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Separation of magnesium chloride from sea water by preferential salt

separation (PSS)

Article · January 2013

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 ISSN: 2278-778X
Research Article
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SEPARATION OF MAGNESIUM CHLORIDE FROM SEA WATER BY PREFERENTIAL SALT

SEPARATION (PSS)
Khaled Zohdy, Maha Abdel Kareem and Hussein Abdel-Aal*
Department of Chemical Engineering, Higher Technological Institute, Tenth of Ramadan, Egypt

*Corresponding Author: Dr. Hussein Abdel-Aal, Professor Emeritus of Chemical Eng. / Petroleum Refining, NRC
Founding Member and Fellow, IAHE, USA
Address: 18, Jeddah Street, Doki, Cairo, Egypt.

Received for publication: November 27, 2012; Accepted: January 13, 2013.

Abstract: Magnesium chloride is typically extracted from sea water on an industrial scale by precipitating
it as magnesium hydroxide, then converting it to the chloride by adding hydrochloric acid. This process is
known as the Dow process which uses the chemical approach in producing magnesium chloride. Kettani
and Abdel-Aal [1], proposed a physical separation procedure known as the Preferential Salt Separation
(PSS) to obtain magnesium chloride directly from sea water. In principle, the PSS concept is based on the
selective separation of salts during the evaporation. In this paper, analysis of the PSS concept is carried
out for two proposed distinctive designs: the dynamic (continuous) flow model and the static (batch)
flow model. Separation of magnesium chloride is anticipated using solar energy for evaporating sea
water. Preliminary experimental results for simulated systems are reported for each case.

Keywords: Magnesium Chloride, Preferential Salt Separation (PSS), Seawater, Solar Energy, Brine

INTRODUCTION
Separation Sequence of Salts during Evaporation:
The major components of natural sea water
determining their solubility properties are: Na+, K+,
Mg++ , Cl- and SO4 --. According to Chr. Balarew [2], it is
usually assumed that the major constituents present in
the sea show constant relative proportions. This means
that the variations in the composition of waters from
different seas are due only to the changes in the
amount of water present. It follows that the
composition-density diagram shown in Fig. 1 for the
initial composition of Black Sea water, as well as for the
changes in the concentrations of the constituents is
valid for every sea water type.

Upon evaporation, the crystallization of the salts

dissolved in seawater occurs at different concentration
levels. Brine concentration, promoted by the
evaporation of its water content, results on the
successive precipitation of the least soluble salts,
CaCO3 e CaSO4, followed by the production of NaCl
and finally Mg and K salts as end products.
Fig.1: Composition-density changes during evaporation-
of seawater at 250C (the density of the Black Sea Water
is 1.011), after Reference [2]

International Journal of Bioassays (IJB) 376

Khaled Zohdy et al.:
Fig.2: Sequence of precipitation of salts dissolved in
seawater, after Reference [3]
In support of this crystallization sequence, Fig.2
shows an excellent representation for the successive
salt separation, after Manuel Collares-Pereira et al [3].
Recovery of Magnesium Chloride by the Dynamic
(Continuous) Flow Model:
The concept of PSS was introduced by Kettani and
Abdel-Aal [1] and the model was experimentally tested
for the first time on a semi pilot scale. The concept is
simply based on the fact that whatever the evaporative
process might be, the necessary end product of the
evaporative sequence would be a dense magnesium
chloride solution.
Experimental Set Up:
A process flow diagram is shown in Fig.3 that
depicts the equipment used in the PSS process for the
recovery of magnesium chloride from sea water. This
include: the evaporator, the solar-simulated infra-red
heaters and feed tank and other auxiliaries. The
evaporator is 5 m2 basin (2.5m x2m) made of
galvanized sheets. It consists of 24 channels each is 10
cm in depth and 10 cm high.
A practical scheme for the recovery of high density
MgCl2.6H2O brine would be to use a very long
evaporating channel. A dynamic flow of sea water is
established by introducing the feed at one end to get
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International Journal of Bioassays, 2013, 02 (02), 376-378
evaporated by heating using a solar flux as it proceeds
to the other, dead end. In order to use the minimum
space available, the channel should have a spiral shape
forming a series of steps in series. Heating by solar
energy could be realized through a heat exchanger
with a solar source, heating the bottom of the
evaporator.
Experimental Results:
The results are summarized as follows with respect
to:
a. Calcium: It increases from 550 ppm in the first
channel to 2100 p.p.m. in channel number 6. This
concentration decreases steadily to a value of
1000 p.p.m. indicating the separation of CaCO3
and gypsum CaSO4 around channels 7-8.
b. Soduim: It increases from 15300 ppm at the inlet,
up to a maximum of 87000 ppm at channel
number 8. This corresponds to ℓ = 1.215 at which
NaCl starts to precipitate. From this, the
concentration of Na tends to remain constant up
to channel number 17 in spite of the continuous
evaporation of the flowing water. This means
that the precipitation of Na in the form of halide,
matches the amount of water evaporated. With
further evaporation across the channels, the
concentration decreases sharply from 85000 to
59000 around channel number 19.This sharp
precipitation of Na would eventually lead to the
elimination of the sodium as an important
element in the remaining concentrated brine.
c. Magnesium: It increases steadily from 1850 ppm
at the inlet up to 14400 ppm at channel number
8 corresponding to ℓ= 1.215, then with further
evaporation along the evaporator, it drops to
10,000 ppm. at channels 9-11.This corresponds to
the precipitation of Mg SO4.nH2O. Further after
channel number 11, Mg conc shoots to a peak of
about 29,000 ppm between channels 12-13 to
indicate that the sulfate precipitation is coming
to an end. The peak itself shows that the new
salt consisting partly of Mg is reaching maximum
saturation [probably it is Carnalite
(KCl.MgCl2.6H2O)]. Hence, precipitation occurs
once saturation is reached. Precipitation reaches
its max at channel 17 corresponding to Mg
concentration of 14,000 ppm in the remaining
brine. Further evaporation leads to a sharp
increase in Mg concentration reaching a value of
42,000 ppm in channel number 19, near the end
of the evaporator. This indicates that the brine is
highly concentrated in Mg. It could be named
magnesium-rich-brine. Comparing the ratio of
Mg in the finally obtained brine to that in the
intake sea water, it is found to be = 42000 /1850
≈ 23 times.
377
 Khaled Zohdy et al.:
Recovery of Magnesium Chloride by the Static (Batch)
Model:
Proposed Experimental Set Up: This model of
evaporation implies evaporating sea water using the
batch concept. The evaporation takes place in a tank
using solar-heated water jacket. When salts start to
precipitate, evaporation is stopped and salts are
separated by filtration. Chemical analysis is carried out
to mark the first sample of salts. Evaporation is
resumed, and the procedure is repeated for additional
salt precipitates, until the stage of magnesium-rich-
brine is reached.
Experimental results:
The batch model was implemented as described
above. However, a preliminary experiment was carried
out on a lab scale using a sample of 2 liters of sea
water. Results are shown in Table-1. It is evident that a
similar trend in salt separation is followed in this model
as well. Magnesium chloride rich- brine is observed in
terminal samples. Because of the limited scale of the
initial volume used, very small quantity of separated
salts was obtained.
Table.1: Experimental Results for the Separation of
MgCl2 using Batch Evaporator
Source of support: Nil
Conflict of interest: None Declared
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International Journal of Bioassays, 2013, 02 (02), 376-378
CONCLUSIONS
It is worth mentioning that some specific studies
were performed earlier and shown promising results
for the economical recovery of magnesium chloride
from sea water using the physical approach, as
reported by Abdel-Aal [4]. The concept of preferential
salt separation (PSS) as applied to sea water is
demonstrated for the recovery of magnesium chloride.
Two models are presented: the dynamic continuous-
flow model and the static batch model.
Experimental results are given for each case.
Through these experiments, it can be shown that the
PSS of salts from sea water would lead to concentrated
magnesium chloride brine. With a longer evaporator in
the case of the dynamic model, and with a larger scale
of volume for the batch model, more promising results
could be obtained for an ultimate goal of obtaining
magnesium chloride in large quantity and in a pure
form.
REFERENCES
1. M Ali Kettani and HK Abdel-Aal, Production of Magnesium
Chloride from the brines of Desalination Plants using Solar
Energy, Proceedings of the Fourth International Symposium on
Fresh Water from the Sea, Volume 2, Athens, 1973.
2. Chr. Balarew, Pure &Appl. Chem., 1993, Vol. 65, No. 2, pp. 213-
218.
3. Manuel Collares-Pereira, João Farinha Mendes and Pedro Horta,
Advanced Solar Dryer for Salt Recovery from Brine Effluent of
Desalination Plant, ISES Solar World Congress, Göteborg,
Sweden. 2003.
4. HK Abdel-Aal, Projected Economics of a New Magnesium
Production Process and their Impact on the Cost of Magnesium
Hydrides, International Journal of Hydrogen Energy, 1982, Vol.
7, No. 5, pp. 429-435.