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Chemical Industry & Chemical Engineering Quarterly 18 (1) 8388 (2012) CI&CEQ

RADOUANNE FEZEI EXTRACTIVE PROCESS FOR PREPARING

HALIM HAMMI
ADEL MNIF
Technological pole of Borj Cedria,
National Center of Research in
Materials Sciences, Valorization
Laboratory of Useful Materials,
Soliman, Tunisia
SCIENTIFIC PAPER
UDC 66.06:543.3(611)
DOI 10.2298/CICEQ110815049F
HIGH PURITY MAGNESIUM CHLORIDE
HEXAHYDRATE
This paper reports a method for the preparation of magnesium chloride hexa-
hydrate (bischofite) from Sebkha el Melah of Zarzis Tunisian natural brine. It is
a five-stage process based on crystallization by isothermal evaporation and
chemical precipitation. The first two steps were dedicated to the crystallization
of sodium chloride and potassium-magnesium double salts, respectively. Then,
the resulting liquor was desulfated using calcium chloride solution. After that,
another isothermal evaporation stage was implemented in order to eliminate
potassium ions in the form of carnallite, KClMgCl26H2O. At the end of this
step, the recovered solution, primarily composed of magnesium and chloride
ions, was treated by dioxan in order to precipitate magnesium chloride as
MgCl26H2OC4H8O2. This compound dried at constant temperature of 100 C
gave good quality magnesium chloride hexahydrate. Besides this salt, the va-
rious by-products obtained from the different treatment stages are also useful.
Keywords: process; extraction; magnesium chloride; natural brine.

Brines are seawater-type solutions often assi- Process description

milated to the quinary system Na+, K+, Mg2+/Cl-, SO42
//H2O [1,2]. These solutions, which represent a nearly
endless reserve of dissolved salts, are expected to
play an important role in the economic sector of some
countries and especially those in developing such as
Tunisia. Thus, several works were developed on Tu-
nisian natural brines. The first ones studied geological
aspects as well as solubility diagrams related to the
previously mentioned system [1,3-6]. Then, investiga-
tions were extended to the modeling of phase dia-
grams [7-14]. Recent studies are rather directed to-
wards the extraction of interesting salts [6,15-18].
Among these salts, magnesium chloride is of great
utility in industry as well as agriculture.
The present work is a contribution to the vapo-
rization studies of Tunisian brines. In particular, it deals
with the preparation of magnesium chloride hexahyd-
rate salt from the naturally occurring brine of Sebkha
el Melah of Zarzis.
Correspondening author: R. Fezei, Technological pole of Borj
Cedria, National Center of Research in Materials Sciences, Va-
lorization Laboratory of Useful Materials, Tourist road of Soli-
man B.P. 73 - Soliman 8027, Tunisia.
E-mail: radouanne.fezei@yahoo.fr
Paper received: 15 August, 2011
Paper revised: 10 October, 2011
Paper accepted: 11 October, 2011
Choice of the different treatment stages adopted
in the conceived process was directed by some pre-
vious work [2, 19-22]. The corresponding flowchart is
given by Figure 1. It is a five stage process based
mainly on isothermal evaporation and salts crystalli-
zation as well as chemical precipitation.
The first step consists of evaporating the con-
sidered brine at 35 C in order to crystallize sodium
chloride (halite). During the second treatment, the re-
sulting solution is further concentrated by isothermal
evaporation at the same temperature. The precipi-
tated salts are expected to be sodium chloride and
substantial amounts of kainite (KClMgSO43H2O).
The third step of the process is a chemical precipi-
tation reaction of sulfate ions using calcium chloride
solution. After removing calcium sulphate precipitate,
the mother liquor is subjected to another 35 C iso-
thermal evaporation in order to eliminate partially po-
tassium ions as potassium-magnesium double salt,
carnallite (KClMgCl26H2O). The resulting brine, com-
posed essentially of magnesium and chloride ions, is
treated by 1,4-dioxan (C4H8O2), which is expected to
precipitate the magnesium chloride salt as
MgCl26H2OC4H8O2 [22-25]. This compound was dried
at constant temperature (100 C) to eliminate dioxan

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R. FEZEI, H. HAMMI, A. MNIF: EXTRACTIVE PROCESS FOR PREPARING HIGH PURITY CI&CEQ 18 (1) 8388 (2012)

Figure 1. Flowchart of the process conceived for magnesium chloride hexahydrate extraction from
Sebkha el Melah natural brine (the given compounds are expected theoretically).

molecules and thus obtain magnesium chloride hexa-
hydrate, MgCl26H2O.
EXPERIMENTAL
Chemicals
The principal raw material considered in this
study is natural brine sampled from Sebkha El Melah
of Zarzis. Its chemical composition in major ions is
given in Table 1. Besides this highly concentrated
aqueous solution, two commercial reagents were also
used: calcium chloride dehydrate (99%) and 1,4-di-
oxan (99%) supplied by Fluka.
Apparatus and analysis methods
All treatments were performed at constant tem-
perature (35 C) in a thermostatic bath, except the
third and fifth ones. These two treatment stages were
carried out in a jacketed glass reactor where tempera-
tures (35 and 25 C, respectively) were controlled by
water circulation. In both steps agitation was assured
by a mechanic stirrer.

Table 1. Ionic composition of brines (g L-1)

+ + 2+ 2+ - 2-
Brine Na K Mg Ca Cl SO4
S0 (initial) 41.32 7.36 53.95 0.40 205.14 30.50
S1 21.62 10.95 77.76 0.00 234.57 43.81
S2 13.14 12.77 90.52 0.00 265.97 51.89
S3 6.64 7.55 70.35 0.00 224.73 6.09
S4 4.02 5.88 100.89 0.00 299.35 8.25

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R. FEZEI, H. HAMMI, A. MNIF: EXTRACTIVE PROCESS FOR PREPARING HIGH PURITY CI&CEQ 18 (1) 8388 (2012)

Brines and solid phases collected from the diffe- of the 35 C isotherm of the quinary system Na+, K+,
rent treatment stages of the process were chemically Mg2+/Cl-, SO42-//H2O usually used to describe brines
analyzed. The chemical analysis methods applied for equilibrium states. In this diagram, the coordinates of
sulphate, chloride, magnesium, and alkaline ions a considered solution are expressed as follows:
were respectively gravimetry, potentiometry (Titrino 100nK 2
DMS 716 of mark Metrohm), EDTA complexometry %K 2 ,
D
and flame atomic absorption spectroscopy (SAAF).
100nMg
Furthermore, X-ray diffraction analysis using a %Mg ,
Philips instrument (PW 3040 generator, 3050/60 /2) D
and CoK radiation ( = 1.789 ) were performed. 100n SO4
%SO4 ,
D
RESULTS AND DISCUSSION D nK 2 nMg nSO4 ,

Ionic composition of the original brine (S0) and
circulating solutions (Si, i refers to the corresponding
treatment) are summarized in Table 1.
As expected, the first four treatment stages gave
a magnesium chloride solution (S4) containing smaller
amounts of sodium chloride, potassium chloride and
magnesium sulphate. Thus, such solution may be suit-
able for magnesium chloride salt precipitation by di-
oxan as MgCl26H2OC4H8O2.
Chemical composition evolution of the treated
brine is well seen in Figure 2. It represents a section
where ni is the mole number of the i entity.
Geometrical positions of the original brine (S0)
and the mother liquors resulting from the four consi-
dered treatment stages (S1, S2, S3 and S4) in the
equilibrium diagram show the brines evolution to-
wards the crystallization field of magnesium chloride
hexahydrate (MgCl2.6H2O).
Regarding the recovered solid phases (Sdi),
their ionic compositions are given in Table 2. Besides
chemical analysis, they were also characterized by X-
-ray diffraction. Results of this characterization are
represented by Figures 3 and 4.

Figure 2. 35 C Isotherm of the quinary system Na+, K+, Mg2+/Cl-, SO42-//H2O (NaCl saturated).

Table 2. Ionic compositions of solid phases (mass%)

+ + 2+ 2+ - 2-
Brine Na K Mg Ca Cl SO4
Sd1 35.90 0.26 1.02 0.00 56.25 2.55
Sd2 35.10 0.37 1.27 0.00 55.29 2.42
Sd3 1.92 2.32 1.53 21.06 2.15 50.46
Sd4 0.62 14.02 8.13 0.00 38.32 0.89
Sd5 0.06 0.05 7.94 0.00 23.10 0.00
Sd6 0.11 0.09 11.61 0.00 34.05 0.00

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R. FEZEI, H. HAMMI, A. MNIF: EXTRACTIVE PROCESS FOR PREPARING HIGH PURITY CI&CEQ 18 (1) 83-88 (2012)

Figure 3. Diffractograms of the solid phases Sd1 (a), Sd2 (b), Sd3 (c) and Sd4 (d).

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R. FEZEI, H. HAMMI, A. MNIF: EXTRACTIVE PROCESS FOR PREPARING HIGH PURITY CI&CEQ 18 (1) 8388 (2012)

Figure 4. XRD Patterns of the solid phase precipitated by dioxane a) before drying and b) after drying.

Solids resulting from the first two treatment
stages (Sd1, Sd2) are sodium chloride salts containing
less than 5% impurities (mainly ions from coating so-
lution). The chemically precipitated compound, Sd3, is
almost pure gypsum. Salt Sd4 is basically carnallite
(KClMgCl26H2O) containing little quantities of halite
(NaCl). Solid Sd5 precipitated by dioxan corresponds
to the compound MgCl26H2OC4H8O2 including sub-
stantial amounts of sodium, potassium and sulphate
ions. Finally, the end-product obtained by drying Sd5
solid phase is an extremely pure magnesium chloride
hexahydrate salt. Its purity is more than 99.5%. When
treating one liter of brine, 155 grams of this salt were
recovered, i.e., an overall process yield of 40%.
Considering the information provided by the ex-
perimental results regarding the solid phases reco-
vered, only one difference was noted in comparison
with our predictions. It is the absence of double salt
KClMgSO43H2O (Kanite) in Sd2 solid phase. Lack of
this salt could be explained by its low crystallization
rate. In fact, magnesium ions exist in aqueous solu-
tions predominantly as [Mg(H2O)6]2+ which promote the
formation of salts having six water molecules in their
structures.
To show the importance of prepared salt, we
studied its industrial application in Sorel cement ma-
nufacture. The compressive strength and setting time
of the obtained cement paste were determined and
were 86 MPa and 62 min, respectively. These values
are comparable to those found when using com-
mercial magnesium chloride hexahydrate.

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R. FEZEI, H. HAMMI, A. MNIF: EXTRACTIVE PROCESS FOR PREPARING HIGH PURITY CI&CEQ 18 (1) 8388 (2012)

CONCLUSIONS [9] L. Zayani, R. Rokbani, M. Trabelsi-Ayadi, J. Therm. Anal.

Calorim. 57 (1999) 575585
This work is a contribution to the vaporization [10] H. Hammi, A. Mnif, R. Rokbani, J. de physique IV 11
studies of Tunisian natural resources dealing with the (2001) 157-163
extraction of magnesium chloride hexahydrate salt [11] H. Hammi, J. Musso, A. Mnif, R. Rokbani, J. Calphad 27
from Sebkha el melah natural brine. To perform this (2003) 71-77
task, a five stage process based on isothermal eva- [12] H. Hammi, J. Musso, A. Mnif, R. Rokbani, Desalination
poration and chemical precipitation was performed. 158 (2003) 215-220
The conceived process gave good quality magnesium [13] H. Hammi, J. Musso, A. Mnif, R. Rokbani, J. de physique
chloride hexahydrate (purity higher than 99.5%) which IV 113 (2004) 119-123
was successfully checked in Sorel cement manufac- [14] H. Hammi, J. Musso, A. Mnif, R. Rokbani, Desalination
166 (2004) 205-208
ture. Besides this chloride, all the collected by pro-
ducts are also useful. [15] C. Djebali, L. Zayani, A. Mnif, R. Rokbani, J. Socit Chi-
mique Tunisie 4 (1998) 233244.
[16] L. Zayani, R. Rokbani, J. Therm. Anal. Calorim. 59 (2000)
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RADOUANNE FEZEI DOBIJANJE MAGNEZIJUM HLORID

HALIM HAMMI
ADEL MNIF
Technological pole of Borj Cedria,
National Center of Research in
Materials Sciences, Valorization
Laboratory of Useful Materials, Soliman,
Tunisia
NAUNI RAD
HEKSAHIDRATA VISOKE ISTOE POMOU
PROCESA EKSTRAKCIJE
U ovom radu je predstavljena metoda za pripremu magnezijum-hlorid heksahidrata (bi-
schofite) iz prirodne slane vode Sebkha el Melah u Zarzisu, Tunis. Proces se sastoji iz
pet faza, koji je u sutini zasnovan na kristalizaciji pomou izotermnog isparavanja i he-
mijske precipitacije. Prve dve faze su kristalizacije natrijum hlorida i dvogube soli kali-
juma i magnezijum. Zatim je dobijena smea tretirana rastvorom kalcijum-hlorida radi
desulfatizacije. Nakon toga, izvrena je jo jedna faza izotermnog isparavanja u cilju eli-
minisanja jona kalijuma u obliku karnalita, KClMgCl26H2O. Na kraju ove faze, dobijen
rastvor, primarno sastavljen od jona magnezijuma i hlorida, tretiran je dioksanom radi
precipitacije magnezijum-hlorida u obliku MgCl26H2OC4H8O2. Dobijeno jedinjenje je su-
eno na konstantnoj temperaturi od 100 C, pri emu je dobijen je kvalitetan magnezijum
-hlorid heksahidrat. Pored ove soli, iz razliitih faza procesa dobijeni su sporedni proiz-
vodi, koji su, takoe, korisni.
Kljune rei: proces; ekstrakcija, magnezijum hlorid, prirodna slana voda.

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