Process Safety and Environmental Protection 8 8 ( 2 0 1 0 ) 9196

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep

Understanding and eliminating pressure uctuations in an

extended chlor-alkali plant due to the size detail of seal
pots: A design correlation

Sazal Kumar Kundu

Global Heavy Chemicals Limited (GHCL), Hasnabad, Keranigonj, Dhaka 1311, Bangladesh

a b s t r a c t

When chlorine lines from a new caustic soda plant were added to chlorine lines from an older plant that used the same
chlorine compression and liquefaction systems, we encountered abnormal pressure uctuations on the chlorine side
of the new plant. These uctuations were being transmitted to the chlorine cycle in the older plant, posing a safety
hazard in both facilities. After checking the pressure control systems, a design correlation for positive-pressure seal
pot was observed and it was found from the inconsistency in the sizes of those equipments in the two plants. The
problem was solved by reducing the diameter of the chlorine pipeline in the positive-pressure seal pot of the new
plant. After implementing this solution, pressure uctuations were fully removed, and satisfactory pressure control
was attained in both plants.
2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Chlorine plant; Pressure control; Chlorine cycle; Pressure seal pot

1. Introduction ing the electrolyte compartments, the gaselectrolyte mixture

The private company Global Heavy Chemicals Limited (GHCL)
mainly produces caustic soda and chlorine at a plant located in
the southern part of Dhaka district in Hasnabad union under
the Keranigonj police station. Keranigonj is on the south bank
of the river Buriganga. This plant produces 35 tons per day
(TPD) of caustic soda. In May 2007 a second caustic soda plant,
having a production capacity of approximately 50% of rst,
was added to the site.
Elemental chlorine, caustic soda, and elemental hydrogen
can be obtained by the electrolytic decomposition of sodium
chloride solutions (brine). There are three processes for doing
so: a mercury cell process, a diaphragm cell process, and a
membrane cell process. The GHCL plants use the membrane
cell process, which is shown schematically in Fig. 1. In this pro-
cess, an ion-selective membrane separates anodic reactions
from cathodic reactions, and the membrane passes sodium
ions and small amounts of water from anode compartment to
cathode compartment (Leather and Minty, 2001; Kundu, 2006).
Hydrogen is produced in the cathode compartment while
chlorine is produced in the anode compartment. After leav-
starts to separate and separation is completed in two sep-
arating units. Hydrogen gas is removed from the caustic
soda solution in a catholyte separator while chlorine gas is
removed from depleted brine in an anolyte separator. The
hydrogen gas pressure measured downstream of the catholyte
separator is called the hydrogen header pressure; the chlorine
gas pressure measured downstream of the anolyte separa-
tor is called the chlorine header pressure. For safe operation of
the membrane cell, a steady differential pressure of hydro-
gen over chlorine is always maintained (Leather and Minty,
2001).
Usually this pressure difference is 200 mmWC. In par-
ticular, under normal operating conditions of 34.35 kA/m2
current densities, the hydrogen header pressure is maintained
at 450 mmWC while the chlorine header pressure is main-
tained at 250 mmWC (Leather and Minty, 2001).
In this paper the following problem is described and ana-
lyzed: when, in May 2007, the second caustic soda plant was
brought online with the rst, the pressure in the chlorine cycle
became difcult to control. In fact, chlorine pressure uctu-
ations would become so large that they posed a hazard to

Correspondence address: Priority Research Centre for Energy, ATC Building, University of Newcastle, Callaghan, NSW 2308, Australia.
Tel.: +61 431184077.
E-mail address: sazal94@yahoo.com.
Received 17 July 2009; Received in revised form 29 November 2009; Accepted 23 December 2009
0957-5820/$ see front matter 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.psep.2009.12.002
92 Process Safety and Environmental Protection 8 8 ( 2 0 1 0 ) 9196

through two chlorine coolers: a primary cooler and secondary

Nomenclature one (#2 and #3 in Fig. 2). The cooled chlorine then passes
through a unit that removes sodium chloride mist (#4 in Fig. 2);
Ag cross-sectional area of chlorine pipeline in the chlorine stream leaving the mist eliminator contains little
positive-pressure seal pot moisture. That chlorine stream branches in two: one connects
Av cross-sectional area of positive-pressure seal to a waste air de-chlorination unit (WAD) and the other con-
pot nects to a chlorine compressor via a chlorine-drying unit (#5
ChWR chilled water return in Fig. 2).
ChWS chilled water supply The WAD unit is actually a sodium hypochlorite plant
CWR cooling water return (Fig. 3). All gas streams containing chlorine (including those
CWS cooling water supply from the cell room, the liquid chlorine storage tanks, the chlo-
Dg diameter of chlorine pipeline connected to the rine compression and liquefaction units, the chlorine lling
seal pot station, and the brine de-chlorination unit) are fed to this chlo-
Dv diameter of positive-pressure seal pot rine neutralization section. Therefore, the WAD unit serves as
Fg force exerted by chlorine gas on the liquid a safety unit for the plant; in addition, it produces sodium
surface of chlorine pipeline portion of positive- hypochlorite, which is an important by-product.
pressure seal pot There are two towers in the WAD unit (see Fig. 3). The
Fv force exerted by chlorine gas on the whole liq- rst tower is primarily a reaction tower in which chlorine is
uid surface of positive-pressure seal pot neutralized with a stream of dilute caustic soda solution (ini-
ID inside diameter tial conc.: 1821 wt%; nal conc.: 22.5 wt%). The other tower
kA/m2 kilo-amps per square meter serves as a safety unit; it also supplies chilled NaOH solutions
mmWC millimeters water column to the tanks of the rst tower. When electrolysis is started,
PW process water chlorine production is low and produced chlorine is trans-
TPD tons per day mitted to the WAD unit. However, once chlorine production
becomes signicant (above 1.0 kA/m2 current density), chlo-
rine is gradually rerouted from the WAD unit to the chlorine
equipment and personnel. Careful testing and analyses of compressor via the chlorine-drying unit.
processes and pressure control systems failed to reveal any The chlorine is dried by contacting with a countercurrent
operational source of the problem. Finally, the problem was ow of 98% sulfuric acid (Krebs Swiss website, 2008). In the
traced to a design inconsistency in the positive-pressure seal GHCL plant, chlorine is dried in a tower (#5 in Fig. 2) that is
pots of the two plants. And a correlation in designing positive- comprised of a packed bed section plus a tunnel-cap tray sec-
pressure seal pot was observed. Below, it is discussed how the tion. After drying, the chlorine rst passes through a sulfuric
problem was identied and how the design fault was corrected acid separator (#6 in Fig. 2), and then it enters a compressor
in an operating environment. (Fig. 4) that is designed to compress chlorine to a pressure
suitable for liquefaction (EKA website, 2008). On leaving the
2. Methods and materials compressor, the chlorine is divided into two main streams.
One compressed chlorine stream is decompressed and
Brine from the anode side of the membrane cell (Fig. 1) is fed transmitted to an HCl plant. The required pressure for feed-
to an anolyte separator (#1 in Fig. 2) that completely removes ing both H2 and Cl2 into the HCl plant is 1700 mmWC, which
chlorine gas. The depleted brine, along with liquid from the is higher than the cell room header pressures. Hence, Cl2 is
chlorinated liquid disposal seal pot (#8 in Fig. 2), is sent to fed to the HCl plant from a point downstream of the chlorine
a brine de-chlorination unit, then a salt saturation unit, and compressor.
nally to a brine purication unit for reuse. The chlorine gas The other compressed chlorine stream is sent to a chlorine
that leaves the anolyte separator is saturated with water vapor liquefaction unit. Liquefaction is accomplished by condensing
and contains some brine mist. This wet chlorine gas passes the compressed chlorine in the presence of vaporizing liquid
freon. The liquid chlorine leaving the condenser ows by grav-
ity into liquid chlorine storage tanks (EKA website, 2008). By
means of air padding, this liquid chlorine can be transferred
from the storage tanks to the liquid chlorine lling station.

3. Analyses

Fig. 1 Membrane cell process to produce sodium
hydroxide, hydrogen, and chlorine.
There are three primary seal pots in the chlorine cycle. The
rst one is a positive-pressure seal pot (#7 in Fig. 2); an
enlarged view is shown in Fig. 5. This seal pot protects the
electrolyzer from unexpected positive-pressures. When unex-
pected positive-pressures occur, this seal pot releases chlorine
gas to the WAD unit. In the GHCL plant, this positive-pressure
seal pot starts working when the chlorine header pressure
rises above 600 mmWC.
The second is a vacuumpressure seal pot (#9 in Fig. 2);
an enlarged view is shown in Fig. 6. This seal pot protects
the electrolyzer from unexpected vacuum pressures. When
 Process Safety and Environmental Protection 8 8 ( 2 0 1 0 ) 9196 93

Fig. 2 Chlorine cycle before union of chlorine streams (plant 1/plant 2).

unexpected vacuum pressures occur, this seal pot takes air
from the environment and sends it to the electrolyzer. In
the GHCL plant, the vacuumpressure seal pot starts working
when the chlorine header pressure unexpectedly falls below
250 mmWC.
The third is a chlorinated liquid disposal seal pot (#8 in
Fig. 2); an enlarged view is shown in Fig. 7. This seal pot
receives chlorinated liquid from the primary chlorine cooler,
the secondary chlorine cooler, and the mist eliminator and
sends the combined liquids to the anolyte tank.

Fig. 3 Waste air de-chlorination unit.

94 Process Safety and Environmental Protection 8 8 ( 2 0 1 0 ) 9196

Fig. 4 Chlorine cycle from union of chlorine streams of both plants.

Fig. 7 Chlorinated liquid disposal seal pot.

Fig. 5 Positive-pressure seal pot before the modication.

checked; no problem was found. Therefore, the possibilities

Although the primary purposes of the rst two seal pots are
of design aws were explored: the dimensions of all equip-
to protect the electrolyzer and the purpose of the third is to
ment in the pressure control systems, including seal pots,
dispose of chlorinated liquid, all three strongly affect the pres-
were checked. An inconsistency was found in the sizes of the
sure in the chlorine cycle. Those effects became detrimental
positive-pressure seal pots in the two plants. The data on the
when the second caustic soda plant was initially started up
positive-pressure seal pots of both plants were as follows:
in May 2007. In the second plant, the normal operating chlo-
rine header pressure is 250 mmWC; however, that can vary
between 700 mmWC and 220 mmWC. These variations were Dv1 = 600 mm
adversely affecting the pressure in the chlorine cycle of the Dv2 = 450 mm
rst plant. Dg = 101.6 mm
When the unacceptable pressure variations were rst Dw = 101.6 mm
encountered, all possible operational sources of the problem,
including related control valves, pipelines, and software, were Here Dv1 is the inside diameter of the positive-pressure seal
pot in plant 1, Dv2 is the same for plant 2, Dg is the inside
diameter of the chlorine pipeline into the seal pot (same in
both plants), and Dw is the inside diameter of the WAD line
leaving the seal pot (also the same in both plants), see Fig. 5.
From these data, we nd
   600 2
Dv1
For plant 1, = = 34.9 (1)
Dg 101.6

 2  450 2
Dv2
For plant 2, = = 19.6 (2)
Dg 101.6

Note in Fig. 5 that the length of the submerged por-

tion of the chlorine pipeline is 600 mmWC, so the seal pot
starts evacuating when the chlorine header pressure exceeds
600 mmWC. In (1) and (2), the important quantities are the
Fig. 6 Vacuumpressure seal pot. squares of the diameters because the cross-sectional area is
 Process Safety and Environmental Protection 8 8 ( 2 0 1 0 ) 9196
Fig. 8 Fluctuations in chlorine header pressure at plant 2
before the modication (data source for this plot: DCS,
GHCL, 28 May 2007).
Fig. 9 Positive-pressure seal pot after the modication.
proportional to the applied force:
Dv 2 Av PAv Fv
= = =
Dg 2 Ag PAg Fg
Here Fv is the force exerted by chlorine gas on the whole liquid
surface of positive-pressure seal pot and Fg is the force exerted
by chlorine gas on the liquid surface of chlorine pipeline por-
tion of positive-pressure seal pot.
Therefore, when the chlorine header pressure exceeds
600 mmWC, the ratio of the square of the diameters (Dv 2 /Dg 2 )
effectively amplies the force exerted by the chlorine gas on
the liquid in the seal pot. However, since the ratio of Dv 2 /Dg 2
for plant 2 was smaller than that for plant 1, the force ampli-
cation and evacuation of liquid from the positive-pressure seal
pot in plant 2 required less time than that usually required
for the force amplication and evacuation of liquid from the
positive-pressure seal pot in plant 1 (when chlorine header
pressure exceeds 600 mmWC).
When electrolysis is started, the chlorine pressure at the
electrolyzer is unsteady and chlorine is being transmitted to
the WAD unit. Subsequently, chlorine transmission to the
WAD unit is gradually stopped and chlorine starts to be trans-
mitted to the chlorine compressor, as discussed earlier. During
this transition, the chlorine header pressure often exceeds
600 mmWC, which starts the force amplication and evacu-
ation of liquid from the positive-pressure seal pot.
95
Fig. 10 Steady chlorine header pressure at plant 2 after
the modication (data source for this plot: DCS, GHCL, 04
June 2007).
During initial start-up of the second plant, the force ampli-
cation and evacuation of liquid from the positive-pressure
seal pot was mostly taking place during the transition of
chlorine transmission from the WAD unit to the compres-
sor. However, while this transition was occurring, the cell
room was facing a vacuumpressure as chlorine could eas-
ily transmitted through the evacuated positive-pressure seal
pot to WAD unit. Consequently, the vacuumpressure seal
pot started to work and control valves for transmitting chlo-
rine to the WAD unit and to the chlorine compressor were
starting to close. Further, the positive-pressure seal pot was
starting to ll from the continuous feed of process water (PW
in Fig. 5). When the chlorine pipeline is submerged in the
liquid, chlorine transmission through the positive-pressure
seal pot does not occur. Accordingly, the chlorine pressure
in the cell room began to rise rapidly, with a high proba-
bility that the chlorine header pressure would again exceed
600 mmWC. If that happened, the lower ratio of Dv 2 /Dg 2
promoted premature evacuation of liquid from the positive-
pressure seal pot in plant 2. In this way, the evacuation and
lling of liquid in the positive-pressure seal pot was cycling
and the pressure in chlorine cycle was unsteady, as shown in
Fig. 8. This analysis suggests that, for maintaining a steady
chlorine header pressure within allowable limits and pro-
tecting the electrolyzer, there is a critical value for the ratio
Dv 2 /Dg 2 below which the chlorine header pressure becomes
unsteady.
4. Conclusions
To change the ratio Dv 2 /Dg 2 in plant 2, we inserted a pipe of
smaller diameter into the existing chlorine line that is nor-
mally submerged in the positive-pressure seal pot (Fig. 5). The
original line has ID = 101.6 mm. If the insert had ID = 76.2 mm,
then the positive-pressure seal pot in plant 2 would have
Dv 2 /Dg 2 = 34.9, which would be the same as the ratio in
plant 1. In the end, we inserted a smaller pipe, which had
ID = 38.1 mm and gave Dv 2 /Dg 2 = 139.5. A schematic diagram
illustrating this change is shown in Fig. 9. This change in the
positive-pressure seal pot in plant 2 eliminated pressure uc-
tuations in the chlorine cycle and, thereafter, we were able to
maintain steady pressures in both plants. This can be seen by
comparing the small pressure variations in Fig. 10 with the
large pressure uctuations in Fig. 8.
96 Process Safety and Environmental Protection 8 8 ( 2 0 1 0 ) 9196
Acknowledgements
The author would like to thank Mr. Dipak Kumar Kundu (Plant
Manager of GHCL) for giving permission to carry out this work
and providing helpful suggestions. All personnel of process
area and chlorine unit of GHCL also deserve thanks for their
assistance.
References
EKA, 2008, Chlorine and Caustic SodaMembrane Cell Process,
http://www.eka.com/Home/Functions/Eka+Engineering/
Products+and+Services/Chlorine+caustic/Default.htm
[Accessed: 26 September 2008].
Krebs Swiss, 2008, Chlorine Gas Drying, website,
http://www.krebs-swiss.com/cl2men.htm [Accessed: 20 July
2008].
Kundu, S.K., 2006, Corrosion control of electrolyzer, anolyte tank
and dechlorination tower tank of a chlor-alkali plant by an
innovative method. Journal of Chemical Engineering, The
Institution of Engineers, Bangladesh, ChE 24(1): 3741. January
2006December 2007
Leather, A. and Minty, J.A., (2001). Bichlor Operating Manual for
Global Heavy Chemicals Limited. (Ineos Chlor Limited).