239

DESIGN AND OPERATION OF EMERGENCY CHLORINE ABSORPTION SYSTEMS

THOMAS F. O'BRIEN
Catalytic Division
United Engineers and Constructors Inc.
Philadelphia, USA.
and IAN F. WHITE
Badger Catalytic Ltd.
New Malden, Surrey, UK.

ABSTRACT

It is inevitable that during its production and processing, there will be

occasions when chlorine is released from its containing equipment. The
established method of dealing with this released gas is by neutralization
with a caustic 1iquor; most often sodium hydroxide. In this chapter
aspects of the design and operation of the systems used to accomplish this
neutralization are discussed.
The need for care in design and operation is brought out by reference
to statistics which show that a significant proportion of chlorine releases
to the atmosphere involve overloading emergency scrubbers.
Considered in greatest detail, as it represents the majority of
neutralization systems in service world wide, is a single stage scrubbing
device using a discrete batch of circulating aqueous sodium hydroxide. The
protected process is assumed throughout to be a chlorine production plant
or other continuous process utilizing the gas.

INTRODUCTION

In the industrial production of chlorine, it is essential that the operator

prevent the release of dangerous quantities of gas to the atmosphere. What
would otherwise be routine emissions from the process are captured and
converted to useful products or simply destroyed by alkaline
neutralization. Various systems are used to allow routine maintenance to
be done safely, and today there is growing interest in the design of
 240

containment and leak mitigation systems for liquid chlorine storage areas.
The designer and operator must also consider the possibility of accidental
release from the process in an emergency. The usual approach is to provide
seals at appropriate locations in the chlorine processing train and to pipe
any releases from them to an absorber. The absorber can take any of a
number of forms and may also have other functions. In this chapter, we
consider it solely as an emergency device. We shall see that development
of a proper system (where "system" includes the operator) involves much
more than the design of a mass-transfer device.

The simplest system, is based on a single scrubbing device through

which a discrete batch of alkaline material (assumed here to be sodium
hydroxide solution) is circulated. More complex arrangements may sometimes
be found more economical, convenient, or reliable, but this minimum system
can be considered the baseline. It is, in fact, the one most often found
in practice and is exemplified by that described by Patel and Scarfe [1].
Any additions or elaborations must be justified by the improved results
which they may offer. First, we shall consider the characteristics of the
single-stage design.
,STARTS
TO ATMOSPHERE I SPARE r ___ .,

A
~ PUMP II _t>Iol ::l--_-1I><1-__. C.W.
r
I I RETURN
I I
@
L_: $
I I
.Jt-T-:;n..--~<l-_C. w.
\ "" SUPPL Y
I
,
, \ 1\

HIGH TO WASTE
LIQUOR HOLD
.----~---._~-~--TANK

r-----------
I
--, I
EMERGENCY ~ /'IK) .J..EMERGENCY
POWE~ I ~ r®POWER
L.!_.J 1/ 1/ L.L_~

Figure 1. Emergency vent scrubber - Flow scheme

 241

A typical example of a scrubbing system is shown in Fig. 1. Here, the

caustic soda solution is circulated around a packed-bed scrubber. Chlorine
vents and releases are piped to the column below the packing. Chlorine,
from sources under pressure, is introduced below the surface of the liquid
in the sump of the column. That sump serves as the storage chamber for the
liquid. The drawing also shows some of the instruments provided to enhance
safety.

With such a system, however, instrumentation alone will not suffice.

Administrative controls are necessary, and plant operators must remain
constantly aware of the state of their system. One can easily hypothesise
many causes of failure if this is not done.

For example, since there is a finite batch of caustic liquor, only

a limited quantity of chlorine can be destroyed. One of the designer's
tasks is to fix the size of this batch. The operator of the plant then has
the problem of maintaining an adequate supply to the scrubber at all times.
This means that the rate of delivery of caustic soda must always be
adequate; either a low flow rate or a low solution concentration can allow
chlorine to break through.

Low flow can result from pump problems or failures in the delivery
system. A pump may fail electrically or mechanically. Flow to the
scrubber can be reduced by improper operation of valves (including opening
the valve intended for removal of waste liquor) or by failure of the
packing. If a spray system were used instead of a packed bed, the failure
analogous to the last named would be plugging of or damage to some of the
spraying devices.

Low caustic concentrations can result from errors in preparation of

solution or from reduction by exposure to chlorine.

The latter could in the limit be avoided by continuous, once-through

supply of caustic soda. This would in most cases create another problem by
generating large volumes of waste [2]. This also can be intolerable. We
must therefore be able to design and operate systems which meet the
constraints on both sides.
 242

We can also list events which lead to an unusually high demand.

These, like the listed causes of an inadequate caustic supply, act
independently. Anyone event then can lead to a failure of the system.
In the construction of a fault tree in hazard analysis, these events would
propagate through "OR gates".

This is the reason for the particular importance of administrative

controls to the successful operation of a scrubber such as that of Fig.l.
In some of our analyses, thirty or more events are linked to the top of a
fault tree solely through OR gates. Given a release of chlorine from the
process, anyone of these events could therefore cause a breakthrough and
allow chlorine to escape to the atmosphere.

This aspect must be partly responsible for the large number of

releases from scrubber systems. A recent ten-year survey by The Chlorine
Institute, for example, showed that 21% of the releases reported by North
American producers were from emergency scrubbers [3]. An earlier study by
EuroChlor [4] showed that 14% of the "incidents" reported in the
manufacture, distribution, and handling of chlorine involved the
overloading of emergency scrubbers.

BASICS

Chemistry
The essential reaction is the destruction of chlorine, with formation of
hypochlorite:

C1 2 + 2 NaOH ---> NaCl + NaOCl + H20 (1)

With proper control, this can be practised commercially at high

efficiency to produce bleach solutions. The basic problem is the
instability of sodium hypochlorite and the need to remove the exothermic
heat of reaction (1463 kJ/kg of chlorine gas).

In emergency operation, the required control may be absent, allowing

other reactions to become important. One of these is disproportionation
 243

of hypochlorite to chloride and chlorate:

3 NaOCl ---> 2 NaCl + NaC10 3 (2)

Another is the decomposition of sodium hypochlorite, which is

favoured by high temperature and by the presence of certain metal ions:

NaOCl ---> NaCl + ~ 02 (3)

For comparison with reaction (1), the complete reactions for the latter two
cases can be written:

3 C1 2 + 6 NaOH ---> 5 NaCl + NaC10 3 + 3 H20 (4)

and
(5)

Heats of reaction (at infinite dilution) become 2002 and 2272 kJ/kg,
respectively.

Mass transfer
This process presents a complex and interesting problem in mass transfer.
Space does not permit a thorough description. Several points should be
made here, however, which we have found to be important in our development
of our design techniques.

1) Liquid-phase mass-transfer coefficients are influenced by

reaction of an absorbate. One of the first studies which
dealt with this phenomenon was the work of Vivian and Whitney
on the absorption of chlorine in water [5]. They explained
apparent inconsistencies in data by recognising that the
equilibrium partial pressure of chlorine is determined by the
liquid-phase concentration of molecular chlorine - not by the
total amount of chlorine dissolved. Development of the theory
of gas-l iquid reactions has now shown that in the case of
rapid consecutive reactions there may be either one or two
reaction planes established in the liquid film. In our case,
the two reactions can be taken to be:
 244

(6)
and
HOCl + OW <--> ocr + H20 (7)

The work of Hikita et al. [6] showed that, with reaction (6)
even more favourable than reaction (7), there will be two
planes of reaction. The mathematics of the system are
affected by this conclusion, and predicted mass-transfer
coefficients are somewhat different from those given by a
single-plane model.

2) In a liquid-film controlled absorption process, the above

considerations are important. Absorption of chlorine from
concentrated gases is unquestionably such a process. With
weak gases, however, the gas film may become controlling.
Makhneva and Gertsen [7] have shown this to occur and have
suggested a criterion to use to identify the regime. Weak
gases are found in some scrubbing applications (e.g., tail gas
destruction), and at the top of a very efficient strong-gas
scrubber.

3) Temperature effects are very important. These are discussed

separately in the next section.

Effects of temperature
Because of the heats of reaction and of condensation of water, the
temperature of the caustic soda solution will increase as it passes through
a scrubber. In those systems without coolers, the temperature will
continue to increase until the flow of chlorine is cut off or the caustic
is consumed. Higher temperatures wi 11 have severa 1 effects on the process:

1. the physical solubility of the chlorine will be lower,

reducing the driving force for diffusion.
2. the vapour pressure of any given solution will be higher,
increasing the concentration of water in the gas phase.
3. in the limit, the probability of boiling or of sudden
decomposition of hypochlorite will be increased.
 245

The first effect is illustrated by Fig. 2. The curve is the result

of our calculations. The one point highlighted is that given by Hikita et
aT. [6]. Agreement is excellent. The second effect reduces the partial
pressure of chlorine and again may impede mass transfer. This was pointed
out by Updike [8], who showed calculated examples of the mole fraction of
chlorine along the length of a column. When the temperature remains low,
the chlorine concentration actually increases as the gas rises. This is
due to the condensation of water and can be very useful in preventing the
onset of gas-phase control .

.........
....
Q) 80
Q)
..c
a.. 70

-
<II
0
E 60
c
cP
~ 50

" <II
0
E
40

30
C')
E
'-" 20
~
:.0 10
:::l
0
(/) 0
20 40 60 80
Temperature ("C)

Figure 2. Solubility of chlorine in water

In a typical design the temperature of the caustic can rise by about

30 deg.C as it passes through the scrubber. If the design event is a
twenty-minute release of cell gas, the batch of caustic will be turned over
nearly three times. The indicated 90 deg.C rise is clearly excessive. It
will be prevented by a change in the process. First, the condensation of
water will stop. Finally, the solution actually will come to a boil, or
the efficiency of absorption of chlorine will drop off. The high
temperature coincides with a low concentration of sodium hydroxide in the
solution. The latter also leads to a deterioration in mass-transfer
 246

capabil ity, because the enhancement of the mass-transfer coefficient by the

reaction is smaller.

While it is possible to install and operate a scrubber without

cooling, many units will have an exchanger on the caustic recirculating
line. Fig. 1 is an example. Other techniques also are used. For example,
an auxiliary supply of solution, besides offering a safety margin, can help
to absorb some of the heat of reaction. In any event, the heat effects and
the possibility of developing excessive temperatures are two more issues
which must be faced by the designer.

Best practice may be to maintain a temperature low enough to

discourage the side reactions discussed earlier. EuroChlor [9] recommends
a maximum of 55°C. While The Chlorine Institute makes no official
recommendation, participants in one of its symposia [1] named the same
temperature as a desirable limit.

Effects of gas composition

Other components in the gas will influence the composition of the scrubbing
liquor and of the final vent. Carbon dioxide will be absorbed while
hydrogen and the components of air will not. The calculations and plots
found in later sections of this chapter apparently do not recognise the
presence of carbon dioxide. It is easily accommodated in final design.
In the generalised approach we present here, it can simply be equated, mole
for mole, with chlorine.

If a unit is used to scrub ventilation air or a gas with a high

carbon dioxide concentrat ion, the 1iquor wi 11 eventually conta in high
concentrations of carbonate. To avoid precipitation, the starting liquor
then must be more dilute. The recommended strength for pure caustic of
about 20% sodium hydroxide would be reduced to something with a higher
freezing point. Normal diaphragm-cell liquor would also require dilution.

When used to scrub air, cont i nuous exposure of the 1i quor can
seriously deplete its capacity for chlorine. A system based on diversion
of air to the scrubber only when chlorine is detected is worth
 247

consideration. The alternative is a more elaborate design or extra

precautions against depletion of the caustic.

Concentrations of hydrogen and oxygen in the gas will increase in the

scrubber. In many cases, the effluent gas can be in the explosive range.
The designer must also consider this problem and will often choose to add
a diluent gas to the scrubber.

EQUIPMENT AND SYSTEMS

Mass-transfer devices
Any of the common mass-transfer devices might be considered for the
absorption of chlorine. In addition, high-pressure gases often are simply
sparged into a pool of caustic solution (usually in a vertical tank). The
two types most frequently found in producers' plants are packed beds and
sprays. These are treated briefly below.

Packed Beds: The diameter of a column must be great enough to allow

the gas to pass through without excessive pressure loss. In a packed bed,
the gas flow rate interacts with the liquid flow rate and the type and size
of packing.

The familiar correlating plot is redrawn for a typical cell gas and
20% caustic soda solution in Fig. 3.

In an emergency scrubber exposed to a release of cell gas, there will

be sudden huge changes along the column in gas flow and in the slope of the
gas pressure profile. There are accompanying changes in liquid holdup.
In the absence of a flow of gas, this holdup is determined by the rate of
liquid circulation and the characteristics of the packing. When the gas
flow begins, the steady state is upset. The system will adjust, and the
effects will be most pronounced at the bottom of the column.

A conservative practice is to design the column to operate below or

in the lower range of the loading zone. The loading zone is that region
of operation in which liquid begins to accumulate on the packing and its
 248

holdup to increase. This reduces the area available for flow of gas and
so increases its pressure drop. Below this zone or at its lower limit, the
sudden introduction of a large flow of gas will have relatively little
effect on the dynamics of liquid flow, and the transient will be less
pronounced. At higher velocities, with greater changes and more severe
transients, there would be a greater risk of instability.

3.5

2.5
,......
a.
u...
.e" 2
'-J
0)
0
1.5

o 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2

log(L/G)

Figure 3. Correlation of packed chlorine scrubber flooding points.

Design points for some of the systems with which we have worked are
marked on Fig. 3. EuroChlor [9] recommends a gas velocity equal to about
60% of flooding. Such a line is also superimposed on the plot.

Spray Systems: Spray columns are often used as alternatives to

packed beds. They can have the advantage of a low pressure drop when cells
are operated at pressures near or below atmospheric. The protective seals
then are often set at a few millibars. The remote possibility of equipment
pluggage does not exist, as it does with a packed bed. Even when a
demisting pad is added, development of unsafe pressures can be avoided.
 249

Packed-bed systems often make use of an exhaust blower. This helps

to offset the pressure drop inherent in the bed, but it also adds another
mechanical component to the system and another failure event to the fault
tree. This is not necessary in a spray system (and perhaps not when
membrane cells are used).

Spray columns on the other hand present a few new problems. While
their mass-transfer capacity can be increased up to a point by producing
finer sprays, there are still deficiencies. A finer spray requires the
input of more energy and increases the probability of entrainment from the
column. The action of a spray always produces backmixing and reduces the
countercurrent nature of the process. While a spray column may have the
capacity for absorption of large quantities of chlorine, a problem can
remain with the residual concentration in the scrubbed gas. Because of the
backmixing, an increase in the volume of a spray chamber does not
necessarily give an equivalent increase in mass-transfer efficiency.
Typical illustrations given by Sherwood and Pigford [10] suggest that
extending the length of a column by the ratio L increases the number of
gas-phase transfer units only by LO. 4 _Lo. 5 • Columns with a practical depth
of packing gave 1.5 to 3 or more times as many transfer units as spray
columns of equal volume.

Without special precautions, then, we can expect more escape of small

quantities of chlorine from a spray column than from a long packed bed.

This consideration should not be allowed to outweigh the advantages

of sprays when they are otherwise the proper choice. One should keep in
mind the fundamental purpose of an emergency scrubber, which is to provide
a highly reliable means of prevention of objectionable releases of
chlorine. While each reduction in effluent concentration is welcome, even
with a system in very infrequent use, the ultimate reliability should not
be compromised for this lesser goal.

Other System Requirements

Space does not permit full development of the details of scrubber design.
As mentioned above, it is equally important that the rest of the system be
properly designed. When we consider an installation which continuously
 250

recycles a fixed batch of scrubbing liquor around an absorber, the size of

the batch and the rate of circulation become of paramount importance.
Usually, a major criterion is the ability of the scrubber to cope with a
release of the full process flow of chlorine for a given period of time.
This fixes the amount of sodium hydroxide which must be available for
reaction. Given the concentrations of sodium hydroxide in the starting
solution and in that defined as "exhausted" solution, we can size the batch
and the circulating system. While a final design must deal with the
specifics of the plant under consideration, it is useful also to have a
generalized method. This gives the designer an intuitive feel for his
task, allows rapid preliminary estimates, and assures some consistency
among projects.

For rapid estimation, we have used the curves shown in Figs. 4 and
5. Consider a plant producing P tonnes a day of chlorine in which a
scrubber is to be made ~apable of absorbing a release of cell gas for T
minutes. A typical cell gas composition is assumed, with all its water
condensing in the scrubber.

1.5
1.4
1.3
:;:: 80
:::J
:r 70
o
o
z 60

0.9 ~ 50
E
0.8 x 40
o
~

o 246 8 o 2 468
Final NoOH Concentration (Wt.%) Final NoOH Concentration (Wt %)

Figure 4. Figure 5.
Caustic batch sizing parameters. Caustic utilization efficiency
 251

The amount of chlorine to be absorbed is PT/1.44 (kg). The

corresponding quantity of sodium hydroxide required in a batch is:

x = PT.f(C) (8)
where
(9)

Values of this function in which the starting weight fraction of

sodium hydroxide is C1 and the final value C2 are shown in Fig. 4.

In order to be able to absorb the last traces of chlorine even at the

end of an incident, one must ensure that the rate of circulation of caustic
soda is adequate. This means that, at the design flow rate of chlorine,
the instantaneous rate of supply to the top of the column must be at least
stoichiometrically equivalent even at the minimum concentration C2 • The
required rate, in kg/h of solution, is about 47 P/C 2• A small safety
factor makes the constant 50. With C2 = 0.05 in such a case, the minimum
circulation rate in te/h of solution is equal to the rate of production of
chlorine in te/day. This is easily remembered and easily converted to
other values of C2 •

When a spent batch of caustic liquor is removed from a scrubber, the

unconverted portion is often wasted. While this may be a secondary
consideration in operation of a safety system, the designer should consider
the environmental impact and make some provision to reduce the amount of
effluent generated. The maximum amount of sodium hydroxide which can be
consumed in a given batch is equivalent to the design loading of chlorine,
PT/1.44 (plus any safety factor). The amount to be charged is given by Eq.
(8). The maximum fractional utilization of sodium hydroxide is the ratio
of these two quantities:

U = 0.7836/f(C) (10)

The achievable efficiency in caustic soda use is therefore fixed by

the starting and ending concentrations of the scrubbing solution. For a
plant of a given capacity, the minimum circulation rate is fixed by C2
only. The batch size also depends on the duration of chlorine release
 252

which is to be designed for. We can now summarize the relationships

between dependent and independent variables:

Depends on
Variable Plant Length of Initial Final
Size Release Cone. Cone.
Batch She X X X X
Circulation Rate X X
Caustic Utilization X X

Of these, only the size of the batch depends on the length of the
release. One might therefore consider simply increasing the size of the
caustic batch in order to be able to cope with a more substantial release
of chlorine. At this point, however, another decision is required. While
a caustic charge may last for, say, fifteen minutes, one must also decide
what to do after a five-minute release. Is the remaining ten-minute
capacity sufficient, or should the batch be replaced after having consumed
only a small fraction of the caustic soda? This is a matter of operating
pol icy.

If the caustic batch were indeed made larger (say, thirty minutes
instead of fifteen), the disposal problem might be aggravated. After the
hypothetical five-minute release, the safety margin again may be deemed too
small or at least no longer to provide the intended improvement. Caustic
utilization would be very low, and nothing would have been accomplished
with the larger batch. If the batch size is increased with the intent of
allowing a minor release without dropping below the minimum acceptable
caustic inventory, however, that small release can be accepted without
violating the minimum or disposing of the batch prematurely.

We might then consider two criteria for design and operation:

1. a mi nimum inventory of caust i c soda wh i ch wou 1d call for

replacement of the liquor
2. provision of some multiple of this minimum amount in order to
improve the utilization of sodium hydroxiae.
 253

The maximum achievable utilization as given by Eq. (10) is not

affected. What does change is the degree of approach to this ideal. If
we were to supply twice the minimum amount of caustic soda, we would be
sure to achieve at least 50% of the maximum efficiency. This would be at
the expense of larger storage volumes.

AUGMENTED SYSTEMS

Improved results may be possible with more complex systems. These will be
more expensive, and the designer must take care that added complexity does
not reduce reliability.

The simplest way conceptually to overcome any perceived deficiencies

of a single-stage design is to add a second column. Fig. 6 is a sketch of
a possible arrangement. Here, the caustic would cascade through the two
scrubbing stages. The existence of the second column would add some
security, and the cascaded arrangement would allow better caustic
utilization.

VENT GAS

WASTE L10UOR FRESH NoOH

,-----d
•

Figure 6. Two column vent scrubber

Fig. 7 keeps the two-stage arrangement within a single shell.

 254

While the upper section could be the same in design as the lower section,
the sketch suggests a tray column mounted above a packed bed. This could
allow a lower inventory and flow rate of caustic in the second stage.
Operation would be somewhat cheaper and simpler, but the security
associated with a greater inventory of caustic would be lacking.

VENT VENT
GAS FRESH GAS
NaOH
FRESH
WASTE WASTE NaOH
LIOUOR LIOUOR

Figure 7. Figure 8.
Two-stage scrubbing column Scrubber with auxiliary caustic supply

Fig. 8 is not a true two-stage operation. An extra supply of caustic

is available, here by way of a head tank. This provides the extra supply
without the need for continuous pumping, but there are more controls and
an uncertain mass-transfer situation when the caustic is released.

Finally, Fig. 9 shows an emergency scrubber in parallel with a bleach

production operation. All the design considerations which pertain to a
single-stage scrubber hold here. Mass-transfer capacity must be adequate
in each column, and excessive temperatures must be avoided.
 255

VENT GAS

U
FRESH
NoOH I SPENT
LIOU R
FRESH NoOH (PRODUCT)

Figure 9. Combined emergency vent scrubber/hypochlorite production.

REFERENCES

1. Patel, H.M. and Scarfe, T.S., Safety aspects of Niachlor membrane

cell plant. Proceedings, 31st Chlorine Plant Operations Seminar, New
Orleans, March 1988.

2. The Chlorine Institute, Minutes, 2nd Chlorine Plant Operations

Workshop, Washington, March 1987.

3. Chlorine Institute Pamphlet 86, Recommendations to Chlor-Alkali

Manufacturing Facilities for the Prevention of Chlorine Releases,
edition 1, October 1990.

4. Papp, R., Chlorine safety and handling in the European situation.

In Modern Chlor-Alkali Technology vo1.2, ed.C. Jackson, Ellis
Horwood Limited, Chichester, 1983, pp. 376-85.
 256

5. Vivian, J.E. and Whitney, R.P., Absorption of chlorine in water.

Chern. Eng. Progr., 1947, 43, 691.

6. Hikita, H., Asai, S., and Takatsuka, T., Absorption of chlorine.

Chern. Eng. J., 1973, ,2, 77.

7. Makhneva, T.A. and Gertsen, P.P., Absorption of chlorine at low

concentrations from gases by alkaline absorbents. Zh. Prik. Khim.,
1970, 43, No.4, 766.

8. Updike, L.J., Emergency vent scrubbers - design considerations.

5th Chlorine Plant Operations Workshop, Houston, March 1990.

9. EuroChlor pamphlet, GEST 76/52, Eguipment for the Treatment of

Gaseous Effluents containing Chlorine, 9th Edition, October 1986.

10. Sherwood, T.K. and Pigford, R.L. Absorption and Extraction. McGraw-
Hill Book Co., New York, 1952, pp 273-4.