The removal of sulphate ionsfrom the chlorine
production process is essentialfor optimal plant operation.
Andrew Barr of Kvaerner Chemetics, Canada, describes the
development and operation of a nanofiltration membrane system
that is said to be environmentally preferable and more cost
effective than existing sulphate removal processes.
Sul Removal by
IManofi
odern industrial not removed it can accumulate and cause
production of chlorine operational problems because the
employs the chloralkali sulphate ions have a detrimental effect on
process. This is a the plant's electrolyzers. The
process where sodium concentration of sulphate ions (SO42-) in
chloride salt (NaC1) is dissolved and the NaC1 solution or brine therefore
electrolyzed to form chlorine gas, hydrogen needs to be controlled. As the brine is
gas and sodium hydroxide (NaOH). continuously recycled from the
Chlorine is used in the paper industry for electrolyzers and salt recovery systems
bleaching purposes, as a disinfectant agent back to the saturation area, progressively
in the water treatment industry, and as a more and more SO42- are dissolved,
feedstock in the manufacture of plastics and reaching concentrations that exceed
pharmaceuticals. The annual worldwide allowable process limits. A number of
production of chlorine is approximately 50 methods are currently used to remove the
million tonnes/year, and it has an expected SO42-. The most common ones include:
annual growth rate of between 2-3%. chemical precipitation as barium sulphate
The salt used in the chloralkali process or calcium sulphate; ion-exchange; and
is not pure and contains a wide variety of brine purge.
impurities including a significant amount Although the purging of the brine is the
of sodium sulphate (Na2SO4). If this is most commonly used method of
18 July/August 2001
controlling sulphate levels in coastal
plants, it results in a relatively high volume
of liquid effluent and has operating costs
associated with the loss of valuable salt in
the purge stream. The use of barium-
containing compounds is popular for
inland plants, in areas where large brine
purge volumes are not tolerated. In this
method the barium-containing compounds
react with the sulphate to form solid parti-
cles that are then filtered out and disposed
of. The major disadvantages of the barium
method are the cost of purchasing barium
reagents, the handling of carcinogen
barium compounds and the generation of a
solid, barium-containing waste that
requires disposal.
Other available methods also suffer
from either high capital/operating costs or
the generation of large volumes of effluent.
Now, a new method that incorporates
nanofiltration (NF) membrane technology
has been developed, patented and
commercially proven to remove sulphate
from chloralkali plants' brine streams. It is
known as the Sulphur Removal System or
SRS (Figure 1).
Research & Development
The idea of using membrane separation as
a method to concentrate Na2SO 4 solutions
from brine streams was first conceived in
1992, and between 1993-1995 the
performance of a variety of commercially
available NF membranes was tested using a
specially designed test apparatus in
Kvaerner Chemetics' laboratory.
NF membranes have previously been
shown to effectively separate multivalent
anions, e.g. SO42- from monovalent ones,
e.g. C I in dilute solutions. However,
Filtration+Separation
 because of an anticipated loss of selectivity stages. Figure 4
and the creation of a high osmotic pressure shows the flow C
a NF method to treat concentrated elec- schematic of a three- 100 ~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . tI " "
trolytes was never explored. stage unit, which has
In the laborarory tests carried out by two membrane g 9e ........ ~ ................................ :...
Kvaerner Chemetics, the NF membranes housings in the first '~ I I I
9 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .I. . . . . . . . .I. . . . . I I...
I
not only effectively rejected SO4 2- in con- and second stage and g+ , , , :
centrated brines, but selectivity was enhan- one in the third 94 .................................
I I I . . . . . . . . . . . x . .W%
............ ,..
l..~
ced because of zero or even negative rejec- stage. Feed brine is I I I I
~': I I I I
tion of the CI. This selectively reduces the fed under high 92 ................................................................
I I I
osmotic pressure difference between the pressure to the first I I
feed brine and the sulphate-free brine per- 9o . '. : I
stage. The
0 30 60 90 120 150 180
meate, allowing the effective separation of concentrate stream, NasSO4 Conc. gpl
Na2SO 4 from chloralkali brine at typical NF enriched in sulphate,
pressures of 2000-4000 kPa (300-600 psi). flows in sequence to
The laboratory work showed that sul- the next stage and is
phate rejection remains high and chloride finally discharged at
rejection low over a wide range of chloride the desired sulphate concentration. The sulphate, is recovered in parallel from each
and sulphate concentrations. The tests permeate stream, which contains little stage and sent back to the brine circuit.
demonstrated that the sulphate rejection
remained above 95% over the whole range
80
of NaC1 concentrations studied. At the same
time the NaC1 rejection was found to be ,~ 70 J
f
very small, so most of the feed salt is
_8 6o /
f
returned to the process in the permeate.
Similarly, sulphate rejection remains high J
even at high sulphate concentrations (Figure
2). Normally the SRS is designed to 4O J
concentrate Na2SO 4 in the reject stream to 58==
"~ 30 j J
between 85-100 grams/litre (gpl) (areaA).
In certain circumstances it is possible to ;| 20
increase the design capacity of the system to lO
produce a 120 gpl Na2SO 4 reject stream
(Area B). Area C in Figure 2 represents the
operability range of the SRS. Wide varia- 50 70 90 110 130 150 170 190
tions in sulphate concentration, i.e. outside
Na2804 Concentndlon
of the design ranges A or B are permissible Concentration Minus Permeate(gpl)
without exceeding the solubility limits of
the NaC1/Na2SO 4 solution. The reason for
this is that NaC1 rejection becomes increas-
ingly negative as the sulphate concentration
of the reject stream increases. Another way
of saying this is that as the NaC1 concen-
tration in the permeate increases its
concentration in the reject decreases at the ~ A
k ,
? I
P m
>

same time the Na2SO 4 concentration of the

reject stream rises. In other words, the
process is somewhat self-regulating, with f~"~l ,.-.--:l
t ;; t
respect to saturation limits in the reject + +I+
+.-++,:+
,,

stream. Figure 3 illustrates the negative t il ~ +I +

NaC1 rejection described above. ~5

i t
+ t
F +I t + t
Ii~sllgn of tllm SRS t +l t i t
i ]
i t
The SRS uses mass produced spiralwound i t
membrane elements to maximise
L. L....g [..... i t
".....J

membrane surface area. The required --~ "-T

membrane area and fluid velocities are ~ z IPage $
obtained by arranging the elements in series
in membrane housings and then arranging a
number of housings in parallel and in

FIItrati~.Separation July/August 2001 19


o Economics
0 In addition to the pollution control benefits
0 200 400
Quantity of Sulfate to be Removed (lb. Na2SO4/h)
Pilot Study
In September 1997 the first flail scale, in-
dustrial grade SRS began operation at a
chloralkali plant located in the Eastern
LISAand owned by a major chloralkali
producer.
Over the last three and a half years the
pilot SRS unit has provided invaluable
information on a number of important
operating factors including the optimum
• 5001hJCI2planl-RIt O0.,4%Nar~O4
• 1000~ Cl~paint -malt • 0 , 4 % 1 ~
A NaCl Cost = $35/t
B N I C l Cost = $35/t
C BuUn Tmolm=ll al Inclu~
¢~o6t = 1NS0/t BsCl=
D B a ~ m T r u t m e n t oH
C o a = $350St BaGI2
E ~ T m a t m ~ t all I n c l u ~ e
Cost = $300,I C.,aCl=
600 800 1000
operating conditions, the expected
life-span of the membranes, and the robust-
ness of the materials of construction. It has
provided the necessary commercial
operating experience to allow full scale
commercialization of the SRS technology.
Operating experience gained from the
pilot unit and other more recent
commercial SRS units has helped determine
the brine preparation steps required for
optimum SRS operation such as filtration of
suspended solids, cooling, complete
dechlorination, and/or pH adjustment.
Kvaerner Chemetics continues to
develop new membrane technologies, and
to identify membranes with improved
performance characteristics.
of the SRS over existing sulphate removal
methods, the system is also more cost
effective. SRS technology recovers most of
the cost of purged salt, or eliminates the
purchase and disposal costs associated with
barium treatment.
Figure 5 compares the typical costs
generated by the SRS, brine purge and
barium/calcium precipitation.
Forfurther information contact:Andrew Barr,
Kvaerner Chernetics, 1818 CornwallAvenue,
Vancouver,British Columbiav6j I c7, Canada.
Tel: +1 604 737 4558;
Fax: +I 604 737 4458;
E-mail:andrew.barr@kcivc.kvaerner.cora;
Website:www.chemetics,kvaerner.com

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