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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.
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.
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
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
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.
Operational
Deviations
Failure Scenarios
Inherently Safer/Passive
Active
Procedural
Overpressure
(Batch, Semibatch, and Plug
Flow Reactors)
Overcharge of
catalyst resulting
in runaway
reaction
Overpressure
(Batch and
Semi-batch
Reactors)
Addition of a
reactant too
rapidly resulting in
runaway reaction
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
Overpressure
(Batch and
Semi -batch
Reactors)
Overcharge or
overfeed of reactant resulting in
runaway reaction
5
(T)
Overpressure
Addition of
incorrect reactant
resulting in
runaway reaction
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
Overpressure
Overactive and/or
wrong catalyst
results in runaway
reaction
Vessel design
accommodating maximum
expected pressure
Use prediluted catalyst
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
Overpressure
Underfeed of
diluent resulting
in insufficient heat
sink
Vessel design
accommodating maximum
expected pressure
Operational
Deviations
Failure Scenarios
Inherently Safer/Passive
Active
Procedural
10
Overpressure
(Batch & Semibatch)
Reactants added in
incorrect order
Vessel design
accommodating maximum
expected pressure
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
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
13
Overpressure
Limit temperature of
heating media
Vessel design
accommodating maximum
expected pressure
14
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
16
Wrong
Composition
Contamination
from leakage of
heating/cooling
media or introduction of other foreign substances
(e.g., corrosion)
17
Wrong
Composition
Reactor or downstream
vessel design accommodating maximum
expected pressure