United States Patent (19) 11 Patent Number: 4,533,536

Bichara et al. (45) Date of Patent: Aug. 6, 1985

(54) PROCESS FOR THE MANUFACTURE OF 56) References Cited
POTASSUMSULPHATE BY TREATING U.S. PATENT DOCUMENTS
SOLUTIONS CONTAINING MAGNESUM
CHLORIDE AND POTASSUM CHLORIDE 2,902,344 9/1959 Cevidalli et al..................... 423/551
3,058,806 10/1962 Ebner ............... ... 42.3/552
3,528,767 9/1970 Garrett ..... ... 42.3/551
75) Inventors: Michel Bichara, Mulhouse; Emile 3,687,638 8/1972 Neitzel .................................. 23/302
Wendling, Morshwiller le Bas; 4,129,642 12/1978 Neitzel ..... ... 423/197
Michel Bodu, Mulhouse, all of 4,306,880 12/1981 Garrett .............................. 23/295 S
France
FOREIGN PATENT DOCUMENTS
73) Assignee: Mines de Potasse d'Alsace S.A., 552948 12/1956 Italy .................................... 423/552
587673 1/1959 Italy ..................... ... 42.3/552
Mulhouse, France 261991 12/1926 United Kingdom. 423/551
298535 6/1971 U.S.S.R. ... 423/551
716979 2/1980 U.S.S.R. ... ... 42.3/551
21 Appl. No.: 474,362 767030 9/1980 U.S.S.R. .............................. 423/552
Primary Examiner-Gary P. Straub
22 Filed: Mar. 11, 1983 Attorney, Agent, or Firm-Millen & White
(30) Foreign Application Priority Data 57 ABSTRACT
Mar. 11, 1982 FR) France ................................ 82 04.078 Process for the manufacture of potassium sulphate from
solutions containing magnesium chloride and potassium
chloride from solutions, more particularly from mother
51) Int. Cl......................... C01D 5/06; C01B 17/96; liquors issuing from the treatment of carnallite. Accord
CO1F 5/34 ing to this process sodium sulphate and potassium chlo
52 U.S. Cl. .................................... 423/551; 423/199; ride are added to the solutions so as to precipitate so
423/166; 423/205; 423/499; 42.3/544; 23/298; dium chloride and schoenite (K2SO4.MgSO4.6H2O)
23/302 R; 23/303; 23/304 and the schoenite is treated in a known manner to pro
58) Field of Search ..................... 23/298, 300, 302 R, duce potassium sulphate.
23/303, 304; 423/166, 178, 191, 193,205, 499,
551, 552, 199 6 Claims, No Drawings
 4,533,536
1. 2
sodium chloride and schoenite, K2SO4.MgSO4.6H2O,
PROCESS FOR THE MANUFACTURE OF and the schoenite obtained is treated in a known manner
POTASSUMSULPHATE BY TREATING to produce potassium sulphate.
SOLUTIONS CONTAINING MAGNESUM In other words, the process of the present invention
CHLORIDE AND POTASSIUM CHLORIDE 5 enables potassium sulphate to be produced from KCl
BACKGROUND OF THE INVENTION
via the intermediate of schoenite, the sulphate ions
being supplied by sodium sulphate.
The present invention relates to a process for the In fact, it may be thought that, according to the pres
manufacture of potassium sulphate from solutions con 10
ent invention, a double decomposition reaction is
taining magnesium chloride, such as solutions of car brought about between sodium sulphate and magnesium
nallite ore and, in particular, the equilibrium mother and potassium chlorides, which could be written:
liquors of a unit for the treatment of carnallite.
Carnallite is a salt having the following composition:
KCl.MgCl2.6H2O. It is found in solid form in a certain
number of deposits, and it is present, in the form of 15
impurities, in larger or smaller amounts, in a certain This double decomposition reaction between sodium
number of other potassium deposits. Otherwise, it can sulphate and magnesium chloride is relatively fast, the
be crystallized from natural brines. equilibrium being established in two hours.
Whatever its origin, carnallite is brought into contact, If the amount of sodium sulphate required and the
for treatment, with a decomposition mother liquor hav whole of the amount of potassium chloride required are
ing a content of MgCl2, KCl and NaCl such that potas added in one single lot, a solid is precipitated, contain
sium chloride and sodium chloride (synthetic sylvinite) ing about 65 to 70% of schoenite and 30 to 35% of
are precipitated in an equilibrium mother liquor. This sodium chloride. The schoenite is subsequently concen
equilibrium mother liquor is saturated with potassium trated by screening, by washing or, more particularly,
chloride and sodium chloride, and it is more or less 25 by flotation.
saturated with magnesium chloride. A particularly advantageous process consists in car
This equilibrium mother liquor is frequently dis rying out the precipitation of the salts in two stages. In
carded, but, in that case, the potassium which it contains a first stage, the whole of the sodium sulphate required
is lost and the potassium yield of the unit is poor. At and, if appropriate, the minimum amount of potassium
tempts have been made to concentrate this equilibrium 30 chloride required to ensure saturation of the solution or
mother liquor in order to recover an additional amount
of carnallite which is recycled. In practice, however, of the mother liquors, containing magnesium chloride,
are introduced.
this evaporation is economical only to the extent that it A solid is then precipitated, containing about 80 to
can be carried out by natural evaporation, for example, 90% of sodium chloride. This solid is separated off by
in solar evaporation pools. 35
filtration or centrifugation. The amount of potassium
SUMMARY OF THE INVENTION chloride, required for obtaining a second precipitate
It is thus an object of the present invention to provide thecontaining from 85 to 95% of schoenite, is then added to
a a process for converting the potassium contained in filtrate. This process is particularly advantageous
these mother liquors, into potassium sulphate. since the schoenite content of this second precipitate is
It is another object of the invention to manufacture sufficiently high for simple washing to enable a product
potassium sulphate from potassium chloride via the to be obtained which, by decomposition, directly
intermediate production of schoenite, the sulphate ions supplies a potassium sulphate having a commercially
being supplied by sodium sulphate. customary K2O content, that is to say higher than, or
45 equal to, 50%. In the presence of NaCl, Na2SO4 is
DETALED DISCUSSION OF THE INVENTION formed by a secondary reaction during decomposition
It is known to prepare potassium sulphate from and glaserite (Na2SO4.3K2SO4) is precipitated at the
schoenite (K2SO4.MgSO4.6H2O), obtained either by same time as K2SO4.
the conversion of kainite (KCI.MgSO4.2/75H2O) or The schoenite is treated in a known manner for re
from magnesium sulphate and potassium chloride. This 50 covering the potassium sulphate. For example, it may
latter process is most frequently carried out at a temper be decomposed at a temperature of 55° C. in the pres
ature higher than ambient temperature. ence of water. After a residence time of about 2 hours,
It is also known to prepare potassium sulphate from the reaction yields a precipitate of K2SO4 and a mother
sodium sulphate and potassium chloride. A double de liquor rich in magnesium sulphate. The reaction may be
composition reaction between these two salts leads to 55 written:
the formation of sodium chloride and potassium sul
phate. The latter combines with unreacted sodium sul
phate to form a double sulphate, Na2SO4.3K2SO4 called
glaserite. An additional amount of potassium chloride is
added to this double salt, so as to produce potassium 60 The theoretical K2SO4 yield (mols of K2SO4/mols of
sulphate. The reactions are relatively slow and a resi schoenite) is 0.47. This yield can be increased by evapo
dence time of several hours is required for the solid/liq ration of the residual mother liquor, with precipitation
uid equilibria to be established. of a fresh amount of schoenite which is then converted
The present invention relates to a process for the again to K2SO4.
production of potassium sulphate from solutions con 65 The conversion of schoenite to potassium sulphate
taining magnesium chloride and potassium chloride, can also be carried out at ambient temperature by addi
according to which sodium sulphate and potassium tion of potassium chloride according to the reaction:
chloride are added to the solutions, so as to precipitate
 4,533,536
3 4.
K2SO4.MgSO4.6H2O.--2KCl-K2SO4- MgCl2--- Schoenite-3.1%
H2O KC-0.6%
The sodium sulphate added to the solutions contain- 2. Epi.
ing magnesium chloride can be anhydrous sodium sul- 5 Schoenite-86.2%
phate or hydrated sodium sulphate, for example the NaCl-7.8%
decahydrate. KC-4.7%
According to a preferred embodiment of the inven- MgCl2-1.3%
tion, the potassium chloride originates from the unit for
the treatment of carnallite. 10 EXAMPLE 3
The required amounts of sodium sulphate and potas 500 g of schoenite salt, prepared according to the
sium chloride are worked out from the equilibrium process described in Example 2 and having the compo
diagrams. The composition of the starting solutions is sition:
calculated and the composition of the final mother li schoenite-85.6%
quor, which it is desired to obtain, is determined from 5 NaCl-7.8%
the equilibrium diagrams. (MgCl2--KCl)-6.6%
If, for example, 1000 g of a mother liquor having the are washed with 100 g of water at 25°C. for 10 minutes.
following composition: After filtration, washing and drying, 381.1 g of a salt
MgCl2: 289 g/liter or 62.2 mols/1000 mols of water, having the following composition are obtained:
MgSO4: 52 g/liter or 8.8 mols/1000 mols of water, 20 schoenite-90%
KCl: 45 g/liter or 12.6 mols/1000 mols of water and
NaCl: 31 g/liter or 10.8 mols/1000 mols of water, NaCl--MgCl2-1%
is initially used, 409.4 g of Na2SO4.10H2O and 118.5g
of KCl have to be added to produce 253.6 g of a solid EXAMPLE 4.
consisting of 71.6% of schoenite and 28.4% of NaCl and 25 500 g of washed schoenite, obtained in accordance
1274 g of a mother liquor having the composition: with Example 2, are treated. 445g of water are added to
MgCl2: 32.0 mols/1000 mols of H2O, it and the mash obtained is stirred at 55 C. for 2 hours,
MgSO4: 14.4 mols/1000 mols of H2O, so as to decompose the schoenite. After filtration, 117.2
NaCl: 36.0 mols/1000 mols of H2O and g of a moist salt are obtained, which, after drying, has
KCI: 24.2 mols/1000 mols H2O. 30 the following composition:
The addition of Na2SO4 and KCl to the solutions K2SO4-96.5% (that is 53.2% K2O)
containing MgCl2 takes place at atmospheric pressure MgSO4-2.8%
and at ambient temperature. MgCl2-0.4%
The examples given below, without implying any NaCl-O.3%
limitation, will make the invention clearer. 35 We claim:
EXAMPLE 1. 1. In a process for the production of schoenite from
an equilibrium mother liquor obtained from a process of
500 cm3 of equilibrium mother liquors originating treating carnallite to precipitate synthetic Sylvinite, said
from the decomposition of a carnallite salt and having equilibrium mother liquor consisting essentially of satu
the following composition: ration quantities of potassium chloride and sodium chlo
MgCl2-289 g/liter, ride, a substantial-saturation quantity of magnesium
MgSO4-52 g/liter, chloride, and magnesium sulphate, wherein the schoe
KCl-45 g/liter and nite is precipitated from said equilibrium mother liquor,
NaCl-31 g/liter, the improvement which comprises in a first step adding
are treated. 45 sodium sulphate to said equilibrium mother liquor to
265 g of sodium sulphate decahydrate and 77 g of form a precipitate containing mainly sodium chloride;
potassium chloride are added. The mixture is stirred for separating said precipitate of sodium chloride from the
90 minutes at 25 C. and the precipitate obtained is resultant mother liquor; and in a second step adding
filtered off, 200 g of moist salt and 576 cm3 of filtrate are potassium chloride to said resultant mother liquor to
obtained. After drying, the recovered salt contains 68% 50 form a precipitate containing mainly schoenite.
of Schoenite and 29.7% of sodium chloride. 2. A process according to claim 1, wherein the potas
EXAMPLE 2 sium chloride added in the second step is obtained from
the process for the treatment of carnallite.
265 g of sodium sulphate decahydrate are added to 3. A process according to claim 1, wherein potassium
500 cm of equilibrium mother liquors, having the same 55 sulphate is recovered from the said precipitate of schoe
composition as in Example 1, and then the mixture is nite.
stirred for 30 minutes at 25 C. and filtered. 48.5g of a 4. A process according to claim 3, wherein the said
first moist precipitate and a first filtrate are recovered. precipitate of schoenite contains sodium chloride and is
76.7 g of KCl are added to this first filtrate and this new washed to separate sodium chloride prior to recovery
mixture is stirred for 60 minutes at 25 C. The reaction 60 of the potassium sulphate.
product is filtered off and 148.3 g of a moist salt of a 5. A process according to claim 3, wherein the schoe
second moist precipitate are thus recovered. nite is decomposed at a temperature of 55° C. in the
After drying (without washing, so as to displace the presence of water.
impregnation mother liquor) the precipitates have the 6. A process according to claim 3, wherein the schoe
following composition: 65 nite is decomposed at ambient temperature by addition
lst precipitate: of potassium chloride.
NaCl-94.5% ck e k