DESALINATION

ELSEVIER Desalination 167 (2004) 319-326

www.elsevier.com/locate/desal

NaNral brine valorisation: Application of the system

K+, Mg 2+/Cl*, SO4 //H2 Et 25 O C
Observations on kinetics formation of K2SO4 and K2SO4 MgSO4-6H2

D.B. Jannet, A. M’nif*, R. Rokbani

Laboratoire des procédes Chimiques, Institut National de Recherche Scientifique et Technique,
BP 95, 2050 Hammam Lif, Tunisie
Tel. +216 (71) 430053, Fax +216 (71) 430934, email: mnif.adel@inrst. run.tu

Received 1 March 2004; accepted 8 March 2004

Abstract
The crystallization ofK2SO, in the system K“, MQ’/Cl‘, SO, / H2O involving the reaction 2KCl + MgS 4 • KzSO,
+ 2KCl was studied. Independently of the experimental procedure applied, it was confirmed that schoenite
(K,SO4.MgSO .6H2O) is an inevitable intermediate product of the considered transformation. The double decom-
position reaction kinetics depend on formation and dissolution rates of intermediate salt and potassium sulphate,
respectively. The formation of schoenite outside of its crystallization field might indicate a metastable space extension of
this domain to cover the K2SO4 one. The formation kinetics rate of MgS 4 K, SO4 6H2O is quicker than the K2SO, one.

Keywords.’ Natural brine valorisation; K 4 crystallization; Formation kinetics rate of schoenite

1. Introduction potassium sulphate production. They are con-

verted by double decomposition in a single or
Potassium sulphate is a good fertiliser, which
multi-stage process according to the reaction:
is rarely found in nature; it has to be produced by
chemical reactions. Potassium chloride and mag-
2KCl + MgSO4 K SO4 * MgC12
nesium sulphate are some of the reagents used for
In the present work, potassium chloride and
*Corresponding author. magnesium sulphate may be recovered from

Presented at the EuroMed 2004 conference on Desalination Strategies in South Mediterranean Countries.‘ Cooperation
between Mediterranean Countries of Europe and the Southern Rim of the Mediterranean. Sponsored by the European
Desalination Society and Office National de l’Eau Potable, Marrakech, Morocco, 30 May-2 June, 2004.
0011-9164/04/$— See front matter0 2004 Elsevier B.V. All rights reserved
doi;10.1016/j.desal.2004.06.141
320 D.B. Jannet et al. 7 Desalination 167 (2004) 319—326

Tunisian natural brines by conventional proce- M, — 200 * [Mg2+] / P

dures, using crystallisation under natural condi-
tions [1,2]. The aim of this study is to outline the So4' 200 [SON‘/ P
process parameters and especially the reaction
time for each stage of the transformation process. Z = 100 [H2O] / P

P — 2 [Mg2“] + [K“] = 2[SON ] + [Cl ]

2. Transformation principle
Transformation obeys the above-mentioned
reaction. At a chosen temperature, the thermo-
dynamic conditions of this transformation are in
conformity with the reciprocal quaternary
diagram: K Cl MgC1 K SO4, MgSO4 /HU O.
Fig. 1 represents the 25°C isotherm of this dia-
gram, which was retraced from data in the
literature [4—6]. The Jänecké coordinates shown
below were utilized to create Fig. 1.
The Jänecké coordinates of points “R” and
“D” at 25°C [2,3] are presented in Table 1. The
proportions of the reagents employed to produce
K2SO4 are calculated using the above-mentioned
co-ordinates.
Considering Fig. 1, it is possible to obtain
potassium sulphate from two different ways:
Mode A: This is a one-stage procedure. The
raw materials in this case are epsomite, potassium
chloride and water. The reaction products are the

K 2S 4 MgStJ 4

04 K2SCI,g.MgSO§ .eHgO
K

MgŒ •6 H O
Fig. 1. 25°C isotherm of the sys-
MQ 12 tem K*, Mg“2 /Cl , SON /H2O.
 D.B. Jannet et al. / Desalination 167 (2004) 319—326
Table 1
Janecké coordinates of points "R" and "D"
Point X Y Z whole process, it is essential to recycle the "R"
"R" 55.42 17.82 888.00
"D" 89.32 19.58 640.00
potassium sulphate and solution“R”. Reaction(l)
corresponds to this transformation:
MgSO .7H,O + 2KCl + H O
4 2
K2SO,(sd) + Solution "R"
A mass balance of the one-stage transformation
was carried out using data in the literature. The
theoretical yield in sulphate ions for the transfor-
mation of the epsomite and KCl into potassium
sulphate is 67.85%.
Mode B: This is a two-stage method. The first
stage consists in the preparation of the schoenite
(K2 4 MgSO4.6HzO) by reacting epsomite
(MgSO,.7H,O), potassium chloride and water in
the proportions of point m' (Fig. 1). The products
of this reaction are schoenite and a solution
whose composition is equivalent to that of point
"D". The second stage consists of transforming
the obtained schoenite into potassium sulphate.
For this purpose, KC1 and H 2O are added in the
proportions of point m“.
The corresponding reactions are written as
below:
• First step:
MgSO4.7H2O(sd) + 2KC1(sd) + H2O
• K SO4.MgSO4 6H2O(sd) + Solution "D" (2)
• Second step:
K2SO4.MgSO4.6H2O(„ ) + 2KC1(, d) + HzO
K,SO(4 „ ) + Solution "R"
The solution corresponding to point "R" is
321
relatively rich in potassium chloride and epso-
mite. To improve the total output of this trans-
formation and to reduce water consumption of the
solution towards the first stage.
The calculated output in sulphate ions for the
first stage transformation is 87.69%, while the
sulphate theoretical yield for the second stage is
) SO4' 83.92%. Moreover, the total output in SO2
of the transformation process is 72.92%. This rate
is higher than that of the transformation per-
formed according to Mode A (72.92 > 67.85%).
In addition, as seen in Fig. 2, we envisaged the
(1) recycling of solution "R" towards the reactor of
the first stage in order to improve the output of
the process and to save the process water. For this
purpose we carried out calculations based on
points "R" and "D" of the compositions.
With an integral recycling of the solution "R",
the sulphate output is Pso‹' 78.0%. This kind of
recycling is not possible without a preliminary
evaporation of 32% water from the considered
solution. This operation constitutes an additional
stage in the transformation process, but it in-
creases the sulphate output of 5% (78% instead of
72.92%). It is important to notice that this
additional stage allowed saving 48% of the total
process water (rare in southern Tunisian).
(3)
Fig. 2. Flow diagram of K2SO preparation.
322 D.B. Jannet et al. / Desalination 167 (2004) 319—326

3. Experimental
3.1. Chemical analysis
The composition of liquid samples and solid
phases was determined by chemical analysis. The
K’ ion concentrations in the phases were
analyzed by spectrophotometer using a Jenway
PFP7 instrument(detection Li ‹0.25 ppm; linear-
ity -£ 5 ppm). The Mg2’ ion concentration was
determined by an EDTA complexometric titra-
tion. Potentiometric titration was applied to Cl
ions (Titrino DMS 716, f2 Metrohm instrument).
The SO4 ioll concentration was determined
gravimetrically. The solid phases were identified
by X-RD; the experimental apparatus is com-
posed of a Philips PW 1730/10 generator, a PW
1050/81 goniometer and a PW 2233/20 copper
cathode.

3.2. Experimental method

The double decomposition reaction was car-
ried out at 25OC in the experimental device
illustrated in Fig. 3. Using this equipment the
experimental tests were initially performed in
Mode A and then in accordance with Mode B.
3.3. One-sta e transformation: Code A
Orientation tests: In order to study the pro-
cedure’s influence on the product quality, we
carried out some orientation tests three different
ways:
1. First method: progressive addition of dry
potassium chloride in an adequately prepared
solution of epsomite.
2. Second method: progressive addition of a
previously prepared solution of epsomite to a
determined amount of potassium chloride.
3. Third method: epsomite and potassium
chloride were mixed together in order to obtain a
homogeneous solid mixture before the addition of
water.
To follow up the evolution of the reactions as
a function of time, every 2 h solids were analyzed
Fig. 3. Experimental device for the transformation of
epsomite and KC1 into potassium sulphate. 1 heating
resistance, 2 and 6 contact thermometers, 3 thermometer,
4 agitation motor, 5 cryoplonge, 7 reactor, 8 agitator,
9 bath thermostat.
by X-ray diffraction. The experiments were
stopped and the phases were separated when it
was checked that the solid corresponded to potas-
sium sulphate.
The above-mentioned methods are numbered
l, 2 and 3, respectively, and the X-ray diffraction
spectra are indicated li, 2i or 3i, according to the
method used. Indices i correspond to: a, b, c, d
and e, and indicate, respectively, K2SO4, the
product formed after 4 h, the product formed after
8 h, KC1 and finally MgSO4 As an example, we
give the XRD obtained from the third method in
Fig. 4.
 D.B. Jannet et al. / Desalination 167 (2004) 319—326
1600
*00
Fig. 4. XRD of the product synthesized according to the third method.
An examination of the results shows that
whichever method is adopted, schoenite is pro-
duced as an intermediate product. The formation
of this salt in the product of methods 2 and 3 is
not coherent with the adopted procedures. Indeed,
in these two cases but contrary to the first one,
the crystallization field of the schoenite was not
crossed to reach K ,SO 4 It seems that the schoe-
nite has kinetics of formation faster than that of
potassium sulphate. This fact is in favor of its
formation as an intermediate product.
In addition, we notice that the transformation
reaction is slow, which can be explained by the
kinetics of decomposition of the intermediate
product and formation of potassium sulphate.
This last salt probably has under these conditions
kinetics of formation slower than that of
schoenite.
It is also significant to note that schoenite was
formed apart from its stable field of existence.
That seems to indicate that the crystallisation
323
(*•)
field of this salt has a metastable space extension,
which partly covers the space reserved for potas-
sium sulphate.
The results of the chemical analyses for the
final liquid and solid phases resulting from the
tests practised according to the previously studied
three modes are indexed in Table 2. The filtrates
are indicated F F2 and F, and salts are noted S„
S2. and S„ respectively for modes 1, 2 and 3.
From thèse analytical results, we calculated the
Jänecké coordinates for each filtrate and each
salt. The obtained results are given in Table 3 for
the liquids and solids.
The coordinates of the experimental points are
comparable with those of the theoretically calcu-
lated point (fi,heo„i, , a ). Subsequent to the preced-
ing tests in which the schoenite appeared as an
intermediate product, we chose to go on with our
investigations using the first method. We propose
hereafter to pursue the evolution of the trans-
formation as a function of time. For this purpose
324 D.B. Jannet et al. / Desalination 167 (2004) 319—326

Table 2
Ionic compositions of the filtrates and solids

Filtrates, g.L ’ Salts, %

F, F,
K’ 90.00 85.00 95.00 39.52 40.08 38.32
Mg2“ 38.73 38.72 37.39 0.25 0.287 0.32
Cl 164.00 160.46 164.72 2.60 3.32 2.47
SO 44.17 43.66 44.21 47.10 45.78 45.54

Table 3
Jänecké coordinates of the filtrates and salts

Coordinates Filtrates Salts

2 F, K 2SO4 S2

X 55.42 57.74 59.01 55.54 0.00 1.98 2.25 2.66

17.82 16.68 16.86 16.64 100 93.98 90.90 93.58

we decided to determine the rate of magnesium in
the aqueous phase.
Evolution of the magnesium ion in the liquid
phase according to time: The samples were car-
ried out every 30 min. The experimental results
obtained are represented in Fig. 5 which shows
that the evolution of the Mg“2 ion concentration
in the liquid phase is subdivided into two parts, Of
and fi.
Initially the Mg2* concentration marks a
reduction from 41.88 g.L to 19.74 g.L '. This
observation confirms the formation of the inter-
mediate product, which requires the consumption
of the considered ion in accordance with the
following reaction:
MgSO4 K2SO4- 6H,O(sd) + 2KCl(sd) + HUO
« K S 4(sd) + MgCl,(aq)
According to this work, we deduced that the
reaction is quasi-complete after 6 h.
3.4. Two-stage transformation, Mode B
Potassium sulphate was prepared in this case
by transforming the epsomite into schoenite in the
first stage. The product was then transformed into
K 2 SO4 in the second stage. The two stages of this
transformation were carried out separately in the
experimental device (Fig. 3) previously used.

2MgSO4(sd) + 2KCl(sd) + H2O 3.5. First stage transformation of the reagents

MgSO4 K2SO4 6H2 (sd) + MgC 2(aq)
Part Of of the curve shows an increase of the Mg“2
ion concentration in solution. This is due to the
previously mentioned transformation (formation
of K2S 4) corresponding to the reaction:
into schoenite
According to Reaction (2), the magnesium
concentration in the aqueous phase stabilizes
when the equilibrium is reached. Therefore, this
ion was selected as an indicator of the evolution
of the reaction.
 D.B. Jannet et al. / Desalination 167 (2004) 319—326 325

60'

0 60 120 180 240

0 30 60 O0 l2W )50 |BD 20 240 270 300 33( 3EJ ))O 420 4*B
Time (min) Time (min)
Fig. S. Evolution of the magnesium concentration (g.L ') Fig. 6. Evolution of[Mg2“] according to time (first stage).
as a function of time.

Evolution of magnesium ion in the liquid

phase according to time: The samples were car-
ried out at 30 min. The experimental results are
represented in Fig. 6, which shows that the
magnesium content during the transformation in
the liquid phase is practically constant, with an 20

error lower than 2%. This means that the trans-

formation of the epsomite/KCl mixture is very
fast. Indeed a residence time of 15 min is suffi- Fig. 7. Evolution of [MJ“] as a function of time (second
cient for obtaining K2SO4.MgSO4.6H2O. stage).

3.6. Second stage. transformation of the
schoenite into potassium sulphate
For the study of this transformation we used
the schoenite obtained experimentally.
Evolution of[Mg2“] as a function of time: The
samples were taken each 15 min and thereafter
every hour. The evolution of the Mg 2’ ion con-
centration as a function of time is represented in
Fig. 7, which shows an increase of the mag-
nesium content in the solution during the trans-
formation. Indeed, the schoenite releases the MQ
ion into the solution to form potassium sulphate
following Reaction (2).
It was considered that this transformation was
finished after a reaction time of 2 h when the
concentration of magnesium in the liquid was
stabilized.
4. ConClusions
The considered transformation can be carried
out in one or two stages, mode A or mode B. We
showed that the second mode allows a better out-
put of the process by partial or integral recycling
of solution “R”. The increase in this output is
proportional to the amount of recycled solution.
326 D.B. Jannet et al. / Desalination 167 (2004) 319—326
In addition the experimental study showed that
whatever the adopted procedure, schoenite is
formed as an intermediate product.
The formation of the intermediate compound
led us to think about the existence of a metastable
field offormation of the schoenite which partially
or completely covers the stable field of existence
of K2SO4. A systematic study of the transfor-
mations showed that the reaction time is about 6 h
for mode A and 2 h for mode B.
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