detection of low diluent addition
Automatic isolation of feed
based on detection of
unexpected reaction rate (i.e.,
abnormal heat balance)

Manual feed isolation on

detection of low diluent addition
Manual isolation of feed based
on detection of unexpected heat
balance

Potential Design Solutions

No.

Operational
Deviations

Failure Scenarios

Inherently Safer/Passive

Active

Procedural

10

Overpressure
(Batch & Semibatch)

Reactants added in
incorrect order

Vessel design
accommodating maximum
expected pressure

Sequence control via

programmable logic controller
Interlock shutdown of reactant
addition based on detection of
mis-sequencing
Automatic isolation of feed
based on detection of
unexpected reaction progress
(i.e, abnormal heat balance)

Manual isolation of feed based

on detection of unexpected
reaction progress
Manual isolation of feed based
on indication of mis-sequencing

11

Overpressure

External fire
initiates runaway
reaction

Fireproof insulation
(reduced heat input)
Slope-away grading under
reactor to remote spill
collection
Locate reactor outside of
fire affected zone

Automatically activated fixed fire

protection - water spray (deluge)
and/or foam systems
Emergency relief device
Automatic reactor dump to
dump tank with diluent, poison,
or short stopping agent
Automatic injection of diluent
poison or short-stopping agent
into reactor

Manual activation of fixed fire

protection
Manual reactor dump to dump
tank with diluent, poison or
short-stopping agent
Manual injection of diluent,
poison or short-stopping agent
into reactor

12
(T)

Overpressure

Feed of monomer
emulsion breaks
into a separate oil
phase on top of a
water phase while
being fed to the
reactor leading to
runaway reaction

Vessel design
accommodating the
maximum pressure arising
from run-away reaction of
bulk (non-emulsified)
monomer phase
Static mixer ahead of
reactor

Emergency relief device

Automatic feed shut-off or
dumping on change of heat
balance

Operator samples the monomer

emulsion feed and observes that
sample is stable without agitation for a predetermined length
of time before feed is begun
Manual feed shut-off or
dumping on change of heat
balance

 Emergency relief device

Automatic depressuring
Automatic injection of inhibitor
Automatic isolation of heating
media or feed
Emergency cooling

13

Overpressure

High reactor temperature due to

failure of heating
system initiates
runaway reaction

Limit temperature of
heating media
Vessel design
accommodating maximum
expected pressure

14

High Temperature (Continuous Packed Bed

or Packed Tube
Reactors)

Hot spot develops

in catalyst exposing vessel wall to
high temperature
and potential
mechanical failure
or initiation of
runaway reaction

Use alternative reactor

High temperature sensors
design (e.g., fluid bed)
interlocked to shut down reactor
Use multiple small diameter Automatic depressuring based
beds to reduce
on detection of high bed
temperatures or low flow
maldistribution
Minimize reactor head
Automatic introduction of
space volume to reduce
quenchfluidinto packed bed or
residence time (partial
tubes based on detection of high
local temperature
oxidation reactors) and
mitigate autoignition

Manual dumping of reactor

contents
Manual injection of inhibitor
Manual isolation of heating
media or feed

Manual shutdown of reactor

upon detection of high
temperature in bed
Monitoring of exterior wall
temperature with infrared
optical detection system
Manual depressuring based on
detection of high bed
temperature
Manual introduction of quench
fluid into packed bed or tubes
on detection of high local
temperature
Procedures for packing tubes to
ensure uniformity of catalyst
filling

Potential Design Solutions

No.

Operational
Deviations

Failure Scenarios

Inherently Safer/Passive

Active

Procedural

15

Reverse Flow

Reactor contents
inadvertently
admitted to
upstream feed
vessel resulting in
runaway reaction

Vessel design
accommodating maximum
expected pressure
Provide positive
displacement feed pump
instead of centrifugal pump
Elevate feed vessel above
reactor with emergency
relief device on reactor set
below feed vessel minimum
operating pressure

Provide check valve(s) in feed

line
Automatic closure of isolation
valve (s) in feed line on detection
of low or noflow,or reverse
pressure differential in feed line
Emergency relief device on feed
vessel or feed line

Manual closure of isolation

valve(s) in feed line on detection
of low or noflowin feed line

16

Wrong
Composition

Contamination
from leakage of
heating/cooling
media or introduction of other foreign substances
(e.g., corrosion)

Use heat transfer fluid that

does not react with process
fluid
Vessel design
accommodating maximum
expected pressure
Use jacket rather than
internal coil for heat
transfer
Upgrade metallurgy or use
resistant liner
Heat transfer loop pressure
lower than process pressure

Emergency relief device

Periodic testing of process fluid

for contamination
Procedures for leak/pressure
testing of jacket, coil or heat
exchanger prior to operation
Procedure for testing liner with
continuity meter

17

Wrong
Composition

Incomplete reaction due to insufficient residence

time, low temperature, etc. leading to unexpected
reaction in subsequent processing
steps (in reactor or
downstream
vessel)

Reactor or downstream
vessel design accommodating maximum
expected pressure

Automatic feed isolation based

on detection of low reactor
temperature
Automatic feed isolation based
on continuous on-line reactor
composition monitoring

Manual feed isolation based on

detection of low reactor
temperature
Manual feed isolation based on
continuous on-line reactor
composition monitoring or
"grab" sampling