II

Reprinted from Salt Research & Industry, Vol. 2, No. 4, October 1965. pp. 126-129

Mixed Salt from Sea Bittern

G. D. BHAT, J. R. SANGHAVI & K. SESHADRI
CSMCRI, Brmvnagar

Mixed salt, a raw m aterial for m anufacturing potassium fertilizers,

is prepared by solar evaporation of sea bittern of 30°B6. Addition of equal
volum e of 36°Be. bittern to the bittern of 30°Be. before evaporation increases
the chloride ion concentration which results in precipitation of potassium
salts at earlier densities, that is between 34-5° and 36-5°B6. instead of 36°
and Thus 7# per cent of the potassium chloride present in the bittern
is recovered as m ixed sa lt containing 18-20 per cent potassium chloride.

OTASSIUM fertilizers are essential as required for evaporation. The evaporation

P plant nutrients and are required in of mixed bittern is carefully controlled and
large quantities. Also several other potas­ carried out in two steps: first to 34/34-5°Be.
sium salts are used in commerce. Most of the -to separate sodium chloride as crude salt
world's demand is met from bedded deposits and then to 36/36-5°Be. to precipitate mixed
of soluble salts chiefly as chloride and sul­ salt containing 18-20 per cent potassium
phate. In India, there are no potassium chloride and about equal concentration of
deposits and requirements of the country sodium chloride. The concentration of mag­
are entirely met by imports. Sea-water and nesium sulphate in inland and sea bitterns
certain inland subsoil brines contain potas­ varies; therefore, mixed salt from sea bittern
sium and are the main source of potassium contains 30-35 per cent magnesium sulphate,
chemicals in the country. • while that from inland brine contains lower
Manufacture of salt from sea-water and proportion of magnesium sulphate depending
inland salt brines (subsoil brines) is exclu­ on the source of bittern. Magnesium chlor­
sively by solar evaporation. After the salt ide is only from adhering mother liquor and
separation between 24° and 29°Be., the varies between 6 and 8 per cent.
solution of 29/30°Be. left over is called The bittern is further concentrated by
bitterns, and contains 2-2-5 per cent (w/v) solar evaporation to reach 36/36-5°Be.;
potassium chloride. As such, it is a poor the composition of 36-5°Be. bittern is
source and hence processes based on bittern approximately: MgCl2, 34-7; MgS04, 7-1;
should be rigorously efficient or, alternatively, KC1, 1-5; and NaCl, 2-5 per cent. Seventy
bittern should be evaporated further to per cent of the total potassium chloride
obtain potassium in more concentrated and present in the original 29/30°Be. bittern
easily extractable form. Mixed salt, a separates as mixed salt. The final checking
material ten. times richer in potassium of the bittern at 36°Be. is also essential.
chloride than bittern, is collected by solar The normal composition of mixed salt is:
evaporation of bittern. The separation of MgS04, 30-35; MgCI2, 6-8; NaCl, 15-20 and
mixed salt from, bittern can be achieved at KC1, 18-20 per cent (wet analysis). Yield of
lower densities with addition of requisite mixed salt per 454-6 litres (100 gallons) of
quantity of magnesium chloride in the form bittern is approximately 39-40 kg.
of 36°B6. bittern produced a t the end of At the beginning of the season when 36°B6.
evaporation cycle thereby saving the time bittern is not available for addition, direct

126
 BHAT el at. : MIXED SALT FROM SEA BITTERN

evaporation of sea bittern from 30° to 38°Be. a t, the rate of 11*2 kg. per hectare; dosage
is to be carried out only during the first varies with the depth of the bittern in the
month. This is also carried out in two steps; salt pans: The laboratory data show that
first 30-35 ■5/36°Be. wherein most of the with the addition of magnesium chloride and
sodium chloride separates as crude salt solivap green, the period- of evaporation is
which is heaped periodically to drain the reduced from 20 days to 9 days to reach
adhering mother liquor. Bittern of 35*5/ 36°B6.
36°Be. is ready for mixed salt crystallization
only when concentrations of both sodium Preparation of mixed salt pans
chloride and potassium chloride are nearly
equal. At this stage it is led to mixed salt (a) Location — The land selected for layout
crystallizing pans and allowed to evaporate of mixed salt pans should naturally be nearer
to 38°Be. when most of the potassium to salt crystallizing pans .area, where all the
chloride separates out as mixed salt. The bulk of the discharged bittern is available,
concentration of potassium chloride in the but should not be in very close proximity
end liquor (36°Be.) should be 1*5-1 per cent. sb as to contaminate and hinder the pro­
After one or two direct evaporation cycles duction of good qulity salt.
it is preferable to recycle th e , bittern as (b) Land requirement — For every 100 tons
described above. of salt production 6-7 tons of mixed salt
can be produced and for every 100 tons of
Systems of irrigation mixed salt production 0*45-0-5 acres of land
is required. The acreage will vary depending
The charging of bittern or brine into on the period available for bittern evapora­
crystallizers is spoken of as irrigation. tion. The above data are based on the
■Irrigation can be single or multiple. Single acreage required in Saurashtra (Gujarat)
irrigation is suitable where there is a threat region where evaporation is faster and nearly
of interruption by rain. Field-scale trials one month more period is available for
at Bhavnagar Salt Works show that it is bittern evaporation.
preferable to follow multiple irrigation sys­ (c) Preparation of beds — The mixed salt
tem. In this method bittern for mixed salt beds are prepared similar to salt crystallizing
crystallization is fed three to four times in pans. The beds are carefully prepared to
mixed salt crystallization pans. When the minimize the percolation losses and are made
crust of the mixed salt is 5-8 cm. thick, the sufficiently hard so that mixed salt is not
end liquor of the 36°Be. is discharged for contaminated with fine clay.
recycling and the top layers are scraped and (d) Layout of pans — The bulk- of the
collected. The main advantage of multiple discharged 29/30°B6. bittern is led first
irrigation system is that it helps in collection to discharge bittern reservoir; this is suffi­
of white mixed salt free from mud which ciently large to accommodate the discharge
facilitates its further processing. from a single set of pans. A pumping set or
manual lifting of bittern is necessary at this
Addition of dye point. The height of the bittern thus raised
helps further conveying to mixed salt pans
Evaporation of bittern after 34°Be. is very •by gravity alone. The mixed 'Salt pans may
slow. In order to facilitate the evaporation be of any suitable size. The layout of pans
and obtain the mixed salt in short period, is changed from place to place so as to suit
the bittern can be treated with solivap green the needs of the salt farm. However, the

127
 SALT RESEARCH & INDUSTRY, VOL. 2, NO. 4, OCTOBER 1965
division of pans into condensers for cru,de
salt deposition and mixed salt crystallization
remains practically constant as it depends
on the reduction of volume of the bittern
during various stages of evaporation. Field-
scale trials a t the Experimental Salt Farm
have shown that in reaching concentration of
bittern from 29/30° to 34-5°Be. the original
volume is reduced to one-third by the time
it enters the mixed salt area. On this basis
for every three acres of land for mixed salt
production, two acres are used for condenser
area and one acre fpr mixed salt crystallizing
pans. The end bittern 36°Be. is discharged
in a common channel which leads to
36°Be. bittern reservoir tank located close
to 30°Be. bittern reservoir. Same pump­
ing set may be used for both the bitterns
alternately.
Storing of mixed salt
The mixed salt contains 6-8 per cent
magnesium chloride which prevents reactions
taking place between potassium or sodium
chloride with magnesium sulphate to form
less soluble double salts such as schoenite,
glaserite, astrakanite, etc. The formation of
these double salts may be useful in certain
processes. However, as double salts also are
not completely insoluble, mixed salt cannot
be stored in open space. During monsoon,
the hygroscopic constituents absorb moisture
and magnesium chloride along with little of
potassium salts are washed away. Storing
of mixed salt is done on raised platforms
either -by covering huge heaps of mixed salt
with grass, paddy or palm, leaves or alter­
natively in open sheds covered with roof of
either cement sheets or even prefabricated
structure. The choice will depend upon the
local conditions and the length of the period
for which mixed salt is to be stored.
The cost estimate for the production of
mixed salt (2800 m. tons/annum) from a
medium size‘salt works is given in Table 1.
128
T a b le 1 — Cost E stim ates f o r t h e P roduc ­
t io n of M ix e d S alt 2800 m . to n s / annum
T otal salt production 40000 m.
tons
B ittern of 29/30°B6, available 40000 tons
or
70-44 lakh
gallons
Approxim ate yield of mixed salt/ 2800 m.
annum tons
C ost e stim a te
A. Capital outlay
Converting about 4-8 hectares (12 Rs 18000
acres) of land into regular pans-
for recovering mixed sa lt with -
requisite arrangem ents for charg­
ing and discharging of the
m other liquor from one stage to
another preferably by gravity or
w ith the help of pum p where
gravity flow is hot possible (Rs
1500/acre)
Pum p w ith electric m otor Rs 10000
Im plem ents - Rs 1000
Mixed sa lt shed (3000 tons) Rs S2000
Open shed covered by a roof of
cement sheets or prefabricated
structure [Rs 8/sq. ft], (100 X
65 X 15 ft ht) '
B. Direct and, indirect cost per year
Preparation of crystallizing pans Rs 2000
and renovation of channels etc.
including land, lease (Rs 500/
acre)
Labour for lifting and stacking of Rs 2332
mixed sa lt on mixed sa lt p la t­
form 3 tons/labour (Rs 2-50)
Fuel or power for pum ps to lift Rs 2817
28-17 lakh gallons (Re 1/1000
gallons)
A ttendant to pum p @ Rs 100/ Rs 600
m onth for 6 months-
Supervision and overhead charges Rs 2800
Re 1/ton
Depreciation charges 10% on Rs -6200
mixed sa lt shed and pum p (Rs
62000) ’ ■
M aintenance 3% on capital in- Rs ,2730
vestm ent
T otal capital outlay (A) Rs 81000
D irect and indirect cost Rs 19479
per year (B)
T otal mixed sa lt produced 2800 m. tons
Cost of production a t salt Rs 6-95/m. tons
works
 BHAT et at, : MIXED SALT FROM SEA BITTERN
Two products, namely crude salt which
contains 80 per cent sodium chloride and
36°Be. bittern which contains 35/36 per cent
magnesium chloride, are not considered in
the above cost estimates.
Crude salt, which will be approximately
5600 m. tons, can be washed in washery unit
to obtain common' salt or alternatively
it can be- dumped in low density brine
to increase the concentration of sodium
chloride, resulting in increased production of
salt during subsequent year. The end liquor
or 36°Be. bittern available at the end of the
season will be approximately 28 lakh gallons
containing high concentration of magnesium
chloride. This can be either easily con­
centrated to produce magnesium chloride or
it can be used for other magnesium chemicals.
129
 Reprinted from Research and Industry, 1967, Vol. 12, No. 2, pp. 78-81

Manufacture of Potash Alum

G. D. B H A T .j! R. SANGHAVI, K. SESHADRI & D. S. DATAR
Central Salt & Marine Chemicals Research Institute, Bhavnagar
Manuscript 'received 11 ,/l«g«sM966

A process for the production of potash alum from mixed salt and
commercial aluminium sulphate (alumina ferric grade B) as raw-
materials is described and a pilot plant based on the above process
has been worked out. Cost estimates based on the pilot plant in­
dicate that potash alum of 99-5 per cent purity can be marketed
@ Rs 250 per tonne with 87 per cent yield (of potassium chloride
and aluminium sulphate employed) and 34-4 per cent return on
capital investment.,

OTASH alum occurs naturally in using mixed salt1'2 as the source of potas­
P such minerals as alunite and kalinite.
But usually, the alums are manu­
factured starting from bauxite as the source
sium. The principle of the process consists
in treating, powdered mixed salt (composi­
tion: chlorides of potassium, sodium and
for aluminium sulphate. Natural deposits magnesium, 20-1, 20-2 and 10-0 per cent
of potash alum do not occur in India and respectively and magnesium sulphate 23-2
so practically ail the alums are made from p e r, cent) with a solution of aluminium
aluminium sulphate.- However, production - sulphate whereby conditions for formation
-of potash alum is not common as there are of potassium alum are brought, about.
no good natural sources of potassium in Consequently, the following reactions take
India aftd potassium sulphate is to be place. - ■
imported. Consequently only ammonium 2KCl+MgS04->MgCla+ K 2S04
alum is manufactured. But a market
survey on the -use of potash alum revealed K.S04-f-AL(S04)3+ 24HaO
that it would be preferred by Indian con­ -»K 2S04-Al2(S04)s-24H2O
sumers to ammonium alum if it is made 2KC1+MgS04+ A12(S04)8-f-24H20
available at the same price, as ammonium . ->K2SO.•A12(S04)3-24H204-MgCl2
alum. In addition, potash alum is preferred
to other alums for sizing the finest papers As small scale attempts were successful,
and as mordant for sensitive colours. pilot plant scale production of the alum
using commercial aluminium sulphate
Hence it was considered worthwhile to (alumina ferric grade B) was carried out. It
attempt production of potash alum cheaply ' was possible to make alum of 99-5 per cent
1
 MANUFACTURE OF- POTASH ALUM

Fig. 1 — Flow sheet for the manufacture of potash alum

purity' conforming to Indian Standards The hot mixture is then filtered through
specifications for technical and pharma­ a pressure filtration unit or wooden plate-
ceutical grade (IS: 258-1950 and IS: 378- and-frame filtration unit, and the clear
1952 respectively). Cost estimates for filtrate is cooled to room temperature in
manufacture of 3363 tonnes per year of wooden vats or cement tank's lined with
potash alum were also worked out on the porcelain tiles. Potash alum crystallizes
basis of the pilot plant trials. An outline on cooling the -solution to room tempera­
of the process and detailed cost estimates ture.
are presented. - -
Based on the data collected, a cost estimate
Process of manufacture for the manufacture of 3363 tonnes of potash
alum using 3000 tonnes of mixed salt and
First the alumina ferric grade B (available 2700 tonnes of alumina ferric grade B per
from manufacturers) is processed by sepa­ annum has been worked out.
rately grinding the lumps into powder in
a jaw crusher followed by a grinder. The The. yield of potash alum is 87 per cent
powder is conveyed through a bucket ele­ based on the weight of aluminium sulphate
vator to ' a solution tank where water is and potassium chloride used. The material
added and the mix stirred well.1 • The slurry balance of th e , pilot plant is shown in
thus obtained is then tapped into a sump Table 1.
from where- clear solution is taken to' the
reaction vat by means of a slurry pump. The process is simple using almost in­
expensive equipment available in the
The mixed salt is ground to a powder and- country and suitable even for small scale
then . conveyed by a bucket elevator industries. . - .
.{Fig. 1) to wooden reaction vats containing
the processed alumina ferric solution. The Price obtained for unit K20 as alum is high.
reactants are stirred by wooden stirrers From the cost estimates it can he seen that
and heated to 100°C. by passing live steam. -very high purity -potash alum can be
2
 MANUFACTURE O F POTASH ALUM

T able 1 — M aterial balance data of P ilo t P lan t

Material Amount KCl Constituents present (kg.)

- NaCl MgSO, Mgq, K aSO, -Al,(SO.)j

Mixed salt 45 kg. 9-1 9-1 10-4 4-5 Nil Nil

Al,(SO,), soln • 60 litres — • --- — --- - — 20-8
Total 9-1 9-1 10-4 4-5 Nil 20-8

P roduct (potash alum) 50-4 ’ __ ' _ _ 9-2** 18-1

End liquor 70 litres 1-8 9-1 4-7 9-1 — 2-7
T otal 1-8 9-1 4-7 9-1 9-2 : : 20-8
Deviation + 0-6 , 0-0 . 0-0 -0 - 4 . 0-0
*KC1 equivalent = 7*9 kg.
Recoveries of KC1 and Alg^i-h^g as potash alum = 87 per -cent.

M anufacture of potash a lu m — C ost e stim a tes Process equipment * Rs

{Basis: 1 tonne oj mixed saUjbdtch', ten batches a day; Piping and fittings on . 9,710
300 days a year) • process equipment
@ 5 per cent ' .
.C a pita l investm ent Rs Electrical equipm ent 9,710
Process equipment installation, etc. on
process equipm ent
Wooden reaction vessels @ 5 per cent ‘ -
2 4,200 T ransport charges on 5,825
2*55 cu.m. / process equipment ■ - ;
Bucket elevator 2 - 12,000
Salt grinder and two jaw @ 3 per cent
crushers capacity 10 13,000 Insurance and taxes on 7,768
• - 'tonnes/8 hr - process equipm ent @
Acid proof . brick- lined 4 per cent
3 j. - 18,000 Instrum entation on 5,826 . -.
cement tanks to hold
*14000 litres of soln process equipment
Filter press 2 4 x 2 4 -in. ' @ 3 per cent
3 ■ 21,000 Contingency on process' . 5,826
12~ plates
Crystallizing wooden vats equipm ent @. 3 per . ..
5. 10,000 -cent
Compressor . 1 10,000
Drier electrically heated 2 15,000
capacity 500 kg./hr . 64,086
Slurry pumps 3 6,000
Boiler capacity steam 10 1 ' 50,000 P lan t and machinery, 2,58,286
tonhe/day erected cost
Weighing machine - 1 2,000 Approx. 2,58,300
Centrifuges (capacity.300 2 30,000
kg'./hr) Building a n d civil works 144,690
Overhead -tank (capacity 1 3,000 Laboratory equipment 3,500
9000 litres)
T otal process equipment 1,94,200 Fixed capital Total 3,76,490
cost
Working capital, based 1,60,915
Overheads 33 per cent of 64,086 on 3 m onths” working
process equipment of cost
c o st’
Installation and erec- 19,420 Total 5,37,405
tion charges oh pro­ Approx. 5,37,500
cess equipment @ 1 0
per cent — contd

3
 MANUFACTURE O F POTASH ALUM

M a n u fa c tu r in g cost R s Maintenance Rs
(p e r annum ) d ir e c t
cost Capital service (replace­ 12,915
m ent and spares % 5 per
Raw materials cent on erected p lant and
machinery)
. (1) Mixed salt 10 30,000 Maintenance on civil 3,440-
tonnes/day @ Ra works @ 3 per cent on
10/tonne a t factory R s 1,14,690
site'
(2) Alumina f e r r i c 4,05,000 Total 16,355
I n d ir e c t cost
grade B 9 tonne/
day @ Rs 120/
tonne for Rs 30/ Depreciation on erected 25,830
tonne for transpor­ p lant and equipm ent @
tation 10 per cent
Depreciation on civil 5,734
T otal 4,35,000 works @ 5 per cent
Interest on working 14,482
capital @ 9 per cent
Utilities Total 46,046
Electricity, 541200 kW h./ 81,180 - T otal cost of production 7,11,061
@ R e 0.15 kWh. of 3363 tonnes of potash,
Steam, 1332 tonne @ Rs 15/ 19,980 alum
tonne Cost per tonne of potash 211.44
W ater, 11250 kilolitres ' - 7,500 alum
@ Re 0,67/kilolitre Selling price of potash 250
alum (assumed) per tonne
1,08,660 Profit per'an n u m 1,29,689
R eturn on capital invest­ 34-4
Labour and supervision m ent on Rs 3,76,490 ex­
cluding working capital,
Chief chemist, 1 @ Rs 7,200 per cent
600 p.m.
Shift chemist, 3 @ Rs . 10,800
300 p.m.
Operators, 17 @ Rs 150 30,600 marketed at Rs 250/tonne with a return,
p.m . . . . . on capital investment of 34-4 per cent.
Helpers, 45 @ Rs 100 . 54,000
p.m.
Mechanic/Electric fitter, 2,400 References
1 @ Rs 200 p.ra. 1. B h a t , G. 0 ., Sanghavi , j . R. & Se s h a d r i , K.„
Salt ges. &■ Ind., 2 (1965), 126.
1,05,000 2. S e s h a d r i , K-, B hat , G. D. & Sanghavi , J. R .,
Indian Pal. 86383 (1963).
 EPSOM SALT FROM SELS MIXTS.
K. V. Lad, J. R. Sanghavi, G. D. Bhat & K, Seshadri
Central Salt & Marine Chemicals Research Institute
Bhavnagar.

Recovery of epsom salt from. “Sels Mixts” is des­

cribed; Sels Mixts is a co-produet in the carnal-
lite process or a fraction produced during solar
evaporation of bittern. Thp process consists of
separation of rich kieserite fraction from sodium
chloride by physical methods either by sieving
or settling in a bittern saturated with magnesium
sulphate. Epsom salt is recovered from kieserite
fraction by digestion at heat and •cooling to room
temperature.

Magnesium sulphate as epsom salt Is manufac­
tured in India1 from magnesite and sulphuric acid.
Total existing capacity is 9500 tonnes of which •6000
tonnes capacity is with sulphuric acid producing units
and 3500 tonnes associated with salt bittern. Recently,
one of the salt bittern units producing about 700 ton­
nes of epsom salt has discontinued and another unit
at Kandla has started manufacturing epsom salt as
a co-product of potassium chloride manufacture from
salt bittern with a capacity of 2000 tonnes per annum.
Actual production Is far less than the Installed
capacity of the units since the pharmaceutical indus­
try has produced more popular laxatives In modern
times than traditional epsom salt, which has consi­
derably affected the magnesium sulphate production.
Recently, due to the high cost of sulphuric aeld, pro­
duction, has fallen below the demand, with the result
that the demand for epsom salt from salt bittern has
risen considerably with a market price as high as
Rs. 600 per tonne. Future demand of epsom salt is
expected to rise In the production of citrate soluble
phosphate and mixed fertilisers. I t is recommended
th at the larger recovery of magnesium sulphate should
be effected through salt bittern in the interest of cost
and with a view to save sulphuric acid use. An econo­
mical process developed for the recovery of epsom
salt from salt bittern Is described in this artiele.
Sels Mixts
Sels Mixts is a mixture of varying compositions of
magnesium sulphate and sodium chloride. It is'obtain­
ed as a fraction during the solar evaporation of sea
bittern between 34-36* Be containing 35-38 percent
magnesium sulphate and 45-50 per cent sodium chlo­
ride. 6 tonnes of Sels Mixts can be obtained from bit­
tern corresponding to 100 tonnes of salt. Sels Mixts
Is also produced as a co-product in the manufacture
of potassium chloride2 from mixed salt by extraction
with 36* Be bittern at 110* C, when it contains 35-40
percent magnesium sulphate and 20-25 percent sodium
chloride.
Solubility Relationships
Epsom salt is generally crystallised out from its
saturated solution In the range 20 to 48° C and, on
crystallisation at temperatures above 4£fQ,' epsom
salt is contaminated with lower hydrates. Solubility
relations of magnesium sulphate with magnesium
chloride and sodium chloride are such that it is found
difficult to prepare a highly concentrated solution of
- magnesium sulphate from Sels Mixts for a good yield
between 20 to 48°C. Therefore, it is the usual practice
to chill the liquors prepared from Sels Mixts to 10”C
to crystallise out magnesium sulphate as epsom salt,
MgSO,. 7H,0, which is separated from the bittern by
centrifuging at 10*C. For a good crop of epsom salt
with high purity, proper control on magnesium chlo­
ride and sodium chloride concentration is needed.
The solubility relationships at various concentrations
that are likely to arise in the process using the Sels
Mixts of the above compositions are shown in Fig. 1.
Physical Separation of Sodium Chloride
The recovery of epsom salt from "Sels Mixts" is
not satisfactory by hot digestion and crystallisation
( to the range 48'C to room temperature, due. to the
presence of a large amount of sodium chloride. Hence,

33
 CHEMICAL AGE OF INDIA, VOL. 19, No. 1, JANUARY 1968

Figure 1. Solubility of Magnesium Sulphate in Magnesium Chloride and Sodium Chloride solutions.

tern were determined. 250 g of Sels Mixts and one

efforts were made for prior separation of sodium chlo­
ride from Sels Mixts by the- physical method of sepa- litre of 39° Be bittern were mixed together, stirred for
'ration for the recovery of epsom salt without chilling.five minutes and transferred in one litre measuring
It was observed that, In the hot extraction pro­ cylinder; height is marked in centimeters from the
cess, the magnesium sulphate was converted into kie- bottom. The clear demarcation line with the time
serlte form due to a change of phase from MgS04,H2O of settling was noted, as well as the compact demar­
to MgS0,,H20 and, as a result, disintegrated into fine cation line. ■The results are plotted In Fig. 2. In
particles while the sodium chloride remained as such some experiments, the compact line was not clear and,
without change in the particle size. Sieve analysis of hence, -was not plotted in the graph. The settling
ground mixed salt and Sels Mixts and compositions period for kieserite was 120 minutes at 30°C (curve, a)
of their various fractions are given in Table 1. Mixed and 30 minutes‘at 120°C (curve, b). When mixed
salt sieve fractions showed that all the constituents, salt contained too many clay particles, the settling
potassium chloride, sodium chioride and magnesium period was 75 minutes (curve, c). The settled zone at
sulphate, were evenly distributed without indicating hot was not compact, but diffused, whereas, in the
possible .separation. Sels Mixts sieve fractions indi­ cold, it was compact with a clear boundary. It was
cated that the sodium chloride was present as coarse observed that coarse particles of sodium chloride took
particles between - 18 to + 150 B.S.S. and kieserite only 3 to 5 minutes to settle, while lesser coarse par­
fraction was present as One particles passing through ticles of sodium chloride with kieserite settle in 15
- 150 B.S.S. Kieserite was so Sine that 60 - 70 per­ minutes, leaving behind fine particles of kieserite in
cent passed through - 300 B.S.S. but, due to the suspension which took a long time to' settle. A set­
difficulty of wet sieving with 300 B.S.S., separation tling period of 15 minutes would mean a .considerable
with - 150 B.S.S. sieve was found practicable. loss of kieserite in the settled zone. The portion not
settled in 3-5 minutes showed 5 to 7 percent sodium
It was observed further that the kieserite remain­
chloride, 35-37 percent magnesium sulphate in the so­
ed in suspension due to fine particle size In high den­lid kieserite suspension, with a recovery of 79 per­
sity bitterns without quick settling, while sodium cent magnesium sulphate. With the above composi­
chloride particles settled quickly. Therefore, It was tion, the recovery of epsom salt by hot digestion and
thought possible to recover the rich kieserite frac­ cooling was found practicable. The above settling
tion by filtering the suspended slurry only after allow­
period of 3-5 minutes was taken as the optimum
ing the slurry to settle for some time, which elimina­period for 33 cms height column.
ted the mechanical sieving. As the high density bit­
tern employed was saturated with magnesium sul­ Based on the settling data of Sels Mixts, two
procedures were possible and examined. In the first
phate and sodium chloride, loss of kieserite by dissolu­
tion would not take place. procedure, entire Sels Mixts was filtered off from the
dissolver without disturbing the operation of the car-
Settling Rates nallite process. The cake was agitated with high
Settling, rates of Sels Mixts slurry in 36‘Be bit­ density bittern of 36“ Be in cold and allowed to

34
 LAD et al.: EPSOM SALT FROM SELS MIXTS.

Table 1
Sieve Analysis of Ground Mixed Salt and Sels Mixts

Constituents g/100 g
Particular.. Quantity Solid ‘ . KC1 NaCl MgSOj MgClj
in g separated
g/100 g , ’
1. Mixed Salt (dry sieve) 1000 — 19.6 23.0 32.6 8.1
Sieve fractions (B.S.S.)
I. -, 1 8 + 3 8 193 19:3 18.6 23.0 — -8.1
II. - 36 + 5 2 82 8.2 16.8 22.9 28.6 8.1
III. - 52 + 100 223 22.3 16.8 22.5 26.6 8.1
IV. - 100 + 180 . 116 . 11.6 17.8 22.9 29.7 8.1
V. - 150 386 38.6 24.0 23.0 .38.5 8.1
2. Sels Mixts (wet sieve) 800 — 1.7 22.4 36.6 12.0
Sieve fractions (B.S.S.)
1.-18+52 40 5.0 1.3 78.5 6.3 3.8
II. - 52 +100 no 13.7 2.4 63.2 9.6 7.9
III.-100 + 150 28 3.5 2.3 70.2 9.0 5.5 ‘
V. - 150 620 77.5 1.4 9.2 .46.2 12.3
Recovery of magnesium sulphate, (— 150 B.S.S. sieve) = 96.5 percent
3. Sels Mixts (wet sieve) 800 — 2.6 22.0 35.0 10.0
Sieve fractions (B.S.8.)
I. - 18 + 150 — 31.9 6.6 51.0 12.5 11.7
II. -150 — 68.1 1.0 8.0 46.0 9.6
Recovery of magnesium sulphate (— 150 B.S. sieve) = 88.0 percent.
settle:, when sodium chloride settled down quickly dissolver, 0.76 meter dia x 1.06 meter ht. equipped
leaving kieserite in suspension. By filtering the kiese- with an agitator rotating at 60 r.p.m. by 2 H. P. motor
rite suspension slurry, rich kieserite fraction was .at 110°C for 15 to 20 minutes and allowed to settle
obtained. In the second procedure, the settling period for ten minutes. Suspended slurry of kieserite was
was allowed after the potassium chloride extraction filtered hot at 110’C through a sparkler pressure filter
from the mixed salt was over by 38’ Be bittern at and settled fraction was filtered on a vacuum horizon­
110’C. Sodium chloride settled quickly leaving behind tal plate filter. Cake obtained from the sparkler
kieserite in suspension. By filtering separately the pressure filter consisted mainly of kieserite, 32-37
suspension slurry by sparkler pressure filter at .hot, percent magnesium sulphate with 13-15 percent mag­
filter cake rich in kieserite was obtained. By filtering nesium chloride, 5-7 percent sodium chloride and 2-3
the settled sediment through the vacuum horizontal percent potassium chloride. Experiments were car­
plate filter, cake rich in sodium chloride was obtained. ried out with average mixed salt containing about
Experimentally, both the procedures gave good separa­ 20 percent sodium chloride and mixed salt, containing
tion, rich in kieserite fraction, and the results obtain­ high percentage of sodium chloride, about 45 percent.
ed by the two procedures are given in Table 2. About 78 percent of magnesium sulphate of the mixed
salt as kieserite fraction was recovered from mixed
Pilot Plant Experiments salt of both the' qualities. The data are given in
On the' basis of settling data of Sels Mixts, pulp' Table 2.
density being kept constant, the settling period was Recovery of Epsom Salt from Kieserite Fraction
worked out at 10-16 minutes for a pilot plant dissolver
(1.06 meter height) and at 30 to 40 minutes for a Kieserite fraction, containing a small amount of
commercial plant dissolver (2.45 meter height x 1.83 sodium chloride,. when dissolved In the calculated
meter dia). quantity of water (approximately 1:1), produced con­
centrated solution of magnesium sulphate, 30-35 per­
The first procedure was suitable for the Sels Mixts cent by volume at 60f°C.. The strength of magnesium
obtained as solar salt bittern fraction between 34-36" sulphate in the liquor depended on the content of
Be. As the second procedure was found simple and magnesium sulphate and residual magnesium chlo­
practicable during the carnallite process, the pilot ride in. the cake. During dissolution, the tempera­
plant experiments were carried out by giving settling ture of the solution would rise normally to 45-50° C
treatment in the dissolver itself during carnallite ex­ due to the heat of dissolution of kieserite. The solu­
traction. tion was heated with slight live steam to raise it- to
The slurry containing mixed' salt (HO kg) and- 60’C for uniform yield. The above solution, when
36° Be bittern (500 1) was stirred in a steam-jacketed cooled to room temperature, crystallised out epsom

35
 CHEMICAL AGE. OF INDIA, VOL. 19, No. 1, JANUARY 1958

Particulars Qty. in leg MgSO,

Constituents g/100 g
separated
g/100 g . ” KC1 NaCl MgSOj MgCL,

a) From Sels Mixts by settling w ith 36° Be’ b ittern a t room tem perature
Settling period: 5 M inutes; P ulp density: 1 kg per 4 litres
Sels Mixts, wet 50.0 — 2.8 22.8 35.2 14.2
Fraction, centrifuged:-
Suspended slurry, 20.9 . 70.0 1.5 9.3 58.9 8.0
(kieserite) w e t'
Settled sedim ent
(sodium chloride), wet 29.0 30.0 . 5.3 30,9 18.8 15J
b) D uring carnalllte extraction a t 110°C w ith mixed salt containing about 20.0 percent, sodium
chloride. .
Settling period: 10 M inutes: Pulp density: 1 kg/4 litres
Mixed salt dry 110.Q 21.0 21.3 36.2 8.0
Fractions Alter cake:- 91.0 79.3 2.2 5.0 34.9 14.0
Suspended slurry
(kieserite) wet
Settled sedim ent ' 43. 20.7 4.8 40.4 12.4 8.5
(sodium chloride), wet
e) as in (b) w ith .mixed salt containing high sodium chloride
S ettling period: 15 m inutes; Pulp density: 1 kg/4 litres
Mixed salt, dry 150 13.0 45.0' 26.0
Fractions filter cake:-
Suspended slurry
(kieserite) wet 88 78.4 2.6 6.5 35.6 15.5 .
Settled sedim ent
(sodium chloride) wet ■90 2i;6 3.3 65.9 10.7 4.8

36
 LAD ET AL.: EPSOM SALT FROM SELS MIXTS.

Table 3.
Recovery of epsom salt from hot kleserite fraction solution

Particulars , Qty. Constituents g/100 ml

KOI NaCl. - MgSOj •MgClj
Kleserite, fraction as 20.9 1.5 9.3 . • . , " 58.9 ,7.9
from Table 2(a), kg
Water, litres 23.0 _ _ — -
■

Residue, kg 2.5 0.6 2.0 32.4, 2.3

Hot solution, litres 28.7 0.9 4.4 ‘35.7 6.0
a t 60°C.
Epsom salt, kg 15.0 -- , 0.1 48.2 0.4
(unwashed)
End-liquor, litres 18.0 1.2 6.9 20.8 10.4
a t room temperature
Epsom salt, kg at
10°C (unwashed) 4.4 _ 0.3 47.0 0.2
End liquor a t 10°C, litres 14.0 1-5 8.7 11.5 13.5

N.B. Epsom salt recovery

a) a t room temperature, from kleserite fraction 58.6 per cent ana from Sels Mixt 41.1 percent.
b) a t 10°C, from kleserite fraction 74.7 percent and from Sels Mixt 52.2 per cent.

salt and the concentration of magnesium sulphate in
the solution decreased to 15-20 per cent by volume.
58.6 per cent of magnesium sulphate was recovered
from hot kleserite solution and overall recovery of
magnesium.sulphate from kleserite fraction was about
41 per cent. If the solution was further chilled to
10"C, an additional crop of epsom salt was obtained.
The recoveries of epsom salt In the range 60°C to 30°C
and 30°C to 10"C are given in Table 3. In the above
data, kleserite fraction used is the centrifuged product,
analysing 58.0% magnesium sulphate and 8,0% magne­
sium chloride. Later experiments showed th a t it was

Table 4.
Material balance data for processing 1200 kg mixed salt per batch
(Average composition of Mixed salt: KCI 13.0, NaCl 45.0, MgSO* 25.0 percent)

(1) Mixed salt, kg 1200 (12) Second crop of Epsom salt at 10”C,
(2) Sels Mixts (kleserite fraction), kg 688 kg 120
(13 Volume of mother liquor a t 10'C
(3) Sodium chloride fraction, kg 720 after the separation of epsom salt,
(4) W ater/sea-water added to dissolve litres 600
the kleserite fraction, litres 690 (This can be used for chilling the first crop,
mixed with coolant.)
(5) Density of the slurry a t 60“C, °Be 36°
(14) Density of the filtrate at 10*C,
(6) Density of the filtrate, °Be 34-35° °B e. 27-28
(7) Volume of the filtrate, litres 966 (15) Epsom Salt yield in kg
(8) Residual cake, after filtration of At room temp. 260
Sels Mixts slurry to be At 10°C . 120
discarded, kg 34-36
380
(9) Yield of Epsom salt a t room
temp., kg 260 Total of epsom salt, taken 600 kg
(10) Volume of mother liquor, Recovery, percent from
after the separation of Mixed salt Kleserite fraction
epsom salt, litres 760’ At room temp. 43 58
(H ) Density of the filtrate, °Be 31° At 10 °C 63 75

37