ISSN 1070-4272, Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 12, pp. 1804−1809.

© Pleiades Publishing, Ltd., 2014.

Original Russian Text © I.I. Goncharik, V.V. Shevchuk, N.P. Krut’ko, A.D. Smychnik, O.A. Kudina, 2014, published in Zhurnal Prikladnoi Khimii, 2014, Vol. 87,
No. 12, pp. 1719−1726.
INORGANIC SYNTHESIS AND INDUSTRIAL
INORGANIC CHEMISTRY

Synthesis of Potassium Sulfate by Conversion of Potassium

Chloride and Magnesium Sulfate

I. I. Goncharik, V. V. Shevchuk, N. P. Krut’ko, A. D. Smychnik, and O. A. Kudina

Institute of General and Inorganic Chemistry, National Academy of Sciences of Belarus,

ul. Surganova 9, Minsk, 220072 Belarus
e-mail: igiclpns@rambler.ru

Received December 29, 2014

Abstract—Possibility was studied of obtaining potassium sulfate by double-stage conversion of potassium

chloride and magnesium sulfate, with schoenite formed in the first stage and then decomposed with water into
potassium sulfate.
DOI: 10.1134/S1070427214120027

A topical task in potassium industry is to substantially
raise the production of chlorine-free potassium fertilizers.
At present, potassium chloride constitutes about 90% of
potassium fertilizers. However, potassium chloride is far
from being a versatile fertilizer because of containing
chlorine. Its introduction for a number of crop cultures
is limited, and is inadmissible in certain cases. To plants
of this kind belong potatoes, citrus cultures, some
vegetables, flowers, etc.
The best potassium fertilizers for chlorophobic
cultures are potassium sulfate and nitrate. It has been
found by comparing various forms of fertilizers on
different soils that, in any case, sulfate fertilizers (K2SO4)
are advantageous because of containing sulfur as a sulfate
ion, which is an irreplaceable nutritional element for plant
growth [1–3].
The problem of obtaining chlorine-free potassium
fertilizers has been recently at the focus of specialists’
attention both in CIS countries and in developed foreign
countries. At present, these fertilizers already are or are
to be manufactured in all countries producing potassium
fertilizers, and also in Japan and Belgium, both having no
potassium raw materials of their own. At the present-day
amounts of manufacture and consumption of chlorine-free
potassium fertilizers they are in deficit. This shows that
further development of the manufacture of chlorine-free
kinds of potassium fertilizers is necessary.
In the last years, particular attention has been given
to a study of conversion methods for manufacture of
potassium sulfate, based on the interaction of potassium
chloride and various kinds of sulfate-containing raw
materials [4] by the reaction
KCl + МSO4 → K2SO4 + МCln, (1)
where M = Na+, NH4+, H+, Ca2+, Mg2+, etc.
However, the described conversion methods are to use
as raw material potassium chloride, which is a product
obtained in processing of natural potassium salts and
thus only replace one kind of potassium fertilizers with
another, rather than raising the output of the product by
the potassium industry.
In the world, there are several major deposits of natural
potassium-magnesium polymineral ores of the sulfate
type, whose processing can yield potassium sulfate or
other kinds of chlorine-free potassium fertilizers. To
these belong the remainder of the Ciscarpathian deposit,
Zhilenskoe deposit of polyhalite ores, hartsaltz German
ores, and the Delowar deposit of langbeinite ores in the
United States.
Analysis of published data shows that manufacture
of chlorine-free potassium fertilizers from natural raw
materials of the magnesium-potassium-sulfate type is
based on the solubility diagram of the four-component

1804
 SYNTHESIS OF POTASSIUM SULFATE 1805

Table 1. Effect of temperature on the synthesis of schoenite. Agitation duration 60 min

Salt composition, wt %
Т, °C Product Degree of potassium utilization, %
KCl MgCl2 MgSO4 K2SO4 sum of salts H2O
25 Schoenite liquor 6.54 7.10 10.83 – 24.47 75.53
67.90
Solid phase – – 29.77 43.30 – 26.93
35 Schoenite liquor 6.72 7.19 12.95 – 26.86 73.14
65.30
Solid phase – – 29.71 42.78 – 27.51
50 Schoenite liquor 9.12 4.28 15.13 – 28.58 71.42
44.60
Solid phase – – 29.61 42.55 – 27.84

water-salt system K+, Mg2+ || Cl–, SO42– –H2O. The
technique for reacting magnesium sulfate and potassium
chloride was developed by Kurnakova and Luk’yanova
[5]. They found that, to provide the maximum conversion
from chloride to sulfate, the process should be performed
in two stages to obtain in the first stage an intermediate
product, schoenite, which decomposes in the second stage
to K2SO4 by the scheme
2KCl + 2MgSO4 + 6H2O
→ K2SO4·MgSO4·6H2O + MgCl2, (2)
K2SO4·MgSO4·6H2O + nH2O
→ K2SO4 + MgSO4 + (n + 6)H2O. (3)
All the known industrial plants manufacturing
potassium sulfate employ this scheme with variations,
depending on the raw material being used. However,
there is no clear understanding of the process in which
schoenite is obtained [reaction (2)]. The effects of
temperature, ratio between the starting components, l : s
ratio, agitation duration have been insufficiently studied.
Our communication presents the results obtained in
synthesis of schoenite and its subsequent decomposition
to K2SO4, with potassium chloride and magnesium
sulfate of reagent grade used as raw materials. Epsomite
(MgSO4·7H2O) was used as magnesium sulfate.
Experiments were performed as follows. Potassium
chloride was poured in the solid form with grain size of
1 mm into a 25% solution of magnesium sulfate. The
conversion was performed under permanent agitation.
After a run was complete, the suspension was filtered
at the temperature of experiment. The starting and final
products were weighed and subjected to a comprehensive
chemical analysis. K+ was determined by the spectral
method (flame photometry); Mg2+, by complexonometric
titration with Trilon B; Cl–, by direct titration with an
AgNO3 solution in the presence of K2CrO4; and SO42–,
by the gravimetric method. The composition of the
solid phase was additionally monitored by X-ray phase
analysis.
We used as the completeness criterion of the process
the degree of utilization of the K+ ion in the solid phase,
calculated as the ratio between the amount of K+ ions in
the resulting solid phase and the content of K+ ions in
the starting product.
Let us consider the effect of temperature, agitation
time, and l : s ratio on the process in which schoenite
(K2SO4 MgSO4·6H2O) is obtained via the interaction of
KCl and MgSO4·7H2O by reaction (2).
The effect of temperature on the degree of conversion
was determined in the temperature range 25–50°C at the
stoichiometric ratio between the starting components in
the course of 1 h. It is known that, all other conditions
being the same, raising the temperature accelerates a
chemical process and reduces the viscosity of the medium,
which must lead to faster collisions between reactant
molecules. However, the data obtained (Table 1) indicate
that the optimal temperature at which the degree of
utilization of potassium ions is 67.9% is 25°C. At 50°C,
this parameter falls to 44.6% because of the increasing
solubility of the salts. For example, the concentrations of
the MgSO4 and KCl salts in solution at 25°C are 10.83 and
6.54%, respectively, whereas at 50°C, their concentrations
increase to 15.13 and 9.12%, respectively. Performing the
conversion at room temperature is the most economically
efficient because of making it possible to carry out the
process without additional energy expenditure for heating
or cooling.
The optimal time was also determined at the
stoichiometric ratio between potassium chloride and
magnesium sulfate. Kinetic curves were recorded

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 87 No. 12 2014

1806 GONCHARIK et al.

Table 2. Effect of the expenditure rate of KCl on the synthesis of schoenite. Temperature 25°C, agitation duration 60 min
Salt composition, wt %
Expenditure rate of KCl relative Degree of potassium
Product sum of
to stoichiometry KCl MgCl2 MgSO4 K2SO4 H2O utilization, %
salts
80 Schoenite 5.43 5.46 12.19 – 23.08 76.91 71.20
liquor
Solid phase – – 29.34 44.79 – 25.87
100 Schoenite 6.71 7.62 9.04 – 23.37 76.63 67.98
liquor
Solid phase – – 29.07 47.83 – 26.10
110 Schoenite 8.56 7.04 9.33 – 24.93 75.04 66.70
liquor
Solid phase – – 29.71 42.43 – 27.06
120 Schoenite 8.41 7.42 8.35 – 24.18 75.82 64.50
liquor
Solid phase – – 30.11 43.29 – 26.59

at agitation durations of 15, 30, 45, and 60 min and
temperatures of 25, 35, and 60°C (see figure).
The reaction is fast even at low temperatures of 25
and 35°C and, already during 15 min, the degree of
utilization of potassium ions reaches large values of 64
and 63%, respectively. Then the process becomes slower
and the ionic composition of the liquid phase starts to
change gradually and slowly. The degree of utilization of
potassium ions increased during 1 h of agitation by only
2–3% to become 67.9 and 65.3%, respectively. At 50°C,
this parameter reaches the maximum value (44.60%)
already in 15 min.
The chemical composition of the solid phases obtained
in the given experiments confirms that schoenite is
ε, %
τ, min
Kinetic curves for the process of schoenite synthesis at various
temperature. (ε) Degree of utilization of potassium ions and (τ)
agitation duration. T (°C): (1) 50, (2) 35, and (3) 25.
formed because their contents of MgSO4, K2SO4, and
H2O are 29.77, 43.30, and 26.93%, respectively (Table 1,
temperature 25°C). That is, it is nearly the same as that
of the chemically pure product (schoenite): 29.9, 43.3,
and 26.5%, respectively. The data were confirmed by
X-ray diffraction patterns measured for these products.
The patterns clearly demonstrate that schoenite is formed.
The effect of changing the expenditure rate of potas-
sium chloride relative to the stoichiometry was examined
using reaction (2) with introduction of various amounts of
the potassium salt: 80, 100, 110, and 120% relative to the
stoichiometry at 25°C and agitation duration of 60 min
(Table 2). It was found that it is the most appropriate to
use in the given case the stoichiometric expenditure rate
of KCl. Raising the expenditure rate of KCl to above
the stoichiometry leads to a decrease in the degree of
utilization of potassium ions in the finished product. For
example, this parameter is 71.2% at a 20% deficiency of
KCl and only 64.5% at its 20% excess.
In the conversion of potassium chloride with
magnesium sulfate in the case when the expenditure
rate of KCl is lower than the stoichiometric value, part
of the unreacted magnesium sulfate remains in solution,
which is indicated by its high content in the liquid phase,
about 12.19% against 9.04 and 8.35% at 100 and 120%
expenditure rates relative to the stoichiometry. At the
same time, raising the expenditure rate of KCl leads to
its accumulation in the liquid phase. Its content increases
from 5.43% at a deficiency of KCl to 8.41% at a 120%
excess of KCl.

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 87 No. 12 2014

 SYNTHESIS OF POTASSIUM SULFATE 1807

Table 3. Effect of the l : s ratio on the synthesis of schoenite

Mineralogical composition of the solid Degree of
Run l : s Salt composition, wt %
Product phase, % potassium
no. ratio
KCl MgCl2 MgSO4 K2SO4 H2O schoenite MgSO4·6H2O K2SO4 KCl utilization, %
1 1:1 Schoenite 4.66 20.08 5.68 – 69.58 – – – – 82.00
liquor
Solid 6.10 – 29.21 37.98 – 87.8 6.1 0 6.1
phase
2 1.4 : 1 Schoenite 5.41 12.55 7.11 – 79.93 – – – – 76.00
liquor
Solid 3.50 – 29.71 39.93 – 92.3 4.2 0 3.5
phase
3 1.7 : 1 Schoenite 6.71 7.6 9.09 – 76.6 – – – – 67.40
liquor
Solid – – 30.02 43.22 – 100 0 0 0
phase
4 2:1 Schoenite 8.59 5.63 9.41 – 76.37 – – – – 41.46
liquor
Solid – – 31.59 40.55 – 100 0 0 0
phase
5 3:1 Schoenite 0.48 3.95 5.90 – 79.67 – – – – 58.42
liquor
Solid – – – – 38.9 0 61.1 0
phase

The effect of the l : s ratio on the qualitative and
quantitative characteristics of the process of potassium
chloride and magnesium sulfate conversion was studied at
the stoichiometric expenditure rate, temperature of 25°C,
and agitation duration of 60 min. The l : s ratio was varied
from 1 : 1 to 3 : 1. The data obtained demonstrate (Table 1)
that raising the share of water leads to a decrease in the
degree of utilization of potassium ions. For example, at
the l : s ratios of 1 : 1, 1.4 : 1, 1.7 : 1, and 2.0 : 1, the
degrees of utilization of potassium ions are 82.0, 76.0,
67.4, and 41.46%, respectively. The results of the study
demonstrate that lowering the amount of introduced water
makes higher the content of starting components in the
finished product. The content of KCl and MgSO4 in the
solid phase, in addition to schoenite, was 6.1% each at
l : s = 1 : 1 and 3.5 and 4.2%, respectively, at l : s = 1.4 : 1.
With the l : s ratio raised further, to 1.7 : 1 and 2 : 1, the
solid phase is 100% composed of schoenite.
Raising the share of water by a factor of 3 (l : s = 3 : 1)
makes it possible to obtain K2SO4-enriched schoenite. It
was found that the solid phase contains 38.9% schoenite
and 61.1% K2SO4. Presumably, two processes occur in
the latter case: conversion of KCl and MgSO4 and simple
decomposition of schoenite, its incongruent dissolution
to give a new solid phase of potassium sulfate, just
which leads to an increase in the degree of utilization of
potassium ions to 58.42%.
It was found that the l : s ratio of 1.7 : 1 is the
optimal for obtaining schoenite by conversion of KCl
and MgSO4. In this case, the total amount of salts in the
liquor is 23.4%. The compositions of the liquid phases
obtained in run nos. 1 and 2 (Table 3) lie in the solubility
diagram of salts in the system K+, Mg2+ || Cl–, SO42– –
H2O in the region that is multiple of the point KCl +
MgSO4·K2SO4·6H2O + MgSO4·7H2O; the compositions
of the liquid phases obtained in run nos. 3 and 4 lie in the
field of schoenite, and the composition of the liquid phase
from run no. 5 lies at the boundary between the schoenite
and arcanite formation regions. Further increase in the
l : s ratio to above the value specified above results in

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 87 No. 12 2014

1808 GONCHARIK et al.

Table 4. Effect of temperature and agitation duration on the composition of the solid phasein the course of schoenite decomposition
by water
Mineralogical composition of the
Agitation Salt composition, wt % Degree of potassium
Т, °C solid phase, %
duration, min utilization, %
MgCl2 MgSO4 K2SO4 H2O schoenite leonite K2SO4
90 – 29.71 43.16 27.13 – 88.5 11.5 21.00
120 – 32.19 48.79 19.09 – 87.7 16.6 22.88
25
360 – 21.79 58.39 17.91 – 73.4 26.6 25.23
1 day – 23.77 54.36 21.86 – 80.3 19.7 29.23
30 0.70 25.13 47.21 26.96 86.6 – 13.4 –
35 60 0.70 23.19 47.21 26.96 77.52 – 22.48 21.30
90 0.70 21.16 47.21 26.96 75.70 – 24.40 23.10
30 1.37 2.71 80.21 15.72 – 19.79 80.90 51.30
50
60 1.15 2.35 80.30 16.19 – 19.70 80.30 51.40

the formation of dilute liquors whose utilization cause
considerable difficulties in their processing.
Aqueous decomposition of schoenite. Production
of potassium sulfate by decomposition of schoenite is
one of the main and final procedures in processing of
polymetallic ores. Schoenite is rather easily dissolved
in water. In its nature schoenite belongs to the class
of incongruently soluble double salts, i.e., schoenite is
dissolved with decomposition of the crystal hydrate,
with potassium sulfate remaining in the solid phase.
Schematically, the process of schoenite decomposition
can be described by the reaction
2K2SO4·MgSO4·6H2O + nH2O → [K2SO4 + 2MgSO4
+ (n + 6)H2O]sol + K2SO4↓. (4)
Experiments of decomposition of schoenite with water
were performed in a single stage. In single-stage runs, the
process was commenced at 77–78°C; after a prescribed
time the slurry was cooled to 50 or 35°C and the agitation
was continued for 20–30 min more to eliminate the
supersaturation with potassium sulfate. For comparison,
we first carried out experiments on decomposition of
schoenite of the same composition at temperatures of 25,
35, and 50°C, with the decomposition time varying from
30 to 90 min (to 360 min at 25°C).
The results obtained are listed in Table 4. The data in
Table 4 suggest that the process depends on the temperature
of experiment. It was found that no decomposition of
schoenite is observed at 25°C, even upon 90 min of
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 87 No. 12 2014
agitation. In these conditions, the solid phase contains
only 11.5% K2SO4, with the rest represented by leonite. A
certain increase in the content of potassium sulfate in the
solid phase to 16.6% is observed as the agitation duration
is raised to 3 h, and to 27.8% in 6 h. About the same
results were obtained in decomposition of schoenite at
35°C. The only difference is that the content of potassium
sulfate is somewhat higher: 24.4% in 1.5 h, which exceeds
by 13% the results obtained at 25°C. Decomposition
of schoenite at 50°C makes it possible to reach a high
degree of schoenite conversion to potassium sulfate. In
this case, the content of potassium sulfate in the finished
product already after 30 min of agitation is up to 80.9%;
the degree of utilization of potassium ions increases to
51.3%. At the same time, making longer (60 min) the
agitation duration at 50°C has no noticeable effect on the
schoenite decomposition process.
Effect of the l : s ratio on the process of schoenite
decomposition by water. An important parameter in
obtaining K2SO4 by decomposition of schoenite with
water is the minimum amount of water at which the
degree of utilization of potassium ions is at the optimum
and the content of K2SO4 in the finished product is high.
An increased expenditure of water will lead to a large
amount of solutions to be evaporated, which will require
a greater expenditure of thermal energy.
Experiments were performed at 50°C, because this
temperature is optimal in decomposition of schoenite with
water at l : s ratios of 0.95 : 1, 1 : 1, 1.1 : 1, and 1.5 : 1.
The agitation duration was 60 min.
 SYNTHESIS OF POTASSIUM SULFATE 1809

Table 5. Effect of the l : s ratio on the composition of sulfate liquor and solid phase in decomposition of schoenite

Mineralogical composition of the solid

Salt composition, wt % Degree of potassium
l : s ratio Product phase, %
utilization, %
KCl MgSO4 K2SO4 H2O schoenite langbeinite K2SO4
0.95 : 1 Sulfate liquor 1.49 18.95 12.77 66.79 – – – 55.39
Solid phase – 5.5 94.48 – – 9.50 90.50
1:1 Sulfate liquor 0.57 16.64 11.31 71.78 – – – 43.77
Solid phase – 1.99 96.49 – 6.20 – 93.80
1.1 : 1 Sulfate liquor – 16.0 10.98 73.02 – – – 39.73
Solid phase – 1.48 97.37 – 4.80 – 95.20
1.5 : 1 Sulfate liquor – 6.04 12.20 81.79 – – – 37.64
Solid phase – 1.14 99.20 – 3.80 – 96.20

The experimental results are listed in Table 5.
As expected, raising the l : s ratio changes the salt
concentrations in both liquid and solid phases. For
example, the content of MgSO 4 and K 2SO 4 in the
liquid phase is 18.95 and 12.77%, respectively, at l : s =
0.95 : 1, whereas at l : s = 1.1 : 1, it decreases to 16.64
and 10.98%, respectively. Because of the enhanced
dissolution of the salts, the degree of utilization of
potassium ions decreases from 55.39% at l : s = 0.95 : 1
to 37.64% at l : s of 1.5 : 1. However, the content of
K2SO4 in the solid phase substantially grows on raising
the l : s ratio, from 90.50% at l : s = 0.95 : 1 to 96.20%
at l : s = 1.5 : 1. Despite the high content of K2SO4 in
the solid phase upon decomposition of schoenite with
water at l : s = 1.5 : 1, it is necessary to consider that
the optimal l : s ratio is 0.95 : 1. This conclusion is in
agreement with published data.
Thus, the study demonstrated the possibility of
obtaining potassium sulfate by double-stage conversion
of KCl and MgSO4, with schoenite formed in the first
stage and then decomposed by water to potassium sulfate.
CONCLUSIONS
(1) The implementation of the double-stage method
for obtaining potassium sulfate was studied. The method
consists in reacting potassium chloride and magnesium
sulfate salts to give schoenite, with its subsequent
decomposition by water to potassium sulfate.
(2) The optimal conditions of both stages of the
process were determined: first stage: temperature 25°C,
interaction duration 1 h, stoichiometric amounts of
the starting components, l : s = 1.75 : 1; second stage:
temperature 48–50°C, agitation duration 1–1.5 h, l : s =
0.95 : 1.
REFERENCES
1. Prokoshev, V.V. and Deryugin, I.P., Kalii i kaliinye
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pochv v intensivnom zemledelii Nechernozemnoi polosy
(Extended Soil Fertility Recovery in Intensive Crop Farming
at the Nonchernozem Belt), Moscow: Rosagropromizdat,
1993.
3. Prokoshev, V.V. and Bogdevich, I.M., Kaliinye udobreniya.
Znachenie, proizvodstvo, primenenie, ekologiya (Potassium
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4. Grabovenko, V.A., Proizvodstvo beskhlornykh kaliinykh
udobrenii (Manufacture of Chlorine-Free Potassium
Fertilizers), Leningrad: Khimiya, 1980.
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