Articles

Indian Journal of Chemical Tec hnol ogy

VoL 10, November 2003, pp. 644-653

Ideas for process improvement emanating from audit of a bromine plant in the
Greater Rann of Kutch
A S Mehta*, P K Ghosh , H N Shah & R 1 Sangha vi
Central Salt & Marine Chemi cals Research Institute, Bhav naga r 364 002, Indi a
Received 30 Julv 2002: revised received 22 April 2003; accepted 28 May 2003

The main effiuent in the 'Steaming Out Process' for recovery of elemental bromine from salt bittern is hot
acidified debrominated bittern. An exercise was undertaken recently in collaboration with a manufacturer in
Greater Rann of Kutch to audit the performance of the plant, evaluate the composition of effiuent discharged from
the bromine plant, and explore the possibility of value addition of the effiuent or, preferably, minimise effiuent at
source. Important recommendations made at the end of the study are: (i) controlled neutralization of acidified
debrominated bittern by lime can produce fine granules of calcium sulphate of ca. 95 % purity, (ii) there is need to
enhance the debromination efficiency as, otherwise, bromate formation is inevitable in the course of neutralization,
(iii) evaporation of dilute brine is essential for recovery of marine chemicals and (iv) debrominated bittern could be
utilised in solar ponds which would be a suitable source of non-conventional energy in the highly remote and arid
region.

Bromine, the third member of halogen group

e lements, is recovered from sea brines, wel l brines or
1
s ub- so il brines • In Indi a, sea bittern (i.e., mother
liquor left after recovery of common sa lt from brine)
is th e main raw material for recovery of bromine2 .
Generally, steaming-out and air-blowing processes
are used for recovery of bromine all over the world 3 .
Central Salt and Marine Chemicals Research Institute
developed the ' Stea ming Out Process' for recovery of
e lemental bromine from sa lt bittern nearly three
decades ago and several plants in Indi a have been
working satisfactori ly based on thi s technology . The
process is most suitable for Indi an producers because
the plant for the process is easy to set-up and its
operation is quite simple. Another advantage is that it
eliminates the requireme nt of alkali in the main
process. Th ere is, however, a need for s mall amount
of alkali in neutralizin g ac idic effluent, a lthough , thi s
advantage is partly offset by the substantiall y hi g her
requirement of steam.
Fi g ure 1 shows the flow sheet of the steaming out Cl 2
CYLINDER
process. The major operations include :
(i) acidification of bittern and ox idation of
bromide to bromine by chlorine,
ITED
(ii ) steam stripping of liberated bromine from the BITTE.H..N

solution,

*For co rrespondence (E-ma il: sa lt @csir.rcs.i n; Fig. !- Process now sheet for recovery of bromine (S tea ming ou t
Fax: 027R-2567562/2566970) process)
Mehta et al.: Ideas for process improvement in bromine plant
ARABIAN SEA
Fig. 2- Map of Gujarat
(iii) condensation of steam-bromine mixture, and
(iv) purification of crude bromine.
Main effluent in the process is hot acidified
debrominated bittern. Heat is recovered from the hot
bittern and is utilized in pre-heating the feed bittern
whi le the debrominated bittern gets cooled to aro und
40°C and is then neutrali zed by lime slurry and
discarded. In the process of neutrali zation of bittern ,
sludge-mainl y calcium sulphate-is produced as
secondary so li d waste. Non -co ndensab le bromine and
chlori ne comi ng out of th e condenser and gravity
separator are absorbed in two scrubbers. Bittern is
used as a stripping medium in the first scrubber and in
the second scrubber caustic soda solution is used.
Bittern coming out of the first scrubber is fed into the
bromine tower along with the feed bittern; whereas
the alkaline bromine so luti on coming out from the
other scrubber is mixed in the bittern reservoir.
The Greater Rann of Kutch (G RK) is bestowed
with profuse quantity of naturally occurring bittern~· 5 .
Articles
Gulf of
Khambhat
Seawater enters through the mouth of Kori Creek and
inundates the vast areas of GRK (- 90 km x 60 km)
during high tides in May and June every year.
Because of basin-type topography of the area, the
seawater cannot recede back to the sea. It travel s up to
and sometimes beyond Indi a Bridge, Khavda (Fig. 2).
Progress ive solar evaporation converts the seawater
into bittern. Large deep salt beds are also formed 1n
Rann as a result.
Two Indi an companies have show n considerable
vision in venturing into this inhospitable terrain and
setting up bromine manufacturing facilities , of which
one of the sites was 'identified by CSMCRI ,
Bhavnagar almost a decade ago. Dilute brine of 20 to
22°Be' density is pumped in the winter months in the
reservo irs and condensers of private companies. Brine
is circul ated in the condenser with the help of natu ral
gradient avai lable in the area and is solar evaporated
to 29°Be' or higher densities. ln summer month s, the
density reaches up to 33°Be'. This is th e feed for the
645
Articles Indian J. Chern. Techno I., November 2003

bromine plant. Relation between specific gravity of
brine and 0 Be' is given by Eq. (1).
Specific gravity of brine= 145/(145-0 Be')
An exercise was undertaken by CSMCRI in
collaboration with a private company manufacturing
bromine in GRK to evaluate the quality of effluent
discharged from their bromine plant. Performance of
the plant, experimental results of upgradation of
sludge, and potentiality of neutralized waste bittern
for recovery of marine chemicals and as heat storing
fluid of solar pond, are described in th e article.
Ideal bromine plant performance
Performance of bromine plant based on steaming
out process can be observed by consumption of raw
material and utility per ton of bromine produced.
Major raw materials are bittern and chlorine.
Stoichiometrically, one mole chlorine requires to
produce one mole bromine, i.e. one ton bromine
production theoretically requires about 0.44 ton
chlorine. In actual bromine plant, 0.5-0.55 ton
chlorine produces one ton bromine . Debromination
efficiency across the tower and overall bromine
recovery should be in the range of 95-99% and 85-
90% respectively. Steam requirement can vary from
16 to 20 ton per ton of bromine depending upon
concentration of bromine in feed bittern. It is not
advisable to operate bromine plant if bromine
concentration in the feed bittern is less than 2 g/L.
While bromine plant is under operation, it can be
monitored by bittern and chlorine flow rate.
Temperature at various points in the plant should be
as under:
Temperature of steam bromine
mixture at the top of the tower
Temperature of effluent coming out
of the tower
Temperature of feed bittern coming
out of the heat exchanger
Temperature drop of coolant across
(I)
the condenser
Temperature of liquid bromine in the
gravity separator
Performance auditing of bromine plant
Samples of feed bittern , liquid effluent and solid
waste were collected in December 1999 and March
2000 from the bromine plant and analyzed in the
Institute. Chemical analysis of feed and effluent of the
plant is given in Tables 1 and 2. Total dissolved solids
(TDS) present in feed in December 1999 varied from
40.25-40.66% (wlv) and in effluent it ranged from
37.04-37.8%. Corresponding TDS values of samples
collected in March 2000 were 40.62-42.33% and
39.64-40.05%, respectively. Thi s indicates that
dilution of bittern takes place in the tower because of
addition of live steam.
Capacity of bromine plant
Debromination efficiency across the tower IS
expressed as follows:
Efficiency = (bromine in feed- bromine in effluent) *
100 I (bromine in feed). . .. (2)
Bromine concentration in feed and effluent varied
from 2.42 to 2.48 and 0.06 to 0.11 gL-1, respectively,
in December 1999. Debromination efficiency varied
from 95.5 to 97.6 per cent. Considering 90 per cent
recovery of elemental bromine from the liberated and
stripped bromine from the tower (this is equivalent to
about 85 per cent over all recovery of bromine), the
capacity of bromine plant works out as under in
winter months :

Table !- Ionic composit ions of feed billern and debromi nated bittern of bromine plant
(samp les collec ted on December 9, 1999)

No Sample Time Density pH of Constutuents % wlv Bromine

0
8e' bittern ca+- Mo+
b so4-2 Cl- g/L

I Feed II A.M 29 .7 1.94 0.004 4.84 5.72 19. 15 2.42

2 Effluent II A.M 28.8 1.29 0.004 4.66 5.65 18.82 0.10
3 Feed I P.M. 29.6 2.37 0.004 4.81 5.72 19.15 2.45
4 Effl uent I P.M. 28.8 1.48 0.004 4.64 5.55 18.49 0.11
5 Feed 3 P.M. 29 .3 4.92 0.004 4.84 5.64 18.82 2.48
6 Effluent 3 P.M. 28.5 1.15 0.004 4.64 5.48 18.49 0.06

646
Mehta et al.: Ideas for process improvement in bromine plant Articles

Table 2- lonic compositions of Feed bittern and debrominated bittern of bromine plant
(samples collected on March 14, 2000)

No. Sample Time Density pH of Constutuents % wlv Bromine

0
8 e' bittern Mg+- so4 2 Cl- g/L

I Feed II A.M 32. 5 1.94 6.95 8.73 20.14 3.46

2 Effluent IIA .M 32.4 1.29 6.80 8.36 19.81 0.33
3 Feed 1 P.M . 33.6 2.37 6.92 8.66 20.47 3.56
4 Effluent I P.M. 32.7 1.48 6.73 8.48 19.81 0.32
5 Feed 3 P.M. 33.7 4.92 6.92 8.76 21.13 3.48
6 Effluent 3 P.M. 31.7 1.15 6.78 8.49 19.81 0.30

Table }--Bromine plant operational data

Item 09/12/1999 14/03/ 2000

Time 11.00 AM l.OOPM 3.00 PM 11.00 AM 1.00 PM 3.00 PM

Feed Bittern temperature (0 C) 21 22 23 28 30 32

Bittern inlet temperature to the tower (0 C) 90 90 90 92 93 94
Effluent outlet temperature from th e tower (°C) 108 108 108 107 107 107
Steam temperature ( C) 148 149 137 149 147 150
Steam flow rate kg/h. 2983 3106 3017 1317 1272 1279
Tower top temperature (0 C) 85 85 83 81 ' 84 83
Bittern flow rate m3/h 80 80 80 38 38 38
Chlorine flow rate kg/h 84 83 83 50 50 50
Feed bittern density (0 Be' ) 30 30 30 31:5 31.5 31.5
Treated effluent pH 7 7 7 7 7 7

Capacity= 2.45 (g. average Br2/L) x I o-6 (Ton/g)
x 80 (m 3/h) x 103 (Lim 3) x 0.9632 (average
debromination efficiency)
x 0.90 (recovery as elemental bromine)
= 0.17 Tlh
= 4 .08 Ton/day.
Similar calculation for March 2000 shows that
bromine production capacity works out to be 5.23 ton
per day. Considering average production as 4 .6
ton/day and 300 working days per annum, annual
production of bromine works out to be 1400 tons
which is in agreement with the design capacity.
Steam consumption
Based on dilution in magnesium ion content in the
effluent compared to feed bittern, steam consumption
in the tower is calculated by the formula (Eq . 3)
" . (3)
where C, and C2 are the concentrations of Mg+2 in
feed and effluent respectively and V2 is the volume of
effluent corresponding to V1 volume of feed.
Difference between V2 and V, indicates steam
consumption corresponding to V1 volume of feed.
Average Mg+ 2 ion concentrations are 4 .83 and 4.65 %
(wlv), respectively, in feed and effluent in December
1999. Steam consumption based on the above formula
works out to be 3096 kglh in December 1999. Some
of the important operational data recorded from the
control room of the plant are given in Table 3. It can
be seen from the table that steam consumption data in
December 1999 tallies with the values recorded from
the control room of the plant. Based on this data, one
ton of bromine requires about 15.65 to 17.81 tons of
steam. Similar results for steam consumption in
March 2000 indicated that its consumption for one ton
bromine works out to be 7.18-9.28 ton. Lower steam
consumption in March 2000 indicates inferior
performance of the plant. This is reflected in the
lower debromination efficiency across the bromine
tower as can be seen from Tables 1 & 2.
Live steam fed to the tower serves two purposes : (i)
to raise temperature of feed bittern from 90°C to
boiling point of bittern (l08°C in this case) and (ii ) to
strip out liberated elemental bromine from the
solution 6 . Sensible heat required by the bittern is
received from the latent heat of steam as shown
below:

647
Articles
Table 4-Chemical ana lysis o f sludge and treated debrominated bittern (Effluent)
No Sample Constituents(% w!w for sludge, % w!v for e fflu ent )
1 Sludge 1.90
2 Effluent (911211999) 29.5 14.9 1
3 Effluent ( 14/3/2000) 31.7 7.58
Sensible heat required by =m *Cp* f'!.T =
bittern to raise temperature 1.41 x 106 Kcal/h
from 90 to 108°C
Latent heat of steam at 148°C = 503 Kcal!Kg
steam temperature
Steam required to raise = 1.41 X 106 /503 =
temperature of feed 2.8 Tons/h
Considering 10 % of 2.8 tons as steam required to
drive out bromine from the tower, total quantity
works out as 3.08 Tons/h and 18.1 tons steam per ton
of bromine. This figure tallies closely with the above
fi gures , which , in turn , indicates that plant
performance in December was ideal but not so in
March. One can see that as concentration of bromine
increases in bittern, steam requirement comes down.
In March , bromine concentration is about 36% higher
as co mpared to December value. Since feed bittern
flow rate and other operating parameters were
maintained constant in December and March , steam
required to raise the temperature of bittern shou ld be
3.08 Tons/h . This corresponds to 14. 13 tons of steam
per ton of bromine, whereas actual values are
substantially lower.
Acid requirement and neutralization of effluent
It can be seen that pH of ac idified feed bittern and
effl uent varies from 1.94 to 4.92 as per tables 1 and 2.
It is essenti al to keep pH of feed bittern in the range
of 3-4 for better recovery of bromi ne 7 . As such,
bittern is acidic in character and when its temperature
becomes 100°C or so, its pH comes down to 5.0, so
addition of only small quantiti es of acid is required. It
was observed on the site that in the upper section of
bromine tower, lot of organic impurity (black in
colour) was getting deposited on the g!ass wall and
oxidation of such organic impurity required more acid
as reported by engineers on the site. Higher acid
usage led to more sludge. It is, therefore, essential to
identify and eliminate th e black impurity from the
tower.
Acidified eftluent coming out of bromine tower is
collected in a pit and is neutralized with the help of
648
Indian J. Chern. Tec hno!., November 2003
Bromine
g/L
58.62 19. 16 20.32
0.01 7. 10 13.57 0.36
Nil 9.95 17.63 0.66
lime slurry. Treated effl uent di scharged from the pit
has a pH around 7. Chemical analysis of sludge and
treated effluent are given in Table 4. Total dissol ved
solid present in the treated effluent varies fro m 28.47
to 35.58 % (wlv). Analysis of sludge shows that it
contains about 58 per cent calcium su lphate.
Presence of oxidizing species in the effluent
If Br2 removal from acidified bittern following the
displacement reaction with Ch is not complete,
neutralization of the acidified bittern effluent with
lime will lead to conversion of Br2 to Br0 3- and Br"
according to Eq . (4) g iven below :
6 Br2 + 6 Ca(OHh ---7 5CaBr2 + Ca(Br0 3 h + 6H20
. .. (4)
Intermediates such as hypobromite (BrO-), bromite
(Br02-) are also poss ible. Presence of such oxidizing
species was analy zed by Iodometry method 8 . It can be
seen from Table 5 that - 5-7 % of the original Br"
content of bittern remains in the effluent di scharged
from the tower. Br" concentration increases marginally
upon neutrali zati on that may be on account of Eq. (4)
above. Accordingly, traces of Br0 3- amount ing to- 6
ppm would be ex pected in the neutralized effl uent.
Actual measurements indi cated an amount
substantially hi gher, i.e., - 18 ppm, as can be seen in
Table 5. The unusual hi gher concentration of Br0 3-
led to exp loration of possible presence of oxidizing
spec ies in the feed bittern. As can be seen from Table
5, such bittern, even pri or to treatment wi th Cl 2 , has a
bromate content of the same magn itude as the
neutralized debrominated effluent bittern . By
ana lyzing bromate content in bittern obtained from
vario us salt works it is confirmed that und er normal
circumsta nces bittern does not contain any such
oxidis ing species. Its probable origin is, therefore, the
discharge of liquid stream from the scrubber which is
fed in to the bittern reservoir. Thus, there is a need and
scope to minimize presence of bromate species in
debrominated neutralized effluent.
Mehta eta!.: Ideas for process improvement in bromine plant Articles

Table 5--Concentration of oxidi zing species present in feed and treated bittern
(samples collected on August 12, 2000)

No Sample Time Bromine as BrO-, Br0 2- and Bromine as Br03- After boiling Bromine as
Br0 3- ppm ppm Bro-, Br0- 2 and Br03- ppm

I Feed 11.00 AM 21.31 18.65 18.65

2 Untreated Effluent 11.00 AM 7.99 4.00 1.33
3 Treated Effluent 11.00 AM 26.64 15.98 21.31
4 Feed 1.00 PM 26.64 18.65 21.31
5 Untreated Effluent 1.00 PM 15.98 13.32 2.66
6 Treated Effluent 1.00 PM 23 .98 17.32 19.98
7 Feed 3.00 PM 25.31 18.65 21.31
8 Untreated Effluelll 3.00 PM
9 Treated Effluent 3.00 PM 25.31 15.98 18.65

Table 6--Chemical analysis of brine, billern and salt fraction obtained during evaporation of 22.3 °Be' Brine

No Sample 0
Be' Constituents (% w/v for brine, % wlw for salt fraction )
NaCI CaS0 4 MgS04 MgCI 2 KCI

Brine 22 .3 16.81 0.17 2.63 6.26 1.15

2 Brine 27 .3 18.33 0.07 0.64 10.79 1.53
3 Bittern 29.0 13.76 0.01 5.65 14. 12 2.0
4 Salt fractio n 94.18 0.65 1.08 2.77 1.32

Evaporation of dilute brine Obviously, the bromine plant effluent, which is

With a view to study evaporation of dilute brine,
certain volume of brine sample (22.3°8e') was
collected in December 1999 from the discharge of the
pump installed at pumping point in the creek. 5 L
brine was taken in open shallow metallic tray and was
subjected to solar evaporation. Salt fractions separated
at 27.3 °Be' and 29 °Be' were collected. Chemical
analysis of brine and salt fraction that separated
between 27.3 "Be' and 29 °Be' is given in Table 6.
Experimental results show that about 40 g salt is
separated during evaporation from 22.3 to 27.3 °8e'
and it is mainly CaS04 (gypsum) . Further evaporation
of brine from 27 to 29 °Be' gave about 566 g common
salt (NaCI). Brine volume decreased from 5 L (22.3
0
Be') to 2.1 L (29 °Be' ). Total dissolved salt present
in 5 L of 22.4 °Be' brine and 2.1 L 29 °8e' bittern was
about 1350 and 747 g, respectively. Thus, amount of
salt crystallized in the evaporation process is about
603 g.
The above data indicated that to process 80 m3
bittern (29°8 e' ) per hour in bromine plant, it is
necessary to have 190 m3 brine (22.4°8e' ) per hour.
Amount of salt present in !90 m3 brine (22.4°Be' )
works out to be 51.3 ton and in the bromine plant
effluent (i.e. 80 m3 of 29°Be' ) salt is 28.5 ton , the
balance being the salt which crysta lli zes out during
evaporation prior to being fed to the bromine plant.
discarded in the creek (Rann), contains Jess absolute
amount of salt than that present in the brine pumped
from the creek. However, its concentration is higher
than that of the dilute brine pumped from the creek,
which contained about 259 g TDS L-1 whereas the
value for the liquid effluent was about 355 g TDS L-1•
Chemical composition of bittern does not change
significantly across the tower except mild dilution
because of the addition of live steam. Even the pH of
treated liquid effluent is comparable to the pH of
dilute brine (22°Be' ) pumped from the creek. Indeed,
the debrominated bittern after neutralization is very
similar in salt composition and pH to the sea bittern
discharged in the sea by solar salt manufacturers.
During early nineties, CSMCRI had carried out
survey of Greater Rann of Kutch to assess potentiality
of GRK to harness marine chemicals from existing
salt beds and entrapped bittern therein 4 . At that time
samples of brine and bittern entrapped in the salt
layers were collected and analyzed throughout the
year. For comparison chemical composition of few
selected samples based on survey results are given
along with the composition of treated bittern of
bromine plant in Table 7.
It is evident from the data given in table 7, that
liquid effluent of bromine plant is almost similar in
co mposition to bittern entrapped in the salt layers. As

649
Articles
Table 7-Comparison of debrominated neutralized effluent of bromine plant with bittern trapped in the salt layers in GRK
Constituents Bittern trapped in salt layers near Udhma post in GRK
(% wlv)
0
8e' 28 28
CaS04 0.02 0.03
MgS04 5.50 10.7
MgCl2 9.02 5.37
NaCI 20.25 24.08
KCl 2.05 1.95
Br2 0.18 0. 19
regards the salt, which crystallizes out from the dilute
brine during concentration prior to use in the bromine
plant, such a process also occurs regularly in the GRK
due to natural ingress of brine and solar evaporation,
leading to formation of vast salt deposits and bittern .
During summer bittern is evaporated all the way up to
33°Be' to enhance capacity of the plant. Unless all of
the salt produced during evaporation is removed from
condenser/crystalliser, its continued deposition would
reduce their working volume. It is, therefore, fe lt that
the salt should either be disposed off elsewhere in the
Rann-this would pose no problem since the Rann , in
any case, is filled with salt deposits-or, preferably,
suitable markets for the salt should be identified.
Recovery of marine chemicals
At present, the bittern, after concentrati ng , up to
densities as high as 33°Be', is used only for bromine
recovery. There is considerable opportunity to recover
other products as well, namely, potash and magnesia,
for which further evaporation of the bittern is
required, which would lead to crystallization of
additional quantities of crude salt followed by sels
mixt. (NaCl!MgS04 ), at around 33-35°Be' and kainite
(KCI.MgS04 .3H 20) at 35-37°Be'. Kainite could be
moved to a factory for recovery of potash 9 although,
admittedly, such recovery is more complex than from
carnallite5 . The mother liquor after recovery of kainite
would contain mainly magnesium chloride (with
some magnesi um sulphate) and can be utili sed for
manufacture of magnesium sulph ate, magnesium
carbonate and magnesia (via intermediate fo rmation
of magnesium hydroxide).
In experiments conducted in the laboratory, when
4.5 L 29.5°Be' bittern was evaporated up to 35.4°Be' ,
its volume decreased to 1.38 L and 1.35 kg salt was
crystalli zed . Based on this data, if 1920 m 3 bittern
(29°Be') per day is evaporated, it will give 576 ton
salt. Considering 300 working days per annum, the
amount of salt that will be crystallized comes to 1.73
650
Indian J. Chern. Techno!., November 2003
Debrominated neutral ized bittern
of bromine plant (% wlv)
3 1.2 31.7 29.5 31.7
0.01
6.58 8.78 7.10 9.95
20.07 17.89 13.57 17.63
7.80 9.65 14.91 7.58
3.20 1.80 2.70 3.00
0.32 0.34 0.14
lakh tons. Chemical analysis of this crude mixture
shows that, as expected, it is a mixture of sels mixt.
and common salt. This salt may be disposed in the
Rann .
Up gradation of gypsum
Acidified debrominated bittern must be neutralized
before discharge. This is done with the help of lime
slurry, the average daily consumption being 3.6 tons
with active lime content of 68-70%. Presently the
sludge that is obtained has the composition given in
Table 4. As is eviden t, CaS04 is the main constituent
along with moisture, although there are still
substantial quantities of impurities. It is possible to
leach out water so luble magnesium chloride and
su lphate from the sludge. Dilute well brine of 2 to
3°Be', which is available near the plant site, was used
for this purpose.
In the first experiment about 84 g wet sludge was
mixed with 150 mL well brine and mixture was
stirred for 15 min. The mixture was fi ltered and
product was dried. In the second similar experiment at
the end of filtration, the product was washed by well
brine to remove adhering impurity of sodium and
magnesium salt. Chemical analysis of each
constituent and material balance is given 111
Tables 8 & 9.
From the analytical results and material balance
calculation, it is clear that almost all gypsum
(CaS04 .2H 2 0) present in the sludge was recovered in
the final upgraded product. Purity of the product
works out to be around 95 %, which is acceptable to
cement industry 10 . Assuming all ac tive lime to be
converted into gypsum, the amount of gypsum that
could be produced in a day works out to be 4.75 ton .
Filtrate that comes out during the upgradation of
sludge is dilute in nature and may be discarded along
with the rest of the liquid effluent. It would , however,
be preferable if the need for washing with well brine
can be elimjnated altogether and CaS0 4 obtained
Mehta et al.: Ideas fo r process improvement in bromine plant Articles

exclusively in pure form in the neutralization process
itself. It is proposed that this may be possible through
finer pH control during neutralization and
incorporation of a seeding technique so as to produce
CaS0 4 in more granular form which settles easily and
is free from impurities.
Feed bittern acidified by hydrochloric acid
When feed bittern to bromine plant is acidified by
sulphuric acid it poses the following problems in the
smooth operation of bromine plant,
(i) if bittern is having density less than 29°Be',
calcium sulphate is precipitated in the tower
resulting in choking of the tower,
(ii) neutralization of acidic bittern with lime generates
more sludge (calcium sulphate), because of more
sulphate in the effluent which in tum creates solid
disposal problem .
0.7 ton gypsum from 80 m3 of bittern processed in the
plant in a day . This compares favourably with the
solid waste production of ca. 7 tons. This can be
ascribed primarily to the reduced level of acidification
of feed bittern, which accounted for a drop in acid use
by ca. 5-8 times. The balance effect was on account of
use of hydrochloric acid instead of sulphuric acid.
Therefore, every effort must be made to prevent over-
acidification of the feed bittern.
Use of bittern reservoir as solar pond
In view of the remote location of GRK, there is no
power grid and, therefore, energy is at a premium.
Solar pond technology is an attractive proposition,
more so because of the arid nature of the region and
the high solar insolation . The attractiveness is further
Table &--Chemical analys is of various streams in the
upgradation of gypsum

Both these problems were addressed during the Constituent Input Output
present study and it was decided to explore possibility Sludge Well Upgraded Fi ltrate
of acidifying feed bittern using hydrochloric acid % (w/w) brine gypsu m % (wlv)
% (w/v) % (w/w)
instead of sulphuric acid. Accordingly, bromine
plant was operated in August 2000 by acidifying feed CaS0 4 32.98 0.37 52 .84 0.24
bittern using hydrochloric acid, and samples were MgS04 5.27 0.03 3.48
collected, their analytical results are given in MgCI2 7.90 0.20 1.06 3.56
Table 10. NaCI 8.95 1.81 1.22 6.62
CaC0 3 1.00 2.00
Extent of acidification was maintained at average 3 1.42 28.81
Moisture
pH of - 2.4 instead of - 1.75 for earlier production
using sulphuric acid as acidifying medium. Chemical Table 9--Material balance of gypsum upgradati on experiment
composition of feed and effl uent remained almost
same. Whatever minor differences were found, they Constituent Input Output
Sludge Well Upgraded Filtrate
are attributed to density variations of bittern . (90 g) brine gy psum (170 mL)
Encouragingly, debrominati on efficiency across the ( 150 mL) (55 g)
tower remained unchanged (93.6-95.5 %). Acidified
effluent di scharged from the tower was neutralized by CaS0 4 29.68 0.56 29.06 0.4 1
MgS04 4.74 0.05 5.9 1
lime. In laboratory experiments with the
MgCI 2 7.11 0.30 0.58 6.05
debrominated bittern, about 8.0 g calcium sulphate NaCI 8.06 2.72 0.67 11.25
was precipitated from one liter effluent on CaC0 3 0.90 1.10
neutralization by lime slurry and this is equivalent to Moisture 28.28 15.85

Table 10--Composition of feed bittern and debrominated bittern of bromine plant

(samples collected on August 12: 2000-feed bittern ac idi fied by HCI)

No. Sample Time Density pH of Constituents (% wlv) Bromine

0
8 e' bittern Mg+ so4· cr g/L

I Feed II A.M 32.2 4.84 6.50 8. 19 19. 15 3.14

2 Effl uent II A.M 31.3 2. 10 6.35 7.93 18.49 0.20
3 Feed I P.M . 32.2 4.97 6.47 8. 12 19.15 3. 17
4 Effl uent I P.M. 31.4 2.85 6.30 7.93 18.82 0.15
5 Feed 3 P.M. 32.1 4.86 6.45 8. 16 19.48 3.09
6 Effluent 3 P.M. 3 1.2 2.64 6.25 7.9 1 18.82 0.14

651
Articles
enhanced in view of the ready availability of high
density bittern free of cost which can serve as the
working fluid in the pond bottom as described below.
Solar pond is considered to be the simplest and
most cost-effective solar collector-cum-energy
storage device. The solar pond is an artifici a lly
created po nd in which den se sa line brine is charged in
the bottom and brines having lower density are
charged to form density gradient. The part of solar
inso lation incident on the po nd reaches the bottom
and gets absorbed. Because of this, th e temperature of
the bottom dense layer increases. However. due to
prevailing density gradi ent, the convect ion currents
are suppressed and the e nergy collected is stored as
thermal energy. Pon d bottom can reach as high as
11 0°C depending on the concentration of dense
brine • 12 , while a temperature of 90°C can be
11
maintained under dynamic load. The thermal ene rgy
collected and stored in the po nd can be utilized
readily as process heat, although, its use in mo re
sophisticated applications like power generation is
13
also possible . CSMCRI had constructed and
o perated a bittern-based so lar pond which yielded the
information and expertise required to design
14
commerciall y viable ponds • Poss ible reduction of
efficiency of the po nd due to factors such as hi g h
wind velocity, low c larity of bittern, and seepage of
the bottom layer are, however, critical issu es which
need to be addressed.
Company manufacturing bromine uses a bitte rn
reservoir of 10,000 sq.m. area with about 3 m depth
for storing bittern for round the clock o peration
through out the year. One such reservoir can be easi ly
converted into solar pond . Thermal energy stored in
the pond can be used to pre-heat boiler feed water.
Based on CSMCRI experience on bittern based so lar
pond, it is possible to collect about I 0 to 12% solar
energy falling on the pond as thermal energy .
Considering about 5000 Kcal/m 2/day solar insolation
in Kutch and 10% heat coll ection efficiency of the
2
pond, 10,000 m pond can yield 5 millio n Kcal
thermal energy per day. If boiler feed water is pre-
heated from 30 to 80°C, the amount of water that can
be pre-heated by the energy stored in the pond works
out to be 100 m 3 , which is equivalent to 100-ton
steam. This is sufficient to pre heat boiler feed water
of a bromine plant that can manufacture 1400 ton
bromine annually.
652
Indian J. Chern. Techno!., November 2003
Conclusions
Based on the auditing of bromine plant in GRK
following points e merged as conclusion:
(i) steam consumption plays an important role in
the operation of the plant. There are different
methods of monitoring steam consumption in
the plant and one should counter check them at
regular interval.
(ii) a pH of 3-4 suffices for the purpose of bromine
di spl acement by chlorine and the requirement of
acid for such acidification of bi ttern is minimal.
Over-acidification is unwarranted as it reduces
bromine recovery and leads to much larger
quantities of sludge formed in the process of
neutra li zation of the debrominated bittern.
(ii i) controlled neutrali zation of acidified
de brominated bittern by lime can produce fine
granules of calcium sulphate of ca. 95 % purity .
(iv) presence of oxidizing species of bromine in the
neutralized bittern is as high as 18 ppm. There is
need to enhance the debromination efficiency as ,
otherwise, bromate formation is inevitable in the
course of neutralization. An interim solution
could be the introduction of a reducing agent
which may deactivate the bromate ion .
(v) evaporation of dilute brine is essential for
recovery of marine chemicals. In turn this
produces large quantities of common salt. It
should be di sposed off in order to increase the
life of condensers and crystallizers.
(vi) kainite type mixed salt can be recovered through
further evaporatio n of the debro minated bittern
and utili sed for potash recovery. The
debrominated bittern could also be utili sed in
solar ponds which would be a s uitable source of
non-conventional energy in this highly remote
and arid region .
Acknowledgement
Authors would like to thank Ms. Ballarpur
Industries Limited, Khavda Bhuj , which is now
rechri stened as Solaris Chemtech. Ltd. for sponsoring
the project, sharing the operational bromine plant data
and valuable discussion with engineers of BILT
during the course of the project.
References
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